CN107626310A - A kind of 2,3 dihydrofuran synthesis copper-based catalysts and preparation method and application - Google Patents
A kind of 2,3 dihydrofuran synthesis copper-based catalysts and preparation method and application Download PDFInfo
- Publication number
- CN107626310A CN107626310A CN201710845498.5A CN201710845498A CN107626310A CN 107626310 A CN107626310 A CN 107626310A CN 201710845498 A CN201710845498 A CN 201710845498A CN 107626310 A CN107626310 A CN 107626310A
- Authority
- CN
- China
- Prior art keywords
- sio
- cuo
- copper
- based catalysts
- 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.)
- Granted
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a kind of 2,3 dihydrofuran synthesis copper-based catalysts and preparation method and application.It is catalyzed the copper-based catalysts CuO/SiO that 1,4 butanediols prepare 2,3 dihydrofuran2‑Al2O3It is made up of following components：CuO、SiO2And Al2O3；The percent mass proportioning of each component：CuO 40~60%；SiO210~40%；Al2O310~40%.Copper-based catalysts CuO/SiO of the present invention2‑Al2O3Have dehydrogenation dehydration difunctional in the reaction for being catalyzed 1,4 butanediols, 2,3 dihydrofuran of preparation：Dehydrogenation functionality component is CuO, and dehydrating function component is SiO2‑Al2O3.The catalytic dehydrogenation ability matches rationally with water separation capability, and 2,3 dihydrofuran selectivity is high.The feed stock conversion of catalytic reaction may be up to 100%, and target product selectivity is higher than 85%.Dehydrogenation of the present invention is dehydrated difunctional CuO/SiO2‑Al2O3Catalyst directly can be used in mixed way with raw material, without offline prereduction, simplify technological process.Compared with the conventional method, dehydrogenation of the present invention is dehydrated difunctional CuO/SiO2‑Al2O3Catalyst is cheap.And the catalytic dehydrogenation and water separation capability are high, and match rationally achievable high selectivity and prepare 2,3 dihydrofuran.
Description
Technical field
The present invention relates to a kind of DHF synthesis copper-based catalysts and preparation method and application, belong to catalyst
Preparing technical field.
Background technology
DHF (2,3-Dihydrofuran, referred to as：2,3-DHF), molecular formula：C4H6O, molecular weight：70.1,
Boiling point：54.5 DEG C, density：0.91g/cm3, it is slightly soluble in water.DHF is a kind of highly important medicine intermediate, property
Matter is active, and its derivative can prepare a variety of pharmaceutical chemicals, such as：7- ethyl tryptophols, different support polyacid, Tegafur, the formaldehyde of ring third,
2- hydroxyl tetrahydrofurans etc..
People, which study, finds that 1,4- butanediols can generate 2,3 dihydro furan through dehydrogenation-dehydration.But at present both at home and abroad
It is relatively fewer for the open research report of 1,4- butanediol dehydrogenations-dehydration synthesis 2,3 dihydro furan.Ludmila Leite etc.
Serial cobalt-base catalyst is developed, dehydrogenation in liquid phase-dehydration is carried out and prepares DHF, the catalyst series cobalt content
For 50% or so, and also need to add precious metal palladium etc. and help reducing agent, cause the higher (Applied of catalyst cost
Ctalyst A:General 362(2009)147-154；Applied Ctalyst A:General 311(2006)86-93)；
In addition, cobalt series catalyst is difficult to reduce, generally require in a hydrogen atmosphere, and need higher reduction temperature (250~400 DEG C)
It could reduce.Because cobalt series catalyst reduction temperature is too high, in-situ reducing in a kettle can not be realized, it is necessary to build it is supporting from
Line reduction apparatus, and reduce after catalyst in reactor process is transferred to, it is necessary to add protective agent to prevent its oxidation.
The characteristics of cobalt series catalyst hardly possible reduces, causes DHF production process route to grow, complex operation, and production cost is higher.
The content of the invention
It is an object of the invention to provide a kind of without prereduction and the synthesis of cheap 2,3 dihydro furan is with copper-based
Catalyst and preparation method thereof, the cost of the copper-based catalysts is low, can simplify catalytic reduction process, so as to reduce Isosorbide-5-Nitrae-fourth
Glycol produces the production cost of 2,3 dihydro furan through dehydrogenation-dehydration.
Catalysis 1,4- butanediols provided by the present invention prepare the copper-based catalysts CuO/SiO of 2,3 dihydro furan2-
Al2O3, it is made up of following components：
CuO、SiO2And Al2O3。
Described copper-based catalysts CuO/SiO2-Al2O3In, the percent mass proportioning of each component is as follows：
CuO 40~60%；
SiO210~40%；
Al2O310~40%；
The percent mass proportioning of each component is preferably following 1) -6) in it is any：
1) CuO 45~55%；
SiO220~35%；
Al2O320~30%；
2) CuO 50%；
SiO220~35%；
Al2O320~30%；
3) CuO 50%；
SiO235%；
Al2O315%；
4) CuO 50%；
SiO230%；
Al2O320%；
5) CuO 50%；
SiO225%；
Al2O325%；
6) CuO 50%；
SiO220%；
Al2O330%.
Copper-based catalysts of the present invention can use conventional co-precipitation method to prepare, each by required proportional arrangement first
The metal salt solution of active component, such as：Nitrate solution；It is reconfigured at precipitating reagent such as：Sodium carbonate liquor.Then in certain temperature
Under pH value, metal salt solution and sodium carbonate liquor cocurrent are added drop-wise in stillpot, stirred, aging is stood, then filters, washes
Wash, dry, be calcined, obtain required dehydrogenation-dehydration bifunctional catalyst.
Specific catalyst preparation comprises the steps：
(1) mixed aqueous solution of copper nitrate and aluminum nitrate is prepared, acidic silicasol is added, stirs, obtain mixed acid
Liquid；
(2) sodium carbonate liquor is prepared as alkali lye；
(3) mix acid liquor and aqueous sodium carbonate cocurrent are added dropwise in stillpot, carry out cocurrent under agitation and be total to
Precipitation；Then the copper-based catalysts CuO/SiO is produced through aging, filtering, drying and roasting successively2-Al2O3。
In above-mentioned preparation method, in step (1), in the mixed aqueous solution, the molar concentration of the copper nitrate can be
Arbitrary value of the copper nitrate in effective solubility range in water, such as 0.5~1mol/L；The molar concentration of the aluminum nitrate can be
Arbitrary value of the aluminum nitrate in effective solubility range in water, such as 0.5~1mol/L；
The addition of the acidic silicasol is according to the copper-based catalysts CuO/SiO2-Al2O3The content of middle silica
And the content of silica determines in acidic silicasol.
In above-mentioned preparation method, in step (2), the molar concentration of the aqueous sodium carbonate can be sodium carbonate in water
Effective solubility range in arbitrary value, such as 0.5~1mol/L.
In above-mentioned preparation method, in step (3), the mix acid liquor extremely precipitates with the alkali lye in a manner of cocurrent is added dropwise
In kettle, the mix acid liquor constant flow rate maintains to precipitate suspension pH in 5~10ml/min by adjusting the alkali lye flow velocity
Value is between 7~8.
In above-mentioned preparation method, in step (3), the condition of the co-precipitation is as follows：
Temperature is 60~80 DEG C；
PH value is 7~8.
In above-mentioned preparation method, in step (3), the time of the aging can be 4~12 hours；
The purpose of the filtering is to remove the sodium ion remained in sediment；
The condition of the drying is as follows：
Temperature is 100~120 DEG C；
Time is 4~12 hours；
The condition of the roasting is as follows：
Temperature is 300~500 DEG C；
Time is 4~9 hours.
Copper-based catalysts CuO/SiO of the present invention2-Al2O32,3- bis- is prepared available for catalysis 1,4- butanediol dehydrogenations-dehydration
Hydrogen furans, the catalytic reaction are carried out in tank reactor, and its process is as follows：
(1) first by the copper-based catalysts CuO/SiO2-Al2O3Crush, be sized to 200~300 mesh, without prereduction；
(2) it is 1 by catalyst/feed mass ratio：10~30 respectively by copper-based catalysts CuO/SiO2-Al2O3With raw material 1,
In 4- butanediols and addition reactor, it is well mixed under vigorous stirring；
Preferable catalyst/feed mass ratio is 1：15~25；
(3) then to reaction tank reactor in be passed through nitrogen with air in metathesis reactor；
(4) air replaces into rear in reactor, and temperature of reactor is gradually heating into reaction temperature (120~220 DEG C),
Reacted at ambient pressure；
Preferable reaction temperature is 140~200 DEG C.
A large amount of hydrogen are produced in above-mentioned course of reaction, reacting gas product collects light component product after cold-trap cools down, gently
Component products are mainly tetrahydrofuran, 2,3 dihydro furan and water.After reaction 20~24 hours, nothing in the cold middle light component product of trap
2,3 dihydro furan generation stops reaction.Primary product gamma-butyrolacton and other heavy constituent products in reactor.
Copper-based catalysts CuO/SiO provided by the invention2-Al2O32,3 dihydro furan is prepared in catalysis 1,4- butanediols
Difunctional with dehydrogenation-dehydration in reaction, wherein dehydrogenation functionality component is CuO, and dehydrating function component is SiO2-Al2O3.This is urged
Agent ability of dehydrogenation matches rationally with water separation capability, and DHF selectivity is high.The feed stock conversion of catalytic reaction can be high
Up to 100%, target product selectivity is higher than 85%.
The present invention has the advantages that：
(1) the difunctional CuO/SiO of dehydrogenation-dehydration provided by the invention2-Al2O3Catalyst can be mixed directly with raw material to be made
With without offline prereduction, simplifying technological process, significantly reduce cost of investment and production cost.And traditional cobalt system urges
Agent reduction temperature is up to 400 DEG C or so, and so high temperature, thus cobalt series catalyst are extremely difficult in general reactor
Need to reduce offline outside reactor, be then transferred under protective atmosphere in reactor and carry out catalytic reaction, cause technique to answer
It is miscellaneous, long flow path.
(2) compared with existing technical method, the difunctional CuO/SiO of dehydrogenation-dehydration provided by the invention2-Al2O3Catalysis
Agent is cheap.And the catalytic dehydrogenation and water separation capability are high, and match rationally achievable high selectivity and prepare 2,3- bis-
Hydrogen furans.
Embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
Material used, reagent etc., unless otherwise specified, are commercially obtained in following embodiments.
Comparative example 1,
First, in terms of the total amount of catalyst：Co3O4Content is 50%, SiO2Content is 50%；According to catalyst components
Ratio prepares 1mol/L cobalt nitrate solution, then adds acidic silicasol, is uniformly mixed, obtains mix acid liquor.Then
1mol/L sodium carbonate liquor is prepared as alkali lye.Under the conditions of strong agitation, it is heavy that above-mentioned acid solution and alkali lye cocurrent are added drop-wise to
In the kettle of shallow lake, co-precipitation is carried out, control ph is 7~8 in precipitation process, and precipitation temperature is 60~80 DEG C.After precipitation terminates,
Aging 12 hours, then filter, wash 5 times, 120 DEG C of dry 12h, 450 DEG C roastings about 4 hours, obtain Co3O4/SiO2Catalysis
Agent.
The Co that will be prepared in above-mentioned comparative example 12O3/SiO2Catalyst under hydrogen, reductase 12 hour at 400 DEG C, so
In being transferred under nitrogen protection afterwards instead, and raw material BDO is added, be well mixed under vigorous stirring, carried out liquid phase and take off
Hydrogen-dehydration.Process conditions are：160 DEG C of temperature, normal pressure, feed/catalyst mass ratio=20:1, reaction result is shown in Table 1.
Embodiment 1,
In terms of the total amount of catalyst：CuO contents are 50%, SiO2Content is 45%, Al2O3Content is 5%.According to catalysis
Agent each component ratio prepares copper nitrate, aluminum nitrate mixed solution, and wherein metal ion total concentration is 1mol/L, then adds acid
Ludox, it is uniformly mixed, obtains mix acid liquor.Then 1mol/L sodium carbonate liquor is prepared as alkali lye.Stirring strongly
Under the conditions of mixing, above-mentioned acid solution and alkali lye cocurrent are added drop-wise in stillpot, progress co-precipitation, control ph in precipitation process
For 7~8, precipitation temperature is 60~80 DEG C.After precipitation terminates, aging 12 hours, then filter, wash 5 times, 120 DEG C of dryings
12h, 450 DEG C are calcined about 4 hours, obtain CuO/SiO2-Al2O3Catalyst.Catalyst is shown in Table 1 labeled as Cat1 reaction results.
Embodiment 2,
In terms of the total amount of catalyst：CuO contents are 50%, SiO2Content is 40%, Al2O3Content is 10%.According to catalysis
Agent each component ratio prepares copper nitrate, aluminum nitrate mixed solution, and wherein metal ion total concentration is 1mol/L, then adds acid
Ludox, it is uniformly mixed, obtains mix acid liquor.Then 1mol/L sodium carbonate liquor is prepared as alkali lye.Stirring strongly
Under the conditions of mixing, above-mentioned acid solution and alkali lye cocurrent are added drop-wise in stillpot, progress co-precipitation, control ph in precipitation process
For 7~8, precipitation temperature is 60~80 DEG C.After precipitation terminates, aging 12 hours, then filter, wash 5 times, 120 DEG C of dryings
12h, 450 DEG C are calcined about 4 hours, obtain CuO/SiO2-Al2O3Catalyst.Catalyst is shown in Table 1 labeled as Cat2 reaction results.
Embodiment 3,
In terms of the total amount of catalyst：CuO contents are 50%, SiO2Content is 35%, Al2O3Content is 15%.According to catalysis
Agent each component ratio prepares copper nitrate, aluminum nitrate mixed solution, and wherein metal ion total concentration is 1mol/L, then adds acid
Ludox, it is uniformly mixed, obtains mix acid liquor.Then 1mol/L sodium carbonate liquor is prepared as alkali lye.Stirring strongly
Under the conditions of mixing, above-mentioned acid solution and alkali lye cocurrent are added drop-wise in stillpot, progress co-precipitation, control ph in precipitation process
For 7~8, precipitation temperature is 60~80 DEG C.After precipitation terminates, aging 12 hours, then filter, wash 5 times, 120 DEG C of dryings
12h, 450 DEG C are calcined about 4 hours, obtain CuO/SiO2-Al2O3Catalyst.Catalyst is shown in Table 1 labeled as Cat3 reaction results.
Embodiment 4,
In terms of the total amount of catalyst：CuO contents are 50%, SiO2Content is 30%, Al2O3Content is 20%.According to catalysis
Agent each component ratio prepares copper nitrate, aluminum nitrate mixed solution, and wherein metal ion total concentration is 1mol/L, then adds acid
Ludox, it is uniformly mixed, obtains mix acid liquor.Then 1mol/L sodium carbonate liquor is prepared as alkali lye.Stirring strongly
Under the conditions of mixing, above-mentioned acid solution and alkali lye cocurrent are added drop-wise in stillpot, progress co-precipitation, control ph in precipitation process
For 7~8, precipitation temperature is 60~80 DEG C.After precipitation terminates, aging 12 hours, then filter, wash 5 times, 120 DEG C of dryings
12h, 450 DEG C are calcined about 4 hours, obtain CuO/SiO2-Al2O3Catalyst.Catalyst is shown in Table 1 labeled as Ca4 reaction results.
Embodiment 5,
In terms of the total amount of catalyst：CuO contents are 50%, SiO2Content is 25%, Al2O3Content is 25%.According to catalysis
Agent each component ratio prepares copper nitrate, aluminum nitrate mixed solution, and wherein metal ion total concentration is 1mol/L, then adds acid
Ludox, it is uniformly mixed, obtains mix acid liquor.Then 1mol/L sodium carbonate liquor is prepared as alkali lye.Stirring strongly
Under the conditions of mixing, above-mentioned acid solution and alkali lye cocurrent are added drop-wise in stillpot, progress co-precipitation, control ph in precipitation process
For 7~8, precipitation temperature is 60~80 DEG C.After precipitation terminates, aging 12 hours, then filter, wash 5 times, 120 DEG C of dryings
12h, 450 DEG C are calcined about 4 hours, obtain CuO/SiO2-Al2O3Catalyst.Catalyst is shown in Table 1 labeled as Ca5 reaction results.
Embodiment 6,
In terms of the total amount of catalyst：CuO contents are 50%, SiO2Content is 20%, Al2O3Content is 30%.According to catalysis
Agent each component ratio prepares copper nitrate, aluminum nitrate mixed solution, and wherein metal ion total concentration is 1mol/L, then adds acid
Ludox, it is uniformly mixed, obtains mix acid liquor.Then 1mol/L sodium carbonate liquor is prepared as alkali lye.Stirring strongly
Under the conditions of mixing, above-mentioned acid solution and alkali lye cocurrent are added drop-wise in stillpot, progress co-precipitation, control ph in precipitation process
For 7~8, precipitation temperature is 60~80 DEG C.After precipitation terminates, aging 12 hours, then filter, wash 5 times, 120 DEG C of dryings
12h, 450 DEG C are calcined about 4 hours, obtain CuO/SiO2-Al2O3Catalyst.Catalyst is shown in Table 1 labeled as Ca6 reaction results.
Embodiment 7,
In terms of the total amount of catalyst：CuO contents are 50%, SiO2Content is 15%, Al2O3Content is 35%.According to catalysis
Agent each component ratio prepares copper nitrate, aluminum nitrate mixed solution, and wherein metal ion total concentration is 1mol/L, then adds acid
Ludox, it is uniformly mixed, obtains mix acid liquor.Then 1mol/L sodium carbonate liquor is prepared as alkali lye.Stirring strongly
Under the conditions of mixing, above-mentioned acid solution and alkali lye cocurrent are added drop-wise in stillpot, progress co-precipitation, control ph in precipitation process
For 7~8, precipitation temperature is 60~80 DEG C.After precipitation terminates, aging 12 hours, then filter, wash 5 times, 120 DEG C of dryings
12h, 450 DEG C are calcined about 4 hours, obtain CuO/SiO2-Al2O3Catalyst.Catalyst is shown in Table 1 labeled as Ca7 reaction results.
Embodiment 8,
In terms of the total amount of catalyst：CuO contents are 50%, SiO2Content is 10%, Al2O3Content is 40%.According to catalysis
Agent each component ratio prepares copper nitrate, aluminum nitrate mixed solution, and wherein metal ion total concentration is 1mol/L, then adds acid
Ludox, it is uniformly mixed, obtains mix acid liquor.Then 1mol/L sodium carbonate liquor is prepared as alkali lye.Stirring strongly
Under the conditions of mixing, above-mentioned acid solution and alkali lye cocurrent are added drop-wise in stillpot, progress co-precipitation, control ph in precipitation process
For 7~8, precipitation temperature is 60~80 DEG C.After precipitation terminates, aging 12 hours, then filter, wash 5 times, 120 DEG C of dryings
12h, 450 DEG C are calcined about 4 hours, obtain CuO/SiO2-Al2O3Catalyst.Catalyst is shown in Table 1 labeled as Ca8 reaction results.
The CuO/SiO for preparing is added in above-described embodiment in a kettle2-Al2O3Catalyst (Cat1-8) and raw material 1,
4- butanediols, are well mixed under vigorous stirring, carry out dehydrogenation in liquid phase-dehydration.Process conditions are：160 DEG C of temperature, often
Pressure, feed/catalyst mass ratio=20:1, reaction result is shown in Table 1.
The product of catalyst 1,4- butanediols prepared by the embodiment 1-8 of table 1 and comparative example 1
It is visible in CuO/SiO by embodiment2-Al2O3On bifunctional catalyst, CuO contents are 50%, SiO2Content is
25%, Al2O3When content is 25% (Cat5), achievable high selectivity prepares DHF, and selectivity is up to 85.2%.
Al2O3When content is relatively low, the weaker primary product of acidity of catalyst is gamma-butyrolacton, and Al2O3When content is higher, acidity of catalyst
Relatively strong, the direct cyclodehydration probability increase of raw material BDO, tetrahydrofuran selectivity is higher, and DHF selects
Property is relatively low.
From data above, the CuO/SiO of preferred mistake in the method for the invention for preparing DHF2-Al2O3It is double
Function catalyst forms：CuO content is 45~55%, SiO2Content be 20~25%, Al2O3Content for 25~
30%.The raw material 1,4- butanediols that the inventive method uses can generate 2 with high selectivity under the effect of above-mentioned bifunctional catalyst,
3- dihydrofuran.
Claims (10)
1. a kind of catalysis 1,4- butanediols prepare the copper-based catalysts CuO/SiO of 2,3 dihydro furan2-Al2O3, it is by following groups
It is grouped into：CuO、SiO2And Al2O3。
2. copper-based catalysts CuO/SiO according to claim 12-Al2O3, it is characterised in that：The copper-based catalysts
CuO/SiO2-Al2O3In, the percent mass proportioning of each component is as follows：
CuO 40~60%；
SiO210~40%；
Al2O310~40%.
3. copper-based catalysts CuO/SiO according to claim 22-Al2O3, it is characterised in that：The copper-based catalysts
CuO/SiO2-Al2O3In, the percent mass proportioning of each component is as follows：
CuO 45~55%；
SiO220~35%；
Al2O320~30%.
4. copper-based catalysts CuO/SiO any one of claim 1-32-Al2O3Preparation method, comprise the steps：
(1) mixed aqueous solution of copper nitrate and aluminum nitrate is prepared, acidic silicasol is added, stirring, obtains mix acid liquor；
(2) sodium carbonate liquor is prepared as alkali lye；
(3) mix acid liquor and aqueous sodium carbonate cocurrent are added dropwise in stillpot, carry out co-precipitation under agitation；
Then the copper-based catalysts CuO/SiO is produced through aging, filtering, drying and roasting successively2-Al2O3。
5. preparation method according to claim 4, it is characterised in that：In step (3), the condition of the co-precipitation is such as
Under：
Temperature is 60~80 DEG C；
PH value is 7~8.
6. the preparation method according to claim 4 or 5, it is characterised in that：In step (3), time of the aging for 4~
12 hours；
The condition of the drying is as follows：
Temperature is 100~120 DEG C；
Time is 4~12 hours；
The condition of the roasting is as follows：
Temperature is 300~500 DEG C；
Time is 4~9 hours.
7. copper-based catalysts CuO/SiO any one of claim 1-42-Al2O3In catalysis 1,4- butanediol dehydrogenations-dehydration
Prepare the application in 2,3 dihydro furan.
8. a kind of preparation method of DHF, comprises the following steps：
In copper-based catalysts CuO/SiO any one of claim 1-42-Al2O3Catalysis under, BDO is through de-
Hydrogen-dehydration obtains the 2,3 dihydro furan.
9. preparation method according to claim 8, it is characterised in that：Dehydrogenation-the dehydration is in tank reactor
Carry out；
The copper-based catalysts CuO/SiO2-Al2O3Granularity be 200~300 mesh.
10. preparation method according to claim 8 or claim 9, it is characterised in that：The condition of the dehydrogenation-dehydration is as follows：
Carry out at ambient pressure；
Temperature is 120~220 DEG C；
The copper-based catalysts CuO/SiO2-Al2O3Mass ratio with the 1,4- butanediols is 1：10~30.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710845498.5A CN107626310B (en) | 2017-09-19 | 2017-09-19 | Copper-based catalyst for synthesizing 2,3-dihydrofuran and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710845498.5A CN107626310B (en) | 2017-09-19 | 2017-09-19 | Copper-based catalyst for synthesizing 2,3-dihydrofuran and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107626310A true CN107626310A (en) | 2018-01-26 |
| CN107626310B CN107626310B (en) | 2020-02-14 |
Family
ID=61102240
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710845498.5A Active CN107626310B (en) | 2017-09-19 | 2017-09-19 | Copper-based catalyst for synthesizing 2,3-dihydrofuran and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107626310B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5163117A (en) * | 1974-11-29 | 1976-06-01 | Mitsui Petrochemical Ind | Gisanmechiruno seizohoho |
| CN101961652A (en) * | 2010-10-14 | 2011-02-02 | 来安县迅能催化剂有限公司 | Catalyst for preparing 2-methyl furan through gas phase hydrogenation of furfural and preparation method thereof |
| CN102764656A (en) * | 2012-08-06 | 2012-11-07 | 久泰能源科技有限公司 | High-efficiency hydrogenation catalyst and method for preparing same |
| CN104245120A (en) * | 2012-03-30 | 2014-12-24 | 巴斯夫公司 | Catalyst for tetrahydrofuran synthesis |
| CN105148913A (en) * | 2015-10-08 | 2015-12-16 | 宁波海越新材料有限公司 | Catalyst for preparation of methyl ethyl ketone from sec-butyl alcohol, and preparation method for catalyst |
| CN105435800A (en) * | 2015-11-19 | 2016-03-30 | 中科合成油技术有限公司 | Catalyst used for preparing 2,5-methyl furan and preparation method thereof |
| CN106732496A (en) * | 2016-12-14 | 2017-05-31 | 中科合成油技术有限公司 | A kind of high activity amorphous silica-alumina, the hydrocracking catalyst with it as carrier and their preparation method |
| CN106732593A (en) * | 2016-12-30 | 2017-05-31 | 天津市长芦化工新材料有限公司 | Copper-based solid-phase catalyst and its preparation method and application |
-
2017
- 2017-09-19 CN CN201710845498.5A patent/CN107626310B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5163117A (en) * | 1974-11-29 | 1976-06-01 | Mitsui Petrochemical Ind | Gisanmechiruno seizohoho |
| CN101961652A (en) * | 2010-10-14 | 2011-02-02 | 来安县迅能催化剂有限公司 | Catalyst for preparing 2-methyl furan through gas phase hydrogenation of furfural and preparation method thereof |
| CN104245120A (en) * | 2012-03-30 | 2014-12-24 | 巴斯夫公司 | Catalyst for tetrahydrofuran synthesis |
| CN102764656A (en) * | 2012-08-06 | 2012-11-07 | 久泰能源科技有限公司 | High-efficiency hydrogenation catalyst and method for preparing same |
| CN105148913A (en) * | 2015-10-08 | 2015-12-16 | 宁波海越新材料有限公司 | Catalyst for preparation of methyl ethyl ketone from sec-butyl alcohol, and preparation method for catalyst |
| CN105435800A (en) * | 2015-11-19 | 2016-03-30 | 中科合成油技术有限公司 | Catalyst used for preparing 2,5-methyl furan and preparation method thereof |
| CN106732496A (en) * | 2016-12-14 | 2017-05-31 | 中科合成油技术有限公司 | A kind of high activity amorphous silica-alumina, the hydrocracking catalyst with it as carrier and their preparation method |
| CN106732593A (en) * | 2016-12-30 | 2017-05-31 | 天津市长芦化工新材料有限公司 | Copper-based solid-phase catalyst and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| L. LEITE: "Copper-promoted cobalt catalysts for 2,3-dihydrofuran synthesis", 《APPLIED CATALYSIS A-GENERAL》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107626310B (en) | 2020-02-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102617518B (en) | One-step preparation method for tetrahydrofuran by employing maleic anhydride gas phase hydrogenation | |
| CN102659724B (en) | A kind of preparation method of succinyl oxide | |
| CN102631930A (en) | Catalyst for preparing furfuryl alcohol from furfural by vapor phase hydrogenation and preparation method thereof | |
| CN107573370A (en) | The method that supported copper ion chitosan microball catalysis prepares organoboron compound and β hydroxy compounds | |
| CN106414383A (en) | Process for the production of alkenols and use thereof for the production of 1,3-butadiene | |
| CN108368076A (en) | Prepare 2,5- furandicarboxylic acids（FDCA）Method | |
| CN107011107A (en) | A kind of method that use load type metal catalyst prepares alcohol | |
| CN101983765B (en) | Catalyst for preparing methyl alcohol by catalytic hydrogenation on assistant modified carbon dioxide and preparation method thereof | |
| CN106622316B (en) | A kind of vanadium-phosphor oxide catalyst, preparation method and application | |
| CN112390712A (en) | Method for preparing 1, 3-butanediol by adopting fixed bed continuous reaction | |
| CN107999083A (en) | A kind of preparation method of synthesizing butynediol CuBiMgSi catalyst | |
| CN102863335A (en) | Preparation method of diethyl succinate | |
| CN105254599B (en) | A method of gamma-butyrolacton is prepared by raw material of furfural | |
| CN102718705B (en) | Method for preparing methyl pyridine nitrogen oxide | |
| CN108440262B (en) | Method for preparing 4-oxoisophorone by catalytic oxidation of beta-isophorone with solid-liquid two-phase | |
| CN102190582B (en) | Method of simultaneously producing dimethyl succinate and 1,4-butyl glycol | |
| CN104549318A (en) | Catalyst for preparing furfuryl alcohol through hydrogenating furfural liquid phase and preparation method of catalyst | |
| CN104230635B (en) | The method of hydrogenation of acetophenone ethylbenzene processed | |
| CN107626310A (en) | A kind of 2,3 dihydrofuran synthesis copper-based catalysts and preparation method and application | |
| CN110975884A (en) | Preparation method of transition metal-containing catalyst for preparing benzaldehyde by selectively oxidizing toluene | |
| CN105688877B (en) | Iron-based catalyst for Fischer-Tropsch synthesis and preparation method thereof | |
| CN111135831A (en) | Preparation method of catalyst for preparing 2-methyltetrahydrofuran by gas-phase hydrogenation of 2-methylfuran | |
| CN110354854A (en) | A kind of liquid phase selective adds hydrogen furfural to prepare the catalyst of furfuryl alcohol | |
| CN110560072A (en) | Catalyst for producing 1, 6-hexanediol by hydrogenation of adipate and preparation method thereof | |
| CN107930627B (en) | Furfural hydrogenation catalyst, preparation method and application thereof, and method for preparing furfuryl alcohol by furfural liquid-phase hydrogenation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | 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 | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 101407 No.1, south 2nd Yueyuan street, C District, Yanqi Economic Development Zone, Huairou District, Beijing Patentee after: Zhongke synthetic oil Technology Co.,Ltd. Address before: 101407 No.1, south 2nd Yueyuan street, C District, Yanqi Economic Development Zone, Huairou District, Beijing Patentee before: SYNFUELS CHINA TECHNOLOGY Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder |