CN106674013A - Technique for co-production of dimethyl carbonate and oxamide - Google Patents
Technique for co-production of dimethyl carbonate and oxamide Download PDFInfo
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- CN106674013A CN106674013A CN201611071459.6A CN201611071459A CN106674013A CN 106674013 A CN106674013 A CN 106674013A CN 201611071459 A CN201611071459 A CN 201611071459A CN 106674013 A CN106674013 A CN 106674013A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/10—Preparation of carboxylic acid amides from compounds not provided for in groups C07C231/02 - C07C231/08
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses a technique for co-production of dimethyl carbonate and oxamide. According to the method, urea and dimethyl oxalate are taken as raw materials, and two products of the dimethyl carbonate and oxamide are obtained by simultaneous synthesis through ester-ammonia exchange reaction under the action of a catalyst. According to the method, amino in the urea and methoxyl in the dimethyl oxalate can be efficiently recombined, so that losses of two groups in forms of ammonia gas and methanol are avoided; the problems of low raw material utilization rate and poor atom economy in a raw material conversion path in the original process of synthesizing the dimethyl carbonate through urea alcoholysis and the original process of synthesizing the oxamide through dimethyl oxalate ammonolysis are mainly solved; and meanwhile, the adverse effects of by-products of the ammonia gas generated in the urea alcoholysis process and the methanol generated in the dimethyl oxalate ammonolysis process on reaction balance are effectively eliminated.
Description
Technical field
The invention belongs to organic catalysis synthesis technical field, it is related to a kind of amino of utilization urea and the first of dimethyl oxalate
Epoxide is efficiently recombinated, the process of co-producing dimethyl carbonate and oxamides.
Background technology
Dimethyl carbonate as emerging important organic chemical industry's intermediate, the characteristics of its green, environmental protection medicine, it is biological and
Energy field has attracted the extensive concern of numerous researchers.It is former that dimethyl carbonate is mainly used in large chemical industry such as polycarbonate synthesis
Material；Can replace severe toxicity phosgene participate in organic synthesis methylate with carbonylation process；As additive, can improve
The anti-knock properties of gasoline.The initial production method of dimethyl carbonate is phosgenation, but the toxicity of phosgene and corrosivity limit this
The application of one method.Early 1980s, Italy EniChem companies realize with CuCl as catalyst by methyl alcohol oxygen
Change the commercialization of carbonylation process for synthesizing methyl carbonate.This is first and realizes industrialized non-phosgene Synthesis of dimethyl carbonate
Technique, the deactivation phenomenom of catalyst is serious when the defect of this technique is high conversion, and its conversion per pass is only 20%.It is beautiful
Texaco companies of state develop and first generate ethylene carbonate by oxirane and carbon dioxide reaction, then are given birth to through ester exchange with methyl alcohol
The technique for producing dimethyl carbonate, this technique coproduction ethylene glycol and can realize industrialization in 1992, but this process yield it is relatively low,
Production cost is higher, and the market competitiveness is not enough.It is a kind of new to obtain dimethyl carbonate by urea alcoholysis reaction in methyl alcohol
Emerging synthesis technique, the process is generally carried out under the catalytic action of metal composite oxide, generates dimethyl carbonate and ammonia.Should
If process can combine with urea production carrying out, it is possible to decrease cost simultaneously be expected to realize commercialization, but the process association ammonia in solvent
Solubility in methyl alcohol is very high, and limit reaction is carried out to product direction,
Oxamides as a kind of ureaformaldehyde class slow release fertilizer, with nonhazardous, easily storage, difficult leaching loss the characteristics of.These features
Its utilization rate as chemical fertilizer in process of crop growth is improve, extend the fertilising cycle in cultivating procedure, it is to avoid be right
The pollution of water resource.In addition, the characteristics of it is progressively sustained meets the growth rhythm of crop, disposable a large amount of administrations will not burn out work
Thing or excessive consumption cause crop teratogenesis, meet demand of the crop whole growth stage to nitrogenous fertilizer, and this is at home and abroad
It is confirmed in agricultural practice.Compared with the quick-acting fertilizer such as urea, oxamides reduces agricultural production process as slow release fertilizer
In chemical fertilizer, manpower and time cost, the optimal selection of the agricultural production that potential replacement urea turns into.At present, oxamides master
To be synthesized by the oxalate ammonolysis process under hyperbaric environment and obtained.Japanese Ube companies take the lead in developing and are coupled synthesis of oxalic acid by CO
Ester and then ammonolysis obtain the process route of oxamides, and 600 tons of oxamides commercial plants of scale of annual output were built up in 1981.
In recent years, the method for CO oxidative couplings synthesis of oxalate has successfully realized that ton is industrialized, is oxalate ammonolysis process synthesis grass
The large-scale production of acid amides is laid a good foundation.Chinese patent CN102267921 is with coal, water and air as base stock, it is proposed that
A kind of continuous processing for synthesizing oxamides.Chinese patent CN103288666A replaces batch reactor using fluidized-bed reactor
Realize the continuous production of oxamides.United States Patent (USP) US5393319 and Chinese patent CN103242188A solve oxamides and exist
Molding, granulating problem in building-up process.However, some are still present urgently through the process route of oxalate ammonolysis synthesis oxamides
The problem that need to be solved.Once influence of the different technical parameters to oxalate ammonolysis reaction was discussed in United States Patent (USP) US6348626 in detail,
Influence of the content of by-product carbinol to oxamides yield is discussed, and proposes to need constantly to remove first during the course of the reaction
Alcohol is normally carried out with ensureing what is reacted.Because the generation of a large amount of methyl alcohol not only dilutes raw material, reaction rate is reduced, also
Reaction equilibrium constant is reduced, makes balance be difficult to be moved to product direction.Additionally, the methoxy group of mass efficient is taken by amino
Low value-added methyl alcohol is can be only generated after generation, the Atom economy of reaction is poor；Amino molecule of the amino group in gas phase,
This causes that reaction can only be carried out at the interface of gas-liquid two-phase, and the utilization rate of ammonia is very low, and the ammonia for having little time to react away can not be straight
Run in and put, in addition it is also necessary to which special resistant to ammonia corrosion device is circulated recovery, thus brings the increase of equipment and process costs.For example
Ammonia is all additionally added in Chinese patent 103242188A and method disclosed in Chinese patent CN103288666A to absorb, condense
And the circulatory system.
The content of the invention
It is an object of the invention to provide a kind of co-producing dimethyl carbonate and the process of oxamides, specifically with urea
It is raw material with dimethyl oxalate, by the simultaneously synthesizing dimethyl carbonate that obtains of ester ammonia exchange reaction with grass in the presence of catalyst
Acid amides.
The process of co-producing dimethyl carbonate provided by the present invention and oxamides, reactional equation is as shown in Equation 1：
(NH2)2CO+(COOCH3)2—(CH3O)2CO+(NH2CO)2(formula 1)
Concrete technology step is：
A. urea, dimethyl oxalate and methyl alcohol are packed into stirring-type autoclave in proportion, wherein methyl alcohol, urea
It is 2~48 with the mol ratio of dimethyl oxalate：1~6：1, preferably mol ratio is 2~24：1~3：1.
B. weigh during catalyst adds above-mentioned stirring-type autoclave, wherein the mass ratio of catalyst and dimethyl oxalate
It is 4~30%, more excellent mass ratio is 8~12%；It is passed through N2Displace the air in kettle and be pressurized to 1~5MPa, at 70 DEG C
Lower stirring 1h, in continuously stirring 5~10h of reaction at 150~190 DEG C.
Described catalyst is the multicomponent composite oxide catalyst with CuO as main active component, is expressed as：CuO/
MO, wherein auxiliary agent MO are Li2O、Na2O、CaO、MgO、B2O3、Al2O3、In2O3、CdO、ZnO、Ag2O、CeO2、La2O3、Y2O3、
Nd2O3Deng a kind of oxide or 2,3 kind compound.Wherein, CuO accounts for 50~95%, MO of catalyst gross mass to account for catalyst total
The 5~50% of quality.
C. when reacted between reach home after close heating, after question response temperature in the kettle is down to room temperature, open reactor gas
Body atmospheric valve, pressure is down to 1 atmospheric pressure in question response kettle, opens reactor and takes out reacted material and be separated by filtration solid-liquid
Two-phase.Liquid product is carried out into vacuum distillation under 30~120 DEG C and 0.01~0.1MPa pressure, the cut condensate being collected into
As dimethyl carbonate, preferably vacuum distillation condition is：Enter at a temperature of 50~90 DEG C and under 0.01~0.05MPa pressure
OK.Solid product be impregnated in into 3~6h of acidification in the inorganic acid solution that concentration is 0.5~3mol/L, consolidated after filtering
Body, then by more than 3 times washings, filtering, obtain white powder product oxamides.The inorganic acid is nitric acid, sulfuric acid, phosphorus
One of acid, hydrochloric acid, hydrobromic acid.
D. collect the filtrate after acidifying and washing, concentration carried out by vacuum distillation, it is to be distilled to filtrate volume not
Again during significant change, instilled in the alkaline solution that pH value is 8~12, made catalyst CuO/MO Precipitations therein, then
It is aged successively, filtered, being dried and being calcined, the catalyst after being regenerated is realized the recycling of catalyst.The alkalescence
Solution is NH4OH、(NH4)2CO3、NH4HCO3、NaOH、NaHCO3、LiOH、Ca(OH)2、Mg(OH)2In one kind.More preferably
NH4OH、LiOH、NaOH、Na2CO3In one kind..
The method can realize the efficient restructuring of the amino and methoxyl group in raw material, it is to avoid both effective groups are independent anti-
The poorly efficient loss in the form of ammonia and methyl alcohol in answering；Meanwhile, solve original anti-caused by byproducts build-up in independent reaction
Answering the equilibrium constant reduces, the problem for causing reaction to be difficult to be moved to product direction to a certain extent afterwards.
Fig. 1 is to carry out the qualitative analysis to solid product using infrared spectrum, and the red of solid product can be observed by Fig. 1
Outer characteristic peak is consistent with standard oxamides sample, illustrates that solid product is oxamides.
Fig. 2 is the testing result to the liquid product before and after reaction using hydrogen ion flame gas-chromatography, by Fig. 2 observables
Comprise only the characteristic peak of raw material dimethyl oxalate in material before to reaction, and occur in reacting rear material product dimethyl carbonate and
The characteristic peak of accessory substance methyl carbamate, and the characteristic peak of raw material dimethyl oxalate has been wholly absent, and illustrates raw material oxalic acid two
Methyl esters is converted completely.
Beneficial effects of the present invention are embodied in：
(1) replace ammonia with urea, all reactants is in liquid phase, enhance the phase mutual connection between reactant
Touch, be conducive to the carrying out of reaction；
(2) coproduction obtains oxamides and carbonic acid dicarboxylic acid esters, realizes the efficient restructuring of amino and methoxyl group, it is to avoid this two
Effective group poorly efficient loss in the form of ammonia and methyl alcohol in independent reaction is planted, the atom economy of the reaction system is improve
Property；Using the co-production, the yield of oxamides can reach 97.9%, while the yield of dimethyl carbonate can reach 35
~55%.
(3) accessory substances such as methyl alcohol and ammonia, product oxamides is not produced to be insoluble in the solid of reaction raw materials in reacting,
Constantly removed from system in course of reaction, reaction is carried out to product direction all the time；
(4) whole course of reaction without the concern for ammonia and methyl alcohol timely removal, reclaim and recycle problem, it is to avoid
The increase of the technique and equipment cost thus brought.
Figure of description
Fig. 1：Product oxamides and the infrared spectrum comparison diagram of standard oxamides sample prepared by embodiment 1.
Fig. 2：Embodiment 1 reacts the gas-chromatography comparison diagram of front and rear liquid phase material.
Specific embodiment
Embodiment 1：
11.8g dimethyl oxalates are weighed respectively, and 6g urea, 6.4g absolute methanols are packed into stirring-type autoclave,
The mol ratio of methyl alcohol, urea and dimethyl oxalate is 2：1：1.1g CuO/CaO-In are weighed again2O3- CdO Catalyst packings enter instead
Answer in kettle, catalyst is 8.5% with the mass ratio of dimethyl oxalate, and CuO accounts for 50%, CaO of catalyst gross mass in catalyst
Account for 5%, In of catalyst gross mass2O340%, the CdO for accounting for catalyst gross mass accounts for the 10% of catalyst gross mass.It is passed through N2Put
Change and be pressurized to 1MPa in kettle after air, be warming up to 70 DEG C of temperature and continuously stir 1h in the speed of 100rpm.150 are warming up to again
DEG C, the successive reaction 5h under the mixing speed of 100rpm.Heating is closed afterwards, and question response temperature in the kettle opens reaction after being down to room temperature
Kettle gas atmospheric valve, treats that pressure is down to 1 atmospheric pressure in kettle, opens reactor and takes out reacted material.Material was passed through
Filter is separated into solid-liquid two-phase, and liquid phase is carried out into distillation under pressure obtains product dimethyl carbonate.Solid product impregnated in into concentration is
Acidification 5h in the salpeter solution of 0.5mol/L, obtains solid after filtering, then obtains grass by the process of 3 washing-filterings
Acid amides white powder.
The filtrate after above-mentioned acidifying and washing is collected, acid treatment is concentrated and caught up with by vacuum distillation, it is to be distilled to filter
When liquid accumulates no longer significant change, the NH that pH is 11 is added dropwise to4Co-precipitation treatment, mistake after ageing 10h are carried out in OH solution
Filter obtains colloidal precursors, be placed on baking oven in dry 12h in 120 DEG C, then be placed in Muffle furnace 3h, cooling be calcined in 650 DEG C
Catalyst after being regenerated to room temperature.
Solid product is tested and analyzed by infrared spectrum, Fig. 1 is as a result seen；It is re-weighed and is calculated the receipts of oxamides
Rate, the results are shown in Table 1；By liquid product methanol dilution to 100ml, each group in hydrogen ion flame gas Chromatographic Determination material is used
The concentration divided, is as a result shown in Fig. 2；The yield of dimethyl carbonate is calculated simultaneously, the results are shown in Table 1.
Embodiment 2：
With embodiment 1, difference is that reaction pressure is 3MPa.Product analysis the results are shown in Table 1.
Embodiment 3：
With embodiment 1, difference is that reaction temperature is 180 DEG C.Product analysis the results are shown in Table 1.
Embodiment 4：
With embodiment 1, difference is that the loadings of catalyst are 2g, and catalyst is with the mass ratio of dimethyl oxalate
17%.Product analysis the results are shown in Table 1.
Embodiment 5：
With embodiment 1, difference is that the catalyst for loading is CuO/Na2O-In2O3- CdO, wherein CuO account for catalyst
50%, Na of gross mass2O accounts for 5%, In of catalyst gross mass2O340%, the CdO for accounting for catalyst gross mass accounts for the total matter of catalyst
The 5% of amount；It also differ in that used in step D coprecipitation process be that pH value is that 11, cation is Na+It is alkaline molten
Liquid.Product analysis the results are shown in Table 1.
Embodiment 6：
With embodiment 1, difference is that the catalyst for loading is CuO/Li2O-In2O3- CdO, wherein CuO account for catalyst
50%, Li of gross mass2O accounts for 5%, In of catalyst gross mass2O340%, the CdO for accounting for catalyst gross mass accounts for the total matter of catalyst
The 5% of amount；It also differ in that used in step D coprecipitation process be that pH value is that 11, cation is Li+It is alkaline molten
Liquid.Product analysis the results are shown in Table 1.
Embodiment 7：
With embodiment 1, difference is to add 12g urea and 12.8g absolute methanols, methyl alcohol, urea and oxalic acid diformazan
The mol ratio of ester is 4：2：1.Product analysis the results are shown in Table 1.
Embodiment 8：
With embodiment 1, difference is to add 18g urea and 19.2g absolute methanols, methyl alcohol, urea and oxalic acid diformazan
The mol ratio of ester is 6：3：1.Product analysis the results are shown in Table 1.
Embodiment 9：
With embodiment 1, difference is that the addition of absolute methanol is 25.6g, methyl alcohol, urea and dimethyl oxalate
Mol ratio is 4：1：1.Product analysis the results are shown in Table 1.
Embodiment 10：
With embodiment 1, difference is that the addition of absolute methanol is 38.4g, methyl alcohol, urea and dimethyl oxalate
Mol ratio is 6：1：1.Product analysis the results are shown in Table 1.
Embodiment 11：
With embodiment 1, difference is that the addition of absolute methanol is 51.2g, methyl alcohol, urea and dimethyl oxalate
Mol ratio be 8：1：1.Product analysis the results are shown in Table 1.
Embodiment 12：
With embodiment 3, difference is that the addition of absolute methanol is 38.4g, methyl alcohol, urea and dimethyl oxalate
Mol ratio is 12：3：1.Product analysis the results are shown in Table 1.
Embodiment 13：
With embodiment 3, difference is that the addition of absolute methanol is 57.6g, methyl alcohol, urea and dimethyl oxalate
Mol ratio is 18：3：1.Product analysis the results are shown in Table 1.
Embodiment 14：
With embodiment 3, difference is that the addition of absolute methanol is 76.8g, methyl alcohol, urea and dimethyl oxalate
Mol ratio is 24：3：1.Product analysis the results are shown in Table 1.
Table 1：The conversion ratio of reactant and the yield of product
Claims (2)
1. the process of a kind of co-producing dimethyl carbonate and oxamides, comprises the following steps that：
A. urea, dimethyl oxalate and methyl alcohol are packed into stirring-type autoclave in proportion, wherein methyl alcohol, urea and grass
The mol ratio of dimethyl phthalate is 2~48：1~6：1；
B. weigh in the catalyst above-mentioned stirring-type autoclave of addition, wherein catalyst and the mass ratio of dimethyl oxalate is 4
~30%；It is passed through N2Displace the air in kettle and be pressurized to 1~5MPa, 1h is stirred at 70 DEG C, connect at 150~190 DEG C
5~10h of continuous stirring reaction；
Described catalyst is the multicomponent composite oxide catalyst with CuO as main active component, is expressed as：CuO/MO, its
Middle auxiliary agent MO is Li2O、Na2O、CaO、MgO、B2O3、Al2O3、In2O3、CdO、ZnO、Ag2O、CeO2、La2O3、Y2O3、Nd2O3In
1 kind or 2,3 kind compound；Wherein, CuO account for catalyst gross mass 50~95%, MO account for catalyst gross mass 5~
50%；
C. when reacted between reach home after close heating, question response temperature in the kettle is down to room temperature, opens the emptying of reactor gas
Valve, pressure is down to 1 atmospheric pressure in question response kettle, opens reactor and takes out reacted material and be separated by filtration solid-liquid two-phase；
By liquid product vacuum distillation under 30~120 DEG C and 0.01~0.1MPa pressure, the cut condensate as carbonic acid being collected into
Dimethyl ester；Solid product be impregnated in into 3~6h of acidification in the inorganic acid solution that concentration is 0.5~3mol/L, filtering retains
Solid, then by more than 3 times washings, obtain white powder product oxamides；
The inorganic acid is one of nitric acid, sulfuric acid, phosphoric acid, hydrochloric acid, hydrobromic acid；
D. the filtrate after collection step C acidifyings and washing, concentration is carried out by vacuum distillation, it is to be distilled to filtrate volume not
Again during significant change, instilled in the alkaline solution that pH value is 8~12, made catalyst CuO/MO Precipitations therein, then
It is aged successively, filtered, being dried and being calcined, being obtained catalyst CuO/MO, is realized the recycling of catalyst；The alkalescence is molten
Liquid is NH4OH、(NH4)2CO3、NH4HCO3、NaOH、NaHCO3、LiOH、Ca(OH)2、Mg(OH)2In one kind.
2. the process of co-producing dimethyl carbonate according to claim 1 and oxamides, it is characterized in that described in step A
The mol ratio of methyl alcohol, urea and dimethyl oxalate is 2~24：1~3：1；The matter of catalyst and dimethyl oxalate described in step B
Amount ratio is 8~12%；Liquid product vacuum distillation condition described in step C is：At a temperature of 50~90 DEG C and 0.01~
Carried out under 0.05MPa pressure；Alkaline solution described in step D is NH4OH、LiOH、NaOH、Na2CO3In one kind.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102267921A (en) * | 2011-05-26 | 2011-12-07 | 陈贻盾 | Continuous processing technology for synthesis of oxamide |
| EP2629889A2 (en) * | 2010-10-19 | 2013-08-28 | Yeda Research and Development Co. Ltd. | Novel ruthenium complexes and their uses in processes for formation and/or hydrogenation of esters, amides and derivatives thereof |
| CN103288666A (en) * | 2013-05-21 | 2013-09-11 | 江苏丹化煤制化学品工程技术有限公司 | Method for continuous gas phase synthesis of oxamide |
| CN105367439A (en) * | 2015-09-07 | 2016-03-02 | 中国科学院福建物质结构研究所 | Process method of co-production of oxamide and carbamic acid ester through ammonia ester exchange method |
-
2016
- 2016-11-29 CN CN201611071459.6A patent/CN106674013B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2629889A2 (en) * | 2010-10-19 | 2013-08-28 | Yeda Research and Development Co. Ltd. | Novel ruthenium complexes and their uses in processes for formation and/or hydrogenation of esters, amides and derivatives thereof |
| CN102267921A (en) * | 2011-05-26 | 2011-12-07 | 陈贻盾 | Continuous processing technology for synthesis of oxamide |
| CN103288666A (en) * | 2013-05-21 | 2013-09-11 | 江苏丹化煤制化学品工程技术有限公司 | Method for continuous gas phase synthesis of oxamide |
| CN105367439A (en) * | 2015-09-07 | 2016-03-02 | 中国科学院福建物质结构研究所 | Process method of co-production of oxamide and carbamic acid ester through ammonia ester exchange method |
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