CN102219681B - Method for producing oxalic acid ester through CO gas phase coupling - Google Patents
Method for producing oxalic acid ester through CO gas phase coupling Download PDFInfo
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- CN102219681B CN102219681B CN201010147033.0A CN201010147033A CN102219681B CN 102219681 B CN102219681 B CN 102219681B CN 201010147033 A CN201010147033 A CN 201010147033A CN 102219681 B CN102219681 B CN 102219681B
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- 238000010168 coupling process Methods 0.000 title claims abstract description 15
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 13
- 230000008878 coupling Effects 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- 150000003901 oxalic acid esters Chemical class 0.000 title abstract 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 232
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 38
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 26
- 239000007789 gas Substances 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 57
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 claims description 42
- 238000006709 oxidative esterification reaction Methods 0.000 claims description 34
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical compound CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 claims description 25
- 238000000926 separation method Methods 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 18
- 230000000694 effects Effects 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 2
- 239000011324 bead Substances 0.000 claims description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 13
- -1 nitrite ester Chemical class 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 8
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 230000032050 esterification Effects 0.000 abstract description 3
- 238000005886 esterification reaction Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract 8
- 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 12
- 239000000047 product Substances 0.000 description 12
- 238000011160 research Methods 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- QQZWEECEMNQSTG-UHFFFAOYSA-N Ethyl nitrite Chemical compound CCON=O QQZWEECEMNQSTG-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- HZHMMLIMOUNKCK-UHFFFAOYSA-N dipropyl oxalate Chemical compound CCCOC(=O)C(=O)OCCC HZHMMLIMOUNKCK-UHFFFAOYSA-N 0.000 description 5
- 239000012808 vapor phase Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- KAOQVXHBVNKNHA-UHFFFAOYSA-N propyl nitrite Chemical compound CCCON=O KAOQVXHBVNKNHA-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000009466 transformation Effects 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
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 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
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000006227 byproduct Substances 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
- 239000003034 coal gas 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
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000012043 crude product Substances 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
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 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
- 238000005755 formation reaction Methods 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
- 239000003317 industrial substance Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005457 optimization 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
- 238000011020 pilot scale process Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052725 zinc 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 acid ester through CO gas phase coupling. The use of the method is aimed to mainly solving the technical problems of low nitric oxide utilization ratio and low conversion rate of raw materials in the prior art. A technical scheme is adopted as follows: the method comprises the following steps of: (a) firstly, leading gas containing CO and nitrite ester into a coupling reactor, then contacting with a palladium-containing catalyst, and reacting to produce reaction effluent I containing nitric oxide and the oxalic acid ester; (b) separating the reaction effluent I to obtain reaction effluent II containing the oxalic acid ester and reaction effluent III containing nitric oxide, and leading the reaction effluent III into an oxidation and esterification reactor and reacting with oxygen and C1-C4 monohydric alcohol, thus producing gas effluent IV containing nitrite ester; and (c) separating the reaction effluent II to obtain an oxalic acid ester product, wherein the reaction pressure of the oxidation and esterification reactor is lower than the pressure in the coupling reactor, thus better solving the problems of low nitric oxide utilization ratio and the low conversion rate of the raw materials and being used for industrial production of the oxalic acid ester.
Description
Technical field
The present invention relates to a kind of method of CO gas phase coupling producing oxalic ester, particularly about vapor phase process CO, react the method for producing dimethyl oxalate or oxalic acid diethyl ester with methyl nitrite or ethyl nitrite.
Background technology
Barkite is important Organic Chemicals, in a large number for fine chemistry industry, prepares 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, 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, carry out various condensation reactions with fatty acid ester, hexamethylene phenyl methyl ketone, amido alcohol and many heterogeneous ring compounds.It can also synthesize pharmaceutically as the chest acyl alkali of hormone.In addition, barkite low-voltage hydrogenation can be prepared very important industrial chemicals ethylene glycol, and ethylene glycol mainly relies on petroleum path to prepare at present, and cost compare Gao， 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 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.
For Oxidation of Carbon Monoxide coupling method synthesis of oxalate, from development course, divide 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 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 Yu Buxingchan company exploitation, reaction pressure 0.5MPa, temperature is 80 ℃～150 ℃.
Along with Oxidation of Carbon Monoxide coupling method in the world, prepare the research and development of barkite Technology, domestic many research institutions have also carried out research work to this field.According to china natural resources characteristic distributions, the carbon monoxide of take is prepared organic oxygen-containing compound as raw material, for alleviate petroleum products pressure, rationally utilize coal and natural gas source to there is very important strategic importance.At present, by Oxidation of Carbon Monoxide coupling method synthesis of oxalate to become important research topic in domestic one-carbon chemical and organic chemical industry field, successively You Duojia research institution and research institutions are devoted to catalyst preparation, process exploitation and the engineering amplification work in this field, and have obtained greater advance.
Although above-mentioned numerous research institution, has obtained technically compared with much progress, technology itself still needs to be further improved and develops, and especially how, improves the aspects such as oxynitride utilization ratio, all needs further research and improves.
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 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, this invention is on the basis of lab scale research in early stage, the industrial production of take is carried out as background, continuous operation examination is amplified in the mould examination and the pilot scale that have completed under industrial operation condition.But this technology is not mentioned and how is more effectively improved the technology such as oxynitride utilization ratio.
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, this technology does not relate to and how more effectively improves the technology such as oxynitride utilization ratio.
Summary of the invention
Technical problem to be solved by this invention is in prior art, to exist oxynitride utilization ratio low, and the technical problem that feed stock conversion is low provides a kind of method of new CO gas phase coupling producing oxalic ester.It is high that the method has oxynitride utilization ratio, the advantage that feed stock conversion 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 method of CO gas phase coupling producing oxalic ester, comprises the following steps:
A) first the gas that contains CO and nitrous acid ester enter coupler reactor, contacts with palladium-containing catalyst, and reaction generates the reaction effluent I that contains oxynitride and barkite;
B) reaction effluent I, after separation, obtains containing the reaction effluent II of barkite and the reaction effluent III that contains oxynitride, and the reaction effluent III that contains oxynitride enters oxidative esterification reaction device, with oxygen, C
1～C
4monohydroxy-alcohol reaction, generate the gaseous effluent IV that contains nitrous acid ester;
C) the reaction effluent II containing barkite obtains barkite product after separation;
Wherein, the reaction pressure of oxidative esterification reaction device is lower than the pressure of coupler reactor, and the reaction pressure of oxidative esterification reaction device is-0.09～0MPa, and the reaction pressure of coupler reactor is 0.001～1.0MPa.
In technique scheme, coupler reactor operational condition is: temperature of reaction is 60～180 ℃, and reaction volume air speed is 500～10000 hours
-1, reaction pressure is 0.005～1.0MPa, the mol ratio of CO and nitrous acid ester is 1～3: 1; Coupler reactor preferred operations condition is: temperature of reaction is 80～160 ℃, and reaction volume air speed is 800～6000 hours
-1, reaction pressure is 0.01～0.8MPa, the mol ratio of CO and nitrous acid ester is 1～2.5: 1.
Oxidative esterification reaction device operational condition in technique scheme: 0～80 ℃ of temperature of reaction, reaction contact time is 0.1～100 second, reaction pressure is-0.08～0MPa, oxynitride: O
2: C
1～C
4the mol ratio of monohydroxy-alcohol be 1: 0.10～0.25: 1～10; Oxidative esterification reaction device operation conditions optimization is: 10～60 ℃ of temperature of reaction, and reaction contact time is 0.5～50 second, reaction pressure is-0.08～-0.01MPa, oxynitride: O
2: C
1～C
4the mol ratio of monohydroxy-alcohol be 1: 0.15～0.25: 1～5.
In technique scheme, the carrier of palladium-containing catalyst is selected from least one in aluminum oxide, silicon oxide, molecular sieve, 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 0.02～1.5% with vehicle weight, and preferable range is 0.05～1%, and more preferably scope is 0.1～0.8%.
C in technique scheme
1～C
4monohydroxy-alcohol preferred version be selected from methyl alcohol, ethanol or its mixture, more preferably scheme is selected from methyl alcohol.
In the present invention: the oxidative esterification reaction that adopts coupler reactor and the operation of oxidative esterification (regeneration) reactor continuous circulation to realize CO linked reaction and NO generates carrying out continuously of nitrous acid ester reaction, guarantee reaction process self-closing circulating, whole process is non-pollution discharge almost.In addition, as everyone knows, in the oxidative esterification reaction process of NO, except generating the main reaction of nitrous acid ester, also can generate the side reaction of nitric acid, the generation of side reaction has not only aggravated the corrosion of equipment, but also has reduced the utilization ratio of raw material oxynitride (NO), thereby cause the increase of system oxynitride additional amount, the increase of material consumption and energy consumption.A large amount of researchs show, in NO oxidative esterification reaction process, generate side reaction and the N of nitric acid
4o
2generation closely related, N
4o
2concentration higher, the probability that generates the by products such as nitric acid is just larger, and deep research is found, the pressure of oxidative esterification reaction system and N
4o
2generation closely related, pressure is higher, N
4o
2formation reaction more easily occur, pressure is lower, to generating N
4o
2the reaction effect of drawing up more obvious.But research is also found, in CO coupling reaction process, can effectively improve the selectivity of transformation efficiency and the product of raw material under suitable pressure existence.The present invention adopts the lower working pressure in oxynitride (NO) oxidative esterification reaction unit for this reason, and the relatively high reaction pressure in CO linked reaction unit, both effectively prevented the generation of oxynitride oxidative esterification unit side reaction, improved the utilization ratio of oxynitride, meanwhile, guaranteed that again the transformation efficiency of raw material of CO linked reaction unit and the selectivity of product improve.
Adopt technical scheme of the present invention, in coupler reactor operational condition, be: temperature of reaction is 80～160 ℃, reaction volume air speed is 800～6000 hours
-1, reaction pressure is 0.01～0.8MPa, the mol ratio of CO and nitrous acid ester is: 1～2.5: and 1, catalyzer is for take the palladium catalyst that aluminum oxide is carrier, and the content of palladium counts 0.1～0.8% with catalyst weight; Oxidative esterification reaction device operational condition: 10～60 ℃ of temperature of reaction, reaction contact time is 0.5～50 second, reaction pressure is-0.08～-0.01MPa, oxynitride: O
2: C
1～C
4the mol ratio of monohydroxy-alcohol be 1: 0.15～0.25: 1～5, C wherein
1～C
4monohydroxy-alcohol be selected under the condition of methyl alcohol or ethanol, the utilization ratio of oxynitride can reach 99.8%, obtains good technique effect.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
Catalyzer preparation:
Iron nitrate is dissolved in water, is heated to 80 ℃, vacuum rotating is immersed in the α-Al of 5 millimeters
2o
3on bead, then in 120 ℃, be dried 4 hours.Repone K and ammonium palladic chloride are dissolved in the water respectively, with HCl regulator solution, making its pH value is 4 left and right, then this solution is heated to 80 ℃, again be impregnated on carrier, then in 140 ℃ dry 4 hours, then 450 ℃ of roastings 4 hours, be down to room temperature, obtain required catalyzer, take vehicle weight as benchmark (as follows), its weight consists of: 0.45%Pd+0.40%K+0.22%Fe/ α-Al
2o
3.
Take 10 grams of the above-mentioned catalyzer making, pack in the tubular type coupler reactor that diameter is 18 millimeters, reaction procatalyst is in 100 ml/min, hydrogen molar content 20%, under nitrogen molar content 80% condition, from room temperature, with 3 ℃/min, be raised to 300 ℃, constant temperature, after 3 hours, is down to temperature of reaction and is fed intake.
By containing CO, first enter coupler reactor contact with palladium-containing catalyst with the gas of methyl nitrite, reaction generates the reaction effluent I that contains oxynitride and dimethyl oxalate; Reaction effluent I is after separation, obtain containing the reaction effluent II of dimethyl oxalate and the reaction effluent III that contains oxynitride, the reaction effluent III that contains oxynitride enters oxidative esterification reaction unit, reacts with oxygen, methyl alcohol, generates the gaseous effluent IV that contains methyl nitrite; Reaction effluent II containing dimethyl oxalate obtains dimethyl oxalate product after separation.Wherein, coupler reactor reaction conditions is: 90 ℃ of temperature of reaction, reaction volume air speed is 1000 hours
-1, reaction pressure is 0.2MPa, the mol ratio of CO and methyl nitrite is: 1.2: 1; Oxidative esterification reaction device operational condition: 40 ℃ of temperature of reaction, be 0.5 second duration of contact, reaction pressure is-0.02MPa, NO: O
2: the mol ratio of methyl alcohol is 1: 0.2: 1, and its effect is: NO utilization ratio is 99.3%, CO per pass conversion 70%, and the selectivity of dimethyl oxalate is 99.2%.
[embodiment 2]
According to the identical method of embodiment 1, make and consist of 0.17%Pd+0.12%Fe/ α-Al
2o
3required catalyzer.
Take 10 grams of the above-mentioned catalyzer making, pack in the tubular type coupler reactor that diameter is 18 millimeters, reaction procatalyst is in 100 ml/min, hydrogen molar content 20%, under nitrogen molar content 80% condition, from room temperature, with 3 ℃/min, be raised to 300 ℃, constant temperature, after 3 hours, is down to temperature of reaction and is fed intake.
By containing CO, first enter coupler reactor contact with palladium-containing catalyst with the gas of methyl nitrite, reaction generates the reaction effluent I that contains oxynitride and dimethyl oxalate; Reaction effluent I is after separation, obtain containing the reaction effluent II of dimethyl oxalate and the reaction effluent III that contains oxynitride, the reaction effluent III that contains oxynitride enters oxidative esterification reaction unit, react with oxygen, methyl alcohol, the gaseous effluent IV that generation contains methyl nitrite, gaseous effluent IV returns to coupler reactor and proceeds reaction after mixing with CO; Reaction effluent II containing dimethyl oxalate obtains dimethyl oxalate product after separation.Wherein, coupler reactor reaction conditions is: 120 ℃ of temperature of reaction, reaction volume air speed is 2000 hours
-1, reaction pressure is 0.5MPa, the mol ratio of CO and methyl nitrite is 1.5: 1; Oxidative esterification reaction device operational condition: 70 ℃ of temperature of reaction, be 5 seconds duration of contact, reaction pressure is-0.08MPa, NO: O
2: the mol ratio of methyl alcohol is 1: 0.1: 3, and its effect is: NO utilization ratio is 99.1%, CO per pass conversion 60%, and the selectivity of dimethyl oxalate is 98.5%.
[embodiment 3]
According to the identical method of embodiment 1, make and consist of 0.34%Pd+1.0%K+0.46%Mn/ α-Al
2o
3required catalyzer.
Take 10 grams of the above-mentioned catalyzer making, pack in the tubular type coupler reactor that diameter is 18 millimeters, reaction procatalyst is in 100 ml/min, hydrogen molar content 20%, under nitrogen molar content 80% condition, from room temperature, with 3 ℃/min, be raised to 300 ℃, constant temperature, after 3 hours, is down to temperature of reaction and is fed intake.
By containing CO, first enter coupler reactor contact with palladium-containing catalyst with the gas of methyl nitrite, reaction generates the reaction effluent I that contains oxynitride and dimethyl oxalate; Reaction effluent I is after separation, obtain containing the reaction effluent II of dimethyl oxalate and the reaction effluent III that contains oxynitride, the reaction effluent III that contains oxynitride enters oxidative esterification reaction unit, react with oxygen, methyl alcohol, the gaseous effluent IV that generation contains methyl nitrite, gaseous effluent IV returns to coupler reactor and proceeds reaction after mixing with CO; Reaction effluent II containing dimethyl oxalate obtains dimethyl oxalate product after separation.Wherein, coupler reactor reaction conditions is: 160 ℃ of temperature of reaction, reaction volume air speed is 4000 hours
-1, reaction pressure is 0.8MPa, the mol ratio of CO and methyl nitrite is 3: 1; Oxidative esterification reaction device operational condition: 25 ℃ of temperature of reaction, be 80 seconds duration of contact, reaction pressure is-0.03MPa, NO: O
2: the mol ratio of methyl alcohol is 1: 0.2: 8, and its effect is: NO utilization ratio is 99.0%, CO per pass conversion 27%, and the selectivity of dimethyl oxalate is 98.2%.
[embodiment 4]
According to the identical method of embodiment 1, make and consist of the magnesian required catalyzer of 0.11%Pd+0.6%Ba+0.2%Fe/.
Take 10 grams of the above-mentioned catalyzer making, pack in the tubular type coupler reactor that diameter is 18 millimeters, reaction procatalyst is in 100 ml/min, hydrogen molar content 20%, under nitrogen molar content 80% condition, from room temperature, with 3 ℃/min, be raised to 300 ℃, constant temperature, after 3 hours, is down to temperature of reaction and is fed intake.
By containing CO, first enter coupler reactor contact with palladium-containing catalyst with the gas of methyl nitrite, reaction generates the reaction effluent I that contains oxynitride and dimethyl oxalate; Reaction effluent I is after separation, obtain containing the reaction effluent II of dimethyl oxalate and the reaction effluent III that contains oxynitride, the reaction effluent III that contains oxynitride enters oxidative esterification reaction unit, react with oxygen, methyl alcohol, the gaseous effluent IV that generation contains methyl nitrite, gaseous effluent IV returns to coupler reactor and proceeds reaction after mixing with CO; Reaction effluent II containing dimethyl oxalate obtains dimethyl oxalate product after separation.Wherein, coupler reactor reaction conditions is: 140 ℃ of temperature of reaction, reaction volume air speed is 3000 hours
-1, reaction pressure is 0.4MPa, the mol ratio of CO and methyl nitrite is 1.3: 1; Oxidative esterification reaction device operational condition: 45 ℃ of temperature of reaction, reaction contact time is 20 seconds, reaction pressure is-0.05MPa, NO: O
2: the mol ratio of methyl alcohol is 1: 0.15: 1.4, and its effect is: NO utilization ratio is 99.1%, CO per pass conversion 70%, and the selectivity of dimethyl oxalate is 99.4%.
[embodiment 5]
According to the identical method of embodiment 1, make and consist of 0.8%Pd/TiO
2required catalyzer.
Take 10 grams of the above-mentioned catalyzer making, pack in the tubular type coupler reactor that diameter is 18 millimeters, reaction procatalyst is in 100 ml/min, hydrogen molar content 20%, under nitrogen molar content 80% condition, from room temperature, with 3 ℃/min, be raised to 300 ℃, constant temperature, after 3 hours, is down to temperature of reaction and is fed intake.
By containing CO, first enter coupler reactor contact with palladium-containing catalyst with the gas of methyl nitrite, reaction generates the reaction effluent I that contains oxynitride and dimethyl oxalate; Reaction effluent I is after separation, obtain containing the reaction effluent II of dimethyl oxalate and the reaction effluent III that contains oxynitride, the reaction effluent III that contains oxynitride enters oxidative esterification reaction unit, react with oxygen, methyl alcohol, the gaseous effluent IV that generation contains methyl nitrite, gaseous effluent IV returns to coupler reactor and proceeds reaction after mixing with CO; Reaction effluent II containing dimethyl oxalate obtains dimethyl oxalate product after separation.Wherein, coupler reactor reaction conditions is: 160 ℃ of temperature of reaction, reaction volume air speed is 8000 hours
-1, reaction pressure is normal pressure, the mol ratio of CO and methyl nitrite is 2: 1; Oxidative esterification reaction device operational condition: 50 ℃ of temperature of reaction, reaction contact time is 10 seconds, reaction pressure is-0.03MPa, NO: O
2: the mol ratio of methyl alcohol is 1: 0.23: 10, and its effect is: NO utilization ratio is 99.3%, CO per pass conversion 47%, and the selectivity of dimethyl oxalate is 98.91%.
[embodiment 6]
According to the identical method of embodiment 1, make and consist of 0.3%Pd+10%Ce+0.507%Fe/ α-Al
2o
3required catalyzer.
Take 10 grams of the above-mentioned catalyzer making, pack in the tubular type coupler reactor that diameter is 18 millimeters, reaction procatalyst is in 100 ml/min, hydrogen molar content 20%, under nitrogen molar content 80% condition, from room temperature, with 3 ℃/min, be raised to 300 ℃, constant temperature, after 3 hours, is down to temperature of reaction and is fed intake.
By containing CO, first enter coupler reactor contact with palladium-containing catalyst with the raw material of ethyl nitrite, reaction generates the reaction effluent I that contains oxynitride and oxalic acid diethyl ester; Reaction effluent I is after separation, obtain containing the reaction effluent II of oxalic acid diethyl ester and the reaction effluent III that contains oxynitride, the reaction effluent III that contains oxynitride enters oxidative esterification reaction unit, with oxygen, ethanol synthesis, the effluent IV that generation contains ethyl nitrite, effluent IV returns to coupler reactor and proceeds reaction after mixing with CO; Reaction effluent II containing oxalic acid diethyl ester obtains oxalic acid diethyl ester product after separation.Wherein, coupler reactor reaction conditions is: 100 ℃ of temperature of reaction, reaction volume air speed is 800 hours
-1, reaction pressure is normal pressure, the mol ratio of CO and ethyl nitrite is 2: 1; Oxidative esterification reaction device operational condition: 30 ℃ of temperature of reaction, reaction contact time is 10 seconds, reaction pressure is-0.08MPa, NO: O
2: the mol ratio of ethanol is 1: 0.13: 5, and its effect is: NO utilization ratio is 99.7%, CO per pass conversion 45%, and the selectivity of oxalic acid diethyl ester is 98.7%.
[embodiment 7]
According to the identical method of embodiment 1, make and consist of 0.6%Pd+0.2%Cu+0.08%Fe/ α-Al
2o
3required catalyzer.
Take 10 grams of the above-mentioned catalyzer making, pack in the tubular type coupler reactor that diameter is 18 millimeters, reaction procatalyst is in 100 ml/min, hydrogen molar content 20%, under nitrogen molar content 80% condition, from room temperature, with 3 ℃/min, be raised to 300 ℃, constant temperature, after 3 hours, is down to temperature of reaction and is fed intake.
By containing CO, first enter coupler reactor contact with palladium-containing catalyst with the raw material of propyl nitrite, reaction generates the reaction effluent I that contains oxynitride and dipropyl oxalate; Reaction effluent I is after separation, obtain containing the reaction effluent II of dipropyl oxalate and the reaction effluent III that contains oxynitride, the reaction effluent III that contains oxynitride enters oxidative esterification reaction unit, react with oxygen, propyl alcohol, the effluent IV that generation contains propyl nitrite, effluent IV returns to coupler reactor and proceeds reaction after mixing with CO; Reaction effluent II containing dipropyl oxalate obtains dipropyl oxalate product after separation.Wherein, coupler reactor reaction conditions is: 80 ℃ of temperature of reaction, reaction volume air speed is 500 hours
-1, reaction pressure is 0.4MPa, the mol ratio of CO and propyl nitrite is 1.5: 1; Oxidative esterification reaction device operational condition: 30 ℃ of temperature of reaction, reaction contact time is 10 seconds, reaction pressure is-0.05MPa, NO: O
2: under the condition that the mol ratio of propyl alcohol is 1: 0.23: 10, its effect is: NO utilization ratio is 99.6%, CO per pass conversion 40%, and the selectivity of dipropyl oxalate is 98.5%.
[embodiment 8]
According to the identical method of embodiment 1, make the required catalyzer that consists of 0.05%Pd+0.015%La.
Take 10 grams of the above-mentioned catalyzer making, pack in the tubular type coupler reactor that diameter is 18 millimeters, reaction procatalyst is in 100 ml/min, hydrogen molar content 20%, under nitrogen molar content 80% condition, from room temperature, with 3 ℃/min, be raised to 300 ℃, constant temperature, after 3 hours, is down to temperature of reaction and is fed intake.
By containing CO, first enter coupler reactor contact with palladium-containing catalyst with the gas of methyl nitrite, reaction generates the reaction effluent I that contains oxynitride and dimethyl oxalate; Reaction effluent I is after separation, obtain containing the reaction effluent II of dimethyl oxalate and the reaction effluent III that contains oxynitride, the reaction effluent III that contains oxynitride enters oxidative esterification reaction unit, react with oxygen, methyl alcohol, the gaseous effluent IV that generation contains methyl nitrite, gaseous effluent IV returns to coupler reactor and proceeds reaction after mixing with CO; Reaction effluent II containing dimethyl oxalate obtains dimethyl oxalate product after separation.Wherein, coupler reactor reaction conditions is: 150 ℃ of temperature of reaction, reaction volume air speed is 5000 hours
-1, reaction pressure is normal pressure, the mol ratio of CO and methyl nitrite is 1.3: 1; Oxidative esterification reaction device operational condition: 40 ℃ of temperature of reaction, reaction contact time is 30 seconds, reaction pressure is-0.06MPa, NO: O
2: the mol ratio of methyl alcohol is 1: 0.18: 10, and its effect is: NO utilization ratio is 99.8%, CO per pass conversion 65%, and the selectivity of dimethyl oxalate is 98.8%.
[embodiment 9]
According to the identical method of embodiment 1, make the required catalyzer that consists of 0.5%Pd+0.01%Zn.
Take 10 grams of the above-mentioned catalyzer making, pack in the tubular type coupler reactor that diameter is 18 millimeters, reaction procatalyst is in 100 ml/min, hydrogen molar content 20%, under nitrogen molar content 80% condition, from room temperature, with 3 ℃/min, be raised to 300 ℃, constant temperature, after 3 hours, is down to temperature of reaction and is fed intake.
By containing CO, first enter coupler reactor contact with palladium-containing catalyst with the gas of methyl nitrite, reaction generates the reaction effluent I that contains oxynitride and dimethyl oxalate; Reaction effluent I is after separation, obtain containing the reaction effluent II of dimethyl oxalate and the reaction effluent III that contains oxynitride, the reaction effluent III that contains oxynitride enters oxidative esterification reaction unit, react with oxygen, methyl alcohol, the gaseous effluent IV that generation contains methyl nitrite, gaseous effluent IV returns to coupler reactor and proceeds reaction after mixing with CO; Reaction effluent II containing dimethyl oxalate obtains dimethyl oxalate product after separation.Wherein, coupler reactor reaction conditions is: 130 ℃ of temperature of reaction, reaction volume air speed is 2000 hours
-1, reaction pressure is normal pressure, the mol ratio of CO and methyl nitrite is 1.3: 1; Oxidative esterification reaction device operational condition: 10 ℃ of temperature of reaction, reaction contact time is 30 seconds, reaction pressure is-0.08MPa, NO: O
2: the mol ratio of methyl alcohol is 1: 0.18: 10, and its effect is: NO utilization ratio is 99.5%, CO per pass conversion 65%, and the selectivity of dimethyl oxalate is 99.5%.
[comparative example 1]
Employing is with the identical catalyzer of embodiment 4 and condition, just the reaction pressure of NO oxidative esterification unit and CO linked reaction unit is 0.4MPa, its reaction result is: NO utilization ratio is 93.1%, CO per pass conversion 63%, and the selectivity of dimethyl oxalate is 96.2%.
Claims (1)
1. a method for CO gas phase coupling producing oxalic ester, step is as follows:
Iron nitrate is dissolved in water, is heated to 80 ℃, vacuum rotating is immersed in the α-Al of 5 millimeters
2o
3on bead, then in 120 ℃, be dried 4 hours; Repone K and ammonium palladic chloride are dissolved in the water respectively, with HCl regulator solution, making its pH value is 4, then this solution is heated to 80 ℃, again be impregnated on carrier, then in 140 ℃ dry 4 hours, then 450 ℃ of roastings 4 hours, be down to room temperature, obtain required catalyzer, take vehicle weight as benchmark, its weight consists of: 0.45%Pd+0.40%K+0.22%Fe/ α-Al
2o
3;
Take 10 grams of the above-mentioned catalyzer making, pack in the tubular type coupler reactor that diameter is 18 millimeters, reaction procatalyst is in 100 ml/min, hydrogen molar content 20%, under nitrogen molar content 80% condition, from room temperature, with 3 ℃/min, be raised to 300 ℃, constant temperature, after 3 hours, is down to temperature of reaction and is fed intake;
By containing CO, first enter coupler reactor contact with palladium-containing catalyst with the gas of methyl nitrite, reaction generates the reaction effluent I that contains oxynitride and dimethyl oxalate; Reaction effluent I is after separation, obtain containing the reaction effluent II of dimethyl oxalate and the reaction effluent III that contains oxynitride, the reaction effluent III that contains oxynitride enters oxidative esterification reaction unit, reacts with oxygen, methyl alcohol, generates the gaseous effluent IV that contains methyl nitrite; Reaction effluent II containing dimethyl oxalate obtains dimethyl oxalate product after separation; Wherein, coupler reactor reaction conditions is: 90 ℃ of temperature of reaction, reaction volume air speed is 1000 hours
-1, reaction pressure is 0.2MPa, the mol ratio of CO and methyl nitrite is: 1.2:1; Oxidative esterification reaction device operational condition: 40 ℃ of temperature of reaction, be 0.5 second duration of contact, reaction pressure is-0.02MPa, NO:O
2: the mol ratio of methyl alcohol is 1:0.2:1, and its effect is: NO utilization ratio is 99.3%, CO per pass conversion 70%, and the selectivity of dimethyl oxalate is 99.2%.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1149047A (en) * | 1996-09-18 | 1997-05-07 | 天津大学 | Diethyl oxalate by gas phase CO link-coupled regeneration catalyzing circulation |
| CN101143821A (en) * | 2007-10-23 | 2008-03-19 | 天津大学 | CO coupling prepares the method for diethyl oxalate |
| 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 |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1149047A (en) * | 1996-09-18 | 1997-05-07 | 天津大学 | Diethyl oxalate by gas phase CO link-coupled regeneration catalyzing circulation |
| CN101143821A (en) * | 2007-10-23 | 2008-03-19 | 天津大学 | CO coupling prepares the method for diethyl oxalate |
| 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 |
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