CN1226272C - Method for preparing methyl-carbonate - Google Patents
Method for preparing methyl-carbonate Download PDFInfo
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- CN1226272C CN1226272C CN 03137273 CN03137273A CN1226272C CN 1226272 C CN1226272 C CN 1226272C CN 03137273 CN03137273 CN 03137273 CN 03137273 A CN03137273 A CN 03137273A CN 1226272 C CN1226272 C CN 1226272C
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Abstract
The present invention discloses dimethyl carbonate synthesized by gas phase catalysis in which chlorine containing organic substances are added in the raw materials of carbon monoxide, oxygen gas and methanol and a separation method thereof. The separation method is azeotropic rectification using the chlorine contained organic substances as azeotrpic agents. The preparation method of the dimethyl carbonate of the present invention overcomes the disadvantages of the prior art and has the advantages of simple technique of separation processes, little device investment, convenient operation and high yield of products, and catalysts have the advantages of high activity, high stability and no need of regeneration.
Description
Technical field
The present invention relates to a kind of preparation method of methylcarbonate, specifically, relate to a kind of gas phase catalysis Synthesis of dimethyl carbonate and separation method thereof.
Background technology
Methylcarbonate be the new in recent ten years pollution that emerges less, broad-spectrum basic chemical industry raw material.Can methylate, reaction such as carbonylation, methoxylation and carbonyl methylate.It can replace methyl-sulfate, phosgene and multiple alcohol, phenol, amine, hydrazine and the ester compound of severe toxicity to react, and is widely used in medicine, agricultural chemicals, dyestuff, fine-chemical intermediate, used in electronic industry chemical, foodstuff additive, oxidation inhibitor, tensio-active agent, industrial naptha additive etc.Its effect more and more causes people's attention, is called as the green material of organic compound.
Oxidative carbonylation of methanol method be the carbon current dimethyl phthalate synthetic in research at most, the synthetic method of tool development prospect.This method is a raw material with carbon monoxide, methyl alcohol and oxygen, and without phosgene, raw material is cheap, and toxicity is little, and technology is simple, and cost is low.This method comprises liquid phase method and two kinds of technologies of vapor phase process.
J.Org.Chem has reported with CuCl among 39 (1974) 701-706
2Be catalyzer, the method for the synthetic methylcarbonate of methanol solution phase oxidation carbonylation, catalyzer has higher activity and selectivity.EP534545 (1993) and document Ind Eng Chem Prod Res Dev, 19 (1980): having reported a kind of among the 396-403 is catalyzer with CuCl, the technology of the synthetic methylcarbonate of methanol solution phase oxidation carbonylation.Temperature of reaction is 80-120 ℃, pressure 2.0-4.0Mpa, methanol conversion 11%, in the selectivity of the methylcarbonate of methyl alcohol greater than 98%.
Adopt the liquid phase method Synthesis of dimethyl carbonate, the reaction pressure height, catalyst life is short, etching apparatus, and have problems such as catalyzer and reaction system separation difficulty.
Disclose a kind of among the EP528498 (1993) with CuCl
2/ AC is the method for catalyzer gas phase Synthesis of dimethyl carbonate.At temperature 100-150 ℃, under the pressure 2.0Mpa condition, the generating rate of methylcarbonate is (5.3-5.4) * 10
-4Mol/ (g.s), selectivity 80%.Chemistry world, 2000 (4): it is carrier loaded CuCl that 195-197 has reported a kind of gac with the HPA modification
2Catalyzer.After the HPA modification, catalyst activity and selectivity all increase.120 ℃ of pressure 2.0Mpa, temperature, air speed 2000h
-1Reaction conditions under, methanol conversion is 35.4%, selectivity is 77.4%, catalyst life 24 hours.
Appl.Catal.A:General, 238 (2003): 131-139 has reported a kind of activated carbon supported PdCl
2-CuCl
2-CH
3The COOK catalyzer 152 ℃ of temperature, is a raw material with carbon monoxide, oxygen and methyl alcohol, and gas and liquid air speed are respectively 1483h
-1And 4h
-1, charging CO/O2 is 2.83 o'clock, and the space time yield of methylcarbonate is 317-361g/l.cat.h, and methanol conversion is 14.8-16.9%.React after tens hours, catalyst activity is continuous downtrending.The methanol solution of the methyl chloroacetate of employing 20% carries out pre-treatment to catalyzer, and catalyst activity and stability all increase, but after moving 30-40 hour, obvious decline still appears in catalyst activity.The document reports also and adopts the methanol solution contain 0.05% methyl chloroacetate during as liquid starting material that activity of such catalysts is lower, the life-span is shorter; In raw material, add chlorinated organics and make the product separation difficulty.
Catalyst activity is low, poor stability is to be the main drawback that catalyzer carries out the gas-phase oxidation/carbonylation Synthesis of dimethyl carbonate with the metal chloride at present, also is to achieve industrialized major obstacle.
Summary of the invention
The present invention mainly solves problems such as catalyst activity is low in the prior art, inactivation is fast, the life-span is short, need frequent regeneration, and the gas phase catalysis Synthesis of dimethyl carbonate and the azeotropic distillation separation method thereof of a kind of catalyst activity height, good stability is provided.
The preparation method of methylcarbonate provided by the invention is that employing methyl alcohol, carbon monoxide, oxygen and chlorinated organics are that raw material is with activated carbon supported PdCl
2-CuCl
2-CH
3COOK is catalyzer gas phase catalysis Synthesis of dimethyl carbonate and azeotropic distillation product separation, its processing step is: pack the mixture of catalyzer and quartz sand in the tubular reactor (1), under nitrogen gas atmosphere, the beds in the reactor is heated to 130-170 ℃; (2) the molar percentage raw material that consists of carbon monoxide 25-50%, oxygen 8-20%, methyl alcohol 40-65% and chlorinated organics 1-5% is preheated to 120-170 ℃ through preheater; (3) material that comes out of preheater enters tubular reactor from the upper end of reactor, and material gaseous phase volume air speed is 1800-8000h
-1, be that 130-170 ℃ and pressure are to react under the condition of 0.1-0.4MPa in temperature; (4) material that comes out from reactor is divided into gas-liquid two-phase through condenser condenses, and gas phase recycles, and liquid phase enters azeotropy rectification column at the middle part of azeotropy rectification column, is entrainer with the chlorinated organics in the raw material, and azeotropic distillation Tata still obtains the methylcarbonate product.
Described chlorinated organics preferentially is selected from methylene dichloride, trichloromethane, monochloroethane, ethylene dichloride, trichloroethane, trieline, tetrachloroethylene, tetracol phenixin.
Described Rectification Column's Theoretical Plate Number is the 10-15 piece, and reflux ratio is 0.8-2, and tower top temperature is 38-65 ℃, and pressure is normal pressure, and tower still temperature is 89-91 ℃, and feed entrance point is at 4-7 piece plate place.
Described activated carbon supported PdCl
2-CuCl
2-CH
3COOK Preparation of catalysts method is: a certain amount of PdCl of weighing
2, CuCl
2, CH
3COOK is dissolved in the solvent, makes mixing solutions, after treating to dissolve fully, adopts pickling process to load on the carrier active carbon.After dipping for some time, make catalyst sample through vacuum-drying in the water bath with thermostatic control.Wherein the Palladous chloride degree is 0.4-0.6%, and the cupric chloride degree is 6-10%, and the Potassium ethanoate degree is 2-6%.Catalyst particle size is the 20-40 order.
Described gaseous phase volume air speed is unit time (h), the handled unstripped gas volume of unit volume (L) catalyzer (L).
The space time yield of methylcarbonate of the present invention is 400-800g/l.cat.h.
Described space time yield is the quality (g) of unit time (h), the resulting methylcarbonate of unit volume (L) catalyzer.
Technical scheme of the present invention is compared with prior art, adds chlorinated organics in the raw material, has overcome the problem of catalyzer because of chlorion loss inactivation, and catalyst activity height, good stability need not regenerated; Simultaneously the chlorinated organics of Jia Ruing in the product separation process as entrainer, make sepn process become the azeotropic distillation sepn process, methyl alcohol, water and chlorinated organics steam with the form cat head of azeotrope, the tower still obtains pure methylcarbonate, thereby the facility investment of product separation rectifying tower is low, easy to operate, the product yield height.
Embodiment
Further specify the solution of the present invention with specific embodiment below.
Example 1
Taking by weighing 1ml is 20-40 purpose PdCl with the particle diameter that equi-volume impregnating prepares
2-CuCl
2-CH
3COOK/a.c. the quartz sand mixing of particle diameters such as catalyzer and 1ml and catalyzer, placing internal diameter is the tubular fixed-bed reactor of 8mm.Carbon monoxide 8.02ml/min, oxygen 4.02ml/min mix after preheater is heated to 150 ℃ with the methanol solution that contains ethylene dichloride 10% of 2ml/h, enter reaction bed, air speed 1800h
-1, feed composition: methyl alcohol 56.1%, carbon monoxide 27.1%, oxygen 13.6%, ethylene dichloride 3.2%, 160 ℃ of temperature of reaction, reaction pressure 0.1Mpa.Reaction product is divided into gas-liquid two-phase through condensation, records methanol conversion 18.16% through gas chromatographic analysis, methylcarbonate space time yield 445.1g/l.cat.h.Catalyzer continuously operation 150 hours is activity stabilized.
Example 2
Taking by weighing 1ml is 20-40 purpose PdCl with the particle diameter that equi-volume impregnating prepares
2-CuCl
2-CH
3COOK/a.c. the quartz sand mixing of particle diameters such as catalyzer and 1ml and catalyzer, placing internal diameter is the tubular fixed-bed reactor of 8mm.Carbon monoxide 27.3ml/min, oxygen 10.2ml/min mix after preheater is heated to 150 ℃ with the methanol solution that contains methylene dichloride 10% of 8.0ml/h, enter reaction bed, air speed 6415h
-1, feed composition: methyl alcohol 61.2%, carbon monoxide 25.1%, oxygen 9.4%, methylene dichloride 4.3%, 160 ℃ of temperature of reaction, reaction pressure 0.2Mpa.Reaction product is divided into gas-liquid two-phase through condensation, records methanol conversion 10.9% through gas chromatographic analysis, methylcarbonate space time yield 798g/l.cat.h.Catalyzer continuously operation 150 hours is activity stabilized.
Example 3
Taking by weighing 1ml is 20-40 purpose PdCl with the particle diameter that equi-volume impregnating prepares
2-CuCl
2-CH
3COOK/a.c. the quartz sand mixing of particle diameters such as catalyzer and 1ml and catalyzer, placing internal diameter is the tubular fixed-bed reactor of 8mm.Carbon monoxide 65.9ml/min, oxygen 13.2ml/min mix after preheater is heated to 150 ℃ with the methanol solution that contains trieline 6% of 6ml/h, enter reaction bed, air speed 7989h
-1, feed composition: methyl alcohol 39.5%, carbon monoxide 49.4%, oxygen 9.9%, trieline 1.1%, 170 ℃ of temperature of reaction, reaction pressure 0.3Mpa.Reaction product is divided into gas-liquid two-phase through condensation, records methanol conversion 13.6% through gas chromatographic analysis, methylcarbonate space time yield 781g/l.cat.h.Catalyzer continuously operation 150 hours is activity stabilized.
Example 4
This example is the simultaneous test of not adding chlorinated organics in the raw material, and the present invention program's effect is described.
Taking by weighing 1ml is 20-40 purpose PdCl with the particle diameter that equi-volume impregnating prepares
2-CuCl
2-CH
3COOK/a.c. the quartz sand mixing of particle diameters such as catalyzer and 1ml and catalyzer, placing internal diameter is the tubular fixed-bed reactor of 8mm.Carbon monoxide 41ml/min, oxygen 17ml/min mix after preheater is heated to 150 ℃ with the 6.6ml/h methanol solution, enter reaction bed, air speed 7168h
-1, feed composition: methyl alcohol 53.0%, carbon monoxide 34.9%, oxygen 12.1%.150 ℃ of temperature of reaction, reaction pressure 0.1Mpa.Reaction product is divided into gas-liquid two-phase through condensation, and recording methanol conversion and methylcarbonate space time yield best result through gas chromatographic analysis is not 8.5% and 560g/l.cat.h.Catalyst activity increases with the reaction times and obviously descends.After the catalyzer operation 35 hours, methanol conversion and methylcarbonate space time yield drop to 3.4% and 249g/l.cat.h respectively.
Claims (2)
1. the preparation method of a methylcarbonate is raw material, activated carbon supported PdCl with methyl alcohol, carbon monoxide, oxygen and chlorinated organics
2-CuCl
2-CH
3COOK is catalyzer gas phase catalysis Synthesis of dimethyl carbonate and azeotropic distillation product separation, it is characterized in that its processing step is: pack the mixture of catalyzer and quartz sand in the tubular reactor (1), under nitrogen gas atmosphere, the beds in the reactor is heated to 130-170 ℃; (2) the molar percentage raw material that consists of carbon monoxide 25-50%, oxygen 8-20%, methyl alcohol 40-65% and chlorinated organics 1-5% is preheated to 120-170 ℃ through preheater; (3) material that comes out of preheater enters tubular reactor from the upper end of reactor, and material gaseous phase volume air speed is 1800-8000h
-1, be that 130-170 ℃ and pressure are to react under the condition of 0.1-0.4MPa in temperature; (4) material that comes out from reactor is divided into gas-liquid two-phase through condenser condenses, and gas phase recycles, and liquid phase enters azeotropy rectification column at the middle part of azeotropy rectification column, is entrainer with the chlorinated organics in the raw material, and azeotropic distillation Tata still obtains the methylcarbonate product;
Described chlorinated organics is selected from methylene dichloride, trichloromethane, monochloroethane, ethylene dichloride, trichloroethane, trieline, tetrachloroethylene, tetracol phenixin.
2. according to the preparation method of claim 1, it is characterized in that described Rectification Column's Theoretical Plate Number is the 10-15 piece, reflux ratio is 0.8-2, and tower top temperature is 38-65 ℃, and pressure is normal pressure, and tower still temperature is 89-91 ℃, and feed entrance point is at 4-7 piece plate place.
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|---|---|---|---|
| CN 03137273 CN1226272C (en) | 2003-06-03 | 2003-06-03 | Method for preparing methyl-carbonate |
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|---|---|---|---|
| CN 03137273 CN1226272C (en) | 2003-06-03 | 2003-06-03 | Method for preparing methyl-carbonate |
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| CN101786012B (en) * | 2010-03-10 | 2012-07-25 | 河北工业大学 | Composite carrier polymetallic catalyst and preparation method thereof |
| CN101786955B (en) * | 2010-03-10 | 2013-03-27 | 河北工业大学 | Methanol gas-phase oxidation/carbonylation one-step process for synthesizing methyl carbonate |
| CN102614900B (en) * | 2012-03-08 | 2014-08-20 | 天津大学 | Mesoporous carbon-loaded catalyst for synthesizing diethyl carbonate by gas phase oxidation carbonyl of ethanol and preparation method thereof |
| WO2013164172A1 (en) * | 2012-05-02 | 2013-11-07 | Haldor Topsøe A/S | Process for the production of chemical compounds from carbon dioxide |
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