CN102249953A - Method for converting dimethyl sulfate waste residue into dimethyl sulfate product - Google Patents
Method for converting dimethyl sulfate waste residue into dimethyl sulfate product Download PDFInfo
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- CN102249953A CN102249953A CN2011101317797A CN201110131779A CN102249953A CN 102249953 A CN102249953 A CN 102249953A CN 2011101317797 A CN2011101317797 A CN 2011101317797A CN 201110131779 A CN201110131779 A CN 201110131779A CN 102249953 A CN102249953 A CN 102249953A
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- methyl
- sulfate
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- waste residue
- esterification
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Abstract
The invention discloses a method for converting dimethyl sulfate waste residue into a dimethyl sulfate product, belongs to a method for preparing sulfate, and in particular relates to a method for recycling waste residue generated by a dimethyl sulfate device in the production running process. The method is characterized by comprising the following steps of: hydrolyzing and etherifying dimethyl sulfate in the dimethyl sulfate waste residue to convert the dimethyl sulfate into dimethyl ether; and performing esterification on the generated dimethyl ether and sulfur trioxide to obtain the dimethyl sulfate product. The method comprises the following process steps of: hydrolysis, etherification, separation of distillates, esterification, and distillation. The invention provides a method for converting the dimethyl sulfate waste residue into the dimethyl sulfate product; and the dimethyl ether is recycled from the dimethyl sulfate waste residue and is further converted into the dimethyl sulfate product. The waste residue generated by the dimethyl sulfate device is recycled, and the environmental pollution of the dimethyl sulfate waste residue is eliminated. The purity of the recycled dimethyl ether gas is 99.0 to 99.75 percent; the dimethyl sulfate product has the dimethyl sulfate content of more than or equal to 99.5 percent and the acidity of less than or equal to 0.6 percent; and the content of a byproduct of sulfuric acid is 50 to 70 percent.
Description
Technical field
The present invention is a kind of method that the methyl-sulfate waste residue is changed into the methyl-sulfate product.The preparation method who belongs to sulfuric ester, particularly the waste residue recoverying and utilizing method that produces in the production run of methyl-sulfate device.
Background technology
Can produce a large amount of waste residues during methyl-sulfate is produced, this waste residue main component is methyl-sulfate and sulfuric acid and black body refuse.Directly discharging can cause serious pollution to environment.The method of present domestic processing methyl-sulfate waste residue mainly contains: 1. the methyl-sulfate waste residue is added water and be hydrolyzed, and then carry out neutralizing treatment with liquid caustic soda.2 adopt ammoniacal liquor to neutralize, and generate ammonium sulfate.Its main drawback has: add alkali neutral method after the first hydrolysis and eliminated environmental pollution though 1. adopt, processing cost can strengthen greatly, and is very uneconomical.2. adopt the method for ammonia treatment, increased the consumption of ammoniacal liquor, the ammonium sulfate as fertilizer sources is sold, but this fertilizer is strong because of acidity, can't use substantially.
Chinese patent application 1775718A discloses " a kind of methyl alcohol and vitriolic production technique of reclaiming " from the methyl-sulfate waste residue, be used to handle the methyl-sulfate waste residue.The methanol content of producing 40%～50%, content is low, is applied to big production and must proposes dense processing, and is uneconomical; The sulfuric acid content of producing 40%～50%, content is low, also is difficult to utilize as industrial chemicals again.
Summary of the invention
The objective of the invention is to avoid above-mentioned weak point of the prior art, the methyl-sulfate waste residue is changed into the method for methyl-sulfate product, from the methyl-sulfate waste residue, reclaim dme, and then change into the methyl-sulfate product and provide a kind of.Realize the waste residue resource utilization that the methyl-sulfate device produces, eliminate methyl-sulfate waste residue environmental pollution.
Purpose of the present invention can reach by following measure:
The method that the methyl-sulfate waste residue is changed into the methyl-sulfate product of the present invention, it is characterized in that at first with methyl-sulfate hydrolysis, etherificate in the methyl-sulfate waste residue, be converted into dme, then, the dme that generates again with sulphur trioxide generation esterification, generate the methyl-sulfate product, comprise following processing step:
1.. hydrolysis, etherificate
The methyl-sulfate waste residue is dropped in the reactor, add water, heating, be hydrolyzed, etherification reaction; Methyl alcohol with reaction product dme and moisture that carries and minute quantity steams continuously simultaneously; Product sulfuric acid is stayed in the still;
2.. overhead product separates
The reaction product of step in 1. distillates, and after condensation, water and small amount of methanol enter the Methanol Recovery storage tank, and gas of dimethyl ether enters esterification device;
3.. esterification
Step 2. distilled dme enters the methyl-sulfate esterification device, enters from the esterification pot bottom, contacts with the pyrosulfuric acid dimethyl ester of process metering good absorption sulfur trioxide gas, and esterification takes place in esterification reaction tank, produces methyl-sulfate;
4. distillation
After esterification is finished, underpressure distillation, cat head distillates gas methyl-sulfate product, after condensation, enters product methyl-sulfate finished product storage tank.
Of the present invention the methyl-sulfate waste residue is changed into the method for methyl-sulfate product, reaction formula is as follows:
(CH
3)
2SO
4?+?2H
2O?=2CH
3OH+H
2SO
4
CH
3OH?+?H
2SO
4=CH
3HSO
4?+?H
2O
CH
3HSO
4?+?CH
3OH?=?CH
3OCH
3?+?H
2SO
4
（CH
3）
2S
2O
7＋CH
3OCH
3=2(CH
3)
2SO
4
According to chemical equilibrium theory, by distillation the gas of dimethyl ether that generates is constantly shifted out, chemical equilibrium is moved towards the direction of producing dme, improved speed of response and transformation efficiency greatly.Methyl-sulfate transformation efficiency 100% in the waste residue.
Purpose of the present invention can also reach by following measure:
Of the present invention the methyl-sulfate waste residue is changed into the method for methyl-sulfate product, concrete processing condition are as follows:
1.. hydrolysis, etherificate
Mass ratio 1:0.3～0.7 that feeds intake of methyl-sulfate and water
Etherificate distillation temperature ℃ 70～160
2.. overhead product separates
Condensing temperature ℃-10～10
3.. esterification
Esterification temperature ℃ 70～140
4. distillation
Still temperature ℃ 120 ~ 200
Warm ℃ 100 ~ 180 on top
Vacuum tightness Mpa 0.6 ~ 0.95.
Of the present invention the methyl-sulfate waste residue is changed into the method for methyl-sulfate product, step is distilled intermediate dme 2., purifies the back extraction, sells as the product dme.
The method that the methyl-sulfate waste residue is changed into the methyl-sulfate product of the present invention, the 3. described step of step 2. distilled dme enters normal operating methyl-sulfate device esterification system, enter from the esterification pot bottom, from bottom to top with the pyrosulfuric acid dimethyl ester counter current contact that is absorbed with quantitative sulphur trioxide, esterification takes place, and generates methyl-sulfate.
Of the present invention the methyl-sulfate waste residue is changed into the method for methyl-sulfate product, the step 1. terminal point controlling index of described hydrolysis reaction is that the content of methyl-sulfate in the still liquid is zero.
Of the present invention the methyl-sulfate waste residue is changed into the method for methyl-sulfate product, the surface that the equipment that adopts in the described method contacts with material is lass lining, pottery, glass, graphite-like anticorrosive.
Of the present invention the methyl-sulfate waste residue is changed into the method for methyl-sulfate product, the purity that reclaims gas of dimethyl ether is 99.0% ~ 99.75%; The content of methyl-sulfate is 〉=98.5%, and acidity is≤0.6%; Sell as industrial goods; The sulfuric acid mass content of by-product is 50% ~ 70%, and the waste residue of methyl-sulfate device discharging is applied fully, realizes zero release.
Of the present invention the methyl-sulfate waste residue is changed into the method for methyl-sulfate product, following positively effect is arranged compared to existing technology:
1. provide a kind of the methyl-sulfate waste residue has been changed into the method for methyl-sulfate product, from the methyl-sulfate waste residue, reclaimed dme, and then change into the methyl-sulfate product.Realize the waste residue resource utilization that the methyl-sulfate device produces, eliminate methyl-sulfate waste residue environmental pollution.
2. by distillation the gas of dimethyl ether that generates is constantly shifted out, improved speed of response and transformation efficiency greatly.Methyl-sulfate transformation efficiency 100% in the waste residue.
3. the purity that reclaims gas of dimethyl ether is 99.0% ~ 99.75%; The content of methyl-sulfate is 〉=98.5%, and acidity is≤0.6%; Sell as industrial goods; The sulfuric acid mass content of by-product is 50% ~ 70%, and the waste residue of methyl-sulfate device discharging is applied fully, realizes zero release.
4. the methyl ether gas of Hui Shouing is used to change into methyl-sulfate, has realized the maximum conversion of methyl-sulfate material benzenemethanol, and by-product content is 50% ~ 70% sulfuric acid, can be used as industrial chemicals and utilizes, has improved the economic benefit of methyl-sulfate manufacturing enterprise.
, few, the operating procedure mild condition of facility investment, can use with ortho-sulfuric acid dimethyl ester matched with devices.
Embodiment
The present invention will now be further detailed embodiment:
Embodiment 1
In glassed steel reaction vessels, add methyl-sulfate waste residue 9750kg, slowly add tap water 6200kg, make tap water in 70～140 ℃ of internal controls of temperature and add speed, be hydrolyzed and etherification reaction, the gas that distills out is by condenser condenses, and water and a spot of methyl alcohol under the condensation, the methyl ether gas of higher degree carry out esterification with the sulphur trioxide that absorbs again, methyl-sulfate is produced in 70 ~ 140 ℃ of esterification temperature controls.Reclaim the methyl-sulfate 3100kg of mass content 98.5%, reclaiming phlegma, to obtain mass content be 40% methyl alcohol 100kg, and the raffinate that reclaims simultaneously in the distillation afterreaction still obtains 55 ~ 65% sulfuric acid 12500kg..
Example 2
In glassed steel reaction vessels, add methyl-sulfate waste residue 9750kg, slowly add tap water 5500kg, make tap water in 70～140 ℃ of internal controls of temperature and add speed, be hydrolyzed and etherification reaction, the gas that distills out is by condenser condenses, and water and a spot of methyl alcohol under the condensation, the methyl ether gas of higher degree carry out esterification with the sulphur trioxide that absorbs again, methyl-sulfate is produced in 70 ~ 140 ℃ of esterification temperature controls.Reclaim the methyl-sulfate 2900kg of mass content 98.5%, reclaiming phlegma, to obtain mass content be 40% methyl alcohol 120kg, and the raffinate that reclaims simultaneously in the distillation afterreaction still obtains 55 ~ 65% sulfuric acid 12200kg..
Example 3
In glassed steel reaction vessels, add methyl-sulfate waste residue 9600kg, slowly add tap water 6200kg, make tap water in 70～140 ℃ of internal controls of temperature and add speed, be hydrolyzed and etherification reaction, the gas that distills out is by condenser condenses, and water and a spot of methyl alcohol under the condensation, the methyl ether gas of higher degree carry out esterification with the sulphur trioxide that absorbs again, methyl-sulfate is produced in 70 ~ 140 ℃ of esterification temperature controls.Reclaim the methyl-sulfate 2600kg of mass content 98.5%, reclaiming phlegma, to obtain mass content be 40% methyl alcohol 150kg, and the raffinate that reclaims simultaneously in the distillation afterreaction still obtains 55 ~ 65% sodium sulfate 13000kg..
Example 4
In glassed steel reaction vessels, add methyl-sulfate waste residue 9000kg, slowly add tap water 4500kg, make tap water in 70～140 ℃ of internal controls of temperature and add speed, be hydrolyzed and etherification reaction, the gas that distills out is by condenser condenses, and water and a spot of methyl alcohol under the condensation, the methyl ether gas of higher degree carry out esterification with the sulphur trioxide that absorbs again, methyl-sulfate is produced in 70 ~ 140 ℃ of esterification temperature controls.Reclaim the methyl-sulfate 2520kg of mass content 98.5%, reclaiming phlegma, to obtain mass content be 40% methyl alcohol 80kg, and the raffinate that reclaims simultaneously in the distillation afterreaction still obtains 55 ~ 65% sulfuric acid 10850kg..
Example 5
In glassed steel reaction vessels, add methyl-sulfate waste residue 10500kg, slowly add tap water 5250kg, make tap water in 70～140 ℃ of internal controls of temperature and add speed, be hydrolyzed and etherification reaction, the gas that distills out is by condenser condenses, and water and a spot of methyl alcohol under the condensation, the methyl ether gas of higher degree carry out esterification with the sulphur trioxide that absorbs again, methyl-sulfate is produced in 70 ~ 140 ℃ of esterification temperature controls.Reclaim the methyl-sulfate 2800kg of mass content 98.5%, reclaiming phlegma, to obtain mass content be 40% methyl alcohol 180kg, and the raffinate that reclaims simultaneously in the distillation afterreaction still obtains 55 ~ 65% sulfuric acid 12740kg..
Example 6
In glassed steel reaction vessels, add methyl-sulfate waste residue 10500kg, slowly add tap water 3850kg, make tap water in 70～140 ℃ of internal controls of temperature and add speed, be hydrolyzed and etherification reaction, the gas that distills out is by condenser condenses, and water and a spot of methyl alcohol under the condensation, the methyl ether gas of higher degree carry out esterification with the sulphur trioxide that absorbs again, methyl-sulfate is produced in 70 ~ 140 ℃ of esterification temperature controls.Reclaim the methyl-sulfate 2300kg of mass content 98.5%, reclaiming phlegma, to obtain mass content be 40% methyl alcohol 100kg, and the raffinate that reclaims simultaneously in the distillation afterreaction still obtains 55 ~ 65% sulfuric acid 11900kg..
Claims (7)
1. method that the methyl-sulfate waste residue is changed into the methyl-sulfate product, it is characterized in that at first with methyl-sulfate hydrolysis, etherificate in the methyl-sulfate waste residue, be converted into dme, then, the dme that generates again with sulphur trioxide generation esterification, generate the methyl-sulfate product, comprise following processing step:
1.. hydrolysis, etherificate
The methyl-sulfate waste residue is dropped in the reactor, add water, heating, be hydrolyzed, etherification reaction; Simultaneously reaction product dme and the moisture that carries and minute quantity methyl alcohol are steamed continuously; Product sulfuric acid is stayed in the still;
2.. overhead product separates
The reaction product of step in 1. distillates, and after condensation, water and small amount of methanol enter the Methanol Recovery storage tank, and gas of dimethyl ether enters esterification device;
3.. esterification
Step 2. distilled dme enters the methyl-sulfate esterification device, enter from the esterification pot bottom, contact with pyrosulfuric acid dimethyl ester, esterification takes place in esterification reaction tank, produce the methyl-sulfate crude product through metering good absorption sulfur trioxide gas;
4. distillation
After esterification is finished, underpressure distillation, cat head distillates gas methyl-sulfate product, after condensation, enters product methyl-sulfate finished product storage tank.
2. according to the method that the methyl-sulfate waste residue is changed into the methyl-sulfate product of claim 1, it is characterized in that concrete processing condition are as follows:
1.. hydrolysis, etherificate
Mass ratio 1:0.3～0.7 that feeds intake of methyl-sulfate and water
Etherificate distillation temperature ℃ 70～160
2.. overhead product separates
Condensing temperature ℃-10～10
3.. esterification
Esterification temperature ℃ 70～140
4. distillation
Still temperature ℃ 120 ~ 200
Warm ℃ 100 ~ 180 on top
Vacuum tightness Mpa 0.6 ~ 0.95.
3. according to the method that the methyl-sulfate waste residue is changed into the methyl-sulfate product of claim 1, it is characterized in that 2. distilled intermediate dme of step, purify the back extraction, sell as the product dme.
4. according to the method that the methyl-sulfate waste residue is changed into the methyl-sulfate product of claim 1, it is characterized in that the 3. described step of step 2. the distilled dme enter normal operating methyl-sulfate device esterification system, enter from the esterification pot bottom, from bottom to top with the pyrosulfuric acid dimethyl ester counter current contact that is absorbed with quantitative sulphur trioxide, esterification takes place, and generates methyl-sulfate.
5. according to the method that the methyl-sulfate waste residue is changed into the methyl-sulfate product of claim 1, it is characterized in that step 1. the terminal point controlling index of described hydrolysis reaction be that the content of methyl-sulfate in the still liquid is zero.
6. according to the method that the methyl-sulfate waste residue is changed into the methyl-sulfate product of claim 1, the surface that the equipment that it is characterized in that adopting in the described method contacts with material is lass lining, pottery, glass, the anti-sulfuric acid corrosion material of graphite-like.
7. according to the method that the methyl-sulfate waste residue is changed into the methyl-sulfate product of claim 1, the purity that it is characterized in that reclaiming gas of dimethyl ether is 99.0% ~ 99.75%; The content of methyl-sulfate is 〉=98.5%, and acidity is≤0.6%; Sell as industrial goods; The sulfuric acid mass content of by-product is 50% ~ 70%, and the waste residue of methyl-sulfate device discharging is applied fully, realizes zero release.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101317797A CN102249953A (en) | 2011-05-20 | 2011-05-20 | Method for converting dimethyl sulfate waste residue into dimethyl sulfate product |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101317797A CN102249953A (en) | 2011-05-20 | 2011-05-20 | Method for converting dimethyl sulfate waste residue into dimethyl sulfate product |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659584A (en) * | 2012-05-21 | 2012-09-12 | 天津市碳一有机合成工程设计有限公司 | Chemical reaction system for producing oxalic acid diester as main products by using sodium formate as raw materials |
| CN103570590A (en) * | 2013-10-30 | 2014-02-12 | 临沂远博化工有限公司 | Equipment for producing dimethyl sulfate |
| CN105712903A (en) * | 2016-01-20 | 2016-06-29 | 山东兴辉化工有限公司 | Dimethyl sulfate residue treatment method |
| CN106518731A (en) * | 2016-08-31 | 2017-03-22 | 湖北远大富驰医药化工股份有限公司 | Automatic separator for refining products of dimethyl sulfate |
| CN108997173A (en) * | 2018-08-03 | 2018-12-14 | 湖北远大富驰医药化工股份有限公司 | A method of recycling dimethyl suflfate from vacuum gas |
| CN109748827A (en) * | 2019-02-03 | 2019-05-14 | 山东凯瑞英材料科技有限公司 | The process of continuous synthesis dimethyl suflfate |
| CN115028555A (en) * | 2022-07-04 | 2022-09-09 | 武汉青江化工黄冈有限公司 | Diethyl sulfate continuous synthesis process |
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| CN1760179A (en) * | 2004-10-12 | 2006-04-19 | 山东新华万博化工有限公司 | Technique for preparing dimehtyl sulfate |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659584A (en) * | 2012-05-21 | 2012-09-12 | 天津市碳一有机合成工程设计有限公司 | Chemical reaction system for producing oxalic acid diester as main products by using sodium formate as raw materials |
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| CN106518731A (en) * | 2016-08-31 | 2017-03-22 | 湖北远大富驰医药化工股份有限公司 | Automatic separator for refining products of dimethyl sulfate |
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| CN108997173A (en) * | 2018-08-03 | 2018-12-14 | 湖北远大富驰医药化工股份有限公司 | A method of recycling dimethyl suflfate from vacuum gas |
| CN108997173B (en) * | 2018-08-03 | 2021-01-01 | 湖北远大富驰医药化工股份有限公司 | Method for recovering dimethyl sulfate from vacuum gas |
| CN109748827A (en) * | 2019-02-03 | 2019-05-14 | 山东凯瑞英材料科技有限公司 | The process of continuous synthesis dimethyl suflfate |
| CN109748827B (en) * | 2019-02-03 | 2021-09-14 | 山东凯瑞英材料科技有限公司 | Process for continuous synthesis of dimethyl sulfate |
| CN115028555A (en) * | 2022-07-04 | 2022-09-09 | 武汉青江化工黄冈有限公司 | Diethyl sulfate continuous synthesis process |
| CN115028555B (en) * | 2022-07-04 | 2023-09-29 | 武汉青江化工黄冈有限公司 | Continuous synthesis process of diethyl sulfate |
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Application publication date: 20111123 |