CN102649733A - Method for preparing oxalate through CO gas phase catalytic coupling - Google Patents
Method for preparing oxalate through CO gas phase catalytic coupling Download PDFInfo
- Publication number
- CN102649733A CN102649733A CN2011100456097A CN201110045609A CN102649733A CN 102649733 A CN102649733 A CN 102649733A CN 2011100456097 A CN2011100456097 A CN 2011100456097A CN 201110045609 A CN201110045609 A CN 201110045609A CN 102649733 A CN102649733 A CN 102649733A
- Authority
- CN
- China
- Prior art keywords
- gas
- phase catalytic
- tube
- reaction
- catalytic coupling
- 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
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a method for preparing oxalate through CO gas phase catalytic coupling and mainly solves the technical problem of low oxalate selectivity in the reaction process of preparing the oxalate through the CO gas phase catalytic coupling existing in the prior art. With the adoption of the technical scheme that the method for preparing the oxalate through the CO gas phase catalytic coupling comprises the following steps that: mixed gas containing nitrite and CO is taken as a raw material, methanol, ethanol or water are taken as a terminating agent, and under the conditions that the reaction temperature is 100-180 DEG C, the volume airspeed is 500-10000 hour<-1>, and the reaction pressure is -0.08 MPa to 1.5 MPa, the molar ratio of the CO to the nitrite is (1-5):1, the raw material is in contact with a palladium-contained fluidized bed catalyst in a fluidized bed reactor for reaction to generate an effluent containing the oxalate, so the problem is better solved. The method can be used in the industrial production for preparing the oxalate through the CO gas phase catalytic coupling.
Description
Technical field
The present invention relates to a kind of method of CO gas gas-phase catalytic coupling producing oxalic ester, particularly, divide device soon, be useful in the CO gas coupling producing oxalic ester reaction process about adopting CO gas coupling producing oxalic ester fluidized-bed reactor coupling riser reactor.
Background technology
Barkite is important Organic Chemicals, is used for fine chemistry industry in a large number and produces various dyestuffs, medicine, important solvent, extraction agent and various midbody.Get into 21 century, barkite receives international extensively attention as degradable environment-friendly engineering plastics monomer.In addition, the barkite ordinary-pressure hydrolysis can get oxalic acid, and normal pressure ammonia is separated and can be got high-quality slow chemical fertilizer oxamyl.Barkite can also be used as solvent, produces medicine and dyestuff intermediate etc., for example carries out various condensation reactions with fatty ester, hexamethylene phenyl methyl ketone, amido alcohol and many heterogeneous ring compounds.It can also synthesize at the chest acyl alkali that pharmaceutically is used as hormone.In addition, the barkite low-voltage hydrogenation can prepare crucial industrial chemicals terepthaloyl moietie, and terepthaloyl moietie mainly relies on petroleum path to prepare at present, and cost is higher, and China needs a large amount of import terepthaloyl moietie every year, and import volume was nearly 4,800,000 tons in 2007.
The production route of tradition barkite utilizes oxalic acid to prepare with alcohol generation esterification, and the production technique cost is high, and energy consumption is big, and is seriously polluted, and prepared using is unreasonable.For many years, people are seeking an operational path that cost is low, environment is good always.The sixties in last century; The D.F.Fenton of U.S. Associated Oil Company finds; Carbon monoxide, pure and mild oxygen can pass through the direct synthesis of oxalic acid dialkyl of oxidation carbonylation, and company of Ube Industries Ltd. and U.S. ARCO company have carried out research and development in succession in this field since then.
Divide from development course for carbon monoxide oxidative coupling method synthesis of oxalate and can be divided into liquid phase method and vapor phase process.Wherein, carbon monoxide liquid phase method synthesis of oxalate condition is relatively harsher, and reaction is under high pressure carried out, the liquid-phase system corrosive equipment, and catalyzer is prone to run off in the reaction process.The tool advantage of the vapor phase process of CO coupling producing oxalic ester, external company of Ube Industries Ltd. and Italian Montedisons SPA carried out vapor phase process research in succession in 1978.Wherein, the synthesis of oxalic ester by gaseous catalysis technology of emerging product company of space portion exploitation, reaction pressure 0.5MPa, temperature is 80 ℃～150 ℃.
Along with carbon monoxide oxidative coupling legal system in the world is equipped with the research and development of barkite Technology, domestic many research institutions have also carried out research work to this field.According to the china natural resources characteristic distributions, be the feedstock production organic oxygen-containing compound with the carbon monoxide, for the pressure of alleviating petroleum products, rationally utilize coal and natural gas source to have crucial strategic importance.At present; Become important research project in domestic one-carbon chemical and the organic chemical industry field by carbon monoxide oxidative coupling method synthesis of oxalate; Successively there are how tame research institution and research institutions to be devoted to catalyzer development, process exploitation and the engineering amplification work in this field, and obtained bigger progress.
Although above-mentioned numerous research institution has obtained than much progress technically, technology itself still remains further to be improved and development, especially improves reaction preference how, and aspects such as raising activity of such catalysts all need further research and break through.
Document CN200710060003.4 discloses a kind of method of CO preparing diethyl oxalate by coupling, adopts vapor phase process, and CO is under the participation of ethyl nitrite; Under the catalysis of bimetal loaded catalyst, coupling generates the oxalic acid diethyl ester bullion, reacts to be self-enclosed working cycle; CO gas with get into coupler reactor from the ethyl nitrite of regeneration reactor through mixing preheating, reaction back gas obtains water white oxalic acid diethyl ester lime set through condensation separation; The non-condensable gas that contains NO gets into regeneration reactor, in regeneration reactor, returns coupler reactor and uses continuously with ethanol, the recycling of oxygen reaction generation ethyl nitrite, and this invention is on the basis of lab scale research in early stage; With the industrial production is that background is carried out, and the continuous operation examination is amplified in mould examination and the pilot scale accomplished under the industrial operation condition, and the linked reaction temperature is low; Product concentration improves; Present method is more energy-conservation, and is pollution-free, high efficiency.But per pass conversion that should technology CO is 20～60%, and the purpose selectivity of product all remains further to be improved about 96%.
Document CN 95116136.9 discloses the catalyzer of the synthetic usefulness of a kind of barkite, selects for use Zr to make auxiliary agent, develops novel Pd-Zr/Al with pickling process
2O
3Catalyzer.This catalyzer is to adopt fixed-bed reactor as carbon monoxide and the reaction of nitrous acid ester synthesis of oxalic ester by gaseous catalysis.But the yield of its barkite of catalyzer that is adopted in this patent is lower, and the impurity of virgin gas is had relatively high expectations, and the selectivity of product barkite is 95%, and the per pass conversion of nitrous acid ester is up to 64%, all remains further to be improved.
The subject matter that the related technology of above-mentioned document exists is the low technical problem of selectivity selectivity of barkite.
Summary of the invention
Technical problem to be solved by this invention is the reaction process that in the past was used for CO gas gas-phase catalytic coupling producing oxalic ester in the technical literature, and the technical problem that the purpose selectivity of product is low provides a kind of method of new CO gas gas-phase catalytic coupling producing oxalic ester.This method is used for CO gas coupling producing oxalic ester process, has the high advantage of barkite purpose selectivity of product.
In order to solve the problems of the technologies described above; The technical scheme that the present invention adopts is following: a kind of method of CO gas gas-phase catalytic coupling producing oxalic ester; With the mixed gas that contains nitrous acid ester and CO is raw material; With methyl alcohol, ethanol or water is terminator, and 100～180 ℃ of temperature of reaction, volume space velocity is 500～10000 hours
-1Reaction pressure is-0.08～1.5MPa; The mol ratio of CO and nitrous acid ester is under 1～5: 1 the condition; Raw material contacts with the interior palladium fluid catalyst that contains of fluidized-bed reactor; Reaction generates the elute that contains barkite, and wherein fluidized-bed reactor is made up of settling vessel (5), stripper (11) and interchanger (3) basically; Comprise emulsion zone (A), zone of transition (B), negative area (C), material inlet (1), sparger or grid distributor (2), interchanger (3), riser tube (4), divide device (6), gas tube (7), cyclonic separator (8), collection chamber (9), product gas outlet (10), stripper (11), regenerator sloped tube (12) and inclined tube to be generated (13) soon, wherein emulsion zone (A) is connected with riser tube (4) through zone of transition (B) back of undergauge structure; Riser tube (4) upper end or end are provided with fast minute device (6); The fast spiral arm of device (6) that divides is positioned at outside the riser tube (4), in the coaxial gas tube that communicates of riser tube (4) (7); Gas tube (7) is positioned at settling vessel (5), and the freeboard of fluidized bed on top, negative area (C) is stretched in its upper end, and its lower end is positioned at the outer zone of transition of riser tube (4) (B) outer upper ends; Cyclonic separator (8) is positioned at settling vessel (5), and outside the gas tube (7), its top outlet communicates with collection chamber (9); Collection chamber (9) is positioned at settling vessel (5) top and is connected with product gas outlet (10); Stripper (11) one ends are connected with the bottom of settling vessel (5), and the other end of stripper (11) links to each other with inclined tube to be generated (13); Between the bottom of settling vessel (5) and emulsion zone (A) hypomere, interchanger (3) is set, an end of interchanger (3) is connected with the bottom of settling vessel (5), and the other end of interchanger (3) is connected with emulsion zone (A); Sparger or grid distributor (2) are positioned at emulsion zone (A) bottom, and the bottom of sparger or grid distributor (2) is provided with material inlet (1), it is characterized in that near riser tube (4) lower region, terminator inlet (15) being set.
Terminator inlet 15 is 0～4/5 of riser tube 4 length apart from the vertical range of riser tube 4 bottoms in the technique scheme; Terminator inlet 15 distributes along riser tube 4 lower regions ringwise; The internal diameter of riser tube 4 is 1/15～1/2 of emulsion zone A external diameters, and the height of riser tube 4 is 1/5～5/1 of emulsion zone A height; Regenerator sloped tube 12 is 1/10～1/2 of emulsion zone A vertical height with emulsion zone A communication port apart from emulsion zone A bottom vertical distance; The vertical height of zone of transition B is 1/20～1/2 of an emulsion zone A vertical height; The gas inlet distance set air chamber 9 top vertical ranges of cyclonic separator 8 are 1/10～1/1 of settling vessel diameter.
Reaction conditions is preferably in the technique scheme: temperature of reaction is 100～160 ℃, and volume space velocity is 500～5000 hours
-1, reaction pressure is-0.05～1.0MPa, and the mol ratio of CO and nitrous acid ester is 1～3: 1, contains the preferred self-alumina of palladium fluid catalyst carrier, and the average preferable range of particle diameter is 30～200 microns.
As everyone knows; The reaction of CO and nitrous acid ester gas phase coupling producing oxalic ester is a strong exothermal reaction; Reaction kinetics research shows, being uniformly distributed with very significantly of temperature of reaction to the influence of purpose selectivity of product, and the present invention adopts the temperature uniform distribution that fluidized-bed reactor can the realization response beds; This is remarkable to improving purpose product selectivity effect; And find also in the research process that the decomposition loss of nitrous acid ester and temperature of reaction cognation are very strong in the reactor feed gas, the decomposition loss of the high more inferior acid esters of temperature of reaction is just high more.And adopt in the CO gas coupling producing oxalic ester fluidized-bed reaction process; Under raw material and the catalyzer Long contact time situation; Still can continue to transform; Especially at the settling zone of CO gas coupling producing oxalic ester fluidized-bed reactor, a large amount of unsegregated catalyzer can continue to react with inferior ester under the condition of high temperature, cause inferior ester to decompose and rate of loss is high.The present invention injects terminator through the zone, outlet position of leaving catalytic bed in catalyzer and reaction product; On the one hand, the terminator that temperature is lower contacts with pyroreaction mixture and catalyzer, can significantly reduce the temperature of reaction mixture and catalyzer; This can further quicken the rapid temperature-fall period of pyroreaction mixture and catalyzer; After reaction mixture that temperature sharply reduces and catalyzer left reaction zone, side reaction was few, and it is little to continue the reaction odds; Reduce the rate of loss of raw material, further improved the yield or the selectivity of product.
The reaction process that is used for CO gas gas-phase catalytic coupling producing oxalic ester of the present invention; Use device shown in Figure 1; Adopting precious metal palladium load aluminum oxide is catalyzer, and water, methyl alcohol or ethanol are terminator, are raw material with the mixed gas that contains nitrous acid ester and CO; 100～180 ℃ of temperature of reaction, volume space velocity is 500～10000 hours
-1, reaction pressure is-0.08～1.5MPa, the mol ratio of CO and nitrous acid ester is under 1～5: 1 the condition; Raw material contacts with the interior palladium fluid catalyst that contains of fluidized-bed reactor; Reaction generates the elute that contains barkite, and the selectivity of barkite can obtain better technical effect greater than 99%.
Description of drawings
Fig. 1 is the fluidized-bed reactor synoptic diagram that method adopted of CO gas gas-phase catalytic coupling producing oxalic ester of the present invention.
A is that emulsion zone, B are that zone of transition, C are negative areas, the 1st among Fig. 1, material inlet, the 2nd, sparger or grid distributor, the 3rd, interchanger, the 4th, riser tube; The 5th, settling vessel, the 6th, divide device soon, the 7th, gas tube, the 8th, cyclonic separator; The 9th, collection chamber, the outlet of 10 product gas, the 11st, stripper, the 12nd, regenerator sloped tube; The 13rd, inclined tube to be generated, the 14th, stripped vapor inlet, the 15th, terminator inlet.
Raw material is introduced by material inlet 1 among Fig. 1, and through gas distributor or grid distributor 2 laggard emulsion zone A and the catalyzer contact reacts of going into fluidized-bed that distribute, catalyzer and reaction mixture are through zone of transition B entering riser tube 4; Behind vortex quick separation device 6 sharp separation of riser tube 4 upper ends (end); Most of catalyzer gets into the lower region of settling vessel C; The part catalyzer that reaction mixture is carried secretly gets into settling vessel 5 top dilute phase spaces and carries out secondary separation through cyclonic separator 8; Product gas after the separation gets into collection chamber 9 through the outlet of cyclonic separator 8, is drawn by product gas outlet 10.Return the lower region of settling vessel 5 through the dipleg of cyclonic separator 8 from the catalyzer after cyclonic separator 8 separation.The reclaimable catalyst of the C bottom, negative area in the settling vessel 5 gets into stripper 11; Behind stripped vapor stripping from stripped vapor inlet 14; Get into revivifier (revivifier omits among the figure) through inclined tube 12 to be generated, regenerator gets into CO gas coupling producing oxalic ester fluidized-bed reactor emulsion zone A through regenerator sloped tube 12.In addition, the part catalyzer in the settling vessel 5 gets into CO gas coupling producing oxalic ester fluidized-bed reactor emulsion zone A bottom and continues reaction with catalyst mix after interchanger 3 heat exchange, and whole process circulation is carried out.
Through embodiment the present invention is done further elaboration below.
Embodiment
[embodiment 1]
With device shown in Figure 1, employing palladium content is 0.5% palladium load aluminum oxide fluid catalyst, and its average diameter of particles is 50 microns; Methyl alcohol is terminator; The mol ratio of using CO and methyl nitrite is that 1.2: 1 mixed gas is raw material, and the weight ratio of raw material and terminator is 10: 1, and the terminator feeding temperature is 40 ℃; In temperature of reaction is 130 ℃, and the reaction volume air speed is 2000 hours
-1, reaction pressure is-condition of 0.08MPa under, raw material contacts with catalyzer, reacts, its reaction result is: the selectivity of dimethyl oxalate is 99.2%, the space-time yield of dimethyl oxalate be 800 grams/(the gram catalyzer. hour).
[embodiment 2]
With device shown in Figure 1, employing palladium content is 0.3% palladium load aluminum oxide fluid catalyst, and its average diameter of particles is 80 microns; Ethanol is terminator; The mol ratio of using CO and ethyl nitrite is that 0.6: 1 mixed gas is raw material, and the weight ratio of raw material and terminator is 5: 1, and the terminator feeding temperature is 40 ℃; 120 ℃ of temperature of reaction, the reaction volume air speed is 2000 hours
-1, reaction pressure is under the condition of 0.03MPa, raw material contacts with catalyzer, reacts, its reaction result is: the selectivity of oxalic acid diethyl ester is 98.8%, the space-time yield of dimethyl oxalate be 710 the gram/(gram catalyzer. hour).
[embodiment 3]
With device shown in Figure 1, employing palladium content is 0.2% palladium load aluminum oxide fluid catalyst, and its average diameter of particles is 150 microns; Water is terminator; The mol ratio of using CO and methyl nitrite is that 2.0: 1 mixed gas is raw material, and the weight ratio of raw material and terminator is 50: 1, and the terminator feeding temperature is 60 ℃; In temperature of reaction is 150 ℃, and the reaction volume air speed is 6000 hours
-1, reaction pressure is under the condition of 0.5MPa, raw material contacts with catalyzer, reacts, its reaction result is: the selectivity of dimethyl oxalate is 99.1%, the space-time yield of dimethyl oxalate be 880 the gram/(gram catalyzer. hour).
[embodiment 4]
With device shown in Figure 1, employing palladium content is 0.2% palladium load aluminum oxide fluid catalyst, and its average diameter of particles is 180 microns; Methyl alcohol is terminator; The mol ratio of using CO and methyl nitrite is that 3.0: 1 mixed gas is raw material, and the weight ratio of raw material and terminator is 100: 1, and the terminator feeding temperature is 20 ℃; In temperature of reaction is 160 ℃, and the reaction volume air speed is 4000 hours
-1, reaction pressure is under the condition of 0.8MPa, raw material contacts with catalyzer, reacts, its reaction result is: the selectivity of dimethyl oxalate is 99.4%, the space-time yield of dimethyl oxalate be 980 the gram/(gram catalyzer. hour).
[comparative example 1]
Each step and reaction conditions with reference to embodiment 1; Just CO gas coupling producing oxalic ester reactor drum adopts fixed-bed reactor; And do not add terminator, reaction result is: the selectivity of dimethyl oxalate is 96.1%, the space-time yield of dimethyl oxalate be 705 the gram/(gram catalyzer. hour).
[comparative example 2]
Each step and reaction conditions with reference to embodiment 2; Just CO gas coupling producing oxalic ester reactor drum adopts fixed-bed reactor; And do not add terminator, reaction result is: the selectivity of oxalic acid diethyl ester is 95.6%, the space-time yield of oxalic acid diethyl ester be 650 the gram/(gram catalyzer. hour).
Claims (9)
1. the method for a CO gas gas-phase catalytic coupling producing oxalic ester is a raw material with the mixed gas that contains nitrous acid ester and CO, is terminator with methyl alcohol, ethanol or water, and 100～180 ℃ of temperature of reaction, volume space velocity is 500～10000 hours
-1Reaction pressure is-0.08～1.5MPa; The mol ratio of CO and nitrous acid ester is under 1～5: 1 the condition; Raw material contacts with the interior palladium fluid catalyst that contains of fluidized-bed reactor; Reaction generates the elute that contains barkite, and wherein fluidized-bed reactor is made up of settling vessel (5), stripper (11) and interchanger (3) basically; Comprise emulsion zone (A), zone of transition (B), negative area (C), material inlet (1), sparger or grid distributor (2), interchanger (3), riser tube (4), divide device (6), gas tube (7), cyclonic separator (8), collection chamber (9), product gas outlet (10), stripper (11), regenerator sloped tube (12) and inclined tube to be generated (13) soon, wherein emulsion zone (A) is connected with riser tube (4) through zone of transition (B) back of undergauge structure; Riser tube (4) upper end or end are provided with fast minute device (6); The fast spiral arm of device (6) that divides is positioned at outside the riser tube (4), in the coaxial gas tube that communicates of riser tube (4) (7); Gas tube (7) is positioned at settling vessel (5), and the freeboard of fluidized bed on top, negative area (C) is stretched in its upper end, and its lower end is positioned at the outer zone of transition of riser tube (4) (B) outer upper ends; Cyclonic separator (8) is positioned at settling vessel (5), and outside the gas tube (7), its top outlet communicates with collection chamber (9); Collection chamber (9) is positioned at settling vessel (5) top and is connected with product gas outlet (10); Stripper (11) one ends are connected with the bottom of settling vessel (5), and the other end of stripper (11) links to each other with inclined tube to be generated (13); Between the bottom of settling vessel (5) and emulsion zone (A) hypomere, interchanger (3) is set, an end of interchanger (3) is connected with the bottom of settling vessel (5), and the other end of interchanger (3) is connected with emulsion zone (A); Sparger or grid distributor (2) are positioned at emulsion zone (A) bottom, and the bottom of sparger or grid distributor (2) is provided with material inlet (1), it is characterized in that near riser tube (4) lower region, terminator inlet (15) being set.
2. according to the method for the said CO gas of claim 1 gas-phase catalytic coupling producing oxalic ester, it is characterized in that terminator inlet (15) is 0～4/5 of riser tube (a 4) length apart from the vertical range of riser tube (4) bottom.
3. according to the method for the said CO gas of claim 2 gas-phase catalytic coupling producing oxalic ester, it is characterized in that terminator inlet (15) distributes along riser tube (4) lower region ringwise.
4. according to the method for the said CO gas of claim 1 gas-phase catalytic coupling producing oxalic ester, the internal diameter that it is characterized in that riser tube (4) is 1/15～1/2 of emulsion zone (A) external diameter, and the height of riser tube (4) is 1/5～5/1 of emulsion zone (A) height.
5. according to the method for the said CO gas of claim 1 gas-phase catalytic coupling producing oxalic ester, it is characterized in that regenerator sloped tube (12) and emulsion zone (A) communication port are 1/10～1/2 of emulsion zone (A) vertical heights apart from emulsion zone (A) bottom vertical distance.
6. according to the method for the said CO gas of claim 1 gas-phase catalytic coupling producing oxalic ester, the vertical height that it is characterized in that zone of transition (B) is 1/20～1/2 of emulsion zone (A) vertical height.
7. according to the method for the said CO gas of claim 1 gas-phase catalytic coupling producing oxalic ester, it is characterized in that gas inlet distance set air chamber (9) the top vertical range of cyclonic separator (8) is 1/10～1/1 of a settling vessel diameter.
8. according to the method for the said CO gas of claim 1 gas-phase catalytic coupling producing oxalic ester, it is characterized in that temperature of reaction is 100～160 ℃, volume space velocity is 500～5000 hours
-1, reaction pressure is-0.05～1.0MPa, the mol ratio of CO and nitrous acid ester is 1～3: 1.
9. according to the method for the said CO gas of claim 1 gas-phase catalytic coupling producing oxalic ester, it is characterized in that containing palladium fluid catalyst carrier and be selected from aluminum oxide, 30～200 microns of particle diameter average out to.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110045609.7A CN102649733B (en) | 2011-02-25 | 2011-02-25 | Method for preparing oxalate through CO gas phase catalytic coupling |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110045609.7A CN102649733B (en) | 2011-02-25 | 2011-02-25 | Method for preparing oxalate through CO gas phase catalytic coupling |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102649733A true CN102649733A (en) | 2012-08-29 |
| CN102649733B CN102649733B (en) | 2015-01-07 |
Family
ID=46691863
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110045609.7A Active CN102649733B (en) | 2011-02-25 | 2011-02-25 | Method for preparing oxalate through CO gas phase catalytic coupling |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102649733B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5742654A (en) * | 1980-08-26 | 1982-03-10 | Ube Ind Ltd | Preparation of dimethyl oxalate |
| US4461909A (en) * | 1980-08-26 | 1984-07-24 | Ube Industries, Ltd. | Process for continuously preparing a diester of oxalic acid |
| CN101164684A (en) * | 2006-10-20 | 2008-04-23 | 中国石油化工股份有限公司 | Combined fluidized bed reactor |
| CN101279257A (en) * | 2008-03-27 | 2008-10-08 | 上海焦化有限公司 | Catalyst for synthesizing oxalic ester and preparation method and application thereof |
| CN101475472A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Method for preparing oxalate by coupling reaction of CO in gaseous phase |
| CN101492370A (en) * | 2008-12-18 | 2009-07-29 | 中国石油化工股份有限公司 | Method for producing oxalic ester with CO coupling |
-
2011
- 2011-02-25 CN CN201110045609.7A patent/CN102649733B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5742654A (en) * | 1980-08-26 | 1982-03-10 | Ube Ind Ltd | Preparation of dimethyl oxalate |
| US4461909A (en) * | 1980-08-26 | 1984-07-24 | Ube Industries, Ltd. | Process for continuously preparing a diester of oxalic acid |
| CN101164684A (en) * | 2006-10-20 | 2008-04-23 | 中国石油化工股份有限公司 | Combined fluidized bed reactor |
| CN101279257A (en) * | 2008-03-27 | 2008-10-08 | 上海焦化有限公司 | Catalyst for synthesizing oxalic ester and preparation method and application thereof |
| CN101475472A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Method for preparing oxalate by coupling reaction of CO in gaseous phase |
| CN101492370A (en) * | 2008-12-18 | 2009-07-29 | 中国石油化工股份有限公司 | Method for producing oxalic ester with CO coupling |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102649733B (en) | 2015-01-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101492370B (en) | Method for producing oxalic ester with CO coupling | |
| CN101475472B (en) | Method for preparing oxalate by coupling reaction of CO in gaseous phase | |
| CN101475473B (en) | Method for preparing oxalate by coupling reaction of CO | |
| CN102649735B (en) | Method for producing oxalate through carbon monoxide gas phase-coupled catalytic reaction | |
| CN102219679B (en) | Method for producing oxalic acid ester through CO gas phase coupling | |
| CN102161512A (en) | Material conveying method for horizontal reactor of potassium manganate | |
| CN102649057A (en) | Catalyst for preparing oxalate through coupling reaction of CO (carbon monoxide) | |
| CN102649734B (en) | Method for producing oxalate through catalytic coupling reaction of carbon monoxide | |
| CN102649738B (en) | Method for producing oxalate through gas-phase coupled catalytic reaction of carbon monoxide | |
| CN102649733A (en) | Method for preparing oxalate through CO gas phase catalytic coupling | |
| CN102649739B (en) | Method of synthesizing oxalic ester by carbon monoxide gaseous phase coupling | |
| CN102649732B (en) | Method for producing oxalate through gas-phase coupled catalytic reaction of carbon monoxide | |
| CN102649740B (en) | Method for preparing oxalate through CO catalytic coupling reaction | |
| CN102649729A (en) | Method for producing oxalate through CO gas phase coupled catalytic reaction | |
| CN102219676B (en) | Method for preparing oxalate by CO coupling | |
| CN102649728B (en) | Method for producing oxalate through gas-phase reaction of carbon monoxide | |
| CN102649736B (en) | Method for producing oxalate through carbon monoxide gas phase- coupled catalytic reaction | |
| CN102219678B (en) | Starting-up method for producing oxalic acid ester with CO | |
| CN102219682A (en) | Method for preparing oxalic ester by CO coupling | |
| CN102219681B (en) | Method for producing oxalic acid ester through CO gas phase coupling | |
| CN102649731A (en) | Method for producing oxalate through CO gas phase coupling | |
| CN102649559A (en) | Method for CO gas raw material dehydrogenation through catalytic oxidation reaction | |
| CN102649741A (en) | Method for preparing oxalic ester by carbon monoxide gaseous phase catalytic coupling reaction | |
| CN102649737B (en) | Method for producing oxalate through gas-phase coupling of carbon monoxide | |
| CN102649553B (en) | CO gas oxydehydrogenation method |
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 |