CN105233861A - Cyclohexyl benzene catalyst and synthetic method thereof - Google Patents
Cyclohexyl benzene catalyst and synthetic method thereof Download PDFInfo
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Abstract
The present invention relates to a catalyst for preparing cyclohexyl benzene, a preparation method for the catalyst and a method for synthesizing cyclohexyl benzene by a benzene hydrogenation alkylation one-step process, and aims to solve the technical problem that the content of byproduct methyl cyclopentyl in reaction is high due to the catalyst in the prior art. The cyclohexyl benzene catalyst comprises a carrier and the following components in percentage by weight: (1) 0.05-2.0% of Pd; and (2) 0-3.0% of at least one of lanthanide series elements, wherein technical scheme that the carrier is a hydrogen-zeolite molecular sieve acquires good effect; and the cyclohexyl benzene can be used for preparing cyclohexyl benzene by the benzene hydrogenation alkylation one-step process.
Description
Technical field
The present invention relates to the method for cyclohexyl benzene catalyst, its preparation method and benzene hydrogenation alkylation one-step synthesis method 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.Cyclohexyl benzene class liquid crystal has the features such as the low and good physical properties of high chemical stability, photochemical stability, viscosity, is one of ideal material of display device.Cyclohexyl benzene, as the additive of lithium-ion battery electrolytes, has anti-overcharge performance, can improve the security performance of battery.In addition, phenol and cyclohexanone can be prepared by the peroxidating of cyclohexyl benzene, decomposition reaction process, for the production of large industrial chemicals such as phenolic resins, caprolactam and nylon, have a good application prospect.The essential information of cyclohexyl benzene is as follows: colourless liquid, and No. CAS is 827-52-1, and molecular weight is C
12h
16, density 0.95g/cm
3, boiling point 238 ~ 240 DEG C, fusing point 5 DEG C, flash-point 98 DEG C.
The preparation method of cyclohexyl benzene has: biphenyl selec-tive hydrogenation method, the alkylation process of benzene and cyclohexene, benzene hydrogenation alkylation process.Wherein, to prepare the reaction principle of cyclohexyl benzene as follows in benzene hydrogenation alkylation:
According to the alkylating reaction mechanism of benzene hydrogenation, there is hydrogenation reaction in benzene in a metal in the heart, can selective generation cyclohexene, simultaneously generating portion cyclohexane and cyclohexadiene; Cyclohexene and cyclohexadiene on acid centre with benzene generation alkylated reaction, generate principal product cyclohexyl benzene.Therefore, adopt the bicomponent catalyst with hydrogenating function and alkylation function can realize benzene hydrogenation alkylation and produce cyclohexyl benzene.
The research that cyclohexyl benzene is prepared in benzene hydrogenation alkylation starts from the seventies and eighties in 20th century the earliest.There is the selective lower problem of cyclohexyl benzene in the catalyst of early development, as patent US4094918, US4219689 and US4329531 of Phillips oil company of the U.S., adopt through the zeolite catalyst of Ni-RE-treated, the conversion ratio of benzene and the yield of CHB all lower.ExxonMobil company develops the catalyst (US2011/0015457A1 of load hydrogenation metal based on MCM-22 Series Molecules sieve, US2011/0021841A1), cyclohexyl benzene is prepared for benzene hydrogenation alkylation, there is the selective high advantage of cyclohexyl benzene, but accessory substance methylcyclopentyl benzene content is high in reaction, causes subsequent oxidation to decompose and prepare product separation difficulty in the reaction of phenol ring hexanone.
Summary of the invention
One of technical problem to be solved by this invention is that catalyst of the prior art causes accessory substance methylcyclopentyl benzene content in reaction high, thus subsequent oxidation decomposes the technical problem preparing product separation difficulty in the reaction of phenol ring hexanone.A kind of cyclohexyl benzene catalyst is provided, when using it for benzene and hydrogen reaction synthesizing cyclohexyl benzene, there is the advantage low to accessory substance methylcyclopentyl benzene selective.
Two of technical problem to be solved by this invention is preparation methods of the described catalyst of one of above-mentioned technical problem.
Three of technical problem to be solved by this invention is the synthetic methods of the cyclohexyl benzene adopting one of above-mentioned technical problem described catalyst.
As follows for one of solving the problems of the technologies described above technical scheme of the present invention: cyclohexyl benzene catalyst, comprise carrier and following component by weight percentage:
The Pd of (1) 0.05 ~ 2.0%;
At least one in the lanthanide series of (2) 0 ~ 3.0%;
Wherein said carrier is h-type zeolite molecular sieve; Described lanthanide series preferred La, Ce, Pr, Nd, Yb.But preferably comprise La and Ce simultaneously, or preferably comprise La and Nd simultaneously.
In technique scheme, Pd content is preferably 0.1 ~ 0.5% with parts by weight.
In technique scheme, zeolite molecular sieve is preferably from BEA, MOR or MWW zeolite molecular sieve; Preferred zeolite molecular sieve carrier is MWW zeolite molecular sieve.
In technique scheme, described MWW zeolite molecular sieve is preferably the shaping MWW zeolite molecular sieve of binder free.The mol ratio of the silica/alumina of the shaping MWW zeolite molecular sieve of described binder free is preferably 10 ~ 70, is more preferably 20 ~ 45.
In technique scheme, be preferably 0.5 ~ 2.0% with weight percentage lanthanide content.
For solve the problems of the technologies described above two, technical scheme of the present invention is as follows: the preparation method of catalyst described in the technical scheme of one of above-mentioned technical problem, comprises following steps:
A) described h-type zeolite molecular sieve is obtained;
B) by the compound wiring solution-forming I of aequum Pd; Optional compound such as comprises palladium bichloride, palladium nitrate, ammonium chloropalladate, the one in ammonium chloropalladite, the optional water by hydrochloric acid or nitric acid furnishing acidity of solvent;
C) by the compound wiring solution-forming II of aequum lanthanide series;
D) adopt infusion process by step b) solution I prepared and step c) solution II prepared be carried on step a) described in zeolite molecular sieve carrier on, dry, 350 ~ 550 DEG C of roastings 3 ~ 6 hours, obtained catalyst.
In technique scheme, step b) the preferred palladium bichloride of compound of described Pd.
In technique scheme, step c) the compound preferably nitrate of described lanthanide series.
In technique scheme, steps d) impregnating process can adopt any one of following three kinds, all can reach object of the present invention:
Method 1, first dipping solution I, drying, roasting, and then dipping solution II, dry, roasting;
Method 2, first dipping solution II, drying, roasting, then dipping solution I, drying, roasting;
Method 3, by dipping, dry, roasting together with after the mixing of solution I and solution II.This dipping method in the table 1 of detailed description of the invention referred to as hybrid infusion.
But be surprised to find, the best way is method 2, now benzene conversion ratio and CHB selective higher.
For solve the problems of the technologies described above three technical schemes of the present invention are as follows: the synthetic method of cyclohexyl benzene, with benzene and hydrogen for reaction raw materials, make catalyst exposure according to any one of the technical scheme of one of reaction raw materials and above-mentioned technical problem carry out benzene hydrogenation alkylated reaction and generate cyclohexyl benzene.
In technique scheme, the temperature of reaction is preferably 100 ~ 200 DEG C, more preferably 120 ~ 180 DEG C.
In technique scheme, in reaction raw materials, the mol ratio of benzene and hydrogen is preferably 0.5 ~ 3.0, is more preferably 0.8 ~ 1.3.
In technique scheme, the pressure of reaction is preferably 0.2 ~ 4.0MPa (gauge pressure), is more preferably 2.0 ~ 4.0MPa (gauge pressure).
In technique scheme, the weight space velocity of reaction raw materials benzene is preferably 0.5 ~ 3.0h
-1, be more preferably 0.5 ~ 2.0h
-1.
Catalyst of the present invention is active constituent owing to have employed Pd and La series elements simultaneously, and what reduce methylcyclopentyl benzene is selective.Reaction temperature 150 DEG C, benzene and hydrogen mol ratio 1.0, pressure 3.0MPa, the weight space velocity 1h of benzene
-1condition under, the selective of methylcyclopentyl benzene is only 0.4 ~ 1.0wt%, and prior art methylcyclopentyl benzene on year-on-year basis is selective up to 1.0 ~ 4.9wt%, achieves good technique effect.
Detailed description of the invention
[embodiment 1]
1, catalyst preparing
Weigh 2.0gPdCl
2be dissolved in 1mol/L aqueous hydrochloric acid solution and be made into 80g solution I; Weigh the binder free cylindrical Hydrogen MWW zeolite molecular sieve that 100g diameter is 1mm, length 5mm; Solution I loaded on Hydrogen MWW zeolite molecular sieve, room temperature immersion 12h, 100 DEG C of dry 12h, 450 DEG C of roasting 4h, namely prepare required catalyst.
2, evaluating catalyst
Get 10ml Catalyst packing in fixed bed reactors, carry out activity rating after reduction activation, condition is as follows: the temperature of reaction is 150 DEG C, and in reaction raw materials, the mol ratio of benzene and hydrogen is 1.0, the pressure of reaction is 3.0MPa (gauge pressure), and the weight space velocity of the benzene feedstock of reaction is 1.0h
-1.
For ease of comparing, the composition of catalyst is listed in table 1, evaluation result is listed in table 2.
[comparative example 1]
1, catalyst preparing
Weigh 4.68gLa (NO
3)
36H
2o is soluble in water is made into 80g solution II; Weigh that 100g diameter is 1mm, the binder free cylindrical Hydrogen MWW zeolite molecular sieve of length 5mm (mol ratio of silica/alumina is 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 roasting 4h, namely prepare required catalyst.
2, evaluating catalyst
Evaluating catalyst method is shown in embodiment 1.
For ease of comparing, the composition of catalyst is listed in table 1, evaluation result is listed in table 2.
[comparative example 2]
1, catalyst preparing
Weigh 4.65gCe (NO
3)
36H
2o is soluble in water is made into 80g solution II; Weigh that 100g diameter is 1mm, the binder free cylindrical Hydrogen MWW zeolite molecular sieve of length 5mm (mol ratio of silica/alumina is 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 roasting 4h, namely prepare required catalyst.
2, evaluating catalyst
Evaluating catalyst method is shown in embodiment 1.
For ease of comparing, the composition of catalyst is listed in table 1, evaluation result is listed in table 2.
[comparative example 3]
1, catalyst preparing
Weigh 4.55gNd (NO
3)
36H
2o is soluble in water is made into 80g solution II; Weigh that 100g diameter is 1mm, the binder free cylindrical Hydrogen MWW zeolite molecular sieve of length 5mm (mol ratio of silica/alumina is 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 roasting 4h, namely prepare required catalyst.
2, evaluating catalyst
Evaluating catalyst method is shown in embodiment 1.
For ease of comparing, the composition of catalyst is listed in table 1, evaluation result is listed in table 2.
[embodiment 2]
1, catalyst preparing
Weigh 0.50gPdCl
2be dissolved in 1mol/L aqueous hydrochloric acid solution and be made into 40g solution I; Weigh 3.74gLa (NO
3)
36H
2o is soluble in water is made into 40g solution II; Then solution I and solution II are mixed; Weigh that 100g diameter is 1mm, the binder free cylindrical Hydrogen MWW zeolite molecular sieve of length 5mm (mol ratio of silica/alumina is 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 roasting 4h, namely prepare required catalyst.
2, evaluating catalyst
Evaluating catalyst method is shown in embodiment 1.
For ease of comparing, the composition of catalyst is listed in table 1, evaluation result is listed in table 2.
[embodiment 3]
1, catalyst preparing
Weigh 0.50gPdCl
2be dissolved in 1mol/L aqueous hydrochloric acid solution and be made into 40g solution I; Weigh 3.72gCe (NO
3)
36H
2o is soluble in water is made into 40g solution II; Then solution I and solution II are mixed; Weigh that 100g diameter is 1mm, the binder free cylindrical Hydrogen MWW zeolite molecular sieve of length 5mm (mol ratio of silica/alumina is 30); Loaded to by mixed solution on Hydrogen MWW zeolite molecular sieve, room temperature immersion 12h, 100 DEG C of dry 12h, 450 DEG C of roasting 4h, namely prepare required catalyst.
2, evaluating catalyst
Evaluating catalyst method is shown in embodiment 1.
For ease of comparing, the composition of catalyst is listed in table 1, evaluation result is listed in table 2.
[embodiment 4]
1, catalyst preparing
Weigh 0.50gPdCl
2be dissolved in 1mol/L aqueous hydrochloric acid solution and be made into 40g solution I; Weigh 3.64gNd (NO
3)
36H
2o is soluble in water is made into 40g solution II; Then solution I and solution II are mixed; Weigh that 100g diameter is 1mm, the binder free cylindrical Hydrogen MWW zeolite molecular sieve of length 5mm (mol ratio of silica/alumina is 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 roasting 4h, namely prepare required catalyst.
2, evaluating catalyst
Evaluating catalyst method is shown in embodiment 1.
For ease of comparing, the composition of catalyst is listed in table 1, evaluation result is listed in table 2.
[embodiment 5]
1, catalyst preparing
Weigh 0.50gPdCl
2be dissolved in 1mol/L aqueous hydrochloric acid solution and be made into 40g solution I; Weigh 1.88gLa (NO
3)
36H
2o and 1.86gCe (NO
3)
36H
2o is soluble in water is made into 40g solution II; Then solution I and solution II are mixed; Weigh that 100g diameter is 1mm, the binder free cylindrical Hydrogen MWW zeolite molecular sieve of length 5mm (mol ratio of silica/alumina is 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 roasting 4h, namely prepare required catalyst.
2, evaluating catalyst
Evaluating catalyst method is shown in embodiment 1.
For ease of comparing, the composition of catalyst is listed in table 1, evaluation result is listed in table 2.
[embodiment 6]
1, catalyst preparing
Weigh 0.50gPdCl
2be dissolved in 1mol/L aqueous hydrochloric acid solution and be made into 40g solution I; Weigh 1.88gLa (NO
3)
36H
2o and 1.82gNd (NO
3)
36H
2o is soluble in water is made into 40g solution II; Then solution I and solution II are mixed; Weigh that 100g diameter is 1mm, the binder free cylindrical Hydrogen MWW zeolite molecular sieve of length 5mm (mol ratio of silica/alumina is 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 roasting 4h, namely prepare required catalyst.
2, evaluating catalyst
Evaluating catalyst method is shown in embodiment 1.
For ease of comparing, the composition of catalyst is listed in table 1, evaluation result is listed in table 2.
[embodiment 7]
1, catalyst preparing
Weigh 0.50gPdCl
2be dissolved in 1mol/L aqueous hydrochloric acid solution and be made into 40g solution I; Weigh that 100g diameter is 1mm, the binder free cylindrical Hydrogen MWW zeolite molecular sieve of length 5mm (mol ratio of silica/alumina is 30), solution I is loaded on Hydrogen MWW zeolite molecular sieve; Room temperature immersion 12h, 100 DEG C of dry 12h, 450 DEG C of roasting 4h, obtain CAT1.Weigh 1.88gLa (NO
3)
36H
2o and 1.86gCe (NO
3)
36H
2o is soluble in water is made into 40g solution II; CAT1 is impregnated in solution II; Room temperature immersion 12h, 100 DEG C of dry 12h, 450 DEG C of roasting 4h, namely prepare required catalyst.
2, evaluating catalyst
Evaluating catalyst method is shown in embodiment 1.
For ease of comparing, the composition of catalyst is listed in table 1, evaluation result is listed in table 2.
[embodiment 8]
1, catalyst preparing
Weigh 1.88gLa (NO
3)
36H
2o and 1.86gCe (NO
3)
36H
2o is soluble in water is made into 80g solution II; Weigh that 100g diameter is 1mm, the binder free cylindrical Hydrogen MWW zeolite molecular sieve of length 5mm (mol ratio of silica/alumina is 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 roasting 4h, obtain CAT2; Weigh 0.50gPdCl
2be dissolved in 1mol/L hydrochloric acid and be made into 80g solution I; CAT2 is impregnated in solution I; Room temperature immersion 12h, 100 DEG C of dry 12h, 450 DEG C of roasting 4h, namely prepare required catalyst.
2, evaluating catalyst
Evaluating catalyst method is shown in embodiment 1.
For ease of comparing, the composition of catalyst is listed in table 1, evaluation result is listed in table 2.
[embodiment 9]
1, catalyst preparing
Weigh 0.83gPdCl
2be dissolved in 1mol/L aqueous hydrochloric acid solution and be made into 40g solution I; Weigh 3.12gLa (NO
3)
36H
2o and 3.10gCe (NO
3)
36H
2o is soluble in water is made into 40g solution II; Then solution I and solution II are mixed; Weigh that 100g diameter is 1mm, the binder free cylindrical Hydrogen MWW zeolite molecular sieve of length 5mm (mol ratio of silica/alumina is 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 roasting 4h, namely prepare required catalyst.
2, evaluating catalyst
Except following changes in process parameters, all the other are identical with the evaluating catalyst method in embodiment 1: the temperature of reaction is 100 DEG C, in reaction raw materials, the mol ratio of benzene and hydrogen is 2.0, and the pressure of reaction is 4.0MPa (gauge pressure), and the weight space velocity of the raw material of reaction is 3.0h
-1.
For ease of comparing, the composition of catalyst is listed in table 1, evaluation result is listed in table 2.
[embodiment 10]
1, catalyst preparing
Weigh 0.17gPdCl
2be dissolved in 1mol/L aqueous hydrochloric acid solution and be made into 40g solution I; Weigh 0.53gLa (NO
3)
36H
2o and 0.53gCe (NO
3)
36H
2o is soluble in water is made into 40g solution II; Solution I and solution II are mixed; Weigh that 100g diameter is 1mm, the binder free cylindrical Hydrogen MWW zeolite molecular sieve of length 5mm (mol ratio of silica/alumina is 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 roasting 4h, namely prepare required catalyst.
2, evaluating catalyst
Except following changes in process parameters, all the other are identical with the evaluating catalyst method in embodiment 1: the temperature of reaction is 200 DEG C, in reaction raw materials, the mol ratio of benzene and hydrogen is 0.5, and the pressure of reaction is 0.5MPa (gauge pressure), and the weight space velocity of the raw material of reaction is 0.5h
-1.
For ease of comparing, the composition of catalyst is listed in table 1, evaluation result is listed in table 2.
Table 1 catalyst forms
| Numbering | Catalyst forms | Preparation method |
| Embodiment 1 | Pd1.5wt%+MWW molecular sieve | Hybrid infusion |
| Comparative example 1 | La1.5wt%+MWW molecular sieve | Hybrid infusion |
| Comparative example 2 | Ce1.5wt%+MWW molecular sieve | Hybrid infusion |
| Comparative example 3 | Nd1.5wt%+MWW molecular sieve | Hybrid infusion |
| Embodiment 2 | Pd0.3wt%+La1.2wt%+MWW molecular sieve | Hybrid infusion |
| Embodiment 3 | Pd0.3wt%+Ce1.2wt%+MWW molecular sieve | Hybrid infusion |
| Embodiment 4 | Pd0.3wt%+Nd1.2wt%+MWW molecular sieve | Hybrid infusion |
| Embodiment 5 | Pd0.3wt%+La0.6wt%+Ce0.6wt%+MWW molecular sieve | Hybrid infusion |
| Embodiment 6 | Pd0.3wt%+La0.6wt%+Nd0.6wt%+MWW molecular sieve | Hybrid infusion |
| 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 | Hybrid infusion |
Table 2 (continued) evaluating catalyst result
| Numbering | 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 mol 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 selective (%) | 10.47 | 0 | 0 | 0 | 0.95 | 0.92 |
| CHB selective (%) | 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 |
Table 2 (Continued) evaluating catalyst result
| Numbering | 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 mol 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 selective (%) | 1.03 | 0.78 | 0.82 | 0.88 | 0.37 | 0.90 | 1.12 |
| CHB selective (%) | 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 (10)
1. cyclohexyl benzene catalyst, comprises carrier and following component by weight percentage:
The Pd of (1) 0.05 ~ 2.0%;
At least one in the lanthanide series of (2) 0 ~ 3.0%;
Wherein said carrier is h-type zeolite molecular sieve.
2. catalyst according to claim 1, is characterized by, and Pd content is 0.1 ~ 0.5%.
3. catalyst according to claim 1, is characterized by, and zeolite molecular sieve is selected from BEA, MOR or MWW zeolite molecular sieve.
4. catalyst according to claim 4, is characterized by, and selected MWW zeolite molecular sieve is the shaping MWW zeolite molecular sieve of binder free.
5. catalyst according to claim 4, is characterized by, and the mol ratio of the silica/alumina of the shaping MWW zeolite molecular sieve of binder free is 10 ~ 70.
6. catalyst according to claim 1, is characterized by, with weight percentage lanthanide content for 0.5 ~ 2.0%.
7. the preparation method of catalyst described in claim 1, comprises following steps:
A) described 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) adopt infusion process by step b) solution I prepared and step c) solution II prepared be carried on step a) described in zeolite molecular sieve carrier on, dry, 350 ~ 550 DEG C of roastings 3 ~ 6 hours, obtained catalyst.
8. the synthetic method of cyclohexyl benzene, with benzene and hydrogen for reaction raw materials, makes catalyst exposure according to any one of reaction raw materials and claim 1 to 7 carry out benzene hydrogenation alkylated reaction and generates cyclohexyl benzene.
9. method according to claim 8, is characterized in that the temperature of reacting is 100 ~ 200 DEG C.
10. method according to claim 8, is characterized in that the mol ratio of benzene and hydrogen in reaction raw materials is 0.5 ~ 3.0.
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| CN107866270A (en) * | 2016-09-26 | 2018-04-03 | 中国石油化工股份有限公司 | Catalyst for cyclohexyl benzene synthesis |
| CN107866262A (en) * | 2016-09-26 | 2018-04-03 | 中国石油化工股份有限公司 | The catalyst of cyclohexyl benzene production |
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| CN107866271A (en) * | 2016-09-26 | 2018-04-03 | 中国石油化工股份有限公司 | Catalyst suitable for cyclohexyl benzene production |
| CN107866267A (en) * | 2016-09-26 | 2018-04-03 | 中国石油化工股份有限公司 | Catalyst for synthesizing cyclohexyl benzene |
| CN107866272A (en) * | 2016-09-26 | 2018-04-03 | 中国石油化工股份有限公司 | Prepare the catalyst of cyclohexyl benzene |
| CN107866269A (en) * | 2016-09-26 | 2018-04-03 | 中国石油化工股份有限公司 | Cyclohexyl benzene catalyst and preparation method thereof |
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| CN107866273A (en) * | 2016-09-26 | 2018-04-03 | 中国石油化工股份有限公司 | Cyclohexyl benzene catalyst for synthesizing |
| CN107866274A (en) * | 2016-09-26 | 2018-04-03 | 中国石油化工股份有限公司 | Cyclohexyl benzene production catalyst |
| CN107866270A (en) * | 2016-09-26 | 2018-04-03 | 中国石油化工股份有限公司 | Catalyst for cyclohexyl benzene synthesis |
| CN107866262A (en) * | 2016-09-26 | 2018-04-03 | 中国石油化工股份有限公司 | The catalyst of cyclohexyl benzene production |
| CN107866263A (en) * | 2016-09-26 | 2018-04-03 | 中国石油化工股份有限公司 | Suitable for cyclohexyl benzene production catalyst |
| CN107866266A (en) * | 2016-09-26 | 2018-04-03 | 中国石油化工股份有限公司 | Catalyst for cyclohexyl benzene production |
| CN107866271A (en) * | 2016-09-26 | 2018-04-03 | 中国石油化工股份有限公司 | Catalyst suitable for cyclohexyl benzene production |
| CN107866267A (en) * | 2016-09-26 | 2018-04-03 | 中国石油化工股份有限公司 | Catalyst for synthesizing cyclohexyl benzene |
| CN107866272A (en) * | 2016-09-26 | 2018-04-03 | 中国石油化工股份有限公司 | Prepare the catalyst of cyclohexyl benzene |
| CN107866269A (en) * | 2016-09-26 | 2018-04-03 | 中国石油化工股份有限公司 | Cyclohexyl benzene catalyst and preparation method thereof |
| 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 |
| CN107866272B (en) * | 2016-09-26 | 2019-11-08 | 中国石油化工股份有限公司 | Prepare the catalyst of cyclohexyl benzene |
| CN107866263B (en) * | 2016-09-26 | 2019-11-08 | 中国石油化工股份有限公司 | Suitable for cyclohexyl benzene production catalyst |
| 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 |
| CN107866274B (en) * | 2016-09-26 | 2019-12-10 | 中国石油化工股份有限公司 | Catalyst for producing cyclohexylbenzene |
| 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 |
| CN107866273B (en) * | 2016-09-26 | 2020-06-09 | 中国石油化工股份有限公司 | Catalyst for synthesizing 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 |
| CN107866266B (en) * | 2016-09-26 | 2020-07-07 | 中国石油化工股份有限公司 | Catalyst for production of cyclohexylbenzene |
| CN107866262B (en) * | 2016-09-26 | 2020-09-04 | 中国石油化工股份有限公司 | Catalyst for producing cyclohexylbenzene |
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