CN1446625A - Benzene selection noncrystalline catalyst with hydrogen added and containing ruthenium, boron as well as its preparing method - Google Patents
Benzene selection noncrystalline catalyst with hydrogen added and containing ruthenium, boron as well as its preparing method Download PDFInfo
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Abstract
A non-crystal catalyst for preparing cyclodexene by selectively hydrogenating benzene is prepared from Ru, B meta or metal oxide modified M, and the oxide or metal hydroxide carrier L through reducing Ru ions and M in oxide form, and removing ions of impurities. Its advantage is high selectivity and hydrogenating activity.
Description
Technical field
The invention belongs to chemical technology field, is the new amorphous state Catalysts and its preparation method that is used for producing cyclohexene with benzene selective hydrogenation.
Background technology
Cyclohexene is a kind of important organic synthesis intermediate, can be widely used in the production of medicine, agricultural chemicals, agricultural chemicals, feed addictive, polyester and other fine chemicals.Especially the deep processing product cyclohexanone of cyclohexene and adipic acid are a large amount of intermediates that use in the synthetic polyamide fiber.For example dehydration of cyclohexanol method, cyclohexane halide dehydrohalogenation method and Birch reducing process etc. exist shortcomings such as complex manufacturing, cost height owing to the method for producing cyclohexene traditionally, cause cyclohexene only to be applied to the fine chemical product of high added values such as lysine, cyclohexene oxide, can't be applied in the bigger fields of industrial requirement such as producing cyclohexanol, adipic acid at all.Because benzene selective hydrogenation prepares cyclohexene and has the cheap advantage of cost of material, has economic worth, has caused many major companies and technical staff's attention.For example major companies such as Philips oil company, Allied company, Dong Li company, company of Asahi Chemical Industry, sumitomo chemical company have all carried out the technology development work of this technology.
At present, producing cyclohexene with benzene selective hydrogenation mainly contains three kinds of methods, i.e. liquid phase method, vapor phase method and complexometry.Wherein at most with liquid phase method research.The catalyst of having studied mainly contains: Ru, Ru/ carrier, Pt etc.From the productive rate of cyclohexene, the Ru catalyst effect is best and correlative study is also maximum.Wherein mainly contain the ruthenium catalyst of ruthenium powder, ruthenium black and support type based on the ruthenium-based catalyst of liquid phase method.Preparation of Catalyst generally adopts the precipitation method, infusion process is with the preparation catalyst precursor and then use hydrogen reducing.But most of catalyst and its corresponding benzene selective hydrogenation result are also satisfactory far away.The 1980s amorphous alloy catalyst cause people's attention owing to its amorphous structure and less size, particularly Amorphous Ru B catalyst begins to be applied in benzene selective hydrogenation and prepares on the cyclohexene.The mixed method of chemistry that we get up according to the result of study and the developed recently of RuB powder has been developed the RuB catalyst series of support type.This catalyst is applied to the benzene selective hydrogenation reaction, and the result shows to have benzene selective hydrogenation activity and selectivity preferably.
Summary of the invention
The objective of the invention is to propose a kind of catalytic efficiency height, eco-friendlyly be used for the new amorphous state alloy catalyst that benzene selective hydrogenation prepares cyclohexene, and propose this Preparation of catalysts method.
Provided by the inventionly being used for the amorphous catalyst that benzene selective hydrogenation prepares cyclohexene, is a kind of amorphous alloy catalyst that contains ruthenium and boron, and it is made up of ruthenium, boron, metal or modified metal oxide agent M and material support L.The carrier conversion is the steady oxide form, catalyst activity component and dressing agent then calculate with the weight of wherein metallic element and are 1 with the weight of Ru, then the weight proportion of each component is in the catalyst: the consumption of Ru is 1, boron is 0.002～0.012, M is 0～0.8, L is 0 or 5～70, and M and L are not 0 simultaneously.Wherein ruthenium mainly exists with the form of Ru-B or RuB-M amorphous alloy, and metal or modified metal oxide agent M are meant that corresponding ion can be by BH
4 -In the metal of ion reduction one or more.The atomic ratio of ruthenium and boron is 1.0～100 in the described Ru-B amorphous alloy; Described ruthenium, boron and metal or modified metal oxide agent M can load on the porous carrier materials L, also can individualism.
Preparation of catalysts method provided by the invention is as follows:
To unsupported catalyst, in-10 ℃ to 80 ℃ temperature range, under agitation with Ru
3+Ion solution is to contain BH
4 -The aqueous solution reduction of ion, preferred 20 ℃ to 40 ℃;
To loaded catalyst, can adopt a kind of of following 3 kinds of methods.
First kind is adopted chemistry method mixed and electronation to prepare, and second kind is adopted traditional immersion process for preparing, and the third adopts co-precipitation, the heat treatment three-step approach preparation of electronation again.
The method of the mixed and electronation of first kind of chemistry is specially in-10 ℃ to 80 ℃ temperature range, and the mixed aqueous solution that under agitation will contain ruthenium salt, M salt and carrier material L salt drips molar concentration simultaneously under constant temperature stirs be 0.1～2.0 the BH that contains
4 -Precipitating reagent such as ion solution and ammoniacal liquor.
Second kind of traditional infusion process has been specially with a kind of load the porous carrier materials L of ruthenium salt, M salt and molar concentration and is 0.1～2.0 BH
4 -Ion solution is pressed 0.1～10.0 mol ratio haptoreaction, and wherein the load capacity of ruthenium salt on L is 0.5～15.0 heavy %, and the load capacity of M ion on L is 0～10.0 heavy %.
The third co-precipitation, heat treatment is the three-step approach of electronation again, is specially at first to adopt coprecipitation to prepare catalyst precursor, then presoma is heat-treated catalyst KHB that at last will be after Overheating Treatment in the seal pot below 180 ℃
4Reduction.Wherein the preparation concrete steps of presoma are as follows: the ammoniacal liquor (6M) of capacity is slowly splashed into an amount of RuCl that 50 ℃ of constant temperature stir
3In the mixed solution of aluminum nitrate, the pH value of final mixed solution is 9.2, dropwises to continue stirring hydrolysis 40min, and centrifuge washing gets final product.KHB
4Ru in the reduction step: B=1: 10 (mol ratios).
The load capacity of described ruthenium salt (in ruthenium ion weight) on carrier material L is 0.5～15.0 weight %, and when being unsupported catalyst, the described molar concentration that contains ruthenium ion is 0.02～0.15; The load capacity of described M ion on carrier material L is 0～10.0 weight %; Described precipitating reagent comprises ammoniacal liquor, NaOH, potassium hydroxide.
Ru of the present invention
3+Precursor be selected from RuCl
3, Ru (NO) (NO
3)
3, Ru (acac)
3, Ru
3(CO)
12, preferred RuCl
3BH
4 -The precursor of ion is selected from sodium borohydride or potassium borohydride.
Carrier material L of the present invention refers to one or more in inorganic oxide, the precipitation of hydroxide, inorganic oxide refers to the oxide of periodic table of elements IIA family, group III A, IVA family, IVB family element, one or more in wherein preferred silica, aluminium oxide, the zirconia; Described precipitation of hydroxide is zirconium hydroxide, calcium hydroxide, magnesium hydroxide, aluminium hydroxide etc., and wherein preferred precipitation of hydroxide is zirconium hydroxide, aluminium hydroxide.
Described metal dressing agent M is that its corresponding salt can be contained BH
4 -In the metallic element of ion solution reduction one or more, in the preferred elements periodic table in IB family, IIB family, group vib, the group VIII metallic element one or more, in more preferred IIB family, group vib, the group VIII metallic element one or more, metallic addition commonly used are one or more among Zn, Cr, Fe, the Co; The precursor of described M ion is the M cation, and when being Zn, Cr, Co as M, the precursor of described M ion can be ZnCl
2, ZnSO
4, CrCl
3, CoCl
2, Co (OAc)
2Deng.
According to catalyst provided by the invention, the active component ruthenium all exists with the amorphous state form, and metallic addition M and Ru-B form amorphous alloy, exist with the form of RuB-M amorphous alloy, or metallic addition exists with oxide form separately.At this moment, ° locate a broad diffraction maximum in 2 θ=43 on the X-ray diffraction spectrogram of measuring with CuK α target, be the characteristic diffraction peak of ruthenium series non-crystalline state alloy.Activity of such catalysts provided by the invention can be tested with the following method:
Intermittently investigate catalyst activity in the tank reactor at 0.5 liter of stainless steel.Benzene, a certain amount of water, catalyst, an amount of additive sulfuric acid zinc are put into still.Take a breath 3 times with the hydrogen of 2.2MPa in autoclave sealing back, to remove the air in the still.Be heated to constant hydrogen pressure after the reaction temperature behind the preliminary filling hydrogen 2.2MPa, reaction temperature is 50～200 ℃, more excellent 120～160 ℃, and hydrogen pressure 1～10MPa, more excellent 3～6MPa, and begin to stir, stir speed (S.S.) is greater than 1000 rev/mins.Take out response sample at interval with gas chromatographic analysis cyclohexane, cyclohexene and benzene content wherein with certain hour.
The specific embodiment
The invention is further illustrated by the following examples.
Embodiment 1: the preparation of ultra-fine Ru-B amorphous alloy catalyst
To fill 15mL 0.1M RuCl
3The beaker of the aqueous solution places water bath with thermostatic control, under strong stirring, drips the 10mL1M potassium borohydride aqueous solution.Fully wash the sediment of black earlier with distilled water, clean for several times with absolute ethyl alcohol, the sediment Ru-B powder with black places the absolute ethyl alcohol protection standby at last.Can obtain Ru-B powder under the different temperatures by adjusting bath temperature.The part characterization result of this catalyst is shown in table one.
Embodiment 2: carried non-crystal RuB/Zr (OH)
4XH
2The O Preparation of catalysts
Preparation of catalysts adopts the preparation method of electronation and chemical mixing.In 40 ℃ water bath with thermostatic control, stir down, 20mL 6M ammonia spirit and 10mL 0.2M KBH
4The aqueous solution slowly is added drop-wise to RuCl simultaneously
3(5.3 * 10
-3M) and ZrOCl
2(5.5 * 10
-2M) in the mixed solution.After treating that hydrogen has been put, continue to stir 40min.The gained black precipitate is retained in the mother liquor spends the night, and is washed with distilled water to no Cl then
-Ion.
The catalyst that Zn and Co modify adopts above-mentioned same method preparation, and zinc salt and cobalt salt are dissolved in respectively in the mixed liquid in advance.Catalyst is designated as RuB-Zn/Zr (OH)
4XH
2O and RuB-Co/Zr (OH)
4XH
2O.
Embodiment 3: support type RuB/SiO
2The preparation of amorphous catalyst
Support type RuB/SiO
2Amorphous catalyst adopts the method preparation of dipping reduction.Use certain density RuCl
3Solution impregnation 1g SiO
2Carrier, SiO
2Carrier boils with the 0.5 rare nitric acid that weighs % earlier before use and washes 2h, and after oven dry under 110 ℃ of infrared lamps was spent the night, 500 ℃ of roasting 2h in Muffle furnace were crushed to 40～60 orders then again.Soaked carrier slowly splashes into the solution of potassium borohydride of 0.200M after oven dry under 110 ℃ of infrared lamps is spent the night, and mol ratio is that B/Ru=4/1 is to guarantee that ruthenium ion is by Restore All.Whole operation is carried out in ice-water bath and will be avoided vigorous stirring to slow down reduction reaction speed and to prevent that the ruthenium that reduces is oxidized again.Catalyst is washed with distilled water to pH=7.3～7.8, can use for several times with absolute ethanol washing again, and the gained catalyst is designated as RuB/SiO
2
Embodiment 4: support type RuB/ γ-Al
2O
3The preparation of amorphous catalyst
RuB/ γ-Al
2O
3The Preparation of catalysts method is divided by γ-Al
2O
3Outside carrier, consistent with the process conditions of embodiment 3.Catalyst is designated as RuB/ γ-Al
2O
3
The catalyst that Elements C o modifies adopts RuCl
3And CoCl
3Mixed solution dipping, all the other are the same.Catalyst is designated as RuB-Co/ γ-Al
2O
3
Embodiment 5: support type RuB/Al
2O
3.xH
2The preparation of O amorphous catalyst
Support type RuB/Al
2O
3XH
2The preparation of O amorphous catalyst prepares by three-step approach.At first adopt coprecipitation to prepare catalyst precursor, will heat-treat in the seal pot of presoma under 180 ℃ then, catalyst KBH that at last will be after Overheating Treatment
4Reduction.Wherein the preparation concrete steps of presoma are as follows: the ammoniacal liquor (6M) of capacity is slowly splashed into an amount of RuCl that 50 ℃ of constant temperature stir
3In the mixed solution of aluminum nitrate, the pH value of final mixed solution is 9.2, dropwises to continue stirring hydrolysis 40min, and centrifuge washing gets final product.KBH
4Ru in the reduction step: B=1: 10.
Benzene selective hydrogenation active testing example 1: ultra-fine Ru-B amorphous alloy catalyst
Catalyst amount is 0.15g, 35 milliliters of purified petroleum benzin, and water 100mL, 150 ℃ of reaction temperatures, Hydrogen Vapor Pressure 4.00MPa, 1000 rev/mins of stir speed (S.S.)s, inorganic additive zinc sulfate 1.5g selects hydrogenation to the results are shown in table two.
Benzene selective hydrogenation active testing example 2: carried non-crystal RuB/Zr (OH)
4XH
2O
Catalyst amount is 1.0g, purified petroleum benzin 50mL, and water 100mL, 150 ℃ of reaction temperatures, Hydrogen Vapor Pressure 5.00MPa, 1000 rev/mins of stir speed (S.S.)s, inorganic additive zinc sulfate 4.5g selects hydrogenation to the results are shown in table three.
Benzene selective hydrogenation active testing example 3: carried non-crystal RuB-Zn/Zr (OH)
4XH
2The O catalyst
Catalyst is selected RuB-Zn/Zr (OH) for use
4XH
2O, all the other conditions select hydrogenation to the results are shown in table four with benzene selective hydrogenation active testing example 2.
Benzene selective hydrogenation active testing example 4: carried non-crystal RuB-Co/Zr (OH)
4XH
2The O catalyst
Catalyst is selected RuB-Co/Zr (OH) for use
4XH
2O, all the other conditions select hydrogenation to the results are shown in table five with benzene selective hydrogenation active testing example 2.
Benzene selective hydrogenation active testing example 5: support type RuB/SiO
2Amorphous catalyst
Catalyst is selected RuB/SiO for use
2, all the other conditions select hydrogenation to the results are shown in table six with benzene selective hydrogenation active testing example 2.
Benzene selective hydrogenation active testing example 6: support type RuB/ γ-Al
2O
3Amorphous catalyst
Catalyst is selected RuB/ γ-Al for use
2O
3, all the other conditions select hydrogenation to the results are shown in table seven with benzene selective hydrogenation active testing example 2.
Benzene selective hydrogenation active testing example 7: support type RuB-Co/ γ-Al
2O
3Amorphous catalyst
Catalyst is selected RuB-Co/ γ-Al for use
2O
3, all the other conditions select hydrogenation to the results are shown in table eight with benzene selective hydrogenation active testing example 2.
Benzene selective hydrogenation active testing example 8: support type RuB/Al
2O
3XH
2The O amorphous catalyst
Catalyst is selected RuB/Al for use
2O
3.xH
2O, all the other conditions select hydrogenation to the results are shown in table nine with benzene selective hydrogenation active testing example 2.The preparation temperature of table one, Amorphous Ru B catalyst series, specific area, surface composition
Preparation temperature specific area surface composition Ru active sites
(℃) (m
2/ g) (atomic ratio) (gcat
-1) * 10
-19
-7 10.3 Ru
98.1B
1.9 1.04
1 11.4 Ru
95.8B
4.2 3.63
8 15.1 Ru
93.3B
6.7 4.32
19 16.2 Ru
91.6B
8.4 5.68
30 17.0 Ru
89.9B
10.1?6.98
40 17.8 Ru
90.1B
9.98.42 the benzene selective hydrogenation activity of table two, RuB fine catalyst
Catalyst is formed productive rate (%) conversion ratio (%) selectivity (%) time (min)
Ru 6.3 32.5 19.4 90
Ru
981B
19 7.1 28.1 25.3 55
Ru
95.8B
4.2 13.7 40.8 33.6 65
Ru
93.3B
6.7 21.7 55.7 39.0 85
Ru
91.6B
8.4 27.4 60.4 45.4 85
Ru
a9.9B
10.1 30.4 59.9 50.8 75
Ru
90.1B
9.931.2 61.1 51.1 70 tables three, xwt.%RuB/Zr (OH)
4XH
2The benzene selective hydrogenation activity of O catalyst
Ruthenium load capacity productive rate (%) conversion ratio (%) selectivity (%) time (min)
5 22.8 61.1 37.3 50
9 31.9 64.8 49.2 35
12 31.4 62.3 50.4 25
15 29.6 69.1 42.9 30
18 26.3 65.3 40.3 20 tables four, 9wt.%RuB-xwt.%Zn/Zr (OH)
4XH
2The benzene selective hydrogenation activity of O catalyst
Zn load capacity productive rate (%) conversion ratio (%) selectivity (%) time (min)
0 33.2 66.8 49.7 30
1.0 35.8 67.3 53.2 40
2.5 45.6 73.1 62.3 55
4.0 38.6 63.0 61.3 50 tables five, 12wt.%RuB-xwt.%Co/Zr (OH)
4XH
2The benzene selective hydrogenation activity of O catalyst
Co load capacity productive rate (%) conversion ratio (%) selectivity (%) time (min)
0 30.7 69.3 44.2 25
2.5 32.8 61.0 54.1 30
5.0 37.0 62.8 58.9 40
7.0 34.6 61.6 56.1 50 tables six, 8wt.%RuB/SiO
2The benzene selective hydrogenation activity of amorphous catalyst
PH value productive rate (%) conversion ratio (%) selectivity (%)
～6 18.5 68.4 29.2
7～8 33.4 63.4 52.8
～8.5 26.8 57.2 46.8
～9.3 23.5 63.3 37.1 tables seven, xwt.%RuB/ γ-Al
2O
3The benzene selective hydrogenation activity of amorphous catalyst
Ru load capacity productive rate (%) conversion ratio (%) selectivity (%) time (min)
0.7 24.0 72.6 33.1 120
1.5 22.1 76.4 28.9 110
3 20.4 80.0 25.5 50
5 12.0 83.5 14.4 40
9 6.3 80.8 7.76 25 tables eight, 1.5wt.%RuB-xwt.%Co/ γ-Al
2O
3The benzene selective hydrogenation activity of amorphous catalyst
Co content productive rate (%) conversion ratio (%) selectivity (%) time (min)
0 22.1 76.4 28.9 22.1
0.2 20.5 64.7 31.6 20.4
0.7 29.8 79.6 37.4 29.8
0.9 27.4 64.5 42.4 27.4
1.2 23.9 60.6 39.6 23.9 tables nine, 4wt.%RuB/Al
2O
3XH
2The benzene selective hydrogenation activity of O amorphous catalyst
Carrier form zinc sulfate (g)
aProductive rate (%) conversion ratio (%) selectivity (%) time (min)
Colloidal state 0+0 2.98 62.6 4.76 6
Colloidal state 0+4 5.5 29.9 18.4 8
Colloidal state 4+0 26.6 57.4 46.4 65
Crystallization
b0+4 39.6 77.4 51.1 44
Crystallization
c0+4 34.8 72.3 48.2 43
aThe ZnSO that adds when the numeral before the plus sige is reduced
47H
2The ZnSO that adds when the weight of O, numeral hydrogenation behind the plus sige
47H
2The weight of O
bStir in the crystallization process
cDo not stir in the crystallization process
Claims (10)
1. an amorphous alloy catalyst that contains ruthenium and boron that is used for producing cyclohexene with benzene selective hydrogenation is characterized in that being made up of ruthenium, boron, metal or modified metal oxide agent M and carrier material L; The carrier conversion is the steady oxide form, catalyst activity component and dressing agent then calculate with the weight of wherein metallic element, and be 1 with the weight of Ru, then the weight proportion of each component is in the catalyst: the consumption of Ru is 1, boron is 0.002～0.012, M is 0～0.8, and L is 0 or 5～70, and M and L are not 0 simultaneously; Wherein ruthenium mainly exists with the form of Ru-B or RuB-M amorphous alloy, and metal or modified metal oxide agent M can be by BH for its ion
4 -In the metal of ion reduction one or more, the ruthenium in the RuB amorphous alloy and the atomic ratio of boron are 1.0-100; Ruthenium, boron and metal or metal oxide M load on carrier material L and go up or individualism.
2,, it is characterized in that metal or modified metal oxide agent M are IIB family, group vib in the periodic table of elements, one or more in the VIIIB family metallic element according to the described catalyst of claim 1.
3,, it is characterized in that metal or modified metal oxide agent M are one or more among Zn, Cr, Fe, the Co according to the described catalyst of claim 2.
4,, it is characterized in that described carrier material L is one or more in inorganic oxide, the precipitation of hydroxide according to the described catalyst of claim 1.
5,, it is characterized in that described inorganic oxide and precipitation of hydroxide are one or more in silica, aluminium oxide, zirconia, titanium oxide, magnesia, calcium oxide and magnesium hydroxide, aluminium hydroxide, zirconium hydroxide, the calcium hydroxide according to the described catalyst of claim 1.
6, a kind of preparation method who is used for the amorphous catalyst of producing cyclohexene with benzene selective hydrogenation as claimed in claim 1 is characterized in that unsupported catalyst, in-10 ℃ to 80 ℃ temperature range, under agitation with Ru
3+Ion solution is to contain BH
4 -The aqueous solution reduction of ion; To loaded catalyst, adopt a kind of preparation of following method: the method for first kind of and electronation mixed for chemistry, second kind is traditional immersion process for preparing, the third is co-precipitation, the heat treatment three-step approach of electronation again.
7, Preparation of catalysts method according to claim 6, it is characterized in that chemistry step mixed and chemical reduction method is as follows: in-10 ℃ to 80 ℃ temperature range, the mixed aqueous solution that will contain ruthenium salt, M salt and carrier material L salt is added dropwise to molar concentration simultaneously under constant temperature stirs be 0.1～2.0 the BH that contains
4 -Ion solution and precipitating reagent prepare.
8, Preparation of catalysts method according to claim 6 is characterized in that the step of infusion process is as follows: with a kind of load the carrier material L of ruthenium salt, M salt and molar concentration be 0.1～2.0 BH
4 -Ion solution is pressed 0.1～10.0 ingredient proportion haptoreaction, and wherein the load capacity 0.5～15.0 of ruthenium salt on L weighs %, and the load capacity of M on L is 0～10.0 heavy %.
9, Preparation of catalysts method according to claim 6, the three-step approach step of electronation is as follows again to it is characterized in that co-precipitation, heat treatment: at first adopt coprecipitation to prepare catalyst precursor, then presoma is heat-treated catalyst KHB that at last will be after Overheating Treatment in the seal pot below 180 ℃
4Reduction.
10, according to the described Preparation of catalysts method of claim 6, it is characterized in that described Ru
3+The precursor of ion is selected from RuCl
3, Ru (NO) (NO
3)
3, Ru (acac)
3, Ru
3(CO)
12A kind of, BH
4 -The precursor of ion is selected from sodium borohydride or potassium borohydride.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1304109C (en) * | 2004-08-12 | 2007-03-14 | 郑州大学 | Preparing of cyclobexene catalyst for benzene selective hydrogenation its preparation method and regulating method and regeneration method |
| WO2007065370A1 (en) * | 2005-12-08 | 2007-06-14 | The Hong Kong University Of Science And Technology | Low temperature ammonia remediation catalysts |
| CN1978053B (en) * | 2005-11-30 | 2010-06-23 | 中国石油化工股份有限公司 | Catalyst for preparing cyclohexene by benzene selective hydrogenation, its preparing method and use |
| CN103301837A (en) * | 2013-06-07 | 2013-09-18 | 苏州市泰力达科技有限公司 | Method for preparing aluminum oxide loaded ruthenium catalyst |
| CN103480393A (en) * | 2013-09-03 | 2014-01-01 | 重庆华峰化工有限公司 | Supported catalyst for preparation of cyclohexene through selective hydrogenation of benzene and preparation method thereof |
| CN103665282A (en) * | 2012-08-31 | 2014-03-26 | 台橡股份有限公司 | Method for hydrogenating polymer and hydrogenated polymer thereof |
| CN107008223A (en) * | 2017-05-04 | 2017-08-04 | 贵研工业催化剂（云南）有限公司 | Adsorbent of low-load amount high dispersive type benzene refining desulfurization and preparation method thereof |
| CN107308934A (en) * | 2017-06-27 | 2017-11-03 | 太原理工大学 | A kind of supported ruthenium amorphous alloy catalyst and its preparation method and application |
| CN113634275A (en) * | 2021-08-19 | 2021-11-12 | 浙江工业大学 | Catalyst for catalytic hydrodechlorination and preparation method and application thereof |
| CN114904519A (en) * | 2022-05-25 | 2022-08-16 | 上海昊澜机电设备有限公司 | Preparation method of novel hydrogenation catalyst |
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2003
- 2003-03-06 CN CNB031156665A patent/CN1197651C/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304109C (en) * | 2004-08-12 | 2007-03-14 | 郑州大学 | Preparing of cyclobexene catalyst for benzene selective hydrogenation its preparation method and regulating method and regeneration method |
| CN1978053B (en) * | 2005-11-30 | 2010-06-23 | 中国石油化工股份有限公司 | Catalyst for preparing cyclohexene by benzene selective hydrogenation, its preparing method and use |
| WO2007065370A1 (en) * | 2005-12-08 | 2007-06-14 | The Hong Kong University Of Science And Technology | Low temperature ammonia remediation catalysts |
| CN103665282B (en) * | 2012-08-31 | 2016-12-07 | 台橡股份有限公司 | Method for hydrogenating polymer and hydrogenated polymer thereof |
| CN103665282A (en) * | 2012-08-31 | 2014-03-26 | 台橡股份有限公司 | Method for hydrogenating polymer and hydrogenated polymer thereof |
| CN103301837A (en) * | 2013-06-07 | 2013-09-18 | 苏州市泰力达科技有限公司 | Method for preparing aluminum oxide loaded ruthenium catalyst |
| CN103480393B (en) * | 2013-09-03 | 2015-08-26 | 重庆华峰化工有限公司 | Loaded catalyst of a kind of producing cyclohexene with benzene selective hydrogenation and preparation method thereof |
| CN103480393A (en) * | 2013-09-03 | 2014-01-01 | 重庆华峰化工有限公司 | Supported catalyst for preparation of cyclohexene through selective hydrogenation of benzene and preparation method thereof |
| CN107008223A (en) * | 2017-05-04 | 2017-08-04 | 贵研工业催化剂（云南）有限公司 | Adsorbent of low-load amount high dispersive type benzene refining desulfurization and preparation method thereof |
| CN107008223B (en) * | 2017-05-04 | 2019-08-16 | 贵研工业催化剂（云南）有限公司 | The adsorbent and preparation method thereof of low-load amount high dispersive type benzene refining desulfurization |
| CN107308934A (en) * | 2017-06-27 | 2017-11-03 | 太原理工大学 | A kind of supported ruthenium amorphous alloy catalyst and its preparation method and application |
| CN113634275A (en) * | 2021-08-19 | 2021-11-12 | 浙江工业大学 | Catalyst for catalytic hydrodechlorination and preparation method and application thereof |
| CN113634275B (en) * | 2021-08-19 | 2023-08-22 | 浙江工业大学 | Catalyst for catalytic hydrogenation dechlorination and preparation method and application thereof |
| CN114904519A (en) * | 2022-05-25 | 2022-08-16 | 上海昊澜机电设备有限公司 | Preparation method of novel hydrogenation catalyst |
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