CN107930680B - Catalyst suitable for cyclohexylbenzene production and preparation method thereof - Google Patents

Catalyst suitable for cyclohexylbenzene production and preparation method thereof Download PDF

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CN107930680B
CN107930680B CN201610894497.5A CN201610894497A CN107930680B CN 107930680 B CN107930680 B CN 107930680B CN 201610894497 A CN201610894497 A CN 201610894497A CN 107930680 B CN107930680 B CN 107930680B
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catalyst
molecular sieve
cyclohexylbenzene
benzene
zeolite molecular
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CN107930680A (en
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韩亚梅
王德举
刘仲能
唐之勤
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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    • 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
    • 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
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
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    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina
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    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/46—Ruthenium, rhodium, osmium or iridium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
    • C07C2529/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65 containing iron group metals, noble metals or copper
    • C07C2529/74—Noble metals

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Abstract

The invention relates to a catalyst suitable for producing cyclohexylbenzene, a preparation method thereof and a method for synthesizing cyclohexylbenzene by a benzene hydroalkylation one-step method, and mainly solves the technical problems that a catalyst in the prior art causes high yield of cyclohexane serving as a byproduct in a reaction and low yield of cyclohexylbenzene serving as a main product. The invention adopts a catalyst suitable for producing cyclohexylbenzene, which comprises a carrier and an active component loaded on the carrier; the active component comprises a noble metal and aluminum; the noble metal comprises at least one selected from rhodium and ruthenium; the technical scheme that the carrier is selected from a hydrogen type zeolite molecular sieve obtains better effect, and can be used for preparing cyclohexylbenzene by a benzene hydroalkylation one-step method.

Description

Catalyst suitable for cyclohexylbenzene production and preparation method thereof
Technical Field
The invention relates to a catalyst suitable for producing cyclohexylbenzene, a preparation method thereof and a method for synthesizing cyclohexylbenzene by a benzene hydroalkylation one-step method.
Background
The cyclohexylbenzene is an important intermediate and is widely applied to the fields of liquid crystal, plastics, coatings, adhesives and the like. The cyclohexylbenzene liquid crystal has the characteristics of extremely high chemical stability, photochemical stability, low viscosity, excellent physical properties and the like, and is one of ideal materials of display devices. The cyclohexylbenzene is used as an additive of the lithium ion battery electrolyte, has the overcharge prevention performance and can improve the safety performance of the battery. In addition, phenol and cyclohexanone can be prepared through the peroxidation and decomposition reaction processes of cyclohexylbenzene, and the method is used for producing a large amount of chemical raw materials such as phenolic resin, caprolactam, nylon and the like and has a good application prospect. The basic information for cyclohexylbenzene is as follows: colorless liquid with CAS number 827-52-1 and molecular weight of C12H16Density 0.95g/cm3The boiling point is 238-240 ℃, the melting point is 5 ℃, and the flash point is 98 ℃.
The preparation method of the cyclohexylbenzene comprises the following steps: biphenyl selective hydrogenation, benzene and cyclohexene alkylation, and benzene hydrogenation alkylation. Wherein, the reaction principle of preparing the cyclohexylbenzene by benzene hydroalkylation is as follows (formula 1): according to the reaction mechanism of benzene hydrogenation alkylation, benzene is subjected to hydrogenation reaction on a metal center, so that cyclohexene can be selectively generated, and part of cyclohexane and cyclohexadiene are generated at the same time; cyclohexene and cyclohexadiene undergo alkylation with benzene on an acidic center to produce cyclohexylbenzene as a main product. Therefore, the benzene hydroalkylation can be realized to produce the cyclohexylbenzene by adopting the bi-component catalyst with the hydrogenation function and the alkylation function.
Figure GDA0001216289480000011
The first study on the hydroalkylation of benzene to produce cyclohexylbenzene began in the seventies and eighties of the 20 th century. The catalyst developed in the early stage has the problem of low selectivity of cyclohexylbenzene, for example, a catalyst loaded with hydrogenation metal is developed by ExxonMobil company based on MCM-22 series molecular sieves (U.S. Pat. No. 5,2011/0015457A 1, U.S. Pat. No. 3,2011/0021841A 1) and is used for preparing cyclohexylbenzene by benzene hydroalkylation, and the selectivity of the technology to byproduct cyclohexane is high. U.S. Pat. Nos. US4094918, US4219689 and US4329531 of Phillips oil company, USA, use Ni-rare earth treated zeolite catalyst and Pd as adjuvant, and both the conversion rate of benzene and the yield of CHB are low. The method has the problems of high yield of the cyclohexane as a byproduct and relatively low yield of the cyclohexylbenzene as a product in the process of preparing the cyclohexylbenzene.
Disclosure of Invention
One of the technical problems to be solved by the invention is the problems of high yield of the byproduct cyclohexane and low yield of the main product cyclohexylbenzene in the prior art, and provides a catalyst for producing the cyclohexylbenzene, which has the advantages of low yield of the cyclohexane and high yield of the cyclohexylbenzene when the catalyst is used for synthesizing the cyclohexylbenzene by the reaction of benzene and hydrogen.
The second technical problem to be solved by the present invention is a method for preparing the catalyst.
The invention also provides a synthesis method of cyclohexylbenzene by using the catalyst.
In order to solve one of the above technical problems, the technical solution of the present invention is as follows:
a catalyst suitable for cyclohexylbenzene production, the catalyst comprising a support and an active component supported on the support; the active component comprises a noble metal and aluminum; the noble metal comprises at least one selected from rhodium and ruthenium; the carrier is selected from hydrogen type zeolite molecular sieve.
In the technical scheme, the content of the noble metal is preferably 0.5-20 g/L.
In the technical scheme, the content of aluminum is preferably 1-25 g/L.
In the above technical scheme, the hydrogen type zeolite molecular sieve is preferably selected from BEA, MOR or MWW zeolite molecular sieves.
In the above technical solution, the hydrogen type zeolite molecular sieve is preferably a binder-free molded zeolite molecular sieve.
The invention uses aluminum to replace part of noble metal, which saves the consumption of noble metal.
In the above technical solution, it is more preferable that the noble metal comprises rhodium and ruthenium, and at this time, the noble metal and aluminum have a significant synergistic effect in improving the yield of CHB, and we find that neither rhodium alone nor ruthenium and aluminum alone have a synergistic effect.
As long as rhodium and ruthenium are simultaneously present in the catalyst, the specific ratio of each of rhodium and ruthenium is not particularly limited and both have synergistic effects in the same ratio, for example but not limited to the active components in the catalyst including:
the rhodium content is as follows: 0.5-20 g/L; the content of ruthenium is: 0.5-20 g/L; the content of aluminum is: 1-25 g/L.
In the above technical solution, the mole ratio of silica/alumina of the hydrogen-type zeolite molecular sieve is preferably 10 to 100, for example, but not limited to, 20, 30, 40, 50, 60, 70, 80, 90, and the like.
To solve the second technical problem, the technical solution of the present invention is as follows:
a process for preparing a catalyst as claimed in any one of claims 1 to 6, comprising the steps of:
(1) mixing solutions of desired amounts of Rh compound, Ru compound and Al compound with the hydrogen-form zeolite molecular sieve;
(2) standing and drying;
(3) and roasting in an air atmosphere to obtain the catalyst.
In the above technical solution, the drying process conditions are not particularly limited, for example, but not limited to, the drying temperature is 70-120 ℃ (for non-limiting example, within this range, 80 ℃, 90 ℃, 100 ℃, 110 ℃, etc.), and the drying time is, for example, but not limited to, at least 6 hours, for example, 6-14 hours (for non-limiting example, within this range, 7, 8, 9, 10, 11, 12, etc.); the roasting temperature is preferably 350-550 ℃, and the roasting time is preferably 3-6 hours.
In the above technical solution, the Rh-containing compound in step (1) is preferably at least one selected from rhodium nitrate, rhodium chloride, and rhodium sulfate.
In the above technical solution, the Ru-containing compound in the step (1) is preferably at least one selected from ruthenium sulfate, ruthenium chloride and ruthenium nitrate.
In the above technical solution, the Al-containing compound in step (1) is preferably at least one selected from aluminum sulfate, aluminum nitrate, and aluminum chloride.
In the technical scheme, the solvent adopted in the solution in the step (1) can be water and is adjusted to pH 3-6.5 by hydrochloric acid or nitric acid or acetic acid, and in order to facilitate the same proportion, the examples and comparative examples in the specific implementation mode of the invention are both adjusted to pH 6 by water and acetic acid.
To solve the third technical problem, the technical scheme of the invention is as follows: the synthesis method of the cyclohexylbenzene takes benzene and hydrogen as reaction raw materials, and the reaction raw materials are contacted with the catalyst in any technical scheme of the technical problem to carry out benzene hydroalkylation reaction to generate the cyclohexylbenzene.
In the technical scheme, the reaction temperature is preferably 100-200 ℃, and more preferably 120-180 ℃.
In the above technical scheme, the molar ratio of benzene to hydrogen in the reaction raw material is preferably 0.5 to 2.0, and more preferably 0.5 to 1.3.
In the above-mentioned technical means, the pressure of the reaction is preferably 0.5 to 5.0MPa (gauge pressure), and more preferably 0.5 to 4.0MPa (gauge pressure).
In the technical scheme, the liquid volume of the reaction raw material benzene is preferably 0.2-3 h-1More preferably 0.2 to 1.5 hours-1。
The catalyst of the invention adopts Rh, Ru and Al as active components, thus reducing the yield of cyclohexane as a byproduct, and obviously improving the yield of the target product CHB under the condition of simultaneously comprising Rh, Ru and Al. At the reaction temperature of 150 ℃, the molar ratio of benzene to hydrogen of 0.8, the pressure of 2.0MPa and the mass space velocity of benzene of 0.5h-1Under the conditions, the yield of the cyclohexane can reach below 5.0 percent, the yield of the cyclohexylbenzene can reach up to 30 percent, and a better technical effect is achieved. The invention is further illustrated by the following examples.
Detailed Description
[ COMPARATIVE EXAMPLE 1 ]
Preparing a catalyst: weighing RhCl containing 1.0g Rh3·3H2Dissolving O in 1mol/L acetic acid water solution to prepare 80g of solution; measuring 0.1L of binderless cylindrical hydrogen type BEA zeolite molecular sieve (the molar ratio of silicon dioxide/aluminum oxide is 30) with the diameter of 1mm and the length of 5 mm; loading the solution on a hydrogen type BEA zeolite molecular sieve, soaking for 12h at room temperature, drying for 12h at 100 ℃, and roasting for 4h at 450 ℃ to obtain the required catalyst.
Evaluation of catalyst: 10ml of the catalyst was charged into a fixed bed reactor, and activity evaluation was performed after reduction activation under the following conditions: the reaction temperature is 150 ℃, the molar ratio of benzene to hydrogen in the reaction raw material is 0.8, the reaction pressure is 2.0MPa (gauge pressure), and the liquid volume space velocity of the reaction raw material benzene is 0.5h-1。
The Rh content of the catalyst was 10 g/L. The benzene conversion was calculated to be 70.25%, the yield of CH was 4.43%, and the yield of CHB was 26.08%, and the composition of the catalyst and the evaluation results are shown in Table 1 for convenience of illustration and comparison.
[ COMPARATIVE EXAMPLE 2 ]
Preparing a catalyst: weighing RuCl containing 1.0g Ru3·3H2O solutionPreparing 80g of solution in 1mol/L acetic acid aqueous solution; measuring 0.1L of binderless cylindrical hydrogen type BEA zeolite molecular sieve (the molar ratio of silicon dioxide/aluminum oxide is 30) with the diameter of 1mm and the length of 5 mm; loading the solution on a hydrogen type BEA zeolite molecular sieve, soaking for 12h at room temperature, drying for 12h at 100 ℃, and roasting for 4h at 450 ℃ to obtain the required catalyst.
Evaluation of catalyst: 10ml of the catalyst was charged into a fixed bed reactor, and activity evaluation was performed after reduction activation under the following conditions: the reaction temperature is 150 ℃, the molar ratio of benzene to hydrogen in the reaction raw material is 0.8, the reaction pressure is 2.0MPa (gauge pressure), and the liquid volume space velocity of the reaction raw material benzene is 0.5h-1。
The Ru content of the catalyst was 10 g/L. The benzene conversion was calculated to be 70.63%, the yield of CH was 4.76%, and the yield of CHB was 25.67%, and the composition of the catalyst and the results of the evaluations are shown in Table 1 for ease of illustration and comparison.
[ COMPARATIVE EXAMPLE 3 ]
Preparing a catalyst: al (NO) containing 1.0g of Al is weighed3)3·9H2Dissolving O in 1mol/L acetic acid water solution to prepare 80g of solution; measuring 0.1L of binderless cylindrical hydrogen type BEA zeolite molecular sieve (the molar ratio of silicon dioxide/aluminum oxide is 30) with the diameter of 1mm and the length of 5 mm; loading the solution on a hydrogen type BEA zeolite molecular sieve, soaking for 12h at room temperature, drying for 12h at 100 ℃, and roasting for 4h at 450 ℃ to obtain the required catalyst.
Evaluation of catalyst: 10ml of the catalyst was charged into a fixed bed reactor, and activity evaluation was performed after reduction activation under the following conditions: the reaction temperature is 150 ℃, the molar ratio of benzene to hydrogen in the reaction raw material is 0.8, the reaction pressure is 2.0MPa (gauge pressure), and the liquid volume space velocity of the reaction raw material benzene is 0.5h-1。
The Al content of the catalyst was 10 g/L. The calculated benzene conversion was 0%, the yield of CH was 0%, and the yield of CHB was 0%, and the composition of the catalyst and the evaluation results are shown in table 1 for convenience of illustration and comparison.
[ COMPARATIVE EXAMPLE 4 ]
Preparing a catalyst: separately weighing RhCl containing 0.5g Rh3·3H2O and RuCl containing 0.5g Ru3·3H2Dissolving O in 1mol/L acetic acid water solution to prepare 80g of solution; measuring 0.1L of binderless cylindrical hydrogen type BEA zeolite molecular sieve (the molar ratio of silicon dioxide/aluminum oxide is 30) with the diameter of 1mm and the length of 5 mm; loading the solution on a hydrogen type BEA zeolite molecular sieve, soaking for 12h at room temperature, drying for 12h at 100 ℃, and roasting for 4h at 450 ℃ to obtain the required catalyst.
Evaluation of catalyst: 10ml of the catalyst was charged into a fixed bed reactor, and activity evaluation was performed after reduction activation under the following conditions: the reaction temperature is 150 ℃, the molar ratio of benzene to hydrogen in the reaction raw material is 0.8, the reaction pressure is 2.0MPa (gauge pressure), and the liquid volume space velocity of the reaction raw material benzene is 0.5h-1。
The Rh content of the catalyst was 5g/L, and the Ru content was 5 g/L. The benzene conversion was calculated to be 47.84%, the yield of CH was 1.75%, and the yield of CHB was 27.04%, and the composition of the catalyst and the evaluation results are shown in Table 1 for convenience of illustration and comparison.
[ example 1 ]
Preparing a catalyst: separately weighing RhCl containing 0.8g Rh3·3H2O and Al (NO) containing 0.2g of Al3)3·9H2Dissolving O in 1mol/L acetic acid water solution to prepare 80g of solution I; measuring 0.1L of binderless cylindrical hydrogen type BEA zeolite molecular sieve (the molar ratio of silicon dioxide/aluminum oxide is 30) with the diameter of 1mm and the length of 5 mm; loading the solution on a hydrogen type BEA zeolite molecular sieve, soaking for 12h at room temperature, drying for 12h at 100 ℃, and roasting for 4h at 450 ℃ to obtain the required catalyst.
Evaluation of catalyst: 10ml of the catalyst was charged into a fixed bed reactor, and activity evaluation was performed after reduction activation under the following conditions: the reaction temperature is 150 ℃, the molar ratio of benzene to hydrogen in the reaction raw material is 0.8, the reaction pressure is 2.0MPa (gauge pressure), and the liquid volume space velocity of the reaction raw material benzene is 0.5h-1。
The Rh content of the catalyst was 8g/L and the Al content was 2 g/L. The benzene conversion was calculated to be 45.75%, the yield of CH was 2.58%, and the yield of CHB was 20.97%, and the composition of the catalyst and the evaluation results are shown in table 1 for ease of illustration and comparison.
[ example 2 ]
Preparing a catalyst: weighing RuCl containing 0.8g Ru3·3H2O and Al (NO) containing 0.2g of Al3)3·9H2Dissolving O in 1mol/L acetic acid water solution to prepare 80g of solution I; measuring 0.1L of binderless cylindrical hydrogen type BEA zeolite molecular sieve (the molar ratio of silicon dioxide/aluminum oxide is 30) with the diameter of 1mm and the length of 5 mm; loading the solution on a hydrogen type BEA zeolite molecular sieve, soaking for 12h at room temperature, drying for 12h at 100 ℃, and roasting for 4h at 450 ℃ to obtain the required catalyst.
Evaluation of catalyst: 10ml of the catalyst was charged into a fixed bed reactor, and activity evaluation was performed after reduction activation under the following conditions: the reaction temperature is 150 ℃, the molar ratio of benzene to hydrogen in the reaction raw material is 0.8, the reaction pressure is 2.0MPa (gauge pressure), and the liquid volume space velocity of the reaction raw material benzene is 0.5h-1。
The catalyst has a Ru content of 8g/L and an Al content of 2 g/L. The benzene conversion was calculated to be 46.34%, the yield of CH was 2.43%, and the yield of CHB was 21.16%, and the composition of the catalyst and the evaluation results are shown in table 1 for convenience of illustration and comparison.
[ example 3 ]
Preparing a catalyst: separately weighing RhCl containing 0.2g Rh3·3H2O, RuCl containing 0.6g Ru3·3H2O and Al (NO) containing 0.2g of Al3)3·9H2Dissolving O in 1mol/L acetic acid water solution to prepare 80g of solution; measuring 0.1L of binderless cylindrical hydrogen type BEA zeolite molecular sieve (the molar ratio of silicon dioxide/aluminum oxide is 30) with the diameter of 1mm and the length of 5 mm; loading the solution on a hydrogen type BEA zeolite molecular sieve, soaking for 12h at room temperature, drying for 12h at 100 ℃, and roasting for 4h at 450 ℃ to obtain the required catalyst.
Evaluation of catalyst: 10ml of the catalyst was charged into a fixed bed reactor, and activity evaluation was performed after reduction activation under the following conditions: the reaction temperature was 150 ℃, the molar ratio of benzene to hydrogen in the reaction raw material was 0.8, the reaction pressure was 2.0MPa (gauge pressure), and the liquid volume of the reaction raw material benzeneThe space velocity is 0.5h-1。
The catalyst has Rh content of 2g/L, Ru content of 6g/L and Al content of 2 g/L. The benzene conversion was calculated to be 51.33%, the yield of CH was 1.86%, and the yield of CHB was 29.07%, and the composition of the catalyst and the evaluation results are shown in table 1 for convenience of illustration and comparison.
[ example 4 ]
Preparing a catalyst: separately weighing RhCl containing 0.3g Rh3·3H2O, RuCl containing 0.5g Ru3·3H2O and Al (NO) containing 0.2g of Al3)3·9H2Dissolving O in 1mol/L acetic acid water solution to prepare 80g of solution; measuring 0.1L of binderless cylindrical hydrogen type BEA zeolite molecular sieve (the molar ratio of silicon dioxide/aluminum oxide is 30) with the diameter of 1mm and the length of 5 mm; loading the solution on a hydrogen type BEA zeolite molecular sieve, soaking for 12h at room temperature, drying for 12h at 100 ℃, and roasting for 4h at 450 ℃ to obtain the required catalyst.
Evaluation of catalyst: 10ml of the catalyst was charged into a fixed bed reactor, and activity evaluation was performed after reduction activation under the following conditions: the reaction temperature is 150 ℃, the molar ratio of benzene to hydrogen in the reaction raw material is 0.8, the reaction pressure is 2.0MPa (gauge pressure), and the liquid volume space velocity of the reaction raw material benzene is 0.5h-1。
The catalyst has Rh content of 3g/L, Ru content of 5g/L and Al content of 2 g/L. The benzene conversion was calculated to be 51.54%, the yield of CH was 1.68%, and the yield of CHB was 29.75%, and the composition of the catalyst and the results of the evaluations are shown in Table 1 for ease of illustration and comparison.
[ example 5 ]
Preparing a catalyst: separately weighing RhCl containing 0.4g Rh3·3H2O, RuCl containing 0.4g Ru3·3H2O and Al (NO) containing 0.2g of Al3)3·9H2Dissolving O in 1mol/L acetic acid water solution to prepare 80g of solution; measuring 0.1L of binderless cylindrical hydrogen type BEA zeolite molecular sieve (the molar ratio of silicon dioxide/aluminum oxide is 30) with the diameter of 1mm and the length of 5 mm; loading the above solution on hydrogen type BEA zeolite molecular sieve, soaking at room temperature for 12h, drying at 100 deg.C for 12h, and calcining at 450 deg.C for 4h to obtain the final productPreparing the needed catalyst.
Evaluation of catalyst: 10ml of the catalyst was charged into a fixed bed reactor, and activity evaluation was performed after reduction activation under the following conditions: the reaction temperature is 150 ℃, the molar ratio of benzene to hydrogen in the reaction raw material is 0.8, the reaction pressure is 2.0MPa (gauge pressure), and the liquid volume space velocity of the reaction raw material benzene is 0.5h-1。
The catalyst has Rh content of 4g/L, Ru content of 4g/L and Al content of 2 g/L. The benzene conversion was calculated to be 52.24%, the yield of CH was 1.50%, and the yield of CHB was 30.19%, and the composition of the catalyst and the evaluation results are shown in Table 1 for convenience of illustration and comparison.
[ example 6 ]
Preparing a catalyst: separately weighing RhCl containing 0.5g Rh3·3H2O, RuCl containing 0.3g Ru3·3H2O and Al (NO) containing 0.2g of Al3)3·9H2Dissolving O in 1mol/L acetic acid water solution to prepare 80g of solution; measuring 0.1L of binderless cylindrical hydrogen type BEA zeolite molecular sieve (the molar ratio of silicon dioxide/aluminum oxide is 30) with the diameter of 1mm and the length of 5 mm; loading the solution on a hydrogen type BEA zeolite molecular sieve, soaking for 12h at room temperature, drying for 12h at 100 ℃, and roasting for 4h at 450 ℃ to obtain the required catalyst.
Evaluation of catalyst: 10ml of the catalyst was charged into a fixed bed reactor, and activity evaluation was performed after reduction activation under the following conditions: the reaction temperature is 150 ℃, the molar ratio of benzene to hydrogen in the reaction raw material is 0.8, the reaction pressure is 2.0MPa (gauge pressure), and the liquid volume space velocity of the reaction raw material benzene is 0.5h-1。
The catalyst has Rh content of 5g/L, Ru content of 3g/L and Al content of 2 g/L. The benzene conversion was calculated to be 52.05%, the yield of CH was 1.64%, and the yield of CHB was 29.34%, and the composition of the catalyst and the evaluation results are shown in Table 1 for ease of illustration and comparison.
[ example 7 ]
Preparing a catalyst: separately weighing RhCl containing 0.6g Rh3·3H2O, RuCl containing 0.2g Ru3·3H2O and Al (NO) containing 0.2g of Al3)3·9H2Dissolving O in 1mol/L acetic acid water solution to prepare 80g of solution; measuring 0.1L of binderless cylindrical hydrogen type BEA zeolite molecular sieve (the molar ratio of silicon dioxide/aluminum oxide is 30) with the diameter of 1mm and the length of 5 mm; loading the solution on a hydrogen type BEA zeolite molecular sieve, soaking for 12h at room temperature, drying for 12h at 100 ℃, and roasting for 4h at 450 ℃ to obtain the required catalyst.
Evaluation of catalyst: 10ml of the catalyst was charged into a fixed bed reactor, and activity evaluation was performed after reduction activation under the following conditions: the reaction temperature is 150 ℃, the molar ratio of benzene to hydrogen in the reaction raw material is 0.8, the reaction pressure is 2.0MPa (gauge pressure), and the liquid volume space velocity of the reaction raw material benzene is 0.5h-1。
The catalyst has Rh content of 6g/L, Ru content of 2g/L and Al content of 2 g/L. The benzene conversion was calculated to be 51.57%, the yield of CH was 1.74%, and the yield of CHB was 28.68%, and the composition of the catalyst and the evaluation results are shown in table 1 for ease of illustration and comparison.
[ example 8 ]
Preparing a catalyst: separately weighing RhCl containing 0.5g Rh3·3H2O, RuCl containing 1.0g Ru3·3H2O and Al (NO) containing 1.5g of Al3)3·9H2Dissolving O in 1mol/L acetic acid water solution to prepare 80g of solution; measuring 0.1L of binderless cylindrical hydrogen type BEA zeolite molecular sieve (the molar ratio of silicon dioxide/aluminum oxide is 30) with the diameter of 1mm and the length of 5 mm; loading the solution on a hydrogen type BEA zeolite molecular sieve, soaking for 12h at room temperature, drying for 12h at 100 ℃, and roasting for 4h at 450 ℃ to obtain the required catalyst.
Evaluation of catalyst: 10ml of the catalyst was charged into a fixed bed reactor, and activity evaluation was performed after reduction activation under the following conditions: the reaction temperature is 100 ℃, the molar ratio of benzene to hydrogen in the reaction raw material is 0.5, the reaction pressure is 0.5MPa (gauge pressure), and the liquid volume space velocity of the reaction raw material is 0.2h-1。
The catalyst has Rh content of 5g/L, Ru content of 10g/L and Al content of 15 g/L. The benzene conversion was calculated to be 45.46%, the yield of CH was 2.25%, and the yield of CHB was calculated to be 22.24%, and the composition of the catalyst and the evaluation results are shown in Table 1 for convenience of illustration and comparison.
[ example 9 ]
Preparing a catalyst: separately weighing RhCl containing 0.1g Rh3·3H2O, RuCl containing 0.3g Ru3·3H2O and Al (NO) containing 0.1g of Al3)3·9H2Dissolving O in 1mol/L acetic acid water solution to prepare 80g of solution; measuring 0.1L of binderless cylindrical hydrogen type BEA zeolite molecular sieve (the molar ratio of silicon dioxide/aluminum oxide is 30) with the diameter of 1mm and the length of 5 mm; loading the solution on a hydrogen type BEA zeolite molecular sieve, soaking for 12h at room temperature, drying for 12h at 100 ℃, and roasting for 4h at 450 ℃ to obtain the required catalyst.
Evaluation of catalyst: 10ml of the catalyst was charged into a fixed bed reactor, and activity evaluation was performed after reduction activation under the following conditions: the reaction temperature is 200 ℃, the molar ratio of benzene to hydrogen in the reaction raw material is 2.0, the reaction pressure is 3.0MPa (gauge pressure), and the liquid volume space velocity of the reaction raw material is 2.0h-1。
The catalyst has Rh content of 1g/L, Ru content of 3g/L and Al content of 1 g/L. The benzene conversion was calculated to be 35.24%, the yield of CH was 1.64%, and the yield of CHB was 18.04%, and the composition of the catalyst and the evaluation results are shown in table 1 for ease of illustration and comparison.
TABLE 1 catalyst composition and evaluation results
Figure GDA0001216289480000091
Note: in table 1, CH represents cyclohexane, and CHB represents cyclohexylbenzene.

Claims (9)

1. A method for synthesizing cyclohexylbenzene comprises the steps of taking benzene and hydrogen as reaction raw materials, enabling the reaction raw materials to contact with a catalyst to carry out benzene hydroalkylation reaction to generate cyclohexylbenzene, wherein the catalyst comprises a carrier and an active component loaded on the carrier; the active component comprises a noble metal and aluminum; the noble metal comprises both rhodium and ruthenium; the carrier is selected from hydrogen type zeolite molecular sieve.
2. The synthesis method according to claim 1, wherein the noble metal content is 0.5-20 g/L.
3. The synthesis method according to claim 1, wherein the aluminum content is 1-25 g/L.
4. The synthesis process according to claim 1, characterized in that the zeolitic molecular sieve is selected from the group consisting of BEA, MOR or MWW zeolitic molecular sieves.
5. The synthesis method according to claim 4, wherein the hydrogen form zeolite molecular sieve is a binderless formed zeolite molecular sieve.
6. A synthesis method according to claim 4, characterized in that the silica/alumina molar ratio of the hydrogen-form zeolite molecular sieve is 10-100.
7. A synthesis process according to any one of claims 1 to 6, characterised in that the catalyst is prepared by a process comprising the steps of:
(1) mixing solutions of desired amounts of Rh compound, Ru compound and Al compound with the hydrogen-form zeolite molecular sieve;
(2) standing and drying;
(3) and roasting in an air atmosphere to obtain the catalyst.
8. The synthesis method according to claim 1, wherein the reaction temperature is 100-200 ℃.
9. The synthesis method according to claim 1, wherein the liquid volume space velocity of the reaction raw material benzene is 0.2-3 h-1。
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CN103521268A (en) * 2012-07-03 2014-01-22 中国科学院大连化学物理研究所 Heterogeneous catalysts for alkene hydroformylation reaction and preparation method thereof
CN103599812A (en) * 2013-12-04 2014-02-26 淮南师范学院 Composite pore zeolite molecular sieve loaded noble metal hydrodesulfurization catalyst and preparation method thereof
CN105233862A (en) * 2014-07-11 2016-01-13 中国石油化工股份有限公司 Cyclohexyl benzene catalyst and preparation method therefor

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103521268A (en) * 2012-07-03 2014-01-22 中国科学院大连化学物理研究所 Heterogeneous catalysts for alkene hydroformylation reaction and preparation method thereof
CN103599812A (en) * 2013-12-04 2014-02-26 淮南师范学院 Composite pore zeolite molecular sieve loaded noble metal hydrodesulfurization catalyst and preparation method thereof
CN105233862A (en) * 2014-07-11 2016-01-13 中国石油化工股份有限公司 Cyclohexyl benzene catalyst and preparation method therefor

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