CN102228840A - Preparation method of load type Fe2O3 catalyst and method for synthesizing dimethyl carbonate (DMC) by using load type Fe2O3 catalyst - Google Patents
Preparation method of load type Fe2O3 catalyst and method for synthesizing dimethyl carbonate (DMC) by using load type Fe2O3 catalyst Download PDFInfo
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Abstract
The invention provides a preparation method of a load type Fe2O3 catalyst and a method for synthesizing dimethyl carbonate (DMC) by using the load type Fe2O3 catalyst, relating to a preparation method of a catalyst and a method for synthesizing the dimethyl carbonate by using the catalyst. The invention solves the problems of low yield, poor selectivity, difficulty in separation of the catalyst, incapacity of recycling, high cost, large toxicity, equipment corrosion and need of adding a promoter or cocatalyst in the traditional method for synthesizing the DMC by using a urea alcoholysis process. The catalyst is prepared by the steps of: dipping with a molecular sieve and an iron salt solution, suction-filtering, washing, drying and roasting. Methanol, urea and the load type Fe2O3 catalyst are added in a high-pressure stainless steel agitated reactor for reaction and filtration to synthesize the DMC. The catalyst has the advantages of simple preparation method, no toxicity, easiness in separation, low price, no corrosion to the agitated reactor, capacity of being repeatedly used, and no need of adding a promoter or cocatalyst. By applying the catalyst provided by the invention, the yield of the DMC can reach 36.7 percent, and the selectivity of the DMC can reach 97.4 percent.
Description
Technical field
The present invention relates to a kind of Preparation of catalysts method and with the method for this catalyst Synthesis of dimethyl carbonate.
Background technology
Dimethyl carbonate (DMC) is a kind of water white liquid, toxicity and absolute ethyl alcohol are suitable, 1992, DMC is " non-toxic chemicals " in the Europe registration, belong to nontoxic or little chemical product that poisons, be a kind of have multiple reactivity, environmental friendliness, broad-spectrum basic Organic Chemicals, be described as " the new foundation stone " of 21 century organic synthesis.Simultaneously because it contains CH
3-, CH
3O-, CO-,-multiple functional groups such as CO-, thereby have good reactivity worth, can react with phenol, alcohol, amine, hydrazine, ester type compound under the low temperature.It can replace phosgene (COCl at numerous areas comprehensively
2), dimethyl suflfate (DMS), chloromethanes (CH
3Cl) and reactions such as severe toxicity such as methylchloroformate or carcinogenic substance carry out carbonylation, methylate, methoxylation and ester exchange generate many important chemical products with special nature, can be used to synthetic multiple downstream product good, that have high added value simultaneously.In addition, obtain extensive use in other multiple fields, and DMC has demonstrated the good momentum of development of alternative methyl tertiary butyl ether(MTBE) (MTBE).Its development will be played huge impetus to methanol chemistry, Coal Chemical Industry, the chlorination worker of China.
Nowadays DMC production has been experienced a plurality of stages, develops so far, and the preparation method is varied.Along with the pay attention to day by day of countries in the world environmental pollution, the production of DMC and application have huge attraction and market potential.In recent years, the research of synthetic DMC has obtained domestic and international researcher's extensive concern and research, synthetic route is just towards oversimplifying, do not have the future development that poisons with pollution-freeization, both adapt to strategy of sustainable development trend, satisfied the Green Chemistry requirement, have again economic feasibility, formed the serial process for cleanly preparing take DMC as core.Wherein, alcoholysis of urea is the novel artistic route of the alternative phosgenation of the exploitation nineties in 20th century, though start late, development rapidly.It has that wide material sources, raw material are cheap and easy to get, do not have H in the course of reaction
2O generates, has avoided CH
3OH-DMC-H
2The advantages such as separation problem of O complex system, and unique accessory substance NH
3, and if the urea coproduction, also can be recycled, realize easily reducing production costs industrialization, especially attractive to existing chemical fertilizer factory exploitation downstream product, be a kind of very ideal environment close friend's green chemical industry synthesis technique.To be developed fully in significant period of time from now on, the research that strengthens synthetic route has theory and realistic meaning.
But, have in the method for the synthetic DMC of existing alcoholysis of urea that productive rate is low, the difficult separation of catalyst, selectively low, can not reuse, expensive, toxicity big, etching apparatus, need to add the problems such as co-catalyst or co-catalyst.
Summary of the invention
The objective of the invention is for the method that solves the synthetic DMC of existing alcoholysis of urea exists that productive rate is low, poor selectivity, catalyst are difficultly separated, can not reuse, expensive, toxicity big, etching apparatus, need the problem of adding co-catalyst or co-catalyst, and a kind of support type Fe is provided
2O
3The preparation method of catalyst and use support type Fe
2O
3The method of catalyst Synthesis of dimethyl carbonate.
Support type Fe
2O
3The preparation method of catalyst is as follows: one, 0.5g～5g molecular sieve is flooded 8h～16h in the iron salt solutions of 10ml～60ml, then suction filtration, washing; Two, will in 100 ℃ baking oven, dry through the molecular sieve that step 1 is processed, and then in 300 ℃～600 ℃ Muffle furnace roasting 1h～4h, namely get support type Fe
2O
3Catalyst; Molecular sieve described in the step 1 is SBA-15 molecular sieve, ZSM-5 molecular sieve, ZSM-22 molecular sieve, MCM-49 molecular sieve, HMCM-49 molecular sieve, MCM-41 molecular sieve or HMCM-41 molecular sieve; The concentration of iron salt solutions described in the step 1 is 0.025mol/L～0.50mol/L, and described molysite is ferric nitrate or iron chloride.
Use support type Fe
2O
3The method of catalyst Synthesis of dimethyl carbonate is as follows: one, with methyl alcohol, urea and support type Fe
2O
3Catalyst joins in the high pressure stainless steel cauldron, with nitrogen blowing emptying air, reacts 4h～12h then under 130 ℃～220 ℃, high pressure stainless steel cauldron agitator speed are the condition of 500rpm after the sealing; Two, the product normal pressure with the step 1 gained filters, and namely gets dimethyl carbonate; The mol ratio of methyl alcohol described in the step 1 and urea is 20～200: 1, support type Fe in the step 1
2O
3The input amount of catalyst is support type Fe
2O
30.2%～7% of catalyst, methyl alcohol and urea gross mass.
Support type Fe of the present invention
2O
3Simple, the avirulence of catalyst preparation is easy to separate, and is cheap, and the high pressure stainless steel cauldron is not had corrosion, reusable, need not to add co-catalyst or co-catalyst, support type Fe of the present invention
2O
3Catalyst effect and selective good, the productive rate of dimethyl carbonate can reach 36.7%, selectively can reach 97.4%.
Description of drawings
Fig. 1 is the gas chromatogram of the specific embodiment 30 products obtained therefroms; Fig. 2 is the gas chromatogram of the specific embodiment 33 products obtained therefroms.
The specific embodiment
Technical solution of the present invention is not limited to the following cited specific embodiment, also comprises any combination between each specific embodiment.
The specific embodiment one: support type Fe in the present embodiment
2O
3The preparation method of catalyst is as follows: one, 0.5g～5g molecular sieve is flooded 8h～16h in the iron salt solutions of 10ml～60ml, then suction filtration, washing; Two, will in 100 ℃ baking oven, dry through the molecular sieve that step 1 is processed, and then in 300 ℃～600 ℃ Muffle furnace roasting 1h～4h, namely get support type Fe
2O
3Catalyst; Molecular sieve described in the step 1 is SBA-15 molecular sieve, ZSM-5 molecular sieve, ZSM-22 molecular sieve, MCM-49 molecular sieve, HMCM-49 molecular sieve, MCM-41 molecular sieve or HMCM-41 molecular sieve; The concentration of iron salt solutions described in the step 1 is 0.025mol/L～0.50mol/L, and described molysite is ferric nitrate or iron chloride.
The HMCM-49 molecular sieve is with MCM-49 molecular sieve and NH in the present embodiment
4NO
3Solution exchange system gets, and the HMCM-41 molecular sieve is by MCM-41 molecular sieve and NH
4NO
3Solution exchange system gets.
The specific embodiment two: present embodiment and the specific embodiment one are different is that the amount of iron salt solutions described in the step 1 is 20ml～40ml.Other is identical with the specific embodiment one.
The specific embodiment three: present embodiment and the specific embodiment one are different is that the amount of iron salt solutions described in the step 1 is 30ml.Other is identical with the specific embodiment one.
The specific embodiment four: what present embodiment and the specific embodiment one were different is that dip time described in the step 1 is 9h～14h.Other is identical with the specific embodiment one.
The specific embodiment five: what present embodiment and the specific embodiment one were different is that dip time described in the step 1 is 12h.Other is identical with the specific embodiment one.
The specific embodiment six: what present embodiment and the specific embodiment one were different is in the step 1 0.8g～1.5g molecular sieve to be flooded in iron salt solutions.Other is identical with the specific embodiment one.
The specific embodiment seven: what present embodiment and the specific embodiment one were different is in the step 1 1g molecular sieve to be flooded in iron salt solutions.Other is identical with the specific embodiment one.
The specific embodiment eight: what present embodiment and the specific embodiment one were different is that sintering temperature described in the step 2 is 400 ℃～500 ℃.Other is identical with the specific embodiment one.
The specific embodiment nine: what present embodiment and the specific embodiment one were different is that sintering temperature described in the step 2 is 450 ℃.Other is identical with the specific embodiment one.
The specific embodiment ten: what present embodiment and the specific embodiment one were different is that roasting time described in the step 2 is 2h.Other is identical with the specific embodiment one.
The specific embodiment 11: support type Fe in the present embodiment
2O
3The preparation method of catalyst is as follows: one, the 0.5g molecular sieve is flooded 8h in the iron salt solutions of 10ml, then suction filtration, washing; Two, will in 100 ℃ baking oven, dry through the molecular sieve that step 1 is processed, and then in 300 ℃ Muffle furnace roasting 1h, namely get support type Fe
2O
3/ SBA-15 catalyst; Molecular sieve described in the step 1 is the SBA-15 molecular sieve; The concentration of iron salt solutions described in the step 1 is 0.025mol/L, and described molysite is ferric nitrate.
The specific embodiment 12: support type Fe in the present embodiment
2O
3The preparation method of catalyst is as follows: one, the 0.7g molecular sieve is flooded 9h in the iron salt solutions of 15ml, then suction filtration, washing; Two, will in 100 ℃ baking oven, dry through the molecular sieve that step 1 is processed, and then in 320 ℃ Muffle furnace roasting 1.5h, namely get support type Fe
2O
3/ ZSM-5 catalyst; Molecular sieve described in the step 1 is ZSM-5 molecular sieve; The concentration of iron salt solutions described in the step 1 is 0.028mol/L, and described molysite is ferric nitrate.
The specific embodiment 13: support type Fe in the present embodiment
2O
3The preparation method of catalyst is as follows: one, the 0.8g molecular sieve is flooded 10h in the iron salt solutions of 18ml, then suction filtration, washing; Two, will in 100 ℃ baking oven, dry through the molecular sieve that step 1 is processed, and then in 350 ℃ Muffle furnace roasting 2h, namely get support type Fe
2O
3/ ZSM-22 catalyst; Molecular sieve described in the step 1 is the ZSM-22 molecular sieve; The concentration of iron salt solutions described in the step 1 is 0.03mol/L, and described molysite is ferric nitrate.
The specific embodiment 14: support type Fe in the present embodiment
2O
3The preparation method of catalyst is as follows: one, the 0.9g molecular sieve is flooded 11h in the iron salt solutions of 20ml, then suction filtration, washing; Two, will in 100 ℃ baking oven, dry through the molecular sieve that step 1 is processed, and then in 380 ℃ Muffle furnace roasting 2.5h, namely get support type Fe
2O
3/ MCM-49 catalyst; Molecular sieve described in the step 1 is the MCM-49 molecular sieve; The concentration of iron salt solutions described in the step 1 is 0.035mol/L, and described molysite is iron chloride.
The specific embodiment 15: support type Fe in the present embodiment
2O
3The preparation method of catalyst is as follows: one, the 1g molecular sieve is flooded 12h in the iron salt solutions of 25ml, then suction filtration, washing; Two, will in 100 ℃ baking oven, dry through the molecular sieve that step 1 is processed, and then in 400 ℃ Muffle furnace roasting 3h, namely get support type Fe
2O
3/ HMCM-49 catalyst; Molecular sieve described in the step 1 is the HMCM-49 molecular sieve; The concentration of iron salt solutions described in the step 1 is 0.10mol/L, and described molysite is iron chloride.
The specific embodiment 16: support type Fe in the present embodiment
2O
3The preparation method of catalyst is as follows: one, the 1.2g molecular sieve is flooded 13h in the iron salt solutions of 30ml, then suction filtration, washing; Two, will in 100 ℃ baking oven, dry through the molecular sieve that step 1 is processed, and then in 450 ℃ Muffle furnace roasting 3.5h, namely get support type Fe
2O
3/ MCM-41 catalyst; Molecular sieve described in the step 1 is the MCM-41 molecular sieve; The concentration of iron salt solutions described in the step 1 is 0.2mol/L, and described molysite is iron chloride.
The specific embodiment 17: support type Fe in the present embodiment
2O
3The preparation method of catalyst is as follows: one, the 1.5g molecular sieve is flooded 14h in the iron salt solutions of 35ml, then suction filtration, washing; Two, will in 100 ℃ baking oven, dry through the molecular sieve that step 1 is processed, and then in 480 ℃ Muffle furnace roasting 1h, namely get support type Fe
2O
3/ HMCM-41 catalyst; Molecular sieve described in the step 1 is the HMCM-41 molecular sieve; The concentration of iron salt solutions described in the step 1 is 0.25mol/L, and described molysite is ferric nitrate.
The specific embodiment 18: support type Fe in the present embodiment
2O
3The preparation method of catalyst is as follows: one, the 1.6g molecular sieve is flooded 15h in the iron salt solutions of 38ml, then suction filtration, washing; Two, will in 100 ℃ baking oven, dry through the molecular sieve that step 1 is processed, and then in 500 ℃ Muffle furnace roasting 1.5h, namely get support type Fe
2O
3/ SBA-15 catalyst; Molecular sieve described in the step 1 is molecular sieve; The concentration of iron salt solutions described in the step 1 is 0.30mol/L, and described molysite is iron chloride.
The specific embodiment 19: support type Fe in the present embodiment
2O
3The preparation method of catalyst is as follows: one, the 1.7g molecular sieve is flooded 16h in the iron salt solutions of 40ml, then suction filtration, washing; Two, will in 100 ℃ baking oven, dry through the molecular sieve that step 1 is processed, and then in 550 ℃ Muffle furnace roasting 1.9h, namely get support type Fe
2O
3/ ZSM-5 catalyst; Molecular sieve described in the step 1 is ZSM-5 molecular sieve; The concentration of iron salt solutions described in the step 1 is 0.35mol/L, and described molysite is iron chloride.
The specific embodiment 20: support type Fe in the present embodiment
2O
3The preparation method of catalyst is as follows: one, the 2g molecular sieve is flooded 8h in the iron salt solutions of 50ml, then suction filtration, washing; Two, will in 100 ℃ baking oven, dry through the molecular sieve that step 1 is processed, and then in 600 ℃ Muffle furnace roasting 4h, namely get support type Fe
2O
3/ HMCM-41 catalyst; Molecular sieve described in the step 1 is the HMCM-41 molecular sieve; The concentration of iron salt solutions described in the step 1 is 0.40mol/L, and described molysite is ferric nitrate.
The specific embodiment 21: use support type Fe in the present embodiment
2O
3The method of catalyst Synthesis of dimethyl carbonate is as follows: one, with methyl alcohol, urea and support type Fe
2O
3Catalyst joins in the high pressure stainless steel cauldron, with nitrogen blowing emptying air, reacts 4h～12h then under 130 ℃～220 ℃, high pressure stainless steel cauldron agitator speed are the condition of 500rpm after the sealing; Two, the product normal pressure with the step 1 gained filters, and namely gets dimethyl carbonate; The mol ratio of methyl alcohol described in the step 1 and urea is 20～200: 1, support type Fe in the step 1
2O
3The input amount of catalyst is support type Fe
2O
30.2%～7% of catalyst, methyl alcohol and urea gross mass.
Used high pressure stainless steel cauldron is the WDF-0.5 type reactor that Weihai automatic control reactor Co., Ltd produces in the present embodiment.
The dimethyl carbonate that present embodiment is obtained is through the gas chromatograph analysis, chromatographic condition: the GC9890A type gas chromatograph that Ling Hua Instr Ltd. in Shanghai produces; Chromatographic column is the capillary column of diameter 0.32mm, long 30m; The injector temperature is 300 ℃, and detector temperature is 320 ℃; Hydrogen flame ionization detector; Pure nitrogen gas is done carrier gas, and the nitrogen column cap is pressed and is 10psi; Air pump is the SGK-2LB low noise air pump that Beijing Orient elite garden Science and Technology Ltd. produces; Hydrogen generator is the SGH-300 High Purity Hydrogen generator that Beijing Orient elite garden Science and Technology Ltd. produces; After lighting, signal is transferred to about 32.Heating schedule is set to: per minute heats up 2 ℃ from 54 ℃ to 70 ℃, and per minute heats up 20 ℃ from 70 ℃ to 260 ℃, when being raised to 260 ℃, continues retention time 5min; Maximum level is made as 1000mv in the parameter, and minimum levels is made as-15mv.Each sample size is 0.5 μ m.
The specific embodiment 22: what present embodiment and the specific embodiment 21 were different is to react under 150 ℃～200 ℃ condition in the step 1.Other is identical with the specific embodiment 21.
The specific embodiment 23: what present embodiment and the specific embodiment 21 were different is to react 6h～10h in the step 1.Other is identical with the specific embodiment 21.
The specific embodiment 24: present embodiment and the specific embodiment 21 are different is that the mol ratio of methyl alcohol described in the step 2 and urea is 100: 1.Other is identical with the specific embodiment 21.
The specific embodiment 25: that present embodiment and the specific embodiment 21 are different is the Fe of support type described in the step 2
2O
3The input amount of catalyst is support type Fe
2O
31% of catalyst, methyl alcohol and urea gross mass.Other is identical with the specific embodiment 21.
The specific embodiment 26: use support type Fe in the present embodiment
2O
3The method of catalyst Synthesis of dimethyl carbonate is as follows: one, with methyl alcohol, urea and support type Fe
2O
3Catalyst joins in the high pressure stainless steel cauldron, use nitrogen blowing emptying air after the sealing, under being the condition of 500rpm, 170 ℃, high pressure stainless steel cauldron agitator speed react 6h then, after reaction finishes, treat that the high pressure stainless steel cauldron is cooled to room temperature, turn on after the gas outlet puts pressure, the opening high pressure stainless steel cauldron gets product; Two, the product normal pressure with the step 1 gained filters, and namely gets dimethyl carbonate; The mol ratio of methyl alcohol described in the step 1 and urea is 100: 1, support type Fe in the step 1
2O
3The input amount of catalyst is support type Fe
2O
33% of catalyst, methyl alcohol and urea gross mass.
Support type Fe in the present embodiment
2O
3Catalyst is the Fe of the specific embodiment 18 preparations
2O
3/ SBA-15 catalyst.
(GC and GC-MS instrument detecting), calculating after testing, the productive rate of present embodiment Synthesis of dimethyl carbonate is 10.0%, selectivity is 95.1%.
The specific embodiment 27: use support type Fe in the present embodiment
2O
3The method of catalyst Synthesis of dimethyl carbonate is as follows: one, with methyl alcohol, urea and support type Fe
2O
3Catalyst joins in the high pressure stainless steel cauldron, use nitrogen blowing emptying air after the sealing, under being the condition of 500rpm, 150 ℃, high pressure stainless steel cauldron agitator speed react 8h then, after reaction finishes, treat that the high pressure stainless steel cauldron is cooled to room temperature, turn on after the gas outlet puts pressure, the opening high pressure stainless steel cauldron gets product; Two, the product normal pressure with the step 1 gained filters, and namely gets dimethyl carbonate; The mol ratio of methyl alcohol described in the step 1 and urea is 100: 1, support type Fe in the step 1
2O
3The input amount of catalyst is support type Fe
2O
30.2% of catalyst, methyl alcohol and urea gross mass.
Support type Fe in the present embodiment
2O
3Catalyst is the Fe of the specific embodiment 12 preparations
2O
3/ ZSM-5 catalyst.
(GC and GC-MS instrument detecting), calculating after testing, the productive rate of present embodiment Synthesis of dimethyl carbonate is 8.9%, selectivity is 94.4%.
The specific embodiment 28: use support type Fe in the present embodiment
2O
3The method of catalyst Synthesis of dimethyl carbonate is as follows: one, with methyl alcohol, urea and support type Fe
2O
3Catalyst joins in the high pressure stainless steel cauldron, use nitrogen blowing emptying air after the sealing, under being the condition of 500rpm, 170 ℃, high pressure stainless steel cauldron agitator speed react 12h then, after reaction finishes, treat that the high pressure stainless steel cauldron is cooled to room temperature, turn on after the gas outlet puts pressure, the opening high pressure stainless steel cauldron gets product; Two, the product normal pressure with the step 1 gained filters, and namely gets dimethyl carbonate; The mol ratio of methyl alcohol described in the step 1 and urea is 120: 1, support type Fe in the step 1
2O
3The input amount of catalyst is support type Fe
2O
30.3% of catalyst, methyl alcohol and urea gross mass.
Support type Fe in the present embodiment
2O
3Catalyst is the Fe of the specific embodiment 13 preparations
2O
3/ ZSM-22 catalyst.
(GC and GC-MS instrument detecting), calculating after testing, the productive rate of present embodiment Synthesis of dimethyl carbonate is 10.0%, selectivity is 95.7%.
The specific embodiment 29: use support type Fe in the present embodiment
2O
3The method of catalyst Synthesis of dimethyl carbonate is as follows: one, with methyl alcohol, urea and support type Fe
2O
3Catalyst joins in the high pressure stainless steel cauldron, use nitrogen blowing emptying air after the sealing, under being the condition of 500rpm, 170 ℃, high pressure stainless steel cauldron agitator speed react 6h then, after reaction finishes, treat that the high pressure stainless steel cauldron is cooled to room temperature, turn on after the gas outlet puts pressure, the opening high pressure stainless steel cauldron gets product; Two, the product normal pressure with the step 1 gained filters, and namely gets dimethyl carbonate; The mol ratio of methyl alcohol described in the step 1 and urea is 100: 1, support type Fe in the step 1
2O
3The input amount of catalyst is support type Fe
2O
30.3% of catalyst, methyl alcohol and urea gross mass.
Support type Fe in the present embodiment
2O
3Catalyst is the Fe of the specific embodiment 14 preparations
2O
3/ MCM-49 catalyst.
(GC and GC-MS instrument detecting), calculating after testing, the productive rate of present embodiment Synthesis of dimethyl carbonate is 20.5%, selectivity is 97.2%.
The specific embodiment 30: use support type Fe in the present embodiment
2O
3The method of catalyst Synthesis of dimethyl carbonate is as follows: one, with methyl alcohol, urea and support type Fe
2O
3Catalyst joins in the high pressure stainless steel cauldron, use nitrogen blowing emptying air after the sealing, under being the condition of 500rpm, 180 ℃, high pressure stainless steel cauldron agitator speed react 8h then, after reaction finishes, treat that the high pressure stainless steel cauldron is cooled to room temperature, turn on after the gas outlet puts pressure, the opening high pressure stainless steel cauldron gets product; Two, the product normal pressure with the step 1 gained filters, and namely gets dimethyl carbonate; The mol ratio of methyl alcohol described in the step 1 and urea is 160: 1, support type Fe in the step 1
2O
3The input amount of catalyst is support type Fe
2O
30.3% of catalyst, methyl alcohol and urea gross mass.
Support type Fe in the present embodiment
2O
3Catalyst is the Fe of the specific embodiment 15 preparations
2O
3/ HMCM-49 catalyst.
(GC and GC-MS instrument detecting), calculating after testing, the productive rate of present embodiment Synthesis of dimethyl carbonate is 36.7%, selectivity is 97.4%.
As can be seen from Figure 1, retention time is that the material about 1.6min is a liquid organic reactant methyl alcohol in the present embodiment, and retention time is that the material about 2.5min is the product methyl-carbonate (DMC) of gained, and the two retention time differs about 0.9min.Simultaneously as shown in Figure 1, this chromatogram can not detect the chromatographic peak of SOLID ORGANIC reactant urea.
The specific embodiment 31: use support type Fe in the present embodiment
2O
3The method of catalyst Synthesis of dimethyl carbonate is as follows: one, with methyl alcohol, urea and support type Fe
2O
3Catalyst joins in the high pressure stainless steel cauldron, use nitrogen blowing emptying air after the sealing, under being the condition of 500rpm, 180 ℃, high pressure stainless steel cauldron agitator speed react 6h then, after reaction finishes, treat that the high pressure stainless steel cauldron is cooled to room temperature, turn on after the gas outlet puts pressure, the opening high pressure stainless steel cauldron gets product; Two, the product normal pressure with the step 1 gained filters, and namely gets dimethyl carbonate; The mol ratio of methyl alcohol described in the step 1 and urea is 140: 1, support type Fe in the step 1
2O
3The input amount of catalyst is support type Fe
2O
30.4% of catalyst, methyl alcohol and urea gross mass.
Support type Fe in the present embodiment
2O
3Catalyst is the Fe of the specific embodiment 16 preparations
2O
3/ MCM-41 catalyst.
(GC and GC-MS instrument detecting), calculating after testing, the productive rate of present embodiment Synthesis of dimethyl carbonate is 19.0%, selectivity is 96.5%.
The specific embodiment 32: use support type Fe in the present embodiment
2O
3The method of catalyst Synthesis of dimethyl carbonate is as follows: one, with methyl alcohol, urea and support type Fe
2O
3Catalyst joins in the high pressure stainless steel cauldron, use nitrogen blowing emptying air after the sealing, under being the condition of 500rpm, 170 ℃, high pressure stainless steel cauldron agitator speed react 10h then, after reaction finishes, treat that the high pressure stainless steel cauldron is cooled to room temperature, turn on after the gas outlet puts pressure, the opening high pressure stainless steel cauldron gets product; Two, the product normal pressure with the step 1 gained filters, and namely gets dimethyl carbonate; The mol ratio of methyl alcohol described in the step 1 and urea is 180: 1, support type Fe in the step 1
2O
3The input amount of catalyst is support type Fe
2O
30.5% of catalyst, methyl alcohol and urea gross mass.
Support type Fe in the present embodiment
2O
3Catalyst is the Fe of the specific embodiment 17 preparations
2O
3/ HMCM-41 catalyst.
(GC and GC-MS detect), calculating after testing, the productive rate of present embodiment Synthesis of dimethyl carbonate is 25.3%, selectivity is 96.9%.
The specific embodiment 33: what present embodiment and the specific embodiment 21 were different is: without reaction, with graduated cylinder measure with the specific embodiment 21 in the methyl alcohol same amount, draw a certain amount of dimethyl carbonate DMC (analyzing pure) with 1ml glue head dropper, the two is joined in the conical flask, fully vibration, it is mixed, detect with GC and GC-MS then.Detection mode, parameter are identical with the specific embodiment 21.
Test the standard sample of the product DMC of liquid organic reactant methyl alcohol in the present embodiment and gained with this understanding, the gas chromatogram of present embodiment products obtained therefrom as shown in Figure 2.As can be seen from Figure 2, retention time is that the material about 1.6min is a liquid organic reactant methyl alcohol in this experiment, and retention time is that the material about 2.5min is the product DMC of gained, and the two retention time differs about 0.9min.Simultaneously as shown in Figure 2, this chromatogram can not detect the chromatographic peak of SOLID ORGANIC reactant urea.
Claims (10)
1. support type Fe
2O
3The preparation method of catalyst is characterized in that support type Fe
2O
3The preparation method of catalyst is as follows: one, 0.5g～5g molecular sieve is flooded 8h～16h in the iron salt solutions of 10ml～60ml, then suction filtration, washing; Two, will in 100 ℃ baking oven, dry through the molecular sieve that step 1 is processed, and then in 300 ℃～600 ℃ Muffle furnace roasting 1h～4h, namely get support type Fe
2O
3Catalyst; Molecular sieve described in the step 1 is SBA-15 molecular sieve, ZSM-5 molecular sieve, ZSM-22 molecular sieve, MCM-49 molecular sieve, HMCM-49 molecular sieve, MCM-41 molecular sieve or HMCM-41 molecular sieve; The concentration of iron salt solutions described in the step 1 is 0.025mol/L～0.50mol/L, and described molysite is ferric nitrate or iron chloride.
2. according to the described support type Fe of claim 1
2O
3The preparation method of catalyst, the amount that it is characterized in that iron salt solutions described in the step 1 is 30ml.
3. according to the described support type Fe of claim 1
2O
3The preparation method of catalyst is characterized in that dip time described in the step 1 is 12h.
4. according to the described support type Fe of claim 1
2O
3The preparation method of catalyst is characterized in that sintering temperature described in the step 2 is 400 ℃～500 ℃.
5. according to the described support type Fe of claim 1
2O
3The preparation method of catalyst is characterized in that roasting time described in the step 2 is 2h.
6. with the described support type Fe of claim 1
2O
3The method of catalyst Synthesis of dimethyl carbonate is characterized in that using support type Fe
2O
3The method of catalyst Synthesis of dimethyl carbonate is as follows: one, with methyl alcohol, urea and support type Fe
2O
3Catalyst joins in the high pressure stainless steel cauldron, with nitrogen blowing emptying air, reacts 4h～12h then under 130 ℃～220 ℃, high pressure stainless steel cauldron agitator speed are the condition of 500rpm after the sealing; Two, the product normal pressure with the step 1 gained filters, and namely gets dimethyl carbonate; The mol ratio of methyl alcohol described in the step 1 and urea is 20～200: 1, support type Fe in the step 1
2O
3The input amount of catalyst is support type Fe
2O
30.2%～7% of catalyst, methyl alcohol and urea gross mass.
7. according to the described support type Fe that uses of claim 6
2O
3The method of catalyst Synthesis of dimethyl carbonate is characterized in that reacting under 150 ℃～200 ℃ condition in the step 1.
8. according to the described support type Fe that uses of claim 6
2O
3The method of catalyst Synthesis of dimethyl carbonate is characterized in that reacting in the step 1 6h～10h.
9. according to the described support type Fe that uses of claim 6
2O
3The method of catalyst Synthesis of dimethyl carbonate is characterized in that the mol ratio of methyl alcohol described in the step 2 and urea is 100: 1.
10. according to the described support type Fe that uses of claim 6
2O
3The method of catalyst Synthesis of dimethyl carbonate is characterized in that the Fe of support type described in the step 2
2O
3The input amount of catalyst is support type Fe
2O
31% of catalyst, methyl alcohol and urea gross mass.
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| CN109316903A (en) * | 2018-12-03 | 2019-02-12 | 湖南大学 | One kind being used for richness CO2The preparation method of the mesoporous solid Acid-bast-catalyst of amine aqueous solution desorption |
| CN110252274A (en) * | 2019-06-14 | 2019-09-20 | 湖北三宁碳磷基新材料产业技术研究院有限公司 | The preparation method of ester exchange synthesizing diphenyl carbonate catalyst |
| CN112275317A (en) * | 2020-11-04 | 2021-01-29 | 淮阴工学院 | Preparation of high-dispersity and high-stability metal-loaded molecular sieve catalyst applied to carbon dioxide conversion |
| CN115057777A (en) * | 2022-07-14 | 2022-09-16 | 山东德普新材料科技有限公司 | Method for directly preparing dimethyl carbonate by adopting urea alcoholysis method and application thereof |
| CN115124423A (en) * | 2022-07-14 | 2022-09-30 | 山东德普新材料科技有限公司 | Process for preparing dimethyl carbonate by urea alcoholysis method |
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| CN105251496A (en) * | 2015-09-18 | 2016-01-20 | 四川泸天化股份有限公司 | Catalyst and method preparing dimethyl carbonate by using catalyst |
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| CN108586243B (en) * | 2018-03-30 | 2021-07-16 | 昆明理工大学 | Method for indirectly synthesizing organic carbonate from carbon dioxide and organic amine |
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| CN110252274A (en) * | 2019-06-14 | 2019-09-20 | 湖北三宁碳磷基新材料产业技术研究院有限公司 | The preparation method of ester exchange synthesizing diphenyl carbonate catalyst |
| CN110252274B (en) * | 2019-06-14 | 2022-09-02 | 湖北三宁碳磷基新材料产业技术研究院有限公司 | Preparation method of catalyst for synthesizing diphenyl carbonate by ester exchange |
| CN112275317A (en) * | 2020-11-04 | 2021-01-29 | 淮阴工学院 | Preparation of high-dispersity and high-stability metal-loaded molecular sieve catalyst applied to carbon dioxide conversion |
| CN112275317B (en) * | 2020-11-04 | 2023-05-26 | 淮阴工学院 | Preparation of high-dispersity high-stability metal-loaded molecular sieve catalyst applied to carbon dioxide conversion |
| CN115057777A (en) * | 2022-07-14 | 2022-09-16 | 山东德普新材料科技有限公司 | Method for directly preparing dimethyl carbonate by adopting urea alcoholysis method and application thereof |
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