CN107501152B - A kind of separation method of tert-butyl hydroperoxide - Google Patents
A kind of separation method of tert-butyl hydroperoxide Download PDFInfo
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- CN107501152B CN107501152B CN201710701549.7A CN201710701549A CN107501152B CN 107501152 B CN107501152 B CN 107501152B CN 201710701549 A CN201710701549 A CN 201710701549A CN 107501152 B CN107501152 B CN 107501152B
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- tert
- butyl
- butyl hydroperoxide
- separation method
- peroxide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
- C07C407/003—Separation; Purification; Stabilisation; Use of additives
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of separation methods of tert-butyl hydroperoxide.Di-tert-butyl peroxide present in synthesis technology of this method for tert-butyl hydroperoxide forms azeotropic mixture by the way that the tert-butyl alcohol and di-tert-butyl peroxide is added, realizes efficiently separating for di-tert-butyl peroxide.After separating-purifying, the purity of tert-butyl hydroperoxide is up to 99% or more.It is an advantage of the invention that separating tert-butyl hydroperoxide and di-tert-butyl peroxide using azeotropic distillation method, separative efficiency is high, high income, simple process.
Description
Technical field
The invention belongs to the processes of chemical separation process, specifically, being to be related to the separation of tert-butyl hydroperoxide
Technology.
Background technique
Tert-butyl hydroperoxide is one important point in organic peroxide as active alkane hydroperoxides
Branch.Currently, the technique of synthesizing tertiary butyl hydrogen peroxide maturation has: 1. isobutene peroxide passivations, this method it is inconvenient because raw material stores and
The disadvantages of severe reaction conditions, limits industrial production；2. oxidation of isobutane method, typical technique is ACRO and Texaco work
The added value of product of skill, the two techniques is high, good in economic efficiency, but reaction needs to carry out at high temperature under high pressure, to equipment requirement
Height, cost of investment is big, and potential risk is big；3. tert-butyl alcohol peroxide passivation is domestic industry production uncle because cost of investment is low
The main method of butylhydroperoxide, but a large amount of acid-bearing wastewaters can be generated in production process, seriously pollute environment.Patent CN
The method that 104262222A reports a kind of bionic catalysis oxidation iso-butane preparation tert-butyl hydroperoxide, the reaction can compared with
To carry out under conditions of mild, safety, there is great industrialization value.
There are a certain amount of di-tert-butyl peroxide in tert-butyl hydroperoxide synthesis technology, current separation method has
Chemical extraction method and rectification under vacuum method, chemical extraction method separating effect is bad, can introduce new impurity, and generates a large amount of useless
Liquid.Since the boiling point of two components is very close, therefore also it is difficult to fully achieve the separation of the two using rectification under vacuum method.
To realize the complete of tert-butyl hydroperoxide and di-tert-butyl peroxide in tert-butyl hydroperoxide synthesis technology
Separation, develops the rectificating method of a kind of azeotropic separation tert-butyl hydroperoxide and di-tert-butyl peroxide, for realizing uncle
Butylhydroperoxide industrialization has great importance.
Summary of the invention
It is high that it is an object of the invention to overcome the deficiencies of the prior art and provide a kind of separative efficiencies, tert-butyl with high purity
The separation method of hydrogen peroxide.
To achieve the above object, the technical solution adopted by the present invention is that:
A kind of separation method of tert-butyl hydroperoxide, in the mixing of tert-butyl hydroperoxide and di-tert-butyl peroxide
Entrainer is added in liquid, which can form azeotropic mixture with di-tert-butyl peroxide, then realize tert-butyl mistake by rectifying
Hydrogen oxide and di-tert-butyl peroxide are kept completely separate.
In above-mentioned separation method, preferably, including the following steps: tert-butyl hydroperoxide and di-t-butyl
The mixed liquor of peroxide is mixed with entrainer, is first preheated and is passed through feed inlet afterwards and enter rectifying column, after being separated by rectifying, tower top
Gas-phase product by condenser condense the azeotropic mixture that is formed of di-tert-butyl peroxide and entrainer, a portion are passed through back
Stream returns to tower top, and another part is produced from the discharge port of rectifying column；Tower reactor liquid product is tert-butyl hydroperoxide product, wherein
A part returns to tower reactor by reboiler, and another part is produced from the discharge port of rectifying column.
In above-mentioned separation method, preferably, the entrainer is the tert-butyl alcohol, additive amount is 32 ~ 38 kg/
h。
In above-mentioned separation method, preferably, the preheating refers to that being preheating to temperature is 25 ~ 30 DEG C.
In above-mentioned separation method, preferably, the theoretical cam curve of the rectifying column is 30 ~ 50 pieces, charging
Charging Board position where mouthful is the 7th ~ 12 piece.
In above-mentioned separation method, preferably, 38.3 ~ 58.6 DEG C of the bottom temperature, tower reactor pressure is 6 ~
18 KPa。
In above-mentioned separation method, preferably, the molar ratio of the reflux is 1.9 ~ 2.7:1.
Compared with prior art, the invention has the following beneficial effects: the present invention separates tertiary fourth using azeotropic distillation method
Base hydrogen peroxide and di-tert-butyl peroxide, after separating-purifying, the purity of tert-butyl hydroperoxide is up to 99% or more；Point
From high-efficient, high income, simple process.
Specific embodiment
The present invention is illustrated with following embodiment, but the present invention is not limited to the following embodiments.By three embodiments, to this
Method provided by inventing is further described.
Embodiment 1
The method of the present invention is used for the separation process of tert-butyl hydroperoxide and di-tert-butyl peroxide.The place of mixed liquor
Reason amount is 50 kg/h, and wherein the mass fraction of tert-butyl hydroperoxide is 60%, and the mass fraction of di-tert-butyl peroxide is
40%.35 kg/h of the tert-butyl alcohol is added, by the mixed liquor of tert-butyl hydroperoxide and di-tert-butyl peroxide and the tertiary fourth of entrainer
Alcohol mixing, first preheat and passes through feed inlet afterwards and enter rectifying column, and after being separated by rectifying, top gaseous phase product is by condenser condensation
The azeotropic mixture that is formed of di-tert-butyl peroxide and entrainer, a portion return to tower top by reflux, another part from
The discharge port of rectifying column produces；Tower reactor liquid product is tert-butyl hydroperoxide product, and a portion is returned by reboiler
Tower reactor, another part are produced from the discharge port of rectifying column.Wherein feeding temperature is 30 DEG C, and feed pressure is 18 KPa, feed inlet
Charging Board position be the 7th piece, control reflux ratio be 1.9, control 50.3 DEG C of bottom temperature, tower reactor pressure be 11 KPa, tower reactor
The content that extraction produces di-tert-butyl peroxide in tert-butyl hydroperoxide product is 58 ppm, and the yield of tert-butyl hydroperoxide is
100%。
Embodiment 2
The method of the present invention is used for the separation process of tert-butyl hydroperoxide and di-tert-butyl peroxide.The place of mixed liquor
Reason amount is 50 kg/h, and wherein the mass fraction of tert-butyl hydroperoxide is 70%, and the mass fraction of di-tert-butyl peroxide is
30%.32 kg/h of the tert-butyl alcohol is added, by the mixed liquor of tert-butyl hydroperoxide and di-tert-butyl peroxide and the tertiary fourth of entrainer
Alcohol mixing, first preheat and passes through feed inlet afterwards and enter rectifying column, and after being separated by rectifying, top gaseous phase product is by condenser condensation
The azeotropic mixture that is formed of di-tert-butyl peroxide and entrainer, a portion return to tower top by reflux, another part from
The discharge port of rectifying column produces；Tower reactor liquid product is tert-butyl hydroperoxide product, and a portion is returned by reboiler
Tower reactor, another part are produced from the discharge port of rectifying column.Wherein feeding temperature is 25 DEG C, and feed pressure is 6 KPa, feed inlet
Feeding Board position is the 8th piece, and control reflux ratio is 2.2, controls 38.3 DEG C of bottom temperature, tower reactor pressure is 6 KPa, tower reactor extraction
The content for producing di-tert-butyl peroxide in tert-butyl hydroperoxide product is 38 ppm, and the yield of tert-butyl hydroperoxide is
100%。
Embodiment 3
The method of the present invention is used for the separation process of tert-butyl hydroperoxide and di-tert-butyl peroxide.The place of mixed liquor
Reason amount is 50 kg/h, and wherein the mass fraction of tert-butyl hydroperoxide is 80%, and the mass fraction of di-tert-butyl peroxide is
20%.Add 38 kg/h of the tert-butyl alcohol, the mixed liquor and the entrainer tert-butyl alcohol of tert-butyl hydroperoxide and di-tert-butyl peroxide
Mixing first preheat and passes through feed inlet afterwards and enter rectifying column, and after being separated by rectifying, top gaseous phase product passes through condenser and condenses
The azeotropic mixture that di-tert-butyl peroxide and entrainer are formed, a portion return to tower top by reflux, and another part is from essence
Evaporate the discharge port extraction of tower；Tower reactor liquid product is tert-butyl hydroperoxide product, and a portion returns to tower by reboiler
Kettle, another part are produced from the discharge port of rectifying column.Wherein feeding temperature is 30 DEG C, and feed pressure is 18 KPa, feed inlet
Feeding Board position is the 12nd piece, and control reflux ratio is 2.7, controls 58.6 DEG C of bottom temperature, and tower reactor pressure is 18 KPa, and tower reactor is adopted
The content for producing di-tert-butyl peroxide in tert-butyl hydroperoxide product is 25 ppm, and the yield of tert-butyl hydroperoxide is
100%。
Claims (5)
1. a kind of separation method of tert-butyl hydroperoxide, it is characterised in that: in tert-butyl hydroperoxide and di-t-butyl peroxide
Entrainer is added in the mixed liquor of compound, which can form azeotropic mixture with di-tert-butyl peroxide, then pass through rectifying reality
Existing tert-butyl hydroperoxide and di-tert-butyl peroxide are kept completely separate；
Include the following steps: that the mixed liquor by tert-butyl hydroperoxide and di-tert-butyl peroxide is mixed with entrainer, it is first pre-
Rectifying column is entered by feed inlet after heat, after separating by rectifying, top gaseous phase product condenses to obtain di-t-butyl by condenser
The azeotropic mixture that peroxide and entrainer are formed, a portion return to tower top by reflux, and another part goes out from rectifying column
Material mouth extraction；Tower reactor liquid product is tert-butyl hydroperoxide product, and a portion returns to tower reactor, another portion by reboiler
Divide and is produced from the discharge port of rectifying column；
The entrainer is the tert-butyl alcohol, and additive amount is 32 ~ 38 kg/h.
2. separation method as described in claim 1, which is characterized in that the preheating refers to that being preheating to temperature is 25 ~ 30 DEG C.
3. separation method as described in claim 1, which is characterized in that the theoretical cam curve of the rectifying column is 30 ~ 50 pieces,
Charging Board position where feed inlet is the 7th ~ 12 piece.
4. separation method as described in claim 1, which is characterized in that 38.3 ~ 58.6 DEG C of the bottom temperature, tower reactor pressure
For 6 ~ 18 KPa.
5. separation method as described in claim 1, which is characterized in that the molar ratio of the reflux is 1.9 ~ 2.7:1.
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| CN201710701549.7A CN107501152B (en) | 2017-08-16 | 2017-08-16 | A kind of separation method of tert-butyl hydroperoxide |
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| CN201710701549.7A CN107501152B (en) | 2017-08-16 | 2017-08-16 | A kind of separation method of tert-butyl hydroperoxide |
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| CN107501152A CN107501152A (en) | 2017-12-22 |
| CN107501152B true CN107501152B (en) | 2019-09-20 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3091280B1 (en) * | 2018-12-26 | 2021-06-25 | Arkema France | PURIFICATION OF ALKYL HYDROPEROXIDE BY EXTRACTIVE DISTILLATION |
| FR3091283B1 (en) * | 2018-12-26 | 2021-06-25 | Arkema France | PURIFICATION OF ALKYL HYDROPEROXIDE BY DISTILLATION IN THE PRESENCE OF METHANOL AND WATER |
| CN112300045A (en) * | 2019-12-06 | 2021-02-02 | 广东中准新材料科技有限公司 | Synthesis and purification method of high-purity tert-amyl peroxy-2-ethylhexyl carbonate |
| CN112300044A (en) * | 2019-12-06 | 2021-02-02 | 广东中准新材料科技有限公司 | Synthesis and purification method of high-purity tert-butyl peroxy-2-ethylhexyl carbonate |
| CN112159343A (en) * | 2020-10-26 | 2021-01-01 | 北京水木滨华科技有限公司 | Purification method of tert-butyl hydroperoxide |
| CN112375025A (en) * | 2020-11-27 | 2021-02-19 | 信汇科技有限公司 | Purification method of tert-butyl hydroperoxide |
| CN112300046A (en) * | 2020-11-27 | 2021-02-02 | 信汇科技有限公司 | Purification method of tert-butyl hydroperoxide and recycling method of tert-butyl alcohol |
| CN115850143A (en) * | 2022-12-26 | 2023-03-28 | 兰州助剂厂有限责任公司 | Method for removing light components from tert-butyl hydroperoxide |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105523982A (en) * | 2014-10-23 | 2016-04-27 | 茅海强 | Method for preparing tert-butyl hydroperoxide |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105523982A (en) * | 2014-10-23 | 2016-04-27 | 茅海强 | Method for preparing tert-butyl hydroperoxide |
Non-Patent Citations (1)
| Title |
|---|
| New method for preparation of 9,10-phenanthrenequinone;Saito, Yoshinori等;《Aromatikkusu》;19871031;第202页 * |
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