CN85100761A - Fibrous catalyst for selective hydrogenation of dienes and method for making thereof - Google Patents
Fibrous catalyst for selective hydrogenation of dienes and method for making thereof Download PDFInfo
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- CN85100761A CN85100761A CN 85100761 CN85100761A CN85100761A CN 85100761 A CN85100761 A CN 85100761A CN 85100761 CN85100761 CN 85100761 CN 85100761 A CN85100761 A CN 85100761A CN 85100761 A CN85100761 A CN 85100761A
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- catalyst
- fiber
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- siliceous
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Abstract
A kind of fiber catalyst carrier that is mainly used in the drippolene diene selective hydrotreating, its active component comprise Pd or the Pt of 0.2-1% at least and comprise Na, K, Li, Mg or rare earth element a kind of of 0.05%-2% at least.The specific surface of porous fiber carrier is greater than 20m
2/ g, pore volume is greater than 0.1ml/g.Compare with the similar granular catalyst of industrial present employing, the high 1-2 of a liquid air speed order of magnitude, reaction temperature approaches room temperature, and selectivity is near 100%.At 40 ℃ of reaction temperatures, reaction pressure 40kg/cm
2, under the liquid air speed 40ml/ghr, the 1000 hours activity that turn round continuously do not descend.This catalyst also can be applicable to alkynes or diene selective hydrotreating in other oil products.
Description
The invention belongs to the selection hydrofinishing of oil product, more particularly relate generally to a kind of catalyst of drippolene diene selective hydrotreating.As everyone knows, association contained the drippolene of high concentration diene, monoene and aromatic hydrocarbons when petroleum hydrocarbon cracking was produced ethene and propylene, and monoolefine wherein and aromatic hydrocarbons help improving the octane number of gasoline, but the existence of diolefin then can make gasoline become unstable.For this reason, Kellogg company developed two-section hydrotreating technology in 1961.One-stage hydrogenation makes diolefin wherein become monoolefine to produce stable gasoline; Need make monoolefine become alkane by secondary hydrogenation if extract aromatic hydrocarbons.Catalyst of the present invention is mainly used in the one stage hydrofining of drippolene, certainly, changes the prescription and the process condition of catalyst, also can be used for and H
2The selection hydrogenation of the unsaturated hydrocarbons in the other technologies field of reaction is as the hydrofinishing of alkynes or diene.
The industrial catalyst that is used for one stage hydrofining mainly is Ni/Al at present
2O
3Or Pd/Al
2O
3Carrier is the particle Al of porous
2O
3Because the hydrogenation of alkynes or diene is fast reaction, DIFFUSION CONTROLLED often becomes the governing factor that improves catalyst efficiency, so this class catalyst is difficult to turn round under high-speed.General air speed was at 3 o'clock
-1Below, and poor selectivity.In addition, unsettled diene or alkynes form colloid at catalyst surface easily under the high temperature, make the very fast inactivation of catalyst, and catalyst has to frequently activate and regeneration.Therefore, wish that the diolefin hydrogenation catalyst has higher low temperature active, make material in the reactor keep the liquid phase of larger proportion, so that the polymer of catalyst surface fallen by " flushing ", thus the prolongation life of catalyst.In order to overcome DIFFUSION CONTROLLED, Japan's special permission is clear to be immersed in the Pt salt of PH=2.0～4.8 on the surface of particulate inorganic porous carrier with 47-35670, makes epidermis type catalyst.In order to overcome alkynes and diene " green oil " and solid polymer that polymerization generated at catalyst surface, United States Patent (USP) U.S.P4,061,724 and U.S.P4,073,865, BP U.K.P1,574,840 and European patent E, P, O.058,014A adopts SiO
2Make the carrier of metal Pd or Pt, this polycrystalline Si O
2Be a kind of crystal, can reduce the caused loss in efficiency of catalyst surface high molecular polymer " pollution " with low acidity and planning loose structure.Because these catalyst still adopt bead-type substrate, above-mentioned effort all fails to reach the effect of the phase of giving.
Task of the present invention is to prepare a kind of low temperature active height, selectivity is good, surface acidity is low, and alkynes and diolefin are at the few rugged catalyst of surface aggregate.
Major technique feature of the present invention is the fiber carrier that catalyst adopts porous.This carrier can be that specific surface is greater than 20m
2/ g, pore volume be greater than 0.1mg/g, and diameter has only＜carbon fiber or the Al of 5 μ m
2O
3Fiber or siliceous Al
2O
3Fiber.Its best specific surface is 50-200m
2/ g, best pore volume are 0.1-0.3ml/g.For this reason, must be the roasting in the air of 150-350 ℃ (best) of special carbon fiber, special Al at 200-250 ℃
2O
3Fiber or siliceous Al
2O
5It is 20-150m that fiber roasting in the air of 750-1100 ℃ (best 800-900 ℃) becomes specific surface
2/ g, η-Al of pore volume 0.1-0.25ml/g
2O
3Method is soaked in employing altogether or the branch method of soaking is stated from several reactive metals on the fiber carrier of having handled, wherein have a kind of precious metals pd or Pt at least, its content is that 0.05～2W%(is to carrier), the best is 0.3～0.7W%, have a kind of other metals at least as auxiliary agent, as Na, K, Li, Mg or rare earth element, its content is that 0.01-5W%(is to carrier), the best is 0.05-3W%, and the method for making of catalyst is as follows:
(1) preparing metal content is the PdCl of 0.5-10mg/ml
2, Pd(NO
3)
2Or H
2PtCl
6The aqueous solution.
(2) use Na
2CO
3Or K
2CO
3The PH of above-mentioned solution is adjusted to 0.1-5 or 2-4.
(3) carrier of having handled was flooded 1-8 hour at 15-35 ℃ or 20-30 ℃ in the ratio of every gram fiber carrier 10-50ml solution.
(4) remove mother liquor with filtration method or centrifugal process.
(5) with the catalyst behind the deionized water cyclic washing dipping to there not being Cl
-1
(6) descended dry 4-8 hour at 110-120 ℃.
(7) with Al
2O
3Or siliceous Al
2O
3Fiber is the catalyst of carrier in the air of 400-500 ℃ or 420-450 ℃ roasting 6-8 hour.The catalyst that with the carbon fiber is carrier was 150-350 ℃ or 200-250 ℃ roasting 4-8 hour.
(8) at the H of 100-400 ℃ or 280-350 ℃
2In the reduction above-mentioned catalyst or with wet reducing it.
Another major technique feature of catalyst of the present invention is that surface acidity is low, the metal dispersity height.The method for making of this catalyst is as follows:
(1) 800-900 ℃ of baked siliceous Al
2O
3Fiber flooded 24-100 hour in the ammoniacal liquor of 0.1-2N or 0.5-1N, removed mother liquor, drained.
(2) with above-mentioned siliceous Al
2O
3Fiber is dipping 24-72 hour in the palladium ammino-complex aqueous solution of 0.5-10mg/ml, PH=7-12 or 8-10 in Pd concentration.Then by above-mentioned steps filtration, washing, drying, roasting, reduction.
Compared with the prior art, catalyst of the present invention is used for the drippolene diene selective hydrotreating very outstanding advantage.
At first, it has shown very high initial activity.The liquid air speed that is adopted on the general industry is all at 3 o'clock
-1Below, European patent EP O is when 058,014 liquid air speed is 0.5-6
-1, and liquid air speed of the present invention is tens of to hundreds of, promptly than high 1～2 order of magnitude of prior art, this has significantly reduced catalyst consumption, has dwindled the size of equipment needed thereby.Catalyst of the present invention is used for the result of the test of diolefin hydrogenation and lists in table 1.
Table 1 fiber catalyst drippolene diolefin hydrogenation initial activity
The character of drippolene is before the hydrogenation: 60-140 ℃ of gold-plating journey, and arsenic content＜0.02 μ g/ml, the diene value is a 20gI/100g oil, the bromine valency is a 50gBr/100g oil.Diene value behind the hydrogenation all is lower than industrial to the requirement of cracking gasoline products.Be that the diene value is lower than 0.5gI/ 100g oil.One of reason that activity of such catalysts of the present invention is high just is that fibrous carrier is littler than the resistance to mass tranfer of bead-type substrate, has reduced the influence of the DIFFUSION CONTROLLED in the course of reaction.
The outstanding advantage of another of catalyst of the present invention is that it has good selectivity and stability.Life test shows at 40 ℃ of temperature, pressure 40kg/cm
2, hydrogen/oil ratio 0.5mcl, the liquid air speed is at 40hr
-1Down, turned round 1000 hours continuously with the drippolene diene selective hydrotreating, activity does not descend, and product diene value still is lower than 0.5gI/100g oil, and selectivity is near 100%.Turn round after 1000 hours, again the liquid air speed is brought up to 120h
-1, product is still qualified.We are with the selection hydrogenation catalyst PGC(0.3%Pd-Al of catalyst of the present invention and Japanese Engelhard company
2O
3) performance contrasted, it the results are shown in table 2.
Table 2 Pd-Al
2O
3Fiber catalyst and Pd-Al
2O
3The granular catalyst performance comparison
As shown in Table 2, two kinds of catalyst all are that 0.3% Pd is stated from Al
2O
3, the carrier of the present invention that is not both is fibrous, PGC is granular.In addition, fiber Al of the present invention
2O
3After ammoniacal liquor soaks, reduced surperficial acidity.Just because of these difference, make the present invention almost carry out diene selective hydrotreating at normal temperatures also than the active high order of magnitude of catalyst of using on the general industry and foreign similar catalyst.Because reaction temperature is low, catalyst surface acidity is low, generates the possibility of colloidal state polymer so significantly reduced diene or alkynes at catalyst surface, has both made to generate a spot of colloid, also can be rinsed out, and be unlikely to allow the topped activity of such catalysts of colloid center by the reactant of liquid phase or product.So catalyst of the present invention is brought up to 100h to air speed in running under the condition of table 2 after 1000 hours again
-1More than, the diene value of product is less than 0.1gI/100g oil, but the catalyst of PGC is in running under the condition of table 2 after 150 hours, and the diene value of product is just greater than 0.8gI/100g oil.Reaction temperature is low, makes charging be essentially liquid phase, and this not only makes catalyst surface constantly " renewal ", has prolonged life of catalyst, and has reduced energy consumption.
Embodiment 1
Fiber Al
2O
3Physical property as follows: specific surface 93cm
2/ g pore volume 0.13ml/g, average pore size 28
, filament diameter 3-5 μ, crystalline phase η-Al
2O
3
10gAl
2O
3Fiber boiled in deionized water 20 minutes, removed moisture, drained.Containing the 50mlPdCl of Pd1mg/ml
2Add the 160ml deionized water in the aqueous solution, use 0.5NK
2CO
3The PH of above-mentioned solution is adjusted to 3.5-4.0.With the 10gAl that drains
2O
3Fiber flooded 2-6 hour in this solution, constantly stirred therebetween.Afterwards, with the Al behind the dipping
2O
3The fiber suction filtration is to doing, and being washed till with deionized water does not have Cl in the filtrate
-1Above-mentioned catalyst is at 120 ℃ of dry 4-6 hours, again at 420-450 ℃ of roasting 6-8 hour.H at 260-350 ℃
2Middle reduction.
Embodiment 2
Contain Si-Al
2O
3The physical property of fiber is as follows: specific surface 128.7m
2/ g, pore volume 0.13ml/g, average pore size 20
, filament diameter 3-5 μ, crystalline phase η-Al
2O
3, silicone content 2.8%, Lewis acid 0.03mmol/g pyridine.
10g contains Si-Al
2O
3Fiber flooded 48 hours in the ammoniacal liquor of 0.5N, decant, drained.Get the solution 12ml that contains Pd3mg/ml, add 0.5N ammoniacal liquor 12ml, and add deionized water and be diluted to 50ml, the PH that makes this solution is greater than 8, the Al that the 10g that handled is siliceous
2O
3Fiber flooded 48-72 hour in this solution.Press embodiment 1 described step filtration, washing, drying, activation, reduction then.
Claims (13)
1, a kind of catalyst that is used for selective hydrogenation of diolefin as, it can be stated from porous and granular Al by reactive metal Pd or Pt
2O
3, SiO
2Form on zeolite or the activated carbon, the invention is characterized in and adopt the surface greater than 20cm
2/ g, pore volume is greater than the porous fibrous carrier of 0.1ml/g.
2, catalyst according to claim 1 is characterized in that containing 0.05-2W%(to carrier) Pd or Pt or its mixture, 0.01-5W%(is to carrier) salt or its two or more mixture of Na, K, Li, Mg or rare earth.
3, as catalyst as described in the claim 2, it is characterized in that containing 0.05-0.7W%(to carrier) Pd or Pt or its mixture, 0.05-3W%(is to carrier) N
2, K, Li, Mg or rare earth salt or its two or more mixture.
4, as catalyst as described in the claim 1,2 or 3, it is characterized in that described porous fibrous carrier specific surface is 20-200m
2/ g, pore volume are the Al of 0.1-0.3ml/g
2O
3Fiber, siliceous Al
2O
3Fiber or carbon fiber.
5, a kind of processing method of giving as carbon fiber as described in the claim 4 is characterized in that roasting in the air of 150-350 ℃ or 200-250 ℃.
6, a kind of as Al as described in the claim 4
2O
3Fiber or siliceous Al
2O
3Fiber give processing method, it is characterized in that in the air of 750～1100 ℃ or 800-900 ℃ it is 20-150m that roasting becomes specific surface
2/ g, pore volume are 0.1-0.25ml/g η-Al
2O
3Or the Al of other forms
2O
3Fiber.
7, as catalyst as described in the claim 3, it is characterized in that the weight ratio of each component is: Al
2O
3: Pd: K=100: 0.2-0.7: 0.05-2.0.
8, as catalyst as described in the claim 3, it is characterized in that the weight ratio of each component is: siliceous Al
2O
3: Pd=100: 0.05-0.7.
9, a kind of method for making as catalyst as described in the claim 1,2,3,7 or 8 is characterized in that adopting and soaks method altogether or branch soaks method, and its step is as follows:
(1) preparation Pd or Pt or its mixture tenor PdCl that is 0.5-10mg/ml
2, Pd(NO
3)
2Or H
2PtCl
6The aqueous solution
(2) use Na
2CO
3Or K
2CO
3The pH value of above-mentioned solution is adjusted to 0.1-5 or 2-4.
(3) carrier of having handled was flooded 1 to 8 hour at 15-35 ℃ or 20-30 ℃ in the ratio of every gram fiber carrier 10-50ml solution.
(4) remove mother liquor with filtration method or centrifugal process.
(5) with the catalyst behind the deionized water cyclic washing dipping to there not being Cl
-
(6) descended dry 4-8 hour at 110-120 ℃.
(7) with Al
2O
3Or siliceous Al
2O
3Fiber is the catalyst of carrier in the air of 400 ℃-500 ℃ or 420-450 ℃ roasting 6-8 hour.The catalyst that with the carbon fiber is carrier was 150-350 ℃ or 200-250 ℃ roasting 4-8 hour.
(8) at the H of 100-400 ℃ or 280-350 ℃
2In the reduction above-mentioned catalyst or with wet reducing it.
10, a kind of as catalyst method for making as described in the claim 9, it is characterized in that:
(1) 800-900 ℃ of baked siliceous Al
2O
3Fiber flooded 24-100 hour in the ammoniacal liquor of 0.1-2N or 0.5-1N, removed mother liquor, drained.
(2) with above-mentioned siliceous Al
2O
3Fiber is dipping 24-72 hour in the palladium ammino-complex aqueous solution of 0.5-10mg/ml, PH=7-12 or 8-10 in Pd concentration.
11, a kind of claim 1,2,3,7 or 8 described catalyst as hydrorefined method, it is characterized in that it is the selection hydrogenation of alkynes or diolefin in the oil product.
12, a kind ofly be used for the method for drippolene diene selective hydrotreating, it is characterized in that reaction temperature is lower than 100 ℃, reaction pressure 30-60kg/cm as catalyst as described in the claim 11
2, liquid air speed 10-600ml/gh, product diene value 0.1gI/100g oil.
13, method as claimed in claim 12 is characterized in that reaction temperature 40-60 ℃, reaction pressure 40-60kg/cm
2, liquid air speed 40-500ml/gh, product diene value 0.1gI/100g oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85100761 CN85100761A (en) | 1985-04-01 | 1985-04-01 | Fibrous catalyst for selective hydrogenation of dienes and method for making thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85100761 CN85100761A (en) | 1985-04-01 | 1985-04-01 | Fibrous catalyst for selective hydrogenation of dienes and method for making thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN85100761A true CN85100761A (en) | 1986-09-24 |
Family
ID=4791413
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85100761 Withdrawn CN85100761A (en) | 1985-04-01 | 1985-04-01 | Fibrous catalyst for selective hydrogenation of dienes and method for making thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN85100761A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1101261C (en) * | 1999-11-12 | 2003-02-12 | 中国石化集团齐鲁石油化工公司 | Selective hydrogenation catalyst for alkyne and diene |
| WO2009079905A1 (en) | 2007-12-13 | 2009-07-02 | Petrochina Company Limited | A selective hydrogenation catalyst and the preparation thereof |
| CN101992102A (en) * | 2009-08-17 | 2011-03-30 | Ifp公司 | Method for preparing a support catalyst made from ni and a metal of the IB group for selective hydrogenation of polyunsaturated hydrocarbons |
| CN101733097B (en) * | 2009-12-07 | 2012-11-14 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing gamma-valerolactone by alpha-angelica lactone, preparation method and application |
| CN103657644A (en) * | 2013-10-31 | 2014-03-26 | 内蒙古工业大学 | Preparation method of novel porous carbon nano fiber loaded palladium nanoparticle composite catalyst |
| CN106391029A (en) * | 2016-10-21 | 2017-02-15 | 东南大学 | Preparation method and application of carbon nanofiber-bimetal composite catalyst |
| US9597668B2 (en) | 2007-11-01 | 2017-03-21 | Petrochina Company Limited | Selective nickel based hydrogenation catalyst and the preparation thereof |
-
1985
- 1985-04-01 CN CN 85100761 patent/CN85100761A/en not_active Withdrawn
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1101261C (en) * | 1999-11-12 | 2003-02-12 | 中国石化集团齐鲁石油化工公司 | Selective hydrogenation catalyst for alkyne and diene |
| US9597668B2 (en) | 2007-11-01 | 2017-03-21 | Petrochina Company Limited | Selective nickel based hydrogenation catalyst and the preparation thereof |
| WO2009079905A1 (en) | 2007-12-13 | 2009-07-02 | Petrochina Company Limited | A selective hydrogenation catalyst and the preparation thereof |
| US8211823B2 (en) | 2007-12-13 | 2012-07-03 | Petrochina Company Limited | Selective hydrogenation catalyst and the preparation thereof |
| CN101992102A (en) * | 2009-08-17 | 2011-03-30 | Ifp公司 | Method for preparing a support catalyst made from ni and a metal of the IB group for selective hydrogenation of polyunsaturated hydrocarbons |
| CN101733097B (en) * | 2009-12-07 | 2012-11-14 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing gamma-valerolactone by alpha-angelica lactone, preparation method and application |
| CN103657644A (en) * | 2013-10-31 | 2014-03-26 | 内蒙古工业大学 | Preparation method of novel porous carbon nano fiber loaded palladium nanoparticle composite catalyst |
| CN106391029A (en) * | 2016-10-21 | 2017-02-15 | 东南大学 | Preparation method and application of carbon nanofiber-bimetal composite catalyst |
| CN106391029B (en) * | 2016-10-21 | 2018-12-28 | 东南大学 | A kind of preparation method and application of carbon nano-fiber-double-metal composite catalyst |
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| C06 | Publication | ||
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| WW01 | Invention patent application withdrawn after publication |