CN114213251A - A kind of technology of catalyzing synthesis of dimethyl carbonate - Google Patents
A kind of technology of catalyzing synthesis of dimethyl carbonate Download PDFInfo
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Abstract
本发明公开一种催化合成碳酸二甲酯的工艺，包括：(1)对化学镀镍废水进行破络处理，然后加入沉淀剂，分离出沉淀后粉碎成氢氧化物粉体。(2)将所述氢氧化物粉体、二氧化硅粉、氧化钙粉、粘结剂混匀后造粒，将得到的微粒在空气气氛中煅烧，得催化剂前驱体。(3)将该催化剂前驱体置于清水中浸泡后清洗，反复执行本步骤至清洗液酸碱值恒定后取出固体产物烘干，即得多孔催化剂。(4)以所述多孔催化剂为催化剂，采用甲醇—二氧化碳直接法制备碳酸二甲酯，且在制备时在甲醇液面处插入超声振动棒，完成后分离出碳酸二甲酯。本发明的工艺采用工业废液为原料，经过改性后制备成催化剂，不仅降低了催化剂的成本，而且对甲醇的转化率得到了有效提升。The invention discloses a process for catalyzing synthesis of dimethyl carbonate, which comprises: (1) decomplexing chemical nickel-plating wastewater, adding a precipitant, separating the precipitate, and pulverizing it into hydroxide powder. (2) Mixing the hydroxide powder, silicon dioxide powder, calcium oxide powder, and binder into granules, and calcining the obtained particles in an air atmosphere to obtain a catalyst precursor. (3) The catalyst precursor is soaked in clean water and then cleaned, and this step is repeatedly performed until the pH value of the cleaning solution is constant, and then the solid product is taken out and dried to obtain a porous catalyst. (4) Using the porous catalyst as a catalyst, the methanol-carbon dioxide direct method is used to prepare dimethyl carbonate, and an ultrasonic vibrating rod is inserted at the methanol liquid level during preparation, and the dimethyl carbonate is separated after completion. The process of the invention uses industrial waste liquid as a raw material, and is modified to prepare a catalyst, which not only reduces the cost of the catalyst, but also effectively improves the conversion rate of methanol.
Description
Technical Field
The invention relates to the technical field of dimethyl carbonate preparation, in particular to a process for catalytically synthesizing dimethyl carbonate.
Background
Because the toxicity of the dimethyl carbonate is low, the dimethyl carbonate is an industrial raw material with excellent environmental protection performance and wide application, has the characteristics of safe and convenient use, little pollution, easy transportation and the like, and is widely applied to the preparation of pesticides, medicines, chemical industry, food additives and the like at present. At present, the mature preparation process of the dimethyl carbonate comprises a phosgene method, an oxidative carbonylation method and an ester exchange method, wherein the phosgene method uses a highly toxic raw material phosgene, the by-product pollutes the environment and corrodes equipment, and the chlorine content of the product is basically eliminated, so the oxidative carbonylation method and the ester exchange method are two processes which are really and industrially practical at present. The process for directly synthesizing the dimethyl carbonate by using the carbon dioxide and the methanol has the advantages of cheap and easily-obtained reaction raw materials, little harm to the environment, very economic and green process route and good application prospect, has effectively developed at present, is still in the stages of exploration and experiment, has a longer path from industrial application value, and has the problems that the reaction is difficult to be carried out under the conventional condition, a catalyst needs to be added to promote the reaction, the price of the noble metal catalyst adopted at present is high, the preparation process is complex, and the process has low conversion rate to the methanol, difficult regeneration of the catalyst and the like, so that the overall cost ratio of the process is low, and needs to be further improved and optimized.
Disclosure of Invention
Aiming at the problems, the invention provides a process for catalytically synthesizing dimethyl carbonate, which adopts industrial waste liquid as a raw material, prepares a catalyst after modification, is beneficial to reducing the cost of the catalyst, and effectively improves the conversion rate of methanol. In order to achieve the purpose, the invention adopts the following technical scheme.
A process for catalytically synthesizing dimethyl carbonate comprises the following steps:
(1) carrying out complex breaking treatment on the chemical nickel plating wastewater, then adding a precipitator to enable metal ions in the chemical nickel plating wastewater to form hydroxide precipitate, separating out the hydroxide precipitate, airing the hydroxide precipitate in the shade, and then crushing the hydroxide precipitate into hydroxide powder for later use.
(2) And uniformly mixing the hydroxide powder, the silicon dioxide powder, the calcium oxide powder and the binder, granulating, and calcining the obtained particles in an air atmosphere to obtain a catalyst precursor for later use.
(3) And (3) soaking the catalyst precursor in clear water, cleaning, repeatedly executing the step until the pH value of the cleaning solution is constant, taking out a solid product, and drying to obtain the porous catalyst.
(4) And (2) taking the porous catalyst as a catalyst, preparing dimethyl carbonate by a methanol-carbon dioxide direct method, inserting an ultrasonic vibration rod at the liquid level of the methanol during preparation, and separating the dimethyl carbonate from the reaction liquid after the preparation is finished.
Further, in the step (1), the chemical nickel plating wastewater is an acidic waste liquid, wherein the metal ions include: ni2+13000～19000mg/L、Fe2+2.0～3.5mg/L、Cu2+25.0～60mg/L、Zn2+ 8.0～15mg/L。
Further, in the step (1), hydrogen peroxide or sodium hypochlorite is added to carry out decomplexation treatment on the chemical nickel plating wastewater. Optionally, the concentration of hydrogen peroxide or sodium hypochlorite in the chemical nickel plating wastewater is preferably controlled to be 1150-1300 mmol/L. Although the chemical nickel plating wastewater contains high-concentration nickel, the nickel exists in a complex state, and a complex of the nickel in the wastewater is converted into nickel ions through complex breaking treatment, so that subsequent precipitation is facilitated.
Further, in the step (1), the precipitant includes any one of sodium hydroxide, potassium hydroxide, ammonia water, and the like. The addition of the precipitant can completely precipitate metal ions in the chemical nickel plating wastewater. The hydrogen ions ionized by the precipitator react with the metal ions to form precipitates, so that the metal elements in the wastewater are extracted, and the subsequent further modification treatment into the catalyst is facilitated.
Further, in the step (1), hydroxide precipitates are separated out in a filtering mode, the obtained filter cake is placed in a shade place for 1-2 days, and then the filter cake is crushed into micron-sized powder, so that hydroxide powder is obtained.
Further, in the step (2), the weight parts of the hydroxide powder, the silicon dioxide powder and the calcium oxide powder are as follows: 4-7 parts of: 15-20 parts of: 1-1.5 parts of binder, wherein the binder is used for binding hydroxide powder, silicon dioxide powder and calcium oxide powder so as to facilitate wet granulation, and the addition amount of the binder can be selected according to needs and is not particularly limited.
Further, in the step (2), the binder includes any one of water glass, epoxy resin, glycerin, and the like.
Further, in the step (2), the particle size of the particles obtained by granulation is between 2 and 3 mm.
Further, in the step (2), the calcining temperature is 700-850 ℃ and the time is 2-3 hours. The particles are calcined at high temperature to form a granular solid catalyst with good strength, and meanwhile, hydroxide in the granular solid catalyst is decomposed into corresponding metal oxide which is dispersedly distributed on the surface of a silica framework to be used as an active site for catalytic reaction.
Further, in the step (3), drying the solid product to constant weight at the temperature of 40-65 ℃ to obtain the catalyst. The catalyst precursor obtained by calcination is repeatedly soaked and washed by clean water, so that part of calcium oxide in the catalyst precursor can be soaked out to form a catalyst with a porous surface layer and a relatively dense center, and the catalyst has good strength, is convenient to recycle repeatedly, is beneficial to increase the surface area of the catalyst and improves the reaction efficiency.
Further, in the step (4), the ratio of the methanol to the catalyst is 100 ml: 4.0 to 7.0 g.
Further, in the step (4), the reaction is carried out at the temperature of 110-135 ℃ and under the pressure of 2.5-3.8 MPa, and after the reaction is finished, the dimethyl carbonate in the reaction liquid is rectified, so that the target product is obtained.
Further, in the step (4), the power of the ultrasonic vibrating rod is 300-500W, and the ultrasonic vibration treatment is continuously carried out on the liquid level of the methanol liquid in the whole reaction process.
Based on the technical scheme, the invention has the following beneficial effects:
(1) the catalyst of the invention is prepared by adopting nickel electroplating wastewater which contains a large amount of Ni2+Containing a portion of Fe2+、Cu2+Although a large amount of the metal ions exist in the nickel electroplating wastewater, the nickel electroplating wastewater has no catalytic capability on the direct methanol-carbon dioxide method for preparing dimethyl carbonate, and the wastewater cannot be directly used as a catalyst. Furthermore, the hydroxide precipitates formed after the elements are extracted from the nickel electroplating wastewater lay the foundation for converting the metal ions into the catalytic active components, and the hydroxide precipitates of the metals are further analyzed by the invention, so that the hydroxides of the metals are unstable at high temperature, are easily decomposed into nickel oxide, iron oxide and copper oxide, and release water, on one hand, the wastewater is modified into the catalyst specially for the process of preparing the dimethyl carbonate by the direct methanol-carbon dioxide method because the metal oxides have the catalytic capability of preparing the dimethyl carbonate by the direct methanol-carbon dioxide method, on the other hand, the water released in the process of decomposing the hydroxide precipitates forms water vapor which overflows and then leaves mesopores in the catalyst, namely, the hydroxide precipitates also serve as pore-forming agents, effectively improves the surface area of the catalyst, thereby improving the efficiency. On the other hand, after calcination, the metal oxides are dispersedly distributed on the silicon dioxide framework, and the multiple metal oxides have higher catalytic activity in cooperation with a single metal oxide, so that the conversion rate of methanol is improved, and the utilization rate of raw materials and the yield of products are improved. Finally, the added calcium oxide component does not change in the calcining process, and after the calcium oxide component is repeatedly soaked and cleaned by clean water, part of the calcium oxide in the calcium oxide component can be usedThe components are soaked out to form the catalyst with porous surface layer and relatively dense center, which not only has good strength and is convenient for repeated recycling, but also is beneficial to increasing the surface area of the catalyst and further improving the reaction efficiency.
In conclusion, the process of the invention adopts the industrial waste liquid as the raw material, and the catalyst is prepared after modification, thereby not only reducing the cost of the catalyst, but also obtaining the noble metal catalyst which takes nickel oxide as the main catalytic component, and ensuring the catalytic efficiency.
(2) The invention also adopts a process that an ultrasonic vibration rod is inserted into the liquid level of the methanol in the process of preparing the dimethyl carbonate by the direct methanol-carbon dioxide method (hereinafter referred to as direct process), and ultrasonic vibration treatment is continuously carried out on the liquid level of the methanol liquid in the whole reaction process, because the direct process has lower conversion rate of the methanol, the carbon dioxide has low solubility in the methanol, the carbon dioxide and the methanol mainly react at the liquid level of the methanol, the reaction surface is small, the reaction activity is low, most of the methanol cannot be utilized, the reaction efficiency is low, and the separation difficulty of products is greatly increased. Therefore, the invention adopts the measures to enable the carbon dioxide to vibrate violently at the liquid level of the methanol, so that the reaction activity of the carbon dioxide is obviously improved, and the dissolution of the carbon dioxide in the methanol is improved, thereby increasing the reaction efficiency and promoting the conversion rate of the methanol.
Detailed Description
The present invention will be further described by the following specific examples, which are illustrative only and not intended to be limiting, and the scope of the present invention is not limited thereby.
In the following examples, the nickel electroplating wastewater comes from a certain enterprise in Shandong, the pH of the wastewater after solid impurities are removed by filtering is 4.1-4.6, and a plurality of batches of wastewater with different metal ion concentrations are adopted in the following examples.
Example 1
A process for catalytically synthesizing dimethyl carbonate comprises the following steps:
(1) taking the chemical nickel plating wastewater with pH 4.4 as acidic waste liquid, whereinThe metal ion content is: ni2+ 14732mg/L、Fe2+2.93mg/L、Cu2+43.51mg/L、Zn2+12.44 mg/L. Adding hydrogen peroxide into the chemical nickel plating wastewater for decomplexing treatment, wherein the concentration of the hydrogen peroxide in the wastewater is 1200 mmol/L.
(2) Adding sodium hydroxide powder into the chemical nickel plating wastewater subjected to the decomplexation treatment to enable metal ions in the chemical nickel plating wastewater to form hydroxide precipitates, filtering the reaction solution by using a filter after no precipitate is formed, placing the obtained filter cake in a shade place for 2 days, then crushing the filter cake into powder, and sieving the powder by using a 300-mesh sieve to obtain hydroxide powder for later use.
(3) The preparation method comprises the following steps of (1) mixing the hydroxide powder, the silicon dioxide powder and the calcium oxide powder in parts by weight of 5: 16 parts by weight: 1 part by weight of the raw materials are uniformly mixed to obtain mixed powder, and then the weight ratio of the mixed powder is as follows: 1 part by weight of glycerin: 0.3 part by weight of the raw materials are uniformly mixed and then are granulated into particles with the diameter of 2-3 mm in a granulator by a wet method. And then calcining the particles in a tubular heating furnace in air atmosphere at 800 ℃ for 2.5 hours to obtain a catalyst precursor for later use.
(4) And (4) soaking the catalyst precursor obtained in the step (3) in clear water, cleaning, repeatedly executing the step until the pH value of the cleaning solution is constant, taking out a solid product, and drying at 40 ℃ to constant weight to obtain the catalyst.
(5) Methanol and the catalyst obtained in the step (4) are mixed according to a mixing ratio of 100 ml: the reaction vessel was filled with 6.5g of the above solution, and an ultrasonic vibrator was inserted into the liquid surface of methanol at a power of 450W, and the ultrasonic vibration treatment was continued for the whole reaction. Then introducing carbon dioxide to purge and discharge air in the reaction vessel, continuously introducing the carbon dioxide after the reaction is finished, heating the reaction vessel to 120 ℃, controlling the pressure to be 3.0MPa, cooling the reaction vessel to room temperature after reacting for 2.5h, then discharging the gas in the reaction vessel, discharging the reaction liquid, filtering the reaction liquid to separate out a liquid phase and a catalyst, separating out the dimethyl carbonate in the liquid phase by a rectification process, and keeping the separated catalyst for later use.
Example 2
A process for catalytically synthesizing dimethyl carbonate comprises the following steps:
(1) taking the chemical nickel plating wastewater with pH 4.3 as acidic waste liquid, wherein the content of metal ions is as follows: ni2+ 19004mg/L、Fe2+3.51mg/L、Cu2+24.87mg/L、Zn2+7.94 mg/L. Adding hydrogen peroxide into the chemical nickel plating wastewater for decomplexing treatment, wherein the concentration of the hydrogen peroxide in the wastewater is 1300 mmol/L.
(2) Adding ammonia water into the chemical nickel plating wastewater subjected to the decomplexation treatment to enable metal ions in the chemical nickel plating wastewater to form hydroxide precipitates, filtering the reaction solution by using a filter after no precipitate is formed, placing the obtained filter cake in a shade place for 2 days, then crushing the filter cake into powder, and sieving the powder by using a 350-mesh sieve to obtain hydroxide powder for later use.
(3) The preparation method comprises the following steps of (1) mixing the hydroxide powder, the silicon dioxide powder and the calcium oxide powder according to the weight ratio of 7: 20 parts by weight: 1.5 parts by weight of the following components are uniformly mixed to obtain mixed powder, and then the weight ratio of the mixed powder is as follows: 1 part of water glass: 0.25 part by weight of the raw materials are uniformly mixed and then are granulated into particles with the diameter of 2-3 mm in a granulator by a wet method. And then calcining the particles in a tubular heating furnace in air atmosphere at 850 ℃ for 2 hours to obtain a catalyst precursor for later use.
(4) And (4) soaking the catalyst precursor obtained in the step (3) in clear water, cleaning, repeatedly executing the step until the pH value of the cleaning solution is constant, taking out a solid product, and drying at 55 ℃ to constant weight to obtain the catalyst.
(5) Methanol and the catalyst obtained in the step (4) are mixed according to a mixing ratio of 100 ml: a proportion of 7g is placed in a reaction vessel, an ultrasonic vibration rod with the power of 350W is inserted at the liquid level of the methanol, and the ultrasonic vibration treatment is continuously carried out on the liquid level of the methanol liquid in the whole reaction process. Then introducing carbon dioxide to purge and discharge air in the reaction vessel, continuously introducing the carbon dioxide after the completion of the reaction, then heating the reaction vessel to 110 ℃, controlling the pressure at 3.8MPa, cooling the reaction vessel to room temperature after reacting for 2.5h, then discharging the gas in the reaction vessel, discharging the reaction liquid, filtering the reaction liquid to separate out a liquid phase and a catalyst, and separating out the dimethyl carbonate in the liquid phase through a rectification process.
Example 3
A process for catalytically synthesizing dimethyl carbonate comprises the following steps:
(1) taking the chemical nickel plating wastewater with pH 4.1 as acidic waste liquid, wherein the content of metal ions is as follows: ni2+ 17218mg/L、Fe2+2.25mg/L、Cu2+59.96mg/L、Zn2+15.1 mg/L. Adding hydrogen peroxide into the chemical nickel plating wastewater for decomplexing treatment, wherein the concentration of the hydrogen peroxide in the wastewater is 1250 mmol/L.
(2) Adding sodium hydroxide powder into the chemical nickel plating wastewater subjected to the decomplexation treatment to enable metal ions in the chemical nickel plating wastewater to form hydroxide precipitates, filtering the reaction solution by using a filter after no precipitate is formed, placing the obtained filter cake in a shade place for 1 day, then crushing the filter cake into powder, and sieving the powder by using a 300-mesh sieve to obtain hydroxide powder for later use.
(3) The preparation method comprises the following steps of (1) mixing the hydroxide powder, the silicon dioxide powder and the calcium oxide powder according to the weight ratio of 4: 16 parts by weight: 1.2 parts by weight of the following components are uniformly mixed to obtain mixed powder, and then the weight ratio of the mixed powder is as follows: 1 part by weight of epoxy resin: 0.25 part by weight of the raw materials are uniformly mixed and then are granulated into particles with the diameter of 2-3 mm in a granulator by a wet method. And then, calcining the particles in a tubular heating furnace in air atmosphere at the calcining temperature of 750 ℃ for 2.5 hours to obtain a catalyst precursor for later use.
(4) And (4) soaking the catalyst precursor obtained in the step (3) in clear water, cleaning, repeatedly executing the step until the pH value of the cleaning solution is constant, taking out a solid product, and drying at 65 ℃ to constant weight to obtain the catalyst.
(5) Methanol and the catalyst obtained in the step (4) are mixed according to a mixing ratio of 100 ml: 5.5g of the mixture is placed in a reaction vessel, an ultrasonic vibration rod with the power of 500W is inserted at the liquid level of the methanol, and the ultrasonic vibration treatment is continuously carried out at the liquid level of the methanol liquid in the whole reaction process. Then introducing carbon dioxide to purge and discharge air in the reaction vessel, continuously introducing the carbon dioxide after the reaction is finished, heating the reaction vessel to 130 ℃, controlling the pressure to be 3.0MPa, cooling the reaction vessel to room temperature after reacting for 2.5h, then discharging the gas in the reaction vessel, discharging the reaction liquid, filtering the reaction liquid to separate out a liquid phase and a catalyst, and separating out the dimethyl carbonate in the liquid phase through a rectification process.
Example 4
A process for catalytically synthesizing dimethyl carbonate comprises the following steps:
(1) taking the chemical nickel plating wastewater with pH 4.6 as acidic waste liquid, wherein the content of metal ions is as follows: ni2+ 13013mg/L、Fe2+1.97mg/L、Cu2+38.72mg/L、Zn2+8.03 mg/L. Adding hydrogen peroxide into the chemical nickel plating wastewater for decomplexing treatment, wherein the concentration of the hydrogen peroxide in the wastewater is 1150 mmol/L.
(2) Adding sodium hydroxide powder into the chemical nickel plating wastewater subjected to the decomplexation treatment to enable metal ions in the chemical nickel plating wastewater to form hydroxide precipitates, filtering the reaction solution by using a filter after no precipitate is formed, placing the obtained filter cake in a shade place for 2 days, then crushing the filter cake into powder, and sieving the powder by using a 300-mesh sieve to obtain hydroxide powder for later use.
(3) The preparation method comprises the following steps of (1) mixing the hydroxide powder, the silicon dioxide powder and the calcium oxide powder according to 6 parts by weight: 15 parts by weight: 1.1 parts by weight of the following components are uniformly mixed to obtain mixed powder, and then the weight ratio of the mixed powder is as follows: 1 part by weight of glycerin: 0.3 part by weight of the raw materials are uniformly mixed and then are granulated into particles with the diameter of 2-3 mm in a granulator by a wet method. And then, calcining the particles in a tubular heating furnace in air atmosphere at 700 ℃ for 3 hours to obtain a catalyst precursor for later use.
(4) And (4) soaking the catalyst precursor obtained in the step (3) in clear water, cleaning, repeatedly executing the step until the pH value of the cleaning solution is constant, taking out a solid product, and drying at 50 ℃ to constant weight to obtain the catalyst.
(5) Methanol and the catalyst obtained in the step (4) are mixed according to a mixing ratio of 100 ml: 4g of the mixture is placed in a reaction vessel, an ultrasonic vibrating rod with the power of 300W is inserted at the liquid level of the methanol, and the ultrasonic vibration treatment is continuously carried out on the liquid level of the methanol liquid in the whole reaction process. Then introducing carbon dioxide to purge and discharge air in the reaction vessel, continuously introducing the carbon dioxide after the completion of the reaction, then heating the reaction vessel to 135 ℃, controlling the pressure at 2.5MPa, cooling the reaction vessel to room temperature after reacting for 2.5h, then discharging the gas in the reaction vessel, discharging the reaction liquid, filtering the reaction liquid to separate out a liquid phase and a catalyst, and separating out the dimethyl carbonate in the liquid phase through a rectification process.
Example 5
A process for the catalytic synthesis of dimethyl carbonate, similar to example 1, is distinguished in that no ultrasonic oscillation treatment is carried out in step (5).
Example 6
A process for catalytically synthesizing dimethyl carbonate, which is the same as the process in example 1, and is characterized in that calcium oxide powder is not added in the step (3).
Example 7
A process for the catalytic synthesis of dimethyl carbonate, which is the same as example 1, except that the catalyst precursor obtained in step (3) is not subjected to the cleaning treatment after soaking in step (4), but the catalyst precursor obtained in step (3) is directly subjected to the synthesis of dimethyl carbonate as the catalyst in step (5).
Example 8
A process for the catalytic synthesis of dimethyl carbonate, similar to example 1, is different in that the catalyst precursor obtained in step (3) is not calcined, but the particles obtained by granulating in step (3) are directly dried naturally in the shade for 2 days and then used as the catalyst in step (5) for the synthesis of dimethyl carbonate.
Example 9
The process for catalytically synthesizing dimethyl carbonate is the same as that in example 1, except that the catalyst separated in the step (5) in the example 1 is used as a catalyst to directly synthesize dimethyl carbonate, and the synthesis conditions are the same as those in example 1.
Example 10
A process for catalytically synthesizing dimethyl carbonate, which is the same as example 9, except that the catalyst separated in the step (5) of example 9 is used as a catalyst to directly synthesize dimethyl carbonate, and the synthesis conditions are the same as those in example 9.
The conversion of methanol and the selectivity to dimethyl carbonate in each of the above examples were measured, and the results are shown in table 1.
TABLE 1
| Example number | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| Conversion of methanol/%) | 21.2 | 23.7 | 19.6 | 22.4 | 14.9 | 17.7 | 16.3 | 6.6 | 20.5 | 19.8 |
| Selectivity of dimethyl carbonate/%) | 98.8 | 99.1 | 98.3 | 99.5 | 96.8 | 80.1 | 87.6 | 7.8 | 98.2 | 97.4 |
It can be seen that the catalysts prepared in examples 1-4 have good catalytic ability for the direct methanol-carbon dioxide process for preparing dimethyl carbonate and excellent selectivity. The detection results of example 9 and example 10 show that the catalyst prepared by the method of the present invention has good repeatability, which indicates that the catalyst has excellent stability and can be repeatedly used. The performances of the catalysts prepared in examples 5 to 8 are all obviously reduced, wherein the detection results of example 5 show that the ultrasonic oscillation treatment can cause the carbon dioxide to violently oscillate at the liquid level of the methanol, so that the reaction activity of the carbon dioxide is obviously improved, the dissolution of the carbon dioxide in the methanol is improved, the reaction efficiency is increased, and the conversion rate of the methanol is promoted.
Finally, it should be understood that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Although the present invention has been described with reference to the specific embodiments, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (10)
1. A process for catalytically synthesizing dimethyl carbonate is characterized by comprising the following steps:
(1) carrying out complex breaking treatment on the chemical nickel plating wastewater, then adding a precipitator to enable metal ions in the chemical nickel plating wastewater to form hydroxide precipitate, separating out the hydroxide precipitate, airing the hydroxide precipitate in the shade, and then crushing the hydroxide precipitate into hydroxide powder for later use;
(2) uniformly mixing the hydroxide powder, the silicon dioxide powder, the calcium oxide powder and the binder, granulating, and calcining the obtained particles in an air atmosphere to obtain a catalyst precursor for later use;
(3) soaking the catalyst precursor in clear water, cleaning, repeatedly executing the step until the pH value of the cleaning solution is constant, taking out a solid product, and drying to obtain the porous catalyst;
(4) and (2) taking the porous catalyst as a catalyst, preparing dimethyl carbonate by a methanol-carbon dioxide direct method, inserting an ultrasonic vibration rod at the liquid level of the methanol during preparation, and separating the dimethyl carbonate from the reaction liquid after the preparation is finished.
2. The process for catalytic synthesis of dimethyl carbonate according to claim 1, wherein in step (1), the electroless nickel plating wastewater is an acidic waste solution, wherein the metal ions comprise: ni2+13000～19000mg/L、Fe2+2.0～3.5mg/L、Cu2 +25.0～60mg/L、Zn2+8.0～15mg/L；
Preferably, the precipitant comprises any one of sodium hydroxide, potassium hydroxide and ammonia water.
3. The process for catalytically synthesizing dimethyl carbonate according to claim 1, wherein in the step (1), hydrogen peroxide or sodium hypochlorite is added to carry out decomplexation treatment on the chemical nickel plating wastewater; preferably, the concentration of hydrogen peroxide or sodium hypochlorite in the chemical nickel plating wastewater is 1150-1300 mmol/L.
4. The process for catalytic synthesis of dimethyl carbonate according to claim 1, wherein in the step (1), hydroxide is precipitated and separated by filtration, the obtained filter cake is placed in the shade for 1-2 days, and then the filter cake is crushed into micron-sized powder, so that the hydroxide powder is obtained.
5. The process for catalytic synthesis of dimethyl carbonate according to claim 1, wherein in the step (2), the weight ratio of the hydroxide powder, the silicon dioxide powder and the calcium oxide powder is as follows: 4-7 parts of: 15-20 parts of: 1-1.5 parts;
preferably, in the step (2), the binder comprises any one of water glass, epoxy resin and glycerin;
preferably, in the step (2), the particle size of the particles obtained by granulation is between 2 and 3 mm.
6. The process for catalytic synthesis of dimethyl carbonate according to claim 1, wherein in the step (2), the calcination temperature is 700-850 ℃ and the calcination time is 2-3 hours.
7. The process for catalytic synthesis of dimethyl carbonate according to claim 1, wherein in step (3), the solid product is dried to constant weight at a temperature of 40-65 ℃ to obtain the catalyst.
8. The process for catalytic synthesis of dimethyl carbonate according to claim 1, wherein in step (4), the ratio of methanol to catalyst is 100 ml: 4.0 to 7.0 g.
9. The process for catalytic synthesis of dimethyl carbonate according to claim 1, wherein in the step (4), the power of the ultrasonic vibrating rod is 300-500W, and the ultrasonic vibration treatment is continuously carried out on the liquid level of the methanol liquid in the whole reaction process.
10. The process for catalytically synthesizing dimethyl carbonate according to any one of claims 1 to 9, wherein in the step (4), the reaction is carried out at a temperature of 110 to 135 ℃ and under a pressure of 2.5 to 3.8MPa, and the dimethyl carbonate in the reaction solution is rectified after the reaction is completed, so that the dimethyl carbonate is obtained.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN115322097A (en) * | 2022-09-21 | 2022-11-11 | 胜华新材料集团股份有限公司 | Method for preparing dimethyl carbonate by direct reaction of carbon dioxide and methanol |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20110196167A1 (en) * | 2010-02-09 | 2011-08-11 | Almusaiteer Khalid A | Synthesis of dimethyl carbonate from carbon dioxide and methanol |
| CN111039441A (en) * | 2018-10-12 | 2020-04-21 | 北京化工大学 | Method for treating chemical plating wastewater by generating colloid |
| CN112657434A (en) * | 2020-12-11 | 2021-04-16 | 陕西延长石油（集团）有限责任公司 | Reactor, reaction system and method for directly synthesizing dimethyl carbonate from methanol and carbon dioxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110196167A1 (en) * | 2010-02-09 | 2011-08-11 | Almusaiteer Khalid A | Synthesis of dimethyl carbonate from carbon dioxide and methanol |
| CN111039441A (en) * | 2018-10-12 | 2020-04-21 | 北京化工大学 | Method for treating chemical plating wastewater by generating colloid |
| CN112657434A (en) * | 2020-12-11 | 2021-04-16 | 陕西延长石油（集团）有限责任公司 | Reactor, reaction system and method for directly synthesizing dimethyl carbonate from methanol and carbon dioxide |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN115322097A (en) * | 2022-09-21 | 2022-11-11 | 胜华新材料集团股份有限公司 | Method for preparing dimethyl carbonate by direct reaction of carbon dioxide and methanol |
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