CN107930679A - Catalyst for cyclohexyl benzene production and preparation method thereof - Google Patents
Catalyst for cyclohexyl benzene production and preparation method thereof Download PDFInfo
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- CN107930679A CN107930679A CN201610892399.8A CN201610892399A CN107930679A CN 107930679 A CN107930679 A CN 107930679A CN 201610892399 A CN201610892399 A CN 201610892399A CN 107930679 A CN107930679 A CN 107930679A
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7415—Zeolite Beta
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/74—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition with simultaneous hydrogenation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- 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
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Abstract
The present invention relates to the method for catalyst produced for cyclohexyl benzene and preparation method thereof and benzene hydrogenation alkylation one-step synthesis method cyclohexyl benzene, mainly solves catalyst of the prior art and causes by-product cyclic hexane high income and the low technical problem of principal product cyclohexyl benzene yield in reaction.The present invention includes carrier and the active component being carried on carrier by using the catalyst produced for cyclohexyl benzene, the catalyst;The active component includes noble metal and molybdenum;The noble metal includes being selected from least one of platinum and ruthenium;The technical solution that the carrier is selected from h-type zeolite molecular sieve achieves preferable effect, and cyclohexyl benzene is prepared available for benzene hydrogenation alkylation one-step method.
Description
Technical field
The present invention relates to catalyst produced for cyclohexyl benzene and preparation method thereof and benzene hydrogenation alkylation 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, has 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):According to the alkylated reaction machine of 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.
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 there are cyclohexyl benzene it is selectively relatively low the problem of, as ExxonMobil companies be based on MCM-22 Series Molecules sieve develop load
The catalyst (US2011/0015457A1, US2011/0021841A1) of hydrogenation metal, hexamethylene is prepared for benzene hydrogenation alkylation
Base benzene, high selectivity of this technology to by-product cyclic hexane.The patent US4094918 of Phillips oil companies of the U.S.,
US4219689 and US4329531, using the zeolite catalyst through Ni- rare earth treatment, and using Pd as auxiliary agent, the conversion ratio of benzene and
The yield of CHB is all than relatively low.High income and production of the above method during cyclohexyl benzene is prepared there are by-product cyclic hexane
The yield of thing cyclohexyl benzene than it is relatively low the problem of.
The content of the invention
The first technical problem to be solved by the present invention is the high income and main product of by-product cyclic hexane of the prior art
The problem of yield of thing cyclohexyl benzene is low, there is provided suitable for cyclohexyl benzene production catalyst, use it for benzene and hydrogen reaction is closed
Have the advantages that hexamethylene yield is low and cyclohexyl benzene high income during into cyclohexyl benzene.
The second technical problem to be solved by the present invention is the preparation method of one of above-mentioned technical problem catalyst.
The third technical problem to be solved by the present invention is the cyclohexyl using one of the above-mentioned technical problem catalyst
The synthetic method of benzene.
To solve one of above-mentioned technical problem, technical scheme is as follows:
For the catalyst of cyclohexyl benzene production, the catalyst includes carrier and the active component being carried on carrier;
The active component includes noble metal and molybdenum;The noble metal includes being selected from least one of platinum and ruthenium;The carrier choosing
From h-type zeolite molecular sieve.
In above-mentioned technical proposal, bullion content is preferably 0.5~20g/L.
In above-mentioned technical proposal, the content of molybdenum is preferably 1~25g/L.
In above-mentioned technical proposal, the h-type zeolite molecular sieve preferably is selected from BEA, MOR or MWW zeolite molecular sieve.
In above-mentioned technical proposal, the h-type zeolite molecular sieve is preferably binder free moulded zeolite molecular sieve.
The present invention has saved the dosage of noble metal with molybdenum replacement part noble metal.
More preferably described noble metal includes platinum and ruthenium at the same time in above-mentioned technical proposal, and noble metal is improving CHB with molybdenum at this time
Yield in terms of there is obvious synergy, and we have found that single platinum or single ruthenium do not cooperate with effect with molybdenum
Fruit.
As long as platinum and ruthenium are present in the catalyst at the same time, each specific ratio is not particularly limited for platinum and ruthenium, has
There is year-on-year synergy, such as, but not limited to active component includes in the catalyst:
The content of platinum is:0.5~20g/L;The content of ruthenium is:0.5~20g/L;The content of molybdenum is:1~25g/L.
In above-mentioned technical proposal, the molar ratio of silica/molybdenum oxide of the h-type zeolite molecular sieve is preferably 10
~100, such as, but not limited to 20,30,40,50,60,70,80,90 etc..
To solve the two of above-mentioned technical problem, technical scheme is as follows:
The preparation method of catalyst any one of claim 1~6, comprises the following steps:
(1) by the solution of the compound of the compound of aequum Pt, the compound of Ru and Mo and the h-type zeolite molecule
Sieve mixing;
(2) it is dry after standing;
(3) roasted in air atmosphere, obtain the catalyst.
In above-mentioned technical proposal, dry process conditions are not particularly limited, and the temperature 70 such as, but not limited to dried~
120 DEG C (80 DEG C, 90 DEG C, 100 DEG C, 110 DEG C etc. of non limiting example within this range), the dry time is such as, but not limited to
When at least six is small, for example, 6~14 it is small when (non limiting example 7,8,9,10,11,12 etc. within this range);The temperature of roasting
Degree is preferably 350~550 DEG C, when the time of roasting is preferably 3~6 small.
In above-mentioned technical proposal, the compound containing Pt described in step (1) preferably is selected from platinum nitrate, platinum chloride, platinic sulfate
It is at least one.
In above-mentioned technical proposal, the compound containing Ru described in step (1) preferably is selected from ruthenium sulfate, ruthenic chloride, nitric acid ruthenium
It is at least one.
In above-mentioned technical proposal, the compound containing Mo described in step (1) preferably is selected from ammonium molybdate, nitric acid molybdenum, molybdenum chloride
It is at least one.
In above-mentioned technical proposal, solution described in step (1) use the optional water of solvent and by hydrochloric acid or nitric acid or acetic acid
It is 3~6.5 to be tuned into pH, and for ease of year-on-year, embodiment and comparative example in the specific embodiment of the invention with water and use acetic acid
PH is transferred to as 6.
To solve the three of above-mentioned technical problem, technical scheme is as follows: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 solution 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, the molar ratio of benzene and hydrogen is preferably 0.5~2.0 in reaction raw materials, more preferably 0.5~
1.3。
In above-mentioned technical proposal, the pressure of reaction is preferably 0.5~5.0MPa (gauge pressure), more preferably 0.5~4.0MPa
(gauge pressure).
In above-mentioned technical proposal, the liquid volume of reaction raw materials benzene is preferably 0.2~3h-1, more preferably 0.2~1.5h-1。
The catalyst of the present invention is active constituent as a result of Pt, Ru and Mo, reduces the yield of by-product cyclic hexane,
In the case of including Pt, Ru and Mo at the same time, the yield of target product CHB is also significantly improved.In 150 DEG C of reaction temperature, benzene
With hydrogen molar ratio 0.8, pressure 2.0MPa, the mass space velocity 0.5h of benzene-1Under conditions of, the yield of hexamethylene up to 5.0% with
Under, cyclohexyl benzene high income achieves preferable technique effect up to 30%.The present invention is further explained below by embodiment
State.
Embodiment
【Comparative example 1】
Catalyst preparation:Weigh the PtCl of the Pt containing 1.0g2It is dissolved in 1mol/L aqueous acetic acids and is made into 80g solution;Measure
Binder free cylinder Hydrogen BEA zeolite molecular sieve (moles of silica/alumina of a diameter of 1mm of 0.1L, length 5mm
Than for 30);By on above-mentioned solution loadings to Hydrogen BEA zeolite molecular sieves, room temperature immersion 12h, 100 DEG C of dry 12h, 450 DEG C roast
4h is burnt, that is, required catalyst is prepared.
Evaluating catalyst:10ml Catalyst packings are taken to carry out activity rating, bar after reduction activation into fixed bed reactors
Part is as follows:The temperature of reaction is 150 DEG C, and the molar ratio of benzene and hydrogen is 0.8 in reaction raw materials, and the pressure of reaction is 2.0MPa
(gauge pressure), the liquid volume air speed of the benzene feedstock of reaction is 0.5h-1。
The Pt contents of the catalyst are 10g/L.It is 4.97%, CHB to be computed the yield that benzene conversion ratio is 72.56%, CH
Yield be 25.98%, for convenience of description and compare, the composition of catalyst and evaluation result be listed in table 1.
【Comparative example 2】
Catalyst preparation:Weigh the RuCl of the Ru containing 1.0g3·3H2O is dissolved in 1mol/L aqueous acetic acids that to be made into 80g molten
Liquid;Measure a diameter of 1mm of 0.1L, the binder free cylinder Hydrogen BEA zeolite molecular sieve (silica/aluminas of length 5mm
Molar ratio for 30);By on above-mentioned solution loadings to 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.
Evaluating catalyst:10ml Catalyst packings are taken to carry out activity rating, bar after reduction activation into fixed bed reactors
Part is as follows:The temperature of reaction is 150 DEG C, and the molar ratio of benzene and hydrogen is 0.8 in reaction raw materials, and the pressure of reaction is 2.0MPa
(gauge pressure), the liquid volume air speed of the benzene feedstock of reaction is 0.5h-1。
The Ru contents of the catalyst are 10g/L.It is 4.76%, CHB to be computed the yield that benzene conversion ratio is 70.63%, CH
Yield be 25.67%, for convenience of description and compare, the composition of catalyst and evaluation result be listed in table 1.
【Comparative example 3】
Catalyst preparation:The ammonium molybdate for weighing the Mo containing 1.0g is dissolved in 1mol/L aqueous acetic acids and is made into 80g solution;Amount
Take a diameter of 1mm of 0.1L, the binder free cylinder Hydrogen BEA zeolite molecular sieves of length 5mm (rub by silica/alumina
You are than for 30);By on above-mentioned solution loadings to Hydrogen BEA zeolite molecular sieves, room temperature immersion 12h, 100 DEG C of dry 12h, 450 DEG C
4h is roasted, that is, required catalyst is prepared.
Evaluating catalyst:10ml Catalyst packings are taken to carry out activity rating, bar after reduction activation into fixed bed reactors
Part is as follows:The temperature of reaction is 150 DEG C, and the molar ratio of benzene and hydrogen is 0.8 in reaction raw materials, and the pressure of reaction is 2.0MPa
(gauge pressure), the liquid volume air speed of the benzene feedstock of reaction is 0.5h-1。
The Mo contents of the catalyst are 10g/L.Being computed the yield that the yield that benzene conversion ratio is 0%, CH is 0%, CHB is
0%, for convenience of description and compare, the composition of catalyst and evaluation result are listed in table 1.
【Comparative example 4】
Catalyst preparation:The PtCl of the Pt containing 0.5g is weighed respectively2With the RuCl of the Ru containing 0.5g3·3H2O is dissolved in 1mol/L
80g solution is made into aqueous acetic acid;Measure a diameter of 1mm of 0.1L, the binder free cylinder Hydrogen BEA zeolites of length 5mm
Molecular sieve (molar ratio of silica/alumina is 30);By on above-mentioned solution loadings to Hydrogen BEA zeolite molecular sieves, room temperature
12h, 100 DEG C of dry 12h are impregnated, 450 DEG C of roasting 4h, that is, be prepared required catalyst.
Evaluating catalyst:10ml Catalyst packings are taken to carry out activity rating, bar after reduction activation into fixed bed reactors
Part is as follows:The temperature of reaction is 150 DEG C, and the molar ratio of benzene and hydrogen is 0.8 in reaction raw materials, and the pressure of reaction is 2.0MPa
(gauge pressure), the liquid volume air speed of the benzene feedstock of reaction is 0.5h-1。
The Pt contents of the catalyst are 5g/L, and Ru contents are 5g/L.It is computed the yield that benzene conversion ratio is 49.15%, CH
It is 27.01% for the yield of 1.92%, CHB, for convenience of description and compares, the composition of catalyst and evaluation result is listed in table
1。
【Embodiment 1】
Catalyst preparation:The PtCl of the Pt containing 0.8g is weighed respectively21mol/L acetic acid is dissolved in the ammonium molybdate of the Mo containing 0.2g
80g solution Is are made into aqueous solution;Measure a diameter of 1mm of 0.1L, the binder free cylinder Hydrogen BEA zeolite molecules of length 5mm
Sieve (molar ratio of silica/alumina is 30);By on above-mentioned solution loadings to 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.
Evaluating catalyst:10ml Catalyst packings are taken to carry out activity rating, bar after reduction activation into fixed bed reactors
Part is as follows:The temperature of reaction is 150 DEG C, and the molar ratio of benzene and hydrogen is 0.8 in reaction raw materials, and the pressure of reaction is 2.0MPa
(gauge pressure), the liquid volume air speed of the benzene feedstock of reaction is 0.5h-1。
The Pt contents of the catalyst are 8g/L, and Mo contents are 2g/L.It is computed the yield that benzene conversion ratio is 46.26%, CH
It is 20.38% for the yield of 2.51%, CHB, for convenience of description and compares, the composition of catalyst and evaluation result is listed in table
1。
【Embodiment 2】
Catalyst preparation:Weigh the RuCl of the Ru containing 0.8g3·3H2The ammonium molybdate of the O and Mo containing 0.2g is dissolved in 1mol/L acetic acid
80g solution Is are made into aqueous solution;Measure a diameter of 1mm of 0.1L, the binder free cylinder Hydrogen BEA zeolite molecules of length 5mm
Sieve (molar ratio of silica/alumina is 30);By on above-mentioned solution loadings to 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.
Evaluating catalyst:10ml Catalyst packings are taken to carry out activity rating, bar after reduction activation into fixed bed reactors
Part is as follows:The temperature of reaction is 150 DEG C, and the molar ratio of benzene and hydrogen is 0.8 in reaction raw materials, and the pressure of reaction is 2.0MPa
(gauge pressure), the liquid volume air speed of the benzene feedstock of reaction is 0.5h-1。
The Ru contents of the catalyst are 8g/L, and Mo contents are 2g/L.It is computed the yield that benzene conversion ratio is 46.58%, CH
It is 21.16% for the yield of 2.47%, CHB, for convenience of description and compares, the composition of catalyst and evaluation result is listed in table
1。
【Embodiment 3】
Catalyst preparation:The PtCl of the Pt containing 0.2g is weighed respectively2, the Ru containing 0.6g RuCl3·3H2O and Mo containing 0.2g
Ammonium molybdate be dissolved in 1mol/L aqueous acetic acids and be made into 80g solution;Measure a diameter of 1mm of 0.1L, the binder free of length 5mm
Cylindrical Hydrogen BEA zeolite molecular sieves (molar ratio of silica/alumina is 30);By above-mentioned solution loadings to Hydrogen BEA
On zeolite molecular sieve, room temperature immersion 12h, 100 DEG C of dry 12h, 450 DEG C of roasting 4h, that is, be prepared required catalyst.
Evaluating catalyst:10ml Catalyst packings are taken to carry out activity rating, bar after reduction activation into fixed bed reactors
Part is as follows:The temperature of reaction is 150 DEG C, and the molar ratio of benzene and hydrogen is 0.8 in reaction raw materials, and the pressure of reaction is 2.0MPa
(gauge pressure), the liquid volume air speed of the benzene feedstock of reaction is 0.5h-1。
The Pt contents of the catalyst are 2g/L, and Ru contents are 6g/L, and Mo contents are 2g/L.Being computed benzene conversion ratio is
The yield that the yield of 50.81%, CH are 1.85%, CHB is 29.04%, for convenience of description and is compared, by the composition of catalyst
Table 1 is listed in evaluation result.
【Embodiment 4】
Catalyst preparation:The PtCl of the Pt containing 0.3g is weighed respectively2, the Ru containing 0.5g RuCl3·3H2O and Mo containing 0.2g
Ammonium molybdate be dissolved in 1mol/L aqueous acetic acids and be made into 80g solution;Measure a diameter of 1mm of 0.1L, the binder free of length 5mm
Cylindrical Hydrogen BEA zeolite molecular sieves (molar ratio of silica/alumina is 30);By above-mentioned solution loadings to Hydrogen BEA
On zeolite molecular sieve, room temperature immersion 12h, 100 DEG C of dry 12h, 450 DEG C of roasting 4h, that is, be prepared required catalyst.
Evaluating catalyst:10ml Catalyst packings are taken to carry out activity rating, bar after reduction activation into fixed bed reactors
Part is as follows:The temperature of reaction is 150 DEG C, and the molar ratio of benzene and hydrogen is 0.8 in reaction raw materials, and the pressure of reaction is 2.0MPa
(gauge pressure), the liquid volume air speed of the benzene feedstock of reaction is 0.5h-1。
The Pt contents of the catalyst are 3g/L, and Ru contents are 5g/L, and Mo contents are 2g/L.Being computed benzene conversion ratio is
The yield that the yield of 50.71%, CH are 1.69%, CHB is 29.58%, for convenience of description and is compared, by the composition of catalyst
Table 1 is listed in evaluation result.
【Embodiment 5】
Catalyst preparation:The PtCl of the Pt containing 0.4g is weighed respectively2, the Ru containing 0.4g RuCl3·3H2O and Mo containing 0.2g
Ammonium molybdate be dissolved in 1mol/L aqueous acetic acids and be made into 80g solution;Measure a diameter of 1mm of 0.1L, the binder free of length 5mm
Cylindrical Hydrogen BEA zeolite molecular sieves (molar ratio of silica/alumina is 30);By above-mentioned solution loadings to Hydrogen BEA
On zeolite molecular sieve, room temperature immersion 12h, 100 DEG C of dry 12h, 450 DEG C of roasting 4h, that is, be prepared required catalyst.
Evaluating catalyst:10ml Catalyst packings are taken to carry out activity rating, bar after reduction activation into fixed bed reactors
Part is as follows:The temperature of reaction is 150 DEG C, and the molar ratio of benzene and hydrogen is 0.8 in reaction raw materials, and the pressure of reaction is 2.0MPa
(gauge pressure), the liquid volume air speed of the benzene feedstock of reaction is 0.5h-1。
The Pt contents of the catalyst are 4g/L, and Ru contents are 4g/L, and Mo contents are 2g/L.Being computed benzene conversion ratio is
The yield that the yield of 52.61%, CH are 1.39%, CHB is 30.16%, for convenience of description and is compared, by the composition of catalyst
Table 1 is listed in evaluation result.
【Embodiment 6】
Catalyst preparation:The PtCl of the Pt containing 0.5g is weighed respectively2, the Ru containing 0.3g RuCl3·3H2O and Mo containing 0.2g
Ammonium molybdate be dissolved in 1mol/L aqueous acetic acids and be made into 80g solution;Measure a diameter of 1mm of 0.1L, the binder free of length 5mm
Cylindrical Hydrogen BEA zeolite molecular sieves (molar ratio of silica/alumina is 30);By above-mentioned solution loadings to Hydrogen BEA
On zeolite molecular sieve, room temperature immersion 12h, 100 DEG C of dry 12h, 450 DEG C of roasting 4h, that is, be prepared required catalyst.
Evaluating catalyst:10ml Catalyst packings are taken to carry out activity rating, bar after reduction activation into fixed bed reactors
Part is as follows:The temperature of reaction is 150 DEG C, and the molar ratio of benzene and hydrogen is 0.8 in reaction raw materials, and the pressure of reaction is 2.0MPa
(gauge pressure), the liquid volume air speed of the benzene feedstock of reaction is 0.5h-1。
The Pt contents of the catalyst are 5g/L, and Ru contents are 3g/L, and Mo contents are 2g/L.Being computed benzene conversion ratio is
The yield that the yield of 51.82%, CH are 1.47%, CHB is 29.46%, for convenience of description and is compared, by the composition of catalyst
Table 1 is listed in evaluation result.
【Embodiment 7】
Catalyst preparation:The PtCl of the Pt containing 0.6g is weighed respectively2, the Ru containing 0.2g RuCl3·3H2O and Mo containing 0.2g
Ammonium molybdate be dissolved in 1mol/L aqueous acetic acids and be made into 80g solution;Measure a diameter of 1mm of 0.1L, the binder free of length 5mm
Cylindrical Hydrogen BEA zeolite molecular sieves (molar ratio of silica/alumina is 30);By above-mentioned solution loadings to Hydrogen BEA
On zeolite molecular sieve, room temperature immersion 12h, 100 DEG C of dry 12h, 450 DEG C of roasting 4h, that is, be prepared required catalyst.
Evaluating catalyst:10ml Catalyst packings are taken to carry out activity rating, bar after reduction activation into fixed bed reactors
Part is as follows:The temperature of reaction is 150 DEG C, and the molar ratio of benzene and hydrogen is 0.8 in reaction raw materials, and the pressure of reaction is 2.0MPa
(gauge pressure), the liquid volume air speed of the benzene feedstock of reaction is 0.5h-1。
The Pt contents of the catalyst are 6g/L, and Ru contents are 2g/L, and Mo contents are 2g/L.Being computed benzene conversion ratio is
The yield that the yield of 51.36%, CH are 1.58%, CHB is 29.17%, for convenience of description and is compared, by the composition of catalyst
Table 1 is listed in evaluation result.
【Embodiment 8】
Catalyst preparation:The PtCl of the Pt containing 0.5g is weighed respectively2, the Ru containing 1.0g RuCl3·3H2O and Mo containing 1.5g
Ammonium molybdate be dissolved in 1mol/L aqueous acetic acids and be made into 80g solution;Measure a diameter of 1mm of 0.1L, the binder free of length 5mm
Cylindrical Hydrogen BEA zeolite molecular sieves (molar ratio of silica/alumina is 30);By above-mentioned solution loadings to Hydrogen BEA
On zeolite molecular sieve, room temperature immersion 12h, 100 DEG C of dry 12h, 450 DEG C of roasting 4h, that is, be prepared required catalyst.
Evaluating catalyst:10ml Catalyst packings are taken to carry out activity rating, bar after reduction activation into fixed bed reactors
Part is as follows:The temperature of reaction is 100 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 liquid volume air speed of the raw material of reaction is 0.2h-1。
The Pt contents of the catalyst are 5g/L, and Ru contents are 10g/L, and Mo contents are 15g/L.Being computed benzene conversion ratio is
The yield that the yield of 45.37%, CH are 2.43%, CHB is 22.46%, for convenience of description and is compared, by the composition of catalyst
Table 1 is listed in evaluation result.
【Embodiment 9】
Catalyst preparation:The PtCl of the Pt containing 0.1g is weighed respectively2, the Ru containing 0.3g RuCl3·3H2O and Mo containing 0.1g
Ammonium molybdate be dissolved in 1mol/L aqueous acetic acids and be made into 80g solution;Measure a diameter of 1mm of 0.1L, the binder free of length 5mm
Cylindrical Hydrogen BEA zeolite molecular sieves (molar ratio of silica/alumina is 30);By above-mentioned solution loadings to Hydrogen BEA
On zeolite molecular sieve, room temperature immersion 12h, 100 DEG C of dry 12h, 450 DEG C of roasting 4h, that is, be prepared required catalyst.
Evaluating catalyst:10ml Catalyst packings are taken to carry out activity rating, bar after reduction activation into fixed bed reactors
Part is as follows:The temperature of reaction is 200 DEG C, and the molar ratio of benzene and hydrogen is 2.0 in reaction raw materials, and the pressure of reaction is 3.0MPa
(gauge pressure), the liquid volume air speed of the raw material of reaction is 2.0h-1。
The Pt contents of the catalyst are 1g/L, and Ru contents are 3g/L, and Mo contents are 1g/L.Being computed benzene conversion ratio is
The yield that the yield of 35.45%, CH are 1.69%, CHB is 17.16%, for convenience of description and is compared, by the composition of catalyst
Table 1 is listed in evaluation result.
1 catalyst of table forms and evaluation result
Note:In table 1, CH represents hexamethylene, and CHB represents cyclohexyl benzene.
Claims (10)
1. for the catalyst of cyclohexyl benzene production, the catalyst includes carrier and the active component being carried on carrier;Institute
Stating active component includes noble metal and molybdenum;The noble metal includes being selected from least one of platinum and ruthenium;The carrier is selected from
H-type zeolite molecular sieve.
2. catalyst according to claim 1, it is characterized in that bullion content is 0.5~20g/L.
3. catalyst according to claim 1, it is characterized in that the content of molybdenum is 1~25g/L.
4. catalyst according to claim 1, it is characterised in that the zeolite molecules are boiled screened from BEA, MOR or MWW
Stone molecular sieve.
5. catalyst according to claim 4, it is characterised in that the h-type zeolite molecular sieve is molded for binder free
Zeolite molecular sieve.
6. catalyst according to claim 4, it is characterised in that silica/oxidation of the h-type zeolite molecular sieve
The molar ratio of molybdenum is 10~100.
7. the preparation method of catalyst any one of claim 1~6, comprises the following steps:
(1) solution of the compound of the compound of aequum Pt, the compound of Ru and Mo and the h-type zeolite molecular sieve are mixed
Close;
(2) it is dry after standing;
(3) roasted in air atmosphere, obtain the catalyst.
8. 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 6
The item catalyst contact carries out benzene hydrogenation alkylated reaction generation cyclohexyl benzene.
9. according to the method described in claim 8, it is characterized in that the temperature of reaction is 100~200 DEG C.
10. according to the method described in claim 8, it is characterized in that the liquid volume air speed of reaction raw materials benzene is 0.2~3h-1。
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CN114130420B (en) * | 2020-09-04 | 2024-01-30 | 中国石油化工股份有限公司 | Benzene hydroalkylation catalyst and preparation method and application thereof |
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