CN105618136B - A kind of rhodium base catalyst of the Polymer-supported containing iodine for methanol carbonyl - Google Patents
A kind of rhodium base catalyst of the Polymer-supported containing iodine for methanol carbonyl Download PDFInfo
- Publication number
- CN105618136B CN105618136B CN201410582556.6A CN201410582556A CN105618136B CN 105618136 B CN105618136 B CN 105618136B CN 201410582556 A CN201410582556 A CN 201410582556A CN 105618136 B CN105618136 B CN 105618136B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- polymer
- containing iodine
- rhodium
- methanol
- 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.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A kind of rhodium base catalyst of the Polymer-supported containing iodine for methanol carbonyl.It is made up of main active component and carrier two parts, main active component is rhodium and transition metal promoter, and weight is the 0.01~20.0% of catalyst weight；Carrier is phenolic resin and Lauxite polymer containing iodine, and the specific surface area of phenolic resin is 5~800m in carrier2/ g, average pore size are 1~200nm, and the specific surface area of Lauxite is 5~800m in carrier2/ g, average pore size are 1~200nm.By the CH provided by the invention under the conditions of certain temperature and stress reaction3OH/CO is converted into the rhodium base catalyst of the Polymer-supported containing iodine of methyl acetate and acetic acid.In fixed bed reactors, under certain temperature and pressure and this catalyst action, CH3OH/CO can high activity, be converted into methyl acetate and acetic acid with high selectivity.
Description
Technical field
The invention belongs to the invention belongs to technical field of chemical engineering catalysts, and in particular to a kind of containing for methanol carbonyl
The rhodium base catalyst of iodine Polymer-supported, relate more specifically to a kind of be converted into methyl acetate and acetic acid with methanol/CO raw materials
Rhodium base catalyst of the Polymer-supported containing iodine and preparation method thereof.
Technical background
Acetic acid is one of most important organic acid, is mainly used in vinyl acetate, acetic anhydride, acetate fiber, acetic acid esters and metal
Acetate etc., the solvent and raw material of the industry such as agricultural chemicals, medicine and dyestuff are also served as, be an important composition portion of national economy
Point.Methyl acetate gradually replaces acetone, butanone, ethyl acetate, pentamethylene etc. in the world.Because it is not belonging to what limitation used
Organic pollution discharges, and can reach the new environmental protection standard of coating, ink, resin, adhesive producing works.Acetic acid and methyl acetate hydrogenation
Synthesizing alcohol is also one of main path of current coal ethanol.
Methanol carbonylation process is occupied an leading position in the industrialized production of acetic acid, is filled at present using the acetic acid production of the technique
The production capacity put has accounted for the 94% of acetic acid total productive capacity.In past 50 years, methanol carbonyl metaplasia produces the industrialization of acetic acid
Process substantially experienced three developing stage：
First stage：BASF AG's nineteen sixty using Co catalysts under higher reaction temperature and pressure (250 DEG C,
The industrialized production with methanol carbonylation production acetic acid 60MPa) is realized first, and the yield of acetic acid calculates yield by methanol is
90%, yield 70% is calculated by CO, the acetic acid purity of this method production is not high, and Main By product is higher alcohol, advanced aldehyde and height
Level carboxylic acid, product separation costs are higher.
Second stage：Monsanto companies develop reactivity and selective higher rhodium-iodide (RhI3) catalysis
System.The temperature and pressure of reaction also exists than relatively low (175 DEG C or so, 3.0MPa), selection rate of the acetic acid on the basis of methanol
More than 99%, the selection rate on the basis of CO has also reached more than 90%.The mass concentration of iodomethane and water point in reaction system
Wei 10~15% and 8~20%.Therefore, device is corrosion-resistant requires very high, it is necessary to full zircaloy reactor.The technique is in 1970
Year establishes first commercial plant in Texas, USA.
Phase III：The industrialization of iridium catalyst is methanol carbonylation production acetic acid.1986, Monsanto companies will
Methanol acetic acid technology is sold to BP companies, and BP companies are successfully developed in nineteen ninety-five using iridium as main catalyst methanol carbonyl
Change the new catalyst system and catalyzings of CativaTM of acetic acid processed, the system is better than Monsanto rhodium catalysis system, the technique in many aspects
The big stability for improving catalyst, reacts and is carried out under conditions of water content is relatively low, and reduces the generation of liquid by-product,
Improve CO conversion ratio.Celanese chemical companies develop its proprietary AO Plus (acid optimization) the 1980s
New technology, the technique greatly improve Monsanto techniques.By adding the inorganic iodide (mainly lithium iodide) of high concentration,
The stability of rhodium catalyst is improved, adds lithium iodide with that after iodomethane auxiliary agent, water content in reactor can be made to significantly reduce (about
4%~5%) higher carbonylation rate, while can be maintained again, make the separation costs of new technology significantly reduce.
Thousand generations field (Chiyoda) company of Japan and Uop Inc. have developed jointly Acetica techniques, and the technique is based on one kind
Multiphase rhodium catalyst, wherein active Rh complex compounds are chemically fixed on polyvinylpyridine resin.The technique is 1999
Year confirms its performance by operating a set of pilot-plant.Thousand Dai Tian companies claim, compared with traditional soluble rhodium catalyst, its
Immobilized catalyst can obtain high yield, and acetic acid producing rate (in terms of methanol) is higher than 99%；Catalyst treatment is easy because be not required to from
Rhodium is isolated in reaction solution and reclaims rhodium；Reactor is run under the conditions of low water content (3%~8%), can suppress accessory substance
Generation；Iodide concentration is low in reactor, and etching problem is small.
Yuan state of Institute of Chemistry, Academia Sinica minister in ancient times studies the sequestering polymer catalyst of strong and weak fit key being combined into also shape
Into independent intellectual property right system, the catalyst system has the characteristics that high stability, high activity, can improve CO selectivity,
Numerous domestic uses the production of acetic acid producer of the catalyst, has added up to produce 708.7 ten thousand tons of acetic acid, has accounted for domestic acetic acid total yield
The 1/3 of amount.Therefore the project obtains 2013 annual National Technical invention second prizes.It can be seen that high molecular polymer loads carbonyl
Rhodium catalyst has preferable application prospect.
Although homogeneous rhodium base and iridium base catalyst system and catalyzing achieve good commercial Application, at a relatively high catalytic activity is achieved
And selectivity, the selectivity of acetic acid are more than 99%.But homogeneous catalyst system has taken on certain lack from its birth
Point, such as, noble metal catalyst is easy to run off, product separates difficult, catalyst circulation and recovery complexity etc. with catalyst.Either
Rh catalyst or Ir catalyst, homogeneous iodide are required for as co-catalyst.This just needs expensive energy resistant to hydrogen iodine
The zircaloy production equipment of acid corrosion, and inevitably contain a small amount of iodide in acetic acid and methyl acetate product, enter
And the quality and purposes of product are influenceed, to make acetic acid product quality further improve, it is necessary to which these iodide contents are further
Reduce, therefore, it is necessary to special technology removes iodide in acetic acid.
For above-mentioned homogeneous reaction catalyst system and catalyzing deficiency, a part of researcher is by using cheap metal catalyst, preparation
The methods of composition catalyst, addition ionic liquid auxiliary agent, further improves homogeneous catalysis system, and another part researcher is then
Sight support type heterogeneous catalysis system has been invested.Compared with homogeneous catalysis system, heterogeneous catalysis system has natural
Advantage, such as, catalyst and convenient product separation, catalyst concn, can be dense by increasing catalyst not by solubility limit
Spend to improve production capacity etc..Support type heterogeneous catalysis system can be roughly divided into polymer support, activated carbon according to carrier difference
The systems such as carrier, inorganic oxide carrier, but load type catalyst system is lower than homogeneous catalysis system, active there is activity
The problems such as composition easily removes, be higher to carrier media, on the other hand, researcher has carried out substantial amounts of work, although above-mentioned catalyst all takes
Certain effect was obtained, but due to, still using iodide as co-catalyst, not being avoided that equipment corrosion in above-mentioned reaction system
And iodide ion separates the problems such as difficult in late-stage products.Therefore, high activity, high selectivity do not need the iodomethane auxiliary agent to consolidate
Body catalyst can more reduce production cost, be the target of numerous studies for many years.
The content of the invention
It is an object of the invention to provide a kind of rhodium base catalyst of the Polymer-supported containing iodine for methanol carbonyl, uses
In the rhodium base catalyst for the Polymer-supported containing iodine that methyl acetate and acetic acid are converted into using CO and methanol as raw material.
The following technical proposals of the present invention are for realizing goal of the invention above：
A kind of rhodium base catalyst of the Polymer-supported containing iodine for methanol carbonyl, the catalyst by main active component and
Carrier two parts form, and main active component is rhodium and transition metal promoter, and weight is the 0.01~20.0% of catalyst weight；Carry
Body is phenolic resin and Lauxite polymer containing iodine, and the specific surface area of phenolic resin is 5~800m in carrier2/ g, it is average
Aperture is 1~200nm, and the specific surface area of Lauxite is 5~800m in carrier2/ g, average pore size are 1~200nm.
According to described catalyst, wherein main active component rhodium weight is the 0.1~10.0% of catalyst weight.
According to described catalyst, wherein main active component rhodium weight is the 0.05~5.0% of catalyst weight.
According to described catalyst, wherein transition metal is the one or more in Mn, La, Zr in main active component, it is heavy
Measure as the 0.1~10.0% of catalyst weight.
According to described catalyst, the phenols and amine monomers wherein used in phenolic resin and Lauxite polymer is
The one or more of 4- iodophenols and 4- Iodoanilines, aldehyde monomers be formaldehyde, 3- pyridine carboxaldehydes and 4- pyridine carboxaldehydes one kind or
It is several.
According to described catalyst, the wherein specific surface area of carrier iodized phenol urea formaldehyde is 40~400m2/ g, average pore size
Most preferably 5~100nm；The specific surface area of carrier Lauxite containing iodine is 40~400m2/ g, average pore size most preferably 5~
100nm。
A kind of preparation method of the rhodium base catalyst of described Polymer-supported containing iodine for methanol carbonyl, use
Reactor is fixed bed reactors, and in ethanol and water mixed solvent, the monomer containing iodine of complexing metal is in acid or base catalysis
Under the conditions of in-situ polymerization generation Polymer-supported containing iodine rhodium base catalyst, and by further solidification, be calcined, activation.
According to described preparation method, the methanol that wherein CO carrying constant flow pumps are pumped into is to equipped with particulate catalytic of the invention
In the fixed bed reactors of agent, CO carbonylations and esterification are carried out, is converted into acetic acid and methyl acetate, reaction temperature is
180 DEG C, reaction pressure 3.0MPa, methanol air speed is 1h-1, CO air speeds are 1500h-1。
A kind of rhodium base catalyst of described Polymer-supported containing iodine for methanol carbonyl turns with methanol/CO raw materials
Turn to the application in the rhodium base catalyst of the Polymer-supported containing iodine of methyl acetate and acetic acid.
A kind of rhodium base catalyst of described Polymer-supported containing iodine for methanol carbonyl is in CH3OH/CO is converted into
Application in methyl acetate and acetic acid.
Compared with prior art, heterogeneous catalyst of the invention is relatively easy in terms of product separation, meanwhile, only work
Skill water, water content is relatively low, and methyl acetate is primary product, and therefore, the corrosivity of product is relatively low, and Hastelloy material is possible to replace
For material of the Zirconium alloy material as reaction unit, have and invest relatively low advantage.The conversion of methanol is significantly improved simultaneously
Rate and acetyl based selective.
Embodiment
Further illustrate the essentiality content of the present invention with embodiments of the invention below, but this is not limited with this
Invention.
The concrete scheme of the embodiment of the present invention is as follows：The catalyst of the present invention is used under certain temperature and pressure, CO
It is that raw material efficiently produces acetic acid and methyl acetate reaction with methanol.Catalyst is made up of main active component and carrier two parts.It is main
Active component is rhodium and transition metal promoter.Carrier is phenolic resin and Lauxite polymer containing iodine.In fixed bed reaction
CO closes the reaction raw materials of methanol composition in device, and under this catalyst action, CO carbonylations and esterification occurs, can be high living
Property, acetic acid and methyl acetate are converted into high selectivity.
In the reaction system of the present invention, the methanol that CO carrying constant flow pumps are pumped into is to equipped with pellet type catalyst of the invention
In fixed bed reactors, CO carbonylations are carried out.
The present invention catalyst, the preferable weight percentage of metal be 0.1~10.0%, optimum weight content be 0.05~
5.0%；The specific surface area of carrier iodized phenol urea formaldehyde is preferably 5~800m2/ g, average pore size are 1~200nm, optimal ratio
Surface area is 40~400m2/ g, average pore size most preferably 5~100nm；The specific surface area of carrier Lauxite containing iodine is preferably 5
~800m2/ g, average pore size are 1~200nm, and optimal specific surface area is 40~400m2/ g, average pore size most preferably 5~
100nm。
The reaction temperature of the present invention is 180 DEG C, reaction pressure 3.0MPa, and methanol air speed is 1h-1, CO air speeds are 1500h-1。
Embodiment 1
Iodophenol between weighing 4.0 grams, 2.0 grams of Pyridine-4-Carboxaldehydes, the isometric solution of 40mL ethanol/waters is configured, be added dropwise about
The dense HCl of 4mL, pH≤1 is adjusted, then add and be dissolved with 0.1 gram of RhCl3·3H2O 5mL ethanol solutions, stir 3h.80 DEG C of water-baths
Evaporation solvent, 120 DEG C of curing ovens 8h, 210 DEG C of Ar protective roasts 6h.
Embodiment 2
Iodophenol between weighing 4.0 grams, the isometric solution of 40mL ethanol/waters is configured, the dense HCl of about 4mL is added dropwise, adjust pH≤1,
2.0 grams of 37wt% formalins are added dropwise, then adds and is dissolved with 0.1 gram of RhCl3·3H2O 5mL ethanol solutions, stir 3h.80
DEG C water-bath evaporation solvent, 120 DEG C of curing ovens 8h, 210 DEG C of Ar protective roasts 6h.
Embodiment 3
Iodophenol between weighing 4.0 grams, 1.0 grams of 4- pyridine carboxaldehydes, the isometric solution of 40mL ethanol/waters is configured, about 4mL is added dropwise
Dense HCl, pH≤1 is adjusted, 1.0 grams of 37wt% formalins are added dropwise, then added and be dissolved with 0.1 gram of RhCl3·3H2O 5mL second
Alcoholic solution, stir 3h.80 DEG C of water-bath evaporation solvents, 120 DEG C of curing ovens 8h, 210 DEG C of Ar protective roasts 6h.
Embodiment 4
4.0 grams of paraiodoanilines are weighed, 2.0 grams of 3- pyridine carboxaldehydes, configure the isometric solution of 40mL ethanol/waters, about 4mL is added dropwise
Dense HCl, pH≤1 is adjusted, then add and be dissolved with 0.1 gram of RhCl3·3H2O 5mL ethanol solutions, stir 3h.80 DEG C of water-baths are steamed
Send out solvent, 120 DEG C of curing ovens 8h, 210 DEG C of Ar protective roasts 6h.
Embodiment 5
4.0 grams of paraiodoanilines are weighed, configure the isometric solution of 40mL ethanol/waters, the dense HCl of about 4mL are added dropwise, adjust pH≤1,
2.0 grams of 37wt% formalins are added dropwise, then adds and is dissolved with 0.1 gram of RhCl3·3H2O 5mL ethanol solutions, stir 3h.80
DEG C water-bath evaporation solvent, 120 DEG C of curing ovens 8h, 210 DEG C of Ar protective roasts 6h.
Embodiment 6
4.0 grams of paraiodoanilines are weighed, 1.0 grams of pyridine -3- formaldehyde, configure the isometric solution of 40mL ethanol/waters, are added dropwise about
The dense HCl of 4mL, pH≤1 is adjusted, 1.0 grams of 37wt% formalins are added dropwise, then added and be dissolved with 0.1 gram of RhCl3·3H2O 5mL
Ethanol solution, stir 3h.80 DEG C of water-bath evaporation solvents, 120 DEG C of curing ovens 8h, 210 DEG C of Ar protective roasts 6h.
Embodiment 7
2.0 grams of paraiodoanilines are weighed, 2.0 grams, to iodophenol, configure the isometric solution of 40mL ethanol/waters, it is dense that about 4mL is added dropwise
HCl, pH≤1 is adjusted, 2.0 grams of 37wt% formalins are added dropwise, then added and be dissolved with 0.1 gram of RhCl3·3H2O 5mL ethanol
Solution, stir 3h.80 DEG C of water-bath evaporation solvents, 120 DEG C of curing ovens 8h, 210 DEG C of Ar protective roasts 6h.
Embodiment 8
4.0 grams of paraiodoanilines are weighed, configure the isometric solution of 40mL ethanol/waters, the dense HCl of about 4mL are added dropwise, adjust pH≤1,
2.0 grams of 37wt% formalins are added dropwise, then add 0.1 gram of RhCl3·3H2O, 2mL dense HCl, 0.06 gram of La2O3The 5mL of composition
Ethanol/water solution, stir 3h.80 DEG C of water-bath evaporation solvents, 120 DEG C of curing ovens 8h, 210 DEG C of Ar protective roasts 6h.
Embodiment 9
4.0 grams of paraiodoanilines are weighed, configure the isometric solution of 40mL ethanol/waters, the dense HCl of about 4mL are added dropwise, adjust pH≤1,
2.0 grams of 37wt% formalins are added dropwise, then adds and is dissolved with 0.1 gram of RhCl3·3H2O and 0.072 gram of MnCl2·4H2O's
5mL ethanol solutions, stir 3h.80 DEG C of water-bath evaporation solvents, 120 DEG C of curing ovens 8h, 210 DEG C of Ar protective roasts 6h.
Embodiment 10
4.0 grams of paraiodoanilines are weighed, configure the isometric solution of 40mL ethanol/waters, the dense HCl of about 4mL are added dropwise, adjust pH≤1,
2.0 grams of 37wt% formalins are added dropwise, then adds and is dissolved with 0.1 gram of RhCl3·3H2O and 0.084 gram of ZrCl45mL ethanol
Solution, stir 3h.80 DEG C of water-bath evaporation solvents, 120 DEG C of curing ovens 8h, 210 DEG C of Ar protective roasts 6h.
Above-mentioned catalyst is before use, CO (GHSV=5000h in the reactor-1) in-situ reducing activation, condition are carried out in stream
For：Normal pressure, 5 DEG C/min keep being cooled to reaction temperature in CO streams in 3 hours from room temperature to 210 DEG C.CO carbonylations
Condition is：180 DEG C, 3.0Mpa, CO GHSV=1500h-1, methanol LHSV=1.0h-1.Reaction end gas is after cold-trap absorbs, gas
Phase product carries out on-line analysis, and chromatographic apparatus is Agilent 3000A Micro GC, molecular sieve, Plot Q, Al2O3With OV-1 tetra-
Capillary post, TCD detectors.Liquid product off-line analysis, FFAP capillary chromatographic columns, fid detector.Internal standard method is analyzed,
Isobutanol alcohol is internal standard compound.Acetic acid is quantified by acid base titration.
Reaction result is summarised in table 1.
Table 1：Reaction result of the methanol carbonyl on embodiment catalyst
* in terms of the methanol of conversion, including the methanol in generation methyl acetate.
Claims (7)
1. a kind of rhodium base catalyst of Polymer-supported containing iodine for methanol carbonyl, the catalyst is by main active component and load
Body two parts form, and main active component is rhodium and transition metal promoter, and weight is the 0.01~20.0% of catalyst weight；Carrier
For the phenolic resin containing iodine and/or Lauxite polymer, the specific surface area of phenolic resin is 5~800m in carrier2/ g, it is average
Aperture is 1~200nm, and the specific surface area of Lauxite is 5~800m in carrier2/ g, average pore size are 1~200nm, wherein phenol
The phenols and amine monomers used in urea formaldehyde and Lauxite polymer is the one or more of 4- iodophenols and 4- Iodoanilines,
Aldehyde monomers are the one or more of formaldehyde, 3- pyridine carboxaldehydes and 4- pyridine carboxaldehydes；The wherein polymer containing iodine of methanol carbonyl
The preparation method of the rhodium base catalyst of load, the reactor used is fixed bed reactors, in ethanol and water mixed solvent, network
The rhodium base catalyst of the monomer containing iodine of alloy category in-situ polymerization generation Polymer-supported containing iodine under the conditions of acid or base catalysis,
And pass through further solidification, it is calcined, activation, the fixation of the methanol that CO carrying constant flow pumps are pumped into the pellet type catalyst being equipped with
In bed reactor, CO carbonylations and esterification are carried out, is converted into acetic acid and methyl acetate, reaction temperature is 180 DEG C,
Reaction pressure is 3.0MPa, and methanol air speed is 1h-1, CO air speeds are 1500h-1。
2. catalyst according to claim 1, it is characterised in that wherein main active component rhodium weight is catalyst weight
0.1~10.0%.
3. catalyst according to claim 1, it is characterised in that wherein main active component rhodium weight is catalyst weight
0.05~5.0%.
4. catalyst according to claim 1, it is characterised in that transition metal is Mn, La, Zr in wherein main active component
In one or more, weight be catalyst weight 0.1~10.0%.
5. catalyst according to claim 1, it is characterised in that wherein the specific surface area of carrier iodized phenol urea formaldehyde is 40
~400m2/ g, average pore size are 5~100nm；The specific surface area of carrier Lauxite containing iodine is 40~400m2/ g, average pore size
For 5~100nm.
6. a kind of rhodium base catalyst of Polymer-supported containing iodine for methanol carbonyl described in claim 1 with methanol/
CO raw materials are converted into the application in the rhodium base catalyst of the Polymer-supported containing iodine of methyl acetate and acetic acid.
7. a kind of rhodium base catalyst of Polymer-supported containing iodine for methanol carbonyl described in claim 1 is in CH3OH/CO
The application being converted into methyl acetate and acetic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410582556.6A CN105618136B (en) | 2014-10-27 | 2014-10-27 | A kind of rhodium base catalyst of the Polymer-supported containing iodine for methanol carbonyl |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410582556.6A CN105618136B (en) | 2014-10-27 | 2014-10-27 | A kind of rhodium base catalyst of the Polymer-supported containing iodine for methanol carbonyl |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105618136A CN105618136A (en) | 2016-06-01 |
| CN105618136B true CN105618136B (en) | 2017-12-19 |
Family
ID=56033709
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410582556.6A Active CN105618136B (en) | 2014-10-27 | 2014-10-27 | A kind of rhodium base catalyst of the Polymer-supported containing iodine for methanol carbonyl |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105618136B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106316846B (en) * | 2016-08-26 | 2018-12-25 | 西南化工研究设计院有限公司 | A kind of production method of methyl acetate |
| CN107999127B (en) * | 2017-11-28 | 2020-03-31 | 西南化工研究设计院有限公司 | Catalyst for preparing methyl acetate by methanol one-step method and application |
| CN111111774A (en) * | 2018-11-01 | 2020-05-08 | 中国科学院大连化学物理研究所 | Organic phosphine-containing polymer carrier loaded rhodium and heteropoly acid catalyst, preparation and application thereof |
| CN114515604A (en) * | 2020-11-20 | 2022-05-20 | 中国科学院大连化学物理研究所 | Quaternary phosphonium salt polymer loaded bimetallic monatomic catalyst, preparation method and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1058154A (en) * | 1990-06-12 | 1992-01-29 | 英国石油有限公司 | The carbonylation of methyl alcohol |
| CN104774284A (en) * | 2014-01-14 | 2015-07-15 | 山东华夏神舟新材料有限公司 | Preparation method of porous perfluorinated sulfonic acid resin for catalysts |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5460288A (en) * | 1977-10-21 | 1979-05-15 | Rikagaku Kenkyusho | Catalyst carrier for isotope exchange reaction between water and hydrogen |
-
2014
- 2014-10-27 CN CN201410582556.6A patent/CN105618136B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1058154A (en) * | 1990-06-12 | 1992-01-29 | 英国石油有限公司 | The carbonylation of methyl alcohol |
| CN104774284A (en) * | 2014-01-14 | 2015-07-15 | 山东华夏神舟新材料有限公司 | Preparation method of porous perfluorinated sulfonic acid resin for catalysts |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105618136A (en) | 2016-06-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106140156A (en) | A kind of activated carbon supported rhodium base catalyst and its preparation method and application | |
| CN105618136B (en) | A kind of rhodium base catalyst of the Polymer-supported containing iodine for methanol carbonyl | |
| CN103319337B (en) | A kind of method of ethylene synthase methyl propionate | |
| CN102847550B (en) | Catalyst for preparation of acetic acid and methyl acetate through carbonylation of methanol and preparation method thereof | |
| CN103896768A (en) | Method used for preparing methyl acetate | |
| CN109453815A (en) | The rhodium base catalyst of organic load of polymer support containing phosphine and its preparation and application | |
| CN108067226A (en) | A kind of activated carbon supported iridium based catalyst and its preparation and application | |
| CN110746357B (en) | Imidazole diionic liquid and method for catalytic synthesis of cyclic carbonate by using same | |
| CN105585455A (en) | Method of preparing ethylene glycol monomethyl ether through continuous etherification method | |
| CN107159217A (en) | A kind of Cu ZnO/SiO2Aeroge bimetallic catalyst and its production and use | |
| CN106866360A (en) | A kind of method that 5 hydroxymethyl furfural catalyzed conversion prepares 1,6-HD | |
| CN108069857A (en) | A kind of activated carbon supported iridium based catalyst and its application for methanol vapor-phase carbonylation methyl acetate | |
| CN104710282A (en) | Method for production of ethanol and co-production of methanol | |
| CN107141213A (en) | A kind of method of acetic acid synthesis from methanol carbonylation | |
| CN102863335A (en) | Preparation method of diethyl succinate | |
| CN106807367A (en) | A kind of iridium based catalyst of carbon-based material load and its preparation method and application | |
| CN107486191A (en) | A kind of iridium based catalyst of acid treatment high-area carbon load and its preparation method and application | |
| CN108067222A (en) | The iridium based catalyst of the sulphur promotion of absorbent charcoal carrier load and its preparation and application | |
| CN106944050A (en) | A kind of catalyst for synthesizing 1,3 propane diols and its preparation method and application | |
| CN106807368A (en) | A kind of activated carbon supported iridium based catalyst and its preparation method and application | |
| CN103894232B (en) | A kind of Catalysts and its preparation method of methyl nitrite formylated synthesis methyl formate and application | |
| CN110078603A (en) | The preparation method of purification and device of methacrolein | |
| CN102153446A (en) | Cu/MgO catalyst, preparation method thereof and method for catalyzing glycerin hydrogenolysis | |
| CN102173977A (en) | Cu/Al2O3 catalyst and preparation method thereof as well as method for catalyzing hydrolysis of glycerol | |
| CN101992084B (en) | Rhodium heterogeneous catalyst for carbonylation as well as preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |