CN106345512B - A kind of bianry alloy catalyst and its preparation method and application - Google Patents
A kind of bianry alloy catalyst and its preparation method and application Download PDFInfo
- Publication number
- CN106345512B CN106345512B CN201610628802.6A CN201610628802A CN106345512B CN 106345512 B CN106345512 B CN 106345512B CN 201610628802 A CN201610628802 A CN 201610628802A CN 106345512 B CN106345512 B CN 106345512B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- acetic acid
- carrier
- temperature
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
- B01J29/0352—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites containing iron group metals, noble metals or copper
- B01J29/0356—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
- B01J29/044—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
Abstract
The present invention relates to a kind of catalyst, a kind of bianry alloy catalyst and its preparation method and application is refered in particular to.Contain active component and catalyst carrier in the catalyst, catalyst activity component is copper (Cu) and palladium (Pd), catalyst carrier is one of SBA-15 molecular sieve and MCM-41 molecular sieve, and the quality of Ni metal and Pd and catalyst carrier is respectively 10-30% and 1-3% than range.The catalyst is suitable for high pressure fixed bed reactors, directlys adopt glacial acetic acid as raw material.Catalyst has biggish specific surface area, and catalyst surface has finely dispersed sour position, has good catalytic activity and stability during the reaction.
Description
Technical field
The present invention relates to a kind of catalyst, a kind of bianry alloy catalyst and its preparation method and application is refered in particular to, vinegar is used for
Acid catalysis preparation of ethanol through hydrogenation belongs to organic catalysis field.
Background technique
Ethyl alcohol is a kind of important organic solvent, is also important one of basic chemical industry raw material, is widely used in organic conjunction
At, medicine, pesticide, the industries such as chemical industry.Ethyl alcohol is also used as vehicle fuel, is that the free of contamination high-octane gasoline of one kind adds
Add agent.Currently, the industrial process of ethyl alcohol mainly has grain fermentation method and ethylene hydration method, in recent years, using coal or naturally
Gas is that the method for raw material ethyl alcohol is also increasingly taken seriously.Acetic acid is a kind of widely used industrial chemicals, can be used for preparing
Acetate, vinyl acetate, cellulose acetate etc..In recent years, since low-pressure methanol carbonyl process synthesizes the high demand for investment of acetic acid plant,
Cause China's acetic acid industry production capacity seriously superfluous, there is an urgent need to develop the downstream product of acetic acid, the industrial chain of acetic acid industry is improved,
Therefore, acetic acid preparation of ethanol by hydrogenating all has a very important significance acetic acid industry or even entire coal chemical industry.
There are mainly two types of approach for acetic acid preparation of ethanol by hydrogenating: one is acetic acid direct hydrogenations to produce ethyl alcohol, and another kind is first will
Acetic acid esterified repeated hydrogenation obtains ethyl alcohol, and as disclosed in some patents, the ethanol selectivity of this method generally compares a step hydrogenation method
Height, but its is cumbersome, and equipment investment is also much higher than directed hydrogenation, produces ethyl alcohol using acetic acid direct hydrogenation, undoubtedly will
Easier industrialization route and higher economic benefit are provided.
The acetic acid hydrogenation reaction of early stage mainly uses autoclave as reactor, generally requires more than ten or even tens megapascal
A possibility that Hydrogen Vapor Pressure, this proposes harsher requirement to reaction unit, also limits its industrial application.In contrast to this to the greatest extent
Reaction temperature outline needed for pipe fixed bed reactors is higher than tank reactor, but its reaction pressure can be greatly lowered and have
There is continual continuous production ability, has a good application prospect, therefore be rapidly progressed in recent years.
Chinese patent CN102311311A, CN102149661A and CN102304018A are disclosed a series of to be added for acetic acid
Pt and Sn are supported on SiO by the loaded catalyst of hydrogen ethyl alcohol respectively2, CaSiO3, graphite and SiO2-A12O3Composite oxides
On carrier, at 250 DEG C, under the conditions of 22bar, acetic acid conversion ratio 70%-85%, ethanol selectivity is greater than 93%.Chinese patent
CN86102420A is prepared for 2.5%Pd-5.1%Mo/ graphite catalyst using infusion process, at 249 DEG C, Hydrogen Vapor Pressure 10.3bar
Under the conditions of, acetic acid conversion 58%, the overall selectivity of ethyl alcohol and ester is 82.7% in product.Chinese patent CN102229520A
It describes using 10%W-5%Re-2%Ru/ almond Pd/carbon catalyst prepared by infusion process at 250 DEG C, 10MPa, LHSV 1.0h-1
Under the conditions of react 50h, take liquid phase sample to analyze, acetic acid conversion ratio be greater than 99%, ethanol selectivity 98.1%.Chinese patent
CN102300635A discloses Pt-Sn/SiO2Catalyst is at 280 DEG C, ethanol selectivity 85%.
Acetic acid preparation of ethanol by hydrogenating method disclosed above mostly uses active component of the noble metal as catalyst, many institute's weeks
Know, the price of noble metal catalyst costly, increases the production cost of ethyl alcohol.By base metal to noble metal catalyst
Catalyst cost can be reduced by being modified, and have very important realistic meaning.Reasonable modification also can be further improved
The stability of catalyst.
Summary of the invention
The purpose of the present invention is to provide a kind of catalyst with high activity and stability, are used for acetic acid preparation of ethanol by hydrogenating
Reaction, the catalyst be suitable for high pressure fixed bed reactors, directly adopt glacial acetic acid as raw material.
SBA-15 molecular sieve and the well-regulated duct of MCM-41 molecular sieve and biggish specific surface area, are highly suitable as
Catalyst carrier.Contain active component and catalyst carrier in the catalyst, catalyst activity component is copper (Cu) and palladium
(Pd), catalyst carrier is one of SBA-15 molecular sieve and MCM-41 molecular sieve.Ni metal and Pd and catalyst carrier
Quality is respectively 10-30% and 1-3% than range.
Acetic acid hydrogenation catalyst preparation method of the present invention is equi-volume impregnating, the raw material packet of catalyst preparation
Include copper nitrate (Cu (NO3)2·3H2O), palladium nitrate (Pd (NO3)2·2H2O), SBA-15 molecular sieve and MCM-41 molecular sieve.Specifically
Preparation the following steps are included:
(1) the dipping volume for measuring SBA-15 molecular sieve or MCM-41 molecular sieve first, using Cu (NO3)2·3H2O conduct
Copper source, Pd (NO3)2·2H2O weighs the Cu (NO of corrresponding quality according to the quality of catalyst than composition requirement as palladium source3)2·
3H2O and Pd (NO3)2·2H2O is added deionized water and is configured to dipping mixed aqueous solution, and carrier is added and soaks in equal volume at normal temperature
Stain 6h, per half an hour stirring once makes it be uniformly dispersed therebetween, and sample is dried overnight at 120 DEG C after dipping, 500 DEG C of roastings
Sample tabletting is sieved into the particle of 40-60 mesh, catalyst Precursors is made by 4h；Impregnate the volume matter of mixed aqueous solution and carrier
Amount is than being 10mL:1g.
(2) catalyst Precursors are carried out to reduction activation pretreatment in the gaseous mixture of nitrogen and hydrogen, under normal pressure, with 2
DEG C/min temperature programming to 200 DEG C, H in this section of process gaseous mixture2Volume fraction is 20%；Again with 1.0 DEG C/min temperature programming
To 260 DEG C, H during this2Volume fraction is adjusted to 40%, restores 3h in 260 DEG C of constant temperature, the catalyst after must restoring, i.e. Cu
Load capacity is the catalyst that 10-30%, Pd load capacity are 1-3%.
(3) by glacial acetic acid, (250 DEG C of gasification temperature) entrance is mounted with reducing catalyst described in step (2) after gasification
Fixed bed reactors (long 20cm, internal diameter 0.5cm) in carry out vapor catalytic dehydrogenation reaction, wherein loaded catalyst be 2g,
Sample introduction flow velocity 4mL/h, carrier gas H2Flow velocity is 50ml/min, and reaction is depressed in 3.0MPa and carried out, 280-340 DEG C of reaction temperature,
Product is collected in continuous sampling lh under given temperature, ice-water bath condensation.
Bimetallic catalyst preparation process used by notable feature of the invention is simple, and catalyst compares table with biggish
Area, catalyst surface have finely dispersed sour position, have good catalytic activity and stability during the reaction；Example
Such as, using catalyst of the invention, it is 2g, sample introduction flow velocity 4mL/h in loaded catalyst, reacts 3.0MPa, reaction temperature 340
Under DEG C reaction condition, the conversion per pass of acetic acid can reach 95%, and the selection performance of ethyl alcohol reaches 90%.
Specific embodiment
Below with reference to specific implementation example, the present invention will be further described
Embodiment 1
The preparation of catalyst:
(1) the dipping volume for measuring SBA-15 molecular sieve first, using Cu (NO3)2·3H2O is as copper source, Pd (NO3)2·
2H2O weighs the Cu (NO of 3.775g according to the quality of catalyst than composition requirement as palladium source3)2·3H2O and 0.0217g Pd
(NO3)2·2H2O is configured to 100mL mixed aqueous solution, 10g carrier incipient impregnation 6h at normal temperature is added, therebetween per half an hour
Stirring once makes it be uniformly dispersed.Sample is dried overnight at 120 DEG C after dipping, 500 DEG C of roasting 4h, by sample tabletting, screening
At the particle of 40-60 mesh, catalyst Precursors are made.
(2) catalyst Precursors are carried out to reduction activation pretreatment in the gaseous mixture of nitrogen and hydrogen, under normal pressure under, with
2 DEG C/min temperature programming is to 200 DEG C, H in this section of process gaseous mixture2Volume fraction is 20%；Again with 1.0 DEG C/min temperature programming
To 260 DEG C, H during this2Volume fraction is adjusted to 40%, restores 3h in 260 DEG C of constant temperature, the catalyst after must restoring, i.e. Cu
Load capacity is the catalyst that 10%, Pd load capacity is 1%.
(3) by glacial acetic acid, (250 DEG C of gasification temperature) entrance is mounted with reducing catalyst described in step (2) after overflash
Fixed bed reactors (long 20cm, internal diameter 0.5cm) in carry out vapor catalytic dehydrogenation reaction, wherein loaded catalyst be 2g,
Sample introduction flow velocity 4mL/h, carrier gas H2Flow velocity is 50ml/min, and reaction is depressed in 3.0MPa and carried out, 280-340 DEG C of reaction temperature,
Product is collected in continuous sampling lh under given temperature, ice-water bath condensation.The result of catalyst reaction is as shown in the table:
Table 1.Cu (10)-Pd (1)/SBA-15 catalysis acetic acid adds acetate hydrogen conversion ratio and ethanol selectivity
Embodiment 2
With embodiment 1, the load capacity of Pd in catalyst is only changed into 2%, the result for being catalyzed reaction is as shown in the table:
Table 2.Cu (10)-Pd (2)/SBA-15 catalysis acetic acid adds acetate hydrogen conversion ratio and ethanol selectivity
Embodiment 3
With embodiment 1, the load capacity of Pd in catalyst is only changed into 3%, the result for being catalyzed reaction is as shown in the table:
Table 2.Cu (10)-Pd (3)/SBA-15 catalysis acetic acid adds acetate hydrogen conversion ratio and ethanol selectivity
Embodiment 4
With embodiment 1, it is anti-that the load capacity that the load capacity of Cu in catalyst changes into 20%, Pd is only changed into 3% catalysis
The result answered is as shown in the table:
Table 4.Cu (20)-Pd (3)/SBA-15 catalysis acetic acid adds acetate hydrogen conversion ratio and ethanol selectivity
Embodiment 5
With embodiment 1, it is anti-that the load capacity that the load capacity of Cu in catalyst changes into 30%, Pd is only changed into 3% catalysis
The result answered is as shown in the table:
Table 5.Cu (30)-Pd (3)/SBA-15 catalysis acetic acid adds acetate hydrogen conversion ratio and ethanol selectivity
Embodiment 6
With embodiment 1, catalyst carrier is only changed to HZSM-5 molecular sieve, the load capacity of Cu is changed into catalyst
The load capacity of 20%, Pd change into 3%, and the result for being catalyzed reaction is as shown in the table:
Table 6.Cu (20)-Pd (3)/HZSM-5 catalysis acetic acid adds acetate hydrogen conversion ratio and ethanol selectivity
Claims (7)
1. a kind of bianry alloy catalyst, active component and catalyst carrier are contained in the catalyst, it is characterised in that: catalysis
Agent active component is copper and palladium, and catalyst carrier is SBA-15 molecular sieve, the mass ratio of Ni metal and catalyst carrier is 10,
20,30%, Pd and the mass ratio of catalyst carrier are 3%.
2. a kind of preparation method of bianry alloy catalyst as described in claim 1, is prepared using equi-volume impregnating, special
Sign is to carry out in accordance with the following steps:
(1) the dipping volume for measuring SBA-15 molecular sieve first, using Cu (NO3)2·3H2O is as copper source, Pd (NO3)2·2H2O
Cu (the NO of corrresponding quality is weighed according to the quality of catalyst than composition requirement as palladium source3)2·3H2O and Pd (NO3)2·
2H2O is added deionized water and is configured to dipping mixed aqueous solution, carrier incipient impregnation 6h at normal temperature is added, every half is small therebetween
When stirring once it is made to be uniformly dispersed, sample is dried overnight at 120 DEG C after dipping, 500 DEG C of roasting 4h, and sample tabletting is sieved
It is divided into the particle of 40-60 mesh, catalyst Precursors is made；
(2) catalyst Precursors are carried out to reduction activation pretreatment in the gaseous mixture of nitrogen and hydrogen, under normal pressure, with 2 DEG C/
Min temperature programming is to 200 DEG C, H in this section of process gaseous mixture2Volume fraction is 20%；Again extremely with 1.0 DEG C/min temperature programming
260 DEG C, H during this2Volume fraction is adjusted to 40%, restores 3h in 260 DEG C of constant temperature, the catalyst after must restoring, i.e. Cu is negative
Carrying capacity is 10,20,30%, Pd load capacity be 3% catalyst.
3. a kind of preparation method of bianry alloy catalyst as claimed in claim 2, it is characterised in that: dipping mixed aqueous solution
Volume mass ratio with carrier is 10mL:1g.
4. the purposes that a kind of bianry alloy catalyst as described in claim 1 prepares ethyl alcohol for acetic acid catalytic hydrogenation.
5. purposes as claimed in claim 4, the catalyst is suitable for high pressure fixed bed reactors, directlys adopt glacial acetic acid work
For raw material, it is characterised in that: enter in the fixed bed reactors for being mounted with the catalyst glacial acetic acid after gasification and carry out
Vapor catalytic dehydrogenation reaction, wherein loaded catalyst is 2g, sample introduction flow velocity 4mL/h, carrier gas H2Flow velocity is 50ml/min, reaction
It depresses and carries out in 3.0MPa, 340 DEG C of reaction temperature, product is collected in continuous sampling lh, ice-water bath condensation at a given temperature.
6. purposes as claimed in claim 5, it is characterised in that: the gasification temperature of glacial acetic acid is 250 DEG C.
7. purposes as claimed in claim 5, it is characterised in that: fixed bed reactors long 20cm, internal diameter 0.5cm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610628802.6A CN106345512B (en) | 2016-08-03 | 2016-08-03 | A kind of bianry alloy catalyst and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610628802.6A CN106345512B (en) | 2016-08-03 | 2016-08-03 | A kind of bianry alloy catalyst and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106345512A CN106345512A (en) | 2017-01-25 |
| CN106345512B true CN106345512B (en) | 2019-03-05 |
Family
ID=57843744
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610628802.6A Expired - Fee Related CN106345512B (en) | 2016-08-03 | 2016-08-03 | A kind of bianry alloy catalyst and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106345512B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1935375A (en) * | 2006-10-19 | 2007-03-28 | 复旦大学 | Method for preparing catalyst for preparing 1,4-cis-butanediol by dimethyl maleate hydrogenation |
| CN102333588A (en) * | 2009-10-26 | 2012-01-25 | 国际人造丝公司 | Be used for preparing the catalyst of ethanol by acetate |
| CN103113187A (en) * | 2013-02-19 | 2013-05-22 | 新地能源工程技术有限公司 | Method for producing ethanol and coproducing ethyl acetate with acetic acid |
| CN105268439A (en) * | 2014-07-25 | 2016-01-27 | 中国科学院大连化学物理研究所 | Catalyst of hydrogenation reaction as well as preparation method and purpose thereof |
| CN105308015A (en) * | 2013-04-26 | 2016-02-03 | 加利福尼亚大学董事会 | Methods to produce fuels |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8501652B2 (en) * | 2008-07-31 | 2013-08-06 | Celanese International Corporation | Catalysts for making ethanol from acetic acid |
| CN105363485B (en) * | 2015-09-07 | 2017-10-03 | 中国科学院福建物质结构研究所 | A kind of indirect vapor phase method Synthesis of dimethyl carbonate catalyst and preparation method thereof |
-
2016
- 2016-08-03 CN CN201610628802.6A patent/CN106345512B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1935375A (en) * | 2006-10-19 | 2007-03-28 | 复旦大学 | Method for preparing catalyst for preparing 1,4-cis-butanediol by dimethyl maleate hydrogenation |
| CN102333588A (en) * | 2009-10-26 | 2012-01-25 | 国际人造丝公司 | Be used for preparing the catalyst of ethanol by acetate |
| CN103113187A (en) * | 2013-02-19 | 2013-05-22 | 新地能源工程技术有限公司 | Method for producing ethanol and coproducing ethyl acetate with acetic acid |
| CN105308015A (en) * | 2013-04-26 | 2016-02-03 | 加利福尼亚大学董事会 | Methods to produce fuels |
| CN105268439A (en) * | 2014-07-25 | 2016-01-27 | 中国科学院大连化学物理研究所 | Catalyst of hydrogenation reaction as well as preparation method and purpose thereof |
Non-Patent Citations (3)
| Title |
|---|
| "Acetic acid hydroconversion over mono and bimetallic indium doped catalysts supported on alumina and silicas of various textures";Gyorgy Onyestyak et al.;《Open Chemistry》;20141201;第13卷;第526页左栏第2段 |
| "Bimetallic Pd–Cu catalysts for selective CO2 hydrogenation to methanol";Xiao Jiang et al.;《Applied Catalysis B：Environmental》;20150112;第173-185页 |
| "Pd–Cu interaction in Pd/Cu-MCM-41 catalysts: Effect of silica source and metal content";Patricia Benito et al.;《Catalysis Today》;20140922;第246卷;第108-115页 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106345512A (en) | 2017-01-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102847544B (en) | Catalytic agent for preparing ethanol by using acetic acid hydrogenation and preparation method thereof | |
| CN103769094B (en) | A kind of egg-shell catalyst for selective hydrogenation, preparation method and application | |
| CN102600842A (en) | Catalyst for preparing ethanol through hydrogenation of acetic acid as well as preparation method and application thereof | |
| CN102746087B (en) | Method for preparing cyclohexane by catalyzing and hydrogenising benzene at room temperature | |
| CN111054390A (en) | Catalyst for preparing methyl propionate by hydrogenating methyl acrylate and preparation and application thereof | |
| CN101445427A (en) | Method for selective hydrogenation reaction in heterogeneous catalysis of cinnamic aldehyde | |
| CN102847535A (en) | Catalyst for preparation of ethanol through acetic acid hydrogenation and preparation method thereof | |
| CN109232188B (en) | Preparation method of hydrogenated bisphenol A | |
| CN106866364A (en) | A kind of method that 1,3- ring pentanediols are prepared by furfuryl alcohol | |
| CN113731441B (en) | Cobalt-reduced graphene oxide Co/rGO catalyst and preparation method and application thereof | |
| CN114163404A (en) | Method for synthesizing gamma-valerolactone by catalytic hydrogenation of levulinic acid | |
| CN106345512B (en) | A kind of bianry alloy catalyst and its preparation method and application | |
| CN106824268B (en) | A kind of method and its application improving loaded catalyst catalytic selectivity | |
| CN103566933B (en) | A kind of acetate preparation of ethanol by hydrogenating catalyst and preparation method thereof | |
| CN114196429A (en) | Method for preparing alkane diesel oil by catalytic oil hydrodeoxygenation | |
| CN103638962A (en) | Preparation and application of Ni/Cu/SBA-15 composite catalyst | |
| CN103623861B (en) | A kind of preparation of Ni/Ag/MCM-41 composite catalyst and application thereof | |
| CN102872862A (en) | Carrier type platinum-ruthenium catalyst and application of carrier type platinum-ruthenium catalyst in hydrogenation of aromatic nitro compound | |
| CN112452340B (en) | Catalyst for preparing propylene by selective hydrogenation of propyne, preparation method and application thereof | |
| CN111068662B (en) | Metal nano catalyst and preparation method and application thereof | |
| CN113117682A (en) | Method for catalytic hydrogenation upgrading of Pickering emulsion system biomass platform compound | |
| CN113426475A (en) | Alpha, beta-unsaturated aldehyde ketone hydrogenation catalyst and preparation method thereof | |
| CN108940341B (en) | Catalyst for preparing alkane by catalytic hydrogenation and preparation method thereof | |
| CN106281526A (en) | A kind of two-step method prepares the method for liquefied petroleum gas | |
| CN111151293A (en) | Nitrogen-doped tungsten carbide catalyst and preparation and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190305 Termination date: 20200803 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |