CN1318384C - Polyphosphoric acid catalyzed dimethyl carbonate synthesizing process - Google Patents
Polyphosphoric acid catalyzed dimethyl carbonate synthesizing process Download PDFInfo
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- CN1318384C CN1318384C CNB2005100427328A CN200510042732A CN1318384C CN 1318384 C CN1318384 C CN 1318384C CN B2005100427328 A CNB2005100427328 A CN B2005100427328A CN 200510042732 A CN200510042732 A CN 200510042732A CN 1318384 C CN1318384 C CN 1318384C
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Abstract
The present invention discloses a method for synthesizing dimethyl carbonate by the catalysis of polyphosphoric acid. Polyphosphoric acid is used as an ammonia gas absorbing agent and a catalyst, urea, methanol and the polyphosphoric acid are proportionally added in a reaction kettle to be swept by carbon dioxide or nitrogen gas, pressure is preset to 0.4 to 1.0MPa, and the reaction kettle is heated to 90 to 150 DEG C; after a reaction is carried out for 1 to 10 hours with stirring, reaction temperature is reduced to room temperature, and the pressure is released; a liquid-phase component and a solid-phase component are respectively obtained by centrifugal separation of the reaction mixed liquid and the liquid-phase component is distilled at normal atmosphere to obtain the mixture of the methanol and dimethyl carbonate; distillation residues return to the reaction kettle to be recycled, and the solid-phase component is compound fertilizer ammonium phosphate. The present invention can use intermittent operation or continuous operation, and when the continuous operation is carried out, the yield of the dimethyl carbonate is high. The present invention has the characteristics of moderate reaction conditions, simple operation, rapid reaction speed, high yield of the dimethyl carbonate, good product quality, etc.
Description
Technical field
The present invention relates to a kind of preparation method of methylcarbonate, particularly by the method for polyphosphoric acid catalyzed dimethyl carbonate synthesizing.
Background technology
Methylcarbonate (DMC) is a kind of environmental friendliness chemical, as nonpoisonous chemicla was classified it in 1992 in Europe, data shows, with the DMC blended gasoline, not only can boosting of octane rating, and all little to the physical properties of gasoline such as freezing point and water-soluble influence, so DMC is that a kind of comparatively ideal methyl tertiary butyl ether (MTBE) substitutes gasoline dope.On the other hand, owing to contain-CH in the DMC molecule
3,-CH
3O, CH
3O-, CO-, functional groups such as-CO-, thereby has a good reaction activity, can with alcohol, phenol, amine, chemical reaction takes place in hydrazine and ester etc., so can derive a series of important Chemicals, substitute phosgene as DMC at numerous areas comprehensively, methyl-sulfate (DMS), hypertoxic carcinogens such as methyl chloride and methyl-chloroformate carries out carbonylation, methylate, reaction such as esterification and transesterify generates multiple important Chemicals, simultaneously, with DMC is the meticulous specialty chemicals that raw material can be developed the multiple high added value of preparation, at medicine, agricultural chemicals, synthetic materials, dyestuff, lubricating oil additive, food flavoring agent, fields such as electronic chemical product obtain widespread use, so DMC has been described as the new foundation stone in the 21 century organic synthesis field.DMC also is with a wide range of applications as solvent, solvent, extraction agent etc. non-reacted.Just because of the tempting prospects for commercial application of methylcarbonate, countries in the world particularly the U.S., Japan and Italy etc. all in the research of paying close attention to its synthetic route and the exploitation of novel process, methylcarbonate synthetic just towards route oversimplify, process do not having poison, the technical development of production pollution-free green.
At present, the industrialized preparing process of methylcarbonate has phosgenation, oxidative carbonylation of methanol method and ester-interchange method.Phosgenation is traditional synthetic method, adopts phosgene and methyl alcohol to react and produces DMC, though mature production technology, raw material phosgene severe toxicity, poor stability, " three wastes " amount is big, belongs to phasing-out model technology.Methanol solution phase oxidation carbonylation method is the most a kind of production method of domestic and international application at present, but the employed CuCl catalyzer of this method produces HCl and etching apparatus in reaction process, and catalyst life shortens, there is water to generate simultaneously in the product, easily form methanol-water-dimethyl carbonate azeotrope, increase separation purification difficulty, also had hidden peril of explosion.(the Ube Industries of Co., Ltd. of Ube Industries Ltd., Ltd) by the methyl nitrite gas-phase oxidation/carbonylation synthesis method of having improved catalyst development, the shortcoming of this technology is to need two-step reaction, complex process, the reaction that generates methyl nitrite is quick strong exothermal reaction, and the blending ingredients of reactant is easily blasted, and has introduced deleterious NO, and generation by product dimethyl oxalate, easily blocking pipeline.Ester-interchange method is to adopt propylene carbonate or NSC 11801 and methyl alcohol to carry out transesterify under catalyst action to produce.Though ester-interchange method reaction conditions gentleness, productive rate is higher, but the preparation of raw material propylene carbonate or NSC 11801 is another gordian technique in this route, influence the investment and the cost of suitability for industrialized production, therefore have that investment is big, cost is high, and problems such as the generation of a large amount of by product second (or third) glycol and isolation technique complexity are arranged.
It is a kind of new production technique of developing in recent years that alcoholysis of urea prepares methylcarbonate, with wide material sources, cheap urea and methyl alcohol as basic raw material, because anhydrous generation in this art production process, avoided the formation of methanol-water-dimethyl carbonate azeotrope, later separation has been purified oversimplify.At present, the catalyzer that is used for Synthesis of Dimethyl Carbonate from Urea mainly is: organo-tin compound, basic metal and alkaline earth metal compound.US5565603 (Process for manufacturing dialkyl carbonatefrom urea and alcohol, October 15,1996) reported that Dibutyltin oxide, dibutyl dimethoxy tin, dibutyl methoxyl group isocyanate group tin makes catalyzer, with Urethylane or urea and methyl alcohol reaction, steam simultaneously methylcarbonate continuously, though such catalyzer can obtain higher product yield, decomposition reaction that also can the catalytic amino methyl-formiate.US6392078 " Process and catalyst formaking dialkyl carbonates " (open day on May 21st, 2002) has reported and has adopted high boiling triglyme to form promotor as solvent and with organo-tin compound, the decomposition of intermediate product Urethylane and the generation of the side reaction that methylates have been suppressed effectively, its Urethylane transformation efficiency can reach 98.3%, and the selectivity of methylcarbonate reaches 98.2% simultaneously.Though organo-tin compound has good catalytic activity, their toxicity is big, price is high, and speed of reaction is slower.Chinese patent 02156481.7 " Synthesis of Dimethyl Carbonate from Urea usefulness metal oxide catalyst and preparation method thereof " (discloses day on May 14th, 2003, publication number 416949) reported the oxide compound that adopts lithium, magnesium, nickel, zinc, lead, aluminium, iron, molybdenum, zirconium, lanthanum and be mixed into catalyzer, discharge the by product ammonia continuously, the highest yield of DMC is 49.7%.Chinese patent 01130478.2 " a kind of method with urea and methyl alcohol Synthesis of dimethyl carbonate " (open day on July 23rd, 2003, publication number 1431190) has been reported employing organometallic compound C
4H
9Li, R
2Sn
x, R
2SnO is a Primary Catalysts, Ph
3P, BF
3, 4-dimethylamine pyridine is a promotor, the highest yield of DMC is 24.42%.In above preparation method, though adopted the measure of continuous discharge by product ammonia, under high pressure carried out owing to react, so still have the ammonia of higher concentration in the reaction system, be subjected to the influence of molecular balance, thereby limited the further raising of DMC yield.Exist temperature of reaction higher simultaneously, side reaction is more, and speed of reaction is slower, contains a spot of ammonia in the still lower and product of DMC yield and is difficult for removing clean and has a strong impact on the final quality of DMC.
Summary of the invention
The method that the purpose of this invention is to provide a kind of polyphosphoric acid catalyzed dimethyl carbonate synthesizing, this method have solved problems such as the DMC yield that exists in the prior art is low, speed of response is slow, quality product is bad.
The technical solution adopted in the present invention is, the method of polyphosphoric acid catalyzed dimethyl carbonate synthesizing, with urea, methyl alcohol and polyphosphoric acid add in the reactor, the mol ratio of urea and methyl alcohol is 1: 2～11, the mol ratio of polyphosphoric acid and urea is 0.5～1.5: 1, with carbonic acid gas or nitrogen purging and set pressure is 0.4～1.0MPa, heat to 90 ℃～150 ℃ then, stir, react after 1～10 hour, temperature of reaction is reduced to room temperature, pressure release, reaction mixture obtains liquid phase and solid components respectively through centrifugation, solid components is composite fertilizer's ammonium phosphate, is to distill under 60 ℃～80 ℃ conditions liquid phase component at normal pressure and temperature, obtains the mixture of methyl alcohol and methylcarbonate, further separation and purification finally obtains methylcarbonate again.
Polyphosphoric acid is by P
2O
5H with concentration 85%
3PO
4Prepared in reaction obtains H under 40 ℃～100 ℃ temperature
3PO
4With P
2O
5Mass ratio be 2.0: 1.0.
The invention has the beneficial effects as follows:
(1) used reaction raw materials is cheap and easy to get, remarkable in economical benefits;
(3) reaction process can adopt intermittently or operate continuously, and the DMC yield is higher during operate continuously;
(4) the reaction conditions gentleness is simple to operate;
(5) speed of response is fast, DMC yield height, good product quality;
(6) when obtaining DMC, also can obtain the higher composite fertilizer's ammonium phosphate of economic worth;
(7) introduce CO in the reactive system
2To reach the generation that suppresses side reaction.
Description of drawings
Accompanying drawing is the employed plant system drawing of method of the present invention.
Among the figure, 1. carbonic acid gas or nitrogengas cylinder, 2. mixed solution storage tank, 3. agitator, 4. ram pump, 5. reactor, 6. rectifying column, 7. overhead condensation pipe, 8. prolong.
Embodiment
The present invention is described in detail below in conjunction with accompanying drawing and example.
Referring to accompanying drawing, the method of polyphosphoric acid catalyzed dimethyl carbonate synthesizing, be 1: 2～11 mixed in molar ratio in mixed solution storage tank 2 with urea and methyl alcohol, add polyphosphoric acid again as ammonia absorption agent and catalyzer, polyphosphoric acid is averaged molecular weight: 337.9, with the mol ratio of urea be 0.5～1.5: 1, polyphosphoric acid can be by P
2O
5H with concentration 85%
3PO
4Prepared in reaction obtains H under 40 ℃～100 ℃ temperature
3PO
4With P
2O
5Mass ratio be 1.0: 2.0, with ram pump 4 mixed solution is squeezed in the reactor 5, in order to suppress the generation of side reaction, purge by carbonic acid gas or nitrogengas cylinder 1 output carbonic acid gas or nitrogen, and set pressure is 0.4～1.0MPa, heat to 90 ℃～150 ℃ then, after reacting 1～10 hour under the stirring that agitator 3 per minutes 600 change, temperature of reaction is reduced to room temperature, pressure release, reaction mixture is to obtain liquid phase and solid components respectively under 1000 rev/mins the separation through centrifuge speed, and the solid components that obtains is composite fertilizer's ammonium phosphate, is to distill under 60 ℃～80 ℃ conditions liquid phase component at normal pressure and temperature, promptly obtain the mixture of methyl alcohol and methylcarbonate, further again extracting rectifying finally obtains methylcarbonate, and distillation residue return reactor 5 and recycle.
Adopt the GC122 gas chromatograph to analyze to the DMC product that obtains, 190 ℃ of column temperatures, 200 ℃ of vaporizer temperature, TCD detector, thermal conductivity cell electric current are 100mA, carrier gas is a hydrogen, pressure is 0.1MPa before the post, and chromatographic column is external diameter 3mm, the stainless steel packed column of long 2m, monomer is Gaskuropack-54, adopts external standard method to analyze.
Method of the present invention, its reaction process can adopt periodical operation, also can adopt operate continuously, and when adopting operate continuously, the yield of DMC is higher.
The H of 100g concentration 85%
3PO
4Add in the 300ml flask, add 50gP for 40～100 ℃ in temperature
2O
5Reacted 3～4 hours, and can obtain polyphosphoric acid, after the polyphosphoric acid of urea, 3mol methyl alcohol and the 0.1mol of 0.5mol is mixed in mixed solution storage tank 2, squeeze in the autoclave 5, use CO with ram pump 4
2Purging also, set pressure is 0.6MPa, in 40 minutes, temperature is elevated to 150 ℃, reaction is 3 hours under the stirring that agitator 3 per minutes 600 change, reduce to room temperature fast, reaction mixture obtains liquid phase and solid components respectively through centrifugation, the solid components composite fertilizer ammonium phosphate 20g that gets, with liquid phase component under normal pressure, 64 ℃～80 ℃ distillations of temperature, steam is through rectifying column 6, overhead condenser 7 and prolong 8 obtain the mixture of methyl alcohol and methylcarbonate, further again extracting rectifying, distillating mixture adopts gas chromatographic analysis, and the yield of DMC is 70.1%, and distillation residue are added in the autoclave 5 again, add the polyphosphoric acid of 0.03mol simultaneously, other condition is the same, continues reaction, obtains solid components composite fertilizer ammonium phosphate 34g, adopt gas chromatographic analysis, the yield of DMC is 68.5%.
Use the polyphosphoric acid of 0.5mol urea, 1mol methyl alcohol and 0.25mol, use N instead
2Replaced C O
2Purge, preset 1MPa pressure, temperature of reaction is 90 ℃, reacts 10 hours, and all the other conditions adopt gas chromatographic analysis with embodiment 1, and the yield of DMC is 63.5%.
Embodiment 3
Adopt operate continuously, the polyphosphoric acid of urea, 5.5mol methyl alcohol and the 7.5mol of 0.5mol is joined in the autoclave 5, use CO
2Purge and preset 0.4MPa pressure, in 40 minutes, temperature is elevated to 100 ℃, under agitation total reflux reaction is 1 hour, squeeze into urea with ram pump 4 with the flow of 2ml/min then through preheating, methyl alcohol and polyphosphoric acid mixture, consisting of of they: urea 4%, methyl alcohol 95.8%, polyphosphoric acid 0.2% (mass ratio), reaction mixture flows out reaction system with the speed of 1.5～2ml/min simultaneously, operated again successive reaction 10 hours with this, stop reinforced and discharging, continue under total reflux, to react 2～3 hours, adopt gas chromatographic analysis, last DMC yield is 80.4%.
Embodiment 4
Use the polyphosphoric acid of 1mol urea, 5mol methyl alcohol and 1mol, use N
2Purge, preset 0.8MPa pressure, temperature of reaction is 120 ℃, reacts 6 hours, and all the other conditions adopt gas chromatographic analysis with embodiment 1, and the yield of DMC is 65.5%.
Use the polyphosphoric acid of 1mol urea, 8mol methyl alcohol and 1.2mol, use CO
2Purge, preset 0.5MPa pressure, temperature of reaction is 140 ℃, reacts 10 hours, and all the other conditions adopt gas chromatographic analysis with embodiment 1, and the yield of DMC is 63.5%.
Claims (3)
1. the method for a polyphosphoric acid catalyzed dimethyl carbonate synthesizing, it is characterized in that, with urea, methyl alcohol and polyphosphoric acid add in the reactor, the mol ratio of urea and methyl alcohol is 1: 2～11, the mol ratio of polyphosphoric acid and urea is 0.5～1.5: 1, with carbonic acid gas or nitrogen purging and set pressure is 0.4～1.0MPa, heat to 90 ℃～150 ℃ then, behind the stirring reaction 1～10 hour, temperature of reaction is reduced to room temperature, pressure release, reaction mixture obtains liquid phase and solid components respectively through centrifugation, is to distill under 60 ℃～80 ℃ conditions liquid phase component at normal pressure and temperature, obtains the mixture of methyl alcohol and methylcarbonate, further separation and purification finally obtains methylcarbonate again.
2. according to the described synthetic method of claim 1, it is characterized in that described polyphosphoric acid is by P
2O
5With percentage concentration be 85% H
3PO
4Prepared in reaction obtains H under 40 ℃～100 ℃ temperature
3PO
4With P
2O
5Mass ratio be 2.0: 1.0.
3. the method for a polyphosphoric acid catalyzed dimethyl carbonate synthesizing is characterized in that, at first is 85% H with the 100g percentage concentration
3PO
4Add 50g P
2O
5, in the reaction 3～4 hours down of 40 ℃～100 ℃ of temperature, obtain polyphosphoric acid, after the polyphosphoric acid of urea, 3mol methyl alcohol and the 0.1mol of 0.5mol is mixed in the mixed solution storage tank, squeeze in the autoclave with ram pump, use CO
2Purging also, set pressure is 0.6MPa, in 40 minutes, temperature is elevated to 150 ℃, reaction is 3 hours under agitator stirs, reduce to room temperature fast, reaction mixture obtains liquid phase and solid components respectively through centrifugation, with liquid phase component under normal pressure, 64 ℃～80 ℃ distillations of temperature, steam obtains the mixture of methyl alcohol and methylcarbonate through rectifying column, overhead condenser and prolong, and further separation and purification finally obtains methylcarbonate again.
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| CN114539516A (en) * | 2022-03-09 | 2022-05-27 | 长江师范学院 | Method for preparing PET (polyethylene terephthalate) by using nonmetal catalyst |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2834799A (en) * | 1955-11-18 | 1958-05-13 | Frank J Sowa | Methods of producing esters of carbamic and carbonic acids |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2834799A (en) * | 1955-11-18 | 1958-05-13 | Frank J Sowa | Methods of producing esters of carbamic and carbonic acids |
Non-Patent Citations (1)
| Title |
|---|
| 合成碳酸二甲酯的技术进展 潘鹤林，浙江化工，第30卷第1期 1999 * |
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