CN106699499B - A method of improving isomerization of bridge-type tetrahydro-dicyclopentadiene selectivity - Google Patents
A method of improving isomerization of bridge-type tetrahydro-dicyclopentadiene selectivity Download PDFInfo
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- C07C2529/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract
The present invention discloses a kind of method for improving isomerization of bridge-type tetrahydro-dicyclopentadiene selectivity, isomerization catalyst is prepared using the higher super-stable Y molecular sieves of sodium content, improve the content of super-stable Y molecular sieves in catalyst, trace chlorinated organics are added in reaction raw materials bridge-type tetrahydro-dicyclopentadiene solution, isomerization reaction is carried out using relatively low reaction temperature and Hydrogen Vapor Pressure and higher hydrogen-oil ratio simultaneously.Using method of the invention, isomerization of bridge-type tetrahydro-dicyclopentadiene reaction conversion per pass can reach 95% or more, yield and reach 90% or more, the lock out operation difficulty after reducing reaction.
Description
Technical field
The present invention relates to a kind of methods for improving isomerization of bridge-type tetrahydro-dicyclopentadiene selectivity, pass through the system of catalyst
The control of Preparation Method and reaction condition reduces the generation of side reaction during isomerization of bridge-type tetrahydro-dicyclopentadiene.
Background technique
It is first hydrogenated to obtain bridge-type tetrahydro-dicyclopentadiene (endo-THDCPD) with dicyclopentadiene (DCPD) for raw material,
Then hanging type tetrahydrochysene dicyclopentadiene is isomerized under acidic catalyst effect, and (exo-THDCPD is a kind of function admirable
Low temperature liquid fuel is widely used in the propulsion of guided missile, aircraft and torpedo, becomes the indispensable fuel of aerospace cause.
Isomerization of bridge-type tetrahydro-dicyclopentadiene, which prepares hanging type tetrahydrochysene dicyclopentadiene, can be used the anhydrous trichlorine of the strong L acid of tradition
Change aluminium, molecular sieve or solid super-strong acid as catalyst.Catalyzed by Anhydrous Aluminium Chloride reaction conversion ratio is high, and selectivity is good, reaction
It is easy to carry out, but its high polymer production quantity is big, and catalyst amount is big, and the service life is short, can only carry out intermittent reaction, and tri-chlorination
After heavy constituent generates complex compound in aluminium and product, catalyst cannot regenerate, and generate a large amount of wastes, and post-processing needs alkali neutralization,
Product separation and purification are difficult, generate a large amount of acid waste waters in treatment process, cause serious pollution to the environment.
It is solution using the solid acid catalysts such as porous molecular screen with appropriate pore size and fixed bed isomerization process
The certainly effective way of the above problem, but since molecular sieve surface acid density is lower than AlCl3, thus need higher reaction temperature
The problems such as degree, that there are conversion ratios is lower for catalyst, selectivity is poor, molecular sieve easy carbon distribution inactivation, especially selectivity is poor leads
It causes to generate what the boiling points such as large number of trans-decalin, adamantane were very close to purpose product hanging type tetrahydrochysene dicyclopentadiene
By-product causes to refine after product relatively difficult, it is difficult to obtain the target product for meeting purity requirement.
In the prior art, the molecular sieves such as NH4Y, NaY, ReY, NH4-USY, NH4-SSY, H-beta, HZSM-5 are between autoclave
Catalysis endo-TCD isomerization in reactor of having a rest prepare exo-TCD react in catalytic activity, wherein H-USY effect is best,
Under 195 DEG C of reaction temperature, the yield that endo-TCD conversion ratio is 94.93%, exo-TCD is 89.69%, by-product adamantane
Yield be 3.03%.
In order to simplify whole preparation process, the prior art prepares hydroisomerization bifunctional catalyst, and dicyclopentadiene exists
Hydro-isomerised reaction is carried out simultaneously under catalyst action, directly generates hanging type tetrahydrochysene dicyclopentadiene.And use different sial
H-beta, HY molecular sieve of ratio, rare-earth Y molecular sieve, ultra-steady Y molecular sieve, super steady rare-earth Y molecular sieve load a certain number of Pd,
Pt, Rh, Ni prepare one-step catalytic agent.In the prior art, hydrogenation catalyst is attached to reactor top, isomerization catalyst dress
To reactor lower part, but catalyst loads Rh, expensive, and reaction selectivity is not high, and only 86.1%.
Using molecular sieve as isomerization of bridge-type tetrahydro-dicyclopentadiene catalyst, ask there are isomerisation selectivity is poor
Topic.In addition the technique that dicyclopentadiene one-step method prepares hanging type tetrahydrochysene dicyclopentadiene may be to the service life for extending catalyst
Unfavorable, the reason is that reaction condition required for hydro-isomerised the two has larger difference: hydrogenation reaction needs relatively low
Reaction temperature and higher Hydrogen Vapor Pressure, isomerization reaction then just on the contrary, in order to look after isomerisation conversion, add hydrogen-isomery
Change process is both needed to carry out under relatively low Hydrogen Vapor Pressure and higher reaction temperature, in this way can the use of serious curtailment catalyst
Service life is not able to satisfy industrial requirement.
Summary of the invention
In view of problem above, the present invention prepares isomerization catalyst using the higher super-stable Y molecular sieves of sodium content, higher
Sodium content can reduce the highly acid position of molecular sieve surface, it is possible to reduce the generation of side reaction.Improve superstable gamma-type point in catalyst
The content of son sieve improves isomerization of bridge-type tetrahydro-dicyclopentadiene activity so as to improve the surface acid density of catalyst.?
Trace chlorinated organics are added in reaction raw materials solution, can be caused at reaction conditions as the carbonium ion of isomerization reaction
Agent, so as to further increase work of the catalyst by isomerization of bridge-type tetrahydro-dicyclopentadiene for hanging type tetrahydrochysene dicyclopentadiene
Property.Side reaction, lower Hydrogen Vapor Pressure and higher hydrogen oil can be reduced using relatively low isomerization reaction temperature
Gasify at reaction conditions than being conducive to raw material, so that gas phase reaction is converted into, when shortening the stop of reactant on a catalyst
Between, to be further reduced the generation of side reaction.Using method of the invention, isomerization of bridge-type tetrahydro-dicyclopentadiene reaction is single
Journey conversion ratio can reach 95% or more, and yield reaches 90% or more, and it is difficult that higher selectivity reduces the lock out operation after reaction
Degree.
Specific technical solution of the present invention is as follows:
A method of improving isomerization of bridge-type tetrahydro-dicyclopentadiene selectivity, the specific steps are as follows:
(1) molding of the super-stable Y molecular sieves containing sodium: in terms of mass percentage, by the oxygen of Kong Rongwei 0.2-0.6cm3/g
Change the aluminium oxide 5%-20% of aluminium 5%-40%, Kong Rongwei 0.8-1.2cm3/g, sesbania powder 2% is sufficiently mixed uniformly, then plus
Enter the nitric acid solution of mass concentration 10%, nitric acid solution additional proportion is that gluey bonding is made in the 15-25% of raw material powder gross mass
Then agent is added the super-stable Y molecular sieves original powder 40%-90% of sodium mass percentage 0.5%-3.0%, and is added and adds
The glacial acetic acid solution of mass concentration 5%, glacial acetic acid solution additional proportion are the 15-25% of raw material powder gross mass, and abundant puddling is equal
The cylindrical type strip of diameter 1.6mm is extruded into after even, after natural drying, 120 DEG C of dry 3-4h, 400-600 DEG C of roasting 4h, after taking-up
The particle of 2-3mm long, super-stable Y molecular sieves shaped granule carrier obtained is made；
(2) supported active metals: super-stable Y molecular sieves shaped granule carrier obtained by Accurate Determining step (1) first
Water absorption rate, the lyotropic salt of active metal is then weighed according to certain metal oxide supported amount, prepares the leaching of respective volume
Stain solution impregnates each solution using isometric single impregnation method, after drying at room temperature, changes through drying, roasting to get different metal
The catalyst of property, specifically:
The preparation of the catalyst of Supported Pt Nanoparticles: being the molding of super-stable Y molecular sieves obtained by step (1) according to platinum load capacity
The 0.1%-1.0% of grain carrier quality prepares chloroplatinic acid-hydrochloric acid solution, superstable gamma-type obtained by incipient impregnation step (1) point
Son sieve shaped granule carrier, after drying at room temperature, through 120 DEG C of dry 3-4h, 400-500 DEG C of roasting 4h urging to get Supported Pt Nanoparticles
Agent Pt-HUSY；
Load iron, cobalt, nickel, copper, molybdenum catalyst preparation: according to content of metal be step (1) obtained by super steady Y
The 5%-20% of the molecular sieve molded particulate vector quality of type prepares the nitrate solution or ammonium molybdate solution of iron, cobalt, nickel, copper, molybdenum,
Super-stable Y molecular sieves shaped granule carrier obtained by incipient impregnation step (1), after drying at room temperature, through 120 DEG C of dry 3-
4h, 400-500 DEG C roasting 4h to get load iron, cobalt, nickel, copper, molybdenum catalyst Fe-HUSY, Co-HUSY, Ni-HUSY, Cu-
HUSY,Mo-HUSY；
The preparation of supported copper-molybdenum or the catalyst of nickel-molybdenum: being superstable gamma-type obtained by step (1) point according to molybdenum load capacity
3%-12%, nickel or the copper load capacity of son sieve shaped granule carrier quality are the molding of super-stable Y molecular sieves obtained by step (1)
The 2%-8% of particulate vector quality prepares corresponding ammonium molybdate solution and nickel nitrate or copper nitrate solution, first incipient impregnation
Nickel nitrate or copper nitrate solution, by 120 DEG C of dry 3-4h, after 200-300 DEG C of low-temperature bake, then incipient impregnation ammonium molybdate is molten
Liquid, 120 DEG C of dry 3-4h, 400-500 DEG C of roasting 4h are to get load nickel-molybdenum or copper-molybdenum catalyst n iMo-HUSY, CuMo-
HUSY；
(3) isomerization of bridge-type tetrahydro-dicyclopentadiene reacts: the catalyst 20mL dress fixed bed reaction for taking step (2) to prepare
Isomerization of bridge-type tetrahydro-dicyclopentadiene reaction is carried out in device:
Wherein:
Isomerate feeds: making solvent with hexamethylene, mass ratio, hexamethylene: bridge-type tetrahydro-dicyclopentadiene=2:1, in original
Expect the halogenated organic matters that 10-100 μ g/g is added in solution；
Isomerization reaction condition: isomerization of bridge-type tetrahydro-dicyclopentadiene reaction, catalyst are carried out in fixed bed reactors
After reduction, sample introduction after temperature is down to 100 DEG C, plunger pump liquid phase Feed space velocities 1.0h-1, enter catalyst bed to reaction raw materials
After be gradually heated to 120-160 DEG C, control Hydrogen Vapor Pressure 0.1-1.0MPa, hydrogen to oil volume ratio 1000:1-3000:1.
The method of the described raising isomerization of bridge-type tetrahydro-dicyclopentadiene selectivity, the superstable gamma-type molecule in step (1)
The sodium mass percentage for sieving original powder is 1%-2.5%, mass percent meter, the super-stable Y molecular sieves original powder in step (1)
Content is 70%-85%.
The method of the described raising isomerization of bridge-type tetrahydro-dicyclopentadiene selectivity, the isomerate feeds in step (3),
The halogenated organic matters of 30-60 μ g/g are added in material solution, halogenated organic matters are methylene chloride, dichloroethanes, ethylene chlorhydrin, two
Any one in bromomethane or Bromofume.
The method of the described raising isomerization of bridge-type tetrahydro-dicyclopentadiene selectivity, the isomerization reaction in step (3)
Condition, isomerization reaction temperature are 145-155 DEG C, Hydrogen Vapor Pressure 0.5-0.8MPa, the preferred 1500:1-2000 of hydrogen to oil volume ratio:
1。
Beneficial effects of the present invention: the hair of various side reactions during isomerization of bridge-type tetrahydro-dicyclopentadiene can be reduced
It is raw, the production quantity of the Main By products such as trans-decalin, adamantane is reduced, so that the purification for reducing isomerization reaction product is difficult
Degree.
Specific embodiment
The present invention is further illustrated below with reference to the preferred embodiment of the present invention.
Embodiment 1
A method of improving isomerization of bridge-type tetrahydro-dicyclopentadiene selectivity, the specific steps are as follows:
(1) molding of the super-stable Y molecular sieves containing sodium: in terms of mass percentage, by the oxygen of Kong Rongwei 0.2-0.6cm3/g
Change the aluminium oxide 5%-20% of aluminium 5%-40%, Kong Rongwei 0.8-1.2cm3/g, sesbania powder 2% is sufficiently mixed uniformly, then plus
Enter the nitric acid solution of mass concentration 10%, nitric acid solution additional proportion is that gluey bonding is made in the 15-25% of raw material powder gross mass
Then agent is added the super-stable Y molecular sieves original powder 40%-90% of sodium mass percentage 0.5%-3.0%, and is added and adds
The glacial acetic acid solution of mass concentration 5%, glacial acetic acid solution additional proportion are the 15-25% of raw material powder gross mass, and abundant puddling is equal
The cylindrical type strip of diameter 1.6mm is extruded into after even, after natural drying, 120 DEG C of dry 3-4h, 400-600 DEG C of roasting 4h, after taking-up
The particle of 2-3mm long, super-stable Y molecular sieves shaped granule carrier obtained is made；
(2) supported active metals: super-stable Y molecular sieves shaped granule carrier obtained by Accurate Determining step (1) first
Water absorption rate, the lyotropic salt of active metal is then weighed according to certain metal oxide supported amount, prepares the leaching of respective volume
Stain solution impregnates each solution using isometric single impregnation method, after drying at room temperature, changes through drying, roasting to get different metal
The catalyst of property, specifically:
The preparation of the catalyst of Supported Pt Nanoparticles: being the molding of super-stable Y molecular sieves obtained by step (1) according to platinum load capacity
The 0.1%-1.0% of grain carrier quality prepares chloroplatinic acid-hydrochloric acid solution, superstable gamma-type obtained by incipient impregnation step (1) point
Son sieve shaped granule carrier, after drying at room temperature, through 120 DEG C of dry 3-4h, 400-500 DEG C of roasting 4h urging to get Supported Pt Nanoparticles
Agent Pt-HUSY；
Load iron, cobalt, nickel, copper, molybdenum catalyst preparation: according to content of metal be step (1) obtained by super steady Y
The 5%-20% of the molecular sieve molded particulate vector quality of type prepares the nitrate solution or ammonium molybdate solution of iron, cobalt, nickel, copper, molybdenum,
Super-stable Y molecular sieves shaped granule carrier obtained by incipient impregnation step (1), after drying at room temperature, through 120 DEG C of dry 3-
4h, 400-500 DEG C roasting 4h to get load iron, cobalt, nickel, copper, molybdenum catalyst Fe-HUSY, Co-HUSY, Ni-HUSY, Cu-
HUSY,Mo-HUSY；
The preparation of supported copper-molybdenum or the catalyst of nickel-molybdenum: being superstable gamma-type obtained by step (1) point according to molybdenum load capacity
3%-12%, nickel or the copper load capacity of son sieve shaped granule carrier quality are the molding of super-stable Y molecular sieves obtained by step (1)
The 2%-8% of particulate vector quality prepares corresponding ammonium molybdate solution and nickel nitrate or copper nitrate solution, first incipient impregnation
Nickel nitrate or copper nitrate solution, by 120 DEG C of dry 3-4h, after 200-300 DEG C of low-temperature bake, then incipient impregnation ammonium molybdate is molten
Liquid, 120 DEG C of dry 3-4h, 400-500 DEG C of roasting 4h are to get load nickel-molybdenum or copper-molybdenum catalyst n iMo-HUSY, CuMo-
HUSY；
(3) isomerization of bridge-type tetrahydro-dicyclopentadiene reacts: the catalyst 20mL dress fixed bed reaction for taking step (2) to prepare
Isomerization of bridge-type tetrahydro-dicyclopentadiene reaction is carried out in device:
Wherein:
Isomerate feeds: making solvent with hexamethylene, mass ratio, hexamethylene: bridge-type tetrahydro-dicyclopentadiene=2:1, in original
Expect the halogenated organic matters that 10-100 μ g/g is added in solution；
Isomerization reaction condition: isomerization of bridge-type tetrahydro-dicyclopentadiene reaction, catalyst are carried out in fixed bed reactors
After reduction, sample introduction after temperature is down to 100 DEG C, plunger pump liquid phase Feed space velocities 1.0h-1, enter catalyst bed to reaction raw materials
After be gradually heated to 120-160 DEG C, control Hydrogen Vapor Pressure 0.1-1.0MPa, hydrogen to oil volume ratio 1000:1-3000:1.
Embodiment 2
Reaction step is same as Example 1, it is preferable that raising bridge-type tetrahydro-dicyclopentadiene described in embodiment 1 is different
The method of structureization selectivity, the sodium mass percentage of the super-stable Y molecular sieves original powder in step (1) are 1%-2.5%, quality
Percentages, the content of the super-stable Y molecular sieves original powder in step (1) are 70%-85%.The raising bridge-type tetrahydro is bicyclic
The method of pentadiene isomerisation selectivity, the isomerate feeds in step (3) add the halogenated of 30-60 μ g/g in material solution
Organic matter, halogenated organic matters are any one in methylene chloride, dichloroethanes, ethylene chlorhydrin, methylene bromide or Bromofume.
The method of the described raising isomerization of bridge-type tetrahydro-dicyclopentadiene selectivity, the isomerization reaction condition in step (3), isomery
Changing reaction temperature is 145-155 DEG C, Hydrogen Vapor Pressure 0.5-0.8MPa, the preferred 1500:1-2000:1 of hydrogen to oil volume ratio.
Embodiment 3:
Take aluminium oxide original powder 20g, the Kong Rongwei 0.85-0.95cm3/g of Kong Rongwei 0.35cm3/g aluminium oxide original powder 10g,
Sesbania powder 4g is sufficiently mixed uniformly, and the nitric acid solution 40mL of mass percentage 10% is added, sodium content is added after abundant kneading
1.5% super-stable Y molecular sieves original powder 170g adds the glacial acetic acid solution 40mL and deionization of mass percentage 5%
Water 40mL continues the cylindrical type strip that diameter 1.6mm is extruded into after abundant kneading.After natural drying, 120 DEG C of dry 3h, 550 DEG C of roastings
4h is burnt, the particle of 2-3mm long is made after taking-up.
Embodiment 4
Nickel nitrate 19.5g is weighed, wiring solution-forming in about 22g deionized water is dissolved in.Weigh carrier prepared by embodiment 1
50g impregnates nickel nitrate solution using equi-volume impregnating, after drying at room temperature, through 120 DEG C of dry 3h, 500 DEG C of roasting 4h, i.e.,
Obtain isomerization catalyst Ni-USY.The mass percentage content of nickel oxide is about 9.1% in catalyst, the matter of ultra-steady Y molecular sieve
Measuring degree is about 77%.
Embodiment 5
Chloroplatinic acid 1g is weighed, is dissolved in about 30g deionized water, about 0.3g concentrated hydrochloric acid is added dropwise and is made into homogeneous phase solution.It weighs
Carrier 50g prepared by embodiment 1 impregnates platinum acid chloride solution using equi-volume impregnating, after drying at room temperature, through 120 DEG C of dryings
3h, 500 DEG C of roasting 4h are to get isomerization catalyst Pt-USY, and the mass percentage content of platinum is about 0.74% in catalyst, surpass
The mass percentage content of steady Y molecular sieve is about 84%.
Embodiment 6
It is different that catalyst 20mL prepared by Example 4,5 is fitted into progress bridge-type tetrahydro-dicyclopentadiene in fixed bed reactors
Structureization reaction, reaction raw materials are hexamethylene: the mixed solution of bridge-type tetrahydro-dicyclopentadiene mass ratio 2:1, add 40 μ in raw material
The dichloroethanes of the g/g perhaps ethylene chlorhydrin of the Bromofume of 45 μ g/g or 50 μ g/g, in reaction temperature 144,148,152
DEG C, Hydrogen Vapor Pressure 0.6MPa, investigate under conditions of hydrogen to oil volume ratio 1800 isomerization of bridge-type tetrahydro-dicyclopentadiene conversion ratio and
Selectivity, experimental result are as shown in table 1.
Comparative example 1: preparing isomerization catalyst using the ultra-steady Y molecular sieve of sodium content 0.05%, preparation method with
Embodiment 3,4 is identical, and prepared comparative catalyst 20mL is taken to be fitted into progress bridge-type tetrahydro bicyclic penta 2 in fixed bed reactors
Isomerizalion reaction, investigates its isomerisation conversion and selectivity under reaction condition same as Example 6, experimental result is shown in
Shown in table 1.
Comparative example 2: molecular sieve quality percentage in catalyst is prepared using the super-stable Y molecular sieves of sodium content 1.5%
The isomerization catalyst that content is 50%, other preparation methods are identical as embodiment 3,4, take prepared comparative catalyst 20mL
It is fitted into progress isomerization of bridge-type tetrahydro-dicyclopentadiene reaction in fixed bed reactors, in reaction condition same as Example 6
Lower its isomerisation conversion of investigation and selectivity, experimental result are shown in Table shown in 1.
Table Bridge 1 formula tetrahydro-dicyclopentadiene isomerization reaction result
In isomerization catalyst of the invention and appropriate anti-it can be seen from the isomerization reaction result of above embodiments
Under the conditions of answering, isomerization of bridge-type tetrahydro-dicyclopentadiene conversion ratio can achieve 95% or more, and purpose product hanging tetrahydrochysene is bicyclic
Pentadiene yield can achieve 90% or more, can achieve higher isomerisation selectivity.The higher ultra-steady Y molecular sieve of sodium content
The comparative catalyst 1 of preparation, although there is higher isomerisation conversion, react the by-products such as trans-decalin that generate compared with
It is more, cause selectivity poor；And the lower comparative catalyst of molecular sieve content in catalyst, although having preferable selecting response
Property, but the overall activity of catalyst is poor, it is lower so as to cause target product yield.Trace is added in isomerate feeds solution
Chlorinated organics can significantly improve isomerisation conversion, and can reduce the production quantity of by-product trans-decalin and adamantane,
So as to significantly improve isomerisation selectivity.
The above is only the preferred embodiment of the present invention, the range implemented of the present invention that therefore, it cannot be limited according to, i.e., according to
Equivalent changes and modifications made by the invention patent range and description, should still be within the scope of the present invention.
Claims (3)
1. a kind of method for improving isomerization of bridge-type tetrahydro-dicyclopentadiene selectivity, which is characterized in that specific step is as follows:
(1) molding of the super-stable Y molecular sieves containing sodium: in terms of mass percentage, by Kong Rongwei 0.2-0.6cm3The aluminium oxide of/g
5%-40%, Kong Rongwei 0.8-1.2cm3The aluminium oxide 5%-20% of/g, sesbania powder 2% are sufficiently mixed uniformly, add quality
The nitric acid solution of concentration 10%, nitric acid solution additional proportion are the 15-25% of raw material powder gross mass, gluey binder are made, so
The super-stable Y molecular sieves original powder 70%-85% of sodium mass percentage 1%-2.5% is added afterwards, adds mass concentration 5%
Glacial acetic acid solution, glacial acetic acid solution additional proportion are the 15-25% of raw material powder gross mass, are extruded into diameter after abundant puddling is uniform
2-3mm long is made after taking-up in the cylindrical type strip of 1.6mm, after natural drying, 120 DEG C of dry 3-4h, 400-600 DEG C of roasting 4h
Particle, super-stable Y molecular sieves shaped granule carrier obtained；
(2) supported active metals: the suction of super-stable Y molecular sieves shaped granule carrier obtained by Accurate Determining step (1) first
Water rate, then weighs the lyotropic salt of active metal according to certain metal oxide supported amount, and the dipping for preparing respective volume is molten
Liquid impregnates each solution using isometric single impregnation method, after drying at room temperature, modified to get different metal through drying, roasting
Catalyst, specifically:
The preparation of the catalyst of Supported Pt Nanoparticles: being that super-stable Y molecular sieves shaped granule obtained by step (1) carries according to platinum load capacity
The 0.1%-1.0% of weight prepares chloroplatinic acid-hydrochloric acid solution, super-stable Y molecular sieves obtained by incipient impregnation step (1)
Shaped granule carrier, after drying at room temperature, through 120 DEG C of dry 3-4h, 400-500 DEG C roasts 4h to get the catalyst of Supported Pt Nanoparticles
Pt-HUSY；
Load iron, cobalt, nickel, copper, molybdenum catalyst preparation: be superstable gamma-type point obtained by step (1) according to content of metal
The 5%-20% of son sieve shaped granule carrier quality prepares the nitrate solution or ammonium molybdate solution of iron, cobalt, nickel, copper, molybdenum, waits bodies
Super-stable Y molecular sieves shaped granule carrier obtained by product impregnation steps (1), after drying at room temperature, through 120 DEG C of dry 3-4h,
400-500 DEG C roasting 4h to get load iron, cobalt, nickel, copper, molybdenum catalyst Fe-HUSY, Co-HUSY, Ni-HUSY, Cu-
HUSY,Mo-HUSY；
The preparation of supported copper-molybdenum or the catalyst of nickel-molybdenum: being super-stable Y molecular sieves obtained by step (1) according to molybdenum load capacity
3%-12%, nickel or the copper load capacity of shaped granule carrier quality are super-stable Y molecular sieves shaped granule obtained by step (1)
The 2%-8% of carrier quality prepares corresponding ammonium molybdate solution and nickel nitrate or copper nitrate solution, first incipient impregnation nitric acid
Nickel or copper nitrate solution, by 120 DEG C of dry 3-4h, after 200-300 DEG C of low-temperature bake, then incipient impregnation ammonium molybdate solution,
120 DEG C of dry 3-4h, 400-500 DEG C of roasting 4h are to get load nickel-molybdenum or copper-molybdenum catalyst n iMo-HUSY, CuMo-
HUSY；
(3) isomerization of bridge-type tetrahydro-dicyclopentadiene reacts: Pt-HUSY the or Ni-HUSY catalyst 20mL for taking step (2) to prepare
It fills and carries out isomerization of bridge-type tetrahydro-dicyclopentadiene reaction in fixed bed reactors:
Wherein:
Isomerate feeds: making solvent with hexamethylene, mass ratio, hexamethylene: bridge-type tetrahydro-dicyclopentadiene=2:1, molten in raw material
Add the halogenated organic matters of 10-100 μ g/g in liquid, halogenated organic matters are dichloroethanes, ethylene chlorhydrin, any in Bromofume
It is a kind of；
Isomerization reaction condition: isomerization of bridge-type tetrahydro-dicyclopentadiene reaction, catalyst reduction are carried out in fixed bed reactors
Later, sample introduction after temperature is down to 100 DEG C, plunger pump liquid phase Feed space velocities 1.0h-1, after reaction raw materials enter catalyst bed by
It is gradually warming up to 120-160 DEG C, controls Hydrogen Vapor Pressure 0.1-1.0MPa, hydrogen to oil volume ratio 1000:1-3000:1.
2. the method according to claim 1 for improving isomerization of bridge-type tetrahydro-dicyclopentadiene selectivity, it is characterised in that:
Isomerate feeds in step (3) add the halogenated organic matters of 30-60 μ g/g in material solution.
3. the method according to claim 1 for improving isomerization of bridge-type tetrahydro-dicyclopentadiene selectivity, it is characterised in that:
Isomerization reaction condition in step (3), isomerization reaction temperature is 145-155 DEG C, Hydrogen Vapor Pressure 0.5-0.8MPa, hydrogen are oily
Volume ratio is 1500:1-2000:1.
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| CN109395772B (en) * | 2017-08-18 | 2021-05-11 | 中国石油大学(华东) | Isomerization catalyst and preparation method and application thereof |
| CN108187727A (en) * | 2017-12-29 | 2018-06-22 | 中国人民解放军62025部队 | A kind of preparation method and reaction method of the catalyst for improving bridge-type tetrahydro-dicyclopentadiene stereoselectivity |
| CN108212199B (en) * | 2017-12-29 | 2020-11-03 | 中国人民解放军62025部队 | Preparation method of catalyst for improving isomerization selectivity of bridge type tetrahydro dicyclopentadiene |
| CN108906115B (en) * | 2018-06-19 | 2021-07-02 | 泉州宇极新材料科技有限公司 | Catalyst for synthesizing 1,2,3,3,4, 4-hexafluoro-cyclobutene, preparation method and application thereof |
| CN111939967A (en) * | 2019-05-15 | 2020-11-17 | 中国石油化工股份有限公司 | Catalyst for synthesizing exo-tetrahydrodicyclopentadiene and preparation method and application method thereof |
| CN111943803B (en) * | 2019-05-15 | 2022-10-21 | 中国石油化工股份有限公司 | Method for synthesizing exo-tetrahydrodicyclopentadiene |
| CN114054056B (en) * | 2020-07-30 | 2023-12-22 | 中国石油化工股份有限公司 | Hydroisomerization bifunctional catalyst, and preparation method and application thereof |
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Effective date of registration: 20220105 Address after: 102300 Beijing city Mentougou District Three Street No. 1 Patentee after: Institute of Military New Energy Technology, Institute of Systems Engineering, Academy of Military Sciences Address before: 102300 Beijing city Mentougou District Three Street No. 1 Patentee before: Institute of Military New Energy Technology, Institute of Systems Engineering, Academy of Military Sciences Patentee before: China University of Petroleum (East China) |