CN103787817A - Preparation method of cyclohexene - Google Patents
Preparation method of cyclohexene Download PDFInfo
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- CN103787817A CN103787817A CN201210427756.5A CN201210427756A CN103787817A CN 103787817 A CN103787817 A CN 103787817A CN 201210427756 A CN201210427756 A CN 201210427756A CN 103787817 A CN103787817 A CN 103787817A
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- benzene
- tetrahydrobenzene
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Abstract
The invention discloses a cyclohexene preparation process by partial hydrogenation of benzene. The method uses phenol-containing benzene as a raw material, and carries out a partial hydrogenation reaction in the presence of a hydrogenation catalyst to prepare cyclohexene under the following reaction conditions: hydrogen partial pressure of 0.1-5.0 MPa, reaction temperature of 100-300 DEG C, volume space velocity of 0.5-10.0 / h, and volume ratio of gas and agent of 200-2000, wherein the phenol accounts for 0.5-10 wt% in the raw material. The method can simultaneously improve the conversion rate of benzene and the selectivity of cyclohexene.
Description
Technical field
The present invention relates to a kind of preparation method of tetrahydrobenzene, relate in particular to a kind of method of partial hydrogenation of benzene cyclohexene.
Background technology
Tetrahydrobenzene has active two keys, is a kind of important Organic Chemicals.As a kind of intermediate, tetrahydrobenzene can be widely used in the production of medicine, agricultural chemicals, dyestuff, washing composition, explosive, fodder additives, polyester and other fine chemicals.
Industrial, the method that obtains tetrahydrobenzene is more.There is traditionally the method such as dehydration of cyclohexanol, cyclohexane halide dehydrohalogenation.Be raw material owing to having used hexalin, the cyclohexane halide that cost is higher, and complex process, the production cost that traditional method obtains tetrahydrobenzene is higher.Common only suitable being applied to of tetrahydrobenzene that traditional method obtains prepared the product that demand is less, added value is higher.Benzene catalysis selective hydrogenation is a kind of take cheap benzene as material choice Hydrogenation is for the novel method of tetrahydrobenzene.The exploitation of the method and industrial applicability significantly decline tetrahydrobenzene production cost, and the large-scale industrialization that can apply to the staple products such as hexalin, pimelinketone, hexanodioic acid is produced, and these products are important source material of industrial production nylon-6 and nylon-66.
In recent years, along with the exploitation of Downstream Products from Cyclohexene, the demand of tetrahydrobenzene constantly expands both at home and abroad, carry out the research of benzene selective hydrogenation synthesizing cyclohexene, the further catalyst system of exploitation high reactivity, highly selective energy, be conducive to break through the production of Japanese technical monopoly expansion tetrahydrobenzene, there is important economic implications.
USP4197415 discloses a kind of partial hydrogenation of benzene and has prepared tetrahydrobenzene technology, used catalyst is the ruthenium catalyst of dipping, carrier mordenite, the phosphide of IIb-VIII metal in promotor containing element periodictable, catalyzer is that ruthenium-nickelalloy loads on zinc oxide carrier, obtain tetrahydrobenzene selectivity 29%, the result of yield 14%.USP3912787 carries out the partial hydrogenation cyclohexene of benzene with the ruthenium catalyst that is promotor containing magnesium, cobalt or nickel, the reaction times, while being 62 minutes, obtains tetrahydrobenzene selectivity 34%, the result that yield is 20%.EPA55495 adopts benzene and hydrogen counter current contact, in catalyzer, except ruthenium, also contains one or more and selects the elements such as iridium, chlorine, gallium, tin, zinc, nickel, sodium, and the shorter residence time has obtained higher cyclohexene conversion rate and selectivity.This novel process object is to shorten the residence time, improves selectivity and the yield of tetrahydrobenzene.USP4678861 disclose a kind of under suspended state the technology of partial hydrogenation of benzene cyclohexene, catalyzed reaction is to complete in two-phase, the weak point of this process is from organic phase Zhong Yao sub-department's catalyzer and possible salt more difficult.The utilization of the disclosed partial hydrogenation of benzene cyclohexene of EP-A552809 water, catalyzer is suspended in wherein, in organic phase, contain reactant, in gas phase, contain hydrogen, a deficiency of this technology is that this process is discontinuous, in the time carrying out the separating of organic phase and inorganic phase, reaction needed stops.The disclosed partial hydrogenation of benzene cyclohexene of EP-B55495 is to complete in gas phase, and maximum tetrahydrobenzene yield is 8.4%.Japanese Patent JP59186932 adopts chemical preparation catalyzer, but benzene hydrogenation transformation efficiency only has 14.4%, and tetrahydrobenzene selectivity only has 6.3%.Chinese patent CN1597099A discloses a kind of with dipper precipitation method, and metal oxide zirconium dioxide is that carrier has been prepared ruthenium base supported catalyst, and the yield of tetrahydrobenzene is the highest can only reach 40%, and catalyzer is take zirconium white as carrier, the recovery difficulty of precious metal.U.S. Pat 4734536 discloses a typical ruthenium black catalyzer, and this catalyzer adopts precipitator method preparation, and the ruthenium content in catalyzer is high, and cost is higher.Chinese patent CN1714932A, has introduced the preparation method of carried non-crystal alloy partial hydrogenation of benzene cyclohexene catalyzer in CN1446625A.The catalyzer of introducing in CN1714932 is that the amorphous alloy that adopts metal Ru and light rare earths and metalloid boron to form loads on zirconium white, when catalyzer uses, first be mixed with catalyst slurry with catalyzer, water, zinc sulfate and zirconium white, then prepare under certain conditions catalyzer, the method need to repeatedly be washed generation waste water, catalyzer use procedure complexity, the separation difficulty of reactant.
From thermodynamics, what diminished than the free energy that generates hexanaphthene by the free energy change of benzene hydrogenation generation tetrahydrobenzene is many.Therefore,, in the reaction of benzene hydrogenation, molecular balance tends to the more stable hexanaphthene of Heat of Formation mechanics; The activity of the reaction of substrate, benzene is a typical aromatic nucleus, has higher chemical stability.Tetrahydrobenzene has a unconjugated carbon-carbon double bond, and two keys of tetrahydrobenzene have active many of the conjugated double bond of aroma properties than phenyl ring.Therefore, on catalyzer, tetrahydrobenzene has higher activity, is more prone to carry out hydrogenation reaction.Even generated tetrahydrobenzene in reaction, if desorption from catalyzer rapidly, and use a good method to prevent that tetrahydrobenzene from adsorbing again, benzene hydrogenation is difficult to rest on the stage that generates tetrahydrobenzene.
The research of benzene selective hydrogenation synthesizing cyclohexene, key is how to improve the selectivity of tetrahydrobenzene.By finding the analysis of benzene hydrogenation process, benzene hydrogenation more easily obtains hexanaphthene, and the absorption again of the desorption of tetrahydrobenzene and prevention tetrahydrobenzene is the key that benzene hydrogenation method obtains tetrahydrobenzene.
Because the solubleness of tetrahydrobenzene in water is lower than benzene, by introduce hydroaropic substance in catalyzer, be conducive to the desorption of the weak tetrahydrobenzene of adsorptive power from catalyst surface, and stop the tetrahydrobenzene after desorption again to be adsorbed by active sites.But the transformation efficiency of benzene is on the low side.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of partial hydrogenation of benzene cyclohexene method, the method can improve the selectivity of transformation efficiency and the tetrahydrobenzene of benzene simultaneously
A preparation method for tetrahydrobenzene, take containing the benzene of phenol as raw material, under the effect of hydrogenation catalyst, be that 0.1MPa ~ 5.0MPa, temperature of reaction are that 100 ℃ ~ 300 ℃, volume space velocity are 0.5 h in hydrogen partial pressure
-1~ 10.0h
-1, carry out partial hydrogenation reaction cyclohexene under the gas agent volume ratio reaction conditions that is 200 ~ 2000, the weight percentage of phenol in raw material is 0.5% ~ 10%.
In technique of the present invention, preferably hydrogen partial pressure is that 0.5MPa ~ 3.0MPa, temperature of reaction are that 120 ℃ ~ 250 ℃, volume space velocity are 2 h
-1~ 5h
-1, gas agent volume ratio is 800 ~ 1500, the content of phenol in raw material is 1% ~ 5%.
In technique of the present invention, described hydrogenation catalyst can be disclosed arbitrary catalyzer that is suitable for partial hydrogenation of benzene cyclohexene in prior art, also can adopt the self-control hydrogenation catalyst of following composition.This catalyzer is take titania-silica composite oxides as carrier, with
one or more in family's element are active metal component, and take boron oxide as promotor, by the weight content of final catalyzer, boron oxide content is 0.2 ~ 10.0%, preferably 0.5 ~ 6%, the
family's active metal component content is 0.1% ~ 10%, preferably 0.3% ~ 5%, and surplus is titania-silica composite oxides.In titania-silica composite oxide carrier, the mol ratio of silicon-dioxide and titanium dioxide is 1:5 ~ 1:100, is preferably 1:10 ~ 1:50; Specific surface area is 475 ~ 737m
3/ g; Pore volume is 0.56 ~ 0.92cm3/g.Described self-control hydrogenation catalyst is adopted with the following method preparation: by metering than load boron and the on titania-silica composite oxide carrier successively
one or more in family's element, the precursor of boron is boric acid, borax, the
family's element is selected from one or more in platinum, palladium or ruthenium, preferably ruthenium.Described load can adopt at present all carrying methods, and for example pickling process or spray method is preferably saturated pickling process.In loading process, be dried with roasting condition and be respectively: drying conditions is normal temperature ~ 300 ℃ maintenance 1h ~ 48h, and roasting condition is 400 ℃ ~ 900 ℃ and keeps 0.5h ~ 10.0h.
Compared with prior art, preparation method's tool of a kind of tetrahydrobenzene of the present invention has the following advantages:
(1) in the raw material of process using of the present invention, contain appropriate phenol, phenol hydroxyl generation hydrogenolysis under the effect of hydrogenation catalyst generates water and benzene feedstock, the timely desorption of tetrahydrobenzene that utilizes the water generating in hydrogenolysis process that partial hydrogenation of benzene is generated, improve the selectivity of tetrahydrobenzene, phenol add improve tetrahydrobenzene optionally reason one be the active sites that phenol has occupied tetrahydrobenzene deep hydrogenation, the 2nd, the generation water of phenol alcohol hydrogenolysis has reduced the concentration of tetrahydrobenzene at catalyst surface, has avoided the deep hydrogenation of tetrahydrobenzene;
(2) technique of the present invention is generation water and the benzene utilizing in reaction process, the disadvantageous effect of the watery that greatly reduces catalyst surface to benzene absorption, therefore technique of the present invention can improve the selectivity of transformation efficiency and the tetrahydrobenzene of benzene simultaneously, has solved in prior art for the selectivity that improves tetrahydrobenzene all need to be take the transformation efficiency of sacrifice benzene as cost;
(3) in technique of the present invention, adopt homemade Ru/B
2o
3/ SiO
2-TiO
2hydrogenation catalyst carries out the reaction of partial hydrogenation of benzene cyclohexene, have optionally catalyzed reaction effect of higher benzene transformation efficiency and tetrahydrobenzene, this is to react with partial hydrogenation of benzene and the hydrogenolysis of phenol has better coordinated effect due to the structure from controlling catalyst, character;
(4) in technique of the present invention, after phenol hydrogenolysis, generate benzene feedstock, do not have by product to generate.
Embodiment
Further illustrate advantage and the effect of technique of the present invention below by embodiment and comparative example, but invention should not be deemed limited in following embodiment.
The embodiment of the present invention and comparative example adopt continuous fixed bed reaction or continuous technique, and raw material is the benzene that contains phenol, and loaded catalyst is 100ml.Catalyst runs was carried out composition analysis to product after 8 hours, calculated the selectivity of transformation efficiency and the tetrahydrobenzene of benzene, and concrete method of calculation are as follows:
Benzene transformation efficiency=[(entering the weight of weight-reactor outlet benzene of reactor benzene)/enter the weight of reactor benzene] × 100%
Tetrahydrobenzene selectivity=[amount (mol) that amount (the mol)/benzene of reactor outlet tetrahydrobenzene transforms] × 100%
embodiment 1 (if there is no below special indicating, degree is all weight percentage)
Processing condition are as follows: hydrogen partial pressure 0.8MPa, 160 ℃ of temperature of reaction, volume space velocity 3.0h
-1, gas agent volume ratio 1200, the composition of hydrogenation catalyst E-1 and evaluation result are in table 1 and table 2.
The preparation process of hydrogenation catalyst is as follows: (1), get 1 mole of tetraethoxy and 20 moles of tetrabutyl titanates mix, in the salpeter solution that 100 liters of pH values that are added drop-wise to slowly 35 ℃ are 2, rapid stirring, is hydrolyzed, after dropwising, continue to stir 20 minutes, leave standstill aging 4 hours, isolate solid wherein, 110 ℃ are dried 8 hours, 580 ℃ of roastings 3 hours, the mol ratio that obtains silicon-dioxide and titanium dioxide is 1:20, specific surface area is 506m
3/ g, pore volume is 0.71cm
3the silicon-dioxide of/g and titania composite oxide; (2), get that to contain boron oxide be 400 grams of the boric acid aqueous solutions of 15 grams, 475 grams of the composite oxides that obtain with (1) step, fully mix under normal temperature, leave standstill 12 as a child, 130 ℃ dry 4 hours, 380 ℃ of roastings 4 hours, obtain the composite oxides of boron modification; (3), get that to contain ruthenium be 100 grams of the ruthenium chloride aqueous solutions of 2 grams, 98 grams of the composite oxides of the boron modification obtaining with (2) step, fully mix under normal temperature, left standstill 24 as a child, 80 ℃ dry 12 hours, 480 ℃ of roastings 4 hours, obtain the catalyzer E-1 that technique of the present invention is used.
embodiment 2
Processing condition are as follows: hydrogen partial pressure 0.8MPa, 180 ℃ of temperature of reaction, volume space velocity 4.0h
-1, gas agent volume ratio 1000, the composition of hydrogenation catalyst E-2 and evaluation result are in table 1 and table 2.
The preparation method of catalyzer is with embodiment 1, and difference is that in silicon-dioxide and titania composite oxide that (1) step makes, the mol ratio of silicon-dioxide and titanium dioxide is 1:5, and specific surface area is 537m
3/ g, pore volume is 0.68cm3/g; (2) boric acid amount difference used in step.Obtain the catalyzer E-2 that technique of the present invention is used.
embodiment 3
Processing condition are as follows: hydrogen partial pressure 1.5MPa, 160 ℃ of temperature of reaction, volume space velocity 3.0h
-1, gas agent volume ratio 900, the composition of hydrogenation catalyst E-3 and evaluation result are in table 1 and table 2.
The preparation method of catalyzer is with embodiment 1, and difference is that in silicon-dioxide and titania composite oxide that (1) step makes, the mol ratio of silicon-dioxide and titanium dioxide is 1:10, and specific surface area is 637m
3/ g, pore volume is 0.60cm3/g; (3) in step, active metal component used is palladium, and content difference.Obtain the catalyzer E-3 that technique of the present invention is used.
embodiment 4
Processing condition are as follows: hydrogen partial pressure 0.8MPa, 160 ℃ of temperature of reaction, volume space velocity 3.0h
-1, gas agent volume ratio 1200, the composition of hydrogenation catalyst E-4 and evaluation result are in table 1 and table 2.
The preparation method of catalyzer is with embodiment 1, difference is that (1) step silicon source used is water glass, titanium source is titanium tetrachloride, and drip respectively simultaneously, in the silicon-dioxide and titania composite oxide making, the mol ratio of silicon-dioxide and titanium dioxide is 1:50, and specific surface area is 520m
3/ g, pore volume is 0.70cm3/g; (2) boric acid amount difference used in step; (3) in step, active metal component used is platinum, and content difference.Obtain the catalyzer E-4 that technique of the present invention is used.
embodiment 5
Processing condition are as follows: hydrogen partial pressure 0.8MPa, 160 ℃ of temperature of reaction, volume space velocity 3.0h
-1, gas agent volume ratio 1200, the composition of hydrogenation catalyst E-5 and evaluation result are in table 1 and table 2.
The preparation method of catalyzer is with embodiment 1, and in silicon-dioxide and titania composite oxide that difference is to make, the mol ratio of silicon-dioxide and titanium dioxide is 1:100, and specific surface area is 601m
3/ g, pore volume is 0.65cm3/g; (2) boric acid amount difference used in step; (3) in step, active metal component used is ruthenium, and content difference.Obtain the catalyzer E-5 that technique of the present invention is used.
embodiment 6
Processing condition are as follows: hydrogen partial pressure 0.8MPa, 160 ℃ of temperature of reaction, volume space velocity 3.0h
-1, gas agent volume ratio 1200, the composition of hydrogenation catalyst E-6 and evaluation result are in table 1 and table 2.
The preparation method of catalyzer is with embodiment 1, and difference is that active metal component used in (3) step is ruthenium and palladium, and the weight ratio of ruthenium and palladium is 2:1, and total content is in table 1.Obtain the catalyzer E-6 that technique of the present invention is used.
comparative example 1
Processing condition are with embodiment 1, and the preparation method of catalyzer is with embodiment 1, and difference is to obtain only containing in (1) step the solid of silicon-dioxide.The composition of hydrogenation catalyst C-1 and evaluation result are in table 1 and table 2.
comparative example 2
Processing condition are with embodiment 1, and the preparation method of catalyzer is with embodiment 1, and difference is to obtain only containing in (1) step the solid of titanium dioxide.The composition of hydrogenation catalyst C-2 and evaluation result are in table 1 and table 2.
comparative example 3
Processing condition are with embodiment 1, and the preparation method of catalyzer, with embodiment 1, does not just contain phenol in raw material.The composition of hydrogenation catalyst C-3 and evaluation result are in table 1 and table 2.
the composition of the each embodiment of table 1 (comparative example) catalyzer(unreceipted content is weight percent content)
| Catalyzer | SiO
2:TiO
2  |
Boron oxide, % | Active metal component, % |
| E-1 | 1:20 | 3.0 | 2.0(Ru) |
| E-2 | 1:5 | 0.5 | 2.0(Ru) |
| E-3 | 1:10 | 3.0 | 1.0(Pb) |
| E-4 | 1:50 | 2.0 | 0.3(Pt) |
| E-5 | 1:100 | 5.0 | 5.0(Ru) |
| E-6 | 1:20 | 3.0 | 3.0(Ru)+ 0.5(Pb) |
| C-1 | 100:0 | 3.0 | 2.0(Ru) |
| C-2 | 0:100 | 3.0 | 2.0(Ru) |
| C-3 | 1:20 | 3.0 | 2.0(Ru) |
Note:
mol ratio
the reactivity worth of table 2 different catalysts
| Catalyzer | Phenol, %
 |
Benzene transformation efficiency, % | Tetrahydrobenzene selectivity, % | Tetrahydrobenzene yield, % |
| E-1 | 3 | 77.5 | 61.4 | 47.6 |
| E-2 | 3 | 82.8 | 58.1 | 48.1 |
| E-3 | 2 | 85.6 | 59.8 | 51.2 |
| E-4 | 4 | 91.4 | 52.3 | 47.8 |
| E-5 | 1 | 77.3 | 65.6 | 50.7 |
| E-6 | 5 | 86.8 | 55.7 | 48.3 |
| C-1 | 3 | 82.9 | 20.6 | 17.1 |
| C-2 | 3 | 96.2 | 6.5 | 6.3 |
| C-1 | 0 | 94.7 | 13.7 | 13.0 |
Note:
with respect to raw material weight degree
From the results shown in Table 2, technique of the present invention is in the reaction of partial hydrogenation of benzene cyclohexene, and the selectivity of tetrahydrobenzene and yield are apparently higher than correlation technique.
Claims (10)
1. a preparation method for tetrahydrobenzene, is characterized in that: the method take containing the benzene of phenol as raw material, under the effect of hydrogenation catalyst, be that 0.1MPa ~ 5.0MPa, temperature of reaction are that 100 ℃ ~ 300 ℃, volume space velocity are 0.5 h in hydrogen partial pressure
-1~ 10.0h
-1, carry out partial hydrogenation reaction cyclohexene under the gas agent volume ratio reaction conditions that is 200 ~ 2000, the weight percentage of phenol in raw material is 0.5% ~ 10%.
2. method according to claim 1, is characterized in that: selecting hydrogen partial pressure is that 0.5MPa ~ 3.0MPa, temperature of reaction are that 120 ℃ ~ 250 ℃, volume space velocity are 2 h
-1~ 5h
-1, gas agent volume ratio is 800 ~ 1500, the content of phenol in raw material is 1% ~ 5%.
3. method according to claim 1, is characterized in that: described hydrogenation catalyst is take titania-silica composite oxides as carrier, with
one or more in family's element are active metal component, and take boron oxide as promotor, by the weight content of final catalyzer, boron oxide content is 0.2 ~ 10.0%, the
family's active metal component content is 0.1% ~ 10%, and surplus is titania-silica composite oxides.
4. method according to claim 3, is characterized in that: boron oxide content is 0.5 ~ 6%, the
family's active metal component content is 0.3% ~ 5%.
5. method according to claim 3, is characterized in that: in titania-silica composite oxide carrier, the mol ratio of silicon-dioxide and titanium dioxide is 1:5 ~ 1:100, and specific surface area is 475 ~ 737m
3/ g; Pore volume is 0.56 ~ 0.92cm3/g.
6. method according to claim 5, is characterized in that: in titania-silica composite oxide carrier, the mol ratio of silicon-dioxide and titanium dioxide is 1:10 ~ 1:50.
7. according to the method described in claim 1 or 3, it is characterized in that: described hydrogenation catalyst is adopted with the following method preparation: by metering than load boron and the on titania-silica composite oxide carrier successively
one or more in family's element.
8. method according to claim 7, is characterized in that: the precursor of boron is boric acid, borax, the
family's element is selected from one or more in platinum, palladium or ruthenium.
9. method according to claim 7, is characterized in that: described load adopts pickling process or sprays method.
10. method according to claim 7, is characterized in that: in loading process, be dried with roasting condition and be respectively: drying conditions is normal temperature ~ 300 ℃ maintenance 1h ~ 48h, and roasting condition is 400 ℃ ~ 900 ℃ and keeps 0.5h ~ 10.0h.
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|---|---|---|---|
| CN201210427756.5A CN103787817B (en) | 2012-11-01 | 2012-11-01 | A kind of preparation method of tetrahydrobenzene |
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|---|---|---|---|
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1080273A (en) * | 1992-02-26 | 1994-01-05 | 催化剂股份有限公司 | Partial hydrogenation aromatic hydrocarbons is produced improving one's methods of cycloolefin and the catalyzer through washing |
| CN1535942A (en) * | 2003-04-09 | 2004-10-13 | 中国石油化工股份有限公司 | Preparation method of Ru-B load type catalyst |
-
2012
- 2012-11-01 CN CN201210427756.5A patent/CN103787817B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1080273A (en) * | 1992-02-26 | 1994-01-05 | 催化剂股份有限公司 | Partial hydrogenation aromatic hydrocarbons is produced improving one's methods of cycloolefin and the catalyzer through washing |
| CN1535942A (en) * | 2003-04-09 | 2004-10-13 | 中国石油化工股份有限公司 | Preparation method of Ru-B load type catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 唐雷等: "钌催化剂上苯加氢制环己烯的影响因素", 《工业催化》 * |
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