CN103785382B - A kind of high stability preparing cyclohexene from benzene added with hydrogen catalyst and its preparation method and application - Google Patents
A kind of high stability preparing cyclohexene from benzene added with hydrogen catalyst and its preparation method and application Download PDFInfo
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Abstract
Open a kind of high stability preparing cyclohexene from benzene added with hydrogen catalyst of the present invention and preparation method thereof, this catalyst is with titanium dioxide and silicon dioxide composite oxides as carrier, with one or more in the VIIIth race's element as active metal component, with boron oxide and zinc oxide as promoter, based on the weight content of final catalyst, boron oxide content is 0.2 ~ 10.0 %, zinc oxide content is 0.5 ~ 10.0%, VIIIth race's active metal component content is 0.1% ~ 10%, and surplus is titanium dioxide and silicon dioxide composite oxides.The preparation method of a kind of high stability preparing cyclohexene from benzene added with hydrogen catalyst, loads boron oxide, zinc oxide and the VIIIth race's active metal component on titanium dioxide and silicon dioxide composite oxide carrier and prepares.This catalyst can significantly improve the conversion ratio of benzene and the selectivity of cyclohexene.
Description
Technical field
The present invention relates to a kind of high stability preparing cyclohexene from benzene added with hydrogen catalyst and its preparation method and application.
Background technology
Cyclohexene has active double bond, is a kind of important Organic Chemicals.As a kind of intermediate, cyclohexene can
It is widely used in the production of medicine, pesticide, dyestuff, detergent, explosive, feed additive, polyester and other fine chemicals.
Industrial, it is thus achieved that the method for cyclohexene is more.There is the side such as dehydration of cyclohexanol, cyclohexane halide dehydrohalogenation traditionally
Method.Owing to employing relatively costly Hexalin, cyclohexane halide is raw material, and complex process, and traditional method obtains cyclohexene
Production cost higher.The cyclohexene that traditional method obtains generally is only suitable for being applied to preparation, and demand is less, added value is higher
Product.Benzene catalysis selective hydrogenation be a kind of with cheap benzene for material choice Hydrogenation for the new method of cyclohexene.The method
Exploitation and industrial applicability make cyclohexene production cost be remarkably decreased, and can apply to the important products such as Hexalin, Ketohexamethylene, adipic acid
The industrialization large-scale production of product, and these products are the important source material of commercial production nylon-6 and nylon-66.
In recent years, along with the exploitation of Downstream Products from Cyclohexene, the demand of domestic and international cyclohexene constantly expands, and carries out benzene and selects
The research of synthesizing cyclohexene by hydrogenation, develops high activity, the high catalyst system selecting performance further, is conducive to breaking through Japan
Technical monopoly expands the production of cyclohexene, has important economic implications.
USP4197415 discloses a kind of partial hydrogenation of benzene and prepares cyclohexene technology, and used catalyst is the ruthenium catalysis of dipping
Agent, carrier modenite, accelerator comprises the phosphide of IIb-VIII metal in the periodic table of elements, and catalyst is that ruthenium-nickel closes
Gold loads on zinc oxide carrier, has obtained cyclohexene selectivity 29%, the result of yield 14%.USP3912787 is with containing magnesium, cobalt
Or the ruthenium catalyst that nickel is accelerator carries out the partial hydrogenation cyclohexene of benzene, when the response time is 62 minutes, obtains hexamethylene
Alkene selectivity 34%, yield is the result of 20%.EPA55495 uses benzene and hydrogen counter current contacting, except ruthenium in catalyst, also contains
Having one or more to select the elements such as iridium, chlorine, gallium, stannum, zinc, nickel, sodium, the shorter time of staying has obtained higher cyclohexene and has turned
Rate and selectivity.This new technology purpose is to shorten the time of staying, improves selectivity and the yield of cyclohexene.USP4678861
Disclosing a kind of technology of partial hydrogenation of benzene cyclohexene under suspended state, catalytic reaction is to complete in biphase, this mistake
Journey is disadvantageous in that from organic facies Zhong Yao sub-department catalyst and possible salt relatively difficult.Benzene disclosed in EP-A552809
The technology of partial hydrogenation cyclohexene employs aqueous phase, and catalyst is suspended in wherein, containing reactant in organic facies, contains in gas phase
Have hydrogen, a deficiency of this technology be this process be discontinuous, when carrying out the separation of organic facies and inorganic phase, reaction need
Stop.Partial hydrogenation of benzene cyclohexene disclosed in EP-B55495 is to complete in the gas phase, and maximum cyclohexene yield is
8.4%.Japan Patent JP59186932 uses chemical reduction method to prepare catalyst, but benzene hydrogenation conversion ratio only has 14.4%,
Cyclohexene selectivity only has 6.3%.Chinese patent CN1597099A discloses a kind of with dipper precipitation method, metal-oxide dioxy
Changing zirconium is that carrier is prepared for ruthenio loaded catalyst, and the yield of cyclohexene only up to reach 40%, and catalyst is with oxidation
Zirconium is carrier, the recovery difficulty of noble metal.United States Patent (USP) US4734536 discloses a typical ruthenium black catalyst, this catalysis
Agent uses the sedimentation method to prepare, and the ruthenium content in catalyst is high, relatively costly.Chinese patent CN1714932A, in CN1446625A
Describe the preparation method of carried non-crystal alloy partial hydrogenation of benzene cyclohexene catalyst.That introduces in CN1714932 urges
Agent is that the amorphous alloy using metal Ru and light rare earth and metalloid boron to be formed is supported on zirconium oxide, and catalyst uses
Time, first it is configured to catalyst slurry with catalyst, water, zinc sulfate and zirconium oxide, prepares the most under certain conditions and urge
Agent, the method needs repeatedly to wash generation waste water, and catalyst uses process complicated, the separation difficulty of reactant.
For thermodynamically, benzene hydrogenation the free energy of the free energy change ratio generation hexamethylene generating cyclohexene diminishes
Many.Therefore, in the reaction of benzene hydrogenation, molecular balance tends to generate the hexamethylene that thermodynamics is more stable；From the reaction of substrate
Activity on from the point of view of, benzene is a typical aromatic rings, has higher chemical stability.Cyclohexene have one unconjugated
Carbon-carbon double bond, the double bond of cyclohexene has active many of the conjugated double bond of aroma properties than phenyl ring.Therefore, on a catalyst,
Cyclohexene has higher activity, is more prone to carry out hydrogenation reaction.Even if generating cyclohexene in Fan Ying, if can not be rapid
Being desorbed from catalyst, and use a preferable method to prevent cyclohexene from adsorbing again, benzene hydrogenation is difficult to rest on life
Become the stage of cyclohexene.
The research of benzene selective hydrogenation synthesizing cyclohexene, it is important to how to improve the selectivity of cyclohexene.By to benzene hydrogenation
The analysis of process is it is found that benzene hydrogenation is easier to obtain hexamethylene, and the desorption of cyclohexene and the absorption again of prevention cyclohexene are
Benzene hydrogenation method obtains the key of cyclohexene.
Owing to cyclohexene dissolubility in water is lower than benzene, by introducing hydroaropic substance in the catalyst, be conducive to inhaling
The more weak cyclohexene of attached ability is from the desorption of catalyst surface, and stops the cyclohexene after desorption again to be adsorbed by active sites.But
The conversion ratio being benzene is on the low side.
Summary of the invention
For the deficiencies in the prior art, the present invention provides a kind of high stability preparing cyclohexene from benzene added with hydrogen catalyst and preparation thereof
Methods and applications.This catalyst can significantly improve the conversion ratio of benzene and the selectivity of cyclohexene.
A kind of high stability preparing cyclohexene from benzene added with hydrogen catalyst, this catalyst is with titania-silica combined oxidation
Thing is carrier, withOne or more in race's element are active metal component, with boron oxide and zinc oxide as co-catalysis
Agent, based on the weight content of final catalyst, boron oxide content is 0.2 ~ 10.0%, preferably 0.5 ~ 6%, zinc oxide content is 0.5 ~
10.0%, preferably 1 ~ 6%, theRace's active metal component content is 0.1% ~ 10%, preferably 0.3% ~ 5%, surplus be titanium dioxide-
Silica composite oxide.
In catalyst titania-silica composite oxides of the present invention silicon dioxide and titanium dioxide and mol ratio
For 1:5 ~ 1:100, preferably 1:10 ~ 1:50；Specific surface area is 475 ~ 737m3/g；Pore volume is 0.56 ~ 0.92cm3/g.
The preparation method of a kind of high stability preparing cyclohexene from benzene added with hydrogen catalyst, in titania-silica composite oxygen
Compound supported on carriers boron oxide, zinc oxide andRace's active metal component prepares, it is preferred to use first load boron oxide,
Use co-impregnation load zinc oxide and theRace's active metal component, specifically includes following steps:
(1), coprecipitation method is used to prepare titania-silica composite oxides；
(2), on the composite oxides that step (1) obtains, load the compound of boron, through being dried and roasting, obtain boron and change
The composite oxides of property；
(3) co-impregnation load zinc oxide and the is used on the composite oxides of the boron modification obtained in step (2)
Race's active metal component, through being dried and roasting, obtains catalyst of the present invention.
In step (1), silicon source is silicon-containing compound, can be organosilicon and inorganic silicon, such as sodium silicate, tetraethyl orthosilicate
Deng；Titanium source is titanium-containing compound, can be organic titanium compound and inorganic titanium compound, such as butyl titanate, Titanium Nitrate, titanium sulfate
Deng；Select suitable precipitant, such as nitric acid etc. according to different silicon sources and titanium source, carry out co-precipitation and obtain silicon dioxide and two
Titania composite oxide.
In step (2), the compound of boron can be Organic substance or the inorganic matter of boracic, the preferably inorganic matter of boracic, example
Such as boric acid, Borax etc., load can use current all of carrying method, such as infusion process or spray method, the most saturated leaching
Stain method.
In step (3), zinc oxide derives from the zinc salt being dissolvable in water water, such as zinc nitrate, zinc chloride；TheRace's activity
Metal component is one or more in platinum, palladium or ruthenium, preferably ruthenium.
Step (1), (2) with described in (3) be dried can be identical with roasting condition, it is also possible to difference, drying condition is normal
Temperature ~ 300 DEG C of holding 1h ~ 48h, roasting condition is 400 DEG C ~ 900 DEG C and keeps 0.5h ~ 10.0h.
The application of a kind of high stability preparing cyclohexene from benzene added with hydrogen catalyst, uses formalin to carry out also original place before using
Reason, reaction process condition is, hydrogen partial pressure 0.1MPa ~ 5.0MPa, reaction temperature 100 DEG C ~ 300 DEG C, volume space velocity 0.5 h-1~
10.0h-1, gas agent volume ratio 200 ~ 2000, optimum condition is: hydrogen partial pressure 0.5MPa ~ 3.0MPa, reaction temperature 120 DEG C ~ 250
DEG C, volume space velocity 2 h-1~5h-1, gas agent volume ratio 800 ~ 1500.
Catalyst of the present invention is with titania-silica composite oxides as carrier, particularly to have suitable mole
Ratio, pore volume, aperture, the titania-silica composite oxides of specific surface area are carrier, at titania-silica
First load boron oxide on composite oxide carrier and load zinc oxide and againRace's active metal component, complex carrier, helps and urges
Agent andThe triangular interaction of race's active metal component makes promoter andRace's active metal component tool
There are the absorption of more preferably distribution mode, beneficially benzene and the desorption of cyclohexene, enable cyclohexene to diffuse quickly into catalyst
Outer surface, it is therefore prevented that the deep hydrogenation of cyclohexene, when improve catalyst, the selectivity of cyclohexene and long-term operation simultaneously
Stability.
Detailed description of the invention
The preparation process of catalyst of the present invention is further illustrated below by embodiment, but it is not considered that the present invention only office
It is limited in below example.
Catalyst of the present invention uses front mass fraction to be that 10% formalin carries out reduction treatment, makes on catalyst
Active metal component is converted into elemental stage, and preferred reducing condition is at normal pressure, and under the conditions of temperature is 400 DEG C, backflow 4 ~ 6 is little
Time.Catalyst of the present invention is to use the medium-sized fixed bed reactors of 100ml to be evaluated, and loaded catalyst is 100ml, specifically comments
Valency condition is: hydrogen partial pressure 0.8MPa, reaction temperature 160 DEG C, volume space velocity 3.0h-1, gas agent volume ratio 1200.Catalyst length week
Phase carries out component analysis to product after operating 20 hours, calculates the conversion ratio of benzene and the selectivity of cyclohexene, concrete calculating
Method is as follows:
Benzene conversion ratio=[weight of (entering the weight of the weight-reactor outlet benzene of reactor benzene)/enter reactor benzene] ×
100%
Cyclohexene selectivity=[amount (mol) that the amount (mol) of reactor outlet cyclohexene/benzene converts] × 100%.
Embodiment 1 (indicating without special below, degree is all weight percentage)
The preparation process of a kind of catalyst of the present invention is as follows:
(1), take 1 mole of tetraethyl orthosilicate and 20 moles of butyl titanate mixing, be added drop-wise to 100 liters of PH of 35 DEG C slowly
Value is in the salpeter solution of 2, quickly stirs, is hydrolyzed, and after waiting to drip, continues stirring 20 minutes, stands aging 4 little
Time, isolate solid therein, 110 DEG C are dried 8 hours, 580 DEG C of roastings 3 hours, obtain rubbing of silicon dioxide and titanium dioxide
That ratio is 1:20, and specific surface area is 506m3/ g, pore volume is 0.71cm3The silicon dioxide of/g and titania composite oxide.
(2), take containing the boric acid aqueous solution that boron oxide is 15 grams 400 grams, the composite oxides 475 obtained with (1) step
Gram, it is sufficiently mixed under room temperature, stood 12 as a child, 130 DEG C are dried 4 hours, 380 DEG C of roastings 4 hours, obtain the compound of boron modification
Oxide；
(3), take containing 5.4 grams of ruthenic chlorides (ruthenium content is 37%) and the aqueous solution of 4.2 grams of zinc chloride (Zn content is 48%)
100 grams, with the composite oxides 98 grams of the boron modification that (2) step obtains, it is sufficiently mixed under room temperature, stood 24 as a child, 80 DEG C
Being dried 12 hours, 480 DEG C of roastings 4 hours, obtain one catalyst of the present invention, numbered E-1, its composition is shown in Table 1, benzene portion
The reaction result dividing Hydrogenation cyclohexene is shown in Table 2.
Embodiment 2
The preparation method of a kind of catalyst of the present invention is with embodiment 1, and difference is the silicon dioxide that (1) step prepares
With in titania composite oxide, the mol ratio of silicon dioxide and titanium dioxide is 1:5, and specific surface area is 537m3/ g, pore volume
For 0.68cm3/g；(2) boric acid amount used in step is different；(3) zinc compound used in step is zinc nitrate, and contains
Amount difference.Obtaining one catalyst of the present invention, numbered E-2, its composition is shown in Table 1, partial hydrogenation of benzene cyclohexene anti-
2 should be the results are shown in Table.
Embodiment 3
The preparation method of a kind of catalyst of the present invention is with embodiment 1, and difference is the silicon dioxide that (1) step prepares
With in titania composite oxide, the mol ratio of silicon dioxide and titanium dioxide is 1:10, and specific surface area is 637m3/ g, hole
Hold for 0.60cm3/g；(3) active metal component used in step is palladium, and content is different.Obtain one of the present invention catalysis
Agent, numbered E-3, its composition is shown in Table 1, and the reaction result of partial hydrogenation of benzene cyclohexene is shown in Table 2.
Embodiment 4
The preparation method of a kind of catalyst of the present invention is with embodiment 1, and difference is that the silicon source used by (1) step is water
Glass, titanium source is titanium tetrachloride, and is simultaneously added dropwise respectively, in the silicon dioxide prepared and titania composite oxide, two
The mol ratio of silicon oxide and titanium dioxide is 1:50, and specific surface area is 520m3/ g, pore volume is 0.70cm3/g；(2) institute in step
Boric acid amount different；(3) active metal component used in step is platinum, and content is different, obtains one of the present invention catalysis
Agent, numbered E-4, its composition is shown in Table 1, and the reaction result of partial hydrogenation of benzene cyclohexene is shown in Table 2.
Embodiment 5
The preparation method of a kind of catalyst of the present invention is with embodiment 1, and difference is silicon dioxide and the dioxy prepared
Changing in titanium composite oxide, the mol ratio of silicon dioxide and titanium dioxide is 1:100, and specific surface area is 601m3/ g, pore volume is
0.65cm3/g；(2) boric acid amount used in step is different；(3) in step, ruthenium is different with the content of zinc, obtains the present invention a kind of
Catalyst, numbered E-5, its composition is shown in Table 1, and the reaction result of partial hydrogenation of benzene cyclohexene is shown in Table 2.
Embodiment 6
The preparation method of a kind of catalyst of the present invention is with embodiment 1, and difference is in (3) step activity gold used
Belonging to the weight ratio that component is ruthenium and palladium, ruthenium and palladium is 2:1, and total content is shown in Table 1, obtains one catalyst of the present invention, numbered E-
6, its composition is shown in Table 1, and the reaction result of partial hydrogenation of benzene cyclohexene is shown in Table 2.
Comparative example 1
The preparation method of a kind of comparative catalyst of the present invention with embodiment 1, difference be in (1) step to obtain containing only
There is the solid of silicon dioxide.Obtaining catalyst of the present invention, numbered C-1, its composition is shown in Table 1, partial hydrogenation of benzene hexamethylene
The reaction result of alkene is shown in Table 2.
Comparative example 2
The preparation method of a kind of comparative catalyst of the present invention with embodiment 1, difference be in (1) step to obtain containing only
There is the solid of titanium dioxide.Obtaining catalyst of the present invention, numbered C-2, its composition is shown in Table 1, partial hydrogenation of benzene hexamethylene
The reaction result of alkene is shown in Table 2.
Comparative example 3
The preparation method of a kind of comparative catalyst of the present invention is with embodiment 1, and difference is in catalyst not contain zinc.
Obtaining catalyst of the present invention, numbered C-3, its composition is shown in Table 1, and the reaction result of partial hydrogenation of benzene cyclohexene is shown in Table 2.
The composition (unreceipted content is weight percent content) of table 1 each embodiment (comparative example) catalyst
| Catalyst | SiO2:TiO2 | Zinc oxide, % | Boron oxide, % | Active metal component, % |
| E-1 | 1:20 | 2.0 | 3.0 | 2.0(Ru) |
| E-2 | 1:5 | 4.0 | 0.5 | 2.0(Ru) |
| E-3 | 1:10 | 2.0 | 3.0 | 1.0(Pb) |
| E-4 | 1:50 | 2.0 | 2.0 | 0.3(Pt) |
| E-5 | 1:100 | 1.0 | 5.0 | 5.0(Ru) |
| E-6 | 1:20 | 2.0 | 3.0 | 3.0(Ru)+ 0.5(Pb) |
| C-1 | 100:0 | 2.0 | 3.0 | 2.0(Ru) |
| C-2 | 0:100 | 2.0 | 3.0 | 2.0(Ru) |
| C-3 | 1:20 | 0 | 3.0 | 2.0(Ru) |
Note:Mol ratio
The reactivity worth of table 2 different catalysts
| Catalyst | Benzene conversion ratio, % | Cyclohexene selectivity, % | Cyclohexene yield, % |
| E-1 | 69.4 | 64.4 | 44.7 |
| E-2 | 70.8 | 63.6 | 45.0 |
| E-3 | 70.5 | 62.3 | 43.9 |
| E-4 | 72.1 | 61.6 | 44.4 |
| E-5 | 69.3 | 63.1 | 43.7 |
| E-6 | 70.9 | 62.5 | 44.3 |
| C-1 | 60.8 | 40.9 | 24.9 |
| C-2 | 68.5 | 26.5 | 18.2 |
| C-3 | 65.2 | 55.7 | 36.3 |
From the results shown in Table 2, catalyst of the present invention in the reaction of partial hydrogenation of benzene cyclohexene, cyclohexene
Selectivity and yield are apparently higher than the reaction result of comparative catalyst.
Table 3 catalyst reaction stability result
From the results shown in Table 3, catalyst long-term operation is after 60 hours, and catalyst of the present invention is in benzene part
In the reaction of Hydrogenation cyclohexene, reactivity and selective reduction rate, significantly lower than the result of comparative example, illustrate catalyst
Stability preferable.
Claims (9)
1. a high stability preparing cyclohexene from benzene added with hydrogen catalyst, it is characterised in that: this catalyst is with titania-silica
Composite oxides are carrier, withOne or more in race's element are active metal component, with boron oxide and zinc oxide are
Promoter, based on the weight content of final catalyst, boron oxide content is 0.2 ~ 10.0%, zinc oxide content is 0.5 ~
10.0%, theRace's active metal component content is 0.1% ~ 10%, and surplus is titania-silica composite oxides, institute
In the titania-silica composite oxides stated silicon dioxide and titanium dioxide and mol ratio be 1:5 ~ 1:100, compare table
Area is 475 ~ 737m3/g；Pore volume is 0.56 ~ 0.92cm3/g。
Catalyst the most according to claim 1, it is characterised in that: described titania-silica composite oxides
Middle silicon dioxide and titanium dioxide and mol ratio be 1:10 ~ 1:50.
3. the preparation method of catalyst described in claim 1, it is characterised in that: at titania-silica composite oxides
Supported on carriers boron oxide, zinc oxide andRace's active metal component prepares, and specifically includes following steps:
(1), coprecipitation method is used to prepare titania-silica composite oxides；
(2), on the composite oxides that step (1) obtains, load the compound of boron, through being dried and roasting, obtain boron modification
Composite oxides；
(3) co-impregnation load zinc oxide and the is used on the composite oxides of the boron modification obtained in step (2)Race's activity
Metal component, through being dried and roasting, obtains described catalyst.
Method the most according to claim 3, it is characterised in that: in step (1), silicon source is sodium silicate, tetraethyl orthosilicate；Titanium
Source is butyl titanate, Titanium Nitrate, titanium sulfate.
Method the most according to claim 3, it is characterised in that: in step (2), the compound of boron is boric acid, Borax, load
Use infusion process or spray method.
Method the most according to claim 3, it is characterised in that: in step (3), zinc oxide derives from zinc nitrate, zinc chloride；
TheRace's active metal component is one or more in platinum, palladium or ruthenium.
Method the most according to claim 3, it is characterised in that: the drying condition described in step (2) and (3) is room temperature ~ 300
DEG C keep 1h ~ 48h, roasting condition be 400 DEG C ~ 900 DEG C keep 0.5h ~ 10.0h.
8. claim 1-2 arbitrary described catalyst application in partial hydrogenation of benzene cyclohexene, it is characterised in that: before use
Using formalin to carry out reduction treatment, reaction process condition is, hydrogen partial pressure 0.1MPa ~
5.0MPa, reaction temperature 100 DEG C ~ 300 DEG C, volume space velocity 0.5 h-1~10.0h-1, gas agent volume ratio 200 ~ 2000.
Application the most according to claim 8, it is characterised in that: hydrogen partial pressure 0.5MPa ~ 3.0MPa, reaction temperature 120 DEG C ~
250 DEG C, volume space velocity 2 h-1~5h-1, gas agent volume ratio 800 ~ 1500.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4197415A (en) * | 1976-10-08 | 1980-04-08 | Toray Industries, Inc. | Process for preparing cyclic olefins by selective partial hydrogenation of aromatic hydrocarbons |
| US4734536A (en) * | 1985-10-03 | 1988-03-29 | Asahi Kasei Kogyo Kabushiki Kaisha | Process for producing cycloolefins |
| 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 |
| CN1714932A (en) * | 2005-05-17 | 2006-01-04 | 郑州大学 | Catalyst for preparing cyclohexene by benzene hydrogenation, its preparing method and using method |
| CN1915517A (en) * | 2005-08-15 | 2007-02-21 | 中国石油化工股份有限公司 | Catalyst in use for producing cyclohexene |
| CN1978056A (en) * | 2005-11-30 | 2007-06-13 | 中国石油化工股份有限公司 | Catalyst for preparing cyclohexene by benzene selectine hydrogenation, its preparing method and use |
-
2012
- 2012-11-01 CN CN201210427767.3A patent/CN103785382B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4197415A (en) * | 1976-10-08 | 1980-04-08 | Toray Industries, Inc. | Process for preparing cyclic olefins by selective partial hydrogenation of aromatic hydrocarbons |
| US4734536A (en) * | 1985-10-03 | 1988-03-29 | Asahi Kasei Kogyo Kabushiki Kaisha | Process for producing cycloolefins |
| 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 |
| CN1714932A (en) * | 2005-05-17 | 2006-01-04 | 郑州大学 | Catalyst for preparing cyclohexene by benzene hydrogenation, its preparing method and using method |
| CN1915517A (en) * | 2005-08-15 | 2007-02-21 | 中国石油化工股份有限公司 | Catalyst in use for producing cyclohexene |
| CN1978056A (en) * | 2005-11-30 | 2007-06-13 | 中国石油化工股份有限公司 | Catalyst for preparing cyclohexene by benzene selectine hydrogenation, its preparing method and use |
Non-Patent Citations (4)
| Title |
|---|
| 液相法 Ru-M-B/ZrO2 催化苯选择加氢制环己烯反应条件的研究;刘寿长 等;《催化学报》;20020731;第23卷(第4期);第317-320页 * |
| 苯选择加氢催化剂载体、助剂的研究;钟晓亮 等;《化工科技》;20111231;第19卷(第2期);第45-48页 * |
| 苯选择加氢制环己烯Ru-Zn-B/ZrO2非晶催化剂研究;刘寿长 等;《化学通报》;20021231;第65卷;第1-6页 * |
| 负载型非晶态Ru-B合金催化剂催化苯选择性加氢制环己烯;唐雷;《中国优秀博硕士论文全文数据库（硕士）工程科技Ⅰ辑》;20061015(第10期);第20-21、56-63页 * |
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