CN104028267A - Method for preparing cyclohexane precious metal Ru catalyst by benzene selective hydrogenation - Google Patents
Method for preparing cyclohexane precious metal Ru catalyst by benzene selective hydrogenation Download PDFInfo
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Abstract
The invention relates to a method for preparing a cyclohexane precious metal Ru catalyst by benzene selective hydrogenation. The cyclohexane precious metal Ru catalyst is characterized by consisting of precious metal Ru, an additive M1, an additive M2 and carriers, wherein M1 refers to one of Fe, Co, Ni, Cu and Zn; M2 refers to one of Ba and Ca; the carriers refer to aluminum oxide, silicon oxide and zirconia; the elementary substance content of precious metal Ru accounts for 1wt%-30wt% of the mass of the catalyst; M1 accounts for 0.2wt%-5wt% of the total mass of the catalyst; M2 accounts for 0.1wt%-3wt% of the total mass of the catalyst; the content of the carriers, namely aluminum oxide, silicon oxide and zirconia, account for 70wt%-90wt% of the total mass of the catalyst. A precipitation method is adopted for preparing the catalyst and comprises the following steps: adding mixed powder of aluminum oxide, silicon oxide and zirconia into a soluble saline solution of ruthenium, M1 and M2, and stirring uniformly; then adding an alkaline precipitator dropwise to obtain black precipitates, filtering, washing, drying, tabletting for molding, packaging into a fixed bed reactor, and reducing by hydrogen under certain conditions to obtain the cyclohexane catalyst by nano Ru-M1-M2/A12O3-SiO2-ZrO2 benzene selective hydrogenation.
Description
Technical field
The present invention relates to catalyst technical field, be specially a kind of method for making of benzene selective hydrogenation to prepare cyclohexene noble metal Ru catalyst.
Background technology
Cyclohexene is very important chemical intermediate, because its active two keys can direct oxidation be prepared cyclohexanone and adipic acid, and hydration cyclohexanol processed, in addition cyclohexene is also widely used in medicine, agricultural chemicals and other fine chemicals.Cyclohexene is made by dehydration of cyclohexanol conventionally, but this complex process, Atom economy are low, and has the problems such as strong to equipment corrosion, environmental pollution is serious.Benzene selective Hydrogenation has energy-conservation, the feature such as Atom economy is high, environmental friendliness for cyclohexene technique, has represented the advanced level of this technical field and the developing direction of process greenization.The technique of the production adipic acid generally adopting both at home and abroad is at present that benzene complete hydrogenation is produced cyclohexane, and cyclohexane is oxidized to the mixture of cyclohexanone and cyclohexanol, and cyclohexanone and cyclohexanol are further oxidized to adipic acid.There is the shortcomings such as long flow path, oxidized byproduct is many, target product selectivity is poor, adipic acid yield is low, energy consumption is large in this technique.And adopt benzene selective Hydrogenation for this technique of cyclohexene, than traditional handicraft conservation, accessory substance is few, flow process is short, safe and reliable, environmental friendliness, has by contrast better economic benefit and social benefit, is subject in recent years extensive concern.But the thermodynamic stability of cyclohexane is more much higher than cyclohexene, so benzene hydrogenation is difficult to be controlled in the cyclohexene stage that generates, most of end product cyclohexane that generates, therefore, high conversion, high selectivity by prepared from benzene and hydrogen, for cyclohexene, be still a challenging difficult problem.For this reason, researcher has done a large amount of research both at home and abroad, and at present, benzene selective hydrogenation be take Ru catalyst as main, generally adopts different preparation methods, different carriers or adds the second one-tenth and assign to improve catalyst activity and selectivity.
Patent CN101961661A discloses a kind of organo-metallic catalyst preparation method, by RuCl
3s1 reacts with part, then Ru-S1 is reacted with part S2, then reacts and make Ru-S1-S2 with natrium carbonicum calcinatum.N-methylimidazole and chloro-normal butane are reacted to obtain to [BMIM] Cl, Ru-S1-S2 and [BMIM] Cl reaction is obtained to ionic-liquid catalyst for benzene hydrogenation, benzene conversion ratio reaches 20～35%, cyclohexene selectively reach 65～87%.Patent CN102319562A discloses a kind of nanometer ruthenium zinc catalyst, the aqueous solution of surfactant, ruthenium salt and zinc salt is evenly mixed, then drip alkali lye and make it precipitation, with reducing agent reduction, form nanometer ruthenium zinc again, after filtration, washing obtains high-dispersion nano ruthenium zinc catalyst, benzene conversion ratio 40.5～66.6, cyclohexene selective 54.2～69.9%.Patent CN1978056A discloses a kind of Ru of take, Fe and B is active component, the benzene hydrogenating catalyst that zeolite and zirconia are carrier, and cyclohexene selectively reduces gradually with the reaction time, talks about 30% left and right when initial reaction stage selectivity reaches 79%, 60 minute.Patent CN102600841A discloses a kind of Monolayer Dispersion benzene selective hydrogenation to prepare cyclohexene catalyst, and this catalyst is comprised of subsulfate and the orthosilicic acid polymer of Ru, auxiliary agent M.Benzene conversion ratio and selectively all reaching more than 70%.Patent CN101549292A discloses a kind of by activated carbon supported Ru and the benzene hydrogenating catalyst of auxiliary agent, the yield 50.6%～65.2% of cyclohexene.Patent CN102744084A discloses a kind of method of the catalyst system and catalyzing catalysis producing cyclohexene with benzene selective hydrogenation being comprised of nanometer Ru catalyst, alkaline matter M, zinc salt and water, and nanometer Ru catalyst is with NaOH, RuCl
3with polyethylene glycol be that initiation material adopts parallel-flow precipitation legal system standby, at 150 ℃, 5.0MPa, reaction 15～25min, benzene conversion ratio 40～60%, cyclohexene selective 75～85%.Patent CN102671659A discloses a kind of by Ru, ZnO and Zr (OH)
4the catalyst forming, benzene conversion ratio can reach 77.5%, cyclohexene selective 72.3%.CN102836711A discloses a kind of metal Ru catalyst, and two kinds of transition metal are auxiliary agent, and NaOH is precipitating reagent, and coprecipitation makes catalyst precursor, through hydrogen reducing, obtains catalyst, and benzene conversion ratio can reach 80.6%, cyclohexene selective 60.6%.Patent CN101269326A discloses that a kind of to take cordierite ceramic honeycomb or metal beehive be carrier, scribbles noble metal Ru, Pt, Pd or Rh, auxiliary agent A l
2o
3, SiO
2, TiO
2, ZrO
2, La
2o
3, Fe
2o
3, ZnO, Cr
2o
3, one or more the catalyst in GaO, CuO, BaO, CaO, the conversion ratio of benzene is lower.
US5589600 discloses a kind of Ru-Ni bimetallic catalyst that uses coprecipitation to prepare, the highest yield 40% of cyclohexene.The Japan patent US4734536 of Asahi Kasei Corporation discloses a kind of Ru-Zn catalyst, and the highest yield of cyclohexene can reach 50%, and successful industrialization.This catalyst Ru content reaches 60%, causes catalyst cost higher.US5973218 discloses a kind of preparation method of cyclohexene, and wherein catalyst used is the Ru catalyst of non-loading type, regulates the sulfate concentration be soluble in the aqueous phase to improve the selective of cyclohexene in benzene hydrogenation in course of reaction.It is carrier that US606043 discloses a kind of gallium oxide/zinc oxide double oxide, supported V III family metal, the preferably catalyst of ruthenium.In its preparation process, adopt the active component precursor of load on chemical reduction method reduction carrier, preferred chemical reducing agent is sodium borohydride.This catalyst is selective by higher cyclohexene, but benzene activity of conversion is not high.
The problem such as in the above patent, benzene selective hydrogenation catalyst mostly exists that Ru load capacity is high, complicated process of preparation, cyclohexene yield are low.And catalyst of the present invention is by adding a kind of auxiliary agent of doing in VIIIB group transition metal element of Fe, Co, Ni, Cu and Zn, utilize the existence of their d electron orbits that itself and cyclohexene are interacted, the cyclohexene generating is left behind from Ru surface, avoid its further reaction generation cyclohexane, thereby improve the selective of catalyst, other auxiliary agent B a and Ca add, can make itself and Ru competitive Adsorption occupy catalyst surface part active sites, make ruthenium more even in the surface distributed of catalyst.By add zirconia in carrier, do the decentralization that dispersant has improved noble metal Ru, improve the utilization rate of Ru, the in the situation that of lower Ru content, can realize the selective and yield of higher cyclohexene, and catalyst adopts coprecipitation preparation, before catalyst reduction, do not need roasting, simplified preparation technology.
Summary of the invention
The object of the present invention is to provide a kind of method for making of benzene selective hydrogenation to prepare cyclohexene noble metal Ru catalyst, solve that existing catalyst noble metal Ru load capacity is large, complicated process of preparation, problem that cyclohexene yield is low.
The present invention is a kind of method for making of benzene selective hydrogenation to prepare cyclohexene noble metal Ru catalyst, it is characterized in that: noble metal Ru, auxiliary agent M1 and M2, carrier, consist of;
Noble metal Ru be take the 1-30wt% that its content of simple substance is catalyst gross mass;
Described auxiliary agent M1 is a kind of in Fe, Co, Ni, Cu, Zn, and its content accounts for 0.2～5wt% of catalyst gross mass;
M2 is a kind of in Ba, Ca, and its content accounts for 0.1～3wt% of catalyst gross mass, and carrier is aluminium oxide, silica and zirconia, and its content accounts for 70～90wt% of catalyst gross mass;
The preparation of the employing precipitation method, preparation process is:
1. by RuCl
3nH
2o, M1 and M2 soluble-salt are dissolved in deionized water;
2. carrier is added to above-mentioned solution, be warming up to 60～80 ℃, stir and make it dispersed;
3. precipitating reagent is slowly splashed into above-mentioned solution, the pH of regulator solution in 7～9 scopes, ageing 8～12h, described precipitating reagent is selected the aqueous solution of NaOH, KOH;
4. above-mentioned precipitation after filtration, washing is extremely neutral, after 120～150 ℃ of oven dry 8～12h are dry, compressing tablet obtains preformed catalyst precursor;
5. the catalyst precarsor after compressing tablet is packed in fixed bed reactors and with hydrogen reducing, obtains nanometer Ru-M1-M2/Al under certain condition
2o
3-SiO
2-ZrO
2producing cyclohexene with benzene selective hydrogenation catalyst.
According to method for making of the present invention, it is characterized in that: described noble metal Ru accounts for catalyst gross mass in its content of simple substance and is preferably 10～20wt%, M1 accounts for catalyst gross mass and is preferably 2.0～4.0wt%, and M2 accounts for catalyst gross mass and is preferably 0.5～2.0wt%.
According to method for making of the present invention, it is characterized in that: 10～30wt%, the zirconia content that 40～80wt%, the silica content that described alumina catalyst support content accounts for carrier total amount accounts for carrier total amount accounts for 10～30wt% of carrier total amount.
According to method for making of the present invention, it is characterized in that: the soluble-salt of described M1 is preferably ZnCl
2, FeCl
36H2O, CoCl
26H
2o, Ni (NO
3)
26H2O, Cu (NO
3)
23H
2o, the soluble-salt solution of M2 is preferably CaCl
26H
2o, BaCl
2.
According to method for making of the present invention, it is characterized in that: the reducing condition of described catalyst is, 200～350 ℃ of temperature, pressure 0.5～3MPa, hydrogen flowing quantity 8～10L/h, the recovery time is 2～5h.
The activity rating of catalyst of the present invention carries out on 20mL high-pressure hydrogenation micro anti-evaluation device, reaction raw materials is benzene and water 1:2 mixing by volume, mixed material and hydrogen enter reactor by reactor top, and product, after gas-liquid separation, enters products pot after liquid material is cooling.Reaction condition is: pressure 4～5MPa, 130 ℃-180 ℃ of reaction temperatures, raw material volume space velocity 0.5-2h
-1, hydrogen to oil volume ratio 300-1000:1.
Specific embodiments of the invention are as follows:
Embodiment 1
By 27gRuCl
3nH
2o (Ru content 37%), 4.2gZnCl
2, 2.7gCaCl
26H
2o is dissolved in 2L deionized water, then by 44g γ-Al
2o
3, 26gSiO
2(gas phase), 17.5gZrO
2add above-mentioned solution to be heated to 60 ℃, vigorous stirring, it is mixed, then the NaOH aqueous solution of 2mol/L is slowly added to above-mentioned solution, after precipitation, the pH value of mixed liquor is 8, after ageing 8h, filter, wash to neutral, then compression molding after sediment being dried to 12h at 120 ℃, obtains catalyst precarsor, packs 20mL moulding rear catalyst precursor into 20mL fixed bed reactors, under 200 ℃, 3.0MPa, hydrogen flowing quantity 10L/h, reduce 5h, obtain Ru-Zn-Ca/Al
2o
3-SiO
2-ZrO
2catalyst.
Embodiment 2
By 40.5gRuCl
3nH
2o (Ru content 37%), 14.5gFeCl
36H
2o, 2.3gBaCl
2be dissolved in 2L deionized water, then by 48.3g γ-Al
2o
3, 16.1gSiO
2(gas phase), 16.1gZrO
2add above-mentioned solution to be heated to 70 ℃, vigorous stirring, it is mixed, then the NaOH aqueous solution of 2mol/L is slowly added to above-mentioned solution, the pH value of regulator solution is 9, after ageing 10h, filter, wash to neutral, then compression molding after sediment being dried to 8h at 150 ℃, obtains catalyst precarsor, packs 20mL moulding rear catalyst precursor into 20mL fixed bed reactors, under 250 ℃, 2.0MPa, hydrogen flowing quantity 9L/h, reduce 4h, obtain Ru-Fe-Ba/Al
2o
3-SiO
2-ZrO
2catalyst.
Embodiment 3
By 54.0gRuCl
3nH
2o (Ru content 37%), 16.1gCoCl
26H
2o, 10.9gCaCl
26H
2o is dissolved in 2L deionized water, then by 59.2g γ-Al
2o
3, 7.4gSiO
2(gas phase), 7.4gZrO
2add above-mentioned solution to be heated to 80 ℃, vigorous stirring, it is mixed, then the NaOH aqueous solution of 2mol/L is slowly added to above-mentioned solution, the pH value of regulator solution is 8, after ageing 12h, filter, wash to neutral, then compression molding after sediment being dried to 10h at 130 ℃, obtains catalyst precarsor, packs 20mL moulding rear catalyst precursor into 20mL fixed bed reactors, reductase 12 h under 300 ℃, 1.5MPa, hydrogen flowing quantity 8L/h, obtains Ru-Co-Ca/Al
2o
3-SiO
2-ZrO
2catalyst.
Embodiment 4
By 40.5gRuCl3nH
2o (Ru content 37%), 14.8gNi (NO
3)
26H
2o, 8.2gCaCl
26H
2o is dissolved in 2L deionized water, then by 32.2g γ-Al
2o
3, 26.0gSiO
2(gas phase), 24.2gZrO
2add above-mentioned solution to be heated to 70 ℃, vigorous stirring, it is mixed, then the NaOH aqueous solution of 2mol/L is slowly added to above-mentioned solution, the pH value of regulator solution is 8, after ageing 10h, filter, wash to neutral, then compression molding after sediment being dried to 10h at 130 ℃, obtains catalyst precarsor, packs 20mL moulding rear catalyst precursor into 20mL fixed bed reactors, under 350 ℃, 0.5MPa, hydrogen flowing quantity 9L/h, reduce 4h, obtain Ru-Ni-Ca/Al
2o
3-SiO
2-ZrO
2catalyst.
Embodiment 5
By 40.5gRuCl
3nH
2o (Ru content 37%), 11.4gCu (NO
3)
23H
2o, 8.2gCaCl
26H
2o is dissolved in 2L deionized water, then by 48.3g γ-Al
2o
3, 16.1gSiO
2(gas phase), 16.1gZrO
2add above-mentioned solution to be heated to 70 ℃, vigorous stirring, it is mixed, then the NaOH aqueous solution of 2mol/L is slowly added to above-mentioned solution, the pH value of regulator solution is 8, after ageing 10h, filter, wash to neutral, then compression molding after sediment being dried to 10h at 130 ℃, obtains catalyst precarsor, packs 20mL moulding rear catalyst precursor into 20mL fixed bed reactors, under 250 ℃, 2.0MPa, hydrogen flowing quantity 9L/h, reduce 4h, obtain Ru-Cu-Ca/Al
2o
3-SiO
2-ZrO
2catalyst.
Embodiment 6
By 40.5gRuCl
3nH
2o (Ru content 37%), 11.4gCu (NO
3)
23H
2o, 2.3gCaCl
26H
2o is dissolved in 2L deionized water, then by 48.3g γ-Al
2o
3, 16.1gSiO
2(gas phase), 16.1gZrO
2add above-mentioned solution to be heated to 70 ℃, vigorous stirring, it is mixed, then the NaOH aqueous solution of 2mol/L is slowly added to above-mentioned solution, the pH value of regulator solution is 8, after ageing 10h, filter, wash to neutral, then compression molding after sediment being dried to 10h at 130 ℃, obtains catalyst precarsor, packs 20mL moulding rear catalyst precursor into 20mL fixed bed reactors, under 250 ℃, 2.0MPa, hydrogen flowing quantity 9L/h, reduce 4h, obtain Ru-Cu-Ca/Al
2o
3-SiO
2-ZrO
2catalyst.
Embodiment 7
By 40.5gRuCl
3nH
2o (Ru content 37%), 11.4gCu (NO
3)
23H
2o, 8.2g BaCl
2be dissolved in 2L deionized water, then by 48.3g γ-Al
2o
3, 16.1gSiO
2(gas phase), 16.1gZrO
2add above-mentioned solution to be heated to 70 ℃, vigorous stirring, it is mixed, then the NaOH aqueous solution of 2mol/L is slowly added to above-mentioned solution, the pH value of regulator solution is 8, after ageing 10h, filter, wash to neutral, then compression molding after sediment being dried to 10h at 130 ℃, obtains catalyst precarsor, packs 20mL moulding rear catalyst precursor into 20mL fixed bed reactors, under 250 ℃, 2.0MPa, hydrogen flowing quantity 9L/h, reduce 4h, obtain Ru-Cu-Ba/Al
2o
3-SiO
2-ZrO
2catalyst.
Reference example
By 40.5gRuCl
3nH
2o (Ru content 37%), 11.4gCu (NO
3)
23H
2o, 2.3gCaCl
26H
2o is dissolved in 2L deionized water, then by 48.3g γ-Al
2o
3, 32.2gSiO
2(gas phase) adds above-mentioned solution to be heated to 70 ℃, vigorous stirring, it is mixed, then the NaOH aqueous solution of 2mol/L is slowly added to above-mentioned solution, the pH value of regulator solution is 8, after ageing 10h, filter, wash to neutral, then compression molding after sediment being dried to 10h at 130 ℃, obtains catalyst precarsor, packs 20mL moulding rear catalyst precursor into 20mL fixed bed reactors, under 250 ℃, 2.0MPa, hydrogen flowing quantity 9L/h, reduce 4h, obtain Ru-Cu-Ca/Al
2o
3-SiO
2catalyst.
Embodiment 1-7 and reference example evaluating catalyst are selected 20mL fixed bed high-pressure hydrogenation micro anti-evaluation device, after catalyst reduction finishes, cool the temperature to 170 ℃, pressure 4.5MPa, and liquid hourly space velocity (LHSV) is 1.0h
-1, hydrogen, benzene volume ratio 400:1, raw material is water and benzene 2:1 (volume ratio) mixed liquor.Evaluating catalyst the results are shown in Table 1 (take from and evaluate 100h stable data afterwards).
Table 1 catalyst benzene selective hydrogenation activity
| Project | Benzene conversion ratio, % | Cyclohexene is selective, % | Cyclohexene yield, % |
| Embodiment 1 | 80.2 | 70.2 | 56.3 |
| Embodiment 2 | 84.5 | 68.8 | 58.1 |
| Embodiment 3 | 85.2 | 70.1 | 59.7 |
| Embodiment 4 | 84.7 | 68.5 | 58.0 |
| Embodiment 5 | 84.1 | 69.1 | 58.1 |
| Embodiment 6 | 82.0 | 68.8 | 56.4 |
| Embodiment 7 | 85.3 | 69.8 | 59.5 |
| Reference example | 80.5 | 55.2 | 44.4 |
As seen from the above table, zirconic adding the selective of cyclohexene obviously improved.The noble-metal-supported amount of catalyst of the present invention is few, and preparation technology is simple, and benzene conversion ratio is high, and cyclohexene is selectively good, and cyclohexene yield approaches 60%.
Claims (5)
1. a method for making for benzene selective hydrogenation to prepare cyclohexene noble metal Ru catalyst, is characterized in that: noble metal Ru, auxiliary agent M1 and M2, carrier, consist of;
Noble metal Ru be take the 1-30wt% that its content of simple substance is catalyst gross mass;
Described auxiliary agent M1 is a kind of in Fe, Co, Ni, Cu, Zn, and its content accounts for 0.2～5wt% of catalyst gross mass;
M2 is a kind of in Ba, Ca, and its content accounts for 0.1～3wt% of catalyst gross mass, and carrier is aluminium oxide, silica and zirconia, and its content accounts for 70～90wt% of catalyst gross mass;
The preparation of the employing precipitation method, preparation process is:
1. by RuCl
3nH
2o, M1 and M2 soluble-salt are dissolved in deionized water;
2. carrier is added to above-mentioned solution, be warming up to 60～80 ℃, stir and make it dispersed;
3. precipitating reagent is slowly splashed into above-mentioned solution, the pH of regulator solution in 7～9 scopes, ageing 8～12h, described precipitating reagent is selected the aqueous solution of NaOH, KOH;
4. above-mentioned precipitation after filtration, washing is extremely neutral, after 120～150 ℃ of oven dry 8～12h are dry, compressing tablet obtains preformed catalyst precursor;
5. the catalyst precarsor after compressing tablet is packed in fixed bed reactors and with hydrogen reducing, obtains nanometer Ru-M1-M2/Al under certain condition
2o
3-SiO
2-ZrO
2producing cyclohexene with benzene selective hydrogenation catalyst.
2. according to method for making claimed in claim 1, it is characterized in that: described noble metal Ru be take its content of simple substance and accounted for catalyst gross mass as 10～20wt%, and it is 2.0～4.0wt% that M1 accounts for catalyst gross mass, and it is 0.5～2.0wt% that M2 accounts for catalyst gross mass.
3. according to method for making claimed in claim 1, it is characterized in that: 10～30wt%, the zirconia content that 40～80wt%, the silica content that described alumina catalyst support content accounts for carrier total amount accounts for carrier total amount accounts for 10～30wt% of carrier total amount.
4. according to method for making claimed in claim 1, it is characterized in that: the soluble-salt of described M1 is ZnCl
2, FeCl
36H2O, CoCl
26H
2o, Ni (NO
3)
26H2O, Cu (NO
3)
23H
2o, the soluble-salt solution of M2 is CaCl
26H
2o, BaCl
2.
5. according to method for making claimed in claim 1, it is characterized in that: the reducing condition of described catalyst is, 200～350 ℃ of temperature, pressure 0.5～3MPa, hydrogen flowing quantity 8～10L/h, the recovery time is 2～5h.
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| CN201410219983.8A CN104028267B (en) | 2014-05-23 | 2014-05-23 | A kind of method for making of benzene selective Hydrogenation cyclohexene noble metal Ru catalyst |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105327701A (en) * | 2015-12-01 | 2016-02-17 | 中国海洋石油总公司 | Preparation method of dibasic ester aromatic ring saturation catalyst containing benzene ring |
| CN105727944A (en) * | 2016-03-25 | 2016-07-06 | 福州大学 | A kind of preparation method of ZrO2 nano sheet supported ruthenium catalyst |
| CN109331821A (en) * | 2018-11-21 | 2019-02-15 | 湘潭大学 | Preparation method and application of zirconia modified sepiolite supported Ru-based catalyst |
| CN112439425A (en) * | 2019-09-02 | 2021-03-05 | 中国石油化工股份有限公司 | Hydrofining method and hydrofining agent for crude ethylene glycol |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102836711A (en) * | 2012-09-21 | 2012-12-26 | 河北科技大学 | Catalyst for preparing cyclohexene via selective hydrogenation of benzene and preparation method thereof |
| CN102861572A (en) * | 2012-10-12 | 2013-01-09 | 李建修 | Catalyst for preparing cyclohexene, preparation method of catalyst, preparation method of cyclohexene and preparation device of cyclohexene |
| CN102989521A (en) * | 2012-12-17 | 2013-03-27 | 中国科学院大连化学物理研究所 | Zirconium-containing spinel supported honeycomb monolithic catalyst for selective hydrogenation of benzene and preparation method for same |
-
2014
- 2014-05-23 CN CN201410219983.8A patent/CN104028267B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102836711A (en) * | 2012-09-21 | 2012-12-26 | 河北科技大学 | Catalyst for preparing cyclohexene via selective hydrogenation of benzene and preparation method thereof |
| CN102861572A (en) * | 2012-10-12 | 2013-01-09 | 李建修 | Catalyst for preparing cyclohexene, preparation method of catalyst, preparation method of cyclohexene and preparation device of cyclohexene |
| CN102989521A (en) * | 2012-12-17 | 2013-03-27 | 中国科学院大连化学物理研究所 | Zirconium-containing spinel supported honeycomb monolithic catalyst for selective hydrogenation of benzene and preparation method for same |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105327701A (en) * | 2015-12-01 | 2016-02-17 | 中国海洋石油总公司 | Preparation method of dibasic ester aromatic ring saturation catalyst containing benzene ring |
| CN105727944A (en) * | 2016-03-25 | 2016-07-06 | 福州大学 | A kind of preparation method of ZrO2 nano sheet supported ruthenium catalyst |
| CN105727944B (en) * | 2016-03-25 | 2018-06-15 | 福州大学 | A kind of ZrO2The preparation method of nanometer sheet supported ruthenium catalyst |
| CN109331821A (en) * | 2018-11-21 | 2019-02-15 | 湘潭大学 | Preparation method and application of zirconia modified sepiolite supported Ru-based catalyst |
| CN109331821B (en) * | 2018-11-21 | 2021-07-30 | 湘潭大学 | Preparation method and application of zirconia modified sepiolite supported Ru-based catalyst |
| CN112439425A (en) * | 2019-09-02 | 2021-03-05 | 中国石油化工股份有限公司 | Hydrofining method and hydrofining agent for crude ethylene glycol |
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|---|---|
| CN104028267B (en) | 2016-06-29 |
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