CN105233861B - The synthetic method of cyclohexyl benzene catalyst and cyclohexyl benzene - Google Patents
The synthetic method of cyclohexyl benzene catalyst and cyclohexyl benzene Download PDFInfo
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- CN105233861B CN105233861B CN201410329012.9A CN201410329012A CN105233861B CN 105233861 B CN105233861 B CN 105233861B CN 201410329012 A CN201410329012 A CN 201410329012A CN 105233861 B CN105233861 B CN 105233861B
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Abstract
The present invention relates to a kind of methods of catalyst preparation method for preparing cyclohexyl benzene and benzene hydrogenation alkylation one-step synthesis method cyclohexyl benzene, solve catalyst in the prior art and cause the technical problem that by-product methylcyclopentyl benzene content is high in reaction.The present invention is by using cyclohexyl benzene catalyst, including carrier and by weight percentage following component: (1) 0.05~2.0% Pd；(2) 0~3.0% at least one of lanthanide series；Wherein the carrier is that the technical solution of h-type zeolite molecular sieve achieves preferable effect, can be used for benzene hydrogenation alkylation one-step method and prepares cyclohexyl benzene.
Description
Technical field
The present invention relates to cyclohexyl benzene catalyst, preparation method and benzene hydrogenations to be alkylated one-step synthesis method cyclohexyl benzene
Method.
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 prepare cyclohexyl benzene reaction principle it is as follows:
According to the alkylated reaction mechanism of benzene hydrogenation, hydrogenation reaction occurs in the heart in a metal for benzene, and the property of can choose generates
Cyclohexene, while generating portion hexamethylene and cyclohexadiene；With benzene alkyl occurs for cyclohexene and cyclohexadiene on acid centre
Change reaction, generates principal product cyclohexyl benzene.Therefore, use the bicomponent catalyst with hydrogenating function and alkylation function can be with
Realize benzene hydrogenation alkylation production cyclohexyl benzene.
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, as the oil company Phillips, the U.S. patent US4094918,
US4219689 and US4329531, using the zeolite catalyst through Ni- rare earth treatment, the conversion ratio of benzene and the yield of CHB all compare
It is lower.ExxonMobil company develops the catalyst (US2011/ of load hydrogenation metal based on MCM-22 Series Molecules sieve
0015457A1, US2011/0021841A1), cyclohexyl benzene is prepared for benzene hydrogenation alkylation, has cyclohexyl benzene selectivity high
The advantages of, but by-product methylcyclopentyl benzene content is high in reacting, and subsequent oxidation decomposition is caused to prepare the anti-of phenol cyclohexanone
Answer middle product separation difficult.
Summary of the invention
The first technical problem to be solved by the present invention is that catalyst in the prior art causes by-product methyl in reaction
Cyclopenta benzene content is high, so that subsequent oxidation decomposition prepares the technical problem that product separation is difficult in the reaction of phenol cyclohexanone.
A kind of cyclohexyl benzene catalyst is provided, is used for having when benzene and hydrogen reaction synthesizing cyclohexyl benzene to by-product methyl ring penta
The low advantage of base benzene selective.
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: cyclohexyl benzene catalyst one of to solve above-mentioned technical problem, including carrier and
Following component by weight percentage:
(1) 0.05~2.0% Pd；
(2) 0~3.0% at least one of lanthanide series；
Wherein the carrier is h-type zeolite molecular sieve；The lanthanide series preferred La, Ce, Pr, Nd, Yb.But it is excellent
It selects while including La and Ce, or preferably simultaneously include La and Nd.
In above-mentioned technical proposal, Pd content is preferably 0.1~0.5% in parts by weight.
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 MWW zeolite molecular sieve.
In above-mentioned technical proposal, the MWW zeolite molecular sieve is preferably binder free molding MWW zeolite molecular sieve.It is described
The molar ratio that binder free forms the silica/alumina of MWW zeolite molecular sieve is preferably 10~70, more preferably 20~
45。
It is preferably 0.5~2.0% with weight percentage lanthanide content in above-mentioned technical proposal.
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 for example including palladium chloride, palladium nitrate, chlorine palladium
Sour ammonium, one of ammonium chloropalladite, solvent is optional to be tuned into acid water by hydrochloric acid or nitric acid；
C) by the compound wiring solution-forming II of aequum lanthanide series；
D) solution II that the step b) solution I prepared and step c) are prepared is carried on described in step a) using infusion process
Dry on zeolite molecular sieve carrier, 350~550 DEG C roast 3~6 hours, and catalyst is made.
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 impregnating process of step d) can use any one of following three kinds, can achieve
The purpose of the present invention:
Method 1, first dipping solution I, drying, roasting, then dipping solution II, drying roast again；
Method 2, first dipping solution II, drying, roasting, then dipping solution I, drying, roasting；
Method 3 impregnates together after mixing solution I and solution II, dries, roasts.The dipping method is in specific embodiment party
It is referred to as mixed with dipping in the table 1 of formula.
But it has surprisingly been found that the best way is that method 2, at this time benzene conversion ratio and CHB selectivity are higher.
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 0.5~3.0, more preferably 0.8~
1.3。
In above-mentioned technical proposal, the pressure of reaction is preferably 0.2~4.0MPa (gauge pressure), more preferably 2.0~4.0MPa
(gauge pressure).
In above-mentioned technical proposal, the weight space velocity of reaction raw materials benzene is preferably 0.5~3.0h-1, more preferably 0.5~
2.0h-1。
Catalyst of the invention is reduced due to using Pd and La series elements simultaneously as active constituent to methylcyclopentyl
The selectivity of benzene.At 150 DEG C of reaction temperature, benzene and hydrogen molar ratio 1.0, pressure 3.0MPa, the weight space velocity 1h of benzene-1Condition
Under, the selectivity of methylcyclopentyl benzene is only 0.4~1.0wt%, and the selectivity of prior art methylcyclopentyl benzene is high on year-on-year basis
Up to 1.0~4.9wt%, preferable technical effect is achieved.
Specific embodiment
[embodiment 1]
1, catalyst preparation
Weigh 2.0gPdCl2It is dissolved in 1mol/L aqueous hydrochloric acid solution and is made into 80g solution I；Weighing 100g diameter is 1mm, length
Spend the binder free cylinder Hydrogen MWW zeolite molecular sieve of 5mm；Solution I is loaded on Hydrogen MWW zeolite molecular sieve, room temperature
12h is impregnated, required catalyst is prepared in 100 DEG C of dry 12h, 450 DEG C of roasting 4h.
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 1.0 in reaction raw materials, and the pressure of reaction is 3.0MPa (gauge pressure), reaction
The weight space velocity of benzene feedstock is 1.0h-1。
To be listed in table 1 convenient for the composition for comparing catalyst, evaluation result is listed in table 2.
[comparative example 1]
1, catalyst preparation
Weigh 4.68g La (NO3)3·6H2O is soluble in water to be made into 80g solution II；Weighing 100g diameter is 1mm, length
The binder free cylinder Hydrogen MWW zeolite molecular sieve (molar ratio of silica/alumina is 30) of 5mm, solution II is born
It is downloaded on Hydrogen MWW 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.
[comparative example 2]
1, catalyst preparation
Weigh 4.65g Ce (NO3)3·6H2O is soluble in water to be made into 80g solution II；Weighing 100g diameter is 1mm, length
The binder free cylinder Hydrogen MWW zeolite molecular sieve (molar ratio of silica/alumina is 30) of 5mm, solution II is born
It is downloaded on Hydrogen MWW 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.
[comparative example 3]
1, catalyst preparation
Weigh 4.55g Nd (NO3)3·6H2O is soluble in water to be made into 80g solution II；Weighing 100g diameter is 1mm, length
The binder free cylinder Hydrogen MWW zeolite molecular sieve (molar ratio of silica/alumina is 30) of 5mm, solution II is born
It is downloaded on Hydrogen MWW 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 2]
1, catalyst preparation
Weigh 0.50gPdCl2It is dissolved in 1mol/L aqueous hydrochloric acid solution and is made into 40g solution I；Weigh 3.74g La (NO3)3·
6H2O is soluble in water to be made into 40g solution II；Then solution I and solution II are uniformly mixed；Weighing 100g diameter is 1mm, length
The binder free cylinder Hydrogen MWW zeolite molecular sieve (molar ratio of silica/alumina is 30) of 5mm, by mixed solution
It loads on Hydrogen MWW zeolite molecular sieve, 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 3]
1, catalyst preparation
Weigh 0.50g PdCl2It is dissolved in 1mol/L aqueous hydrochloric acid solution and is made into 40g solution I；Weigh 3.72g Ce (NO3)3·
6H2O is soluble in water to be made into 40g solution II；Then solution I and solution II are uniformly mixed；Weighing 100g diameter is 1mm, length
The binder free cylinder Hydrogen MWW zeolite molecular sieve of 5mm (molar ratio of silica/alumina is 30)；By mixed solution
It loads on Hydrogen MWW zeolite molecular sieve, 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 4]
1, catalyst preparation
Weigh 0.50g PdCl2It is dissolved in 1mol/L aqueous hydrochloric acid solution and is made into 40g solution I；Weigh 3.64g Nd (NO3)3·
6H2O is soluble in water to be made into 40g solution II；Then solution I and solution II are uniformly mixed；Weighing 100g diameter is 1mm, length
The binder free cylinder Hydrogen MWW zeolite molecular sieve (molar ratio of silica/alumina is 30) of 5mm, by mixed solution
It loads on Hydrogen MWW zeolite molecular sieve, 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 5]
1, catalyst preparation
Weigh 0.50g PdCl2It is dissolved in 1mol/L aqueous hydrochloric acid solution and is made into 40g solution I；Weigh 1.88g La (NO3)3·
6H2O and 1.86g Ce (NO3)3·6H2O is soluble in water to be made into 40g solution II；Then solution I and solution II are uniformly mixed；Scale
Taking 100g diameter is 1mm, the binder free cylinder Hydrogen MWW zeolite molecular sieve of length 5mm (rub by silica/alumina
You are than being 30), mixed solution to be loaded on Hydrogen MWW 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 6]
1, catalyst preparation
Weigh 0.50g PdCl2It is dissolved in 1mol/L aqueous hydrochloric acid solution and is made into 40g solution I；Weigh 1.88g La (NO3)3·
6H2O and 1.82g Nd (NO3)3·6H2O is soluble in water to be made into 40g solution II；Then solution I and solution II are uniformly mixed；Scale
Taking 100g diameter is 1mm, the binder free cylinder Hydrogen MWW zeolite molecular sieve of length 5mm (rub by silica/alumina
You are than being 30), mixed solution to be loaded on Hydrogen MWW 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 7]
1, catalyst preparation
Weigh 0.50g PdCl2It is dissolved in 1mol/L aqueous hydrochloric acid solution and is made into 40g solution I；Weigh 100g diameter be 1mm,
The binder free cylinder Hydrogen MWW zeolite molecular sieve (molar ratio of silica/alumina is 30) of length 5mm, by solution I
It loads on Hydrogen MWW zeolite molecular sieve；Room temperature immersion 12h, 100 DEG C of dry 12h, 450 DEG C of roasting 4h obtain CAT1.It weighs
1.88g La(NO3)3·6H2O and 1.86gCe (NO3)3·6H2O is soluble in water to be made into 40g solution II；CAT1 is impregnated into solution
In II；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 8]
1, catalyst preparation
Weigh 1.88g La (NO3)3·6H2O and 1.86g Ce (NO3)3·6H2O is soluble in water to be made into 80g solution II；Scale
Taking 100g diameter is 1mm, the binder free cylinder Hydrogen MWW zeolite molecular sieve of length 5mm (rub by silica/alumina
You are than being that 30), solution II is loaded on Hydrogen MWW zeolite molecular sieve；Room temperature immersion 12h, 100 DEG C of dry 12h, 450 DEG C of roastings
4h is burnt, CAT2 is obtained；Weigh 0.50g PdCl2It is dissolved in 1mol/L hydrochloric acid and is made into 80g solution I；CAT2 is impregnated into solution I
In；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 9]
1, catalyst preparation
Weigh 0.83g PdCl2It is dissolved in 1mol/L aqueous hydrochloric acid solution and is made into 40g solution I；Weigh 3.12g La (NO3)3·
6H2O and 3.10g Ce (NO3)3·6H2O is soluble in water to be made into 40g solution II；Then solution I and solution II are uniformly mixed；Scale
Taking 100g diameter is 1mm, the binder free cylinder Hydrogen MWW zeolite molecular sieve of length 5mm (rub by silica/alumina
You are than being that 30), mixed solution is loaded on Hydrogen MWW 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
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 4.0MPa (gauge pressure), the raw material of reaction
Weight space velocity be 3.0h-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 0.17g PdCl2It is dissolved in 1mol/L aqueous hydrochloric acid solution and is made into 40g solution I；Weigh 0.53g La (NO3)3·
6H2O and 0.53g Ce (NO3)3·6H2O is soluble in water to be made into 40g solution II；Solution I and solution II are uniformly mixed；It weighs
100g diameter is binder free cylinder Hydrogen MWW zeolite molecular sieve (mole of silica/alumina of 1mm, length 5mm
Than for 30), mixed solution is loaded on Hydrogen MWW zeolite molecular sieve；Room temperature immersion 12h, 100 DEG C of dry 12h, 450 DEG C of roastings
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 200 DEG C, and the molar ratio of benzene and hydrogen is 0.5 in reaction raw materials, and the pressure of reaction is 0.5MPa (gauge pressure), the raw material of reaction
Weight space velocity be 0.5h-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
| Number | Catalyst composition | Preparation method |
| Embodiment 1 | Pd1.5wt%+MWW molecular sieve | It is mixed with dipping |
| Comparative example 1 | La1.5wt%+MWW molecular sieve | It is mixed with dipping |
| Comparative example 2 | Ce1.5wt%+MWW molecular sieve | It is mixed with dipping |
| Comparative example 3 | Nd1.5wt%+MWW molecular sieve | It is mixed with dipping |
| Embodiment 2 | Pd0.3wt%+La1.2wt%+MWW molecular sieve | It is mixed with dipping |
| Embodiment 3 | Pd0.3wt%+Ce1.2wt%+MWW molecular sieve | It is mixed with dipping |
| Embodiment 4 | Pd0.3wt%+Nd1.2wt%+MWW molecular sieve | It is mixed with dipping |
| Embodiment 5 | Pd0.3wt%+La0.6wt%+Ce0.6wt%+MWW molecular sieve | It is mixed with dipping |
| Embodiment 6 | Pd0.3wt%+La0.6wt%+Nd0.6wt%+MWW molecular sieve | It is mixed with dipping |
| Embodiment 7 | Pd0.3wt%+La0.6wt%+Ce0.6wt%+MWW molecular sieve | First dipping solution I, rear dipping solution II |
| Embodiment 8 | Pd0.3wt%+La0.6wt%+Ce0.6wt%+MWW molecular sieve | First dipping solution II, rear dipping solution I |
| Embodiment 9 | Pd0.5wt%+La1.0wt%+Ce1.0wt%+MWW molecular sieve | It is mixed with dipping |
Table 2 (continued) evaluating catalyst result
| Number | Embodiment 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Embodiment 2 | Embodiment 3 |
| Reaction temperature (DEG C) | 150 | 150 | 150 | 150 | 150 | 150 |
| Benzene/hydrogen molar ratio | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
| Reaction pressure (MPa) | 3.0 | 3.0 | 3.0 | 3.0 | 3.0 | 3.0 |
| Reaction velocity (h-1) | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
| Benzene conversion ratio (%) | 75.29 | 0 | 0 | 0 | 42.11 | 40.79 |
| MCPB selectivity (%) | 10.47 | 0 | 0 | 0 | 0.95 | 0.92 |
| CHB selectivity (%) | 37.58 | 0 | 0 | 0 | 48.69 | 52.71 |
| MCPB yield (%) | 7.88 | 0 | 0 | 0 | 0.40 | 0.38 |
| CHB yield (%) | 28.29 | 0 | 0 | 0 | 20.50 | 21.50 |
2 (Continued) evaluating catalyst result of table
| Number | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 |
| Reaction temperature (DEG C) | 150 | 150 | 150 | 150 | 150 | 120 | 180 |
| Benzene/hydrogen molar ratio | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.3 | 0.8 |
| Reaction pressure (MPa) | 3.0 | 3.0 | 3.0 | 3.0 | 3.0 | 4.0 | 2.0 |
| Reaction velocity (h-1) | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 2.0 | 0.5 |
| Benzene conversion ratio (%) | 41.53 | 45.58 | 43.43 | 40.99 | 50.21 | 60.56 | 21.92 |
| MCPB selectivity (%) | 1.03 | 0.78 | 0.82 | 0.88 | 0.37 | 0.90 | 1.12 |
| CHB selectivity (%) | 46.59 | 58.62 | 49.29 | 46.97 | 62.78 | 29.77 | 70.82 |
| MCPB yield (%) | 0.43 | 0.36 | 0.36 | 0.36 | 0.19 | 0.55 | 0.25 |
| CHB yield (%) | 19.35 | 26.72 | 21.41 | 19.25 | 31.52 | 18.03 | 15.52 |
Claims (9)
1. the synthetic method of cyclohexyl benzene contacts reaction raw materials with cyclohexyl benzene catalyst using benzene and hydrogen as reaction raw materials
It carries out benzene hydrogenation alkylated reaction and generates cyclohexyl benzene；The wherein cyclohexyl benzene catalyst, including carrier and with weight percent
Than counting following component:
(1) 0.05~2.0% Pd；
(2) it is greater than 0 and 3.0% lanthanide series below；
Wherein the carrier is h-type zeolite molecular sieve；
The lanthanide series is made of La and Nd or the lanthanide series is made of La and Ce.
2. synthetic method according to claim 1, it is characterized in that, Pd content is 0.1~0.5%.
3. synthetic method according to claim 1, it is characterized in that, zeolite molecules are screened from BEA, MOR or MWW zeolite molecules
Sieve.
4. synthetic method according to claim 3, it is characterized in that, selected MWW zeolite molecular sieve be binder free at
Type MWW zeolite molecular sieve.
5. synthetic method according to claim 4, it is characterized in that, binder free forms the titanium dioxide of MWW zeolite molecular sieve
Silicon/aluminium oxide molar ratio is 10~70.
6. synthetic method according to claim 1, it is characterized in that, with weight percentage lanthanide content be 0.5~
2.0%.
7. the synthetic method in claim 1, the catalyst is using the preparation method preparation comprised 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) solution II that the step b) solution I prepared and step c) are prepared is carried on by zeolite described in step a) using infusion process
Dry on molecular sieve carrier, 350~550 DEG C roast 3~6 hours, and catalyst is made.
8. according to the method described in claim 1, it is characterized in that the temperature of reaction is 100~200 DEG C.
9. according to the method described in claim 1, it is characterized in that the molar ratio of benzene and hydrogen is 0.5~3.0 in reaction raw materials.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107866270B (en) * | 2016-09-26 | 2020-01-03 | 中国石油化工股份有限公司 | Catalyst for synthesis of cyclohexylbenzene |
| CN107866271B (en) * | 2016-09-26 | 2019-12-10 | 中国石油化工股份有限公司 | Catalyst suitable for producing cyclohexylbenzene |
| CN107866267B (en) * | 2016-09-26 | 2020-07-07 | 中国石油化工股份有限公司 | Catalyst for synthesizing cyclohexylbenzene |
| CN107866269B (en) * | 2016-09-26 | 2019-11-08 | 中国石油化工股份有限公司 | Cyclohexyl benzene catalyst and preparation method thereof |
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