CN105435779B - Carbon monoxide vapor- phase synthesis oxalate catalyst - Google Patents
Carbon monoxide vapor- phase synthesis oxalate catalyst Download PDFInfo
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Abstract
The present invention relates to a kind of catalyst of carbon monoxide vapor- phase synthesis oxalate, mainly solving the technical problems that existing in the prior art, catalyst activity is low, nitrous acid ester conversion ratio and the low problem of oxalate space-time yield during carbon monoxide vapor- phase synthesis oxalate.The present invention by using at least one of aluminium oxide, silica or molecular sieve for carrier, it loads 0.03~3wt% active constituents palladium and 0~3wt% is selected from least one of barium, magnesium, lanthanum, nickel, copper, samarium, calcium, zirconium, cerium, titanium, zinc, cerium auxiliary agent, wherein, the technical solution that palladium bridged adsorption carbon monoxide and wire type sorbing carbon monoxide ratio are 0.5~5 preferably solves the problems, such as this, can be used in carbon monoxide vapor- phase synthesis oxalate industrial production.
Description
Technical field
The present invention relates to a kind of catalyst for carbon monoxide vapor- phase synthesis oxalate, are especially used for carbon monoxide gas
It is combined to the catalyst of dimethyl oxalate or diethy-aceto oxalate.
Background technology
Oxalate is a kind of important Organic Chemicals, is largely used to fine chemistry industry and prepares various dyestuffs, medicine, molten
Agent, extractant and various intermediates.In addition, oxalic acid ester through hydrogenation can prepare highly important industrial chemicals ethylene glycol, this route
The method that may replace the higher petroleum path production ethylene glycol of current cost.
Traditional oxalate production line has starch nitric acid oxidation method, cellulose alkali fusion, sodium formate method, one step of ethylene glycol
Oxidizing process, oxidation of propylene and oxalic acid alcohol esterification reaction method, but above-mentioned traditional handicraft there are of high cost, energy consumption is big, it is seriously polluted,
Raw material utilizes the shortcomings of unreasonable.So having to look for an environmental-friendly process route at low cost.Nineteen sixty-five American Association
Oil company be found that carbon monoxide, alcohol and oxygen palladium chtalyst effect under can direct synthesis of oxalate, Ube is emerging since then
Production company and ARCO companies of the U.S. have carried out research and development in succession in this field, and Ube Industries Ltd. just proposes within 1977
Normal pressure gas-phase synthesis of oxalate technology, with Pd/A12O3For catalyst, under the conditions of 80~150 DEG C of temperature, pressure 0.5MPa, grass
The yield 98% of dimethyl phthalate.Nitrogen oxide in methanol and tail gas uses dioxygen oxidation, synthesis methyl nitrite cycle at high temperature
It uses.
China is a coal resources relative abundance, and carbon monoxide source is sufficient, is coupled and is synthesized using carbon monoxide gas phase
The route of oxalate repeated hydrogenation preparing ethylene glycol tallies with the national condition, and is an economically viable technology path.So domestic many
Enterprise and research institution have made a large amount of work to this field.It is used for for example, patent 200810035248.6 discloses one kind
The catalyst and its preparation method and application of oxalic acid Lipase absobed, the catalyst using Alpha-alumina as carrier, including 0.01~
The auxiliary agent Ir of the active constituent Pd, 0.01~0.5wt% of 1wt%, the catalyst oxalate space-time yield are 750g/L.cat.Specially
Sharp CN200710061392 discloses the catalyst and preparation method thereof of CO low-voltage gas-phase synthesizing of oxalic ester, and the catalyst is with metal
Palladium is main active constituent, and using titanium and cerium as co-catalyst, carrier is that modified Alpha-alumina is carrier, the catalyst oxalic acid two
The space-time yield of methyl esters is 700g/L.cat.H.But such research report is mostly concentrated on to catalyst formulation and carrier structure
Improvement in terms of, the space-time yield of developed catalyst oxalate also need to be improved.
Since CO catalyst for synthesizing oxalic ester by gas-phase is the catalyst of a structure sensitive, the height of the catalyst activity is not
It is only related with catalyst formulation, carrier structure, also and activity over catalysts component palladium the suction type to raw material carbon monoxide
It is related, improve the conversion ratio that active component palladium in catalyst is conducive to improve nitrous acid ester to the bridged adsorption intensity of carbon monoxide
With the space-time yield of oxalate.
Invention content
It is low the technical problem to be solved by the present invention is to which catalyst activity exists in the prior art, carbon monoxide vapor- phase synthesis
Nitrous acid ester conversion ratio and the low problem of oxalate space-time yield during oxalate provide a kind of new carbon monoxide gas and are harmonious
At oxalic acid ester catalyst.The second technical problem to be solved by the present invention is to provide a kind of new carbon monoxide gas phase coupling synthesis
The preparation method of oxalic acid ester catalyst, the catalyst prepared using this method are had during carbon monoxide vapor- phase synthesis oxalate
Active component palladium is high to carbon monoxide bridged adsorption ratio, methyl nitrite conversion ratio and the high spy of oxalate space-time yield
Point.The third technical problem to be solved by the present invention is to provide one kind and is used for the corresponding catalyst of one of technical problem is solved
The method of carbon monoxide vapor- phase synthesis oxalate.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：One kind being used for carbon monoxide vapor- phase synthesis
The catalyst of oxalate at least one of aluminium oxide, silica or molecular sieve for carrier, and loads 0.03~3wt% and lives
Property component palladium and 0~3wt% be selected from barium, magnesium, lanthanum, nickel, copper, samarium, calcium, zirconium, cerium, titanium, zinc, at least one of cerium auxiliary agent, wherein
Palladium bridged adsorption carbon monoxide and wire type sorbing carbon monoxide ratio are 0.5~5.
In above-mentioned technical proposal, the dispersion degree of palladium is 7~35%, preferably 26~35% in catalyst.
In above-mentioned technical proposal, palladium bridged adsorption carbon monoxide and wire type sorbing carbon monoxide ratio are preferably in catalyst
1~5, more preferably 1.5~5.
In above-mentioned technical proposal, in catalyst the average grain diameter of palladium crystal grain be 2~20 nanometers, preferably 2~10.
To solve above-mentioned technical problem two, the preparation method of heretofore described catalyst mainly includes the following steps that：
Include the following steps：
A) soluble-salt of active constituent palladium and auxiliary agent is dissolved into the water containing anion surfactant, it is to be dissolved
It is 2~7 to adjust pH value of solution after the completion, obtains maceration extract I；
B) maceration extract I is impregnated or is sprayed at carrier, obtain catalyst precarsor；
C) by catalyst precarsor in air aging, drying, roasting, reduction to get required catalyst.
Content is preferably 0.01~0.5wt% in anion surfactant water described in above-mentioned technical proposal.
PH described in above-mentioned technical proposal is 3~6
To solve above-mentioned technical problem three, the technical solution adopted by the present invention is as follows：A kind of carbon monoxide vapor- phase synthesis
The method of oxalate, in 100~180 DEG C, 0~1MPa of reaction pressure of reaction temperature, raw material carbon monoxide and nitrous acid ester rub
, than being 0.5~5, volume space velocity is 800~5000h for you-1Under the conditions of with catalyst haptoreaction of the present invention, generate containing grass
The effluent of acid esters.
Active constituent palladium in palladium catalyst can be divided into two ways to the absorption of carbon monoxide, and one kind is that bridge-type is inhaled
Attached, another kind is that wire type is adsorbed.And in the reaction of carbon monoxide vapor- phase synthesis producing oxalic ester, only deposited in a manner of bridged adsorption
Carbon monoxide could participate in reacting, with methyl nitrite generate oxalate.So the active constituent palladium in ensureing catalyst
In the case of reaching certain dispersion degree, the ratio for improving palladium bridged adsorption carbon monoxide in catalyst is conducive to improve nitrous acid ester
Conversion ratio and oxalate space-time yield.
The present invention effectively adjusts catalysis by the method added anion surfactant in maceration extract and adjust pH value
The dispersion degree of palladium and the suction type to carbon monoxide in agent, Gu compared with prior art, catalyst metals palladium of the invention point
Dissipate good, and palladium is high to the bridged adsorption ratio of carbon monoxide, be conducive to improve in catalyst the utilization rate of active constituent palladium and
Catalytic activity.Using the method for the present invention, nitrous acid ester conversion ratio can reach 89%, and oxalate space-time yield can reach 1100g/
L.H-1 achieves preferable technique effect.
In the method for the present invention, using following test method：
1) dispersion degree of palladium：
Palladium dispersion degree is measured by pulse hydroxide titration method, and catalyst is specially packed into the sample cell of chemical adsorption instrument
In, it is purged with nitrogen, switches hydrogen, temperature programming is kept for half an hour to 200 DEG C.Hydrogen is switched into nitrogen after half an hour, is blown
It sweeps half an hour, finally uses quantity tube into pure hydrogen, record the ml every time into hydrogen, total milli of hydrogen reduction is obtained by calculation
Rise number.
Dispersion degree=2 × VIt inhales×M(Pd)/ (3 × 22.4 × example weight × sample palladium content)
VIt inhales：Hydrogen adsorption amount；M(Pd)：The atomic weight of palladium
2) palladium crystal grain average grain diameter：The grain size of palladium crystal grain is measured by x-ray diffractometer (XRD).
3) palladium is to carbon monoxide determining adsorption：Catalyst is ground into 500 mesh powder below, 20mg is taken to be pressed into diameter
The good thin slice of translucency of 12mm, thickness 0.1mm, are placed in In-situ Infrared pond.First use 200 degree of reductase 12 hours of hydrogen, reduction
After by sample cell pumping high vacuum, then be passed through CO gas, Catalyst Adsorption allowed to be saturated, infrared test instrument is utilized to survey
Determine palladium in catalyst and peak intensity is adsorbed to carbon monoxide bridge-type and wire type.
Below by specific embodiment, the invention will be further described.
Specific implementation mode
【Embodiment 1】
Take 60g through the alumina support of 1100 DEG C of roastings 4 hours.0.3g palladium bichlorides are taken to be dissolved in 30ml containing 0.1% fat
In the deionized water of alcohol polyoxyethylene ether phosphate, addition sodium carbonate adjusts pH and obtains maceration extract I for 4.0 after dissolving.It will leaching
Stain liquid I is slowly added in carrier, and stirring carrier keeps solution dipping uniform, and catalyst precarsor is made.Catalyst precarsor is existed
80 DEG C of drying after aging 20 hours in air, then 450 DEG C of roastings in Muffle furnace are put in, it places into reactor internal program and is warming up to
300 DEG C of hydrogen reducings obtain carbon monoxide vapor- phase synthesis oxalate catalyst cat-1A after 8 hours.
The palladium dispersion degree of analysis test catalyst, palladium crystal grain average grain diameter, carbon monoxide absorption test result are shown in Table 1.
【Embodiment 2】
Take 60g through the alumina support of 1100 DEG C of roastings 4 hours.0.3g palladium bichlorides are taken to be dissolved in 30ml containing 0.1% fat
In the deionized water of alcohol polyoxyethylene ether phosphate, addition sodium carbonate adjusts pH and obtains maceration extract I for 2.0 after dissolving.It will leaching
Stain liquid I is slowly added in carrier, and stirring carrier keeps solution dipping uniform, and catalyst precarsor is made.Catalyst precarsor is existed
80 DEG C of drying after aging 20 hours in air, then 450 DEG C of roastings in Muffle furnace are put in, it places into reactor internal program and is warming up to
300 DEG C of hydrogen reducings obtain carbon monoxide vapor- phase synthesis oxalate catalyst cat-2A after 8 hours.
The palladium dispersion degree of analysis test catalyst, palladium crystal grain average grain diameter, carbon monoxide absorption test result are shown in Table 1.
【Embodiment 3】
Take 60g through the alumina support of 1100 DEG C of roastings 4 hours.0.3g palladium bichlorides are taken to be dissolved in 30ml containing 0.01% fat
In the deionized water of alcohol polyoxyethylene ether phosphate, addition sodium carbonate adjusts pH and obtains maceration extract I for 4 after dissolving.It will dipping
Liquid I is slowly added in carrier, and stirring carrier keeps solution dipping uniform, and catalyst precarsor is made.By catalyst precarsor in sky
80 DEG C of drying after aging 20 hours in gas, then 450 DEG C of roastings in Muffle furnace are put in, it places into reactor internal program and is warming up to 300
DEG C hydrogen reducing obtains carbon monoxide vapor- phase synthesis oxalate catalyst cat-3A after 8 hours.
The palladium dispersion degree of analysis test catalyst, palladium crystal grain average grain diameter, carbon monoxide absorption test result are shown in Table 1.
【Embodiment 4】
Take 60g through the alumina support of 1100 DEG C of roastings 4 hours.0.3g palladium bichlorides are taken to be dissolved in 30ml containing 0.5% fat
In the deionized water of alcohol polyoxyethylene ether phosphate, addition sodium carbonate adjusts pH and obtains maceration extract I for 4.0 after dissolving.It will leaching
Stain liquid I is slowly added in carrier, and stirring carrier keeps solution dipping uniform, and catalyst precarsor is made.Catalyst precarsor is existed
80 DEG C of drying after aging 20 hours in air, then 450 DEG C of roastings in Muffle furnace are put in, it places into reactor internal program and is warming up to
300 DEG C of hydrogen reducings obtain carbon monoxide vapor- phase synthesis oxalate catalyst cat-4A after 8 hours.
The palladium dispersion degree of analysis test catalyst, palladium crystal grain average grain diameter, carbon monoxide absorption test result are shown in Table 1.
【Embodiment 5】
Take 60g through the alumina support of 1100 DEG C of roastings 4 hours.0.3g palladium bichlorides are taken to be dissolved in 30ml containing 0.1% fat
In the deionized water of alcohol polyoxyethylene ether phosphate, addition sodium carbonate adjusts pH and obtains maceration extract I for 7.0 after dissolving.It will leaching
Stain liquid I is slowly added in carrier, and stirring carrier keeps solution dipping uniform, and catalyst precarsor is made.Catalyst precarsor is existed
80 DEG C of drying after aging 20 hours in air, then 450 DEG C of roastings in Muffle furnace are put in, it places into reactor internal program and is warming up to
300 DEG C of hydrogen reducings obtain carbon monoxide vapor- phase synthesis oxalate catalyst cat-5A after 8 hours.
The palladium dispersion degree of analysis test catalyst, palladium crystal grain average grain diameter, carbon monoxide absorption test result are shown in Table 1.
【Embodiment 6】
Take 60g through the alumina support of 1100 DEG C of roastings 4 hours.It takes 0.3g palladium bichlorides to be dissolved in 30ml and contains 0.005% fat
In the deionized water of fat alcohol polyoxyethylene ether phosphate, addition sodium carbonate adjusts pH and obtains maceration extract I for 4.0 after dissolving.It will
Maceration extract I is slowly added in carrier, and stirring carrier keeps solution dipping uniform, and catalyst precarsor is made.By catalyst precarsor
80 DEG C of drying after aging 20 hours in air, then 450 DEG C of roastings in Muffle furnace are put in, it places into reactor internal program and is warming up to
300 DEG C of hydrogen reducings obtain carbon monoxide vapor- phase synthesis oxalate catalyst cat-6A after 8 hours.
The palladium dispersion degree of analysis test catalyst, palladium crystal grain average grain diameter, carbon monoxide absorption test result are shown in Table 1.
【Embodiment 7】
Take 60g through the alumina support of 1100 DEG C of roastings 4 hours.0.3g palladium bichlorides and 0.5g lanthanum nitrates is taken to be dissolved in 30ML
In deionized water containing 0.2% odium stearate, addition sodium carbonate adjusts pH and obtains maceration extract I for 2.0 after dissolving.By maceration extract
I is slowly added in carrier, and stirring carrier keeps solution dipping uniform, and catalyst precarsor is made.By catalyst precarsor in air
80 DEG C of drying after middle aging 20 hours, then 500 DEG C of roastings in Muffle furnace are put in, carbon monoxide vapor- phase synthesis oxalic acid is obtained after roasting
Ester catalyst cat-7A.
The palladium dispersion degree of analysis test catalyst, palladium crystal grain average grain diameter, carbon monoxide absorption test result are shown in Table 1.
【Embodiment 8】
Take 60g silica supports.It takes 0.44g palladium nitrates, 2g copper nitrates to be dissolved in 45ML and contains 0.1% NaLS
Deionized water in, it is 5.0 to obtain maceration extract I that addition sodium carbonate, which adjusts pH, after dissolving.Maceration extract I is slowly added to carrier
In, and stirring carrier keeps solution dipping uniform, and catalyst precarsor is made.By after catalyst precarsor in air aging 20 hours 80
DEG C drying, then 300 DEG C of roastings are put in Muffle furnace, carbon monoxide vapor- phase synthesis oxalate catalyst cat-8A is obtained after roasting.
The palladium dispersion degree of analysis test catalyst, palladium crystal grain average grain diameter, carbon monoxide absorption test result are shown in Table 1.
【Embodiment 9】
Take 60g4A type molecular sieve carriers.It takes 0.1g palladium bichlorides, 0.5g barium nitrates to be dissolved in 25ML and contains 0.1% dodecyl
In the deionized water of benzene sulfonic acid sodium salt, addition sodium carbonate adjusts pH and obtains maceration extract I for 3.0 after dissolving.Maceration extract I is slowly added
Enter into carrier, and stirring carrier keeps solution dipping uniform, and catalyst precarsor is made.By catalyst precarsor aging 20 in air
80 DEG C of drying after hour, then 600 DEG C of roastings in Muffle furnace are put in, carbon monoxide vapor- phase synthesis oxalate catalyst is obtained after roasting
cat-9A。
The palladium dispersion degree of analysis test catalyst, palladium crystal grain average grain diameter, carbon monoxide absorption test result are shown in Table 1.
【Embodiment 10~14】
According to【Embodiment 1】Preparation method, only change palladium catalyst content, auxiliary agent type and content, prepare and urge
Agent cat-10~14A.
The palladium dispersion degree of analysis test catalyst, palladium crystal grain average grain diameter, carbon monoxide absorption test result are shown in Table 1.
【Comparative example 1】
Formula according to embodiment 1 is：Take 60g through 1100 DEG C roasting 4 hours alumina support and 0.3g palladium bichlorides by
Catalyst cat-1B is prepared according to the method for patent 200810035248.6.
The palladium dispersion degree of analysis test catalyst, palladium crystal grain average grain diameter, carbon monoxide absorption test result are shown in Table 1.
【Comparative example 2】
Formula according to embodiment 2 is：Take 60g through the alumina support of 1100 DEG C of roastings 4 hours.Take 0.3g palladium bichlorides,
0.5g lanthanum nitrates, then carbon monoxide vapor- phase synthesis oxalate catalyst is prepared by the method for patent 200810114383.X
cat-2B。
The palladium dispersion degree of analysis test catalyst, palladium crystal grain average grain diameter, carbon monoxide absorption test result are shown in Table 1.
【Comparative example 3】
According to【Embodiment 2】Preparation method, only change lanthanum nitrate additive amount, prepare catalyst cat3B.
The palladium dispersion degree of analysis test catalyst, palladium crystal grain average grain diameter, carbon monoxide absorption test result are shown in Table 1.
【Comparative example 4】
According to【Embodiment 2】Preparation method, anion surfactant is not added in maceration extract only, prepares and urges
Agent cat4B.
The palladium dispersion degree of analysis test catalyst, palladium crystal grain average grain diameter, carbon monoxide absorption test result are shown in Table 1.
【Comparative example 5】
According to【Embodiment 2】Preparation method, do not adjust the pH value (pH value be less than 1) of maceration extract only, prepare catalysis
Agent cat5B.
The palladium dispersion degree of analysis test catalyst, palladium crystal grain average grain diameter, carbon monoxide absorption test result are shown in Table 1.
Table 1
Wherein ACO bridge-types/ACO wire typesFor palladium bridged adsorption carbon monoxide and wire type sorbing carbon monoxide ratio
【Embodiment 15】
This example demonstrates that 1~14 gained catalyst of embodiment has been coupled answering in synthesizing dimethyl oxalate reaction in CO
With.
1~14 gained catalyst of the embodiment of the present invention is taken to carry out reaction examination, in 140 DEG C of reaction temperature, reaction pressure is
0.2MPa, CO are 1.5 with methyl nitrite molar ratio, and volume space velocity is 2500 hours-1Under conditions of carry out CO coupling synthesis grass
Dimethyl phthalate reacts, and product is condensed by methanol absorption after reaction, and gas-liquid separation does sampling analysis to gas phase and liquid phase respectively.Instead
2 should be the results are shown in Table.
【Comparative example 6】
Take catalyst obtained by the Comparative Examples 1 to 5 to carry out reaction examination, using reducing condition raw material identical with embodiment 15 and
Reaction condition.Reaction result is shown in Table 2.
Table 2
The catalyst of the present invention is in carbon monoxide vapor- phase synthesis oxalic acid it can be seen from test result and synthetic reaction effect
In ester reaction, reference sample is apparently higher than to the space-time yield of nitrous acid ester conversion ratio, oxalate, have apparent progress with it is excellent
Gesture.
【Embodiment 16】
This example demonstrates that 8 gained catalyst of embodiment is in the reaction that carbon monoxide gas phase is coupled synthesizing dimethyl oxalate
Change the test result of process conditions, reaction condition and the results are shown in Table 3.
Table 3
Claims (7)
1. one kind being used for carbon monoxide vapor- phase synthesis oxalate catalyst, at least one in aluminium oxide, silica or molecular sieve
Kind be carrier, and load 0.03~3wt% active constituents palladium and 0~3wt% be selected from barium, magnesium, lanthanum, copper, samarium, calcium, zirconium, cerium, titanium,
At least one of zinc, cerium auxiliary agent, wherein palladium bridged adsorption carbon monoxide and wire type sorbing carbon monoxide ratio are 1.5~5；
The dispersion degree of palladium is 26~35% in catalyst；
The catalyst is prepared by method comprising the following steps：
A) soluble-salt of active constituent palladium and auxiliary agent is dissolved into the water containing anion surfactant, completion to be dissolved
It is 2~7 to adjust pH value of solution afterwards, obtains maceration extract I；
B) maceration extract I is impregnated or is sprayed at carrier, obtain catalyst precarsor；
C) by catalyst precarsor in air aging, drying, roasting, reduction to get required catalyst.
2. being used for carbon monoxide vapor- phase synthesis oxalate catalyst according to claim 1, it is characterised in that palladium in catalyst
The average grain diameter of crystal grain is nanometer 2~20.
3. being used for carbon monoxide vapor- phase synthesis oxalate catalyst according to claim 2, it is characterised in that palladium in catalyst
The average grain diameter of crystal grain is nanometer 2~10.
4. the preparation method of claims 1 to 3 any one of them carbon monoxide vapor- phase synthesis oxalate catalyst, including it is following
Step：
A) soluble-salt of active constituent palladium and auxiliary agent is dissolved into the water containing anion surfactant, completion to be dissolved
It is 2~7 to adjust pH value of solution afterwards, obtains maceration extract I；
B) maceration extract I is impregnated or is sprayed at carrier, obtain catalyst precarsor；
C) by catalyst precarsor in air aging, drying, roasting, reduction to get required catalyst.
5. the preparation method of carbon monoxide vapor- phase synthesis oxalate catalyst according to claim 4, it is characterised in that institute
Stating anion surfactant, content is 0.01~0.5wt% in water.
6. the preparation method of carbon monoxide vapor- phase synthesis oxalate catalyst according to claim 4, it is characterised in that leaching
Stain liquid pH is 3~6.
7. a kind of method of carbon monoxide vapor- phase synthesis oxalate, in 100~180 DEG C, 0~1MPa of reaction pressure of reaction temperature,
The molar ratio of raw material carbon monoxide and nitrous acid ester is 0.5~5, and volume space velocity is 800~5000h-1Under the conditions of with claim 1
Any one of~3 catalyst haptoreactions, generate the effluent containing oxalate.
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| CN105903466A (en) * | 2016-05-03 | 2016-08-31 | 中国科学院福建物质结构研究所 | Catalyst for dimethyl oxalate synthesis and preparation method of catalyst for dimethyl oxalate synthesis |
| CN106925263B (en) * | 2017-02-20 | 2019-12-31 | 宁波中科远东催化工程技术有限公司 | Catalyst for synthesizing dimethyl oxalate from CO |
| CN110523412A (en) * | 2018-05-24 | 2019-12-03 | 中国石油化工股份有限公司 | It is coupled synthesizing dimethyl oxalate palladium catalyst and preparation method thereof |
| CN112441922B (en) * | 2019-09-02 | 2023-04-07 | 中国石油化工股份有限公司 | Method for preparing oxalate through CO oxidative coupling, catalyst and preparation method thereof |
| CN114433081A (en) * | 2022-02-25 | 2022-05-06 | 中国科学院福建物质结构研究所 | Preparation method of catalyst for CO-production of carbonic ester and formic ester by synthesizing oxalate with CO |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1148589A (en) * | 1995-10-20 | 1997-04-30 | 中国科学院福建物质结构研究所 | Oxalate synthesis catalyst |
| CN1381310A (en) * | 2002-05-09 | 2002-11-27 | 华东理工大学 | Catalyst for gas-phase synthesis of oxalate and its preparing process |
| CN102218330A (en) * | 2011-04-15 | 2011-10-19 | 上海浦景化工技术有限公司 | Supported catalyst used in selective synthesis, and preparation method and purpose thereof |
| CN103041826A (en) * | 2013-01-14 | 2013-04-17 | 中国科学院福建物质结构研究所 | Bimetal nanometer catalyst as well as preparation and application method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013086691A1 (en) * | 2011-12-14 | 2013-06-20 | 中国科学院福建物质结构研究所 | Nano pd catalyst for preparation of oxalate by gas phase co oxidative coupling, and preparation process thereof |
-
2014
- 2014-08-27 CN CN201410428976.9A patent/CN105435779B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1148589A (en) * | 1995-10-20 | 1997-04-30 | 中国科学院福建物质结构研究所 | Oxalate synthesis catalyst |
| CN1381310A (en) * | 2002-05-09 | 2002-11-27 | 华东理工大学 | Catalyst for gas-phase synthesis of oxalate and its preparing process |
| CN102218330A (en) * | 2011-04-15 | 2011-10-19 | 上海浦景化工技术有限公司 | Supported catalyst used in selective synthesis, and preparation method and purpose thereof |
| CN103041826A (en) * | 2013-01-14 | 2013-04-17 | 中国科学院福建物质结构研究所 | Bimetal nanometer catalyst as well as preparation and application method thereof |
Non-Patent Citations (1)
| Title |
|---|
| "CO催化偶联制草酸二甲酯反应机理、催化剂和动力学的研究";计扬;《中国优秀博士学位论文全文数据库工程科技Ⅰ辑》;20101015(第10期);第10期 * |
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