CN1413127A

CN1413127A - Hydrocarbon hydrogenation catalyst and process

Info

Publication number: CN1413127A
Application number: CN00817094A
Authority: CN
Inventors: J·J·博格梅斯特; T－T·P·彻恩; G·A·德尔泽; S·A·齐斯曼; S·H·布朗; M·M·约翰逊; J·D·拜尔斯; D·B·泰德克; D·A·扬
Original assignee: Phillips Petroleum Co
Current assignee: Phillips Petroleum Co
Priority date: 1999-12-13
Filing date: 2000-11-10
Publication date: 2003-04-23
Also published as: AU3969301A; WO2001041923A1; EP1259319A1; CA2392259A1; BR0016337A; EP1259319A4

Abstract

A catalyst composition which can be used for hydrogenating a highly unsaturated hydrocarbon such as an alkyne or a diolefin to a less unsaturated hydrocarbon is disclosed. The catalyst composition contains palladium, an inorganic support, and a catalyst component of silver and an alkali metal compound. The catalyst composition can additionally contain a halide, preferably a halide of a non-alkali metal halide. A process of making such catalyst composition is also disclosed. The process of using such catalyst composition involves contacting a hydrocarbon-containing fluid, which contains a highly unsaturated hydrocarbon, with a catalyst composition in the presence of hydrogen under a hydrogenation condition sufficient to effect a hydrogenation of the highly unsaturated hydrocarbon. The process of using such catalyst composition can be conducted in the presence or absence of a sulfur impurity such as a sulfur compound.

Description

Hydrocarbon hydrogenation catalyst and method

Technical field

The present invention relates to a kind of carbon monoxide-olefin polymeric and make the method for highly undersaturated hydrocarbon hydrogenation with this carbon monoxide-olefin polymeric.

Background technology

Those skilled in the art are known can to produce low undersaturated hydrocarbon compound by thermal cracking process.For example, the fluid stream that contains saturated hydrocarbons such as ethane, propane, butane, pentane, naphtha etc. and composition thereof can be infeeded heat (or high temperature) cracking funace, in stove, make saturated hydrocarbons change into low undersaturated hydrocarbon compound such as ethene or propylene.These low undersaturated hydrocarbon are class important chemical that many commercial Application are arranged.For example, ethene can be used as monomer or comonomer is used to produce polyolefin.Other purposes of low unsaturated hydrocarbons is as well known to those skilled in the art.

Yet the low unsaturated hydrocarbons of producing by thermal cracking process generally comprises the undersaturated hydrocarbon of undesired height such as the alkynes or the alkadienes of appreciable amount.For example, ethene is generally polluted by highly undersaturated hydrocarbon such as acetylene, must make it to select to be hydrogenated to low unsaturated hydrocarbons such as ethene but be not hydrogenated to saturated hydrocarbons such as ethane in hydrogenation process.Similarly, propylene is generally polluted by acetylene, allylene and allene, must make it to select to be hydrogenated to low unsaturated hydrocarbons such as ethene or propylene in hydrogenation process but is not hydrogenated to saturated hydrocarbons such as ethane or propane.

In addition, the catalyst that comprises palladium and inorganic carrier such as aluminium oxide is the known catalysts that is used for height unsaturated hydrocarbons such as alkynes and/or alkadienes hydrogenation.Making acetylene select to be hydrogenated under the situation of ethene, can adopt the palladium and the silver catalyst that are carried on the aluminium oxide.Referring to the US4484015 of for example US4404124 and division, be incorporated herein for reference.The operating temperature of this hydrogenation process select like this so that basically all height unsaturated hydrocarbons such as alkynes (for example acetylene) all be hydrogenated to the low unsaturated hydrocarbons such as the olefine (as ethene) of its correspondence, have only very a spot of olefine to be hydrogenated to saturated hydrocarbons such as alkane (for example ethane) simultaneously thereby from product stream, remove alkynes.This selects hydrogenation process to make the low unsaturated hydrocarbons loss of requirement minimum, avoids unmanageable " out of control " reaction in early stage, total cracked gas was handled.

Those skilled in the art also know impurity such as carbon monoxide and the sulphur impurity such as the H that may exist in the charging that contains alkynes or the product stream ₂S, COS, mercaptan and organic sulfur compound can make palladium-containing catalyst poison and inactivation.For example, known carbon monoxide makes this hydrogenation catalyst reversible poisoning or inactivation.Those skilled in the art know that also sulphur impurity such as sulphur compound are (as H ₂S, COS, mercaptan and organic sulfur compound) hydrogenation catalyst is poisoned and inactivation.Because many equipment move under the situation that has various sulphur impurities continuously or at least off and on, so can under the situation that has and do not exist various sulphur impurities, operation be favourable.Because equipment and performance constraint, in depropanizer and unstripped gas hydrogenation process (but also can in any hydrogenation process), often there be sulphur impurity.Send into the feed stream that takes off acetylene unit (being also referred to as " ARU ") and may contain a small amount of and/or instantaneous sulphur impurity.Therefore, exploitation carbon monoxide-olefin polymeric and under the situation that has or do not exist sulphur impurity, make height unsaturated hydrocarbons such as alkadienes (alkadiene) or alkynes to the application in the hydrogenation process of low unsaturated hydrocarbons such as monoolefine (olefine) very big contribution be arranged to technology and economy.

Summary of the invention

Be desirable to provide a kind of carbon monoxide-olefin polymeric, can be used for making height unsaturated hydrocarbons such as alkynes or alkadienes to select to be hydrogenated to low unsaturated hydrocarbons such as olefine.This carbon monoxide-olefin polymeric can be adapted at wherein may existing the height unsaturated hydrocarbons of sulphur impurity such as sulphur compound to be used as catalyst to the hydrogenation of low unsaturated hydrocarbons.

It would also be desirable to provide the preparation method of this carbon monoxide-olefin polymeric and make height unsaturated hydrocarbons such as alkynes or alkadienes be hydrogenated to low unsaturated hydrocarbons such as olefine and further be not hydrogenated to the method for saturated hydrocarbons such as alkane with this carbon monoxide-olefin polymeric.

The invention has the advantages that the selectivity reduction that compares the oligomer of unwanted by-products such as acetylene with the carbon monoxide-olefin polymeric of method except that the inventive method disclosed herein preparation.

According to first embodiment of the invention, provide a kind of and can be used for making height unsaturated hydrocarbons such as alkynes or alkadienes to select to be hydrogenated to the carbon monoxide-olefin polymeric of low unsaturated hydrocarbons such as olefine.Described carbon monoxide-olefin polymeric comprises palladium, inorganic carrier and comprises silver and the catalytic component of alkali metal compound.Described carbon monoxide-olefin polymeric can also comprise halide, the halide of preferred non-alkali halide.This carbon monoxide-olefin polymeric can be by comprising the method preparation that makes inorganic carrier blending palladium and comprise the catalytic component of silver and alkali metal compound.Described carbon monoxide-olefin polymeric can also be mixed with halide, preferred non-alkali halide.

According to second embodiment of the invention, provide a kind of and can be used for making the height unsaturated hydrocarbons to select to be hydrogenated to the method for low unsaturated hydrocarbons.Described method comprises makes the hydrocarbon-containifluids fluids that comprises the height unsaturated hydrocarbons be enough to make described height unsaturated hydrocarbons select to contact under the hydrogenation conditions of hydrogenation in the presence of the hydrogen with carbon monoxide-olefin polymeric.In addition, described hydrogenation process can carry out under the situation that has or do not exist sulphur impurity such as sulphur compound.Described carbon monoxide-olefin polymeric can be identical with disclosed composition in the first embodiment of the invention.

Other purpose of the present invention and advantage will embody in detailed Description Of The Invention and appended claims.

Among the present invention, gas, liquid, steam or its mixture represented in term " fluid ".Term " palladium " means any type of palladium, includes but not limited to palladium metal and palladium oxide.Term " silver " means any type of silver, includes but not limited to silver metal and silver oxide.Term " significantly (substantial) " or " significantly " generally mean more than insignificant (trivial).Term " saturated hydrocarbons " means any hydrocarbon that does not contain any carbon-to-carbon double bond or carbon-to-carbon triple bond.The example of saturated hydrocarbons includes but not limited to ethane, propane, butane, pentane, hexane, octane, decane, naphtha etc. and composition thereof.

Term " height unsaturated hydrocarbons " means the hydrocarbon that the individual triple bond of one (or many) or two or more pair of key are arranged between the carbon atom in the molecule.The example of height unsaturated hydrocarbons includes but not limited to aromatic compounds such as benzene and naphthalene; Alkynes such as acetylene, propine (being also referred to as allylene) and butine; Alkadienes such as allene, butadiene, pentadiene (comprising isoprene), hexadiene, octadiene and decadinene; Deng and composition thereof.

Term " low unsaturated hydrocarbons " mean wherein the individual carbon-to-carbon triple bond of one (or many) in the height unsaturated hydrocarbons be hydrogenated to the hydrocarbon of carbon-to-carbon double bond or wherein carbon-to-carbon double bond quantity than lack in the unsaturated hydrocarbons highly one at least less one hydrocarbon or the hydrocarbon of at least one carbon-to-carbon double bond is arranged.The example of low unsaturated hydrocarbons includes but not limited to monoolefine such as ethene, propylene, butylene, amylene, hexene, octene, decene etc. and composition thereof.

Term " hydrogenation process " means the process that makes the height unsaturated hydrocarbons be hydrogenated to low unsaturated hydrocarbons or saturated hydrocarbons.Term " selection " means and wherein makes the height unsaturated hydrocarbons be hydrogenated to low unsaturated hydrocarbons and further not make described low unsaturated hydrocarbons be hydrogenated to the hydrogenation process of saturated hydrocarbons.For example, make the height unsaturated hydrocarbons be hydrogenated to low unsaturated hydrocarbons and when further not making this minuent unsaturated hydrocarbons be hydrogenated to saturated hydrocarbons, when described hydrogenation process ratio makes described height unsaturated hydrocarbons be hydrogenated to low unsaturated hydrocarbons further to be hydrogenated to saturated hydrocarbons then " selectivity is higher ".

Term " epidermis " means the outer surface of described carbon monoxide-olefin polymeric, can comprise the component such as the palladium of described carbon monoxide-olefin polymeric.Described epidermis can be any thickness, as long as this thickness can promote hydrogenation process disclosed herein.

According to first embodiment of the invention, provide a kind of and can be used for making the height unsaturated hydrocarbons to select to be hydrogenated to the carbon monoxide-olefin polymeric of low unsaturated hydrocarbons.Described carbon monoxide-olefin polymeric comprises (a) palladium, (b) inorganic carrier and (c) comprises the catalytic component of silver and alkali metal compound, wherein said palladium can " epidermis " form be present on the surface of described carbon monoxide-olefin polymeric or near the surface of described carbon monoxide-olefin polymeric, and described silver and alkali metal compound can distribute with the epidermis form or are distributed in the whole composition with described palladium.Described carbon monoxide-olefin polymeric can also comprise halide, the halide of preferred non-alkali halide, and described halide can distribute with the epidermis form or is distributed in the whole composition with described palladium.

Usually, the thickness of described epidermis can be to make the height unsaturated hydrocarbons select to be hydrogenated to any thickness of low unsaturated hydrocarbons.Usually, this thickness can be about 1 to the scope of about 1000 μ m, preferably about 5 to the scope of about 900 μ m, more preferably about 5 to the scope of about 800 μ m.

Many epidermis catalyst have been developed.Referring to the US4484015 of for example US4404124 and division, be incorporated herein for reference.

Available any suitable method is measured the concentration of palladium in the epidermis of described carbon monoxide-olefin polymeric.The concentration of determining palladium in the epidermis of carbon monoxide-olefin polymeric also helps to determine the thickness of described epidermis.One of at present favourable technology is an electron microprobe well known by persons skilled in the art.Another technology relates to breaks carbon monoxide-olefin polymeric sample (catalyst granules form), uses N, the N-dimethyl-acetone or alcohol weak solution of nitrosoaniline is handled described catalyst granules.Described Treatment Solution and palladium reaction produce red, can be used for assessing the distribution of palladium.

Usually, palladium can be present in the described carbon monoxide-olefin polymeric by any weight percent, as long as described palladium concentrates on the surface of described carbon monoxide-olefin polymeric or the surface of approaching described catalyst with the epidermis form significantly, and this weight percent can make the height unsaturated hydrocarbons select to be hydrogenated to low unsaturated hydrocarbons effectively.Usually, described carbon monoxide-olefin polymeric comprises based on the carbon monoxide-olefin polymeric gross weight at about 0.0001 palladium (by palladium metal) to about 3% (weight) scope, preferably at about 0.0005 palladium (by palladium metal) to about 1.5% (weight) scope, the more preferably palladium (by palladium metal) in 0.001 to 1.0% (weight) scope.

Described carbon monoxide-olefin polymeric also comprises the catalytic component that comprises silver and alkali metal compound.Silver can be present in the described carbon monoxide-olefin polymeric by any weight percent, need only this weight percent and can make the height unsaturated hydrocarbons select to be hydrogenated to low unsaturated hydrocarbons effectively, and can make the operating characteristics of this carbon monoxide-olefin polymeric in this selection hydrogenation effectively than the not carbon monoxide-olefin polymeric improvement of argentiferous.Usually, described carbon monoxide-olefin polymeric comprises based on the carbon monoxide-olefin polymeric gross weight at about 0.0003 silver (by silver metal) to about 0.06% (weight) scope, preferably at about 0.0005 silver (by silver metal) to about 0.02% (weight) scope, more preferably at about 0.0005 silver (by silver metal) to about 0.009% (weight) scope, the most preferably silver (by silver metal) in 0.001 to 0.005% (weight) scope.

Outside the desilver, described carbon monoxide-olefin polymeric also comprises a kind of alkali metal compound.Alkali metal compound can be present in the described carbon monoxide-olefin polymeric by any weight percent, as long as this weight percent can make the height unsaturated hydrocarbons select to be hydrogenated to low unsaturated hydrocarbons effectively, and can make of the carbon monoxide-olefin polymeric improvement of the operating characteristics of this carbon monoxide-olefin polymeric in this selection hydrogenation effectively than alkali-free metallic compound.Usually, described carbon monoxide-olefin polymeric comprises based on the carbon monoxide-olefin polymeric gross weight at about 0.001 alkali metal compound to about 10% (weight) scope, preferably at about 0.005 alkali metal compound to about 5% (weight) scope, more preferably at 0.01 alkali metal compound to about 2% (weight) scope.

Described carbon monoxide-olefin polymeric can also comprise a kind of halide.Preferred this halide is non-alkali halide.This halide can be present in the described carbon monoxide-olefin polymeric by any weight percent, and unsaturated hydrocarbons selects to be hydrogenated to low unsaturated hydrocarbons as long as this weight percent can make height effectively.Usually, when having this halide (preferred non-alkali halide), described carbon monoxide-olefin polymeric comprises based on the carbon monoxide-olefin polymeric gross weight at about 0.001 halide to about 10% (weight) scope, preferably at about 0.005 halide to about 5% (weight) scope, more preferably at 0.01 halide to about 2% (weight) scope.Preferred this halide is fluoride.

Carbon monoxide-olefin polymeric is by the inventive method disclosed herein preparation and when comprising palladium, inorganic carrier, comprise the halide of the catalytic component of silver and alkali metal compound and optional non-alkali halide and being used for the height unsaturated hydrocarbons to the hydrogenation of low unsaturated hydrocarbons, compare with the carbon monoxide-olefin polymeric for preparing by the method except that the inventive method disclosed herein, to the selectivity raising of want product such as low unsaturated hydrocarbons.

Described carbon monoxide-olefin polymeric can be fresh carbon monoxide-olefin polymeric, also can be to use the carbon monoxide-olefin polymeric of oxidation regeneration later.Described carbon monoxide-olefin polymeric can have any suitable shape as spherical, cylindrical, trilobal or its combination.Preferred shape is spherical or cylindrical.The particle of described carbon monoxide-olefin polymeric is generally in about scope of 0.5 to about 10mm, preferably in about scope of 1 to about 8mm, more preferably in 1 to 7mm scope.The surface area of described carbon monoxide-olefin polymeric generally about 1 to about 200m ²In the scope of/g (measuring) by the BET method, preferably about 1 to about 150m ²In the scope of/g, more preferably about 2 to about 125m ²In the scope of/g, most preferably 2 to 80m ²In the scope of/g.

Described carbon monoxide-olefin polymeric can by cause palladium concentrate on the catalytic component that comprises silver and alkali metal compound in the appearance cortex of carbon monoxide-olefin polymeric be distributed in the described epidermis or be distributed in the whole carbon monoxide-olefin polymeric and when needing halide (preferred non-alkali halide) be distributed in the described epidermis or any appropriate methodology or the means that are distributed in the whole carbon monoxide-olefin polymeric prepare.Can be by causing carbon monoxide-olefin polymeric to be included in any suitable means of the carbon monoxide-olefin polymeric component in the weight percent scope disclosed herein and making the palladium component of described carbon monoxide-olefin polymeric and comprise that the silver and the catalytic component of alkali metal compound (preferred fluorinated potassium) and halide (if present) are deposited on described inorganic carrier (preferred aluminium oxide) and go up and/or incorporate into or blending extremely in the described inorganic carrier with any suitable order.

Palladium is mixed, incorporates into or sneak among (for example by ion-exchange or dipping) described inorganic carrier (preferred aluminium oxide) or on.Preferred palladium dipping utilizes just wet dipping technique, and the solution of wherein said blending element is full of the hole of base material (as inorganic carrier) basically fully.The also available maceration extract that comprises palladium compound sprays described inorganic carrier.Usually, the concentration of palladium compound can be any concentration that can produce the carbon monoxide-olefin polymeric that is included in the palladium in the weight percent scope disclosed herein in the described maceration extract.The solvent of described maceration extract is preferably water or pure as ethanol or its mixture.Comprising the maceration extract of palladium compound and the weight ratio of inorganic carrier can be any ratio that can produce the carbon monoxide-olefin polymeric that is included in the palladium in the weight percent scope disclosed herein.

For example, with at least a Pd compound (as H ₂PdCl ₄) dipping inorganic carrier (preferred aluminium oxide) obtains the material of palladium-impregnated, make described impregnated material drying obtain drying material then under composition dries condition described herein, heating (roasting) obtains dry and baked palladium/inorganic carrier composition under composition roasting condition described herein then.Described palladium/inorganic carrier composition is contacted with the solution (preferred aqueous solutions) (being Ag-containing solution) of the preferred silver nitrate of at least a silver compound and the solution (being the solution of alkali metal-containing compound) of alkali metal compound preferred fluorinated potassium, drying obtains drying material under composition dries condition described herein then, and heating (roasting) obtains being included in palladium, silver and alkali-metal carbon monoxide-olefin polymeric of the present invention in the weight percent scope disclosed herein under composition roasting condition described herein then.

Among another preparation method, described palladium/inorganic carrier composition is contacted with the solution (preferred aqueous solutions) (being Ag-containing solution) of silver compound, drying obtains drying material under composition dries condition described herein then, and heating (roasting) obtains palladium/silver/inorganic carrier composition under composition roasting condition described herein then.This palladium/silver/inorganic carrier composition is contacted with the solution (being the solution of alkali metal-containing compound) of alkali metal compound, drying obtains drying material under composition dries condition described herein then, and heating (roasting) obtains being included in palladium, silver and alkali-metal carbon monoxide-olefin polymeric of the present invention in the weight percent scope disclosed herein under composition roasting condition described herein then.

In addition, alkali metal compound (or solution of alkali metal-containing compound) can mix in (for example by dipping or injection) inorganic carrier (preferred aluminium oxide) before at palladium compound (or containing palladium solution) that described carrier blending is fit to and the silver compound (or Ag-containing solution) that is fit to.Alkali metal compound also can with the blending of the palladium compound that is fit to simultaneously or mix afterwards in (for example by dipping or spray) inorganic carrier.Alkali metal compound also can mix in the described inorganic carrier between the blending step of palladium and silver or after the blending step of palladium and silver.

When described carbon monoxide-olefin polymeric also comprised halide (preferred non-alkali halide), halid any suitable mode and any suitable order that this halide can cause carbon monoxide-olefin polymeric of the present invention to comprise in the weight percent scope disclosed herein mixed in described palladium/inorganic carrier composition.This halide is preferably fluoride.Preferred this non-alkali halide is to be selected from HF, NH ₄F, NH ₄HF ₂Deng and composition thereof non-alkali metal fluoride.More preferably this non-alkali halide is NH ₄F.Can make described inorganic carrier mix (preferred dipping) halide (preferred non-alkali metal fluoride, more preferably NH ₄F), preferably mix with alkali metal compound.

As described hereinly make described inorganic carrier mix palladium, comprise the catalytic component of silver and alkali metal compound and optionally after the halide, make the gained material dry under composition dries condition described herein, roasting under composition roasting condition described herein then.Alternatively, make material reduction after the described roasting with hydrogen then, preferably reduction about 0.1 to about 20 hours under about 30 temperature to about 300 ℃ of scopes.

In the preparation of one preferred catalyst compositions, palladium/silver/alumina load type the catalyst material that obtains with disclosed method among the US4484015 of the aqueous solution of alkali halide (preferred fluorinated potassium) dipping by US4404124 and division, dry under composition dries condition described herein then, roasting under composition roasting condition described herein then.In another preferred catalyst compositions preparation, with alkali halide (preferred fluorinated potassium) and non-alkali halide (preferred non-alkali metal fluoride, more preferably NH ₄F) palladium/silver/alumina load type catalyst material that disclosed method obtains among the US4484015 of aqueous solution dipping by US4404124 and division, dry under composition dries condition described herein then, roasting under composition roasting condition described herein then.

Usually, the concentration of silver compound and alkali metal compound and optional halide (preferred non-alkali halide) can be any concentration that can produce carbon monoxide-olefin polymeric disclosed herein in the described contact solution (preferred aqueous solutions).Preferred silver-colored contact method is by soaking into, and promptly the volume of the solution of Ag-containing compound surpasses the pore volume of described inorganic carrier.Preferred alkali metal compound contact method and halide (preferred non-alkali halide) contact method are " just wet dippings ", and promptly the hole of inorganic carrier is full of the solution of alkali metal-containing compound and the solution of (when needing) halide basically fully.Usually, the weight ratio of the solution of the solution of Ag-containing compound solution and alkali metal-containing compound and optional halide and described inorganic carrier can be any ratio that can produce the carbon monoxide-olefin polymeric of the halide (preferred non-alkali halide) that is included in interior silver of weight percent scope disclosed herein and alkali metal and needs when.Make described impregnated material dry under composition dries condition described herein then, roasting obtains carbon monoxide-olefin polymeric of the present invention under composition roasting condition described herein then.

Usually, indication composition dries condition comprises temperature about 35 to about 290 ℃ scope herein, preferably about 40 to about 280 ℃ scope, more preferably in 45 to 275 ℃ scope.This composition dries condition comprises carries out this dry time cycle generally about 0.1 to about 6 hours scope, preferably about 0.15 to about 5 hours scope, more preferably 0.2 to about 4 hours scope.Usually, described composition can be dry under any suitable pressure.Preferred this composition dries condition comprises that pressure is at about normal pressure (promptly about 101.2kPa) extremely in the scope of about 689kPa (about 14.7 to about 100psia), more preferably under about normal pressure.

Usually, herein indication composition roasting condition be included in the air or in nonoxidizing atmosphere about 200 to about 900 ℃ of scopes, preferably about 250 to about 750 ℃ of scopes, the more preferably described composition of roasting temperature in 350 to 600 ℃ of scopes.This composition roasting condition generally comprises the time cycle about 0.5 to about 40 hours scope, and the preferred time cycle, more preferably the time cycle was in 1 to 20 hour scope about 0.75 to about 30 hours scope.This composition roasting condition generally comprise pressure at about 48kPa to the scope of about 5.167MPa (about 7 to about 750psia), preferably at about 48kPa to the scope of about 3.10MPa (about 7 to about 450psia), more preferably in the scope of 48kPa to 1.03MPa (7 to 150psia).

The example that can be used for preparing the suitable palladium compound of carbon monoxide-olefin polymeric of the present invention includes but not limited to that palladium bromide, palladium bichloride, palladium iodide, palladium nitrate, nitric hydrate palladium, nitric acid tetramine close palladium, palladium oxide, aqua oxidation palladium, palladium sulfate etc. and composition thereof.Described palladium can have any suitable oxidation state.At present preferred palladium compound is a palladium bichloride.More preferably to this palladium bichloride (PdCl ₂) the middle hydrochloric acid formation PdCl that adds ₄ ^-2Complex.When adding in the carrier by dipping from solution, some compounds can add from the aqueous solution, but other need nonaqueous solvents as alcohol, hydrocarbon, ether and ketone etc.

The example that can be used for preparing the suitable silver compound of carbon monoxide-olefin polymeric of the present invention includes but not limited to silver nitrate, silver acetate, silver cyanide etc. and composition thereof.At present preferred silver compound is silver nitrate.

The example that can be used for preparing the suitable alkali metal compound of carbon monoxide-olefin polymeric of the present invention includes but not limited to alkali halide, alkali metal hydroxide, alkali carbonate, alkali metal hydrogencarbonate, alkali nitrates, alkali metal carboxylate etc. and composition thereof.Preferred described alkali metal compound is an alkali halide, and more preferably described alkali metal compound is alkaline metal iodide or alkali metal fluoride.Usually, the alkali metal of this alkali metal compound is selected from potassium, rubidium, caesium etc. and composition thereof.The alkali metal of preferred this alkali metal compound is potassium.Most preferably described alkali metal compound is potassium fluoride (KF).

Other example of the alkali metal compound that is suitable for includes but not limited to sodium fluoride, lithium fluoride, rubidium fluoride RbF, cesium fluoride, sodium iodide, KI, lithium iodide, rubidium iodide, cesium iodide, sodium chloride, potassium chloride, lithium chloride, rubidium chloride, cesium chloride, sodium bromide, KBr, lithium bromide, rubidium bromide, cesium bromide, NaOH, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, sodium oxide molybdena, potassium oxide, lithia, rubidium oxide, cesium oxide, sodium carbonate, potash, lithium carbonate, rubidium carbonate, cesium carbonate, sodium nitrate, potassium nitrate, lithium nitrate, rubidium nitrate, cesium nitrate etc. and composition thereof.

The example of the inorganic carrier that is suitable for includes but not limited to aluminium oxide, silica, zirconia, titanium oxide, alumino-silicate (as clay and/or zeolite), spinelle such as zinc aluminate, calcium aluminate and magnesium aluminate, zinc titanate etc. and composition thereof.

Preferred inorganic carrier is any suitable aluminium oxide, as (but being not limited to) Alpha-alumina, beta-alumina, δ-aluminium oxide, η-aluminium oxide, gama-alumina, θ-aluminium oxide etc. and composition thereof.Preferred this aluminium oxide is an Alpha-alumina.Described aluminium oxide can also comprise other composition of trace, for example at about 1 silica to about 10% (weight) scope, the quality of described inorganic carrier is had no adverse effect.Usually, wish to make described inorganic carrier with pure basically aluminium oxide, preferred pure basically Alpha-alumina.Described aluminium oxide can be by any way known in the art or method preparation.Described aluminium oxide can have any surface area, pore volume, average pore size and the granularity that can produce carbon monoxide-olefin polymeric disclosed herein.

According to second embodiment of the invention, provide a kind of method for hydrogenation.Method for hydrogenation of the present invention comprise make the hydrocarbon-containifluids fluids and the carbon monoxide-olefin polymeric disclosed herein that comprise one or more height unsaturated hydrocarbons in the presence of the hydrogen hydrogenation zone can make described one or more highly unsaturated hydrocarbons be hydrogenated under the hydrogenation conditions of low unsaturated hydrocarbons and contact.This hydrogenation process can carry out under the situation that has or do not exist sulphur impurity such as sulphur compound.

Hydrogen can be present in the described hydrocarbon-containifluids fluids or be present in and contain in the hydrogen fluid, described contain hydrogen fluid with mix with described hydrocarbon-containifluids fluids before carbon monoxide-olefin polymeric disclosed herein contacts.Contain hydrogen fluid if use, it can be that any fluid of pure basically hydrogen or the hydrogen that comprises enough concentration is to realize hydrogenation disclosed herein.Also can comprise other gas such as nitrogen, methane, carbon monoxide, carbon dioxide, water vapour or its mixture, as long as describedly contain the hydrogen that hydrogen fluid comprises the enough concentration that is enough to realize hydrogenation disclosed herein.

Alternatively, before hydrogenation disclosed herein, can make described carbon monoxide-olefin polymeric activation with the described carbon monoxide-olefin polymeric of hydrogeneous fluid treatment earlier.This reduction or activation processing can be carried out under the following conditions: temperature is generally about 20 to about 400 ℃ scope, preferably about 30 to about 200 ℃ scope; Duration about 1 minute to about 30 hours scope, preferably about 0.5 to about 25 hours scope, more preferably in 1 to 20 hour scope; Pressure is generally in the scope of about 6.89 to 6890kPa (about 1 to about 1000psia), preferably in the scope of about 101.2 to about 3445kPa (about 14.7 to about 500psia), more preferably in the scope of 413 to 1378kPa (60 to 200psia).In this reduction treatment process, the palladium and the silver compound that may be present in the described carbon monoxide-olefin polymeric after the composition calcination steps described herein are reduced into palladium and silver significantly.Do not carry out this and optionally reduce when handling, the hydrogen that exists in the reaction medium is finished this reduction at the hydrogenation process disclosed herein initial stage.

Described height unsaturated hydrocarbons generally is present in the described hydrocarbon-containifluids fluids as impurity with common amount in the typical industry feed stream.The amount of described height unsaturated hydrocarbons in described hydrocarbon-containifluids fluids generally at the about 1 weight portion height unsaturated hydrocarbons of per 1,000,000,000 weight portion hydrocarbon-containifluids fluids (promptly about 1ppb) to the scope of about 50% (weight), typically at about 10ppb to the scope of about 30% (weight), more typically in the scope of 20ppb to 20% (weight).

The hydrocarbon-containifluids fluids of hydrogenation process of the present invention can also comprise one or more low unsaturated hydrocarbons such as monoolefine and one or more saturated hydrocarbons such as alkane.The amount of these other hydrocarbon in described hydrocarbon-containifluids fluids can be about 0.001 to the scope of about 99.999% (weight).

The example of the alkynes that is suitable for includes but not limited to acetylene, propine (being also referred to as allylene), 1-butine, 2-butine, 1-pentyne, valerylene, 3-methyl isophthalic acid-butine, 1-hexin, 1-heptyne, 1-octyne, 1-n-heptylacetylene, 1-decine etc. and composition thereof.At present preferred alkynes is acetylene and propine.

Described alkynes preferably is hydrogenated to corresponding olefine.For example, acetylene is hydrogenated to ethene; Propine is hydrogenated to propylene; Butine is hydrogenated to corresponding butylene (for example 1-butylene, 2-butylene).

The example of the alkadienes that is suitable for comprises that per molecule contains 3 those alkadienes to about 12 carbon atoms.This alkadienes includes but not limited to allene, 1, the 2-butadiene, 1, the 3-butadiene, isoprene, 1, the 2-pentadiene, 1, the 3-pentadiene, 1, the 4-pentadiene, 1, the 2-hexadiene, 1, the 3-hexadiene, 1, the 4-hexadiene, 1, the 5-hexadiene, the 2-methyl isophthalic acid, the 2-pentadiene, 2,3-dimethyl-1,3-butadiene, heptadiene, the methyl hexadiene, octadiene, the methyl heptadiene, the dimethyl hexadiene, the ethyl hexadiene, the trimethyl pentadiene, the methyl octadiene, the dimethyl-g diene, the ethyl octadiene, the trimethyl hexadiene, nonadiene, decadinene, 11 carbon diene, 12 carbon diene, cyclopentadiene, cyclohexadiene, methyl cyclopentadiene, cycloheptadiene, methyl cyclohexadiene, the dimethyl cyclopentadiene, the ethyl cyclopentadiene, bicyclopentadiene (is also referred to as three rings [5.2.1] ^2,6The last of the ten Heavenly stems-3, the 8-diene) etc. and composition thereof.

At present preferred alkadienes is an allene, 1, and 2-butadiene, 1,3-butadiene, pentadiene (as 1,3-pentadiene, 1,4-pentadiene, isoprene), cyclopentadiene (as 1, the 3-cyclopentadiene) and bicyclopentadiene (are also referred to as three rings [5.2.1] ^2,6The last of the ten Heavenly stems-3, the 8-diene).These alkadienes preferably are hydrogenated to the per molecule carbon atom quantity corresponding monoolefine identical with described alkadienes.For example, allene is hydrogenated to propylene; 1,2-butadiene and 1,3-butadiene are hydrogenated to 1-butylene and 2-butylene; 1,3-pentadiene and 1,4-pentadiene are hydrogenated to 1-amylene and 2-amylene; Isoprene is hydrogenated to Methyl-1-pentene and methyl-2-amylene; 1, the 3-cyclopentadiene is hydrogenated to cyclopentene.

The example of the aromatic hydrocarbons that may exist in the described hydrocarbon-containifluids fluids includes but not limited to benzene, toluene, ethylbenzene, styrene, dimethylbenzene etc. and composition thereof.

The example of the monoolefine that is fit to includes but not limited to ethene, propylene, the 1-butylene, the 2-butylene, isobutene, the 1-amylene, the 2-amylene, methyl isophthalic acid-butylene (as 2-methyl-1-butene alkene), methyl-2-butene (as the 2-methyl-2-butene), the 1-hexene, the 2-hexene, the 3-hexene, Methyl-1-pentene, 2,3-dimethyl-1-butylene, the 1-heptene, the 2-heptene, the 3-heptene, methyl isophthalic acid-hexene, methyl-2-hexene, methyl-3-hexene, dimethyl pentene, ethylpentene, octene, the methyl heptene, the dimethyl hexene, ethyl hexene, nonene, the methyl octene, the dimethyl heptene, the ethyl heptene, the trimethyl hexene, cyclopentene, cyclohexene, methyl cyclopentene, cycloheptene, methylcyclohexene, dimethylcyclopentene, the ethyl cyclopentene, cyclo-octene, the methyl cycloheptene, the dimethyl cyclohexene, ethyl-cyclohexene, trimethyl cyclohexene, the methyl cyclo-octene, the dimethyl cyclo-octene, ethyl cyclo-octene etc. and composition thereof.

The example of the saturated hydrocarbons that is fit to includes but not limited to methane, ethane, propane, butane, methylpropane, methybutane, dimethylbutane, pentane, hexane etc. and composition thereof.

In addition, described hydrocarbon-containifluids fluids generally can be included in about 0.001 hydrogen to about 20% (weight) scope, preferably about 0.001 to about 15% (weight) scope hydrogen and the carbon monoxide of maximum 10000ppmv.

The example as the sulphur compound of sulphur impurity (being generally comprised within the described hydrocarbon-containifluids fluids) that can exist in the hydrogenation process disclosed herein includes but not limited to hydrogen sulfide, carbonyl sulfide (COS), carbon disulfide (CS ₂), mercaptan (RSH), organic sulfur compound (R-S-R), organic disulfide (R-S-S-R), thiophene, the thiophene of replacement, organic trisulfide, organic tetrasulfide etc. and composition thereof, wherein each R can be alkyl or cycloalkyl or the aryl that contains 1 to 10 carbon atom.There is other compound (as water, alcohol, ether, aldehyde, ketone, carboxylic acid, ester and other oxygenatedchemicals) also within the scope of the invention in the described hydrocarbon-containifluids fluids, as long as described other compound does not have tangible adverse effect to hydrogenation process disclosed herein.

Usually, described sulphur compound is present in the described hydrocarbon-containifluids fluids with trace, the total volume concentration that is preferably based on hydrocarbon-containifluids fluids is lower than about 1000ppmv, preferred concentration at about 0.5ppbv to the scope of about 1000ppmv sulphur, more preferably concentration at about 1ppbv to the scope of about 500ppmv sulphur, most preferably in the scope of 1ppbv to 300ppmv sulphur.

The hydrogenation process of the present invention generally hydrocarbon-containifluids fluids by comprising at least a height unsaturated hydrocarbons and carbon monoxide-olefin polymeric of the present invention carries out contacting under hydrogenation conditions in the presence of the hydrogen.Carbon monoxide-olefin polymeric described herein in can making described hydrocarbon-containifluids fluids and be included in hydrogenation zone by any suitable mode contacts.This hydrogenation zone can comprise for example reaction vessel.

The contact procedure that described hydrocarbon-containifluids fluids is contacted with carbon monoxide-olefin polymeric disclosed herein can intermittence or preferred formal operations with the continuous processing step.In one operation of back, can adopt stationary catalyst bed or moving catalyst bed or fluid catalyst beds.The preferred stationary catalyst bed that adopts.These modes of operation all have pluses and minuses, and those skilled in the art can select to be suitable for most the mode of operation of specific hydrocarbon-containifluids fluids and carbon monoxide-olefin polymeric.

Described contact procedure is preferably carried out in hydrogenation zone, carbon monoxide-olefin polymeric disclosed herein wherein is housed and is in to be fit to promote height unsaturated hydrocarbons described herein to the hydrogenation conditions of the hydrogenation process of low unsaturated hydrocarbons.This hydrogenation conditions should avoid the low unsaturated hydrocarbons of initial existence in the described hydrocarbon-containifluids fluids to be hydrogenated to saturated hydrocarbons such as alkane or cycloalkane significantly.

Usually, this hydrogenation conditions comprises the temperature required and pressure of hydrogenation process of the present invention, depends primarily on the degree of hydrogenation of activity, hydrocarbon-containifluids fluids and the requirement of carbon monoxide-olefin polymeric.Usually, this temperature is about 10 to about 300 ℃ scope, preferably about 20 to about 250 ℃ scope, most preferably in 20 to 200 ℃ scope.The pressure that is fit to is generally at about 136kPa extremely in the scope of about 13.88MPa (about 5 to about 2000psig), preferably at about 170kPa to the scope of about 10.43MPa (about 10 to about 1500psig), most preferably in the scope of 205kPa to 6.99MPa (15 to 1000psig).

This hydrogenation conditions comprises that also hydrocarbon-containifluids fluids is loaded into the flow velocity of hydrogenation zone (being the feed rate of hydrocarbon-containifluids fluids).Described flow velocity is that feed rate generally makes gas hourly space velocity (" GHSV ") above 1 liter/liter/hour.Term used herein " gas hourly space velocity " mean standard temperature and pressure (STP) condition (" STP ") down hydrocarbon-containifluids fluids be loaded into hydrogenation zone speed (rise/hour) divided by the hydrogenation zone that loads described hydrocarbon-containifluids fluids in the numeric ratio of volume (liter) of contained carbon monoxide-olefin polymeric.Typically, the gas hourly space velocity of described hydrocarbon-containifluids fluids about 1 to the scope of about 50000 liters of hydrocarbon-containifluids fluids/rise catalyst/hour (rise/liter/hour), preferably about 250 to about 40000 liters/liter/hours scope, most preferably 500 to about 30000 liters/liter/hours scope.

If will make carbon monoxide-olefin polymeric of the present invention regeneration after being used for hydrogenation process described herein for a long time, described regeneration can be by being no more than as described in about 600 ℃ roasting temperature carbon monoxide-olefin polymeric to burn carbonaceous and the sulphur deposit is finished in oxidizing atmosphere in as air.Alternatively, available palladium and comprise silver and the halide of the catalytic component of the alkali metal compound non-alkali halide when needing floods described carbon monoxide-olefin polymeric again, then as this paper at drying and roasting as described in the production of novel catalyst compositions useful of the present invention.

The specific embodiment

Following examples further specify the present invention, limit the scope of the invention and should not be construed as exceedingly.

Example I

This embodiment explanation is used for the various palladium-containing catalyst preparation of compositions of hydrogenation process.

Catalyst A (the present invention)

Catalyst A is prepared as follows.Silver, potassium and fluoride are added to ProductName " G83A " available from United Catalyst Inc. (UCI), Louisville, the contain about 0.02wt%Pd, surface area of Kentucky are about 3 to 5m ²The Pd/Al of/g ₂O ₃In the catalyst.Earlier silver-colored by wet (hole that is base material is full of the solution that element is mixed by institute basically fully) adding just.With 0.008g AgNO ₃Be dissolved in 22ml distilled water gained solution and add to the described Pd/Al of being purchased of 100g ₂O ₃In the catalyst.Then with gained Pd/Ag/Al ₂O ₃Catalyst in air about 275 ℃ dry about 1 hour down, then in air about 3 hours of about 538 ℃ of following roastings.Add potassium and fluoride by just wetting then.With 0.117g KF and 0.0555g NH ₄HF ₂Be dissolved in 5.5ml distilled water gained solution and add to the described Pd/Ag/Al of 25g ₂O ₃In the catalyst.Then with gained Pd/Ag/K/F/Al ₂O ₃Catalyst in air about 275 ℃ dry about 1.5 hours down, then in air about 3 hours of about 538 ℃ of following roastings, thereby obtain catalyst A of the present invention.Catalyst A of the present invention comprises about 0.02wt%Pd, about 0.005wt%Ag, about 0.3wt%K and about 0.3wt%F.

Catalyst B (contrast)

Catalyst B is the Pd/Ag/K/F/Al for preparing in the mode similar to the invention described above catalyst A ₂O ₃Catalyst.Comparative catalyst B comprises about 0.02wt%Pd, the about 0.3wt%K of about 0.02wt%Ag and about 0.3wt%F.

Catalyst C (contrast)

Catalyst C is the Pd/Ag/K/F/Al for preparing in the mode similar to the invention described above catalyst A ₂O ₃Catalyst.Comparative catalyst C comprises about 0.02wt%Pd, about 0.06wt%Ag, about 0.3wt%K and about 0.3wt%F.

Catalyst D (the present invention)

Catalyst D is prepared as follows.7/32in * 7/32in pill shape aluminium oxide (Al that 200g is purchased ₂O ₃) carrier (being provided by United Catalyst Inc. (UCI)) is at 0.050g palladium (H ₂PdCl ₄Form) is dissolved in the 200ml distilled water gained solution and soaks preparation in about 1 hour and contain about 0.025wt%Pd, surface area about 7 to 8m ²The Pd/Al of/g ₂O ₃Catalyst.In the described immersion process described catalyst pellet's is stirred several times to guarantee that Pd evenly distributes.Decantation clear solution then.With gained Pd/Al ₂O ₃Catalyst in air in about 1 hour of 120 ℃ of dryings, thereby in air, provided Pd/Al in about 3 hours then in 538 ℃ of roastings ₂O ₃Catalyst.Then with the described Pd/Al of 25g ₂O ₃Catalyst is at 0.00495g Ag (AgNO ₃Form) soaks 1 hour in distilled water (25ml) solution at described Pd/Al ₂O ₃Add silver in the catalyst.In the described immersion process described catalyst pellet's is stirred several times to guarantee that Ag evenly distributes.Decantation solution then.With gained Pd/Ag/Al ₂O ₃Catalyst in air in about 1 hour of 120 ℃ of dryings, then in air in about 3 hours of 538 ℃ of roastings.Add potassium by incipient wetness method then.0.037g KF is dissolved in 6.2ml distilled water gained solution adds to the described Pd/Ag/Al of 25g ₂O ₃In the catalyst.Then with gained Pd/Ag/K/F/Al ₂O ₃Catalyst in air in about 1 hour of 120 ℃ of dryings, then in air in about 3 hours of 538 ℃ of roastings, thereby obtain catalyst D of the present invention.Catalyst D of the present invention comprises about 0.025wt%Pd, about 0.01wt%Ag, about 0.1wt%K and about 0.05wt%F.

Catalyst E (contrast)

Catalyst E prepares by the mode similar to the invention described above catalyst D, but adds silver in the mode similar to the invention described above catalyst A.Comparative catalyst E comprises about 0.025wt%Pd, about 0.04wt%Ag, about 0.1wt%K and about 0.05wt%F.

Catalyst F (the present invention)

Catalyst F is prepared as follows.Silver, potassium and fluoride are added to ProductName " G83A " available from United Catalyst Inc. (UCI), Louisville, the contain about 0.02wt%Pd, surface area of Kentucky are about 3 to 5m ²The Pd/Al of/g ₂O ₃In the catalyst.Earlier silver is added described Pd/Al in the mode similar to the invention described above catalyst A ₂O ₃In the catalyst.In the mode similar potassium and fluoride are added in the described catalyst then, but use NH to the invention described above catalyst A ₄F replaces NH ₄HF ₂As the F source.Catalyst F of the present invention comprises about 0.02wt%Pd, about 0.005wt%Ag, about 0.5wt%K and about 0.5wt%F.

Catalyst G (contrast)

Catalyst G prepares in the mode similar to the invention described above catalyst F.Comparative catalyst G comprises about 0.02wt%Pd, about 0.06wt%Ag, about 0.5wt%K and about 0.5wt%F.

Example II

This embodiment illustrates the performance of catalyst described in the example I in hydrogenation process.

Above-mentioned each catalyst of about 23g (promptly about 20cc) is placed on internal diameter 0.62in, is about in the stainless steel tube reactor of 18in.Described catalyst (is positioned in the middle of the reactor; 6ml 3mm bead is equipped with at the reactor two ends) under the hydrogen that flows with 12l/hr under the 200psig, reducing about 1 hour under about 38 ℃.Add hydrocarbon-containifluids fluids then in described reactor, described hydrocarbon-containifluids fluids is from the typical feed of ethylene plant's front end depropanizer, comprises (except as otherwise noted, all based on weight) hydrogen approx, 2.1%; Methane, 22%; Ethene, 54%; Propylene, 21%; Acetylene, 4300 to 5400ppm; Allene, 4300 to 5400ppm; Propine, 4300 to 5400ppm; And carbon monoxide, 300ppm (volume).Described hydrocarbon-containifluids fluids and hydrogen add described reactor with the speed of 900ml/min continuously under 200psig (translating into gas hourly space velocity is about 2500hr ^-1).Temperature of reactor raises and can not control until described hydrogenation, and uncontrollable hydrogenation of ethene can take place.During uncontrollable hydrogenation of described ethene, heat of hydrogenation collection is tired to make temperature of reactor surpass about 120 ℃ (promptly about 120 to about 150 ℃).Before the beginning image data reactor is cooled to below 38 ℃.

Continue to make described hydrocarbon-containifluids fluids and hydrogen under 200psig, to cross described catalyst then, discharge the logistics sample by the gas chromatography collection simultaneously and before keep described temperature-resistant with the data rate stream of 900ml/min.By thermocouple being inserted thermocouple sheath (stretching into reactor and catalyst bed center) and changing its position until observing maximum temperature, the assaying reaction actuator temperature.Furnace temperature is raise the several years, repeat described test loop.

For predicting the performance of above-mentioned catalyst in the hydrogenation process that comprises catalyst poison such as sulphur impurity more practically, continue the anti-sulfur poisoning that above-mentioned test loop is measured above-mentioned catalyst in the following manner.Reactor is heated in about 55 temperature to about 85 ℃ of scopes, on described catalyst, introduce high concentration carbonyl sulfide (COS) (standard temperature and pressure (STP) (STP) down about 300ml contain the nitrogen of 5000ppmvCOS).Then by blend (COS/H with COS and hydrogen ₂Blend) instead of part hydrogen stream (flowing with 12l/hr at 200psig) is regulated COS concentration.Set described hydrocarbon-containifluids fluids, hydrogen and COS/H ₂The flow of blend is to obtain to account for the concentration of combined feed 12ppmv COS.

Make reactor be lower than " rapidly mobile (line out) " under the temperature of whole acetylene conversion (being that acetylene and ethane concentration keep substantially constant) then.Elevate the temperature then, reactor is moved rapidly.Repeat this " move rapidly " process until all acetylene all be hydrogenated or described reaction uncontrollable.Whole test is carried out in a continuous manner, has hydrocarbon-containifluids fluids to flow through described catalyst all the time.By the gc analysis reactor effluent is product stream.

In result shown in the Table I, T1 is called " removing " temperature, is that concentration of acetylene is reduced to the temperature of 20ppm (i.e. 20 weight portion acetylene/1,000,000 weight portion hydrocarbon-containifluids fluids) when following.In hydrogenation process, T1 is low to be desirable.The low more expression activity of such catalysts of T1 is high more and service life is long more.When described catalyst is used for hydrogenation process, must in time stably improve the activity decline of operating temperature with compensate for catalyst.But temperature upper limit (T2) is arranged, be higher than this temperature the uncontrollable hydrogenation of ethene to ethane will take place.Therefore, the low terminal life of catalyst that makes of T1 prolongs.In the Table I, T2 is called " out of control " temperature, is the temperature when producing 3wt% ethane (based on whole hydrocarbon).In the Table I, Δ T is the poor of T2 and T1.This Δ T is the tolerance of ethylene selectivity, also can be considered the window of operation performance.T2 that catalyst obtained and the difference of T1 big more (being that Δ T is big more), then described catalyst are more suitable for as hydrogenation catalyst composition.

In addition, " selectivity of hydrocarbon under T1 " means the molar percentage that acetylene conversion becomes particular hydrocarbon in the Table I.If the selectivity to particular hydrocarbon (except the ethene) surpasses 100%, then ethene will be consumed and be used to constitute this particular hydrocarbon.Equally, if be negative value to selectivity of ethylene, then ethene has been consumed and has produced another hydrocarbon." ethane (C under T1 for example ₂) selectivity " mean the molar percentage that under T1, changes into the acetylene of ethane.Any hydrocarbon (saturated and undersaturated) that per molecule contains 4 carbon atoms all is called " C ₄".Similarly, per molecule contain 6 or any hydrocarbon of more carbon atoms all be called " heavy hydrocarbon ".Selectivity is determined by following formula:

To the selectivity of X=[(producing the molal quantity of X)/(consuming the molal quantity of acetylene) * is used to constitute the quantity * 100 of the acetylene unit of X]

Table I

Catalyst	Temperature (°F)			The selectivity of hydrocarbon under T1
	Temperature (°F)			The selectivity of hydrocarbon under T1			????T1	????T2	???ΔT	????C ₂ ^h	????C ₄ ¹	Heavy hydrocarbon ^j
	Catalyst A (the present invention) ^aNo COS has COS	? ????122 ????153	? ????164 ????205	? ????42 ????52	? ????21.9 ????66.6	? ????15.3 ????5.5	????T1	????T2	???ΔT	????C ₂ ^h	????C ₄ ¹	Heavy hydrocarbon ^j	? ????7.3 ????0.0
Catalyst B (contrast) ^bNo COS has COS	Catalyst A (the present invention) ^aNo COS has COS	? ????122 ????153	? ????164 ????205	? ????42 ????52	? ????21.9 ????66.6	? ????15.3 ????5.5	? ????130 ????154	? ????173 ????199	? ????43 ????45	? ????12.1 ????40.9	? ????13.9 ????8.5	? ????9.3 ????1.4	? ????7.3 ????0.0
Catalyst B (contrast) ^bNo COS has COS	Catalyst C (contrast) ^cNo COS has COS	? ????128 ????153	? ????172 ????201	? ????44 ????48	? ????17.4 ????57.0	? ????14.8 ????6.8	? ????130 ????154	? ????173 ????199	? ????43 ????45	? ????12.1 ????40.9	? ????13.9 ????8.5	? ????9.3 ????1.4	? ????7.8 ????0.6
Catalyst D (the present invention) ^dNo COS has COS	Catalyst C (contrast) ^cNo COS has COS	? ????128 ????153	? ????172 ????201	? ????44 ????48	? ????17.4 ????57.0	? ????14.8 ????6.8	? ????128 ????181	? ????ND ^k????ND	? ????ND ????ND	? ????14.0 ????72.1	? ????11.6 ????4.8	? ????8.7 ????1.6	? ????7.8 ????0.6
Catalyst D (the present invention) ^dNo COS has COS	Catalyst E (contrast) ^eNo COS has COS	? ????131 ????185	? ????192 ????226	? ????61 ????41	? ????8.1 ????110.8	? ????6.3 ????5.0	? ????128 ????181	? ????ND ^k????ND	? ????ND ????ND	? ????14.0 ????72.1	? ????11.6 ????4.8	? ????8.7 ????1.6	? ????7.0 ????1.5
Catalyst F (the present invention) ^fNo COS has COS	Catalyst E (contrast) ^eNo COS has COS	? ????131 ????185	? ????192 ????226	? ????61 ????41	? ????8.1 ????110.8	? ????6.3 ????5.0	? ????125 ????ND	? ????163 ????ND	? ????38 ????ND	? ????22.0 ????ND	? ????13.7 ????ND	? ????11.8 ????ND	? ????7.0 ????1.5
Catalyst F (the present invention) ^fNo COS has COS	Catalyst G (contrast) ^gNo COS has COS	? ????128 ????169	? ????177 ????205	? ????49 ????36	? ????17.3 ????116.3	? ????13.3 ????4.7	? ????125 ????ND	? ????163 ????ND	? ????38 ????ND	? ????22.0 ????ND	? ????13.7 ????ND	? ????11.8 ????ND	? ????4.7 ????0
^aCatalyst A (0.02wt%Pd/0.005wt%Ag/0.3wt%K/0.3wt%F) ^bCatalyst B (0.02wt%Pd/0.02wt%Ag/0.3wt%K/0.3wt%F) ^cCatalyst C (0.02wt%Pd/0.06wt%Ag/0.3wt%K/0.3wt%F) ^dCatalyst D (0.025wt%Pd/0.01wt%Ag/0.1wt%K/0.05wt%F) ^eCatalyst E (0.025wt%Pd/0.04wt%Ag/0.1wt%K/0.05wt%F) ^fCatalyst F (0.02wt%Pd/0.005wt%Ag/0.5wt%K/0.5wt%F) ^gCatalyst G (0.02wt%Pd/0.06wt%Ag/0.5wt%K/0.5wt%F) ^hC ₂Represent ethane ⁱC ₄Representative contains the hydrocarbon of 4 carbon atoms ^jHeavy hydrocarbon representative contains 6 or the hydrocarbon of more carbon atoms ^kThe ND representative is not measured													? ????4.7 ????0

The bright catalyst of the present invention of test tables of data is at the several importances such as the T1 and better to the selectivity ratios comparative catalyst of various hydrocarbon compounds of hydrogenation in the Table I.The comparative catalyst that the catalyst of the present invention that digital proof silver consumption is low is higher than silver-colored consumption is better.

Under the situation that does not have COS, catalyst A of the present invention and comparative catalyst B compare T1 with C lower and Δ T is similar.And under the situation that does not have COS, catalyst A of the present invention is compared the heavy hydrocarbon selectivity with comparative catalyst B and is descended with C.Exist under the situation of COS, catalyst A of the present invention and comparative catalyst B compare Δ T with C bigger and T1 is similar.In addition, there is under the situation of COS the C of catalyst A of the present invention ₄B goes with C with heavy hydrocarbon selectivity ratios comparative catalyst.The comparative catalyst that the catalyst of the present invention that digital proof silver consumption is low is higher than silver-colored consumption is better.

In addition, under the situation that does not have COS, it is lower that catalyst D of the present invention and comparative catalyst E compare T1.Exist under the situation of COS, catalyst D of the present invention compares the lower and ethane (C of T1 with comparative catalyst E ₂) selectivity is better.Under the situation that does not have COS, it is lower that catalyst F of the present invention and comparative catalyst G compare T1.These data prove that again the low catalyst of the present invention of the silver-colored consumption comparative catalyst higher than silver-colored consumption is better.

Result shown in the above embodiment proves that the present invention is well suited for realizing target described herein and reaches purpose mentioned and that include and advantage herein.

In the scope of disclosed and appended claims, can make rational change, modification and adaptability revision in the case without departing from the scope of the present invention.

Claims

1. method, comprise the hydrocarbon-containifluids fluids and the carbon monoxide-olefin polymeric that comprise the height unsaturated hydrocarbons contacted being enough to make described height unsaturated hydrocarbons selection to be hydrogenated under the hydrogenation conditions of low unsaturated hydrocarbons in the presence of the hydrogen, wherein said carbon monoxide-olefin polymeric comprises palladium, inorganic carrier and comprises silver and the catalytic component of alkali metal compound.

2. the process of claim 1 wherein that described height unsaturated hydrocarbons is selected from alkynes, alkadienes and composition thereof.

3. the method for claim 2, wherein said alkynes is selected from acetylene, propine, 1-butine, 2-butine, 1-pentyne, valerylene, 3-methyl isophthalic acid-butine, 1-hexin, 1-heptyne, 1-octyne, 1-n-heptylacetylene, 1-decine and composition thereof.

4. the method for claim 2, wherein said alkadienes per molecule contains 3 to about 12 carbon atoms.

5. the method for claim 4, wherein said alkadienes is selected from allene, 1, the 2-butadiene, 1, the 3-butadiene, isoprene, 1, the 2-pentadiene, 1, the 3-pentadiene, 1, the 4-pentadiene, 1, the 2-hexadiene, 1, the 3-hexadiene, 1, the 4-hexadiene, 1, the 5-hexadiene, the 2-methyl isophthalic acid, the 2-pentadiene, 2,3-dimethyl-1,3-butadiene, heptadiene, the methyl hexadiene, octadiene, the methyl heptadiene, the dimethyl hexadiene, the ethyl hexadiene, the trimethyl pentadiene, the methyl octadiene, the dimethyl-g diene, the ethyl octadiene, the trimethyl hexadiene, nonadiene, decadinene, 11 carbon diene, 12 carbon diene, cyclopentadiene, cyclohexadiene, methyl cyclopentadiene, cycloheptadiene, methyl cyclohexadiene, the dimethyl cyclopentadiene, the ethyl cyclopentadiene, bicyclopentadiene (is also referred to as three rings [5.2.1] ^2,6The last of the ten Heavenly stems-3, the 8-diene) and composition thereof.

6. the method for claim 1, wherein said low unsaturated hydrocarbons is selected from ethene, propylene, the 1-butylene, the 2-butylene, isobutene, the 1-amylene, the 2-amylene, methyl isophthalic acid-butylene, methyl-2-butene, the 1-hexene, the 2-hexene, the 3-hexene, Methyl-1-pentene, 2,3-dimethyl-1-butylene, the 1-heptene, the 2-heptene, the 3-heptene, methyl isophthalic acid-hexene, methyl-2-hexene, methyl-3-hexene, dimethyl pentene, ethylpentene, octene, the methyl heptene, the dimethyl hexene, ethyl hexene, nonene, the methyl octene, the dimethyl heptene, the ethyl heptene, the trimethyl hexene, cyclopentene, cyclohexene, methyl cyclopentene, cycloheptene, methylcyclohexene, dimethylcyclopentene, the ethyl cyclopentene, cyclo-octene, the methyl cycloheptene, the dimethyl cyclohexene, ethyl-cyclohexene, trimethyl cyclohexene, the methyl cyclo-octene, the dimethyl cyclo-octene, ethyl cyclo-octene and composition thereof.

7. the process of claim 1 wherein that described method also comprises exists sulphur impurity.

8. the method for claim 7, wherein said sulphur impurity is to be selected from hydrogen sulfide, carbonyl sulfide (COS), carbon disulfide (CS ₂), the sulphur compound of mercaptan (RSH), organic sulfur compound (R-S-R), organic disulfide (R-S-S-R), thiophene, the thiophene of replacement, organic trisulfide, organic tetrasulfide and composition thereof, wherein each R can be alkyl or cycloalkyl or the aryl that contains 1 to 10 carbon atom.

9. the method for claim 8, wherein said sulphur compound in described hydrocarbon-containifluids fluids exist concentration at about 0.5ppbv to the scope of about 1000ppmv sulphur.

10. the process of claim 1 wherein that described hydrocarbon-containifluids fluids also comprises monoolefine.

11. the method for claim 10, wherein said monoolefine is selected from ethene, propylene, the 1-butylene, the 2-butylene, isobutene, the 1-amylene, the 2-amylene, methyl isophthalic acid-butylene, methyl-2-butene, the 1-hexene, the 2-hexene, the 3-hexene, Methyl-1-pentene, 2,3-dimethyl-1-butylene, the 1-heptene, the 2-heptene, the 3-heptene, methyl isophthalic acid-hexene, methyl-2-hexene, methyl-3-hexene, dimethyl pentene, ethylpentene, octene, the methyl heptene, the dimethyl hexene, ethyl hexene, nonene, the methyl octene, the dimethyl heptene, the ethyl heptene, the trimethyl hexene, cyclopentene, cyclohexene, methyl cyclopentene, cycloheptene, methylcyclohexene, dimethylcyclopentene, the ethyl cyclopentene, cyclo-octene, the methyl cycloheptene, the dimethyl cyclohexene, ethyl-cyclohexene, trimethyl cyclohexene, the methyl cyclo-octene, the dimethyl cyclo-octene, ethyl cyclo-octene and composition thereof.

12. the method for claim 11, wherein said hydrocarbon-containifluids fluids also comprises the saturated hydrocarbons that is selected from methane, ethane, propane, butane, methylpropane, methybutane, dimethylbutane, pentane, hexane and composition thereof.

13. the process of claim 1 wherein described hydrogenation conditions comprise temperature about 10 to about 300 ℃ scope.

14. the method for claim 13, wherein said hydrogenation conditions also comprise pressure at about 136kPa to the scope of about 13.88MPa (about 5 to about 2000psig).

15. the method for claim 14, wherein said hydrogenation conditions also comprise feed rate that described hydrocarbon-containifluids fluids is loaded into described hydrogenation zone make gas hourly space velocity about 1 to the scope of about 50000 liters of hydrocarbon-containifluids fluids/rise catalyst/hour (rise/liter/hour).

16. the process of claim 1 wherein that described alkali metal compound is selected from alkali halide, alkali metal hydroxide, alkali carbonate, alkali metal hydrogencarbonate, alkali nitrates, alkali metal carboxylate and composition thereof.

17. the method for claim 16, wherein said alkali metal compound is an alkali halide, is alkaline metal iodide or alkali metal fluoride.

18. the method for claim 17, the alkali metal of wherein said alkali metal compound is selected from potassium, rubidium, caesium and composition thereof.

19. the method for claim 18, wherein said alkali metal compound is a potassium fluoride.

20. the process of claim 1 wherein palladium in the described carbon monoxide-olefin polymeric content by palladium metal based on the carbon monoxide-olefin polymeric gross weight about 0.0001 to the scope of about 3% (weight).

21. the method for claim 1, in the wherein said carbon monoxide-olefin polymeric content of silver by silver metal based on the carbon monoxide-olefin polymeric gross weight about 0.0003 to the scope of about 0.06% (weight), in the described carbon monoxide-olefin polymeric alkali-metal content based on the carbon monoxide-olefin polymeric gross weight about 0.001 to the scope of about 10% (weight).

22. the method for claim 21, in the wherein said carbon monoxide-olefin polymeric silver content by silver metal based on the carbon monoxide-olefin polymeric gross weight about 0.0005 to the scope of about 0.02% (weight).

23. the method for claim 21, in the wherein said carbon monoxide-olefin polymeric alkali-metal content based on the carbon monoxide-olefin polymeric gross weight about 0.005 to the scope of about 5% (weight).

24. the process of claim 1 wherein that described carbon monoxide-olefin polymeric also comprises halide.

25. the method for claim 24, in the wherein said carbon monoxide-olefin polymeric halid content based on the carbon monoxide-olefin polymeric gross weight about 0.001 to the scope of about 10% (weight).

26. the method for claim 25, wherein said halide are non-alkali halides.

27. the method for claim 26, wherein said halide is fluoride.

28. the method for claim 27, wherein said non-alkali halide is selected from HF, NH ₄F, NH ₄HF ₂And composition thereof.

29. the process of claim 1 wherein that described organic carrier is selected from aluminium oxide, silica, zirconia, titanium oxide, alumino-silicate, spinelle, zinc titanate and composition thereof.

30. the method for claim 29, wherein said inorganic carrier is an aluminium oxide, and wherein said aluminium oxide is selected from Alpha-alumina, beta-alumina, δ-aluminium oxide, η-aluminium oxide, gama-alumina, θ-aluminium oxide and composition thereof.

31. a carbon monoxide-olefin polymeric comprises palladium, inorganic carrier and comprises silver and the catalytic component of alkali metal compound.

32. the carbon monoxide-olefin polymeric of claim 31, wherein said alkali metal compound is selected from alkali halide, alkali metal hydroxide, alkali carbonate, alkali metal hydrogencarbonate, alkali nitrates, alkali metal carboxylate and composition thereof.

33. the carbon monoxide-olefin polymeric of claim 32, wherein said alkali metal compound is an alkali halide, is alkaline metal iodide or alkali metal fluoride.

34. the carbon monoxide-olefin polymeric of claim 33, the alkali metal of wherein said alkali metal compound is selected from potassium, rubidium, caesium and composition thereof.

35. the carbon monoxide-olefin polymeric of claim 34, wherein said alkali metal compound is a potassium fluoride.

36. the carbon monoxide-olefin polymeric of claim 31, in the wherein said carbon monoxide-olefin polymeric content of palladium by palladium metal based on the carbon monoxide-olefin polymeric gross weight about 0.0001 to the scope of about 3% (weight).

37. the carbon monoxide-olefin polymeric of claim 31, in the wherein said carbon monoxide-olefin polymeric content of silver by silver metal based on the carbon monoxide-olefin polymeric gross weight about 0.0003 to the scope of about 0.06% (weight), in the described carbon monoxide-olefin polymeric alkali-metal content based on the carbon monoxide-olefin polymeric gross weight about 0.001 to the scope of about 10% (weight).

38. the carbon monoxide-olefin polymeric of claim 37, in the wherein said carbon monoxide-olefin polymeric silver content by silver metal based on the carbon monoxide-olefin polymeric gross weight about 0.0005 to the scope of about 0.02% (weight).

39. the carbon monoxide-olefin polymeric of claim 37, in the wherein said carbon monoxide-olefin polymeric alkali-metal content based on the carbon monoxide-olefin polymeric gross weight about 0.005 to the scope of about 5% (weight).

40. the carbon monoxide-olefin polymeric of claim 31, wherein said carbon monoxide-olefin polymeric also comprises halide.

41. the carbon monoxide-olefin polymeric of claim 40, in the wherein said carbon monoxide-olefin polymeric halid content based on the carbon monoxide-olefin polymeric gross weight about 0.001 to the scope of about 10% (weight).

42. the carbon monoxide-olefin polymeric of claim 41, wherein said halide are non-alkali halides.

43. the carbon monoxide-olefin polymeric of claim 42, wherein said halide is fluoride.

44. the carbon monoxide-olefin polymeric of claim 43, wherein said non-alkali halide is selected from HF, NH ₄F, NH ₄HF ₂And composition thereof.

45. the carbon monoxide-olefin polymeric of claim 31, wherein said organic carrier is selected from aluminium oxide, silica, zirconia, titanium oxide, alumino-silicate, spinelle, zinc titanate and composition thereof.

46. the carbon monoxide-olefin polymeric of claim 45, wherein said inorganic carrier is an aluminium oxide, and wherein said aluminium oxide is selected from Alpha-alumina, beta-alumina, δ-aluminium oxide, η-aluminium oxide, gama-alumina, θ-aluminium oxide and composition thereof.

47. the preparation method of a carbon monoxide-olefin polymeric comprises the catalytic component that makes inorganic carrier blending palladium and comprise silver and alkali metal compound.

48. the method for claim 47, wherein said palladium exists with the palladium compound form that is selected from palladium bromide, palladium bichloride, palladium iodide, palladium nitrate, nitric hydrate palladium, nitric acid tetramine and closes palladium, palladium oxide, aqua oxidation palladium, palladium sulfate and composition thereof.

49. the method for claim 47, wherein said silver exists with the silver compound form that is selected from silver nitrate, silver acetate, silver cyanide and composition thereof.

50. the method for claim 47, wherein said alkali metal compound is selected from alkali halide, alkali metal hydroxide, alkali carbonate, alkali metal hydrogencarbonate, alkali nitrates, alkali metal carboxylate and composition thereof.

51. the method for claim 48, wherein said palladium compound is a palladium bichloride, has added hydrochloric acid in the wherein said palladium bichloride and has formed PdCl ₄ ^-2Complex.

52. the method for claim 50, wherein said alkali metal compound is an alkali halide, is alkaline metal iodide or alkali metal fluoride.

53. the method for claim 52, the alkali metal of wherein said alkali metal compound is selected from potassium, rubidium, caesium and composition thereof.

54. the method for claim 53, wherein said alkali metal compound is a potassium fluoride.

55. the method for claim 48, wherein said palladium compound is present in and contains in the palladium solution, the content that the wherein said concentration that contains palladium compound described in the palladium solution makes palladium in the described carbon monoxide-olefin polymeric by palladium metal based on the carbon monoxide-olefin polymeric gross weight about 0.0001 to the scope of about 3% (weight).

56. the method for claim 49, wherein said silver compound is present in the Ag-containing solution, the content that the concentration of silver compound described in the wherein said Ag-containing solution makes in the described carbon monoxide-olefin polymeric silver by silver metal based on the carbon monoxide-olefin polymeric gross weight about 0.0003 to the scope of about 0.06% (weight).

57. the method for claim 50, wherein said alkali metal compound is present in the solution of alkali metal-containing compound, the concentration of alkali metal compound described in the solution of wherein said alkali metal-containing compound make in the described carbon monoxide-olefin polymeric alkali-metal content based on the carbon monoxide-olefin polymeric gross weight about 0.001 to the scope of about 10% (weight).

58. the method for claim 50, wherein said alkali metal compound is an alkali metal fluoride, described alkali metal fluoride is present in the solution of alkali metal containing fluoride, the concentration of alkali metal fluoride described in the solution of wherein said alkali metal containing fluoride make in the described carbon monoxide-olefin polymeric alkali-metal content based on the carbon monoxide-olefin polymeric gross weight about 0.001 to the scope of about 10% (weight).

59. the method for claim 47, wherein said method also comprises makes described inorganic carrier blending halide, described halide is present in the solution of halide, halid concentration described in the solution of wherein said halide make in the described carbon monoxide-olefin polymeric halid content based on the carbon monoxide-olefin polymeric gross weight about 0.001 to the scope of about 10% (weight).

60. the method for claim 59, wherein said halide are non-alkali halides.

61. the method for claim 60, wherein said halide is fluoride.

62. the method for claim 61, wherein said non-alkali halide is selected from HF, NH ₄F, NH ₄HF ₂And composition thereof.

63. it is dry that the method for claim 47, the preparation method of wherein said carbon monoxide-olefin polymeric also are included under the composition dries condition, wherein said composition dries condition comprises:

Temperature is about 35 to about 290 ℃ scope,

Time cycle generally about 0.1 to about 6 hours scope and

Pressure at about normal pressure to the scope of about 689kPa (about 100psia).

64. the method for claim 63, the preparation method of wherein said carbon monoxide-olefin polymeric also is included in roasting under the composition roasting condition, and wherein said composition roasting condition comprises:

Roasting in air or in nonoxidizing atmosphere,

Temperature is about 200 to about 900 ℃ of scopes,

Time cycle about 0.5 to about 40 hours scope and

Pressure at about 48.2kPa to the scope of about 5.17MPa (about 7 to about 750psia).

65. pass through the composition of the arbitrary described method preparation of claim 47-64.

66. method, comprise the hydrocarbon-containifluids fluids and the carbon monoxide-olefin polymeric that comprise the height unsaturated hydrocarbons contacted being enough to make described height unsaturated hydrocarbons to be hydrogenated under the hydrogenation conditions of low unsaturated hydrocarbons at hydrogenation zone in the presence of the hydrogen, wherein said carbon monoxide-olefin polymeric prepares by the arbitrary described method of claim 47-64.

67. the method for claim 66, wherein said height unsaturated hydrocarbons is selected from alkynes, alkadienes and composition thereof.

68. the method for claim 67, wherein said alkynes are selected from acetylene, propine, 1-butine, 2-butine, 1-pentyne, valerylene, 3-methyl isophthalic acid-butine, 1-hexin, 1-heptyne, 1-octyne, 1-n-heptylacetylene, 1-decine and composition thereof.

69. the method for claim 67, wherein said alkadienes per molecule contain 3 to about 12 carbon atoms.

70. the method for claim 69, wherein said alkadienes is selected from allene, 1, the 2-butadiene, 1, the 3-butadiene, isoprene, 1, the 2-pentadiene, 1, the 3-pentadiene, 1, the 4-pentadiene, 1, the 2-hexadiene, 1, the 3-hexadiene, 1, the 4-hexadiene, 1, the 5-hexadiene, the 2-methyl isophthalic acid, the 2-pentadiene, 2,3-dimethyl-1,3-butadiene, heptadiene, the methyl hexadiene, octadiene, the methyl heptadiene, the dimethyl hexadiene, the ethyl hexadiene, the trimethyl pentadiene, the methyl octadiene, the dimethyl-g diene, the ethyl octadiene, the trimethyl hexadiene, nonadiene, decadinene, 11 carbon diene, 12 carbon diene, cyclopentadiene, cyclohexadiene, methyl cyclopentadiene, cycloheptadiene, methyl cyclohexadiene, the dimethyl cyclopentadiene, the ethyl cyclopentadiene, bicyclopentadiene (is also referred to as three rings [5.2.1] ^2,6The last of the ten Heavenly stems-3, the 8-diene) and composition thereof.

71. the method for claim 66, wherein said low unsaturated hydrocarbons is selected from ethene, propylene, the 1-butylene, the 2-butylene, isobutene, the 1-amylene, the 2-amylene, methyl isophthalic acid-butylene, methyl-2-butene, the 1-hexene, the 2-hexene, the 3-hexene, Methyl-1-pentene, 2,3-dimethyl-1-butylene, the 1-heptene, the 2-heptene, the 3-heptene, methyl isophthalic acid-hexene, methyl-2-hexene, methyl-3-hexene, dimethyl pentene, ethylpentene, octene, the methyl heptene, the dimethyl hexene, ethyl hexene, nonene, the methyl octene, the dimethyl heptene, the ethyl heptene, the trimethyl hexene, cyclopentene, cyclohexene, methyl cyclopentene, cycloheptene, methylcyclohexene, dimethylcyclopentene, the ethyl cyclopentene, cyclo-octene, the methyl cycloheptene, the dimethyl cyclohexene, ethyl-cyclohexene, trimethyl cyclohexene, the methyl cyclo-octene, the dimethyl cyclo-octene, ethyl cyclo-octene and composition thereof.

72. also comprising, the method for claim 66, wherein said method have sulphur impurity.

73. the method for claim 72, wherein said sulphur impurity are to be selected from hydrogen sulfide, carbonyl sulfide (COS), carbon disulfide (CS ₂), the sulphur compound of mercaptan (RSH), organic sulfur compound (R-S-R), organic disulfide (R-S-S-R), thiophene, the thiophene of replacement, organic trisulfide, organic tetrasulfide and composition thereof, wherein each R can be alkyl or cycloalkyl or the aryl that contains 1 to 10 carbon atom.

74. the method for claim 73, wherein said sulphur compound in described hydrocarbon-containifluids fluids exist concentration at about 0.5ppbv to the scope of about 1000ppmv sulphur.

75. the method for claim 66, wherein said hydrocarbon-containifluids fluids also comprises monoolefine.

76. the method for claim 75, wherein said monoolefine is selected from ethene, propylene, the 1-butylene, the 2-butylene, isobutene, the 1-amylene, the 2-amylene, methyl isophthalic acid-butylene, methyl-2-butene, the 1-hexene, the 2-hexene, the 3-hexene, Methyl-1-pentene, 2,3-dimethyl-1-butylene, the 1-heptene, the 2-heptene, the 3-heptene, methyl isophthalic acid-hexene, methyl-2-hexene, methyl-3-hexene, dimethyl pentene, ethylpentene, octene, the methyl heptene, the dimethyl hexene, ethyl hexene, nonene, the methyl octene, the dimethyl heptene, the ethyl heptene, the trimethyl hexene, cyclopentene, cyclohexene, methyl cyclopentene, cycloheptene, methylcyclohexene, dimethylcyclopentene, the ethyl cyclopentene, cyclo-octene, the methyl cycloheptene, the dimethyl cyclohexene, ethyl-cyclohexene, trimethyl cyclohexene, the methyl cyclo-octene, the dimethyl cyclo-octene, ethyl cyclo-octene and composition thereof.

77. the method for claim 76, wherein said hydrocarbon-containifluids fluids also comprises the saturated hydrocarbons that is selected from methane, ethane, propane, butane, methylpropane, methybutane, dimethylbutane, pentane, hexane and composition thereof.

78. the method for claim 66, wherein said hydrogenation conditions comprise temperature about 10 to about 300 ℃ scope.

79. the method for claim 78, wherein said hydrogenation conditions also comprise pressure about 136kPa to the scope of about 13.88MPa (about 5 to about 2000psig) and the described hydrocarbon-containifluids fluids feed rate that is loaded into described hydrogenation zone make gas hourly space velocity about 1 to the scope of about 50000 liters of hydrocarbon-containifluids fluids/rise catalyst/hour (liter/liter/hour).