CN102649738B - Method for producing oxalate through gas-phase coupled catalytic reaction of carbon monoxide - Google Patents
Method for producing oxalate through gas-phase coupled catalytic reaction of carbon monoxide Download PDFInfo
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- CN102649738B CN102649738B CN201110046364.XA CN201110046364A CN102649738B CN 102649738 B CN102649738 B CN 102649738B CN 201110046364 A CN201110046364 A CN 201110046364A CN 102649738 B CN102649738 B CN 102649738B
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 62
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 18
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 title abstract description 18
- 238000004519 manufacturing process Methods 0.000 title abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 106
- 239000003054 catalyst Substances 0.000 claims abstract description 44
- 239000002994 raw material Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 29
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 14
- 239000007789 gas Substances 0.000 claims description 41
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical compound CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 claims description 18
- 206010013786 Dry skin Diseases 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 230000004044 response Effects 0.000 claims description 13
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000009826 distribution Methods 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000011324 bead Substances 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 4
- 239000012495 reaction gas Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 18
- -1 nitrous acid ester Chemical class 0.000 abstract description 15
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 150000004706 metal oxides Chemical class 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- 238000011160 research Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000010168 coupling process Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 4
- 239000003507 refrigerant Substances 0.000 description 4
- 229910052702 rhenium Inorganic materials 0.000 description 4
- 239000012808 vapor phase Substances 0.000 description 4
- QQZWEECEMNQSTG-UHFFFAOYSA-N Ethyl nitrite Chemical compound CCON=O QQZWEECEMNQSTG-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- CBSVJWYOTGMOBT-UHFFFAOYSA-N nitric acid rhenium Chemical compound [Re].[N+](=O)(O)[O-] CBSVJWYOTGMOBT-UHFFFAOYSA-N 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Natural products CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 239000005950 Oxamyl Substances 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- KZAUOCCYDRDERY-UHFFFAOYSA-N oxamyl Chemical compound CNC(=O)ON=C(SC)C(=O)N(C)C KZAUOCCYDRDERY-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for producing oxalate through gas-phase coupled catalytic reaction of carbon monoxide, and mainly solves the technical problem in the prior art that in the reaction process of producing oxalate through gas-phase coupled catalytic reaction of carbon monoxide, oxalate is low in selectivity. The method adopts a mixed gas of both nitrous acid ester and carbon monoxide as the raw material and palladium-containing metal oxide as the catalyst, and comprises the step that the raw material is in contact with the catalyst in a reactor to produce an effluent containing oxalate under the conditions that the carbon monoxide/nitrous acid ester molar ratio is 0.8-5:1, the reaction temperature is 100-180 DEG C, the hourly space velocity is 500-10,000 hours <-1> and the reaction pressure is -0.08-1.5MPa. By adopting the technical scheme, the problem is better solved and the method provided by the invention can be used for industrial production of oxalate through gas-phase coupled catalytic reaction of carbon monoxide.
Description
Technical field
The present invention relates to a kind of method that carbon monoxide gas phase coupled catalytic reaction produces barkite, particularly about adopting subregion heat exchanging pipe reactor to realize the reaction that carbon monoxide gas phase coupled catalytic reaction produces barkite.
Background technology
Barkite is important Organic Chemicals, produces various dyestuff, medicine, important solvent in a large number for fine chemistry industry, extraction agent and various intermediate.Enter 21 century, barkite is subject to international extensively attention as degradable environment-friendly engineering plastics monomer.In addition, barkite ordinary-pressure hydrolysis can obtain oxalic acid, and normal pressure ammonia solution can obtain high-quality slow chemical fertilizer oxamyl.Barkite can also be used as solvent, produces medicine and dyestuff intermediate etc., such as, carries out various condensation reaction with fatty acid ester, hexamethylene phenyl methyl ketone, amido alcohol and many heterogeneous ring compounds.It can also synthesize at the chest acyl alkali being pharmaceutically used as hormone.In addition, barkite low-voltage hydrogenation can prepare very important industrial chemicals ethylene glycol, and ethylene glycol mainly relies on petroleum path to prepare at present, and cost is higher, and China needs a large amount of import ethylene glycol every year, 2007 years nearly 4,800,000 tons of import volumes.
The production line of tradition barkite utilizes oxalic acid to prepare with alcohol generation esterification, and production technique cost is high, and energy consumption is large, and seriously polluted, prepared using is unreasonable.For many years, people's, operational path that environment good low at searching cost always.The sixties in last century, American Association oil company D.F.Fenton finds, carbon monoxide, alcohol and oxygen are by the direct synthesis of oxalic acid dialkyl of oxidation carbonylation, and company of Ube Industries Ltd. and AR carbon monoxide company of the U.S. have carried out research and development in succession in this field since then.
From development course, division is carried out for Oxidation of Carbon Monoxide 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 harsher, and reaction is under high pressure carried out, liquid-phase system corrosive equipment, and in reaction process, catalyzer easily runs off.The vapor phase process most advantage of carbon monoxide coupling producing oxalic ester, company of external Ube Industries Ltd. and Italian Montedisons SPA have carried out vapor phase process research in succession in 1978.Wherein, the synthesis of oxalic ester by gaseous catalysis technique of Yu Buxingchan company exploitation, reaction pressure 0.5MPa, temperature is 80 DEG C ~ 150 DEG C.
Along with Oxidation of Carbon Monoxide coupling method prepares the research and development of barkite Technology in the world, domestic many research institutions have also carried out research work to this field.According to china natural resources characteristic distributions, being that organic oxygen-containing compound prepared by raw material with carbon monoxide, for alleviating the pressure of petroleum products, Appropriate application coal and natural gas source, there is very important strategic importance.At present, research topic important in domestic one-carbon chemical and organic chemical industry field has been become by Oxidation of Carbon Monoxide coupling method synthesis of oxalate, successively You Duojia research institution and research institutions are devoted to the catalyst preparation in this field, process exploitation and engineering amplification work, and achieve greater advance.
Although above-mentioned numerous research institution, has obtained comparatively much progress technically, technology itself has still needed to be further improved and has developed, and especially how to improve reaction preference, and improving the aspects such as the activity of catalyzer all needs research further and break through.
Document CN200710060003.4 discloses a kind of method that carbon monoxide coupling prepares oxalic acid diethyl ester, adopt vapor phase process, carbon monoxide is under the participation of ethyl nitrite, under the catalysis of bimetal supported catalyst, coupling oxalic diethyl ester crude product, reaction is self-closing circulating process, carbon monoxide gas enters coupler reactor with the ethyl nitrite from regeneration reactor through mixing preheating, after reaction, gas is through condensation separation, obtain water white oxalic acid diethyl ester lime set, non-condensable gas containing NO enters regeneration reactor, in regeneration reactor and ethanol, the recirculation of oxygen reaction generation ethyl nitrite is returned coupler reactor and is used continuously, this invention is on the basis of lab scale research in early stage, be that background is carried out with industrial production, examination that the mould completed under commercial operating conditions tries and enlarged experiment operates continuously, linked reaction temperature is low, product concentration improves, present method is more energy-conservation, pollution-free, high efficiency.But the per pass conversion of this technology carbon monoxide is 20 ~ 60%, object selectivity of product, about 96%, all needs to be improved further.
Document CN95116136.9 discloses the catalyzer of a kind of barkite synthesis, selects Zr to make auxiliary agent, develops novel Pd-Zr/Al by pickling process
2o
3catalyzer.It is adopt fixed-bed reactor that this catalyzer reacts as carbon monoxide and nitrous acid ester synthesis of oxalic ester by gaseous catalysis.But the yield of its barkite of catalyzer adopted in this patent is lower, and require higher to the impurity of unstripped gas, the selectivity of product barkite is 95%, and the per pass conversion of nitrous acid ester is up to 64%, all needs to be improved further.
The subject matter that technology involved by above-mentioned document exists is that the selectivity of barkite is low, needs to improve further.
Summary of the invention
Technical problem to be solved by this invention exists in previous literature technology to produce in barkite reaction process for carbon monoxide gas phase coupled catalytic reaction, there is the technical problem that barkite selectivity is low, provide a kind of new carbon monoxide gas phase coupled catalytic reaction to produce the method for barkite.The method is used for carbon monoxide gas phase coupled catalytic reaction and produces in barkite reaction process, has the advantage that barkite selectivity is high.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of carbon monoxide gas phase coupled catalytic reaction produces the method for barkite, with the mixed gas containing nitrous acid ester and carbon monoxide for raw material, with palladium-containing metal oxide compound for catalyzer, be 0.8 ~ 5: 1 in the mol ratio of CO and nitrous acid ester, temperature of reaction is 100 ~ 180 DEG C, and volume space velocity is 500 ~ 10000 hours
-1, reaction pressure is that under the condition of-0.08 ~ 1.5MPa, raw material contacts with catalyst reactor, and generate the effluent containing barkite, it is characterized in that, described reactor is the shell-and-tube reactor of subregion heat exchange.
In technique scheme, the reaction conditions of reactor is preferably: the mol ratio of CO and nitrous acid ester is 1 ~ 3: 1, and temperature of reaction is 110 ~ 160 DEG C, and volume space velocity is 1000 ~ 6000 hours
-1, reaction pressure is-0.02 ~ 1.0MPa.Catalyzer preferred version is selected from: alumina supporter, and be catalyst weight with catalyst weight consumption 89 ~ 99.8%; 0.003 ~ 1% active component palladium being catalyst weight in simple substance consumption and 0.005 ~ 10% rhenium, cobalt or the silver-colored auxiliary agent that are catalyst weight in simple substance consumption.
In technique scheme, the reactor of inventive method is primarily of feed(raw material)inlet (1), porous gas sparger (2), gas distribution room (24), bundle of reaction tubes (5), catalyst bed (7), collection chamber (13), porous gas collection plate (11) and product exit (12) composition, it is characterized in that catalyst bed (7) is divided into the first heat exchange block (22), the second heat exchange block (19) and the 3rd heat exchange block (16) according to reaction gas flow direction order; First heat exchange block (22) and first district's heat transferring medium export (23) and are connected with first district's heat transferring medium entrance (21), second heat exchange block (19) exports (20) with second district's heat transferring medium entrance (8) with second district's heat transferring medium and is connected, and exports (17) be connected with the 3rd heat exchange block (16) with the 3rd district's heat transferring medium entrance (15) with the 3rd district's heat transferring medium.Porous gas sparger (2) is positioned at gas distribution room (24), and be connected with feed(raw material)inlet (1), porous gas collection plate (11) is positioned at collection chamber (13), and is connected with product exit (12).Catalyst bed (7) is positioned at bundle of reaction tubes (5), and bundle of reaction tubes (5) is outward heat transferring medium.Separated by the first subregion dividing plate (6) between first heat exchange block (22) and the second heat exchange block (19), separated by the second subregion dividing plate (9) between the second heat exchange block (19) and the 3rd heat exchange block (16).Be 1/8 ~ 1/3 of reactor length under first subregion dividing plate (6) distance reactor upper tubesheet (4); Be 1/8 ~ 1/3 of reactor length under second subregion dividing plate (9) distance the first subregion dividing plate (6).
Due to catalyzed reaction on a catalyst and carry out not according to front and back equal velocity, General reactions device is anterior from balanced remote, speed of response is fast, release reaction heat also many, rear portion is with the close balance of reaction, speed of response slows down, release reaction heat also few, if the same before and after the temperature of refrigerant, if reduce coolant temperature like this, strengthen heat transfer temperature difference and move heat, what reach top or anterior high speed of response and strong reaction heat moves heat request, then reactor lower part or rear portion reaction heat reduce, move heat to be greater than reaction heat and to cause temperature of reaction to decline, speed of response is made to slow down until with regard to stopped reaction below catalyst activity further, therefore be difficult to accomplish that the way made the best of both worlds of all carrying out under optimal reaction temperature is reacted in front and rear part.The present invention is directed to this fundamental contradiction, break through the refrigerant of existing same temperature, and adopt the different section of reactor to adopt differing temps refrigerant to solve, heat exchange in reaction is made to need design by the size that reaction heat shifts out, multiple pieces of districts before and after specifically can being divided into by reaction gas flow direction order in catalyst layer, indirect heat exchange is carried out by heat transfer tube by refrigerant, thus realize the equiblibrium mass distribution of full bed temperature, this is for the efficiency of maximized performance catalyzer, farthest reduce the loss of sub-ester, improve the selectivity of object product, useful effect is provided.
Carbon monoxide gas phase coupled catalytic reaction of the present invention produces the method for barkite, use Fig. 1 shown device, adopt subregion heat exchange, precise control of temperature, with the mixed gas containing nitrous acid ester and carbon monoxide for raw material, with palladium-containing metal oxide compound for catalyzer, be 0.8 ~ 5: 1 in the mol ratio of CO and nitrous acid ester, temperature of reaction 100 ~ 180 DEG C, volume space velocity is 500 ~ 10000 hours
-1, reaction pressure is under the condition of-0.08 ~ 1.5MPa, raw material and catalyst exposure, and nitrous acid ester and reaction of carbon monoxide oxalic ester in raw material, the selectivity of barkite can be greater than 99%, achieves good technique effect.
Accompanying drawing explanation
Fig. 1 is that carbon monoxide gas phase coupled catalytic reaction of the present invention produces reactor schematic diagram in the method for barkite.
In Fig. 1,1 is feed(raw material)inlet, 2 is porous gas spargers, 3 is reactor upper covers, 4 is upper tubesheets, 5 is bundle of reaction tubes, 6 is first subregion dividing plates, 7 is catalyst beds, 8 is reactor tank bodies, 9 is second subregion dividing plates, 10 is lower tubesheets, 11 is porous gas collection plates, 12 is product exit, 13 is collection chambers, 14 is reactor lower covers, 15 is the 3rd district's heat transferring medium entrances, 16 is the 3rd heat exchange blocks, 17 is the heat transferring medium outlets of the 3rd district, 18 is second district's heat transferring medium entrances, 19 is second heat exchange blocks, 20 is the heat transferring medium outlets of the secondth district, 21 is first district's heat transferring medium entrances, 22 is first heat exchange blocks, 23 is the heat transferring medium outlets of the firstth district, 24 is gas distribution rooms,
Fig. 1 Raw is introduced by feed(raw material)inlet 1, gas distribution room 24 is entered after porous gas sparger 2 distributes, enter in bundle of reaction tubes 5 afterwards and catalyst bed 7 contact reacts, the heat produced in reaction process is taken away by the heat transferring medium outside bundle of reaction tubes 5, reacted gas enters collection chamber 13, then by entering follow-up system through product exit 12 after porous gas collection plate 11.Enter in bundle of reaction tubes 5 with catalyst bed 7 contact reacts process at reaction raw materials gas, successively through the first heat exchange block (22), the second heat exchange block (19) and the 3rd heat exchange block (16), the temperature of each heat exchange block controls respectively by the temperature and flow etc. entering the heat transferring medium of each heat exchange block, thus reaches the effect that temperature all walks.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
Be dissolved in by cobalt oxalate in water, be heated to 70 DEG C, it is 10 meters that vacuum rotating is immersed in specific surface agent
2/ gram Al
2o
3on bead, then in 120 DEG C of dryings 6 hours.A certain amount of Palladous nitrate is dissolved in the water, its pH value is made to be about 4 with nitric acid regulator solution, then this solution is heated to 80 DEG C, again be immersed on carrier, then in 140 DEG C of dryings 8 hours, then roasting 4 hours in 450 DEG C of air atmospheres, reductase 12 hour in 400 DEG C of hydrogen atmospheres, obtain catalyst A, consist of 0.17%Pd+0.28% carbon monoxide/Al
2o
3.Take the catalyzer that aequum is obtained, load in reactor shown in accompanying drawing, first, second and third heat transferring medium all adopts saturation steam, just adopts the difference of pressure, realizes the difference of temperature, thus the control of realization response device catalyst bed temperature, then with carbon monoxide and methyl nitrite for raw material, wherein, the mol ratio of carbon monoxide and methyl nitrite is 1.2: 1, be 130 DEG C in temperature of reaction, reaction volume air speed is 2000 hours
-1, reaction pressure is under the condition of-0.08MPa, and raw material and catalyst exposure, react, and its reaction result is: carbon monoxide per pass conversion 78.4%, and the selectivity of dimethyl oxalate is 99.2%.
[embodiment 2]
Be dissolved in by Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES in water, be heated to 80 DEG C, it is 8 meters that vacuum rotating is immersed in specific surface agent
2/ gram Al
2o
3on bead, then in 120 DEG C of dryings 4 hours.Ammonium palladic chloride is dissolved in the water, its pH value is made to be about 4 with nitric acid regulator solution, then this solution is heated to 80 DEG C, again be immersed on carrier, then in 140 DEG C of dryings 4 hours, then roasting 4 hours in 450 DEG C of air atmospheres, reductase 12 hour in 400 DEG C of hydrogen atmospheres, obtain catalyst B, consist of 0.45%Pd+0.40% carbon monoxide/Al
2o
3.Take the catalyzer that aequum is obtained, load in reactor shown in accompanying drawing, first, second and third heat transferring medium all adopts saturation steam, just adopts the difference of pressure, realizes the difference of temperature, thus the control of realization response device catalyst bed temperature, then with carbon monoxide and methyl nitrite for raw material, wherein, the mol ratio of carbon monoxide and methyl nitrite is 1.5: 1, be 110 DEG C in temperature of reaction, reaction volume air speed is 800 hours
-1, reaction pressure is under the condition of-0.05MPa, and raw material and catalyst exposure, react, and its reaction result is: carbon monoxide per pass conversion 63.2%, and the selectivity of dimethyl oxalate is 99.7%.
[embodiment 3]
Be dissolved in the water by Silver Nitrate, vacuum impregnation is 15 meters in specific surface agent
2/ gram Al
2o
3on bead, 140 DEG C of dryings 4 hours.Palladous nitrate is dissolved in ethanolic soln, is again immersed on carrier, 140 DEG C of dryings 4 hours, then roasting 4 hours in 450 DEG C of air atmospheres, reduces 4 hours, then in nitrogen atmosphere, is cooled to room temperature in 300 DEG C of hydrogen atmospheres, obtain catalyzer C, consist of 0.01%Pd+1%Ag/Al
2o
3.Take the catalyzer that aequum is obtained, load in reactor shown in accompanying drawing, first, second and third heat transferring medium all adopts saturation steam, just adopts the difference of pressure, realizes the difference of temperature, thus the control of realization response device catalyst bed temperature, then with carbon monoxide and methyl nitrite for raw material, wherein, the mol ratio of carbon monoxide and methyl nitrite is 2: 1, temperature of reaction 140 DEG C, reaction volume air speed is 3000 hours
-1, reaction pressure is under the condition of-0.02MPa, and raw material and catalyst exposure, react, and its reaction result is: carbon monoxide per pass conversion 45.2%, and the selectivity of dimethyl oxalate is 99.1%.
[embodiment 4]
Be dissolved in the water by Silver Nitrate, it is 20 meters that vacuum rotating is immersed in specific surface agent
2/ gram Al
2o
3on bead, 140 DEG C of dryings 4 hours.By sub-for chlorine palladium acid dissolve in the aqueous solution, again be immersed on carrier, 140 DEG C of dryings 4 hours, then roasting 4 hours in 450 DEG C of air atmospheres, reduce 4 hours in 450 DEG C of hydrogen atmospheres, then in nitrogen atmosphere, be cooled to room temperature, obtain catalyzer D, consist of 0.34%Pd+0.46%Ag/Al
2o
3.Take the catalyzer that aequum is obtained, load in reactor shown in accompanying drawing, first, second and third heat transferring medium all adopts saturation steam, just adopts the difference of pressure, realizes the difference of temperature, thus the control of realization response device catalyst bed temperature, then with carbon monoxide and methyl nitrite for raw material, wherein, the mol ratio of carbon monoxide and methyl nitrite is 4: 1, temperature of reaction 160 DEG C, reaction volume air speed is 6000 hours
-1, reaction pressure is under the condition of 0.02MPa, and raw material and catalyst exposure, react, and its reaction result is: carbon monoxide per pass conversion 22.2%, and the selectivity of dimethyl oxalate is 98.3%.
[embodiment 5]
Be dissolved in the water by nitric acid rhenium, it is 30 meters that vacuum rotating is immersed in specific surface agent
2/ gram Al
2o
3on bead, 140 DEG C of dryings 4 hours.Ammonium palladic chloride is dissolved in ethanolic soln, is again immersed on carrier, 140 DEG C of dryings 4 hours, then 450 DEG C of roastings 4 hours, reduce 4 hours in 350 DEG C of hydrogen atmospheres, then in nitrogen atmosphere, be cooled to room temperature, obtain catalyzer E, consist of 0.11%Pd+0.6%Re/Al
2o
3.Take the catalyzer that aequum is obtained, load in reactor shown in accompanying drawing, first, second and third heat transferring medium all adopts saturation steam, just adopts the difference of pressure, realizes the difference of temperature, thus the control of realization response device catalyst bed temperature, then with carbon monoxide and methyl nitrite for raw material, wherein, the mol ratio of carbon monoxide and methyl nitrite is 1.3: 1, temperature of reaction 170 DEG C, reaction volume air speed is 8000 hours
-1, reaction pressure is under the condition of 0.5MPa, and raw material and catalyst exposure, react, and its reaction result is: carbon monoxide per pass conversion 74.6%, and the selectivity of dimethyl oxalate is 97.3%.
[embodiment 6]
Getting 200 grams of specific surface agent is 40 meters
2/ gram Al
2o
3bead, be immersed in containing in 8.0 grams of Palladous nitrates, 14 grams of nitric acid rhenium aqueous solution, and regulate its pH value to be 2 with nitric acid, dry 4 hours at 140 DEG C after taking-up, then roasting 2 hours in 450 DEG C of air atmospheres, reduce 4 hours in 350 DEG C of hydrogen atmospheres, then in nitrogen atmosphere, be cooled to room temperature, obtain catalyzer F and consist of 0.6%Pd+1.1%Re/Al
2o
3.Take the catalyzer that aequum is obtained, load in reactor shown in accompanying drawing, first, second and third heat transferring medium all adopts saturation steam, just adopts the difference of pressure, realizes the difference of temperature, thus the control of realization response device catalyst bed temperature, then with carbon monoxide and methyl nitrite for raw material, wherein, the mol ratio of carbon monoxide and methyl nitrite is 1.5: 1, temperature of reaction 130 DEG C, reaction volume air speed is 2000 hours
-1, reaction pressure is under the condition of 0.2MPa, and raw material and catalyst exposure, react, and its reaction result is: carbon monoxide per pass conversion 63.8%, and the selectivity of dimethyl oxalate is 99.5%.
[embodiment 7]
Be dissolved in the water by Silver Nitrate, vacuum impregnation is 50 meters in specific surface agent
2/ gram Al
2o
3on bead, 140 DEG C of dryings 4 hours.Ammonium palladic chloride is dissolved in ethanolic soln, is again immersed on carrier, 140 DEG C of dryings 4 hours, then roasting 2 hours in 450 DEG C of air atmospheres, reduces 4 hours, then in nitrogen atmosphere, is cooled to room temperature in 300 DEG C of hydrogen atmospheres, obtain catalyzer G, consist of 0.8%Pd+10%Ag/Al
2o
3.Take the catalyzer that aequum is obtained, load in reactor shown in accompanying drawing, first, second and third heat transferring medium all adopts saturation steam, just adopts the difference of pressure, realizes the difference of temperature, thus the control of realization response device catalyst bed temperature, then with carbon monoxide and methyl nitrite for raw material, wherein, the mol ratio of carbon monoxide and methyl nitrite is 1.3: 1, temperature of reaction 120 DEG C, reaction volume air speed is 1500 hours
-1, reaction pressure is under the condition of 0.1MPa, and raw material and catalyst exposure, react, and its reaction result is: carbon monoxide per pass conversion 73.9%, and the selectivity of dimethyl oxalate is 99.8%.
[embodiment 8]
Be dissolved in the water by nitric acid rhenium, vacuum impregnation is 30 meters in specific surface agent
2/ gram Al
2o
3on bead, 140 DEG C of dryings 4 hours.Ammonium palladic chloride is dissolved in ethanolic soln, is again immersed on carrier, 140 DEG C of dryings 4 hours, then roasting 4 hours in 450 DEG C of air atmospheres, reduces 4 hours, then in nitrogen atmosphere, is cooled to room temperature in 300 DEG C of hydrogen atmospheres, obtain catalyzer H, consist of 0.2%Pd+1%Re/Al
2o
3.Take the catalyzer that aequum is obtained, load in reactor shown in accompanying drawing, first, second and third heat transferring medium all adopts saturation steam, just adopts the difference of pressure, realizes the difference of temperature, thus the control of realization response device catalyst bed temperature, then with carbon monoxide and methyl nitrite for raw material, wherein, the mol ratio of carbon monoxide and methyl nitrite is 0.6: 1, temperature of reaction 120 DEG C, reaction volume air speed is 2000 hours
-1, reaction pressure is under the condition of 0.03MPa, and raw material and catalyst exposure, react, and its reaction result is: carbon monoxide per pass conversion 96.2%, and the selectivity of dimethyl oxalate is 99.1%.
[comparative example 1]
Adopt the catalyzer of [embodiment 1] and [embodiment 1] same reaction conditions and reaction raw materials, just adopt insulation fix bed reactor, its reaction result is: carbon monoxide per pass conversion 77.1%, and the selectivity of dimethyl oxalate is 96.8%.
[comparative example 2]
Adopt the catalyzer of [embodiment 2] and [embodiment 2] same reaction conditions and reaction raw materials, just adopt insulation fix bed reactor, its reaction result is: carbon monoxide per pass conversion 60.4%, and the selectivity of dimethyl oxalate is 94.3%.
Claims (1)
1. carbon monoxide gas phase coupled catalytic reaction produces a method for barkite, and be dissolved in the water by Silver Nitrate, vacuum impregnation is 50 meters in specific surface area
2/ gram Al
2o
3on bead, 140 DEG C of dryings 4 hours; Ammonium palladic chloride is dissolved in ethanolic soln, is again immersed on carrier, 140 DEG C of dryings 4 hours, then roasting 2 hours in 450 DEG C of air atmospheres, reduces 4 hours, then in nitrogen atmosphere, is cooled to room temperature in 300 DEG C of hydrogen atmospheres, obtain catalyzer G, consist of 0.8%Pd+10%Ag/Al
2o
3; Take the catalyzer that aequum is obtained, load in reactor, first, second and third heat transferring medium all adopts saturation steam, just adopts the difference of pressure, realizes the difference of temperature, thus the control of realization response device catalyst bed temperature, then with carbon monoxide and methyl nitrite for raw material, wherein, the mol ratio of carbon monoxide and methyl nitrite is 1.3: 1, temperature of reaction 120 DEG C, reaction volume air speed is 1500 hours
-1, reaction pressure is under the condition of 0.1MPa, and raw material and catalyst exposure, react, and its reaction result is: carbon monoxide per pass conversion 73.9%, and the selectivity of dimethyl oxalate is 99.8%;
Reactor is primarily of feed(raw material)inlet (1), porous gas sparger (2), gas distribution room (24), bundle of reaction tubes (5), catalyst bed (7), collection chamber (13), porous gas collection plate (11) and product exit (12) composition; Catalyst bed (7) is divided into the first heat exchange block (22), the second heat exchange block (19) and the 3rd heat exchange block (16) according to reaction gas flow direction order; First heat exchange block (22) and first district's heat transferring medium export (23) and are connected with first district's heat transferring medium entrance (21), second heat exchange block (19) exports (20) with second district's heat transferring medium entrance (8) with second district's heat transferring medium and is connected, and exports (17) be connected with the 3rd heat exchange block (16) with the 3rd district's heat transferring medium entrance (15) with the 3rd district's heat transferring medium; Porous gas sparger (2) is positioned at gas distribution room (24), and be connected with feed(raw material)inlet (1), porous gas collection plate (11) is positioned at collection chamber (13), and is connected with product exit (12); Catalyst bed (7) is positioned at bundle of reaction tubes (5), and bundle of reaction tubes (5) is outward heat transferring medium; Separated by the first subregion dividing plate (6) between first heat exchange block (22) and the second heat exchange block (19), separated by the second subregion dividing plate (9) between the second heat exchange block (19) and the 3rd heat exchange block (16); Be 1/8 ~ 1/3 of reactor length under first subregion dividing plate (6) distance reactor upper tubesheet (4); Be 1/8 ~ 1/3 of reactor length under second subregion dividing plate (9) distance the first subregion dividing plate (6);
Raw material is introduced by feed(raw material)inlet, gas distribution room is entered after the distribution of porous gas sparger, enter in bundle of reaction tubes afterwards and catalyst bed contact reacts, the heat produced in reaction process is taken away by the heat transferring medium outside bundle of reaction tubes, reacted gas enters collection chamber, then by entering follow-up system through product exit after porous gas collection plate.Enter in bundle of reaction tubes with catalyst bed contact reacts process at reaction raw materials gas, successively through the first heat exchange block, the second heat exchange block (19) and the 3rd heat exchange block, the temperature of each heat exchange block controls respectively by the temperature and flow entering the heat transferring medium of each heat exchange block, thus reaches the effect that temperature all walks.
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| CN101143821A (en) * | 2007-10-23 | 2008-03-19 | 天津大学 | CO coupling prepares the method for diethyl oxalate |
| CN101475473A (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 |
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| CN1988950A (en) * | 2004-05-28 | 2007-06-27 | 住友化学株式会社 | Heat exchange type reactor |
| CN101143821A (en) * | 2007-10-23 | 2008-03-19 | 天津大学 | CO coupling prepares the method for diethyl oxalate |
| CN101475473A (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 |
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