CN103949268A - Copper-manganese catalyst for synthesizing methyl formate, as well as preparation method and application thereof - Google Patents
Copper-manganese catalyst for synthesizing methyl formate, as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN103949268A CN103949268A CN201410153703.8A CN201410153703A CN103949268A CN 103949268 A CN103949268 A CN 103949268A CN 201410153703 A CN201410153703 A CN 201410153703A CN 103949268 A CN103949268 A CN 103949268A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- copper
- solution
- methyl formate
- zro2
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a copper-manganese catalyst for synthesizing methyl formate. The copper-manganese catalyst comprises a catalyst 1 and a catalyst 2, wherein the catalyst 1 consists of copper-manganese oxide; according to metal, a molar ratio of a component Cu to a component Mn is 1:(0.5-2); the catalyst 2 consists of mesoporous ZrO2-CaO or ZrO2-MgO solid alkali; according to the metal, a molar ratio of a component Zr to a component Ca or Mg is 1:(0.1-1.0), wherein the best ratio is 1:(0.5-1.0). The copper-manganese catalyst has the advantages of good in tolerance to water and carbon dioxide and high in catalytic performance.
Description
Technical field
The invention belongs to a kind of catalyst and preparation method and application, relate to specifically a kind of copper Mn catalyst and preparation method and application of synthetic methyl formate.
Background technology
As an emerging field of C1 chemistry, methyl formate (MeF) possesses following advantages simultaneously: (1) large-scale production cost-effectively; (2) suitably (31.5 DEG C) of boiling point, are liquid under normal temperature, are convenient to process, store and transport; (3) downstream product is many, particularly large tonnage product.In addition, methyl formate is owing to having higher reactivity, and be used as the basic system unit of C1 chemistry, methyl formate can derive more than 50 reaction as intermediate, can synthesize a lot of downstreams chemical products, as dimethyl carbonate, ethylene glycol and surpalite, also can be used as bactericide, fumigant and the agent for tobacco treatment etc. of pesticide, cereal crops.In addition, methyl formate can derive as formic acid, dimethyl formamide, acetic acid and high-purity CO etc. by hydrolysis, ammonia solution, rearrangement and thermal decomposition.
The method of synthetic methyl formate mainly contains in the world at present: (1) formic acid esterification method, and formic acid esterification method is methyl formate generation method early, because its cost is high, equipment corrosion is serious, is eliminated already abroad; (2) formaldehyde dimerization method, this reaction is intermolecular redox reaction, the essential bronsted lowry acids and bases bronsted lowry of catalytic reaction activated centre, practicality is not strong; (3) methyl alcohol and hydrogenation of carbon dioxide condensation method, the method mainly last century be to reduce the discharge of greenhouse gases to develop, but methyl formate yield is lower, CO
2conversion ratio is only 3.8%-7.3%; (4) methanol dehydrogenation method, this process is a reaction that is subject to thermodynamics equilibrium limit, and its productive rate is difficult to break through 50%, does not also have effective technical measures to break the restriction of this balance at present in technique, catalyst activity and selectivity used is still on the low side, therefore applies limited; (5) methanol carbonylation, this method is current more advanced MeF production method, its cost is lower, makes catalyst with sodium methoxide, 80 DEG C of reaction temperatures, under pressure 4-6MPa, the conversion ratio of CO and methyl alcohol can reach respectively 95% and 30%, MeF selectively approach 100%.But this technique has two large shortcomings: a) catalyst is to moisture and CO
2sensitivity, b) must working concentration higher than 80% CO; (6) synthesis gas direct synthesis technique, by one-step method from syngas, synthetic MeF is that an efficient atom economy type reacts, being current universally acknowledged state-of-the-art MeF production method, meeting the low-carbon energy advocated in the world and utilize engineering philosophy, is " zero-emission " reaction truly.Therefore, by synthesis gas, directly synthetic MeF is very reasonable in using energy source, is one of the most promising technology path.
In the research of the method for the synthetic methyl formate of one-step method from syngas, studying at present many is the synthetic methyl formate of low temperature liquid phase.CO and H for patent US5384335
2in the catalyst system and catalyzing being made up of Cu-Cr catalyst and alkali metal or alkaline-earth metal compound, synthesized methyl alcohol and methyl formate, reaction temperature is 100-160 DEG C, and reaction pressure is 4.0-6.5MPa, mentions synthesis gas conversion ratio up to 95% in patent.In patent US4731386, also report that in this patent, used catalyst is alkyl salt and the copper catalyst of alkali metal or alkaline-earth metal with synthesis gas one-step synthesis methyl alcohol and methyl formate in low temperature liquid phase.Patent CN1050116 in addition, has also reported in CN1074305 with CO and H
2the synthetic methyl formate of low temperature liquid phase in Cu-Cr catalyst and sodium methoxide system.But in these patents in the past catalyst all use alkali metal or alkaline-earth metal alkoxide, these alkoxide are inactivation under the effect of water byproduct and carbon dioxide, and catalyst overall performance is poor, need to add co-catalyst, this becomes the bottleneck of this technological development at present.
Summary of the invention
The present invention overcomes the problem existing in above-mentioned catalyst system and catalyzing, develops one to water and carbon dioxide better tolerance, the catalyst that catalytic performance is high and preparation method, and for low temperature liquid phase CO and H
2the directly reaction of synthetic methyl formate.
Catalyst of the present invention comprises two kinds, and catalyst 1 is made up of copper-Mn oxide, and in metal, each component mol ratio is Cu:Mn=1:0.5-2; Catalyst 2 is by mesoporous ZrO
2-CaO or ZrO
2-MgO solid base composition, in metal, each component mol ratio is respectively Zr:Ca or Mg=1:0.1-1.0, and optimum value is 1:0.5-1.0.
Copper-manganese oxide catalyst preparation method provided by the invention comprises the following steps:
(1) be 1:0.5-2 by Cu:Mn mol ratio, under vigorous stirring, the manganese nitrate solution of the 0.5-2mol/L of pH=3-5 splashed in the cupric ammine complex solution of pH=10-12;
(2) with red fuming nitric acid (RFNA) regulator solution pH=5.5-7.5, between temperature keeps 30～50 DEG C, aging 2-9h;
(3) filter, washing, at 100-120 DEG C, dry 10-20h, at 500-600 DEG C of roasting 2-6h, obtains required Cu-Mn oxide.
Mesoporous ZrO provided by the invention
2-CaO or ZrO
2-MgO solid base catalyst is preparation method comprise the following steps:
(1) by nonionic template P123(polyoxyethylene-poly-oxypropylene polyoxyethylene) be dissolved in absolute ethyl alcohol cumulative volume 3/5 in, after dissolving, add calcium nitrate or magnesium nitrate, form solution A;
(2) propyl alcohol zirconium and acetylacetone,2,4-pentanedione are joined absolute ethyl alcohol cumulative volume 2/5 in wiring solution-forming B;
(3) solution B is added in solution A, then add deionized water, stir 1-2h;
(4) at 40-80 DEG C after crystallization 12-48h, add the amount of 8-12L NaOH solution by every 1mol Zr, the 24-48h that refluxes in the NaOH of 0.05-0.5mol/L solution, filters, washs, after 60-120 DEG C of dry 12-24h at 500-700 DEG C roasting 4-6h, obtain ZrO
2-CaO or ZrO
2-MgO;
Wherein in catalyst preparation process, each additive mol ratio consists of Zr:P123:M: absolute ethyl alcohol: acetylacetone,2,4-pentanedione: H
2o=1:0.01-0.05:0.1-1.0:40-200:0.1-1.0:5-20.
Copper-Mn oxide and mesoporous ZrO in the present invention
2-CaO or ZrO
2-MgO solid base catalyst catalysis CO and H
2one-step synthesis methyl formate carries out in paste state bed reactor.
Catalyst of the present invention reacts condition used in paste state bed reactor:
(1) activation condition:
Catalyst 1: copper-manganese oxide catalyst is first used 5-10%H before reaction
2/ N
2(volume fraction) activates 5-10h under normal pressure, 200-300 DEG C condition, is down to after room temperature at 1-2%O
2/ Ar(volume fraction) passivation 2-8h under atmosphere;
Catalyst 2:ZrO
2-CaO or ZrO
2-MgO solid base is at N
2middle 500-700 DEG C of pretreatment 1-4h.
(2) reaction condition: reaction temperature T=80-180 DEG C, pressure 4.0-8.0MPa, gas volume air speed 500-2000mL/h/g.cat, H
2/ CO(mol ratio)=1.0-3.0; It is (Cu-Mn): solvent=5-20g:1L that reaction used catalyst 1 closes with solvent, and it is ZrO that catalyst 2 closes with solvent
2-CaO or ZrO
2-MgO: solvent=10-40g:1L; Solvent for use is the mixture of alcohols material and non-proton organic solvent, non-proton organic solvent: the volume ratio=1-3 of alcohol, alcohols wherein can be methyl alcohol, ethanol, propyl alcohol etc., non-proton organic solvent can be N, N dimethyl formamide (DMF), dimethylbenzene, diphenyl ether, tetraethyleneglycol dimethyl ether.
The present invention compared with prior art has following features:
(1) catalyst specific surface of the present invention is large, alkalescence is strong, good stability, life-span are long;
(2) owing to having avoided being subject to CO
2, there is not poisoning problem in the use of co-catalyst with water is poisoned, catalyst can use in direct activation, is highly susceptible to operation, and catalyst can tolerate the CO of higher concentration
2and H
2o;
(3) adopt the prepared catalyst of the present invention for the synthesis of the synthetic methyl formate of gas, reaction condition gentleness, strong adaptability, better performances;
(4) accessory substance of catalyst of the present invention in the synthetic methyl formate of one-step method from syngas is methyl alcohol and ethanol, is easy to separate with principal product.
Detailed description of the invention
Embodiment 1:
Take 6.96g P123 and be dissolved in 167.95mL absolute ethyl alcohol, add until completely dissolved the calcium nitrate of 10.63g, form solution A; Separately take 28.08g propyl alcohol zirconium (propanol solution, content 70wt.%) and 3.00mL acetylacetone,2,4-pentanedione and join wiring solution-forming B in 111.97mL absolute ethyl alcohol; Solution B is added in solution A, stir 0.5h, add the deionized water of 10.80mL, stir 1h, form milky gel; Gained gel is at 80 DEG C after crystallization 36h, and the 24h that refluxes in the NaOH of 640mL0.1mol/L solution, filters, washs, and after 80 DEG C of dry 12h, 600 DEG C of roasting 5h, obtain ZrO
2-CaO solid base, is designated as Cat A, and in Cat A, each component mol ratio is Zr:Ca=1:0.75.In preparation process, each additive mol ratio is P123:Ca: absolute ethyl alcohol: propyl alcohol zirconium: acetylacetone,2,4-pentanedione: deionized water=0.02:0.75:80:1:0.5:10.
In above-mentioned steps, when the calcium nitrate adding is changed to magnesium nitrate, when magnesium nitrate addition is 11.54g, obtain ZrO
2-MgO solid base, is designated as Cat B, and in Cat B, each component mol ratio is Zr:Mg=1:0.75.
Take 24.16g Cu (NO
3)
2.3H
2o solution 100mL deionized water, then uses ammoniacal liquor regulator solution pH=10, stirs 30min, is designated as solution A; Measure 35.79g Mn (NO
3)
2.4H
2the O(50% aqueous solution) solution 75mL deionized water is made into the solution of 1moL/L, then regulates pH=3 with red fuming nitric acid (RFNA), is designated as solution B, then under vigorous stirring, solution B is added drop-wise in solution A, then regulates pH=5.5 with red fuming nitric acid (RFNA), and keeping temperature is 30 DEG C, aging 5h.Then by solution filter, washing, at 100 DEG C of dry 15h, at 550 DEG C of roasting 4h, obtain black powder, be Cu-Mn oxide catalyst, be Cat C, in Cat C, component mol ratio is Cu:Mn=1.
The reaction of synthesis gas one-step synthesis methyl formate is carried out in 250mL magnetic agitation stainless steel cauldron.Before reaction, Cat C is first used to 5%H
2/ N
2(volume fraction) activates 10h at normal pressure, 200 DEG C, is down to after room temperature at 2%O
2/ Ar(volume fraction) passivation 4h under atmosphere; Cat A or Cat B are at N
2in 600 DEG C of pretreatment 2h.By pretreated Cat A and two kinds of catalyst of Cat C or pretreated Cat B and two kinds of catalyst of Cat C are added to reactor, then add dimethylbenzene and methanol solvate to react, investigate ZrO
2-CaO or ZrO
2the impact of two kinds of solid bases of-MgO on catalytic perfomance.Wherein catalyst and solvent pass are CatA: solvent=20.0g:1L or Cat B: solvent=20.0g:1L, and Cat C: solvent=10.0g:1L, solvent for use total amount is 100mL.Wherein V(dimethylbenzene): V (methyl alcohol)=1.5, magnetic agitation rotating speed r=1000r/min, pressure P=5.0MPa, temperature T=160 DEG C, reaction time t=24h, air speed MHSV=1000mL/h/g.cat, H
2/ CO(mol ratio)=2, reaction afterproduct is analyzed in gas-chromatography, and analysis result is in table 1.
The catalytic perfomance of the different solid bases of table 1
Embodiment 2:
This example is illustrated copper-Mn oxide and mesoporous ZrO
2-CaO or ZrO
2-MgO solid base catalyst catalysis CO and H
2in paste state bed reactor when one-step synthesis methyl formate, the impact of solvent for use on catalytic performance, copper-manganese oxide catalyst is Cat C, mesoporous ZrO
2-CaO or ZrO
2-MgO solid base catalyst is Cat A.The amount that just changes dimethylbenzene and methyl alcohol in solvent, remaining reaction condition is with embodiment 1.Dimethylbenzene and quantity of methyl alcohol on the impact of catalytic performance in table 2.
The impact of table 2 quantity of solvent on catalytic performance
Embodiment 3:
This example is illustrated copper-Mn oxide and mesoporous ZrO
2-CaO or ZrO
2-MgO solid base catalyst catalysis CO and H
2in paste state bed reactor when one-step synthesis methyl formate, the impact of reaction temperature on catalytic performance, copper-manganese oxide catalyst is Cat C, mesoporous ZrO
2-CaO or ZrO
2-MgO solid base catalyst is Cat A.Temperature while just changing reaction, remaining reaction condition is with embodiment 1.Reaction temperature on the impact of catalytic performance in table 3.
The impact of table 3 temperature on reactivity worth
Embodiment 4:
This example is illustrated copper-Mn oxide and mesoporous ZrO
2-CaO or ZrO
2-MgO solid base catalyst catalysis CO and H
2in paste state bed reactor when one-step synthesis methyl formate, the impact of solvent for use on catalytic performance, copper-manganese oxide catalyst is Cat C, mesoporous ZrO
2-CaO or ZrO
2-MgO solid base catalyst is Cat A.Pressure while just changing reaction, remaining reaction condition is with embodiment 1.Reaction pressure on the impact of catalytic performance in table 4.
The impact of table 4 pressure on reactivity worth
Embodiment 5:
This example is illustrated copper-Mn oxide and mesoporous ZrO
2-CaO or ZrO
2-MgO solid base catalyst catalysis CO and H
2in paste state bed reactor when one-step synthesis methyl formate, the impact of the amount of copper-Mn oxide in solvent on catalytic performance, copper-manganese oxide catalyst is Cat C, mesoporous ZrO
2-CaO or ZrO
2-MgO solid base catalyst is Cat A.Just change the amount of copper-manganese oxide catalyst in solvent, remaining reaction condition is with embodiment 1.The amount of Cat C in solvent on the impact of catalytic performance in table 5.
The impact of the amount of table 5 catalyst in solvent on reactivity worth
Embodiment 6:
This example is illustrated copper-Mn oxide and mesoporous ZrO
2-CaO or ZrO
2-MgO solid base catalyst catalysis CO and H
2in paste state bed reactor when one-step synthesis methyl formate, the impact of unstripped gas hydrogen-carbon ratio on catalytic performance, copper-manganese oxide catalyst is Cat C, mesoporous ZrO
2-CaO or ZrO
2-MgO solid base catalyst is Cat A.The hydrogen-carbon ratio that just changes the raw materials used gas of reaction, remaining reaction condition is with embodiment 1.Unstripped gas hydrogen-carbon ratio on the impact of catalytic performance in table 6.
The different H of table 6
2the impact of/CO on reactivity worth
Embodiment 7:
This routine mesoporous ZrO
2-CaO or ZrO
2the concrete preparation process of-MgO solid base catalyst is according to embodiment 1, just change the addition of calcium nitrate in preparation process, in the time adding the amount of calcium nitrate to be 7.08g, in preparation process, each additive mol ratio is P123:Ca: absolute ethyl alcohol: propyl alcohol zirconium: acetylacetone,2,4-pentanedione: deionized water=0.02:0.5:80:1:0.5:10, mol ratio Zr:Ca=1:0.5 in the solid base obtaining, gained solid base catalyst is designated as Cat D.
In above-mentioned steps in the time that the amount of the calcium nitrate adding is 14.16g, mol ratio Zr:Ca=1:1 in the solid base obtaining, gained solid base catalyst is designated as Cat E.
The reaction of synthesis gas one-step synthesis methyl formate is carried out in 250mL magnetic agitation stainless steel cauldron.Reaction is front by Cat B 8%H
2/ N
2(volume fraction) activates 6h at normal pressure, 280 DEG C in tube furnace, is down to after room temperature at 1%O
2/ Ar(volume fraction) passivation 8h under atmosphere; Cat A, Cat D and Cat E are at N
2in 500 DEG C of pretreatment 4h.Pretreated Cat A and Cat C, CatD and CatC or Cat E and Cat C catalyst are added in reactor, then add tetraethyleneglycol dimethyl ether and methanol solvate to react.Wherein catalyst and solvent pass are CatA: solvent=30.0g:1L, CatD: solvent=30.0g:1L or CatE: solvent=30.0g:1L, Cat C: solvent=5.0g:1L, solvent for use total amount is 100mL, wherein V (tetraethyleneglycol dimethyl ether): V (methyl alcohol)=2, magnetic agitation rotating speed r=1000r/min, pressure P=6.0MPa, temperature T=160 DEG C, reaction time t=24h, air speed MHSV=2000mL/h/g.cat, H
2/ CO(mol ratio)=2.0, reaction afterproduct is analyzed in gas-chromatography.Investigate ZrO
2the impact of different component contents on catalytic performance in-CaO catalyst, concrete analysis the results are shown in Table 7.
The impact of the different Zr/Ca of table 7 on reactivity worth
Embodiment 8:
Take 24.16g Cu (NO
3)
2.3H
2o solution 100mL deionized water, then uses ammoniacal liquor regulator solution pH=11, stirs 30min, is designated as solution A; Measure 17.89g Mn (NO
3)
2.4H
2the O(50% aqueous solution) solution 75mL deionized water is made into the solution of 1moL/L, then regulates pH=4 with red fuming nitric acid (RFNA), is designated as solution B, then under vigorous stirring, solution B is added drop-wise in solution A, then regulates pH=6.5 with red fuming nitric acid (RFNA), and keeping temperature is 50 DEG C, aging 5h.Then by solution filter, washing, at 110 DEG C of dry 12h, at 550 DEG C of roasting 4h, obtain black powder, be Cu-Mn oxide catalyst, be Cat F, in Cat F, component mol ratio is Cu:Mn=1:0.5.
In above-mentioned steps, work as and add Mn (NO
3)
2.4H
2the O(50% aqueous solution) amount while being 71.58g, the component mol ratio of Cu-Mn oxide is Cu:Mn=1:2, is denoted as Cat G.
| Embodiment 6 | 1914 | 1652 | 1.14 | 0.93 | 81.5 | 2.6 |
| Embodiment 7 | 1527 | 1323 | 0.75 | 0.66 | 88 | 2.2 |
| Embodiment 8 | 1817 | 1552 | 1.01 | 0.82 | 81.1 | 2.0 |
| Embodiment 9 | 2141 | 1620 | 1.21 | 0.91 | 75.1 | 2.65 |
Claims (7)
1. a copper Mn catalyst for synthetic methyl formate, is characterized in that catalyst comprises two kinds, and catalyst 1 is made up of copper-Mn oxide, and in metal, each component mol ratio is Cu:Mn=1:0.5-2; Catalyst 2 is made up of mesoporous ZrO_2-CaO or ZrO2-MgO solid base, and in metal, each component mol ratio is respectively Zr: Ca or Mg=1: 0.1-1.0, optimum value is 1:0.5-1.0.
2. the copper Mn catalyst of a kind of synthetic methyl formate as claimed in claim 1, is characterized in that described catalyst 1 bronze medal-manganese oxide catalyst preparation method comprises the following steps:
(1) be 1:0.5-2 by Cu:Mn mol ratio, under vigorous stirring, the manganese nitrate solution of the 0.5-2mol/ L of pH=3-5 splashed in the cupric ammine complex solution of pH=10-12;
(2) with red fuming nitric acid (RFNA) regulator solution pH=5.5-7.5, between temperature keeps 30～50 DEG C, aging 2-9 h;
(3) filter, washing, at 100-120 DEG C, dry 10-20 h, at 500-600 DEG C of roasting 2-6 h, obtains required Cu-Mn oxide.
3. the copper Mn catalyst of a kind of synthetic methyl formate as claimed in claim 1, is characterized in that described catalyst 2 mesoporous ZrO_2s-CaO or ZrO2-MgO solid base catalyst preparation method comprise the following steps:
(1) by nonionic template P123(polyoxyethylene-poly-oxypropylene polyoxyethylene) be dissolved in absolute ethyl alcohol cumulative volume 3/5 in, after dissolving, add calcium nitrate or magnesium nitrate, form solution A;
(2) propyl alcohol zirconium and acetylacetone,2,4-pentanedione are joined absolute ethyl alcohol cumulative volume 2/5 in wiring solution-forming B;
(3) solution B is added in solution A, then add deionized water, stir 1-2h;
(4) at 40-80 DEG C after crystallization 12-48h, add the amount of 8-12L NaOH solution by every 1mol Zr, 24-48h refluxes in the NaOH of 0.05-0.5mol/L solution, filter, wash, after 60-120 DEG C of dry 12-24h at 500-700 DEG C roasting 4-6h, obtain ZrO2-CaO or ZrO2-MgO;
Wherein in catalyst preparation process, each additive mol ratio consists of Zr: P123: M: absolute ethyl alcohol: acetylacetone,2,4-pentanedione: H2O=1: 0.01-0.05: 0.1-1.0: 40-200:0.1-1.0: 5-20.
4. the application of the copper Mn catalyst of a kind of synthetic methyl formate as described in claim 1-3 any one, is characterized in that copper-Mn oxide and mesoporous ZrO_2-CaO or ZrO2-MgO solid base catalyst catalysis CO and H2 one-step synthesis methyl formate carry out in paste state bed reactor;
(1) activation condition:
Catalyst 1: copper-manganese oxide catalyst first uses 5-10v% H2/N2 to activate 5-10h under normal pressure, 200-300 DEG C condition before reaction, is down to after room temperature passivation 2-8h under 1-2v% O2/Ar atmosphere;
Catalyst 2:ZrO2-CaO or ZrO2-MgO solid base be 500-700 DEG C of pretreatment 1-4h in N2;
(2) reaction condition:
Reaction temperature T=80-180 DEG C, pressure 4.0-8.0MPa, gas volume air speed 500-2000 mL/h/g.cat, H2/CO mol ratio=1.0-3.0; It is catalyst 1 that reaction used catalyst 1 closes with solvent: solvent=5-20 g:1L, it is ZrO2-CaO or ZrO2-MgO: solvent=10-40g:1L that catalyst 2 closes with solvent.
5. the application of the copper Mn catalyst of a kind of synthetic methyl formate as claimed in claim 4, is characterized in that solvent for use is the mixture of alcohols material and non-proton organic solvent, non-proton organic solvent: the volume ratio=1-3 of alcohol.
6. the application of the copper Mn catalyst of a kind of synthetic methyl formate as claimed in claim 4, is characterized in that described alcohols is methyl alcohol, ethanol or propyl alcohol.
7. the application of the copper Mn catalyst of a kind of synthetic methyl formate as claimed in claim 4, is characterized in that described non-proton organic solvent is N, N dimethyl formamide (DMF), dimethylbenzene, diphenyl ether, tetraethyleneglycol dimethyl ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410153703.8A CN103949268B (en) | 2014-04-17 | 2014-04-17 | The synthesis copper Mn catalyst of methyl formate and method for making and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410153703.8A CN103949268B (en) | 2014-04-17 | 2014-04-17 | The synthesis copper Mn catalyst of methyl formate and method for making and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103949268A true CN103949268A (en) | 2014-07-30 |
| CN103949268B CN103949268B (en) | 2016-01-20 |
Family
ID=51326694
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410153703.8A Active CN103949268B (en) | 2014-04-17 | 2014-04-17 | The synthesis copper Mn catalyst of methyl formate and method for making and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103949268B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111774070A (en) * | 2020-07-13 | 2020-10-16 | 陕西延长石油（集团）有限责任公司 | Catalyst for preparing methyl formate by catalyzing dehydrogenation of methanol, preparation method and application thereof |
| CN114700079A (en) * | 2022-04-20 | 2022-07-05 | 陕西延长石油（集团）有限责任公司 | Catalyst for preparing methyl formate by catalyzing synthesis gas in one step and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1365349A (en) * | 2000-02-25 | 2002-08-21 | 新日本制铁株式会社 | Process for preparation of formate esters or methanol and its synthetic catalyst |
| JP4012965B2 (en) * | 2003-04-30 | 2007-11-28 | 独立行政法人産業技術総合研究所 | Catalyst for high temperature CO shift reaction |
| CN103480376A (en) * | 2013-10-14 | 2014-01-01 | 中国科学院山西煤炭化学研究所 | Preparation method and application of synthetic carboxylate copper-mesoporous zirconium bifunctional catalyst |
-
2014
- 2014-04-17 CN CN201410153703.8A patent/CN103949268B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1365349A (en) * | 2000-02-25 | 2002-08-21 | 新日本制铁株式会社 | Process for preparation of formate esters or methanol and its synthetic catalyst |
| JP4012965B2 (en) * | 2003-04-30 | 2007-11-28 | 独立行政法人産業技術総合研究所 | Catalyst for high temperature CO shift reaction |
| CN103480376A (en) * | 2013-10-14 | 2014-01-01 | 中国科学院山西煤炭化学研究所 | Preparation method and application of synthetic carboxylate copper-mesoporous zirconium bifunctional catalyst |
Non-Patent Citations (2)
| Title |
|---|
| 杨迎春: "合成甲酸甲酯用Cu-Mn催化剂的制备", 《应用化学》, vol. 17, no. 5, 31 October 2000 (2000-10-31) * |
| 杨迎春等: "合成气一步法合成甲酸甲酯的研究", 《天然气化工》, vol. 23, no. 1, 31 December 1998 (1998-12-31) * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111774070A (en) * | 2020-07-13 | 2020-10-16 | 陕西延长石油（集团）有限责任公司 | Catalyst for preparing methyl formate by catalyzing dehydrogenation of methanol, preparation method and application thereof |
| CN111774070B (en) * | 2020-07-13 | 2022-12-20 | 陕西延长石油（集团）有限责任公司 | Catalyst for preparing methyl formate by catalyzing dehydrogenation of methanol, preparation method and application thereof |
| CN111774070B9 (en) * | 2020-07-13 | 2023-09-29 | 陕西延长石油（集团）有限责任公司 | Catalyst for preparing methyl formate by catalyzing methanol dehydrogenation and preparation method and application thereof |
| CN114700079A (en) * | 2022-04-20 | 2022-07-05 | 陕西延长石油（集团）有限责任公司 | Catalyst for preparing methyl formate by catalyzing synthesis gas in one step and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103949268B (en) | 2016-01-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103691451B (en) | Catalyst for synthesizing methyl formate by virtue of gas-phase methanol carbonylation as well as preparation method and application of catalyst | |
| CN102600842A (en) | Catalyst for preparing ethanol through hydrogenation of acetic acid as well as preparation method and application thereof | |
| CN106914246B (en) | The preparation method of the supported nickel catalyst of cis-butenedioic anhydride liquid-phase hydrogenatin synthetic gamma butyrolactone | |
| CN102746117B (en) | Method for catalytic conversion preparation of hexahydric alcohol from jerusalem artichoke as raw material | |
| CN103263926A (en) | Catalyst for synthesizing methanol through carbon dioxide hydrogenation as well as preparation method and application thereof | |
| CN101632932A (en) | Dimethyl carbonate supported catalyst directly synthesized by methanol and carbon dioxide | |
| CN106268806B (en) | A kind of catalyst of methanol carbonyl and its preparation and application | |
| CN102950018A (en) | Catalyst used for synthesis of methyl acetate through dimethyl ether carbonylation and preparation method thereof | |
| CN103949268B (en) | The synthesis copper Mn catalyst of methyl formate and method for making and application | |
| CN101658798B (en) | Method for modifying titanium silicate molecular sieve material | |
| CN102921415B (en) | Hydrogenation catalyst, preparation method of hydrogenation catalyst and application of hydrogenation catalyst to 2-methyltetrahydrofuran synthesis | |
| CN101670298B (en) | Method for modifying titanium silicalite zeolite | |
| CN102247833B (en) | Catalyst used in synthesis of methyl mercaptan and preparation method of catalyst | |
| CN109731596A (en) | A kind of copper-based method for preparing catalyst of the modification of Furfural hydrogenation to furfural alcohol | |
| CN103894232B (en) | A kind of Catalysts and its preparation method of methyl nitrite formylated synthesis methyl formate and application | |
| CN105664954A (en) | Method for promoting forming of aurichalcite phase in precursor of copper-based catalyst with calcium salt as additive | |
| CN103480376B (en) | Preparation method and application of synthetic carboxylate copper-mesoporous zirconium bifunctional catalyst | |
| CN106466638A (en) | The ruthenium catalyst of efficient cryogenic anti-poison guard catalyst formic acid hydrogen manufacturing and its preparation method and application | |
| CN103183357B (en) | The modified with noble metals method of HTS | |
| CN103480379A (en) | Method for preparing and synthetizing methanol catalyst from copper-based waste methanol catalyst recovered solution | |
| CN103357427A (en) | Nano-metal/solid alkali composite catalyst, preparation method and applications | |
| CN103752327B (en) | Acetone hydrogenation produces the catalyst of isopropyl alcohol and the method for catalytic production isopropyl alcohol thereof | |
| CN102371180A (en) | Catalyst for use in gas-phase synthesis of diethyl carbonate and preparation method thereof | |
| CN106607029A (en) | Catalyst and method for preparing 1, 3- propylene glycol | |
| CN101658791A (en) | Post-treatment method of titanium silicate molecular sieve material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |