CN103694085A - Crystallization method of high-purity antioxidant BHT (butylated hydroxytoluene) - Google Patents
Crystallization method of high-purity antioxidant BHT (butylated hydroxytoluene) Download PDFInfo
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- CN103694085A CN103694085A CN201310744202.2A CN201310744202A CN103694085A CN 103694085 A CN103694085 A CN 103694085A CN 201310744202 A CN201310744202 A CN 201310744202A CN 103694085 A CN103694085 A CN 103694085A
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/16—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by condensation involving hydroxy groups of phenols or alcohols or the ether or mineral ester group derived therefrom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/84—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by crystallisation
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Abstract
The invention discloses a crystallization method of high-purity antioxidant BHT (butylated hydroxytoluene). The method comprises the following steps: adding paracresol and isobutanol as raw materials, and adding concentrated sulfuric acid as a catalyst; conducting an alkylation reaction by controlling the temperature and time, wherein the reaction comprises two stages, in the first stage, the alkylation reaction is conducted in vacuum and a constant-temperature mode is adopted for crystallization, and in the second stage, the alkylation reaction is conducted under micro-positive pressure and a direct freezing mode is adopted for crystallization; finally reacting in the presence of the catalyst to obtain an alkylated mixed solution based on antioxidant BHT. According to the method, the yield of the alkylation reaction, the output quantity and the finished product content are increased, and crystal scales or crystal scars formed on the wall of a kettle are reduced; a product is uniform in crystal particles, high in purity, good in glossiness and long in quality guarantee period.
Description
Technical field
The invention belongs to oxidation inhibitor crystallization technique field, relate in particular to a kind of highly purified antioxidant BHT crystallization method.
Background technology
The traditional crystallization mode of antioxidant BHT is under the condition of the suitable supersaturation degree of maintenance, and supersaturation degree is based upon on metastable region.Traditional way be by cooling, crystallization, thereby crystallize out.And first antioxidant BHT is realized by alkylated reaction, yet traditional alkylated reaction is synthesis under normal pressure, two kinds of modes of reaction under high pressure.And the problem of most critical is, in the process cooling, be difficult to control the metastable region of supersaturation degree, cause crystal grain that crystallization obtains to there will be the phenomenon of seed uneven (thickness polarization, all seed is excessive, crystal seed is generally thinner).So adopt the product that traditional crystallisation by cooling mode obtains first can not guarantee that product is qualified completely, and the purity of product is generally on the low side.
Summary of the invention
The object of the embodiment of the present invention is to provide a kind of highly purified antioxidant BHT crystallization method; be intended to solve the metastable region that is difficult to control supersaturation degree in the process cooling that existing technology exists; cause the crystal grain that crystallization obtains to there will be seed uneven; thereby can not guarantee that the product obtaining is qualified completely, and the general problem on the low side of product purity.
The embodiment of the present invention is achieved in that a kind of highly purified antioxidant BHT crystallization method, it is characterized in that, this highly purified antioxidant BHT crystallization method comprises the following steps:
Step 1, adds p-cresol, isopropylcarbinol as raw material, and adds the vitriol oil as catalyzer;
Step 2, starts to carry out alkylated reaction by controlling temperature and time, and reaction is divided into two stages;
Step 3, the first stage of reaction is, at vacuum condition, carry out alkylated reaction, adopt the mode crystallization of constant temperature, according to BHT content in material proportion, alkanisation turnover ratio, determine that the nucleation time that BHT in metastable region is in crystallization kettle determines thermostat temperature, and determined that thermostat temperature is preferably in 52-55 ℃;
Step 4, the subordinate phase of reaction is under pressure-fired 0.05Mpa condition, to carry out alkylated reaction, directly freezing mode crystallization of employing, BHT that alkylated reaction is able to is that main alkylation mixed solution content is maximum 96%, by direct crystallisation by cooling, wraps up impurity in crystal;
Step 5, the final alkylation mixed solution that obtains antioxidant BHT that reacts under the effect of catalyzer.
It is main alkylation mixed solution content maximum 96% that another object of the embodiment of the present invention is to provide BHT that alkylated reaction is able to, directly crystallisation by cooling in order to wrap up impurity in crystal, first stage, the time that a large amount of brilliant a small bundle of straw, etc. for silkworms to spin cocoons ons form can not wrapped up the content that impurity has improved output finished product in crystal by hot water constant temperature crystallization before crystallization; Subordinate phase directly adopts freezing and crystallizing, and the row that reduces the brilliant dirt of still wall or brilliant scar becomes, and the row that operation suitably can be stopped brilliant dirt and brilliant scar becomes, and draws product crystal uniform particles, and the product purity of this highly purified antioxidant BHT crystallization method is 99.93%--99.96%.
Another object of the embodiment of the present invention is that it is 18 months that the shelf life of products of highly purified antioxidant BHT crystallization method is provided.
Highly purified antioxidant BHT crystallization method provided by the invention, by the first stage, adopt at vacuum condition and carry out alkylated reaction, subordinate phase is carried out alkylated reaction under pressure-fired condition, improved the yield of alkylated reaction, improved quantum of output, alkylated reaction gained take BHT as main alkylation mixed solution content maximum 96%, directly crystallisation by cooling is easy to wrap up impurity in crystal.First stage of the present invention, by hot water constant temperature crystallization, has been improved the content of output finished product; Subordinate phase directly adopts freezing and crystallizing, reduces the formation of the brilliant dirt of still wall or brilliant scar.Product crystal uniform particles of the present invention, has improved product purity (99.93%--99.96%), and product glossiness is good, and the quality guaranteed period of product is 18 months.
Accompanying drawing explanation
Fig. 1 is the highly purified antioxidant BHT crystallization method schema that the embodiment of the present invention provides.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Below in conjunction with drawings and the specific embodiments, application principle of the present invention is further described.
As shown in Figure 1, the highly purified antioxidant BHT crystallization method of the embodiment of the present invention comprises the following steps:
S101: add p-cresol, isopropylcarbinol as raw material, and add the vitriol oil as catalyzer;
S102: start to carry out alkylated reaction by controlling temperature and time, reaction is divided into two stages;
S103: the first stage of reaction is, at vacuum condition, carry out alkylated reaction, adopt the mode crystallization of constant temperature, according to BHT content in material proportion, alkanisation turnover ratio, determine that the nucleation time that BHT in metastable region is in crystallization kettle determines thermostat temperature, and determined that thermostat temperature is preferably in 52-55 ℃;
S104: the subordinate phase of reaction is, under pressure-fired 0.05Mpa condition, carry out alkylated reaction, adopt directly freezing mode crystallization, BHT that alkylated reaction is able to is that the alkylation mixed solution content led is maximum 96%, by direct crystallisation by cooling, wraps up impurity in crystal;
S105: final reaction under the effect of catalyzer obtains take antioxidant BHT as main alkylation mixed solution.
Principle of work of the present invention: by alkylated reaction, reaction is divided into two stages; The first stage of reaction is at vacuum condition, to carry out alkylated reaction, and adopt the mode crystallization of constant temperature; The subordinate phase of reaction is under pressure-fired condition, to carry out alkylated reaction, and adopt directly freezing mode crystallization; Final reaction under the effect of catalyzer obtains take antioxidant BHT as main alkylation mixed solution.
The crystallization method that antioxidant BHT provided by the invention is novel, synthesis under normal pressure and two kinds of modes of reaction under high pressure of traditional alkylated reaction have been changed, but adopt the first stage to carry out alkylated reaction at vacuum condition, subordinate phase is carried out alkylated reaction under pressure-fired condition, this alkylated reaction mode is higher than the yield of traditional reactive mode, under the constant condition of charging capacity, improved quantum of output.And take BHT as main alkylation mixed solution content maximum 96% due to alkylated reaction gained, directly crystallisation by cooling is easy to wrap up impurity in crystal, yet the first stage of the present invention is by hot water constant temperature crystallization, make when a large amount of brilliant a small bundle of straw, etc. for silkworms to spin cocoons ons form before crystallization can not wrap up impurity in crystal, thereby improved the content of output finished product; Subordinate phase of the present invention directly adopts freezing and crystallizing, reduces the formation of the brilliant dirt of still wall or brilliant scar.So product crystal uniform particles drawing with the present invention, and the present invention has improved product purity (99.93%--99.96%), and in similar industry, product purity is the highest, and product glossiness is good, the present invention has extended the quality guaranteed period (18 months) of product, and the GB like product quality guaranteed period is 3 months.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (3)
1. a highly purified antioxidant BHT crystallization method, is characterized in that, this highly purified antioxidant BHT crystallization method comprises the following steps:
Step 1, adds p-cresol, isopropylcarbinol as raw material, and adds the vitriol oil as catalyzer;
Step 2, starts to carry out alkylated reaction by controlling temperature and time, and reaction is divided into two stages;
Step 3, the first stage of reaction is, at vacuum condition, carry out alkylated reaction, adopt the mode crystallization of constant temperature, according to BHT content in material proportion, alkanisation turnover ratio, determine that the nucleation time that BHT in metastable region is in crystallization kettle determines thermostat temperature, and determined that thermostat temperature is preferably in 52-55 ℃;
Step 4, the subordinate phase of reaction is under pressure-fired 0.05Mpa condition, to carry out alkylated reaction, directly freezing mode crystallization of employing, BHT that alkylated reaction is able to is that main alkylation mixed solution content is maximum 96%, by direct crystallisation by cooling, wraps up impurity in crystal;
Step 5, the final alkylation mixed solution that obtains antioxidant BHT that reacts under the effect of catalyzer.
2. highly purified antioxidant BHT crystallization method as claimed in claim 1, it is characterized in that, BHT that alkylated reaction is able to is main alkylation mixed solution content maximum 96%, directly crystallisation by cooling in order to wrap up impurity in crystal, first stage, the time that a large amount of brilliant a small bundle of straw, etc. for silkworms to spin cocoons ons form can not wrapped up the content that impurity has improved output finished product in crystal by hot water constant temperature crystallization before crystallization; Subordinate phase directly adopts freezing and crystallizing, and the row that reduces the brilliant dirt of still wall or brilliant scar becomes, and the row that operation suitably can be stopped brilliant dirt and brilliant scar becomes, and draws product crystal uniform particles, and the product purity of this highly purified antioxidant BHT crystallization method is 99.93%--99.96%.
3. highly purified antioxidant BHT crystallization method as claimed in claim 1, is characterized in that, the shelf life of products of this highly purified antioxidant BHT crystallization method is 18 months.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107602353A (en) * | 2017-11-14 | 2018-01-19 | 郑程 | A kind of preparation method of antioxidant 264 |
| CN107619366A (en) * | 2016-07-15 | 2018-01-23 | 西安淳甄新材料有限公司 | The synthesis of the antioxidant of a series of new |
| CN110759815A (en) * | 2019-10-31 | 2020-02-07 | 安徽海华科技有限公司 | Processing method of BHT (butylated hydroxytoluene) competitive product |
| CN111233634A (en) * | 2020-02-29 | 2020-06-05 | 陕西宝塔山新材料有限公司 | Method for controlling antioxidant BHT crystallization by program forced cooling |
| CN111269092A (en) * | 2020-02-19 | 2020-06-12 | 江苏迈达新材料股份有限公司 | Method for synthesizing antioxidant BHT (butylated hydroxytoluene) by replacing raffinose with tetrakis |
| CN111943816A (en) * | 2020-07-23 | 2020-11-17 | 安徽海华科技有限公司 | Preparation method of high-purity 2, 6-di-tert-butyl-p-cresol |
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| US1931813A (en) * | 1933-03-03 | 1933-10-24 | Kraft Phenix Cheese Corp | Alimentary substance and process for making the same |
| US3940451A (en) * | 1974-09-06 | 1976-02-24 | Heliodoro Monroy | Process of recovering BHT values from mother liquors of the crystallization of BHT obtained by alkylating p-cresol with isobutylene |
| CN1313270A (en) * | 2000-03-13 | 2001-09-19 | 锦州石化天元集团公司 | Process for preparing 2,6-di-tear-butyl p-cresol |
| CN102311318A (en) * | 2010-06-29 | 2012-01-11 | 如皋市金陵化工有限公司 | Processing technique of 2,6-ditbutyl-4-methylphenol |
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- 2013-12-31 CN CN201310744202.2A patent/CN103694085B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1931813A (en) * | 1933-03-03 | 1933-10-24 | Kraft Phenix Cheese Corp | Alimentary substance and process for making the same |
| US3940451A (en) * | 1974-09-06 | 1976-02-24 | Heliodoro Monroy | Process of recovering BHT values from mother liquors of the crystallization of BHT obtained by alkylating p-cresol with isobutylene |
| CN1313270A (en) * | 2000-03-13 | 2001-09-19 | 锦州石化天元集团公司 | Process for preparing 2,6-di-tear-butyl p-cresol |
| CN102311318A (en) * | 2010-06-29 | 2012-01-11 | 如皋市金陵化工有限公司 | Processing technique of 2,6-ditbutyl-4-methylphenol |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107619366A (en) * | 2016-07-15 | 2018-01-23 | 西安淳甄新材料有限公司 | The synthesis of the antioxidant of a series of new |
| CN107602353A (en) * | 2017-11-14 | 2018-01-19 | 郑程 | A kind of preparation method of antioxidant 264 |
| CN110759815A (en) * | 2019-10-31 | 2020-02-07 | 安徽海华科技有限公司 | Processing method of BHT (butylated hydroxytoluene) competitive product |
| CN111269092A (en) * | 2020-02-19 | 2020-06-12 | 江苏迈达新材料股份有限公司 | Method for synthesizing antioxidant BHT (butylated hydroxytoluene) by replacing raffinose with tetrakis |
| CN111233634A (en) * | 2020-02-29 | 2020-06-05 | 陕西宝塔山新材料有限公司 | Method for controlling antioxidant BHT crystallization by program forced cooling |
| CN111233634B (en) * | 2020-02-29 | 2022-10-18 | 陕西宝塔山新材料有限公司 | Method for controlling antioxidant BHT crystallization by program forced cooling |
| CN111943816A (en) * | 2020-07-23 | 2020-11-17 | 安徽海华科技有限公司 | Preparation method of high-purity 2, 6-di-tert-butyl-p-cresol |
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| CN103694085B (en) | 2016-08-17 |
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Address after: 210047 Nanjing, Henan Province, Nanjing Chemical Industrial Park, South Road, No. 69 irrigation Patentee after: Jiangsu Mai Da new material limited company Address before: 210047 Nanjing, Henan Province, Nanjing Chemical Industrial Park, South Road, No. 69 irrigation Patentee before: JIANGSU MAIDA INVESTMENT DEVELOPMENT CO., LTD. |