CN107866263B - Suitable for cyclohexyl benzene production catalyst - Google Patents
Suitable for cyclohexyl benzene production catalyst Download PDFInfo
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- CN107866263B CN107866263B CN201610852240.3A CN201610852240A CN107866263B CN 107866263 B CN107866263 B CN 107866263B CN 201610852240 A CN201610852240 A CN 201610852240A CN 107866263 B CN107866263 B CN 107866263B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7415—Zeolite Beta
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
- B01J29/22—Noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7476—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/74—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition with simultaneous hydrogenation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The present invention relates to cyclohexyl benzene production catalyst is suitable for, mainly solves catalyst in the prior art and cause by-product cyclic hexane high income and the low technical problem of principal product cyclohexyl benzene yield in reaction.The present invention is by using cyclohexyl benzene production catalyst is suitable for, including carrier and following active component: (1) Pd of 0.5~20g/L；At least one of the lanthanide series of (2) 0~50g/L；At least one of VIII group element of (3) 0~20g/L can be used for benzene hydrogenation alkylation one-step method and prepare cyclohexyl benzene wherein the technical solution that the carrier is h-type zeolite molecular sieve achieves preferable effect.
Description
Technical field
The present invention relates to be suitable for cyclohexyl benzene production catalyst, preparation method and benzene hydrogenation alkylation one-step method to close
At the method for cyclohexyl benzene.
Background technique
Cyclohexyl benzene is a kind of important intermediate, is widely used in the fields such as liquid crystal, plastics, coating, adhesive.Hexamethylene
Base benzene class liquid crystal has the characteristics that high chemical stability, photochemical stability, viscosity is low and good physical properties, is aobvious
Show one of the ideal material of device.Additive of the cyclohexyl benzene as lithium-ion battery electrolytes has anti-overcharge performance, can mention
The security performance of high battery.In addition, phenol and cyclohexanone can be prepared by the peroxidating of cyclohexyl benzene, decomposition reaction process,
For producing large industrial chemicals such as phenolic resin, caprolactam and nylon, have a good application prospect.The base of cyclohexyl benzene
This information is as follows: colourless liquid, and No. CAS is 827-52-1, molecular weight C12H16, density 0.95g/cm3, boiling point 238~240
DEG C, 5 DEG C of fusing point, 98 DEG C of flash-point.
The preparation method of cyclohexyl benzene has: biphenyl selects hydrogenation method, alkylation process, the benzene hydrogenation alkylation of benzene and cyclohexene
Method.Wherein, benzene hydrogenation alkylation prepares the reaction principle of cyclohexyl benzene as follows (formula 1): according to the alkylated reaction machine of benzene hydrogenation
Hydrogenation reaction occurs in the heart in a metal for reason, benzene, and the property of can choose generates cyclohexene, while generating portion hexamethylene and hexamethylene two
Alkene；With benzene alkylated reaction occurs for cyclohexene and cyclohexadiene on acid centre, generates principal product cyclohexyl benzene.Therefore, it adopts
Benzene hydrogenation alkylation production cyclohexyl benzene may be implemented with the bicomponent catalyst with hydrogenating function and alkylation function.
The research that benzene hydrogenation alkylation prepares cyclohexyl benzene starts from the seventies and eighties in 20th century earliest.The catalysis of early development
Agent has that cyclohexyl benzene is selectively lower, develops load as ExxonMobil company is based on MCM-22 Series Molecules sieve
The catalyst (US2011/0015457A1, US2011/0021841A1) of hydrogenation metal, prepares hexamethylene for benzene hydrogenation alkylation
Base benzene, this technology are high to the selectivity of by-product cyclic hexane.The patent US4094918 of the oil company Phillips, the U.S.,
US4219689 and US4329531, using the zeolite catalyst through Ni- rare earth treatment, and using Pd as auxiliary agent, the conversion ratio of benzene and
The yield of CHB is all relatively low.There are the high income of by-product cyclic hexane and productions during preparing cyclohexyl benzene for the above method
The relatively low problem of the yield of object cyclohexyl benzene.
Summary of the invention
The first technical problem to be solved by the present invention is the high income and main product of by-product cyclic hexane in the prior art
The low problem of the yield of object cyclohexyl benzene provides one kind and is suitable for cyclohexyl benzene production catalyst, is used for benzene and hydrogen is anti-
Have the advantages that hexamethylene yield is low and cyclohexyl benzene high income when answering synthesizing cyclohexyl benzene.
The second technical problem to be solved by the present invention is the preparation method of catalyst described in one of above-mentioned technical problem.
The third technical problem to be solved by the present invention is the cyclohexyl using catalyst described in one of above-mentioned technical problem
The synthetic method of benzene.
Technical scheme is as follows one of to solve above-mentioned technical problem: it is suitable for cyclohexyl benzene production catalyst,
Including carrier and following active component:
The Pd of (1) 0.5~20g/L；
At least one of the lanthanide series of (2) 0~50g/L；
At least one of VIII group element of (3) 0~20g/L；
Wherein the carrier is h-type zeolite molecular sieve.
In above-mentioned technical proposal, the lanthanide series preferred La or Sm, but preferably simultaneously include La, Sm.La and Sm exist
There is synergistic effect in terms of improving CHB yield.
In above-mentioned technical proposal, the preferred iron series element of VIII group element, iron series element is selected from Fe, Ni or Co, excellent
Select Co, Co and La or Co and Sm that there is synergistic effect in terms of improving CHB yield.
In above-mentioned technical proposal, Pd content is 0.5~20g/L, preferably 1~10g/L in catalyst.
In above-mentioned technical proposal, zeolite molecular sieve preferably is selected from BEA, MOR or MWW zeolite molecular sieve；Preferred zeolite point
Son sieve carrier is BEA zeolite molecular sieve.
In above-mentioned technical proposal, the BEA zeolite molecular sieve is preferably binder free molding BEA zeolite molecular sieve.It is described
The molar ratio that binder free forms the silica/alumina of BEA zeolite molecular sieve is preferably 10~100, more preferably 20~
60。
In above-mentioned technical proposal, lanthanide content is preferably greater than 0 and is less than or equal to 50g/L in catalyst, and more preferably 4
~30g/L.
In above-mentioned technical proposal, VIII group constituent content is preferably greater than 0 and is less than or equal to 20g/L in catalyst, more preferably
For 2~10g/L.
To solve above-mentioned technical problem two, technical scheme is as follows: the technical side of one of above-mentioned technical problem
The preparation method of catalyst described in case comprising the steps of:
A) the h-type zeolite molecular sieve is obtained；
B) by the compound wiring solution-forming I of aequum Pd；Optional compound is such as, but not limited to palladium chloride, palladium nitrate,
At least one of ammonium chloropalladate and ammonium chloropalladite, the optional water of solvent that the solution uses and by hydrochloric acid or nitric acid or acetic acid
Being tuned into pH is 2.0~6.5, for convenient for year-on-year, embodiment and comparative example in the specific embodiment of the invention use 1mol/L's
Aqueous acetic acid is solvent；
C) by the compound wiring solution-forming II of aequum lanthanide series；
D) by the compound wiring solution-forming III of aequum VIII group element；
E) solution of the solution I, the solution II that step c) is prepared and step d) preparation prepared step b) using infusion process
III is carried on zeolite molecular sieve carrier described in step a), dry, and 350~550 DEG C roast 3~6 hours, and catalysis is made
Agent.
In above-mentioned technical proposal, the preferred palladium chloride of compound of the step b) Pd.
In above-mentioned technical proposal, the compound preferably nitrate of the step c) lanthanide series.
In above-mentioned technical proposal, the compound of step d) the VIII group element is preferably nitrate.
In above-mentioned technical proposal, the impregnating process of step e) can use any one of following three kinds, can achieve
The purpose of the present invention:
Method 1, first dipping solution I, drying, roasting, impregnate together after then again mixing solution II and solution III, do
Dry, roasting.The dipping method is referred to as step impregnation I in the table 1 of specific embodiment.
Method 2 impregnates, dry, roasting after first mixing solution II and solution III, then dipping solution I, drying, roasting.
The dipping method is referred to as step impregnation II in the table 1 of specific embodiment.
Method 3 impregnates together after mixing solution I, solution II and solution III, dries, roasts.The dipping method is having
It is referred to as mixed with dipping in the table 1 of body embodiment.
But it has surprisingly been found that the best way is method 2, CHB yield is higher at this time.
Technical scheme is as follows by three to solve above-mentioned technical problem: the synthetic method of cyclohexyl benzene, with benzene and
Hydrogen is reaction raw materials, make catalyst described in any one of technical solution of one of reaction raw materials and above-mentioned technical problem contact into
Row benzene hydrogenation alkylated reaction generates cyclohexyl benzene.
In above-mentioned technical proposal, the temperature of reaction is preferably 100~200 DEG C, and more preferable 120~180 DEG C.
In above-mentioned technical proposal, in reaction raw materials the molar ratio of benzene and hydrogen be preferably 0.5~2.0, more preferably 0.5~
1.3。
In above-mentioned technical proposal, the pressure of reaction is preferably 0.5~3.0MPa (gauge pressure), more preferably 0.5~2.0MPa
(gauge pressure).
In above-mentioned technical proposal, the liquid volume air speed of reaction raw materials benzene is preferably 0.2~2h-1, more preferably 0.2~
1.5h-1。
Catalyst of the invention is reduced due to using Pd, lanthanide series and VIII group element simultaneously as active constituent
The receipts of target product CHB are also significantly improved in the case where lanthanide series includes simultaneously La and Sm to the yield of hexamethylene
Rate.At 150 DEG C of reaction temperature, benzene and hydrogen molar ratio 0.8, pressure 2.0MPa, the liquid volume air speed 0.5h of benzene-1Condition
Under, the yield of hexamethylene hereinafter, cyclohexyl benzene yield is up to 35%, achieves preferable technical effect up to 5.0%.
Specific embodiment
[embodiment 1]
1, catalyst preparation
Weigh the PdCl of the 1.2g containing Pd2It is dissolved in 1mol/L aqueous hydrochloric acid solution and is made into 80g solution I；Measuring 0.1L diameter is
The binder free cylinder Hydrogen BEA zeolite molecular sieve of 1mm, length 5mm (molar ratio of silica/alumina is 40)；It will
Solution I loads on Hydrogen BEA zeolite molecular sieve, and room temperature immersion 12h, 100 DEG C of dry 12h, 450 DEG C of roasting 4h are prepared into
To required catalyst.
2, evaluating catalyst
It takes 10ml Catalyst packing into fixed bed reactors, activity rating is carried out after reduction activation, condition is as follows: reaction
Temperature be 150 DEG C, the molar ratio of benzene and hydrogen is 0.8 in reaction raw materials, and the pressure of reaction is 2.0MPa (gauge pressure), reaction
The liquid volume air speed of benzene feedstock is 0.5h-1。
To be listed in table 1 convenient for the composition for comparing catalyst, evaluation result is listed in table 2.
[embodiment 2]
1, catalyst preparation
Weigh the PdCl of the 0.3g containing Pd2It is dissolved in 1mol/L aqueous hydrochloric acid solution and is made into 40g solution I；Weigh 0.9g containing La
La (NO3)3·6H2O is soluble in water to be made into 40g solution II；Measurement 0.1L diameter is the binder free cylinder of 1mm, length 5mm
Shape Hydrogen BEA zeolite molecular sieve (molar ratio of silica/alumina is 40), solution I and solution II are born after mixing
It is downloaded on Hydrogen BEA zeolite molecular sieve, room temperature immersion 12h, 100 DEG C of dry 12h, 450 DEG C of roasting 4h are prepared required
Catalyst.
2, evaluating catalyst
Evaluating catalyst method is shown in embodiment 1.
To be listed in table 1 convenient for the composition for comparing catalyst, evaluation result is listed in table 2.
[embodiment 3]
1, catalyst preparation
Weigh the PdCl of the 0.3g containing Pd2It is dissolved in 1mol/L aqueous hydrochloric acid solution and is made into 40g solution I；Weigh 0.9g containing Sm
Sm (NO3)3·6H2O is soluble in water to be made into 40g solution II；Measurement 0.1L diameter is the binder free cylinder of 1mm, length 5mm
Shape Hydrogen BEA zeolite molecular sieve (molar ratio of silica/alumina is 40), solution I and solution II are born after mixing
It is downloaded on Hydrogen BEA zeolite molecular sieve, room temperature immersion 12h, 100 DEG C of dry 12h, 450 DEG C of roasting 4h are prepared required
Catalyst.
2, evaluating catalyst
Evaluating catalyst method is shown in embodiment 1.
To be listed in table 1 convenient for the composition for comparing catalyst, evaluation result is listed in table 2.
[embodiment 4]
1, catalyst preparation
Weigh the PdCl of the 0.3g containing Pd2It is dissolved in 1mol/L aqueous hydrochloric acid solution and is made into 40g solution I；Weigh 0.9g containing Co
Co (NO3)2·6H2O is soluble in water to be made into 40g solution III；Measurement 0.1L diameter is the binder free cylinder of 1mm, length 5mm
Shape Hydrogen BEA zeolite molecular sieve (molar ratio of silica/alumina is 40), solution I and solution III are born after mixing
It is downloaded on Hydrogen BEA zeolite molecular sieve, room temperature immersion 12h, 100 DEG C of dry 12h, 450 DEG C of roasting 4h are prepared required
Catalyst.
2, evaluating catalyst
Evaluating catalyst method is shown in embodiment 1.
To be listed in table 1 convenient for the composition for comparing catalyst, evaluation result is listed in table 2.
[embodiment 5]
1, catalyst preparation
Weigh the PdCl of the 0.3g containing Pd2It is dissolved in 1mol/L aqueous hydrochloric acid solution and is made into 40g solution I；Weigh 0.4g containing La
La (NO3)3·6H2O is soluble in water to be made into 20g solution II；Weigh the Co (NO of the 0.5g containing Co3)2·6H2O is soluble in water to be made into
20g solution III；Measurement 0.1L diameter is the binder free cylinder Hydrogen BEA zeolite molecular sieve (titanium dioxide of 1mm, length 5mm
Silicon/aluminium oxide molar ratio is 40), solution I, solution II and solution III to be loaded to Hydrogen BEA zeolite molecules after mixing
On sieve, required catalyst is prepared in room temperature immersion 12h, 100 DEG C of dry 12h, 450 DEG C of roasting 4h.
2, evaluating catalyst
Evaluating catalyst method is shown in embodiment 1.
To be listed in table 1 convenient for the composition for comparing catalyst, evaluation result is listed in table 2.
[embodiment 6]
1, catalyst preparation
Weigh the PdCl of the Pd containing 0.3g2It is dissolved in 1mol/L aqueous hydrochloric acid solution and is made into 40g solution I；Weigh 0.4g containing Sm
Sm (NO3)3·6H2O is soluble in water to be made into 20g solution II；Weigh the Co (NO of the 0.5g containing Co3)2·6H2O is soluble in water to be made into
20g solution III；Then solution I, solution II and solution III are uniformly mixed；Measurement 0.1L diameter is the nothing of 1mm, length 5mm
Binder cylinder Hydrogen BEA zeolite molecular sieve (molar ratio of silica/alumina is 40), loads to hydrogen for mixed solution
On type BEA zeolite molecular sieve, required catalysis is prepared in room temperature immersion 12h, 100 DEG C of dry 12h, 450 DEG C of roasting 4h
Agent.
2, evaluating catalyst
Evaluating catalyst method is shown in embodiment 1.
To be listed in table 1 convenient for the composition for comparing catalyst, evaluation result is listed in table 2.
[embodiment 7]
1, catalyst preparation
Weigh the PdCl of the Pd containing 0.3g2It is dissolved in 1mol/L aqueous hydrochloric acid solution and is made into 40g solution I；Weigh 0.3g containing La
La (NO3)3·6H2Sm (the NO of the O and 0.1g containing Sm3)3·6H2O is soluble in water to be made into 20g solution II；Weigh 0.5g containing Co
Co (NO3)2·6H2O is soluble in water to be made into 20g solution III；Then solution I, solution II and solution III are uniformly mixed；Amount
Taking 0.1L diameter is 1mm, the binder free cylinder Hydrogen BEA zeolite molecular sieve of length 5mm (rub by silica/alumina
You are than being 40), mixed solution to be loaded on Hydrogen BEA zeolite molecular sieve, room temperature immersion 12h, 100 DEG C of dry 12h, 450 DEG C
4h is roasted, that is, required catalyst is prepared.
2, evaluating catalyst
Evaluating catalyst method is shown in embodiment 1.
To be listed in table 1 convenient for the composition for comparing catalyst, evaluation result is listed in table 2.
[embodiment 8]
1, catalyst preparation
Weigh the PdCl of the Pd containing 0.3g2It is dissolved in 1mol/L aqueous hydrochloric acid solution and is made into 40g solution I；Weigh 0.2g containing La
La (NO3)3·6H2Sm (the NO of the O and 0.2g containing Sm3)3·6H2O is soluble in water to be made into 20g solution II；Weigh 0.5g containing Co
Co (NO3)2·6H2O is soluble in water to be made into 20g solution III；Then solution I, solution II and solution III are uniformly mixed；Amount
Taking 0.1L diameter is 1mm, the binder free cylinder Hydrogen BEA zeolite molecular sieve of length 5mm (rub by silica/alumina
You are than being 40), mixed solution to be loaded on Hydrogen BEA zeolite molecular sieve, room temperature immersion 12h, 100 DEG C of dry 12h, 450 DEG C
4h is roasted, that is, required catalyst is prepared.
2, evaluating catalyst
Evaluating catalyst method is shown in embodiment 1.
To be listed in table 1 convenient for the composition for comparing catalyst, evaluation result is listed in table 2.
[embodiment 9]
1, catalyst preparation
Weigh the PdCl of the Pd containing 0.3g2It is dissolved in 1mol/L aqueous hydrochloric acid solution and is made into 40g solution I；Weigh 0.1g containing La
La (NO3)3·6H2Sm (the NO of the O and 0.3g containing Sm3)3·6H2O is soluble in water to be made into 20g solution II；Weigh 0.5g containing Co
Co (NO3)2·6H2O is soluble in water to be made into 20g solution III；Then solution I, solution II and solution III are uniformly mixed；Amount
Taking 0.1L diameter is 1mm, the binder free cylinder Hydrogen BEA zeolite molecular sieve of length 5mm (rub by silica/alumina
You are than being 40), mixed solution to be loaded on Hydrogen BEA zeolite molecular sieve, room temperature immersion 12h, 100 DEG C of dry 12h, 450 DEG C
4h is roasted, that is, required catalyst is prepared.
2, evaluating catalyst
Evaluating catalyst method is shown in embodiment 1.
To be listed in table 1 convenient for the composition for comparing catalyst, evaluation result is listed in table 2.
[embodiment 10]
1, catalyst preparation
Weigh the PdCl of the Pd containing 0.3g2It is dissolved in 1mol/L aqueous hydrochloric acid solution and is made into 80g solution I, measuring 0.1L diameter is
The binder free cylinder Hydrogen BEA zeolite molecular sieve (molar ratio of silica/alumina is 40) of 1mm, length 5mm, will
Solution I loads on Hydrogen BEA zeolite molecular sieve；Room temperature immersion 12h, 100 DEG C of dry 12h, 450 DEG C of roasting 4h obtain CAT1.
Weigh the La (NO of the 0.1g containing La3)3·6H2Sm (the NO of the O and 0.3g containing Sm3)3·6H2O is soluble in water to be made into 40g solution II；
Weigh the Co (NO of the 0.5g containing Co3)2·6H2O is soluble in water to be made into 40g solution III；Then solution II and solution III mixing are equal
It is even；Mixed solution is impregnated on CAT1；Room temperature immersion 12h, 100 DEG C of dry 12h, 450 DEG C of roasting 4h, that is, needed for being prepared
Catalyst.
2, evaluating catalyst
Evaluating catalyst method is shown in embodiment 1.
To be listed in table 1 convenient for the composition for comparing catalyst, evaluation result is listed in table 2.
[embodiment 11]
1, catalyst preparation
Weigh the La (NO of the 0.1g containing La3)3·6H2Ce (the NO of the O and 0.3g containing Sm3)3·6H2O is soluble in water to be made into 40g
Solution II；Weigh the Co (NO of the 0.5g containing Co3)2·6H2O is soluble in water to be made into 40g solution III；Then by solution II and solution
III is uniformly mixed；Measurement 0.1L diameter is the binder free cylinder Hydrogen BEA zeolite molecular sieve (titanium dioxide of 1mm, length 5mm
Silicon/aluminium oxide molar ratio is that 40), mixed solution is loaded on Hydrogen BEA zeolite molecular sieve；Room temperature immersion 12h, 100 DEG C
Dry 12h, 450 DEG C of roasting 4h obtain CAT2.Weigh the PdCl of the Pd containing 0.3g2It is dissolved in 1mol/L aqueous hydrochloric acid solution and being made into
80g solution I；Solution I is impregnated on CAT2；Room temperature immersion 12h, 100 DEG C of dry 12h, 450 DEG C of roasting 4h are prepared
Required catalyst.
2, evaluating catalyst
Evaluating catalyst method is shown in embodiment 1.
To be listed in table 1 convenient for the composition for comparing catalyst, evaluation result is listed in table 2.
[embodiment 12]
Weigh the PdCl of the Pd containing 0.5g2It is dissolved in 1mol/L aqueous hydrochloric acid solution and is made into 40g solution I；Weigh 1.8g containing La
La (NO3)3·6H2Sm (the NO of the O and 1.2g containing Sm3)3·6H2O is soluble in water to be made into 20g solution II；Weigh the 5g's containing Co
Co(NO3)2·6H2O is soluble in water to be made into 20g solution III；Then solution I, solution II and solution III are uniformly mixed；It measures
0.1L diameter is binder free cylinder Hydrogen BEA zeolite molecular sieve (mole of silica/alumina of 1mm, length 5mm
Than for 40), mixed solution is loaded on Hydrogen BEA zeolite molecular sieve, room temperature immersion 12h, 100 DEG C of dry 12h, 450 DEG C are roasted
4h is burnt, that is, required catalyst is prepared.
2, evaluating catalyst
Other than following process Parameters variation, remaining is identical as the evaluating catalyst method in embodiment 1: the temperature of reaction
Degree is 100 DEG C, and the molar ratio of benzene and hydrogen is 2.0 in reaction raw materials, and the pressure of reaction is 0.5MPa (gauge pressure), the raw material of reaction
Liquid volume air speed be 0.2h-1。
To be listed in table 1 convenient for the composition for comparing catalyst, evaluation result is listed in table 2.
[embodiment 13]
1, catalyst preparation
Weigh the PdCl of the Pd containing 0.1g2It is dissolved in 1mol/L aqueous hydrochloric acid solution and is made into 40g solution I；Weigh 0.3g containing La
La (NO3)3·6H2Sm (the NO of the O and 0.1g containing Sm3)3·6H2O is soluble in water to be made into 20g solution II；Weigh 0.2g containing Co
Co (NO3)2·6H2O is soluble in water to be made into 20g solution III；Then solution I, solution II and solution III are uniformly mixed；Amount
Taking 0.1L diameter is 1mm, the binder free cylinder Hydrogen BEA zeolite molecular sieve of length 5mm (rub by silica/alumina
You are than being 40), mixed solution to be loaded on Hydrogen BEA zeolite molecular sieve, room temperature immersion 12h, 120 DEG C of dry 12h, 430 DEG C
4h is roasted, that is, required catalyst is prepared.
2, evaluating catalyst
Other than following process Parameters variation, remaining is identical as the evaluating catalyst method in embodiment 1: the temperature of reaction
Degree is 200 DEG C, and the molar ratio of benzene and hydrogen is 0.5 in reaction raw materials, and the pressure of reaction is 3.0MPa (gauge pressure), the raw material of reaction
Liquid volume air speed be 2.0h-1。
To be listed in table 1 convenient for the composition for comparing catalyst, evaluation result is listed in table 2.
1 catalyst of table composition
2 evaluating catalyst result of table
Note: in table 2, CH indicates that hexamethylene, CHB indicate cyclohexyl benzene.
Claims (10)
1. being suitable for cyclohexyl benzene production catalyst, including carrier and following active component:
The Pd of (1) 0.5 ~ 20 g/L；
At least one of the lanthanide series of (2) 4 ~ 50 g/L；
At least one of the VIII group element of (3) 2 ~ 20 g/L；
Wherein the carrier is h-type zeolite molecular sieve；The lanthanide series includes Sm and La, and VIII group element is Co.
2. catalyst according to claim 1, it is characterised in that the Pd content is 1 ~ 10 g/L.
3. catalyst according to claim 1, it is characterised in that the zeolite molecules are boiled screened from BEA, MOR or MWW
Stone molecular sieve.
4. catalyst according to claim 3, it is characterised in that selected BEA zeolite molecular sieve is binder free molding
BEA zeolite molecular sieve.
5. catalyst according to claim 4, it is characterised in that the two of the binder free molding BEA zeolite molecular sieve
The molar ratio of silica/alumina is 10 ~ 100.
6. catalyst according to claim 1, it is characterised in that lanthanide content is 4 ~ 30 g/ in the catalyst
L。
7. catalyst according to claim 1, it is characterised in that VIII group constituent content is 2 ~ 10 in the catalyst
g/L。
8. the preparation method of catalyst of any of claims 1-7 comprising the steps of:
A) the h-type zeolite molecular sieve is obtained；
B) by the compound wiring solution-forming I of aequum Pd；
C) by the compound wiring solution-forming II of aequum lanthanide series；
D) by the compound wiring solution-forming III of aequum VIII group element；
E) solution III of the solution I, the solution II that step c) is prepared and step d) preparation prepared step b) using infusion process
It is carried on zeolite molecular sieve carrier described in step a), dry, 350~550 DEG C roast 3~6 hours, and catalyst is made.
9. the synthetic method of cyclohexyl benzene, using benzene and hydrogen as reaction raw materials, make reaction raw materials with it is any in claim 1 to 7
The item catalyst contact carries out benzene hydrogenation alkylated reaction and generates cyclohexyl benzene.
10. according to the method described in claim 9, it is characterized in that the liquid volume air speed of reaction raw materials benzene is 0.2~3h-1。
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| CN105233861A (en) * | 2014-07-11 | 2016-01-13 | 中国石油化工股份有限公司 | Cyclohexyl benzene catalyst and synthetic method thereof |
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