CN107866271A - Catalyst suitable for cyclohexyl benzene production - Google Patents
Catalyst suitable for cyclohexyl benzene production Download PDFInfo
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- CN107866271A CN107866271A CN201610853123.9A CN201610853123A CN107866271A CN 107866271 A CN107866271 A CN 107866271A CN 201610853123 A CN201610853123 A CN 201610853123A CN 107866271 A CN107866271 A CN 107866271A
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- catalyst
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- benzene
- zeolite molecular
- cyclohexyl benzene
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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
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0213—Preparation of the impregnating solution
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
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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
Abstract
The present invention relates to the method for catalyst suitable for cyclohexyl benzene production and preparation method thereof and benzene hydrogenation alkylation one-step synthesis method cyclohexyl benzene, solves catalyst of the prior art and causes accessory substance cyclohexane selectivity height and the selectively low technical problem of cyclohexyl benzene in reaction.The present invention is by using the catalyst suitable for cyclohexyl benzene production, including carrier and following active component：(1) 0.5~20g/L Pd；At least one of (2) 0~50g/L lanthanide series；(3) 0~30g/L Cd, wherein described carrier achieves preferable effect for the technical scheme of h-type zeolite molecular sieve, cyclohexyl benzene is prepared available for benzene hydrogenation alkylation one-step method.
Description
Technical field
The present invention relates to the catalyst, its preparation method and benzene hydrogenation suitable for cyclohexyl benzene production to be alkylated one-step method
The method of synthesizing cyclohexyl benzene.
Background technology
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 ideal material of device.Additive of the cyclohexyl benzene as lithium-ion battery electrolytes, there is anti-overcharge performance, can carry
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, 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)：The reaction machine being alkylated according to benzene hydrogenation
Reason, benzene occur hydrogenation reaction, can selectively produce cyclohexene, while generating portion hexamethylene and hexamethylene two in the heart in a metal
Alkene；On acid centre with benzene alkylated reaction occurs for cyclohexene and cyclohexadiene, generates principal product cyclohexyl benzene.Therefore, adopt
Benzene hydrogenation alkylation production cyclohexyl benzene can be realized 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
There is the problem of cyclohexyl benzene is selectively relatively low in agent, load is developed as ExxonMobil companies are based on MCM-22 Series Molecules sieve
The catalyst (US2011/0015457 A1, US2011/0021841 A1) of hydrogenation metal, ring is prepared for benzene hydrogenation alkylation
Hexyl benzene, this technology are high to the selectivity of by-product cyclic hexane.The patent US4094918 of Phillips oil companies of the U.S.,
US4219689 and US4329531, using the zeolite catalyst through Ni- RE-treateds, and using Pd as auxiliary agent, the conversion ratio of benzene and
CHB yield is all than relatively low.High income and the production of by-product cyclic hexane during cyclohexyl benzene is prepared be present in the above method
The yield of thing cyclohexyl benzene than it is relatively low the problem of.
The content of the invention
One of technical problems to be solved by the invention are the high income and main product of by-product cyclic hexane of the prior art
The problem of yield of thing cyclohexyl benzene is low, there is provided a kind of catalyst suitable for cyclohexyl benzene production, use it for benzene and hydrogen
There is the advantages of cyclohexane selectivity is low and cyclohexyl benzene is selectively high when reacting synthesizing cyclohexyl benzene.
The two of the technical problems to be solved by the invention are the preparation methods of one of above-mentioned technical problem catalyst.
The three of the technical problems to be solved by the invention are the cyclohexyl using one of the above-mentioned technical problem catalyst
The synthetic method of benzene.
It is as follows to solve one of above-mentioned technical problem technical scheme：Catalysis suitable for cyclohexyl benzene production
Agent, including carrier and following active component：
(1) 0.5~20g/L Pd；
At least one of (2) 0~50g/L lanthanide series；
(3) 0~30g/L Cd；
Wherein described carrier is h-type zeolite molecular sieve.
In above-mentioned technical proposal, described lanthanide series preferred Ce, Pr or Sm.
In above-mentioned technical proposal, preferably include Ce and Pr simultaneously, or include Ce and Sm simultaneously, or simultaneously including Pr with
Sm, it has synergy between element in terms of CHB yields are improved two-by-two.
In above-mentioned technical proposal, Ce, Pr and Sm more preferably are included simultaneously, between Ce, Pr and Sm in terms of CHB yields are improved
Acted on trielement synergistic.
In above-mentioned technical proposal, Cd cooperates with having selected from least one of Ce, Pr or Sm in terms of CHB yields are improved
Effect.
In above-mentioned technical proposal, Pd contents are 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 sieves.
In above-mentioned technical proposal, the BEA zeolite molecular sieves are preferably binder free shaping BEA zeolite molecular sieves.It is described
The mol ratio of the silica/alumina of binder free shaping BEA zeolite molecular sieves 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, more preferably 4 in catalyst
~30g/L.
In above-mentioned technical proposal, Cd constituent contents are preferably greater than 0 and are less than or equal to 30g/L in described catalyst, more excellent
Elect 2~20g/L as.
To solve the two of above-mentioned technical problem, technical scheme is as follows：The technical side of one of above-mentioned technical problem
The preparation method of catalyst described in case, is comprised the steps of：
A) the h-type zeolite molecular sieve is obtained；
B) by aequum Pd compound wiring solution-forming I；Optional compound is for example including palladium bichloride, palladium nitrate, chlorine palladium
Sour ammonium, one kind in ammonium chloropalladite, the optional water of solvent that the solution uses and by hydrochloric acid or nitric acid or acetic acid be tuned into pH for
2.0~6.5, for ease of year-on-year, the embodiment and comparative example in the specific embodiment of the invention are water-soluble with 1mol/L acetic acid
Liquid is solvent；
C) by the compound wiring solution-forming II of aequum lanthanide series；
D) by aequum Cd compound wiring solution-forming III；
E) solution of solution I, the solution II that step c) is prepared and the step d) preparations prepared step b) using infusion process
III is carried on the zeolite molecular sieve carrier described in step a), is dried, and 350~550 DEG C are calcined 3~6 hours, and catalysis is made
Agent.
In above-mentioned technical proposal, the step b) the Pd preferred palladium bichloride of compound.
In above-mentioned technical proposal, the compound preferably nitrate of the step c) lanthanide series.
In above-mentioned technical proposal, step d) Cd compound is preferably cadmium nitrate.
In above-mentioned technical proposal, step e) impregnating process be able to can be reached using any one of following three kinds
The purpose of the present invention：
Method 1, first dipping solution I, drying, roasting, impregnate, do together after then again mixing solution II and solution III
Dry, roasting.The dipping method is referred to as step impregnation I in the table 1 of embodiment.
Method 2, impregnate, dry after first mixing solution II and solution III, roasting, then dipping solution I, dry, roasting.
The dipping method is referred to as step impregnation II in the table 1 of embodiment.
Method 3, impregnate, dry together after solution I, solution II and solution III are mixed, being calcined.The dipping method is having
Referred to as it is mixed with dipping in the table 1 of body embodiment.
But it has surprisingly been found that the best way is method 2, now CHB yields are higher.
It is as follows to solve three technical schemes of above-mentioned technical problem：The synthetic method of cyclohexyl benzene, with benzene and
Hydrogen is reaction raw materials, make reaction raw materials contacted with catalyst any one of the technical scheme of one of above-mentioned technical problem into
Row benzene hydrogenation alkylated reaction generates cyclohexyl benzene.
In above-mentioned technical proposal, the temperature of reaction is preferably 100~200 DEG C, more preferably 120~180 DEG C.
In above-mentioned technical proposal, in reaction raw materials the mol 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。
The catalyst of the present invention is active constituent due to employing Pd, lanthanide series and Cd simultaneously, is reduced to hexamethylene
Yield, while add the yield to cyclohexyl benzene.In 150 DEG C of reaction temperature, benzene and hydrogen mol ratio 0.8, pressure
2.0MPa, the liquid volume air speed 0.5h of benzene-1Under conditions of, the yield of hexamethylene is up to less than 5.0%, cyclohexyl benzene high income
Up to 33%, preferable technique effect is achieved.
Embodiment
【Embodiment 1】
1st, catalyst preparation
Weigh the PdCl of the 1.9g containing Pd2It is dissolved in 1mol/L aqueous hydrochloric acid solutions and is made into 80g solution Is；It is a diameter of to measure 0.1L
1mm, length 5mm binder free cylinder Hydrogen BEA zeolite molecular sieves (mol ratio of silica/alumina is 40)；Will
Solution I is loaded on Hydrogen BEA zeolite molecular sieves, room temperature immersion 12h, 100 DEG C of dry 12h, 450 DEG C of roasting 4h, that is, is prepared into
To required catalyst.
2nd, evaluating catalyst
10ml Catalyst packings are taken to carry out activity rating after reduction activation into fixed bed reactors, condition is as follows：Reaction
Temperature be 150 DEG C, in reaction raw materials the mol ratio of benzene and hydrogen be 0.8, the pressure of reaction is 2.0MPa (gauge pressure), reaction
The liquid volume air speed of benzene feedstock is 0.5h-1。
The composition of catalyst and evaluation result are listed in table 1 for ease of comparing.
【Comparative example 1】
1st, catalyst preparation
Weigh the PdCl of the 0.3g containing Pd2It is dissolved in 1mol/L aqueous hydrochloric acid solutions and is made into 40g solution Is；Weigh 1.6g containing Ce
Ce (NO3)3·6H2O is soluble in water to be made into 40g solution IIs；Measure a diameter of 1mm of 0.1L, length 5mm binder free cylinder
Shape Hydrogen BEA zeolite molecular sieves (mol ratio of silica/alumina is 40), bear after solution I and solution II are well mixed
It is downloaded on Hydrogen BEA zeolite molecular sieves, room temperature immersion 12h, 100 DEG C of dry 12h, 450 DEG C of roasting 4h, that is, is prepared required
Catalyst.
2nd, evaluating catalyst
Evaluating catalyst method is shown in embodiment 1.
The composition of catalyst and evaluation result are listed in table 1 for ease of comparing.
【Comparative example 2】
1st, catalyst preparation
Weigh the PdCl of the 0.3g containing Pd2It is dissolved in 1mol/L aqueous hydrochloric acid solutions and is made into 40g solution Is；Weigh 1.6g containing Pr
Pr (NO3)3·6H2O is soluble in water to be made into 40g solution IIs；Measure a diameter of 1mm of 0.1L, length 5mm binder free cylinder
Shape Hydrogen BEA zeolite molecular sieves (mol ratio of silica/alumina is 40), bear after solution I and solution II are well mixed
It is downloaded on Hydrogen BEA zeolite molecular sieves, room temperature immersion 12h, 100 DEG C of dry 12h, 450 DEG C of roasting 4h, that is, is prepared required
Catalyst.
2nd, evaluating catalyst
Evaluating catalyst method is shown in embodiment 1.
The composition of catalyst and evaluation result are listed in table 1 for ease of comparing.
【Comparative example 3】
1st, catalyst preparation
Weigh the PdCl of the 0.3g containing Pd2It is dissolved in 1mol/L aqueous hydrochloric acid solutions and is made into 40g solution Is；Weigh 1.6g containing Sm
Sm (NO3)3·6H2O is soluble in water to be made into 40g solution IIs；Measure a diameter of 1mm of 0.1L, length 5mm binder free cylinder
Shape Hydrogen BEA zeolite molecular sieves (mol ratio of silica/alumina is 40), bear after solution I and solution II are well mixed
It is downloaded on Hydrogen BEA zeolite molecular sieves, room temperature immersion 12h, 100 DEG C of dry 12h, 450 DEG C of roasting 4h, that is, is prepared required
Catalyst.
2nd, evaluating catalyst
Evaluating catalyst method is shown in embodiment 1.
The composition of catalyst and evaluation result are listed in table 1 for ease of comparing.
【Comparative example 4】
1st, catalyst preparation
Weigh the PdCl of the 0.3g containing Pd2It is dissolved in 1mol/L aqueous hydrochloric acid solutions and is made into 40g solution Is；Weigh 1.6g containing Cd
Cd (NO3)2·4H2O is soluble in water to be made into 40g solution IIs；Measure a diameter of 1mm of 0.1L, length 5mm binder free cylinder
Shape Hydrogen BEA zeolite molecular sieves (mol ratio of silica/alumina is 40), mix back loading by solution I and solution II and arrive
On Hydrogen BEA zeolite molecular sieves, room temperature immersion 12h, 100 DEG C of dry 12h, 450 DEG C of roasting 4h, that is, required catalysis is prepared
Agent.
2nd, evaluating catalyst
Evaluating catalyst method is shown in embodiment 1.
The composition of catalyst and evaluation result are listed in table 1 for ease of comparing.
【Embodiment 2】
1st, catalyst preparation
Weigh the PdCl of the 0.3g containing Pd2It is dissolved in 1mol/L aqueous hydrochloric acid solutions and is made into 40g solution Is；Weigh 1.2g containing Ce
Ce (NO3)3·6H2O is soluble in water to be made into 20g solution IIs；Weigh the Cd (NO of the 0.4g containing Cd3)2·4H2O is soluble in water to be made into
20g solution IIIs；Measure a diameter of 1mm of 0.1L, length 5mm binder free cylinder Hydrogen BEA zeolite molecular sieve (titanium dioxides
The mol ratio of silicon/aluminum oxide is 40), solution I, solution II and solution III to be mixed into back loading to Hydrogen BEA zeolite molecular sieves
On, room temperature immersion 12h, 100 DEG C of dry 12h, 450 DEG C of roasting 4h, that is, required catalyst is prepared.
2nd, evaluating catalyst
Evaluating catalyst method is shown in embodiment 1.
The composition of catalyst and evaluation result are listed in table 1 for ease of comparing.
【Embodiment 3】
1st, catalyst preparation
Weigh the PdCl of the 0.3g containing Pd2It is dissolved in 1mol/L aqueous hydrochloric acid solutions and is made into 40g solution Is；Weigh 1.2g containing Pr
Pr (NO3)3·6H2O is soluble in water to be made into 20g solution IIs；Weigh the Cd (NO of the 0.4g containing Cd3)2·4H2O is soluble in water to be made into
20g solution IIIs；Measure a diameter of 1mm of 0.1L, length 5mm binder free cylinder Hydrogen BEA zeolite molecular sieve (titanium dioxides
The mol ratio of silicon/aluminum oxide is 40), solution I, solution II and solution III to be mixed into back loading to Hydrogen BEA zeolite molecular sieves
On, room temperature immersion 12h, 100 DEG C of dry 12h, 450 DEG C of roasting 4h, that is, required catalyst is prepared.
2nd, evaluating catalyst
Evaluating catalyst method is shown in embodiment 1.
The composition of catalyst and evaluation result are listed in table 1 for ease of comparing.
【Embodiment 4】
1st, catalyst preparation
Weigh the PdCl of the 0.3g containing Pd2It is dissolved in 1mol/L aqueous hydrochloric acid solutions and is made into 40g solution Is；Weigh 1.2g containing Sm
Sm (NO3)3·6H2O is soluble in water to be made into 20g solution IIs；Weigh the Cd (NO of the 0.4g containing Cd3)2·4H2O is soluble in water to be made into
20g solution IIIs；Measure a diameter of 1mm of 0.1L, length 5mm binder free cylinder Hydrogen BEA zeolite molecular sieve (titanium dioxides
The mol ratio of silicon/aluminum oxide is 40), solution I, solution II and solution III to be mixed into back loading to Hydrogen BEA zeolite molecular sieves
On, room temperature immersion 12h, 100 DEG C of dry 12h, 450 DEG C of roasting 4h, that is, required catalyst is prepared.
2nd, evaluating catalyst
Evaluating catalyst method is shown in embodiment 1.
The composition of catalyst and evaluation result are listed in table 1 for ease of comparing.
【Embodiment 5】
1st, catalyst preparation
Weigh the PdCl of the Pd containing 0.3g2It is dissolved in 1mol/L aqueous hydrochloric acid solutions and is made into 40g solution Is；Weigh 0.6g containing Ce
Ce (NO3)3·6H2The O and 0.6g containing Pr Pr (NO3)3·6H2O is soluble in water to be made into 20g solution IIs；Weigh 0.4g containing Cd
Cd (NO3)2·4H2O is soluble in water to be made into 20g solution IIIs；Then solution I, solution II and solution III are well mixed；Amount
Take a diameter of 1mm of 0.1L, length 5mm binder free cylinder Hydrogen BEA zeolite molecular sieves (rub by silica/alumina
You are than being 40), mixed solution to be loaded on Hydrogen BEA zeolite molecular sieves, room temperature immersion 12h, 100 DEG C of dry 12h, 450 DEG C
4h is calcined, that is, required catalyst is prepared.
2nd, evaluating catalyst
Evaluating catalyst method is shown in embodiment 1.
The composition of catalyst and evaluation result are listed in table 1 for ease of comparing.
【Embodiment 6】
1st, catalyst preparation
Weigh the PdCl of the Pd containing 0.3g2It is dissolved in 1mol/L aqueous hydrochloric acid solutions and is made into 40g solution Is；Weigh 0.6g containing Ce
Ce (NO3)3·6H2The O and 0.6g containing Sm Sm (NO3)3·6H2O is soluble in water to be made into 20g solution IIs；Weigh 0.4g containing Cd
Cd (NO3)2·4H2O is soluble in water to be made into 20g solution IIIs；Then solution I, solution II and solution III are well mixed；Amount
Take a diameter of 1mm of 0.1L, length 5mm binder free cylinder Hydrogen BEA zeolite molecular sieves (rub by silica/alumina
You are than being 40), mixed solution to be loaded on Hydrogen BEA zeolite molecular sieves, room temperature immersion 12h, 100 DEG C of dry 12h, 450 DEG C
4h is calcined, that is, required catalyst is prepared.
2nd, evaluating catalyst
Evaluating catalyst method is shown in embodiment 1.
The composition of catalyst and evaluation result are listed in table 1 for ease of comparing.
【Embodiment 7】
1st, catalyst preparation
Weigh the PdCl of the Pd containing 0.3g2It is dissolved in 1mol/L aqueous hydrochloric acid solutions and is made into 40g solution Is；Weigh 0.6g containing Pr
Pr (NO3)3·6H2The O and 0.6g containing Sm Sm (NO3)3·6H2O is soluble in water to be made into 20g solution IIs；Weigh 0.4g containing Cd
Cd (NO3)2·4H2O is soluble in water to be made into 20g solution IIIs；Then solution I, solution II and solution III are well mixed；Amount
Take a diameter of 1mm of 0.1L, length 5mm binder free cylinder Hydrogen BEA zeolite molecular sieves (rub by silica/alumina
You are than being 40), mixed solution to be loaded on Hydrogen BEA zeolite molecular sieves, room temperature immersion 12h, 100 DEG C of dry 12h, 450 DEG C
4h is calcined, that is, required catalyst is prepared.
2nd, evaluating catalyst
Evaluating catalyst method is shown in embodiment 1.
The composition of catalyst and evaluation result are listed in table 1 for ease of comparing.
【Embodiment 8】
1st, catalyst preparation
Weigh the PdCl of the Pd containing 0.3g2It is dissolved in 1mol/L aqueous hydrochloric acid solutions and is made into 40g solution Is；Weigh 0.6g containing Ce
Ce (NO3)3·6H2The O and 0.3g containing Pr Pr (NO3)3·6H2The O and 0.3g containing Sm Sm (NO3)3·6H2O is soluble in water to be matched somebody with somebody
Into 20g solution IIs；Weigh the Cd (NO of the 0.4g containing Cd3)2·4H2O is soluble in water to be made into 20g solution IIIs；Then by solution I, molten
Liquid II and solution III are well mixed；Measure a diameter of 1mm of 0.1L, length 5mm binder free cylinder Hydrogen BEA zeolites point
Son sieve (mol ratio of silica/alumina is 40), mixed solution is loaded on Hydrogen BEA zeolite molecular sieves, room temperature leaching
Stain 12h, 100 DEG C of dry 12h, 450 DEG C of roasting 4h, that is, are prepared required catalyst.
2nd, evaluating catalyst
Evaluating catalyst method is shown in embodiment 1.
The composition of catalyst and evaluation result are listed in table 1 for ease of comparing.
【Embodiment 9】
1st, catalyst preparation
Weigh the PdCl of the Pd containing 0.3g2It is dissolved in 1mol/L aqueous hydrochloric acid solutions and is made into 40g solution Is；Weigh 0.3g containing Ce
Ce (NO3)3·6H2The O and 0.6g containing Pr Pr (NO3)3·6H2The O and 0.3g containing Sm Sm (NO3)3·6H2O is soluble in water to be matched somebody with somebody
Into 20g solution IIs；Weigh the Cd (NO of the 0.4g containing Cd3)2·4H2O is soluble in water to be made into 20g solution IIIs；Then by solution I, molten
Liquid II and solution III are well mixed；Measure a diameter of 1mm of 0.1L, length 5mm binder free cylinder Hydrogen BEA zeolites point
Son sieve (mol ratio of silica/alumina is 40), mixed solution is loaded on Hydrogen BEA zeolite molecular sieves, room temperature leaching
Stain 12h, 100 DEG C of dry 12h, 450 DEG C of roasting 4h, that is, are prepared required catalyst.
2nd, evaluating catalyst
Evaluating catalyst method is shown in embodiment 1.
The composition of catalyst and evaluation result are listed in table 1 for ease of comparing.
【Embodiment 10】
1st, catalyst preparation
Weigh the PdCl of the Pd containing 0.3g2It is dissolved in 1mol/L aqueous hydrochloric acid solutions and is made into 40g solution Is；Weigh 0.3g containing Ce
Ce (NO3)3·6H2The O and 0.3g containing Pr Pr (NO3)3·6H2The O and 0.6g containing Sm Sm (NO3)3·6H2O is soluble in water to be matched somebody with somebody
Into 20g solution IIs；Weigh the Cd (NO of the 0.4g containing Cd3)2·4H2O is soluble in water to be made into 20g solution IIIs；Then by solution I, molten
Liquid II and solution III are well mixed；Measure a diameter of 1mm of 0.1L, length 5mm binder free cylinder Hydrogen BEA zeolites point
Son sieve (mol ratio of silica/alumina is 40), mixed solution is loaded on Hydrogen BEA zeolite molecular sieves, room temperature leaching
Stain 12h, 100 DEG C of dry 12h, 450 DEG C of roasting 4h, that is, are prepared required catalyst.
2nd, evaluating catalyst
Evaluating catalyst method is shown in embodiment 1.
The composition of catalyst and evaluation result are listed in table 1 for ease of comparing.
【Embodiment 11】
1st, catalyst preparation
Weigh the PdCl of the Pd containing 0.3g2It is dissolved in 1mol/L aqueous hydrochloric acid solutions and is made into 40g solution Is；Weigh 0.4g containing Ce
Ce (NO3)3·6H2The O and 0.4g containing Pr Pr (NO3)3·6H2The O and 0.4g containing Sm Sm (NO3)3·6H2O is soluble in water to be matched somebody with somebody
Into 20g solution IIs；Weigh the Cd (NO of the 0.4g containing Cd3)2·4H2O is soluble in water to be made into 20g solution IIIs；Then by solution I, molten
Liquid II and solution III are well mixed；Measure a diameter of 1mm of 0.1L, length 5mm binder free cylinder Hydrogen BEA zeolites point
Son sieve (mol ratio of silica/alumina is 40), mixed solution is loaded on Hydrogen BEA zeolite molecular sieves, room temperature leaching
Stain 12h, 100 DEG C of dry 12h, 450 DEG C of roasting 4h, that is, are prepared required catalyst.
2nd, evaluating catalyst
Evaluating catalyst method is shown in embodiment 1.
The composition of catalyst and evaluation result are listed in table 1 for ease of comparing.
【Embodiment 12】
1st, catalyst preparation
Weigh the PdCl of the Pd containing 0.3g2It is dissolved in 1mol/L aqueous hydrochloric acid solutions and is made into 80g solution Is, it is a diameter of measures 0.1L
1mm, length 5mm binder free cylinder Hydrogen BEA zeolite molecular sieves (mol ratio of silica/alumina is 40), will
Solution I is loaded on Hydrogen BEA zeolite molecular sieves；Room temperature immersion 12h, 100 DEG C of dry 12h, 450 DEG C of roasting 4h, obtain CAT1.
Weigh the Ce (NO of the 0.4g containing Ce3)3·6H2O and Pr 0.4g Pr (NO3)3·6H2The O and 0.4g containing Sm Sm (NO3)3·
6H2O is soluble in water to be made into 20g solution IIs；Weigh the Cd (NO of the 0.4g containing Cd3)2·4H2O is soluble in water to be made into 20g solution IIIs；
Then solution II and solution III are well mixed；Mixed solution is impregnated on CAT1；Room temperature immersion 12h, 100 DEG C of dry 12h,
450 DEG C of roasting 4h, that is, be prepared required catalyst.
2nd, evaluating catalyst
Evaluating catalyst method is shown in embodiment 1.
The composition of catalyst and evaluation result are listed in table 1 for ease of comparing.
【Embodiment 13】
1st, catalyst preparation
Weigh the Ce (NO of the 0.4g containing Ce3)3·6H2O and Pr 0.4g Pr (NO3)3·6H2The O and 0.4g containing Sm Sm
(NO3)3·6H2O is soluble in water to be made into 20g solution IIs；Weigh the Cd (NO of the 0.4g containing Cd3)2·4H2O is soluble in water to be made into 20g
Solution III；Then solution II and solution III are well mixed；Measure a diameter of 1mm of 0.1L, length 5mm binder free cylinder
Shape Hydrogen BEA zeolite molecular sieves (mol ratio of silica/alumina is 40), Hydrogen BEA zeolites are loaded to by mixed solution
On molecular sieve；Room temperature immersion 12h, 100 DEG C of dry 12h, 450 DEG C of roasting 4h, obtain CAT2.Weigh the PdCl of the Pd containing 0.3g2It is molten
80g solution Is are made into 1mol/L aqueous hydrochloric acid solutions；Solution I is impregnated on CAT2；Room temperature immersion 12h, 100 DEG C of dryings
12h, 450 DEG C of roasting 4h, that is, be prepared required catalyst.
2nd, evaluating catalyst
Evaluating catalyst method is shown in embodiment 1.
The composition of catalyst and evaluation result are listed in table 1 for ease of comparing.
【Embodiment 14】
Weigh the PdCl of the Pd containing 0.5g2It is dissolved in 1mol/L aqueous hydrochloric acid solutions and is made into 40g solution Is；Weigh 1.8g containing Ce
Ce (NO3)3·6H2O and Pr 1.2g Pr (NO3)3·6H2The O and 1.2g containing Sm Sm (NO3)3·6H2O is soluble in water to be made into
20g solution IIs；Weigh the Cd (NO of the 8g containing Cd3)2·4H2O is soluble in water to be made into 20g solution IIIs；Then by solution I, solution II
It is well mixed with solution III；Measure a diameter of 1mm of 0.1L, length 5mm binder free cylinder Hydrogen BEA zeolite molecular sieves
(mol ratio of silica/alumina is 40), mixed solution is loaded on Hydrogen BEA zeolite molecular sieves, room temperature immersion
12h, 100 DEG C of dry 12h, 450 DEG C of roasting 4h, that is, be prepared required catalyst.
2nd, evaluating catalyst
Evaluating catalyst method is shown in embodiment 1.
The composition of catalyst and evaluation result are listed in table 1 for ease of comparing.
【Embodiment 15】
1st, catalyst preparation
Weigh the PdCl of the Pd containing 0.1g2It is dissolved in 1mol/L aqueous hydrochloric acid solutions and is made into 40g solution Is；Weigh 0.3g containing Ce
Ce (NO3)3·6H2O and Pr 0.2g Pr (NO3)3·6H2The O and 0.1g containing Sm Sm (NO3)3·6H2O is soluble in water to be made into
20g solution IIs；Weigh the Cd (NO of the 0.2g containing Cd3)2·4H2O is soluble in water to be made into 20g solution IIIs；Then by solution I, molten
Liquid II and solution III are well mixed；Measure a diameter of 1mm of 0.1L, length 5mm binder free cylinder Hydrogen BEA zeolites point
Son sieve (mol ratio of silica/alumina is 40), mixed solution is loaded on Hydrogen BEA zeolite molecular sieves, room temperature leaching
Stain 12h, 100 DEG C of dry 12h, 450 DEG C of roasting 4h, that is, are prepared required catalyst.
2nd, evaluating catalyst
Evaluating catalyst method is shown in embodiment 1.
The composition of catalyst and evaluation result are listed in table 1 for ease of comparing.
The catalyst of table 1 forms and evaluation result
Note：In table 1, CH represents hexamethylene, and CHB represents cyclohexyl benzene.
Claims (10)
1. suitable for the catalyst of cyclohexyl benzene production, including carrier and following active component：
(1) 0.5~20g/L Pd；
At least one of (2) 0~50g/L lanthanide series；
(3) 0~30g/L Cd；
Wherein described carrier is h-type zeolite molecular sieve.
2. catalyst according to claim 1, it is characterized in that, Pd contents are 1~10g/L.
3. catalyst according to claim 1, it is characterized in that, zeolite molecules are screened from BEA, MOR or MWW zeolite molecules
Sieve.
4. catalyst according to claim 3, it is characterized in that, selected BEA zeolite molecular sieves are molded for binder free
BEA zeolite molecular sieves.
5. catalyst according to claim 4, it is characterized in that, the silica of binder free shaping BEA zeolite molecular sieves/
The mol ratio of aluminum oxide is 10~100.
6. catalyst according to claim 1, it is characterized in that, lanthanide content is 4~30g/L in catalyst.
7. according to institute's metal catalyst in claim 1, it is characterized in that, Cd contents are 2~20g/L in catalyst.
8. the preparation method of catalyst described in claim 1, is comprised the steps of：
A) the h-type zeolite molecular sieve is obtained；
B) by aequum Pd compound wiring solution-forming I；
C) by the compound wiring solution-forming II of aequum lanthanide series；
D) by aequum Cd compound wiring solution-forming III；
E) solution III of solution I, the solution II that step c) is prepared and the step d) preparations prepared step b) using infusion process is born
It is loaded on the zeolite molecular sieve carrier described in step a), dries, 350~550 DEG C is calcined 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 generation cyclohexyl benzene.
10. according to the method for 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102844115A (en) * | 2010-06-10 | 2012-12-26 | 宇部兴产株式会社 | Catalyst for alkylation and process for producing alkylaromatic hydrocarbon compound using the catalyst |
| 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 |
| CN105582990A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Catalyst for producing cyclohexylbenzene |
| CN105582989A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Catalyst for synthesizing cyclohexylbenzene |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102844115A (en) * | 2010-06-10 | 2012-12-26 | 宇部兴产株式会社 | Catalyst for alkylation and process for producing alkylaromatic hydrocarbon compound using the catalyst |
| 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 |
| CN105582990A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Catalyst for producing cyclohexylbenzene |
| CN105582989A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Catalyst for synthesizing cyclohexylbenzene |
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