CN102847535A - Catalyst for preparation of ethanol through acetic acid hydrogenation and preparation method thereof - Google Patents
Catalyst for preparation of ethanol through acetic acid hydrogenation and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a catalyst for preparation of ethanol through acetic acid hydrogenation and a preparation method thereof, and provides a catalyst for preparation of ethanol through acetic acid hydrogenation, which is environment-friendly, mild in conditions, excellent in catalysis performance and high in stability, and a preparation method thereof. The catalyst comprises the following components in percentage by mass: 0.5-2% of platinum, 0.5-6% of tin and the balance of carrier; and the composition of the catalyst is expressed as x%Pt-y%Sn/carrier, wherein x% represents the mass percent of Pt in the catalyst, y% represents the mass percent of Sn in the catalyst, and the carrier is silicon carbide or carbon nanotube. The preparation method of the catalyst comprises the following steps: mixing surfactant sodium lauryl sulfate with the platinum and tin components; then adding the carrier; performing liquid-phase reduction to prepare a catalyst precursor; and roasting the catalyst precursor under the air atmosphere to obtain the supported platinum-tin bimetallic catalyst for acetic acid hydrogenation. The invention has the advantages of simple preparation process and good repetitiveness, and is easy to implement scale-up production.
Description
Technical field
The present invention relates to a kind of catalyst, especially the Catalysts and its preparation method of acetic acid preparation of ethanol by hydrogenating.
Background technology
Ethanol is a kind of important organic solvent, also is one of important basic chemical industry raw material, is widely used in the industries such as organic synthesis, medicine, agricultural chemicals, chemical industry.Ethanol can also as vehicle fuel, be a kind of free of contamination high-octane gasoline additive.Current, the industrial process of ethanol mainly contains grain fermentation method and the hydration method of ethene on phosphoric acid-diatomite catalyst.In recent years, employing coal or natural gas are that the method for raw material ethanol processed also more and more comes into one's own, and namely make synthesis gas (CO+H by coal or natural gas
2), synthesis gas on support type Rh is catalyst based at 6.0～8.0MPa, can make ethanol, acetaldehyde, ethyl acetate and acetic acid under the 300oC condition is main carbon two oxygenatedchemicals, above carbon two oxygenatedchemicals are selecting hydrogenation just the acetaldehyde in the said mixture, ethyl acetate and acetic acid can be hydrogenated to ethanol through catalyst, realize preparing ethanol by coal or natural gas.Such as the disclosed promoted type CuO/Al of Chinese patent CN1230458A
2O
3Can and Rh/SiO
2Catalyst forms composite catalyst, and for the synthesis of gas ethanol processed, ethanol selectively reaches more than 90%.
Acetic acid is a kind of widely used industrial chemicals, can be used for preparing acetate, vinyl acetate, cellulose acetate etc.China's acetic acid industry production capacity is far longer than actual production at present, downstream product in the urgent need to exploitation acetic acid, improve the industrial chain of acetic acid industry, therefore, the added value that promotes carbon two oxygenatedchemicals by the Dichlorodiphenyl Acetate preparation of ethanol by hydrogenating has very real meaning.The acetic acid preparation of ethanol by hydrogenating mainly contains two kinds of approach: a kind of is that the acetic acid direct hydrogenation is produced ethanol; Another kind is first with acetic acid esterified, adopt again Supported Cu catalyst hydrogenation under relative temperate condition to obtain ethanol, disclosed such as Chinese patent CN102093162A, CN101934228A, CN102327774A, the ethanol of the method is selective general, and to go on foot hydrogenation method than one high, but its complex operation, equipment investment also are much higher than the direct hydrogenation method.Adopt the acetic acid direct hydrogenation to produce ethanol, easier industrialization route and the economic benefit of Geng Gao will be provided undoubtedly.
Early stage acetic acid hydrogenation reaction mainly adopts autoclave as reactor, generally needs the Hydrogen Vapor Pressure of tens even tens MPas, and this has proposed harsher requirement to reaction unit, has also limited the possibility of its commercial Application.In contrast to this, although the required reaction temperature of fixed bed reactors will be a little more than tank reactor, but its reaction pressure decrease and have continual continuous production capacity has good application prospect, is therefore developed fast in recent years.
US Patent No. 4517391 discloses a kind of quaternary composite oxides CoO-CuO-Mn
3O
4-MoO
3Be used for the acetic acid preparation of ethanol by hydrogenating, at acetate solution hourly space velocity (LHSV) 0.126h
-1, under the condition of 250 ℃ of reaction temperatures and Hydrogen Vapor Pressure 300bar, the ethanol yield can reach 97%.Chinese patent CN86102420A adopts infusion process to prepare the 2.5%Pd-5.1%Mo/ graphite catalyst, at 249 ℃, and Hydrogen Vapor Pressure 10.3bar, LHSV=0.35h
-1Under the condition, the acetic acid conversion ratio is 58%, and the overall selectivity of ethanol and ester is 82.7% in the product, wherein alcohol/ester=2.4.When auxiliary agent Mo was substituted with W, under the same terms, the acetic acid conversion ratio was 44.6%, and the overall selectivity of ethanol and ester is 73.1% in the product, wherein alcohol/ester=0.21.The result shows that the adding of W has promoted esterification and etherification reaction, has reduced the yield of ethanol.Chinese patent CN102229520A has described the 10%W-5%Re-2%Ru/ almond Pd/carbon catalyst of employing infusion process preparation at 250 ℃, and 10MPa, LHSV are 1.0h
-1React 50h under the condition, get the analysis of liquid phase sample, the acetic acid conversion ratio is greater than 99%, and ethanol selectively is 98.1%.
Celanese International Corp has applied for a series of Chinese patents about the standby ethanol of acetic acid Hydrogenation.Chinese patent CN102311311A, CN102149661A and CN102304018A disclose Pt and the Sn method by the total immersion stain have been loaded on SiO
2, CaSiO
3, graphite, SiO
2-Al
2O
3On the composite oxide carrier, at 250 ℃, 22bar, hydrogen gas space velocity (GHSV) is 2500h
-1Under the condition, acetic acid conversion ratio 70%～85%, ethanol are selectively greater than 93%.Chinese patent CN102149662A discloses take 10%Co as key component, and adding wherein a kind of of 1% Pd, Pt, Cr, Mo, Sn, W, Zn, Ir, Re, Cu, Ru, Rh is second component, and carrier is SiO
2, CaSiO
3, Al
2O
3, TiO
2, ZrO
2, a kind of in the carbon, in 225～275 ℃ of scopes, acetic acid conversion ratio 18%～70%, ethanol are selectively more than 90%.Chinese patent CN102307657 discloses a kind of reaction process of acetic acid preparation of ethanol by hydrogenating, adopts the multistage catalyst to unite the yield that use can obviously improve target product ethanol.Chinese patent CN102300635A discloses PtSn/SiO
2Catalyst is at 280 ℃, and ethanol selectively is 85%, and catalyst life can reach 100h.Chinese patent CN102333588A discloses at PtSn/SiO
2Add the CaSiO of appropriate amount in the catalyst system
3Can improve the heat endurance of catalyst as auxiliary agent.
Above-mentioned disclosed result's demonstration, the performance of Pt series catalysts is apparently higher than non-Pt series catalysts, and especially take support type PtSn catalyst as good, carrier adopts SiO more
2, Al
2O
3, TiO
2, ZrO
2Deng, preparation method take the infusion process of routine as main.Yet in view of the acetic acid hydrogenation is a catalytic reaction that thermal discharge is large, optimization of catalysts preparation method and the good carrier of selection thermal conductivity with the interaction that further improves between metallic catalyst and carrier, improve performance and the stability of catalyst.
Summary of the invention
The object of the present invention is to provide a kind of have environmental friendliness, mild condition, catalytic performance excellence and the high a kind of acetic acid preparation of ethanol by hydrogenating Catalysts and its preparation method of stability.
Described catalyst is a kind of platinum bimetallic ruthenium/tin catalyst.
Described acetic acid preparation of ethanol by hydrogenating catalyst comprises platinum, bimetallic ruthenium/tin and carrier, the catalyst composition is expressed as: the x%Pt-y%Sn/ carrier, x% represents the mass percent of platinum in catalyst in the formula, y% represents the mass percent of tin in catalyst, carrier is carborundum or CNT (CNT), and catalyst components content is platinum by mass percentage: 0.5%～2%, tin: 0.5%～6%, surplus is carrier; Be preferably platinum: 0.5%～1%, tin: 1%～3%, surplus is carrier.
Described tin can derive from the compound of tin, such as two hydrated stannous chlorides etc.
Described platinum can derive from the compound of platinum, such as six hydration chloroplatinic acids etc.
The caliber of described CNT can be 10～60nm, and length can be 1～15 μ m, and specific area can be 40～300m
2/ g.
The preparation method of described acetic acid preparation of ethanol by hydrogenating catalyst is as follows:
1) carrier is added in the ethylene glycol solution disperses;
In step 1), the ratio of described ethylene glycol and carrier is 5～20mg/mL; The condition of described dispersion can adopt ultrasonic dispersion 0.5～1.5h.
2) then chloroplatinic acid-ethylene glycol solution of preparation 1.5mg/mL and stannous chloride-ethylene glycol solution of 8mg/mL mix by the catalyst component proportioning, get solution A;
3) lauryl sodium sulfate (SDS) of preparation 0.6mg/mL-ethylene glycol solution;
4) with the SDS-ethylene glycol solution of solution A and step 3) preparation, and the product that step 1) obtains after disperseing mixes, and adds reducing agent, continues to stir, and after filtration, secondary ion water washing, oven dry, roasting, obtains acetic acid preparation of ethanol by hydrogenating catalyst.
In step 4), described reducing agent can adopt NaBH
4-ethylene glycol solution etc.; The mol ratio of described reducing agent and metal can be 20～80; The condition of described oven dry can be: at 60～120 ℃ of lower oven dry 4～12h; The condition of described roasting can be: 300～550 ℃ of roasting 4～12h in air atmosphere.
The present invention can adopt the activity of the prepared acetic acid preparation of ethanol by hydrogenating of high pressure fixed bed reaction system thinking catalyst, concrete grammar is that acetic acid preparation of ethanol by hydrogenating catalyst is packed in the reaction tube, pack into the up and down inertia quartz sand of capacity of bed prevents from managing interior gas channel, and then conditioned reaction temperature, pressure, hydrogen flow rate and acetic acid charging rate are carried out activity rating.Acetic acid is squeezed in the reaction system by high pressure constant flow pump, and by high pressure mass flowmenter control flow, reaction pressure is 1～5MPa to hydrogen after the pressure maintaining valve decompression, and reaction temperature is 200～400 ℃, and the hydracid mol ratio is 20～140, and the acetate solution hourly space velocity is 0.1～5h
-1
The present invention makes the better load of metal and is dispersed in carrier surface by anion surfactant SDS, in loaded platinum catalyst, introduce a small amount of tin, effectively promoted the dispersion of platinum, reduced the consumption of platinum, prepared Pt-Sn bimetallic catalyst has good acetic acid and selects preparation of ethanol by hydrogenating active.The catalyst of compositional optimization has the following advantages: (1) under 350 ℃ of reaction temperatures, the acetic acid conversion ratio is greater than 95%, and ethanol is selectively greater than 90%, and ethanol quality space-time yield is greater than 1000mg/g-cat/h; (2) through behind the active testing of 300h, better stable.This catalyst preparation process is simple, good reproducibility, and the scale that is easy to carry out is amplified production.Use the load type platinum-bimetallic ruthenium/tin catalyst of this method preparation, take acetic acid as raw material, carry out catalytic hydrogenation, hydrogenation products comprises ethanol, ethyl acetate, acetone, acetaldehyde, methane, ethane, ethene, carbon monoxide and carbon dioxide.
Description of drawings
Fig. 1 be the 1%Pt-1.2%Sn/CNT catalyst under 350 ℃ of reaction temperatures, adopting the acetate solution hourly space velocity is 1.5h
-1, the hydracid mol ratio is 80, the study on the stability schematic diagram of reaction 300h, and in Fig. 1, abscissa is the time (h) of acetic acid hydrogenation reaction, ordinate is acetic acid conversion ratio or ethanol selective (%); Mark △ represents the conversion ratio of acetic acid; ■ represents the selective of ethanol.
The specific embodiment
The present invention will be further described below by embodiment.
Embodiment 1
The 1%Pt-1.2%Sn/CNT catalyst:
1) with the thick product of CNT (caliber 10～60nm, length 1～15 μ m, the specific area 40～300m that buy
2/ g) 5.0g filters, washs and drying with red fuming nitric acid (RFNA) 80 ℃ of backflow 10h in oil bath of 100mL.Take by weighing the CNT 1.0g of processing, be added in the 100mL ethylene glycol solution, ultrasonic dispersion 1h.
2) measure the stannous chloride of the chloroplatinic acid of 1.5mg/mL-ethylene glycol solution 6.6mL and 8mg/mL-ethylene glycol solution 1.5mL, it is mixed, get solution A.
3) lauryl sodium sulfate (SDS) of preparation 0.6mg/mL-ethylene glycol solution 250mL.
4) with the SDS-ethylene glycol solution of solution A and step 3) preparation, and the CNT of ultrasonic dispersion in the step 1) is at room temperature behind the mix and blend 1h, slowly drips 0.5mol/LNaBH under continuing to stir
4-EG solution 10mL, and then stir 5h, through vacuum filtration, secondary deionized water washing 8 times, after 100 ℃ of oven dry, place Muffle furnace to rise to 350 ℃ with the heating rate of 3 ℃/min it, roasting 4h makes sample and is designated as 1%Pt-1.2%Sn/CNT.
Performance with acetic acid hydrogenation reaction evaluate catalysts.Concrete operations are, adopt the fixed bed reaction system, loaded catalyst 0.2g, reaction temperature rises to 350 ℃, the adjusting Hydrogen Vapor Pressure is 2.0MPa, and the control hydrogen flow rate is 98mL/min, and pumps into acetum with high pressure constant flow pump in reactor, flow rate of liquid is 0.002mL/min, and this moment, the acetate solution hourly space velocity was 0.6h
-1, the hydracid mol ratio is 80, reactant is collected product liquid after gas-liquid separator separates, the interval 1h quantitative analysis on gas-chromatography of taking a sample.Chromatographiccondition: the chromatographic column of flame ionization ditector is KB-Wax, and detecting thing has methane, acetaldehyde, acetone, ethyl acetate, ethanol and acetic acid.The chromatographic column of thermal conductivity detector (TCD) has Gaskuropack post and Active Carbon post, and detecting thing has carbon monoxide, carbon dioxide, methane, ethane, ethene.According to the ratio of each component in the product, adopt the correction factor normalization method to calculate the selective of the conversion ratio of acetic acid and various products.
Reaction 1～2h rear catalyst activity data reaches stable state, and at this moment, acetic acid conversion ratio 99.9%, ethanol selectively are 91.1%, and ethanol quality space-time yield is 440mg/g-cat/h, and the Evaluation results of catalyst sees Table 1.
Embodiment 2
The 1%Pt-2%Sn/CNT catalyst:
The preparation method of CNT support type Pt-Sn bimetallic catalyst is with embodiment 1, but stannous chloride-ethylene glycol solution of 8mg/mL is 2.5mL, other composition is constant, make the 1%Pt-2%Sn/CNT catalyst, the performance evaluation of catalyst Dichlorodiphenyl Acetate preparation of ethanol by hydrogenating and product analysis condition the results are shown in Table 1 with embodiment 1.
Embodiment 3
The 1%Pt-2%Sn/SiC catalyst:
The preparation method of carborundum supporting Pt-Sn bimetallic catalyst just changes CNT into Carboround, and carborundum is not done pre-pre-treatment with embodiment 1.Make the 1%Pt-2%Sn/SiC catalyst, the performance evaluation of catalyst Dichlorodiphenyl Acetate preparation of ethanol by hydrogenating and product analysis condition the results are shown in Table 1 with embodiment 1.
Embodiment 4
The 1%Pt-5%Sn/CNT catalyst:
The preparation method of CNT support type Pt-Sn bimetallic catalyst is with embodiment 1, but stannous chloride-ethylene glycol solution of 8mg/mL is 6.25mL, other composition is constant, make the 1%Pt-5%Sn/CNT catalyst, the performance evaluation of catalyst Dichlorodiphenyl Acetate preparation of ethanol by hydrogenating and product analysis condition the results are shown in Table 1 with embodiment 1.
Embodiment 5
The 0.5%Pt-0.5%Sn/CNT catalyst:
The preparation method of CNT support type Pt-Sn bimetallic catalyst is with embodiment 1, but the chloroplatinic acid of 1.5mg/mL-ethylene glycol solution 3.3mL, stannous chloride-ethylene glycol solution of 8mg/mL is 0.625mL, other composition is constant, make the 0.5%Pt-0.5%Sn/CNT catalyst, the performance evaluation of catalyst Dichlorodiphenyl Acetate preparation of ethanol by hydrogenating and the same embodiment of product analysis condition
1, the results are shown in Table 1.
Comparative Examples 1
1%Pt/CNT：
The preparation method of CNT supported Pt catalysts is with embodiment 1, but do not add stannous chloride-ethylene glycol solution, other composition is constant, makes the 1%Pt/CNT catalyst, the performance evaluation of catalyst Dichlorodiphenyl Acetate preparation of ethanol by hydrogenating and product analysis condition the results are shown in Table 1 with embodiment 1.
Comparative Examples 2
1%Sn/CNT：
The preparation method of CNT support type Sn catalyst is with embodiment 1, but do not add chloroplatinic acid-ethylene glycol solution, other composition is constant, makes the 1%Sn/CNT catalyst, the performance evaluation of catalyst Dichlorodiphenyl Acetate preparation of ethanol by hydrogenating and product analysis condition the results are shown in Table 1 with embodiment 1.
Comparative Examples 3
1%Pt-1.2%Sn/CNT-IM：
Take by weighing CNT, measure chloroplatinic acid-aqueous solution and stannous chloride-aqueous solution by embodiment 1, at room temperature mix, stir 1h, evaporation desolventizing water in 100 ℃ of oven dry, places Muffle furnace to rise to 350 ℃ with the heating rate of 3 ℃/min, roasting 4h obtains catalyst precursor.
Catalyst precursor is packed in the reactor, at normal pressure 5%H
2-95%N
2Under the atmosphere, be warming up to 350 ℃ of reduction 4h with 3 ℃/min, make CNT support type Pt-Sn bimetallic catalyst, be designated as 1%Pt-1.2%Sn/CNT-IM, the performance evaluation of catalyst Dichlorodiphenyl Acetate preparation of ethanol by hydrogenating and product analysis condition the results are shown in Table 1 with embodiment 1.
Table 1 support type Pt-Sn bimetallic catalyst acetic acid hydrogenation reaction performance
1Gas-phase product comprises CO, CO
2, methane, ethene, ethane etc.
Embodiment 6
Adopt the 1%Pt-1.2%Sn/CNT catalyst of embodiment 1, acetate solution hourly space velocity liquid hourly space velocity (LHSV) is got 1.5h
-1, 2.1h
-1And 3.0h
-1, all the other evaluations and product analysis condition the results are shown in Table 2 with embodiment 1.
Table 2 acetate solution hourly space velocity changes the impact on 1%Pt-1.2%Sn/CNT catalyst hydrogenation performance
Embodiment 7
Adopt the 1%Pt-1.2%Sn/CNT catalyst of embodiment 1, acetate solution hourly space velocity liquid hourly space velocity (LHSV) is 1.5h
-1, the hydracid ratio gets 40,60 and 100, and all the other evaluations and product analysis condition the results are shown in Table 3 with embodiment 1.
Table 3 hydracid is than the impact that changes 1%Pt-1.2%Sn/CNT catalyst hydrogenation performance
Embodiment 8
Adopt the 1%Pt-1.2%Sn/CNT catalyst of embodiment 1, acetate solution hourly space velocity liquid hourly space velocity (LHSV) is 1.5h
-1, Hydrogen Vapor Pressure is got 1MPa, 3MPa and all the other evaluations of 4MPa and product analysis condition with embodiment 1, the results are shown in Table 4.
Table 4 Hydrogen Vapor Pressure changes the impact on 1%Pt-1.2%Sn/CNT catalyst hydrogenation performance
1Gas-phase product comprises CO, CO
2, methane, ethene, ethane etc.
Embodiment 9
Adopt the 1%Pt-1.2%Sn/CNT catalyst of embodiment 1, acetate solution hourly space velocity liquid hourly space velocity (LHSV) is 1.5h
-1, reaction temperature is got 320 ℃ and 380 ℃, and all the other evaluations and product analysis condition the results are shown in Table 5 with embodiment 1.
Table 5 1%Pt-1.2%Sn/CNT catalyst acetic acid preparation of ethanol by hydrogenating reaction condition optimization result
1Gas-phase product comprises CO, CO
2, methane, ethene, ethane etc.
Embodiment 10
Adopt the 1%Pt-1.2%Sn/CNT catalyst of embodiment 1, acetate solution hourly space velocity liquid hourly space velocity (LHSV) is got 1.5h
-1, evaluation and the product analysis condition of pressing embodiment 1 are carried out the catalyst stability of 300h and are investigated, and the results are shown in Fig. 1.As we can see from the figure through 300h reaction, the conversion ratio of acetic acid or ethanol selectively still maintain the reaction initial level, show that the stability of catalyst is higher.
Claims (10)
1. acetic acid preparation of ethanol by hydrogenating catalyst, it is characterized in that comprising platinum, tin and carrier, the catalyst composition is expressed as: the x%Pt-y%Sn/ carrier, x% represents the mass percent of platinum in catalyst in the formula, and y% represents the mass percent of tin in catalyst, and carrier is carborundum or CNT (CNT), catalyst components content is by mass percentage, platinum: 0.5%～2%, tin: 0.5%～6%, surplus is carrier.
2. a kind of acetic acid preparation of ethanol by hydrogenating catalyst as claimed in claim 1 is characterized in that catalyst components content is platinum by mass percentage: 0.5%～1%, and tin: 1%～3%, surplus is carrier.
3. a kind of acetic acid preparation of ethanol by hydrogenating catalyst as claimed in claim 1 is characterized in that described tin derives from the compound of tin; Described platinum derives from the compound of platinum.
4. a kind of acetic acid preparation of ethanol by hydrogenating catalyst as claimed in claim 3 is characterized in that the compound of described tin adopts two hydrated stannous chlorides; The compound of described platinum adopts six hydration chloroplatinic acids.
5. a kind of acetic acid preparation of ethanol by hydrogenating catalyst as claimed in claim 1, the caliber that it is characterized in that described CNT is 10～60nm, and length is 1～15 μ m, and specific area is 40～300m
2/ g.
6. the preparation method of a kind of acetic acid preparation of ethanol by hydrogenating catalyst as claimed in claim 1 is characterized in that concrete steps are as follows:
1) carrier is added in the ethylene glycol solution disperses;
2) then chloroplatinic acid-ethylene glycol solution of preparation 1.5mg/mL and stannous chloride-ethylene glycol solution of 8mg/mL mix by the catalyst component proportioning, get solution A;
3) lauryl sodium sulfate (SDS) of preparation 0.6mg/mL-ethylene glycol solution;
4) with the SDS-ethylene glycol solution of solution A and step 3) preparation, and the product that step 1) obtains after disperseing mixes, and adds reducing agent, continues to stir, and after filtration, secondary ion water washing, oven dry, roasting, gets acetic acid preparation of ethanol by hydrogenating catalyst.
7. the preparation method of a kind of acetic acid preparation of ethanol by hydrogenating catalyst as claimed in claim 6 is characterized in that in step 1), and the ratio of described ethylene glycol and carrier is 5～20mg/mL; The condition of described dispersion can adopt ultrasonic dispersion 0.5～1.5h.
8. the preparation method of a kind of acetic acid preparation of ethanol by hydrogenating catalyst as claimed in claim 6 is characterized in that in step 4), and described reducing agent adopts NaBH
4-ethylene glycol solution; The mol ratio of described reducing agent and metal can be 20～80.
9. the preparation method of a kind of acetic acid preparation of ethanol by hydrogenating catalyst as claimed in claim 6 is characterized in that in step 4), and the condition of described oven dry is: at 60～120 ℃ of lower oven dry 4～12h.
10. the preparation method of a kind of acetic acid preparation of ethanol by hydrogenating catalyst as claimed in claim 6 is characterized in that in step 4), and the condition of described roasting is: 300～550 ℃ of roasting 4～12h in air atmosphere.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9024088B1 (en) | 2014-04-28 | 2015-05-05 | Celanese International Corporation | Hydrogenation catalysts comprising a mixed oxide comprising nickel |
| US9073815B1 (en) | 2014-04-28 | 2015-07-07 | Celanese International Corporation | Hydrogenation catalysts comprising a mixed oxide and processes for producing ethanol |
| US9353035B2 (en) | 2014-04-28 | 2016-05-31 | Celanese International Corporation | Process for producing ethanol with zonal catalysts |
| US9382177B2 (en) | 2014-04-28 | 2016-07-05 | Celanese International Corporation | Hydrogenation catalysts comprising a mixed oxide comprising a promoter metal |
| CN108404961A (en) * | 2018-03-27 | 2018-08-17 | 天津大学 | The nitrogenous hollow silica ball load platinum-tin catalyst of acetic acid preparation of ethanol by hydrogenating and preparation |
| CN108671916A (en) * | 2018-05-11 | 2018-10-19 | 福州大学 | A kind of alloy catalyst and preparation method thereof for esters preparation of ethanol by hydrogenating |
| CN108993592A (en) * | 2018-06-13 | 2018-12-14 | 厦门大学 | A kind of efficient hydrogenation catalyst and the preparation method and application thereof of butynediols butanediol |
| CN109201049A (en) * | 2017-07-04 | 2019-01-15 | 神华集团有限责任公司 | The catalyst and its preparation method and application of acetic acid preparation of ethanol by hydrogenating |
| CN111715257A (en) * | 2020-06-15 | 2020-09-29 | 上海大学 | CO2Cycloaddition reaction catalyst, preparation method and application thereof |
| CN112023910A (en) * | 2020-09-23 | 2020-12-04 | 西安凯立新材料股份有限公司 | Preparation method and application of straight-chain double-bond hydrogenation catalyst |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9024088B1 (en) | 2014-04-28 | 2015-05-05 | Celanese International Corporation | Hydrogenation catalysts comprising a mixed oxide comprising nickel |
| US9073815B1 (en) | 2014-04-28 | 2015-07-07 | Celanese International Corporation | Hydrogenation catalysts comprising a mixed oxide and processes for producing ethanol |
| US9353035B2 (en) | 2014-04-28 | 2016-05-31 | Celanese International Corporation | Process for producing ethanol with zonal catalysts |
| US9382177B2 (en) | 2014-04-28 | 2016-07-05 | Celanese International Corporation | Hydrogenation catalysts comprising a mixed oxide comprising a promoter metal |
| US9458072B2 (en) | 2014-04-28 | 2016-10-04 | Celanese International Corporation | Hydrogenation catalysts comprising a mixed oxide and processes for producing ethanol |
| CN109201049A (en) * | 2017-07-04 | 2019-01-15 | 神华集团有限责任公司 | The catalyst and its preparation method and application of acetic acid preparation of ethanol by hydrogenating |
| CN109201049B (en) * | 2017-07-04 | 2022-03-22 | 国家能源投资集团有限责任公司 | Catalyst for preparing ethanol by acetic acid hydrogenation and preparation method and application thereof |
| CN108404961A (en) * | 2018-03-27 | 2018-08-17 | 天津大学 | The nitrogenous hollow silica ball load platinum-tin catalyst of acetic acid preparation of ethanol by hydrogenating and preparation |
| CN108404961B (en) * | 2018-03-27 | 2019-11-19 | 天津大学 | The nitrogenous hollow silica ball load platinum-tin catalyst of acetic acid preparation of ethanol by hydrogenating and preparation |
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