CN103787817B - A kind of preparation method of tetrahydrobenzene - Google Patents
A kind of preparation method of tetrahydrobenzene Download PDFInfo
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- CN103787817B CN103787817B CN201210427756.5A CN201210427756A CN103787817B CN 103787817 B CN103787817 B CN 103787817B CN 201210427756 A CN201210427756 A CN 201210427756A CN 103787817 B CN103787817 B CN 103787817B
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Abstract
The present invention discloses a kind of partial hydrogenation of benzene cyclohexene technique, with containing the benzene of phenol for raw material, under the effect of hydrogenation catalyst, in hydrogen partial pressure be 0.1MPa ~ 5.0MPa, temperature of reaction is 100 DEG C ~ 300 DEG C, volume space velocity is 0.5h
-1~ 10.0h
-1, gas agent volume ratio be carry out under the reaction conditions of 200 ~ 2000 partial hydrogenation reaction cyclohexene, phenol weight percentage is in the feed 0.5% ~ 10%.The method can improve the transformation efficiency of benzene and the selectivity of tetrahydrobenzene simultaneously.
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 double bond, 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 obtaining tetrahydrobenzene is more.There is the method such as dehydration of cyclohexanol, cyclohexane halide dehydrohalogenation traditionally.Owing to employing the higher hexalin of cost, cyclohexane halide is raw material, and complex process, the production cost that traditional method obtains tetrahydrobenzene is higher.The tetrahydrobenzene that traditional method obtains only is suitable for being applied to the product that preparation demand is less, added value is higher usually.Benzene catalysis selective hydrogenation be a kind of with cheap benzene for material choice Hydrogenation is for the novel method of tetrahydrobenzene.The exploitation of the method and industrial applicability make tetrahydrobenzene production cost significantly decline, and can apply to the industrialization scale operation of the staple products such as hexalin, pimelinketone, hexanodioic acid, 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 domestic and international tetrahydrobenzene constantly expands, carry out the research of benzene selective hydrogenation synthesizing cyclohexene, the catalyst system of further exploitation high reactivity, highly selective energy, the technical monopoly being conducive to breaking through Japan expands the production of tetrahydrobenzene, has important economic implications.
USP4197415 discloses a kind of partial hydrogenation of benzene and prepares 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%.The USP3912787 ruthenium catalyst containing magnesium, cobalt or nickel being promotor carries out the partial hydrogenation cyclohexene of benzene, and when the reaction times is 62 minutes, obtain tetrahydrobenzene selectivity 34%, yield is the result of 20%.EPA55495 adopts benzene and hydrogen counter current contact, and except ruthenium in catalyzer, also select the elements such as iridium, chlorine, gallium, tin, zinc, nickel, sodium containing one or more, the shorter residence time obtains higher cyclohexene conversion rate and selectivity.This novel process object shortens the residence time, improves selectivity and the yield of tetrahydrobenzene.USP4678861 discloses a kind of technology of partial hydrogenation of benzene cyclohexene under suspended state, and catalyzed reaction completes in two-phase, the weak point of this process be from organic phase Zhong Yao sub-department catalyzer and possible salt more difficult.Disclosed in EP-A552809, the technology of partial hydrogenation of benzene cyclohexene employs aqueous phase, catalyzer is suspended in wherein, containing reactant in organic phase, containing hydrogen in gas phase, a deficiency of this technology is this process is discontinuous, when carrying out being separated of organic phase and inorganic phase, reaction needed stops.Partial hydrogenation of benzene cyclohexene disclosed in EP-B55495 completes in the 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 one with dipper precipitation method, and metal oxide zirconium dioxide is that carrier has prepared ruthenium base supported catalyst, and the yield of tetrahydrobenzene is the highest can only reach 40%, and catalyzer take zirconium white as carrier, the recovery difficulty of precious metal.US Patent No. 4734536 discloses a typical ruthenium black catalyst, and this catalyzer adopts precipitator method preparation, and the ruthenium content in catalyzer is high, and cost is higher.Chinese patent CN1714932A, describes the preparation method of carried non-crystal alloy partial hydrogenation of benzene cyclohexene catalyzer in CN1446625A.The catalyzer introduced in CN1714932 adopts the amorphous alloy load of metal Ru and light rare earths and the formation of metalloid boron on zirconium white, when catalyzer uses, first catalyst slurry is mixed with catalyzer, water, zinc sulfate and zirconium white, then catalyzer is prepared under certain conditions, the method needs repeatedly to wash generation waste water, catalyzer use procedure is complicated, the separation difficulty of reactant.
From thermodynamics, by benzene hydrogenation generate tetrahydrobenzene free energy change than generation hexanaphthene free energy diminish 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 the double bond of tetrahydrobenzene has active many of the conjugated double bond of aroma properties than phenyl ring.Therefore, on a catalyst, tetrahydrobenzene has higher activity, is more prone to carry out hydrogenation reaction.Even if generate tetrahydrobenzene in reaction, if can not rapidly from desorption catalyzer, and use a good method to prevent tetrahydrobenzene from adsorbing, benzene hydrogenation be difficult to rest on the stage generating tetrahydrobenzene again.
The research of benzene selective hydrogenation synthesizing cyclohexene, key how to improve the selectivity of tetrahydrobenzene.By finding the analysis of benzene hydrogenation process, benzene hydrogenation more easily obtains hexanaphthene, and the desorption of tetrahydrobenzene and the absorption again of prevention tetrahydrobenzene are the keys that benzene hydrogenation method obtains tetrahydrobenzene.
Because the solubleness of tetrahydrobenzene in water is lower than benzene, by introducing hydroaropic substance in the catalyst, being conducive to the desorption of the more weak tetrahydrobenzene of adsorptive power from catalyst surface, and stoping 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 transformation efficiency of benzene and the selectivity of tetrahydrobenzene simultaneously
A preparation method for tetrahydrobenzene, with containing the benzene of phenol for raw material, under the effect of hydrogenation catalyst, in hydrogen partial pressure be 0.1MPa ~ 5.0MPa, temperature of reaction is 100 DEG C ~ 300 DEG C, volume space velocity is 0.5 h
-1~ 10.0h
-1, gas agent volume ratio be carry out under the reaction conditions of 200 ~ 2000 partial hydrogenation reaction cyclohexene, phenol weight percentage is in the feed 0.5% ~ 10%.
In present invention process, preferred hydrogen partial pressure is 0.5MPa ~ 3.0MPa, temperature of reaction is 120 DEG C ~ 250 DEG C, volume space velocity is 2 h
-1~ 5h
-1, gas agent volume ratio is 800 ~ 1500, phenol content is in the feed 1% ~ 5%.
In present invention process, described hydrogenation catalyst can be the catalyzer being suitable for partial hydrogenation of benzene cyclohexene arbitrary disclosed in prior art, also can adopt the self-control hydrogenation catalyst of following composition.This catalyzer with titania-silica composite oxides for carrier, with
one or more in race's element are active metal component, take boron oxide as promotor, and by the weight content of final catalyzer, boron oxide content is 0.2 ~ 10.0%, preferably 0.5 ~ 6%, the
race'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 and is prepared with the following method: by metering than load boron and the on titania-silica composite oxide carrier successively
one or more in race's element, the precursor of boron is boric acid, borax,
race's element is selected from one or more in platinum, palladium or ruthenium, preferred ruthenium.Described load can adopt carrying methods all at present, such as pickling process or spray method, is preferably saturated pickling process.In loading process, drying and roasting condition are respectively: drying conditions is that normal temperature ~ 300 DEG C keep 1h ~ 48h, and roasting condition is 400 DEG C ~ 900 DEG C 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) appropriate phenol is contained in the raw material that present invention process adopts, phenol hydroxyl generation hydrogenolysis under the effect of hydrogenation catalyst generates water and benzene feedstock, the timely desorption of the tetrahydrobenzene utilizing the water generated 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 occupies tetrahydrobenzene deep hydrogenation, two is that the generation water of phenol alcohol hydrogenolysis reduces the concentration of tetrahydrobenzene at catalyst surface, avoids the deep hydrogenation of tetrahydrobenzene;
(2) present invention process utilizes generation water in reaction process and benzene, the disadvantageous effect that the watery greatly reducing catalyst surface is adsorbed benzene, therefore present invention process can improve the transformation efficiency of benzene and the selectivity of tetrahydrobenzene simultaneously, solves in prior art in order to the selectivity improving tetrahydrobenzene all needs to sacrifice the transformation efficiency of benzene for cost;
(3) homemade Ru/B is adopted in present invention process
2o
3/ SiO
2-TiO
2hydrogenation catalyst carries out the reaction of partial hydrogenation of benzene cyclohexene, have higher benzene transformation efficiency and tetrahydrobenzene optionally catalyzed reaction effect, this is due to from structure, the character of controlling catalyst and partial hydrogenation of benzene reacts and the hydrogenolysis of phenol has better coordinated effect;
(4) in present invention process, after phenol hydrogenolysis, generate benzene feedstock, do not have by product to generate.
Embodiment
Further illustrate advantage and the effect of present invention process 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 containing phenol, and loaded catalyst is 100ml.Catalyst runs carried out composition analysis to product after 8 hours, and calculate the transformation efficiency of benzene and the selectivity of tetrahydrobenzene, concrete method of calculation are as follows:
Benzene transformation efficiency=[weight of (entering the weight of the weight-reactor outlet benzene of reactor benzene)/enter reactor benzene] × 100%
Tetrahydrobenzene selectivity=[amount (mol) of amount (mol)/benzene conversion of reactor outlet tetrahydrobenzene] × 100%
embodiment 1 (if do not have special indicating below, degree is all weight percentage)
Processing condition are as follows: hydrogen partial pressure 0.8MPa, temperature of reaction 160 DEG C, 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 the mixing of 20 moles of tetrabutyl titanates, the 100 liters of pH values being added drop-wise to 35 DEG C are slowly in the salpeter solution of 2, and rapid stirring, is hydrolyzed, after dropwising, continue stirring 20 minutes, leave standstill aging 4 hours, isolate solid wherein, 110 DEG C of dryings 8 hours, 580 DEG C of roastings 3 hours, the mol ratio obtaining silicon-dioxide and titanium dioxide is 1:20, and specific surface area is 506m
3/ g, pore volume is 0.71cm
3the silicon-dioxide of/g and titania composite oxide; (2), to get containing boron oxide be the boric acid aqueous solution 400 grams of 15 grams, and the composite oxides obtained with (1) step 475 grams, fully mix under normal temperature, leave standstill 12 as a child, 130 DEG C of dryings 4 hours, and 380 DEG C of roastings 4 hours, obtain the composite oxides of boron modification; (3), to get containing ruthenium be the ruthenium chloride aqueous solution 100 grams of 2 grams, and the composite oxides of the boron modification obtained with (2) step 98 grams, fully mix under normal temperature, left standstill 24 as a child, 80 DEG C of dryings 12 hours, 480 DEG C of roastings 4 hours, obtain the catalyzer E-1 that present invention process uses.
embodiment 2
Processing condition are as follows: hydrogen partial pressure 0.8MPa, temperature of reaction 180 DEG C, 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 in the silicon-dioxide that step that difference is (1) is obtained and titania composite oxide, 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 used in step is different.Obtain the catalyzer E-2 that present invention process uses.
embodiment 3
Processing condition are as follows: hydrogen partial pressure 1.5MPa, temperature of reaction 160 DEG C, 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 in the silicon-dioxide that step that difference is (1) is obtained and titania composite oxide, 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) active metal component used in step is palladium, and content is different.Obtain the catalyzer E-3 that present invention process uses.
embodiment 4
Processing condition are as follows: hydrogen partial pressure 0.8MPa, temperature of reaction 160 DEG C, 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, step that difference is (1) silicon source used is water glass, titanium source is titanium tetrachloride, and drip respectively simultaneously, in obtained silicon-dioxide and titania composite oxide, 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 used in step is different; (3) active metal component used in step is platinum, and content is different.Obtain the catalyzer E-4 that present invention process uses.
embodiment 5
Processing condition are as follows: hydrogen partial pressure 0.8MPa, temperature of reaction 160 DEG C, 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 difference is that in the silicon-dioxide that obtains and titania composite oxide, 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 used in step is different; (3) active metal component used in step is ruthenium, and content is different.Obtain the catalyzer E-5 that present invention process uses.
embodiment 6
Processing condition are as follows: hydrogen partial pressure 0.8MPa, temperature of reaction 160 DEG C, 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 in step that difference is (3), active metal component used 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 present invention process uses.
comparative example 1
Processing condition are with embodiment 1, and the preparation method of catalyzer, with embodiment 1, obtains the solid only containing silicon-dioxide in step that difference is (1).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, with embodiment 1, obtains the solid only containing titanium dioxide in step that difference is (1).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 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:
relative to raw material weight degree
From the results shown in Table 2, present invention process is in the reaction of partial hydrogenation of benzene cyclohexene, and the selectivity of tetrahydrobenzene and yield are apparently higher than correlation technique.
Claims (6)
1. a preparation method for tetrahydrobenzene, is characterized in that: the method with containing the benzene of phenol for raw material, under the effect of hydrogenation catalyst, in hydrogen partial pressure be 0.1MPa ~ 5.0MPa, temperature of reaction is 100 DEG C ~ 300 DEG C, volume space velocity is 0.5 h
-1~ 10.0h
-1, gas agent volume ratio is carry out partial hydrogenation reaction cyclohexene under the reaction conditions of 200 ~ 2000, phenol weight percentage is in the feed 0.5% ~ 10%, described hydrogenation catalyst with titania-silica composite oxides for carrier, with the
one or more in race's element are active metal component, take boron oxide as promotor, and by the weight content of final catalyzer, boron oxide content is 0.2 ~ 10.0%, the
race's active metal component content is 0.1% ~ 10%, and surplus is titania-silica composite oxides, and 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 ~ 0.92cm
3/ g, the precursor of boron is boric acid, borax, the
race's element is selected from one or more in platinum, palladium or ruthenium.
2. method according to claim 1, is characterized in that: select that hydrogen partial pressure is 0.5MPa ~ 3.0MPa, temperature of reaction is 120 DEG C ~ 250 DEG C, volume space velocity is 2 h
-1~ 5h
-1, gas agent volume ratio is 800 ~ 1500, phenol content is in the feed 1% ~ 5%.
3. method according to claim 1, is characterized in that: boron oxide content is 0.5 ~ 6%, the
race's active metal component content is 0.3% ~ 5%.
4. method according to claim 1, is characterized in that: described hydrogenation catalyst is adopted and prepared with the following method: by metering than load boron and the on titania-silica composite oxide carrier successively
one or more in race's element.
5. method according to claim 4, is characterized in that: described load adopts pickling process or sprays method.
6. method according to claim 4, is characterized in that: in loading process, drying and roasting condition are respectively: drying conditions is that normal temperature ~ 300 DEG C keep 1h ~ 48h, and roasting condition is 400 DEG C ~ 900 DEG C and keeps 0.5h ~ 10.0h.
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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 |
|---|
| 钌催化剂上苯加氢制环己烯的影响因素;唐雷等;《工业催化》;20050731;第13卷(第7期);第7-10页 * |
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