CN107488136A - A kind of method for preparing ethero-sulfuric acid - Google Patents
A kind of method for preparing ethero-sulfuric acid Download PDFInfo
- Publication number
- CN107488136A CN107488136A CN201710785694.8A CN201710785694A CN107488136A CN 107488136 A CN107488136 A CN 107488136A CN 201710785694 A CN201710785694 A CN 201710785694A CN 107488136 A CN107488136 A CN 107488136A
- Authority
- CN
- China
- Prior art keywords
- sulfuric acid
- ethero
- ethanol
- catalyst
- sulfate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/24—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfuric acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to chemical industry synthesis field, a kind of specifically method for preparing ethero-sulfuric acid.This method is using ethanol and sulfur trioxide as reactant, the reaction generation ethero-sulfuric acid in the presence of catalyst, the ethero-sulfuric acid purity obtained is high, water content is low, in the still-process of reaction generation dithyl sulfate, the hydrolysis of ethero-sulfuric acid and dithyl sulfate is faint, so that the yield of dithyl sulfate is improved.
Description
Technical field
The present invention relates to chemical industry synthesis field, is related to a kind of method for preparing ethero-sulfuric acid.
Background technology
The existing ethero-sulfuric acid for preparing has a variety of methods, such as：Sulfuric acid-Ethanol Method, sulfuric acid-ethylene process.
The process of sulfuric acid-Ethanol Method is：Sulfuric acid and ethanol are mixed and carry out reaction generation at a certain temperature, due to sulphur
Acid and the reaction of ethanol are reversible reactions, and obtained mixture mainly contains ethero-sulfuric acid, water, and unreacted sulfuric acid,
Unreacted ethanol；According to document and experimental verification, the ethero-sulfuric acid sulfur acid hydrogen ethyl ester obtained by sulfuric acid Ethanol Method
Amount typically 20%~60% scope, and contain substantial amounts of water, for produce the yield of product obtained by dithyl sulfate compared with
It is low.
Sulfuric acid-ethylene process is to be passed through ethene in sulfuric acid under conditions of certain temperature is controlled, and is obtained by this process
Mixture in mainly contain dithyl sulfate, ethero-sulfuric acid, sulfuric acid；According to document, (Zhang Yue is edited, fine-chemical intermediate
Preparation flow illustrates, Chemical Industry Press, 1999, pp372-374) dithyl sulfate that, content is about 43% in mixture,
45% ethero-sulfuric acid, 12% sulfuric acid.
Ethero-sulfuric acid is reacted to generation dithyl sulfate, sulfuric acid at a certain temperature, vacuum distillation can obtain sulfuric acid
Diethylester.Its reactional equation can be expressed as：
The temperature that above-mentioned reaction is evaporated under reduced pressure is usually 100~180 DEG C.
When water in system be present, dithyl sulfate can generate ethanol and sulfuric acid under acid catalysis, and the presence of water makes sulfuric acid
The yield of diethylester reduces, and water content is bigger, and the yield of dithyl sulfate is lower.According to our research, commercial scale
Middle to obtain ethero-sulfuric acid using sulfuric acid Ethanol Method to produce dithyl sulfate, its yield only has 10~30%.
The ethero-sulfuric acid production dithyl sulfate made with sulfuric acid ethylene process has larger advantage than sulfuric acid-Ethanol Method.
Because there is no water or aqueous less in the former, during follow-up vacuum distillation obtains dithyl sulfate, without reversible reaction
Or reversible reaction speed is slower.Sulfuric acid-ethylene process produces the preferable method of dithyl sulfate before being also, this method produces sulphur
Diethyl phthalate is the subsidiary method that oxyethylene sulfate Hydrolyze method prepares co-productiono f ethanol.But current ethene and sulfuric acid reaction hydrolysis prepare second
The method of alcohol is substituted by plant cellulose fermentation method；And ethene is stored, transported and using operation all some difficulties.So mesh
It is preceding no longer to prepare ethero-sulfuric acid with ethene-sulfuric acid, then the method for thus producing dithyl sulfate does not have advantage.
The content of the invention
Present invention the problem of existing for prior art, there is provided a kind of method for preparing ethero-sulfuric acid, this method with
Ethanol and sulfur trioxide are reactant, reaction acquisition ethero-sulfuric acid, the ethero-sulfuric acid obtained in the presence of catalyst
Purity is high, and water content is low, and in distillation reaction, the hydrolysis of ethero-sulfuric acid and dithyl sulfate is faint, so as to sulfuric acid two
The yield of ethyl ester can be improved.
Ethero-sulfuric acid described in the present invention is actually include ethero-sulfuric acid mixture, wherein may comprising ethanol,
Water, sulfuric acid, dithyl sulfate etc., but wherein ethero-sulfuric acid content is higher, and the mixture can be used for synthesizing dithyl sulfate
(yield can reach more than 85%), the manufacture view of the industrial goods such as organic chemical industry, agricultural chemicals, medicine can also be used in.
The concrete technical scheme of the present invention is as follows：
A kind of method for preparing ethero-sulfuric acid, it is characterised in that：Comprise the following steps that：
A certain amount of ethanol, a certain proportion of catalyst are added in the reactor, and sulfur trioxide is added into reaction solution, is added
Controlling reaction temperature obtains ethero-sulfuric acid between -20~100 DEG C during entering；
The dosage of wherein described catalyst is that the mol ratio of catalyst/ethanol is 0.001~1,
Described ethanol is absolute ethyl alcohol or 95% ethanol；
Described catalyst is potassium, sodium, calcium, magnesium, aluminium, zinc, iron, tin, lead, copper, the sulfate of ammonium or hydrochloride or phosphoric acid
Salt or nitrate or carbonate, or sulfuric acid；
Reaction time is preferably 0.1~20h, and the preferably time is 0.5~2h；
Further described ethanol is absolute ethyl alcohol；The mol ratio of the catalyst/ethanol is 0.05~0.15；Institute
The catalyst stated is sodium sulphate or potassium sulfate or ammonium sulfate；
Preferable described reaction temperature is 5~60 DEG C,
The method that offer of the present invention prepares ethero-sulfuric acid, its major advantage are：
1) ethero-sulfuric acid is prepared using absolute ethyl alcohol and sulfur trioxide in the presence of a catalyst, do not produced in course of reaction
Water, so the ethero-sulfuric acid purity prepared is higher.Because adding inorganic salt catalyst in preparation process, can accelerate anti-
The speed answered, avoids ethanol from being carbonized by sulfur trioxide, and the ethero-sulfuric acid of generation is colourless or faint yellow.
2) compared with the ethero-sulfuric acid prepared by sulfuric acid-Ethanol Method, sulfuric acid-Ethanol Method esterification during the course of the reaction
Water is generated, water can promote ester to be hydrolyzed, so reversible reaction be present, can only prepare 20%~60% ethero-sulfuric acid, and
Water is not generated in the preparation process of the present invention, in the absence of reversible reaction, can prepare that purity is higher, the few hydrogen sulfate second of water content
Ester, it thus can greatly improve the yield of subsequent reactions；Compared with sulfuric acid-ethylene process, sulfuric acid-ethylene process is oxyethylene sulfate
The method that Hydrolyze method prepares the subsidiary production dithyl sulfate of co-productiono f ethanol, but ethene and sulfuric acid reaction hydrolysis prepare ethanol at present
Method substituted by plant cellulose fermentation method；And ethene stores, transports and have larger difficulty using operation.So
Method provided by the present invention has stronger advantage than ethene-sulfuric acid process.
In summary, the new method provided by the present invention for preparing ethero-sulfuric acid, can be greatly improved hydrogen sulfate
The purity of ethyl ester, and then the yield that ethero-sulfuric acid prepares dithyl sulfate reaction can be increased substantially, increase economic efficiency.
Embodiment
The present invention is further illustrated with reference to embodiment, can make those skilled in the art that this hair be more completely understood
It is bright, but do not limit the invention in any way.
Embodiment 1
A kind of method for preparing ethero-sulfuric acid, is comprised the following steps that：
1) there-necked flask with stirring is placed in ice-water bath, 100g absolute ethyl alcohols is added into there-necked flask, add sodium sulphate
20g, stirring is opened, sulfur trioxide 174g is added into reaction solution, controlling reaction temperature is at 50 DEG C or so, 50 DEG C after addition
Insulation produces ethero-sulfuric acid after 30 minutes.
By above-mentioned prepared ethero-sulfuric acid, be evaporated under reduced pressure at 150~160 DEG C, vacuum degree control-
0.095MPa, 151g dithyl sulfates are obtained, the product is washed twice, anhydrous magnesium sulfate is dried, and filtration drying agent is
Product 150g, yield 89.6% are obtained, GC shows that main peak is more than 99.3%, and the product is carried out once to be evaporated under reduced pressure (85~130
DEG C/10mmHg), obtain product 148g, GC and show that purity is 99.8%.
Embodiment 2
A kind of method for preparing ethero-sulfuric acid, is comprised the following steps that：
1) there-necked flask with stirring is placed in ice-water bath, 100g absolute ethyl alcohols is added into there-necked flask, add ammonium sulfate
30g, stirring is opened, sulfur trioxide 174g is added into reaction solution, controlling reaction temperature is at 50 DEG C or so, 50 DEG C after addition
Insulation produces ethero-sulfuric acid after 30 minutes.
By above-mentioned prepared ethero-sulfuric acid, be evaporated under reduced pressure at 150~160 DEG C, vacuum degree control-
0.095MPa, 155g dithyl sulfates are obtained, the product is washed twice, anhydrous magnesium sulfate is dried, and filtration drying agent is
Product 154g, yield 91.9% are obtained, GC shows that main peak is more than 99.2%, and the product is carried out once to be evaporated under reduced pressure (85~130
DEG C/10mmHg), obtain product 152g, GC and show that purity is 99.7%.
It can be seen that preparing ethero-sulfuric acid using method provided by the present invention, ethero-sulfuric acid can be greatly improved
Purity, and then the yield of the subsequent reactions using ethero-sulfuric acid can be increased substantially, increase economic efficiency, than existing side
Method is greatly improved.
Claims (3)
- A kind of 1. method for preparing ethero-sulfuric acid, it is characterised in that：Comprise the following steps that：A certain amount of ethanol, a certain proportion of catalyst are added in the reactor, and sulfur trioxide is then added into reaction solution, is added For controlling reaction temperature between -20~100 DEG C, the reaction time is 0.1~20h, obtains ethero-sulfuric acid during entering；The dosage of wherein described catalyst is that the mol ratio of catalyst/ethanol is 0.001~1,Described ethanol is absolute ethyl alcohol or 95% ethanol；Described catalyst be potassium, sodium, calcium, magnesium, aluminium, zinc, iron, tin, lead, copper, the sulfate of ammonium or hydrochloride or phosphate or Nitrate or carbonate, or sulfuric acid.
- 2. according to the method for claim 1, it is characterised in that：Described ethanol is absolute ethyl alcohol；The mol ratio of the catalyst/ethanol is 0.05~0.15；Described catalyst is sulphur Sour sodium or potassium sulfate or ammonium sulfate.
- 3. according to the method for claim 1, it is characterised in that：Described reaction temperature is 5~60 DEG C, and the reaction time is 0.5~2h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710785694.8A CN107488136B (en) | 2017-09-04 | 2017-09-04 | Method for preparing ethyl hydrogen sulfate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710785694.8A CN107488136B (en) | 2017-09-04 | 2017-09-04 | Method for preparing ethyl hydrogen sulfate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107488136A true CN107488136A (en) | 2017-12-19 |
| CN107488136B CN107488136B (en) | 2020-04-14 |
Family
ID=60651505
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710785694.8A Active CN107488136B (en) | 2017-09-04 | 2017-09-04 | Method for preparing ethyl hydrogen sulfate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107488136B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110642755A (en) * | 2019-09-05 | 2020-01-03 | 泰安汉威集团有限公司 | Environment-friendly production process of diethyl 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 |
| CN115449003A (en) * | 2021-06-09 | 2022-12-09 | 中国石油化工股份有限公司 | Preparation method of PVC resin with low involucra content and uniform pores |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3047604A (en) * | 1958-11-14 | 1962-07-31 | Leatherman Martin | Process for manufacture of ethyl sulfuric acid |
| CN104744198A (en) * | 2015-03-25 | 2015-07-01 | 商洛学院 | Method for preparing ethylene in laboratory |
-
2017
- 2017-09-04 CN CN201710785694.8A patent/CN107488136B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3047604A (en) * | 1958-11-14 | 1962-07-31 | Leatherman Martin | Process for manufacture of ethyl sulfuric acid |
| CN104744198A (en) * | 2015-03-25 | 2015-07-01 | 商洛学院 | Method for preparing ethylene in laboratory |
Non-Patent Citations (2)
| Title |
|---|
| DAVID S. BRESLOW ET AL.: "Synthesis of Sodium Ethylenesulfonate from Ethanol", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| 吴志广等: "硫酸二乙酯合成方法的研究", 《化学试剂》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110642755A (en) * | 2019-09-05 | 2020-01-03 | 泰安汉威集团有限公司 | Environment-friendly production process of diethyl sulfate |
| CN115449003A (en) * | 2021-06-09 | 2022-12-09 | 中国石油化工股份有限公司 | Preparation method of PVC resin with low involucra content and uniform pores |
| CN115449003B (en) * | 2021-06-09 | 2023-12-01 | 中国石油化工股份有限公司 | Preparation method of PVC resin with low film content and uniform pores |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107488136B (en) | 2020-04-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107488136A (en) | A kind of method for preparing ethero-sulfuric acid | |
| CN102911086B (en) | Preparation method of trifluoro methanesulfonic anhydride | |
| JPS6256082B2 (en) | ||
| CN102311364B (en) | Preparation method of o(p)-hydroxybenzonitrile | |
| CN110483473B (en) | Method for preparing 1, 3-propane sultone | |
| CN108558700A (en) | A kind of synthetic method of 1,2- pentanediols | |
| CN102491297A (en) | Method for producing ammonium sulfate in S-NPK device by using refined phosphoric acid byproduct tail liquid | |
| CN103212437A (en) | Method for preparing titanium-based catalyst and synthesizing epoxypropane and dicumyl peroxide | |
| CN102503648B (en) | Method for producing ammonium phosphate sulfate by S-NPK (Sulfur-Containing Nitrogen-Phosphorus-Potassium Compounds) device | |
| CN105461748A (en) | Method for preparing di(isooctyl) phosphate from tri-iso-octyl phosphate through phase-transfer catalytic hydrolysis | |
| CN102659088B (en) | Water-phase synthesis method of sodium azide | |
| CA2797442A1 (en) | Process for the production of ferrous sulphate monohydrate | |
| US8728427B2 (en) | Method for the manufacture of concentrated phosphorus acid | |
| CN1218939C (en) | Process for preparing mercaptoacetic acid | |
| CN106008296A (en) | Thiodipropionic acid clean synthesizing technology | |
| CN1218040A (en) | Process for preparation of methanesulfonic acid | |
| CN110862413A (en) | Glyphosate synthesis process and device | |
| CN106317113A (en) | Synthesis method of L-ascorbic acid-2-monophosphate | |
| CN108440348A (en) | A kind of ALS production technologies | |
| CN104098576B (en) | Prepare the method for nitroorotic acid | |
| CN106316902B (en) | A kind of preparation method of N-cyanoimido-S, S-dimethyl-dithiocarbonate | |
| CN113277472B (en) | Method for preparing hydrogen chloride and co-producing ammonium phosphate salt by decomposing ammonium chloride through thermal polyphosphoric acid | |
| CN110981751A (en) | Production method of diacetyl monoxime | |
| CN108975374A (en) | The method and calcium nitrate of calcium nitrate are prepared using ardealite | |
| CN113292597B (en) | Method for preparing triethyl phosphate compound by recovering sodium diethylphosphate and ethyl chloride |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |