CN101993364B - Method for producing oxalic ester by gas phase CO coupling - Google Patents
Method for producing oxalic ester by gas phase CO coupling Download PDFInfo
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- CN101993364B CN101993364B CN2009100578434A CN200910057843A CN101993364B CN 101993364 B CN101993364 B CN 101993364B CN 2009100578434 A CN2009100578434 A CN 2009100578434A CN 200910057843 A CN200910057843 A CN 200910057843A CN 101993364 B CN101993364 B CN 101993364B
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- 238000005859 coupling reaction Methods 0.000 title claims abstract description 15
- 238000010168 coupling process Methods 0.000 title claims abstract description 13
- 230000008878 coupling Effects 0.000 title claims abstract description 12
- 150000002148 esters Chemical class 0.000 title abstract description 11
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 108
- 239000001301 oxygen Substances 0.000 claims abstract description 108
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 108
- 239000007789 gas Substances 0.000 claims abstract description 106
- 239000002994 raw material Substances 0.000 claims abstract description 72
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 26
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 26
- 239000002808 molecular sieve Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims description 102
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 claims description 14
- 230000002779 inactivation Effects 0.000 claims description 11
- 238000013112 stability test Methods 0.000 claims description 10
- QQZWEECEMNQSTG-UHFFFAOYSA-N Ethyl nitrite Chemical compound CCON=O QQZWEECEMNQSTG-UHFFFAOYSA-N 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 14
- -1 nitrous acid ester Chemical class 0.000 abstract description 12
- KYARBIJYVGJZLB-UHFFFAOYSA-N 7-amino-4-hydroxy-2-naphthalenesulfonic acid Chemical compound OC1=CC(S(O)(=O)=O)=CC2=CC(N)=CC=C21 KYARBIJYVGJZLB-UHFFFAOYSA-N 0.000 abstract description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract 3
- 238000009776 industrial production Methods 0.000 abstract 1
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 description 43
- 239000012071 phase Substances 0.000 description 35
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical compound CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 description 19
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 12
- 230000008569 process Effects 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000012752 auxiliary agent Substances 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000012808 vapor phase Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000006709 oxidative esterification reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 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
- 239000005997 Calcium carbide Substances 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 102000002322 Egg Proteins Human genes 0.000 description 1
- 108010000912 Egg Proteins Proteins 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- 239000005950 Oxamyl Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 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
- 235000009508 confectionery Nutrition 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000006392 deoxygenation reaction Methods 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
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 210000003278 egg shell Anatomy 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
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 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
- 239000003317 industrial substance Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000011068 loading method Methods 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
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 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
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
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 producing oxalic ester by gas phase CO coupling, which mainly solves the technical problems of low oxygen removal rate of raw materials, low selectivity of target products and low space-time yield of the oxalic ester in the prior art. The method comprises the following steps: (a) firstly, a CO gas raw material containing oxygen and NO gas enter a deoxidizing reactor and contact with a molecular sieve catalyst, and the oxygen in the raw material reacts with the NO to generate a gas phase effluent I containing NO2, unreacted NO and CO; (b) the gas phase effluent I and nitrous acid ester enter a coupling reactor and contact with a palladium-containing catalyst to react to generate an effluent II containing the oxalic ester; and (c) the effluent II of the oxalic ester is separated to obtain the oxalic ester product and a gas phase effluent III containing nitrogen oxides, wherein the mol ratio of the NO to oxygen in the CO gas raw material containing the oxygen in the step (a) is 4-100:1. By using the technical scheme, the problems are better solved and the method can be used for the industrial production for increasing the yield of the oxalic ester.
Description
Technical field
The present invention relates to a kind of CO gas phase coupling and produce the method for barkite, particularly about the CO raw material that contains oxygen first with NO, react deoxygenation afterwards again with the method for methyl nitrite or ethyl nitrite coupling production dimethyl oxalate or oxalic acid diethyl ester.
Background technology
Barkite is important Organic Chemicals, in a large number for fine chemistry industry, produces various dyestuffs, medicine, important solvent, extraction agent and various intermediate.Enter 21 century, barkite is subject to international extensively attention as degradable environment-friendly engineering plastics monomer.In addition, the 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., for example with fatty acid ester, hexamethylene phenyl methyl ketone, amido alcohol and many heterogeneous ring compounds, carries out various condensation reactions.It can also synthesize pharmaceutically as the chest acyl alkali of hormone.In addition, the 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, and within 2007 years, import volume is nearly 4,800,000 tons.
The production line of tradition barkite utilizes oxalic acid to prepare with alcohol generation esterification, and the production technique cost is high, and energy consumption is large, seriously polluted, and prepared using is unreasonable.For many years, people are finding 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, alcohol and 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 and can be divided into liquid phase method and vapor phase process from development course for Oxidation of Carbon Monoxide coupling method synthesis of oxalate.Wherein, carbon monoxide liquid phase method synthesis of oxalate condition is harsher, and reaction is under high pressure carried out, the liquid-phase system corrosive equipment, and in reaction process, catalyzer easily runs off.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 technique of emerging product company of space section exploitation, reaction pressure 0.5MP, temperature is 80 ℃～150 ℃.
As everyone knows, carbon monoxide can be from various containing separation and Extraction the gas mixture of carbon monoxide, and the industrial unstripped gas that can be used for separating carbon monoxide comprises: the tail gas of synthetic gas, water-gas, semi-water gas and Steel Plant, calcium carbide factory and Yellow Phosphorous Plant that Sweet natural gas and oil transform etc.The main method of existing CO separating-purifying is pressure swing adsorption process, China has many companies to develop pressure-variable adsorption separation carbon monoxide new technology, especially the high-efficiency adsorbent of developing, carbon monoxide is had to high loading capacity and selectivity, can solve a difficult problem of isolating high-purity carbon monooxide from nitrogen or the high unstripped gas of methane content, can design and build up large-scale carbon monoxide tripping device.However, by this technology isolated carbon monoxide from synthetic gas, under the prerequisite of taking into account the carbon monoxide yield, generally the content of its hydrogen can reach more than 1%.And research shows that the existence of hydrogen can cause follow-up CO coupling reaction catalyst activity decreased, until reaction can't be carried out, generally do not advise in CO that hydrogen content is higher than 10ppm, therefore, it by selectivity oxidizing carbon monoxide dehydrogenation technology, is the important component part of CO route synthesis of oxalate technology, but the problem that this technology is brought is to have introduced again oxygen when hydrogen is removed, and the existence of oxygen can cause follow-up CO coupling reaction catalyst activity decreased equally, until reaction can't be carried out, generally should control oxygen concentration in raw material not higher than 5ppm, although the oxygen in CO also can be eliminated by oxidative esterification reaction, but it is large that the problem of bringing is facility investment, the flow process complexity, difficulty maximizes.For this reason, develop new deoxy technology significant.
Document CN200710060003.4 discloses a kind of method of CO preparing diethyl oxalate by coupling, adopt vapor phase process, CO is under the participation of ethyl nitrite, under the catalysis of bimetal supported catalyst, coupling oxalic diethyl ester crude product, reaction is the self-closing circulating process, CO 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, do not mention the purity of CO in the present invention, to whether containing oxygen in raw material and this processing way not mentioned yet.
Document CN 95116136.9 discloses the catalyzer of the synthetic use of a kind of barkite, selects Zr to make auxiliary agent, by pickling process, develops novel Pd-Zr/Al
2O
3Catalyzer.It is to adopt fixed-bed reactor that this catalyzer reacts with nitrous acid fat synthesis of oxalic ester by gaseous catalysis as carbon monoxide.Equally, but this patent do not relate under the industrial application background, containing technical scheme and the reaction result of oxygen condition.
Summary of the invention
Technical problem to be solved by this invention be in previous literature, exist the feed oxygen decreasing ratio low, the low and low technical problem of barkite space-time yield of purpose selectivity of product, a kind of method that provides new CO gas phase coupling to produce barkite.It is high that the method has a feed oxygen decreasing ratio, the high and high advantage of barkite space-time yield of purpose selectivity of product.
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 CO gas phase coupling is produced the method for barkite, comprises the steps:
A) at first the CO gas raw material that contains oxygen enters deoxidation reactor with NO gas, with molecular sieve catalyst, contacts, and in raw material, oxygen and NO react, and generates and contains NO
2, unreacted NO and CO gas phase effluent I;
B) gas phase effluent I and nitrous acid ester enter in coupler reactor, with palladium-containing catalyst, contact, and reaction generates the effluent II that contains barkite;
C) the gas phase effluent III that the effluent II of barkite obtains the barkite product and contains oxynitride after separating;
Wherein, step a) in the mol ratio of oxygen in NO and the CO gas raw material that contains oxygen be 4～100: 1.
In technique scheme, the reaction conditions of deoxidation reactor is: temperature of reaction is 10～180 ℃, reaction pressure is-0.08～1.5MPa, reaction contact time is 0.1～50 second, in NO and the CO gas raw material that contains oxygen, the mol ratio preferable range of oxygen is 4.5～50: 1, and more preferably scope is 4.5～30: 1; Optimizing reaction conditions is: temperature of reaction is 50～160 ℃, and more preferably scope is 80～150, and reaction pressure is-0.05～1.0MPa, and reaction contact time is 0.2～30 second.Deoxidation reactor filling molecular sieve catalyst preferred version is selected from least one in ZSM-5, β-molecular sieve, y-zeolite or MCM-22, and its Si/Al mol ratio preferable range is 10～500: 1; Molecular sieve catalyst more preferably scheme is selected from ZSM-5, and its Si/Al mol ratio more preferably scope is 30～200: 1.
In technique scheme, the reaction conditions of coupler reactor is: the coupler reactor temperature of reaction is 80～160 ℃, and reaction contact time is 0.5～50 second, and reaction pressure is-0.08～1.5MPa, and the mol ratio of CO and nitrous acid ester is: 1～5: 1.The preferred reaction conditions of coupler reactor is: temperature of reaction is 90～150 ℃, and reaction contact time is 0.5～30 second, and reaction pressure is 0.01～1.0MPa, and the mol ratio of CO and nitrous acid ester is: 1.1～3: 1.
In technique scheme, to be selected from least one of take in silicon oxide, aluminum oxide or molecular sieve be carrier to the scheme of the carrier of palladium-containing catalyst, and preferred version is selected from α-Al
2O
3, θ-Al
2O
3, δ-Al
2O
3, γ-Al
2O
3Or at least one in molecular sieve, more preferably scheme is selected from α-Al
2O
3, the shape of carrier can be made different shapes as required, as cylindric, spherical, sheet, tubular, cellular or Raschig ring etc., but spherical be reasonable selection, its diameter is preferably 1～6 millimeter, so that industrial application.The content of palladium counts 0.01～1% with catalyst weight, and preferable range is 0.02～0.6%.Catalyzer need to add different auxiliary agents, the auxiliary agent preferred version is selected from least one in basic metal, alkaline-earth metal or transition metal element compound, its consumption of simple substance of take is catalyst weight 0.01～10%, auxiliary agent more preferably scheme is selected from least one in K, Mg, Ba, Zr, V, Mn, Fe, Sn, Ni, Cu, La or Ce compound, and its consumption of simple substance of take is catalyst weight 0.01～8%.Auxiliary agent most preferably scheme is selected from least one in K, Fe, Ce or Sn compound, take its consumption of simple substance more preferably scope be catalyst weight 0.05～6%.The active ingredient of catalyzer and auxiliary element composition are distributed in carrier shell, present the eggshell state structure of high dispersive.
In technique scheme, nitrous acid ester is selected from methyl nitrite or ethyl nitrite, preferably from methyl nitrite.The CO gas raw material that contains oxygen, its oxygen volume content is 0.0001～10%, oxygen volume content preferable range is 0.01～8%.
Research shows, in CO and nitrous acid ester coupling reaction process, enters in the raw material of coupler reactor and can not have oxygen to exist, or the content of oxygen should be lower than 5ppm, otherwise in reaction process, the transformation efficiency of raw material, the selectivity of product and the stability of catalyzer all significantly reduce.By introducing NO, take full advantage of NO and oxygen speed of reaction on molecular sieve catalyst fast in the present invention, reaction activity is low, and reaction thoroughly, the advantage that the oxygen decreasing ratio is high, significantly reduce oxygen content in raw material, can meet the requirement of subsequent production barkite to feed oxygen content.Simultaneously, the strict mol ratio of controlling NO and oxygen in raw material in the present invention, can ensure NO and the NO of reaction generation
2Mol ratio for being greater than 1: 1, thereby provide useful assurance for the oxalic ester that recycles of reaction end gas.In addition, CO raw material oxygenous in the present invention can mix and directly enter coupler reactor with nitrous acid ester after the NO reaction, and does not need through oxidative esterification reaction, to eliminate again, has significantly reduced equipment size, has optimized flow process.
Adopt technical scheme of the present invention, allow the CO gas raw material that contains oxygen at first with NO gas, enter deoxidation reactor, contact with molecular sieve catalyst, in raw material, oxygen and NO react, and generate and contain NO
2, unreacted NO and CO the gas phase effluent, with nitrous acid ester, enter in coupler reactor afterwards, with palladium-containing catalyst, contact, reaction generates the effluent that contains barkite, wherein the temperature of reaction of deoxidation reactor is 50～120 ℃, reaction pressure is 0.01～1.0MPa, and reaction contact time is 0.5～30 second, and the mol ratio of the oxygen in NO and the CO gas raw material that contains oxygen is 4.5～30: 1; The coupler reactor temperature of reaction is 90～150 ℃, reaction contact time is 0.5～30 second, reaction pressure is 0.01～1.0MPa, the mol ratio of CO and nitrous acid ester is: 1.1～3: under 1 condition, in raw material, oxygen can be removed to below 5ppm, and the selectivity of barkite is the highest is greater than 98%, the space-time yield of barkite be greater than 600 grams/(rise. hour), the stability of catalyzer is greater than 1000 hours, has obtained technique effect preferably.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
At first the CO gas raw material that contains oxygen enters deoxidation reactor with NO gas, and the ZSM-5 molecular sieve catalyzer that is 20: 1 with the Si/Al mol ratio contacts, and in raw material, oxygen and NO react, and generates and contains NO
2, unreacted NO and CO gas phase effluent I; Gas phase effluent I and methyl nitrite enter in coupler reactor, and with palladium-containing catalyst, (its weight consists of: 0.45%Pd+0.40%K+0.22%Fe/ α-Al
2O
3) contact, reaction generates the effluent II that contains dimethyl oxalate; The gas phase effluent III that the effluent II of dimethyl oxalate obtains the dimethyl oxalate product and contains oxynitride after separating; Wherein, in the CO gas raw material that contains oxygen, the carrier of oxygen volume concentrations is 8%, and the operational condition of deoxidation reactor is: temperature of reaction is 20 ℃, and reaction pressure is-0.05MPa, the residence time is 30 seconds, and the mol ratio of the oxygen in NO and the CO gas raw material that contains oxygen is 4.5: 1; The coupler reactor operational condition is: temperature of reaction is 120 ℃, and reaction contact time is 30 seconds, and reaction pressure is-0.05MPa that the mol ratio of CO and methyl nitrite is: 1.2: 1.Its result is: in raw material, oxygen is removed to 3ppm, and the selectivity of dimethyl oxalate is 99.1%, the space-time yield of dimethyl oxalate be 900 grams/(rise. hour).Catalyzer carries out stability test in 1000 hours without the inactivation sign.
[embodiment 2]
At first the CO gas raw material that contains oxygen enters deoxidation reactor with NO gas, and the ZSM-5 molecular sieve catalyzer that is 100: 1 with the Si/Al mol ratio contacts, and in raw material, oxygen and NO react, and generates and contains NO
2, unreacted NO and CO gas phase effluent I; Gas phase effluent I and methyl nitrite enter in coupler reactor, and with palladium-containing catalyst, (its weight consists of: 0.17%Pd+0.12%Fe/ α-Al
2O
3) contact, reaction generates the effluent II that contains dimethyl oxalate; The gas phase effluent III that the effluent II of dimethyl oxalate obtains the dimethyl oxalate product and contains oxynitride after separating; Wherein, in the CO gas raw material that contains oxygen, the carrier of oxygen volume concentrations is 5%, and the operational condition of deoxidation reactor is: temperature of reaction is 50 ℃, and reaction pressure is 0.01MPa, the residence time is 20 seconds, and the mol ratio of the oxygen in NO and the CO gas raw material that contains oxygen is 6: 1; The coupler reactor operational condition is: temperature of reaction is 90 ℃, and reaction contact time is 15 seconds, and reaction pressure is 0.01MPa, and the mol ratio of CO and methyl nitrite is: 2: 1.Its result is: in raw material, oxygen is removed to 2ppm, and the selectivity of dimethyl oxalate is 98.8%, the space-time yield of dimethyl oxalate be 705 grams/(rise. hour).Catalyzer carries out stability test in 1000 hours without the inactivation sign.
[embodiment 3]
At first the CO gas raw material that contains oxygen enters deoxidation reactor with NO gas, and the ZSM-5 molecular sieve catalyzer that is 200: 1 with the Si/Al mol ratio contacts, and in raw material, oxygen and NO react, and generates and contains NO
2, unreacted NO and CO gas phase effluent I; Gas phase effluent I and methyl nitrite enter in coupler reactor, and with palladium-containing catalyst, (its weight consists of: 0.34%Pd+1.0%K+0.46%Mn/ α-Al
2O
3) contact, reaction generates the effluent II that contains dimethyl oxalate; The gas phase effluent III that the effluent II of dimethyl oxalate obtains the dimethyl oxalate product and contains oxynitride after separating; Wherein, in the CO gas raw material that contains oxygen, the carrier of oxygen volume concentrations is 1%, and the operational condition of deoxidation reactor is: temperature of reaction is 80 ℃, and reaction pressure is 0.2MPa, the residence time is 30 seconds, and the mol ratio of the oxygen in NO and the CO gas raw material that contains oxygen is 10: 1; The coupler reactor operational condition is: temperature of reaction is 100 ℃, and reaction contact time is 9 seconds, and reaction pressure is 0.2MPa, and the mol ratio of CO and methyl nitrite is: 3: 1.Its result is: in raw material, oxygen is removed to 0, and the selectivity of dimethyl oxalate is 98.6%, the space-time yield of dimethyl oxalate be 840 grams/(rise. hour).Catalyzer carries out stability test in 1000 hours without the inactivation sign.
[embodiment 4]
At first the CO gas raw material that contains oxygen enters deoxidation reactor with NO gas, and the ZSM-5 molecular sieve catalyzer that is 500: 1 with the Si/Al mol ratio contacts, and in raw material, oxygen and NO react, and generates and contains NO
2, unreacted NO and CO gas phase effluent I; Gas phase effluent I and methyl nitrite enter in coupler reactor, and with palladium-containing catalyst, (its weight consists of: 0.11%Pd+0.6%Ba+0.2%Fe/ α-Al
2O
3) contact, reaction generates the effluent II that contains dimethyl oxalate; The gas phase effluent III that the effluent II of dimethyl oxalate obtains the dimethyl oxalate product and contains oxynitride after separating; Wherein, in the CO gas raw material that contains oxygen, the carrier of oxygen volume concentrations is 0.4%, and the operational condition of deoxidation reactor is: temperature of reaction is 160 ℃, and reaction pressure is 0.5MPa, the residence time is 10 seconds, and the mol ratio of the oxygen in NO and the CO gas raw material that contains oxygen is 8: 1; The coupler reactor operational condition is: temperature of reaction is 140 ℃, and reaction contact time is 2 seconds, and reaction pressure is 0.5MPa, and the mol ratio of CO and methyl nitrite is: 1.2: 1.Its result is: in raw material, oxygen is removed to 1ppm, and the selectivity of dimethyl oxalate is 99.1%, the space-time yield of dimethyl oxalate be 120 grams/(rise. hour) 98.5%.Catalyzer carries out stability test in 1000 hours without the inactivation sign.
[embodiment 5]
At first the CO gas raw material that contains oxygen enters deoxidation reactor with NO gas, and the y-zeolite catalyzer that is 200: 1 with the Si/Al mol ratio contacts, and in raw material, oxygen and NO react, and generates and contains NO
2, unreacted NO and CO gas phase effluent I; Gas phase effluent I and methyl nitrite enter in coupler reactor, and with palladium-containing catalyst, (its weight consists of: 0.8%Pd+10%Ce+0.003%Zr/TiO
2) contact, reaction generates the effluent II that contains dimethyl oxalate; The gas phase effluent III that the effluent II of dimethyl oxalate obtains the dimethyl oxalate product and contains oxynitride after separating; Wherein, in the CO gas raw material that contains oxygen, the carrier of oxygen volume concentrations is 0.03%, and the operational condition of deoxidation reactor is: temperature of reaction is 121 ℃, and reaction pressure is 1MPa, the residence time is 3 seconds, and the mol ratio of the oxygen in NO and the CO gas raw material that contains oxygen is 20: 1; The coupler reactor operational condition is: temperature of reaction is 160 ℃, and reaction contact time is 1 second, and reaction pressure is 1MPa, and the mol ratio of CO and methyl nitrite is: 1.5: 1.Its result is: in raw material, oxygen is removed to 0, and the selectivity of dimethyl oxalate is 98.2%, the space-time yield of dimethyl oxalate be 1020 grams/(rise. hour).Catalyzer carries out stability test in 1000 hours without the inactivation sign.
[embodiment 6]
At first the CO gas raw material that contains oxygen enters deoxidation reactor with NO gas, and the β-molecular sieve catalyst that is 80: 1 with the Si/Al mol ratio contacts, and in raw material, oxygen and NO react, and generates and contains NO
2, unreacted NO and CO gas phase effluent I; Gas phase effluent I and methyl nitrite enter in coupler reactor, and with palladium-containing catalyst, (its weight consists of: 0.6%Pd+0.2%Cu+0.08%Fe/99.11% α-Al
2O
3) contact, reaction generates the effluent II that contains dimethyl oxalate; The gas phase effluent III that the effluent II of dimethyl oxalate obtains the dimethyl oxalate product and contains oxynitride after separating; Wherein, in the CO gas raw material that contains oxygen, the carrier of oxygen volume concentrations is 1%, and the operational condition of deoxidation reactor is: temperature of reaction is 100 ℃, and reaction pressure is normal pressure, the residence time is 0.5 second, and the mol ratio of the oxygen in NO and the CO gas raw material that contains oxygen is 14: 1; The coupler reactor operational condition is: temperature of reaction is 120 ℃, and reaction contact time is 3 seconds, and reaction pressure is normal pressure, and the mol ratio of CO and methyl nitrite is: 2: 1.Its result is: in raw material, oxygen is removed to 1ppm, and the selectivity of dimethyl oxalate is 98.8%, the space-time yield of dimethyl oxalate be 860 grams/(rise. hour).Catalyzer carries out stability test in 1000 hours without the inactivation sign.
[embodiment 7]
At first the CO gas raw material that contains oxygen enters deoxidation reactor with NO gas, and the β-molecular sieve catalyst that is 100: 1 with the Si/Al mol ratio contacts, and in raw material, oxygen and NO react, and generates and contains NO
2, unreacted NO and CO gas phase effluent I; Gas phase effluent I and ethyl nitrite enter in coupler reactor, and with palladium-containing catalyst, (its weight consists of: 0.2%Pd+0.40%Mg+0.22%Fe/ α-Al
2O
3) contact, reaction generates the effluent II that contains oxalic acid diethyl ester; The gas phase effluent III that the effluent II of oxalic acid diethyl ester obtains the oxalic acid diethyl ester product and contains oxynitride after separating; Wherein, in the CO gas raw material that contains oxygen, the carrier of oxygen volume concentrations is 0.008%, and the operational condition of deoxidation reactor is: temperature of reaction is 130 ℃, and reaction pressure is 0.2MPa, the residence time is 5 seconds, and the mol ratio of the oxygen in NO and the CO gas raw material that contains oxygen is 45: 1; The coupler reactor operational condition is: temperature of reaction is 120 ℃, and reaction contact time is 5 seconds, and reaction pressure is 0.2MPa, and the mol ratio of CO and ethyl nitrite is: 1.3: 1.Its result is: in raw material, oxygen is removed to 0, and the selectivity of oxalic acid diethyl ester is 98.8%, the space-time yield of oxalic acid diethyl ester be 1130 grams/(rise. hour).Catalyzer carries out stability test in 1000 hours without the inactivation sign.
[embodiment 8]
At first the CO gas raw material that contains oxygen enters deoxidation reactor with NO gas, and the ZSM-5 molecular sieve catalyzer that is 80: 1 with the Si/Al mol ratio contacts, and in raw material, oxygen and NO react, and generates and contains NO
2, unreacted NO and CO gas phase effluent I; Gas phase effluent I and methyl nitrite enter in coupler reactor, and with palladium-containing catalyst, (its weight consists of: 0.4%Pd+0.20%La+0.31%Fe/ α-Al
2O
3) contact, reaction generates the effluent II that contains dimethyl oxalate; The gas phase effluent III that the effluent II of dimethyl oxalate obtains the dimethyl oxalate product and contains oxynitride after separating; Wherein, in the CO gas raw material that contains oxygen, the carrier of oxygen volume concentrations is 2%, and the operational condition of deoxidation reactor is: temperature of reaction is 140 ℃, and reaction pressure is 0.2MPa, the residence time is 5 seconds, and the mol ratio of the oxygen in NO and the CO gas raw material that contains oxygen is 30: 1; The coupler reactor operational condition is: temperature of reaction is 130 ℃, and reaction contact time is 5 seconds, and reaction pressure is 0.2MPa, and the mol ratio of CO and methyl nitrite is: 1.3: 1.Its result is: in raw material, oxygen is removed to 0, and the selectivity of dimethyl oxalate is 98.9%, the space-time yield of dimethyl oxalate be 1300 grams/(rise. hour), catalyzer carries out stability test in 1000 hours without the inactivation sign.
[embodiment 9]
At first the CO gas raw material that contains oxygen enters deoxidation reactor with NO gas, and the ZSM-5 molecular sieve catalyzer that is 150: 1 with the Si/Al mol ratio contacts, and in raw material, oxygen and NO react, and generates and contains NO
2, unreacted NO and CO gas phase effluent I; Gas phase effluent I and methyl nitrite enter in coupler reactor, and with palladium-containing catalyst, (its weight consists of: 0.23%Pd+5%Bi+0.08%Fe/ α-Al
2O
3) contact, reaction generates the effluent II that contains dimethyl oxalate; The gas phase effluent III that the effluent II of dimethyl oxalate obtains the dimethyl oxalate product and contains oxynitride after separating; Wherein, in the CO gas raw material that contains oxygen, the carrier of oxygen volume concentrations is 0.2%, and the operational condition of deoxidation reactor is: temperature of reaction is 120 ℃, and reaction pressure is normal pressure, the residence time is 1 second, and the mol ratio of the oxygen in NO and the CO gas raw material that contains oxygen is 80: 1; The coupler reactor operational condition is: temperature of reaction is 130 ℃, and reaction contact time is 3 seconds, and reaction pressure is normal pressure, and the mol ratio of CO and methyl nitrite is: 1.2: 1.Its result is: in raw material, oxygen is removed to 0ppm, and the selectivity of dimethyl oxalate is 97.8%, the space-time yield of dimethyl oxalate be 860 grams/(rise. hour).Catalyzer carries out stability test in 1000 hours without the inactivation sign.
[comparative example 1]
Identical catalyzer, condition and the reaction raw materials according to embodiment 8, CO oxygen is not processed, its reaction result is as follows: the selectivity of dimethyl oxalate is 88.9%, the space-time yield of dimethyl oxalate be 500 grams/(rise. hour), catalyzer carries out 300 hours stability inactivation.
Claims (1)
1. a CO gas phase coupling is produced the method for barkite, and at first the CO gas raw material that contains oxygen enters deoxidation reactor with NO gas, and the β-molecular sieve catalyst that is 100: 1 with the Si/Al mol ratio contact, and in raw material, oxygen and NO react, and generation contains NO
2, unreacted NO and CO gas phase effluent I; Gas phase effluent I and ethyl nitrite enter in coupler reactor, with palladium-containing catalyst, contact, and the weight of palladium-containing catalyst consists of: 0.2%Pd+0.40%Mg+0.22%Fe/ α-Al
2O
3, reaction generates the effluent II that contains oxalic acid diethyl ester; The gas phase effluent III that the effluent II of oxalic acid diethyl ester obtains the oxalic acid diethyl ester product and contains oxynitride after separating; Wherein, in the CO gas raw material that contains oxygen, the carrier of oxygen volume concentrations is 0.008%, and the operational condition of deoxidation reactor is: temperature of reaction is 130 ℃, and reaction pressure is 0.2MPa, the residence time is 5 seconds, and the mol ratio of the oxygen in NO and the CO gas raw material that contains oxygen is 45: 1; The coupler reactor operational condition is: temperature of reaction is 120 ℃, and reaction contact time is 5 seconds, and reaction pressure is 0.2MPa, and the mol ratio of CO and ethyl nitrite is: 1.3: 1; Its result is: in raw material, oxygen is removed to 0, and the selectivity of oxalic acid diethyl ester is 98.8%, and the space-time yield of oxalic acid diethyl ester is 1130 grams/(liters per hour); Catalyzer carries out stability test in 1000 hours without the inactivation sign.
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| CN1054765A (en) * | 1990-03-14 | 1991-09-25 | 中国科学院福建物质结构研究所 | Continuous process for synthesizing oxalate by gas phase catalysis |
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