CN1394678A - Catalyst for synthesizing dimethyl carbonate and its preparation method - Google Patents
Catalyst for synthesizing dimethyl carbonate and its preparation method Download PDFInfo
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- CN1394678A CN1394678A CN 02135213 CN02135213A CN1394678A CN 1394678 A CN1394678 A CN 1394678A CN 02135213 CN02135213 CN 02135213 CN 02135213 A CN02135213 A CN 02135213A CN 1394678 A CN1394678 A CN 1394678A
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Abstract
一种合成碳酸二甲酯的催化剂重量比组成为碱土金属的可溶盐∶碱金属化合物∶载体＝0.01～0.3∶0.01～0.5∶1。采用将载体培烧1－1后按催化剂组成将载体等体积浸渍到碱土金属的可溶盐水溶液中、干燥、培烧，再将载体等体积浸渍到碱金属化合物中得到催化剂。具有制备方法简单，易操作，化剂与产物易分离，可重复使用，应条件温和，目的产物收率高的优点。The weight ratio composition of a catalyst for synthesizing dimethyl carbonate is soluble salt of alkaline earth metal:alkali metal compound:carrier=0.01-0.3:0.01-0.5:1. After the carrier is calcined for 1-1, according to the catalyst composition, the carrier is impregnated into the soluble salt solution of alkaline earth metal in equal volume, dried and calcined, and then the equal volume of the carrier is impregnated in the alkali metal compound to obtain the catalyst. The method has the advantages of simple preparation method, easy operation, easy separation of chemical agent and product, reusability, mild application conditions and high yield of target product.
Description
Affiliated field:
The invention belongs to a kind of Catalysts and its preparation method of Synthesis of dimethyl carbonate.
Background technology:
Methylcarbonate (DMC) is as a kind of hypotoxic environmental friendly product, because of it is producing performance resins, solvent, dyestuff intermediate, medicated premix, fields such as food preservatives, lubricating oil additive obtain application more and more widely and are subject to people's attention day by day.In recent years, have both at home and abroad in a large number and deliver about the production of methylcarbonate and the patent of application, and the suitability for industrialized production of existing certain scale.The industrial process of methylcarbonate mainly contains liquid phase methanol carbonylation, gas-phase methanol carbonylation method and ester-interchange method.Wherein, ester-interchange method because of its reaction conditions gentleness, technical process is simple, equipment cost is low comes into one's own day by day.Ester-interchange method mainly is by behind carbonic acid gas and oxyethane (EO) or propylene oxide (PO) reaction generation NSC 11801 (EC) or the propylene carbonate (PC), make DMC by EC or PC and methyl alcohol (MeOH) again, while by-product ethylene glycol (EG) or propylene glycol (PG), concrete reaction formula is as follows:
R＝H，CH
3
In general, the above-mentioned second step transesterify many with (Jiang Qi etc., gas chemical industry, 1997,22 (5), 1) such as alkali metal hydroxide, alkaline carbonate, alkali metal alcoholates as catalyzer.But, cause difficulty for the separation and the repeated use of catalyzer because of it is a homogeneous catalytic reaction.
Summary of the invention:
The purpose of this invention is to provide a kind of solid base catalyst from methyl alcohol and propylene carbonate or NSC 11801 Synthesis of dimethyl carbonate, this catalyzer has high reactivity and is easy to be separated from product.
The object of the present invention is achieved like this, and in two steps with the soluble salt of alkaline-earth metal, and alkali metal compound is impregnated into molecular sieve, on gac, silicon oxide, zinc oxide or the alchlor.The weight ratio of catalyzer consists of:
The soluble salt of alkaline-earth metal: alkali metal compound: carrier=0.01～0.3: 0.01～0.5: 1
The soluble salt of alkaline-earth metal is as mentioned above: magnesium nitrate, calcium acetate, nitrocalcite, strontium nitrate etc.
Alkali metal compound is as mentioned above: the carbonate of sodium, potassium, caesium, nitrate, acetate, fluorochemical and oxyhydroxide etc.
Carrier is a molecular sieve as mentioned above, gac, silicon oxide, zinc oxide or alchlor.
Preparation of catalysts method of the present invention is as follows:
With carrier in 300-1000 ℃ of following roast 1-10 hour, form the carrier incipient impregnation in the soluble salt aqueous solution of alkaline-earth metal by above-mentioned catalyzer then, after room temperature leaves standstill 2-30 hour, through 60-200 ℃ of drying,, reduce to room temperature then at 350-800 ℃ of following roast 1-10 hour, form incipient impregnation in the aqueous solution of alkali metal compound by above-mentioned catalyzer, after room temperature leaves standstill 2-30 hour,, obtained catalyzer at 300-900 ℃ of following roast 1-5 hour through 100-200 ℃ of drying.
The present invention compared with prior art has following advantage:
(1) preparation method is simple, and is easy to operate.
(2) catalyzer and product are easily separated, and be reusable.
(3) reaction conditions gentleness, purpose product yield height.
Embodiment:
Embodiment 1:
With aluminum oxide in 300 ℃ of following roasts 10 hours.Press then 0.01g magnesium nitrate/g aluminum oxide the aluminum oxide incipient impregnation in magnesium nitrate aqueous solution, after leaving standstill 2 hours, through 60 ℃ of dryings, 500 ℃ of roasts 1 hour, the system room temperature is fallen then, press 0.5g potassium hydroxide/g aluminum oxide, incipient impregnation is in potassium hydroxide aqueous solution, after leaving standstill 2 hours,, obtained catalyzer in 2 hours at 500 ℃ of roasts through 100 ℃ of dryings.Methyl alcohol, propylene carbonate and catalyzer are added in the autoclave of 75mL, propylene carbonate, methyl alcohol mol ratio are 1: 4, and catalyst levels is 3% of a raw material gross weight, under the agitation condition, is warming up to 120 ℃, 2 hours reaction times.Product is got the supernatant liquor gas chromatographic analysis through centrifugal settling.Analytical procedure is: reaction product is analyzed with the GC-920 that sea, Shanghai glad chromatogram company limited produces.Chromatographic condition is as follows: chromatographic column: external diameter 3mm, the stainless steel column of long 2m; Carrier: GDX-203 (60-80 order); Detector: thermal conductivity cell; Sampler temperature: 220 ℃; Thermal conductivity cell temperature: 220 ℃; Column temperature temperature programming: 100 ℃ of initial temperature, 7 minutes time; 20 ℃ of heat-up rate per minutes; Temperature is 200 ℃ eventually, 20 minutes time; Sample size: 1 μ L.The results are shown in Table 1.
Embodiment 2:
With the ZSM-5 molecular sieve in 500 ℃ of following roasts 4 hours.Press then 0.3g calcium acetate/g molecular sieve the molecular sieve incipient impregnation in the calcium acetate aqueous solution, after leaving standstill 15 hours, through 100 ℃ of dryings, 500 ℃ of roasts 5 hours, the system room temperature is fallen, press 0.2g salt of wormwood/g molecular sieve, incipient impregnation is in wet chemical, after leaving standstill 15 hours,, obtained catalyzer in 1 hour at 300 ℃ of roasts through 150 ℃ of dryings.Methyl alcohol, propylene carbonate and catalyzer are added in the autoclave of 75mL, propylene carbonate, methyl alcohol mol ratio are 1: 4, and catalyst levels is 3% of a raw material gross weight, under the agitation condition, is warming up to 120 ℃, 2 hours reaction times.Product is got the supernatant liquor gas chromatographic analysis through centrifugal settling.Analytical procedure is with embodiment 1.
Embodiment 3:
With gac in N
2500 ℃ of following roasts 4 hours.Press then 0.15g nitrocalcite/g gac the gac incipient impregnation in calcium nitrate aqueous solution, leave standstill 30 hours after, through 200 ℃ of dryings, at 400 ℃ in N
2The system room temperature falls in roast 10 hours, presses 0.3g saltpetre/g gac, incipient impregnation in the saltpetre aqueous solution, leave standstill 30 hours after, through 200 ℃ of dryings, at 700 ℃ in N
2Roast obtained catalyzer in 5 hours.Methyl alcohol, propylene carbonate and catalyzer are added in the autoclave of 75mL, propylene carbonate, methyl alcohol mol ratio are 1: 4, and catalyst levels is 3% of a raw material gross weight, under the agitation condition, is warming up to 120 ℃, 2 hours reaction times.Product is got the supernatant liquor gas chromatographic analysis through centrifugal settling.Analytical procedure is with embodiment 1.
Embodiment 4:
With aluminum oxide in 1000 ℃ of following roasts 1 hour.Press then 0.10g calcium acetate/g aluminum oxide the aluminum oxide incipient impregnation in the calcium acetate aqueous solution, after leaving standstill 24 hours, through 120 ℃ of dryings, 800 ℃ of roasts 2 hours, the system room temperature is fallen, press 0.35g Potassium monofluoride/g aluminum oxide, incipient impregnation is in potassium fluoride aqueous solution, after leaving standstill 24 hours,, obtained catalyzer in 2 hours at 900 ℃ of roasts through 120 ℃ of dryings.Methyl alcohol, propylene carbonate and catalyzer are added in the autoclave of 75mL, propylene carbonate, methyl alcohol mol ratio are 1: 4, and catalyst levels is 3% of a raw material gross weight, under the agitation condition, is warming up to 120 ℃, 2 hours reaction times.Product is got the supernatant liquor gas chromatographic analysis through centrifugal settling.Analytical procedure is with embodiment 1.
Embodiment 5:
With silicon oxide in 500 ℃ of following roasts 4 hours.Press then 0.20g calcium acetate/g silicon oxide the silicon oxide incipient impregnation in the calcium acetate aqueous solution, after leaving standstill 24 hours, through 120 ℃ of dryings, 350 ℃ of roasts 2 hours, the system room temperature is fallen, press 0.01g cesium hydroxide/g silicon oxide, incipient impregnation is in the cesium hydroxide aqueous solution, after leaving standstill 24 hours,, obtained catalyzer in 2 hours at 500 ℃ of roasts through 120 ℃ of dryings.Methyl alcohol, propylene carbonate and catalyzer are added in the autoclave of 75mL, propylene carbonate, methyl alcohol mol ratio are 1: 4, and catalyst levels is 3% of a raw material gross weight, under the agitation condition, is warming up to 120 ℃, 2 hours reaction times.Product is got the supernatant liquor gas chromatographic analysis through centrifugal settling.Analytical procedure is with embodiment 1.
Embodiment 6:
With zinc oxide in 500 ℃ of following roasts 4 hours.Press then 0.25g calcium acetate/g zinc oxide the zinc oxide incipient impregnation in the calcium acetate aqueous solution, after leaving standstill 24 hours, through 120 ℃ of dryings, 500 ℃ of roasts 2 hours, the system room temperature is fallen, press 0.35g sodium hydroxide/g zinc oxide, incipient impregnation is in aqueous sodium hydroxide solution, after leaving standstill 24 hours,, obtained catalyzer in 2 hours at 500 ℃ of roasts through 120 ℃ of dryings.Methyl alcohol, propylene carbonate and catalyzer are added in the autoclave of 75mL, propylene carbonate, methyl alcohol mol ratio are 1: 4, and catalyst levels is 3% of a raw material gross weight, under the agitation condition, is warming up to 120 ℃, 2 hours reaction times.Product is got the supernatant liquor gas chromatographic analysis through centrifugal settling.Analytical procedure is with embodiment 1.
Embodiment 7:
With zinc oxide in 500 ℃ of following roasts 4 hours.Press then 0.18g calcium acetate/g aluminum oxide the aluminum oxide incipient impregnation in the calcium acetate aqueous solution, after leaving standstill 24 hours, through 120 ℃ of dryings, 500 ℃ of roasts 2 hours, the system room temperature is fallen, press 0.4g cesium nitrate/g aluminum oxide, incipient impregnation is in the cesium nitrate aqueous solution, after leaving standstill 24 hours,, obtained catalyzer in 2 hours at 500 ℃ of roasts through 120 ℃ of dryings.Methyl alcohol, propylene carbonate and catalyzer are added in the autoclave of 75mL, propylene carbonate, methyl alcohol mol ratio are 1: 4, and catalyst levels is 3% of a raw material gross weight, under the agitation condition, is warming up to 120 ℃, 2 hours reaction times.Product is got the supernatant liquor gas chromatographic analysis through centrifugal settling.Analytical procedure is with embodiment 1.
Embodiment 8:
With aluminum oxide in 500 ℃ of following roasts 6 hours.Press then 0.08g strontium nitrate/g aluminum oxide the aluminum oxide incipient impregnation in the strontium nitrate aqueous solution, after leaving standstill 24 hours, through 120 ℃ of dryings, 500 ℃ of roasts 2 hours, the system room temperature is fallen, press 0.5g Sodium Fluoride/g aluminum oxide, incipient impregnation is in sodium fluoride aqueous solution, after leaving standstill 24 hours,, obtained catalyzer in 2 hours at 500 ℃ of roasts through 120 ℃ of dryings.Methyl alcohol, NSC 11801 and catalyzer are added in the autoclave of 75mL, NSC 11801, methyl alcohol mol ratio are 1: 4, and catalyst levels is 3% of a raw material gross weight, under the agitation condition, is warming up to 120 ℃, 2 hours reaction times.Product is got the supernatant liquor gas chromatographic analysis through centrifugal settling.Analytical procedure is with embodiment 1.
Embodiment 9:
With aluminum oxide in 500 ℃ of following roasts 4 hours.Press then 0.10g calcium acetate/g aluminum oxide the aluminum oxide incipient impregnation in the calcium acetate aqueous solution, after leaving standstill 24 hours, through 120 ℃ of dryings, 500 ℃ of roasts 2 hours, the system room temperature is fallen, press 0.15g cesium acetate/g aluminum oxide, incipient impregnation is in the cesium acetate aqueous solution, after leaving standstill 24 hours,, obtained catalyzer in 2 hours at 500 ℃ of roasts through 120 ℃ of dryings.Methyl alcohol, NSC 11801 and catalyzer are added in the autoclave of 75mL, NSC 11801, methyl alcohol mol ratio are 1: 4, and catalyst levels is 3% of a raw material gross weight, under the agitation condition, is warming up to 120 ℃, 2 hours reaction times.Product is got the supernatant liquor gas chromatographic analysis through centrifugal settling.Analytical procedure is with embodiment 1.
Table 1
| Embodiment | PC (EC) transformation efficiency (%) | DMC yield (%) | DMC selectivity (%) |
| Embodiment 1 | ?????36.2 | ????36.0 | ????99.4 |
| Embodiment 2 | ?????35.8 | ????35.4 | ????98.9 |
| Embodiment 3 | ?????32.5 | ????32.1 | ????98.8 |
| Embodiment 4 | ?????39.6 | ????39.1 | ????98.7 |
| Embodiment 5 | ?????30.8 | ????30.4 | ????98.7 |
| Embodiment 6 | ?????35.4 | ????34.7 | ????98.0 |
| Embodiment 7 | ?????40.8 | ????40.1 | ????98.2 |
| Embodiment 8 | ?????64.3 | ????63.5 | ????98.7 |
| Embodiment 9 | ?????63.3 | ????62.9 | ????99.4 |
Claims (5)
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105198744A (en) * | 2014-06-26 | 2015-12-30 | 中国石油化工股份有限公司 | Method for synthesizing dimethyl carbonate |
| CN105344341A (en) * | 2015-10-26 | 2016-02-24 | 常州大学 | Preparation method of solid catalyst used for synthesizing dimethyl carbonate |
| CN105879892A (en) * | 2016-05-27 | 2016-08-24 | 中国科学院山西煤炭化学研究所 | Solid base catalyst for synthesizing dimethyl carbonate through transesterification method and preparation method and application |
| CN107915637A (en) * | 2016-10-08 | 2018-04-17 | 中国石油化工股份有限公司 | It is used to prepare the method for dimethyl carbonate |
| CN107915635A (en) * | 2016-10-08 | 2018-04-17 | 中国石油化工股份有限公司 | The method for preparing dimethyl carbonate |
| CN109232250A (en) * | 2018-10-23 | 2019-01-18 | 山西大学 | A method of preparing dimethyl carbonate |
| CN113318698A (en) * | 2021-06-29 | 2021-08-31 | 西安热工研究院有限公司 | Alkali metal loaded ceramic catalytic filler and preparation method thereof |
| CN113769770A (en) * | 2020-06-09 | 2021-12-10 | 中国科学院成都有机化学有限公司 | Preparation method of catalyst for synthesizing dimethyl carbonate through ester exchange, catalyst and application |
-
2002
- 2002-06-17 CN CNB021352135A patent/CN1136966C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105198744A (en) * | 2014-06-26 | 2015-12-30 | 中国石油化工股份有限公司 | Method for synthesizing dimethyl carbonate |
| CN105198744B (en) * | 2014-06-26 | 2017-03-29 | 中国石油化工股份有限公司 | A kind of method of Synthesis of dimethyl carbonate |
| CN105344341A (en) * | 2015-10-26 | 2016-02-24 | 常州大学 | Preparation method of solid catalyst used for synthesizing dimethyl carbonate |
| CN105879892A (en) * | 2016-05-27 | 2016-08-24 | 中国科学院山西煤炭化学研究所 | Solid base catalyst for synthesizing dimethyl carbonate through transesterification method and preparation method and application |
| CN107915637A (en) * | 2016-10-08 | 2018-04-17 | 中国石油化工股份有限公司 | It is used to prepare the method for dimethyl carbonate |
| CN107915635A (en) * | 2016-10-08 | 2018-04-17 | 中国石油化工股份有限公司 | The method for preparing dimethyl carbonate |
| CN107915637B (en) * | 2016-10-08 | 2020-03-31 | 中国石油化工股份有限公司 | Method for producing dimethyl carbonate |
| CN107915635B (en) * | 2016-10-08 | 2020-04-17 | 中国石油化工股份有限公司 | Method for preparing dimethyl carbonate |
| CN109232250A (en) * | 2018-10-23 | 2019-01-18 | 山西大学 | A method of preparing dimethyl carbonate |
| CN113769770A (en) * | 2020-06-09 | 2021-12-10 | 中国科学院成都有机化学有限公司 | Preparation method of catalyst for synthesizing dimethyl carbonate through ester exchange, catalyst and application |
| CN113769770B (en) * | 2020-06-09 | 2024-04-02 | 中国科学院成都有机化学有限公司 | Preparation method of catalyst for synthesizing dimethyl carbonate by transesterification, catalyst and application |
| CN113318698A (en) * | 2021-06-29 | 2021-08-31 | 西安热工研究院有限公司 | Alkali metal loaded ceramic catalytic filler and preparation method thereof |
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