CN108727158A - A method of catalysis acetic acid hydrogenation ethyl alcohol - Google Patents
A method of catalysis acetic acid hydrogenation ethyl alcohol Download PDFInfo
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- CN108727158A CN108727158A CN201810495073.0A CN201810495073A CN108727158A CN 108727158 A CN108727158 A CN 108727158A CN 201810495073 A CN201810495073 A CN 201810495073A CN 108727158 A CN108727158 A CN 108727158A
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- acetic acid
- ethyl alcohol
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- 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
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The present invention relates to a kind of methods of catalysis acetic acid hydrogenation ethyl alcohol, with graphite phase carbon nitride (g-C3N4) be carrier loaded transitional metal phosphide catalyst, catalyst activity stability is good, and the device stable operation time is long, can avoid reactor reaction and regeneration frequent switching operation, the conversion ratio of acetic acid is 99.9% or more, and the selectivity of ethyl alcohol is 89% or more.
Description
Technical field
The invention belongs to field of fine chemical more particularly to a kind of methods of catalysis acetic acid hydrogenation ethyl alcohol.
Background technology
Ethyl alcohol is basic industries raw material and important organic solvent, is mainly used for food, chemical industry, military project, medicine and other fields,
There is the extensive market demand.Ethyl alcohol or a kind of free of contamination high-knock rating gasoline additive.In recent years, oil price is lasting
Soaring, environmental pressure is increasingly heavy, and new fungible energy source, second all in the development in pluralism for seeking the energy, are developed in countries in the world
Alcohol can be proportionally added into gasoline as emerging one of renewable green energy resource and be used as vehicle alternative fuel, in world's model
Popularization and approval are obtained in enclosing, the U.S. sells ethanol petrol and has more than 20 years history, and Brazilian 40% light-duty vehicle uses second
Alcohol ate.
China is also constantly increasing the demand of vehicle fuel ethyl alcohol, it is contemplated that China's gasoline consumption figure will reach within 2015
To 100,000,000 tons or so, if all calculated by 10% alcohol fuel of blending, the demand to alcohol fuel will reach using ethanol petrol
To 10,000,000 tons, and the production capacity of internal fuel ethyl alcohol only has 1,660,000 tons (statistical data in 2011) at present, therefore, develops fuel
Ethyl alcohol has great market demand.
The production technology of industrial ethyl alcohol mainly uses starch saccharic fermentation method and ethylene direct hydration method at present.Wherein,
Grain or cassava prepare ethyl alcohol route and always exist " striving grain with people ", and the contradiction of " striving ground with grain " is related to than energy in the long term
Source even more serious Food Security safely；Traditional exemplary fermentation method technique, the carbohydrate in cereal hydrolyze first
For carbohydrate, then ferment to obtain ethyl alcohol by yeast.It should about 52% carbon source form sediment in the process for yeast itself metabolic consumption
Powder fermentation method yield only has 55-60%, and high energy consumption, production capacity is low, and economy is extremely restricted.And ethylene hydration rule is deposited
Big in reaction pressure, conversion ratio only has the shortcomings of 4-5%, less economical.Therefore non-cereal crops, Non oil-based route system are developed
The technology of standby ethyl alcohol, effectively reduces ethyl alcohol production cost, is of great significance.
Coal is that China is most abundant, most economical and most reliable energy resources.It is added by coal production liquid fuel and height
The chemical products of value are the important components of China's oil substituted pesticides.Coal ethyl alcohol technology exists from scientific research angle
Three kinds of routes below：Coal is through synthesis gas ethyl alcohol directly processed；Coal is through synthesising gas systeming carbinol, then methanol homologization ethyl alcohol directly processed；
Coal is through methanol acetic acid, acetic acid direct hydrogenation or the repeated hydrogenation ethyl alcohol after esterification.Wherein synthesis gas ethanol yield directly processed
It is low, it is less economical, it cannot achieve industrialization in a short time；Methanol homologation traditionally uses homogeneous reaction, and pressure is high, second
Alcohol yield is low, less economical, in decades technical research blank wall；And coal through acetic acid by preparation of ethanol by hydrogenating in recent years by
It in succeeding in developing for catalyst, makes substantial progress, is most to be hopeful to realize industrialized coal ethyl alcohol technology path.
Acetic acid is important always industrial chemicals and solvent.Several years ago, in order to develop Downstream Products of Methanol, alleviate methanol
Superfluous production capacity, acetic acid industry are flourished, and present China's acetate yield is caused serious superfluous situation occur.It is reported that
China's acetate yield in 2011 is about 7,000,000 tons, the rate of capacity utilization 66%.Due to acetic acid market saturation, acetic acid price in recent years
It persistently drops, continual exploitation acetic acid downstream product extends acetic acid industrial chain, has the very big market demand.Using acetic acid plus
Hydrogen ethyl alcohol can not only solve acetic acid problem of excess production capacity, moreover it is possible to meet the growing ethyl alcohol market demand, realize warp
Ji and social effect two-win.Acetic acid ethyl alcohol has two process routes again：Acetic acid direct hydrogenation ethyl alcohol and acetic acid are after esterification
Repeated hydrogenation ethyl alcohol.Wherein, the conversion ratio of acetate and ethanol selectivity be all very in acetic acid esterified back end hydrogenation ethyl alcohol route
Height, product separation costs are low, and catalyst researches and develops relative maturity, and development difficulty is low, but the technology path technological process is long, has
Half ethyl alcohol needs reflux cycle, needs outsourcing ethyl alcohol at driving initial stage, and energy consumption is larger, and needs in addition to build acetic acid esterified
Device, investment are higher.
The key of acetic acid direct hydrogenation ethyl alcohol technology is to develop the catalysis of high acetic acid conversion ratio, high ethano selectivity
Agent, less due to studying, so development difficulty is larger, but in recent years, this respect is making important progress.
US20100197485A1 is disclosed is added CaSiO3 in Pt-Sn/SiO2 catalyst systems, 250 DEG C,
Under the conditions of 22bar, GHSV2500h-1, the selectivity of ethyl alcohol can reach 92%, but the conversion ratio of acetic acid only has 24%.
CN103170337A discloses a kind of for producing catalyst of ethyl alcohol and preparation method thereof, is urged using bimetallic
Agent, a kind of metal are noble metal platinum, ruthenium or palladium, and another metal is iron, cobalt or tin.But bullion content is relatively high, is
2%.
Recent study finds that transition metal phosphide has excellent catalytic performance in many hydrogen-involved reactions, as
New catalyst has caused the extensive concern of people.For transition metal phosphide because specific surface area is small, catalytic performance is poor.It will
It is loaded on the porous material, is prepared loaded catalyst, is the effective way of increasing specific surface area.Load hydrogenation is catalyzed
Degree of scatter of the performance of agent by catalytic active component load capacity and on carrier is influenced.
Loaded catalyst is prepared using incipient impregnation method, catalytic active component can be effectively utilized.It is impregnating
During in source metal to carrier, by adding complexing agent into dipping solution, dispersion journey of the source metal on carrier is improved
Degree increases metal surface area, improves the high active of hydrogenation catalysis of loaded catalyst.In addition, in source metal dipping process, profit
With the peptizaiton of ultrasonic wave, degree of scatter of the source metal on carrier is improved, the catalytic activity of loaded catalyst is improved.
On the basis of transition metal phosphide loaded catalyst preferable using these method processabilities, acetic acid hydrogenation system is developed
Ethyl alcohol technology has good application value.
Invention content
The present invention is in order to overcome the defect of prior art, and in view of industrial easy to implement, and proposition one kind is with acetone
It is raw material with isopropanol, using non-pure noble metal catalyst, the method for being catalyzed acetic acid hydrogenation ethyl alcohol.
Technical scheme is as follows：
The present invention provides a kind of method of catalysis acetic acid hydrogenation ethyl alcohol, and the method is：In temperature 250~400
DEG C, the ratio between the amount of 0.5~10.0MPa of pressure, mass space velocity 0.2~8.0 hour -1, hydrogen and acetic acid feed substance 1:1~
20:Under conditions of 1, acetic acid and hydrogen are mixed, and loaded transitional metal phosphide catalyst haptoreaction, by acetic acid plus
Hydrogen ethyl alcohol；It regenerates, recycles after catalyst inactivation；The loaded transitional metal phosphide catalyst is with transition metal
Phosphide is active component, with graphite phase carbon nitride (g-C3N4) it is carrier, the transition metal phosphide load quality score
It is 1~20%；
The transition metal phosphide is one or more of nickel phosphide, phosphating sludge, phosphatization cobalt, tungsten phosphide
Mixture.
Graphite phase carbon nitride (g-C3N4) it is a kind of novel no metal material, because it is with numerous special physics and chemistry
Matter shows potential application prospect, mesoporous g- in fields such as heterogeneous catalysis, photocatalysis, fuel cell and gas storages
C3N4Possess high-ratio surface and abundant mesopore orbit, more Adsorptions can be exposed, then promotes it in catalytic hydrogenation
The performance of the application aspects such as reaction.
Further, it is preferable to which the transition metal phosphide mass loading amount is 5%~15%.
Further, the graphite phase carbon nitride (g-C3N4) preparation method be：
Dicyanodiamine is placed in the crucible with lid, 530 are heated to 2 DEG C of speed per minute in Muffle furnace
DEG C, heat preservation, then room temperature is dropped to the speed of 2 DEG C of min mono-, the cake mass of yellow is obtained, here it is obtained blocky g-
C3N4.G-C3N4 is placed in ultrasonic disperse in ultra-pure water, obtained dispersion liquid is centrifuged at 3,000 rpm, is removed
The block g-C3N4 not yet removed to get.
Loaded transitional metal phosphide catalyst of the present invention is prepared using incipient impregnation method：By transition gold
Belong to compound and phosphorus compound and prepares dipping solution, dipping solution volume and catalyst carrier maximum adsorption water with distilled water
Volume is equal, is stirred dipping to catalyst carrier with dipping solution at room temperature, it is stored at room temperature 3~for 24 hours (preferably 5~
8h), dry 3~for 24 hours (preferably 50~70 DEG C dry 5~20h) at a temperature of 40~90 DEG C, catalyst precursor is obtained；So
Afterwards, dry catalyst precursor being fitted into tubular reactor, is passed through nitrogen, nitrogen volume space velocity is 10~1000h-1,
Pressure is 0.2~3.0MPa, is warming up to 200~400 DEG C with the rate of 1~5 DEG C/min, constant temperature handles 1~10h (preferably 50
~800h-1, pressure 0.5~2.0MPa, 1~3 DEG C/min are warming up to 200~300 DEG C, 2~6h of constant temperature), obtain support type mistake
Cross metal phosphide catalyst；The transistion metal compound amount is with the gauge of transition metal material, the phosphorus compound dosage
With the gauge of phosphorus substance, the ratio between amount of substance of transition metal and phosphorus is 1 in the dipping solution:1~1:5 (preferably 1:2~
1:3), in the dipping solution transiting metal concentration be 1.0 × 10-4~1.0 × 10-2mol/mL (preferably 4.0 × 10-4~
3.0 × 10-3mol/mL), the dipping solution volumetric usage with carrier quality be calculated as 0.5~5.5mL/g (preferably 0.8~
1.2mL/g)。
It is of the present invention with the beneficial effect of the method for loaded transitional metal phosphide catalyst acetic acid hydrogenation ethyl alcohol
Fruit is mainly reflected in：
(1) with graphite phase carbon nitride (g-C3N4) be carrier loaded transitional metal phosphide catalyst, catalyst live
Property stability it is good, the device stable operation time is long, can avoid reactor reaction and regenerate frequent switching operation acetic acid conversion ratio
99.9% or more, the selectivity of ethyl alcohol is 89% or more.
(2) catalyst is renewable, can avoid a large amount of dead catalyst post-processings, and effect on environment is small.
Specific implementation mode
Below in conjunction with technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described
Embodiment be only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, originally
The every other embodiment that domain those of ordinary skill is obtained without making creative work is added in neck, all belongs to
In the scope of protection of the invention.
【Embodiment 1】
The preparation of catalyst
S1, the dicyanodiamine of 200g is placed in the crucible with lid, with 2 DEG C of speed per minute in Muffle furnace
530 DEG C are heated to, keeps the temperature, then room temperature is dropped to the speed of 2 DEG C of min mono-, obtains the cake mass of yellow, here it is obtained
Blocky g-C3N4.100g-C3N4 is placed in 5L ultra-pure waters, ultrasound is for 24 hours.Obtained dispersion liquid is carried out at 3,000 rpm
It centrifuges, removes the block g-C3N4 not yet removed, obtain 89gg-C3N4.
S2, be with the g-C3N4 of above-mentioned preparation carrier, Ni (H2PO2) 26H2O nickel sources, Ni (H2PO2) 26H2O and
NaH2PO2H2O phosphorus sources prepare loaded catalyst.The Al2O3 for weighing 10g, by the Ni of 2.0g (6.739 × 10-3mol)
(H2PO2) it is molten to prepare 8.0mL dippings for the NaH2PO2H2O of 26H2O, 1.43g (1.3492 × 10-2mol) and distilled water
Liquid, nickel and phosphorus concentration are respectively 8.4238 × 10-4mol/mL, 3.3713 × 10-3mol/mL, dipping solution volume with urge
The volume of agent carrier maximum adsorption water is equal, and nickel and phosphorus atoms mol ratio are 1 in dipping solution:4.By incipient impregnation
Method carries out room temperature immersion, 8.0mL dipping solutions is added dropwise into 10g carriers, and be stirred continuously.After being added dropwise, it is stored at room temperature
24h.It is dried for 24 hours at a temperature of 50 DEG C；Then, dry catalyst precursor is fitted into tubular reactor, is passed through nitrogen,
Nitrogen volume space velocity is 50h-1, pressure 0.2MPa, is warming up to 300 DEG C with the rate of 5 DEG C/min, constant temperature handles 2h, obtains
The loaded catalyst that Ni2P load quality scores are 5%.
【Embodiment 2】
The preparation of catalyst
S1, the dicyanodiamine of 200g is placed in the crucible with lid, is added with 2 DEG C of speed per minute in Muffle furnace
Heat is to 530 DEG C, heat preservation, then drops to room temperature with the speed of 2 DEG C of min mono-, obtains the cake mass of yellow, here it is obtained
Blocky g-C3N4.100g-C3N4 is placed in 5L ultra-pure waters, ultrasound is for 24 hours.Obtained dispersion liquid is carried out at 3,000 rpm from
The heart detaches, and removes the block g-C3N4 not yet removed, obtains 89gg-C3N4.
S2, be with the g-C3N4 of above-mentioned preparation carrier, Ni (H2PO2) 26H2O nickel sources, Ni (H2PO2) 26H2O and
NaH2PO2H2O phosphorus sources prepare loaded catalyst.The Bio-sil for weighing 10g, by 4.0g's (1.3478 × 10-2mol)
It is molten that the NaH2PO2H2O and distilled water of Ni (H2PO2) 26H2O, 1.43g (1.3492 × 10-2mol) prepare 12mL dippings
Liquid, nickel and phosphorus concentration are respectively 1.1232 × 10-3mol/mL, 3.3707 × 10-3mol/mL, dipping solution volume with urge
The volume of agent carrier maximum adsorption water is equal, and nickel and phosphorus atoms mol ratio are 1 in dipping solution:3.By incipient impregnation
Method carries out room temperature immersion, 12mL dipping solutions is added dropwise into 10g carriers, and be stirred continuously.After being added dropwise, it is stored at room temperature
24h。
Dry 12h at a temperature of 60 DEG C；Then, dry catalyst precursor is fitted into tubular reactor, is passed through nitrogen
Gas, nitrogen volume space velocity are 10h-1, pressure 1.0MPa, are warming up to 250 DEG C with the rate of 2 DEG C/min, constant temperature handles 3h, obtains
The loaded catalyst for being 10% to Ni2P load quality scores.
【Embodiment 3】
The preparation of catalyst
S1, the dicyanodiamine of 200g is placed in the crucible with lid, with 2 DEG C of speed per minute in Muffle furnace
530 DEG C are heated to, keeps the temperature, then room temperature is dropped to the speed of 2 DEG C of min mono-, obtains the cake mass of yellow, here it is obtained
Blocky g-C3N4.100g-C3N4 is placed in 5L ultra-pure waters, ultrasound is for 24 hours.Obtained dispersion liquid is carried out at 3,000 rpm
It centrifuges, removes the block g-C3N4 not yet removed, obtain 89gg-C3N4.
S2, be with the g-C3N4 of above-mentioned preparation carrier, Ni (H2PO2) 26H2O nickel sources, Ni (H2PO2) 26H2O and
NaH2PO2H2O phosphorus sources prepare loaded catalyst.The Bio-sil for weighing 10g, by 4.0g's (1.3478 × 10-2mol)
It is molten that the NaH2PO2H2O and distilled water of Ni (H2PO2) 26H2O, 1.43g (1.3492 × 10-2mol) prepare 12mL dippings
Liquid, nickel and phosphorus concentration are respectively 1.1232 × 10-3mol/mL, 3.3707 × 10-3mol/mL, dipping solution volume with urge
The volume of agent carrier maximum adsorption water is equal, and nickel and phosphorus atoms mol ratio are 1 in dipping solution:3.By incipient impregnation
Method carries out room temperature immersion, 12mL dipping solutions is added dropwise into 10g carriers, and be stirred continuously.After being added dropwise, it is stored at room temperature
24h。
Dry 12h at a temperature of 60 DEG C；Then, dry catalyst precursor is fitted into tubular reactor, is passed through nitrogen
Gas, nitrogen volume space velocity are 10h-1, pressure 1.0MPa, are warming up to 250 DEG C with the rate of 2 DEG C/min, constant temperature handles 3h, obtains
The loaded catalyst for being 10% to Ni2P load quality scores.
【Embodiment 4】
Using fixed-bed reactor, 340 DEG C of temperature, pressure 2.0MPa, quality of acetic acid air speed 0.5h-1, hydrogen with
Acetic acid feed molar ratio 8:Under 1 reaction condition, acetic acid hydrogenation reaction is carried out with the catalyst of above-mentioned preparation, evaluates embodiment
The catalytic performance of catalyst prepared by 1-3, experimental result are listed in table 1.
Table 1
Above description has fully disclosed the specific implementation mode of the present invention.It should be pointed out that being familiar with the field
Technical staff is to any change for being done of specific implementation mode of the present invention all without departing from the model of claims of the present invention
It encloses.Correspondingly, the scope of the claims of the invention is also not limited only to previous embodiment.
Claims (6)
1. a kind of method of catalysis acetic acid hydrogenation ethyl alcohol, it is characterised in that：250~400 DEG C of temperature, pressure 0.5~
The ratio between amount of 10.0MPa, mass space velocity 0.2~8.0 hour -1, hydrogen and acetic acid feed substance 1:1~20:It, will under conditions of 1
Acetic acid and hydrogen mixing, and loaded transitional metal phosphide catalyst haptoreaction, by acetic acid hydrogenation ethyl alcohol；Catalyst loses
It regenerates, recycles after work；The loaded transitional metal phosphide catalyst using transition metal phosphide as active component, with
Graphite phase carbon nitride (g-C3N4) it is carrier, the transition metal phosphide load quality score is 1~20%；The transition
Metal phosphide is one or more of nickel phosphide, phosphating sludge, phosphatization cobalt, tungsten phosphide mixture.
2. the method for catalysis acetic acid hydrogenation ethyl alcohol according to claim 1, it is characterised in that：Select the transition metal phosphorus
Compound mass loading amount is 5%~15%.
3. the method for catalysis acetic acid hydrogenation ethyl alcohol according to claim 1, it is characterised in that：The graphite phase carbon nitride
(g-C3N4) preparation method be：
Dicyanodiamine is placed in the crucible with lid, 530 DEG C are heated to 2 DEG C of speed per minute in Muffle furnace, is protected
Temperature, then room temperature is dropped to the speed of 2 DEG C of min mono-, the cake mass of yellow is obtained, here it is obtained blocky g-C3N4；
G-C3N4 is placed in ultrasonic disperse in ultra-pure water, obtained dispersion liquid is centrifuged at 3,000 rpm, removal is still
Unstripped block g-C3N4 to get.
4. the method for being catalyzed acetic acid hydrogenation ethyl alcohol according to claim 1-3 any one of them, it is characterised in that：The load
Type transition metal phosphide catalyst is prepared using incipient impregnation method.
5. the method for catalysis acetic acid hydrogenation ethyl alcohol according to claim 4, it is characterised in that：By transistion metal compound
Dipping solution is prepared with phosphorus compound and distilled water, dipping solution volume is equal with the volume of catalyst carrier maximum adsorption water,
Dipping is stirred to catalyst carrier with dipping solution at room temperature, it is stored at room temperature 3~for 24 hours, it is done at a temperature of 40~90 DEG C
Dry 3~for 24 hours, obtain catalyst precursor；Then, dry catalyst precursor is fitted into tubular reactor, is passed through nitrogen,
Nitrogen volume space velocity is 10~1000h-1, and pressure is 0.2~3.0MPa, and 200~400 are warming up to the rate of 1~5 DEG C/min
DEG C, constant temperature handles 1~10h, obtains loaded transitional metal phosphide catalyst.
6. the method for catalysis acetic acid hydrogenation ethyl alcohol according to claim 5, which is characterized in that state transistion metal compound
Amount is with the gauge of transition metal material, and the phosphorus compound dosage is with the gauge of phosphorus substance, transition metal in the dipping solution
It is 1 with the ratio between the amount of substance of phosphorus:1~1:5, transiting metal concentration is 1.0 × 10-4~1.0 × 10- in the dipping solution
2mol/mL, the dipping solution volumetric usage are calculated as 0.5~5.5mL/g with carrier quality.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110013868A (en) * | 2019-05-08 | 2019-07-16 | 西安近代化学研究所 | A kind of selection hydrogenation-dechlorination preparation 2,3,3,3- tetrafluoropropene tungsten phosphide catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669372A (en) * | 2015-12-31 | 2016-06-15 | 浙江工业大学 | Method for catalyzing acetic acid hydrogenation for ethanol preparation by using transition metal phosphide catalyst |
| CN107362820A (en) * | 2017-08-16 | 2017-11-21 | 杭州更蓝生物科技有限公司 | It is a kind of to be used to be catalyzed catalyst of chlorinated organics burning and preparation method thereof |
-
2018
- 2018-05-22 CN CN201810495073.0A patent/CN108727158A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669372A (en) * | 2015-12-31 | 2016-06-15 | 浙江工业大学 | Method for catalyzing acetic acid hydrogenation for ethanol preparation by using transition metal phosphide catalyst |
| CN107362820A (en) * | 2017-08-16 | 2017-11-21 | 杭州更蓝生物科技有限公司 | It is a kind of to be used to be catalyzed catalyst of chlorinated organics burning and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110013868A (en) * | 2019-05-08 | 2019-07-16 | 西安近代化学研究所 | A kind of selection hydrogenation-dechlorination preparation 2,3,3,3- tetrafluoropropene tungsten phosphide catalyst |
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Application publication date: 20181102 |
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