CN114163310A - Method for separating and purifying benzenediol isomer - Google Patents
Method for separating and purifying benzenediol isomer Download PDFInfo
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- CN114163310A CN114163310A CN202111547845.9A CN202111547845A CN114163310A CN 114163310 A CN114163310 A CN 114163310A CN 202111547845 A CN202111547845 A CN 202111547845A CN 114163310 A CN114163310 A CN 114163310A
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- C07—ORGANIC CHEMISTRY
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- 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 method for separating and purifying benzenediol isomers, which adopts a solvent crystallization method to crystallize and purify at least one of a pyrocatechol crude product, a hydroquinone crude product or a resorcinol crude product; the crude catechol is crystallized and purified by adopting an aromatic solvent or a mixed solvent, the crude hydroquinone is crystallized and purified by adopting a polar solvent or a mixed solvent, the crude resorcinol is crystallized and purified by adopting a mixed solvent, solid-liquid separation is carried out after crystallization to remove a solution to obtain a filter cake, and the filter cake is dried in vacuum at a melting point to obtain a pure product with the content of more than 99 percent. The method can separate and purify the benzenediol monomer product with the purity of more than 99 percent, increases the dissolving capacity of the solvent, reduces the volatilization loss of the solvent, reduces the proportion of the solvent, saves the energy consumption of solvent recovery, reduces the investment of production equipment, has mild conditions in the whole separation and purification process, simple operation and low production cost, and improves the economic benefit.
Description
Technical Field
The invention relates to the technical field of gasified phenol processing, in particular to a method for separating and purifying benzenediol isomers.
Background
The gasified phenol slag is rich in diphenol isomers with high added value, and accounts for 5-10% of the gasified phenol raw material. In the gasified phenol raw material, after small cresol and xylenol are extracted, useful benzenediol is enriched in phenol residues, and the total content of valuable isomers generally reaches more than 50 percent of the phenol residues.
The gasified phenol residue contains dozens of diphenol isomers such as benzenediol, methyl benzenediol, ethyl benzenediol, dimethyl benzenediol and the like, has complex components and very close boiling points, for example, the boiling point difference between resorcinol and the benzenediol is only 5 ℃, resorcinol and the benzenediol cannot be directly separated by a rectification method, and a single isomeric product with a certain high purity is obtained. After rectification and enrichment, a single isomer raw material with the content of more than 80-85% is obtained, and then a crystallization method is used for obtaining a single isomer product with the content of more than 99%, so that the gasified phenol residues can be recycled, the economic benefit of an enterprise is obviously increased, and the method has important significance.
At present, US4239921(a) and CN102643169A disclose a technology for purifying resorcinol by toluene solvent crystallization, but the boiling point of the used solvent toluene is lower, which results in excessive volatilization loss in the production process, the solvent proportion is higher, which also results in increased investment in production equipment and higher production cost, and the technology is mainly suitable for purifying crude resorcinol obtained by synthesis, and meanwhile, the technology only aims at the purification of resorcinol, and does not disclose that the technology can be used for the crystallization purification of catechol and hydroquinone, and the crystallization purification modes of the two are obviously different.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a method for separating and purifying diphenol isomers, which aims to solve the technical problems in the prior art. The method can separate and purify the benzenediol monomer products (such as catechol, resorcinol and hydroquinone) with the purity of more than 99 percent, increases the dissolving capacity of the solvent, reduces the volatilization loss of the solvent, reduces the proportion of the solvent, saves the energy consumption of solvent recovery, reduces the investment of production equipment, has mild conditions in the whole separation and purification process, is simple to operate, has low production cost, and improves the economic benefit.
The purpose of the invention is realized by the following technical scheme:
a method for separating and purifying isomers of benzenediol comprising: at least one of the catechol crude product, the hydroquinone crude product or the resorcinol crude product is crystallized and purified by adopting a solvent crystallization method as follows:
(1) mixing the catechol crude product with a first organic solvent, wherein the dosage of the first organic solvent is 0.6-1.0 times of the total mass of the catechol crude product, heating to completely dissolve the material, the crystallization temperature is 30-80 ℃, performing solid-liquid separation after crystallization to remove the solution to obtain a filter cake, and performing vacuum drying on the filter cake at the melting point to obtain a pure catechol product with the content of more than 99%; the first organic solvent is an aromatic hydrocarbon solvent or a mixed solvent;
(2) mixing the hydroquinone crude product with a second organic solvent, wherein the dosage of the second organic solvent is 1.5-5.0 times of the total mass of the hydroquinone crude product, heating to completely dissolve the material, the crystallization temperature is 30-70 ℃, performing solid-liquid separation after crystallization to remove the solution to obtain a filter cake, and performing vacuum drying on the filter cake at the melting point to obtain a pure hydroquinone product with the content of more than 99%; the second organic solvent is a polar solvent or a mixed solvent;
(3) mixing the resorcinol crude product with a third organic solvent, wherein the using amount of the third organic solvent is 1.2-1.5 times of the total mass of the resorcinol crude product, heating to completely dissolve the material, the crystallization temperature is 30-60 ℃, performing solid-liquid separation after crystallization to remove the solution to obtain a filter cake, and performing vacuum drying on the filter cake at the melting point to obtain a pure resorcinol product with the content of more than 99%; the third organic solvent is a mixed solvent;
the mixed solvent is formed by mixing an aromatic hydrocarbon solvent and a polar solvent according to the mass ratio of the aromatic hydrocarbon to the polar solvent being 3-4: 1.
Preferably, the aromatic hydrocarbon solvent is a benzene solvent with a boiling point of 136-176 ℃. Preferably, the aromatic hydrocarbon solvent adopts at least one of ethylbenzene, xylene isomer, trimethylbenzene isomer, cumene, propylbenzene and methyl ethylbenzene isomer.
Preferably, the polar solvent adopts alcohols with a boiling point of 105-176 ℃, ketones with a boiling point of 105-176 ℃ or esters with a boiling point of 105-176 ℃. Preferably, the alcohol is at least one of n-butanol, isobutanol, methyl isobutyl carbinol, n-pentanol, isopentanol, n-hexanol, n-heptanol and 2-heptanol; the ketone is at least one of methyl isobutyl ketone and cyclohexanone; the esters are at least one of n-butyl acetate, isobutyl acetate, n-amyl acetate and isoamyl acetate.
Preferably, the gasified phenol residue is rectified to obtain a catechol crude product with the purity of more than 80 percent, a hydroquinone crude product with the purity of more than 80 percent or a resorcinol crude product with the purity of more than 85 percent; and then crystallizing and purifying at least one of the catechol crude product, the hydroquinone crude product or the resorcinol crude product by a solvent crystallization method.
Preferably, the method is used for separating and purifying diphenol monomer from raw material containing diphenol mixture.
Preferably, the method is used for purifying the crude benzenediol produced by the chemical synthesis method.
Preferably, the method is used for separating and purifying hydroquinone monomers from gasified phenol residues.
Compared with the prior art, the method for separating and purifying the isomer of the benzenediol does not use a toluene solvent, but adopts an aromatic hydrocarbon solvent with the boiling point of 136-176 ℃ or a mixed solvent with a specific formula to crystallize and purify a crude benzenediol, adopts a polar solvent with the boiling point of 105-176 ℃ or a mixed solvent with a specific formula to crystallize and purify a crude benzenediol, and adopts a mixed solvent with a specific formula to crystallize and purify a crude resorcinol, so that benzenediol monomer products (such as resorcinol, catechol and hydroquinone) with the purity of more than 99 percent can be separated and purified, the dissolving capacity of the solvent is increased, the volatilization loss of the solvent is reduced, the solvent ratio is reduced, the energy consumption of solvent recovery is saved, the investment of production equipment is reduced, the condition of the whole separation and purification process is mild, the operation is simple, the production cost is low, the economic benefit is improved.
Detailed Description
The technical scheme in the embodiment of the invention is clearly and completely described below; it is to be understood that the described embodiments are merely exemplary of the invention, and are not intended to limit the invention to the particular forms disclosed. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
The terms that may be used herein are first described as follows:
the terms "comprising," "including," "containing," "having," or other similar terms of meaning should be construed as non-exclusive inclusions. For example: including a feature (e.g., material, component, ingredient, carrier, formulation, material, dimension, part, component, mechanism, device, process, procedure, method, reaction condition, processing condition, parameter, algorithm, signal, data, product, or article of manufacture), is to be construed as including not only the particular feature explicitly listed but also other features not explicitly listed as such which are known in the art.
The term "consisting of … …" is meant to exclude any technical feature elements not explicitly listed. If used in a claim, the term shall render the claim closed except for the inclusion of the technical features that are expressly listed except for the conventional impurities associated therewith. If the term occurs in only one clause of the claims, it is defined only to the elements explicitly recited in that clause, and elements recited in other clauses are not excluded from the overall claims.
When concentrations, temperatures, pressures, dimensions, or other parameters are expressed as ranges of values, the ranges are to be understood as specifically disclosing all ranges formed from any pair of upper, lower, and preferred values within the range, regardless of whether ranges are explicitly recited; for example, if a numerical range of "2 ~ 8" is recited, then the numerical range should be interpreted to include ranges of "2 ~ 7", "2 ~ 6", "5 ~ 7", "3 ~ 4 and 6 ~ 7", "3 ~ 5 and 7", "2 and 5 ~ 7", and the like. Unless otherwise indicated, the numerical ranges recited herein include both the endpoints thereof and all integers and fractions within the numerical range.
The method for separating and purifying isomers of benzenediol provided by the present invention is described in detail below. Details which are not described in detail in the embodiments of the invention belong to the prior art which is known to the person skilled in the art. Those not specifically mentioned in the examples of the present invention were carried out according to the conventional conditions in the art or conditions suggested by the manufacturer. The reagents or instruments used in the examples of the present invention are not specified by manufacturers, and are all conventional products available by commercial purchase.
The invention provides a method for separating and purifying benzenediol isomers, which can be used for separating and purifying benzenediol monomers from raw materials containing benzenediol mixtures, such as: separating and purifying hydroquinone monomers from gasified phenol residues, which comprises:
at least one of the catechol crude product, the hydroquinone crude product or the resorcinol crude product is crystallized and purified by adopting a solvent crystallization method as follows:
(1) mixing the catechol crude product with a first organic solvent, wherein the dosage of the first organic solvent is 0.6-1.0 times of the total mass of the catechol crude product, heating to completely dissolve the material, the crystallization temperature is 30-80 ℃, performing solid-liquid separation (for example, the solid-liquid separation can be centrifugal filtration separation) after crystallization to remove the solution and obtain a filter cake, and then performing vacuum drying on the filter cake at the melting point to obtain a pure catechol product with the content of more than 99%; the first organic solvent is an aromatic hydrocarbon solvent or a mixed solvent.
(2) Mixing the hydroquinone crude product with a second organic solvent, wherein the dosage of the second organic solvent is 1.5-5.0 times of the total mass of the hydroquinone crude product, heating to completely dissolve the material, the crystallization temperature is 30-70 ℃, performing solid-liquid separation (for example, the solid-liquid separation can be centrifugal filtration separation) after crystallization to remove the solution and obtain a filter cake, and then performing vacuum drying on the filter cake at the melting point to obtain a pure hydroquinone product with the content of more than 99%; the second organic solvent is a polar solvent or a mixed solvent.
(3) Mixing the resorcinol crude product with a third organic solvent, wherein the using amount of the third organic solvent is 1.2-1.5 times of the total mass of the resorcinol crude product, heating to completely dissolve the material, the crystallization temperature is 30-60 ℃, performing solid-liquid separation (for example, the solid-liquid separation can be centrifugal filtration separation) after crystallization to remove the solution to obtain a filter cake, and then performing vacuum drying on the filter cake at a melting point to obtain a pure resorcinol product with the content of more than 99%; the third organic solvent is a mixed solvent.
The mixed solvent is formed by mixing an aromatic hydrocarbon solvent and a polar solvent according to the mass ratio of the aromatic hydrocarbon to the polar solvent being 3-4: 1.
Specifically, the method for separating and purifying isomers of hydroquinone may include the following embodiments:
(1) the aromatic hydrocarbon solvent adopts a benzene solvent with a boiling point of 136-176 ℃, such as: the aromatic hydrocarbon solvent adopts at least one of ethylbenzene, xylene isomer, trimethylbenzene isomer, cumene, propylbenzene and methyl ethylbenzene isomer.
(2) The polar solvent adopts alcohols with a boiling point of 105-176 ℃, ketones with a boiling point of 105-176 ℃ or esters with a boiling point of 105-176 ℃; the alcohols include but are not limited to at least one of n-butanol, isobutanol, methyl isobutyl carbinol (abbreviated as MIBC), n-pentanol, isopentanol, n-hexanol, n-heptanol, 2-heptanol; the ketones include but are not limited to at least one of methyl isobutyl ketone and cyclohexanone; the esters include but are not limited to at least one of n-butyl acetate, isobutyl acetate, n-pentyl acetate and isoamyl acetate.
(3) The catechol crude product can be a catechol crude product with the purity of more than 80 percent obtained by rectifying gasified phenol residues or a catechol crude product produced by a chemical synthesis method; the hydroquinone crude product can be a hydroquinone crude product with the purity of more than 80 percent which is obtained by rectifying gasified phenol residues or a hydroquinone crude product which is produced by adopting a chemical synthesis method; the resorcinol crude product can be a resorcinol crude product with the purity of more than 85 percent obtained by rectifying gasified phenol residues or a resorcinol crude product produced by adopting a chemical synthesis method.
Further, the method for separating and purifying isomers of benzenediol provided by the present invention can be used for separating and purifying benzenediol monomers from raw materials containing benzenediol mixtures, including but not limited to the purification of crude benzenediol produced by chemical synthesis or the separation and purification of benzenediol monomers from gasified phenol residues. When the method is used for separating and purifying the hydroquinone monomer from the gasified phenol residue, the gasified phenol residue can be rectified to obtain a catechol crude product with the purity of more than 80 percent, a hydroquinone crude product with the purity of more than 80 percent or a resorcinol crude product with the purity of more than 85 percent, and then at least one of the catechol crude product, the hydroquinone crude product or the resorcinol crude product is crystallized and purified by adopting a solvent crystallization method: crystallizing and purifying a crude catechol product by adopting an aromatic hydrocarbon solvent or a mixed solvent with a specific formula (the mixed solvent is formed by mixing an aromatic hydrocarbon solvent and a polar solvent according to the mass ratio of aromatic hydrocarbon to the polar solvent being 3-4: 1), crystallizing and purifying a crude resorcinol product by adopting a polar solvent or a mixed solvent with a specific formula (the mixed solvent is formed by mixing an aromatic hydrocarbon solvent and a polar solvent according to the mass ratio of aromatic hydrocarbon to the polar solvent being 3-4: 1), crystallizing and purifying a crude resorcinol product by adopting a mixed solvent with a specific formula (the mixed solvent is formed by mixing an aromatic hydrocarbon solvent and a polar solvent according to the mass ratio of aromatic hydrocarbon to the polar solvent being 3-4: 1), and performing solid-liquid separation after crystallization (for example, the solid-liquid separation can be centrifugal filtration separation) to remove a solution to obtain a filter cake, vacuum drying the filter cake at a melting point to obtain a pure product with the content of more than 99 percent; the method is a technology combining rectification and crystallization, and can prepare hydroquinone monomer products (such as pure resorcinol, pure catechol and pure hydroquinone) with the purity of more than 99 percent from gasified phenol residues.
Compared with the prior art, the method for separating and purifying the benzenediol isomer at least has the following advantages:
(1) at present, in the industry, gasified phenol residues are mainly used as very inefficient fuels, and resource waste is very serious. The gasified phenol residue is rich in hydroquinone isomer, and the market price of a pure product of hydroquinone monomer with the purity of more than 99 percent is very high, but the components of the gasified phenol residue are very complex, and the separation and purification are difficult, so the technology for preparing the high-purity chemical product by separating and purifying the hydroquinone monomer from the gasified phenol residue is not disclosed in the published documents or patent reports. The isomer of benzenediol in the gasified phenol residue is difficult to separate and purify by rectification only. On the one hand, the content of the diphenol isomers in the gasified phenol residues is not high (generally not more than 25wt percent), and the boiling points of the diphenol isomers are not greatly different from each other, such as the boiling points of resorcinol and hydroquinone are only 5 ℃ different. If more than 99% of the end product is obtained by distillation, it is necessary to have a very high number of theoretical plates, for example 100 or more, in the distillation column. On the other hand, the boiling point of hydroquinone is very high, for example up to 286 ℃ which requires rectification under very high vacuum to avoid its thermal decomposition, for example operating at the top of the column below 5 kPa. If the number of the theoretical plates is more than 100, the pressure difference of the rectifying tower can reach about 10kPa, the pressure of the tower kettle can reach 15kPa, and thus, the temperature of the tower kettle is overhigh, and the thermal decomposition of the benzenediol and the severe coking of equipment are caused. In conclusion, the requirement of high theoretical plate number and low tower bottom operation temperature is a pair of contradictions which are difficult to solve, and the method for obtaining the benzenediol product with the purity of more than 99 percent by pure rectification separation and purification is almost impossible. However, the invention proposes a method for rectifying the gasified phenol residue to obtain a pyrocatechol crude product with the purity of more than 80%, a hydroquinone crude product with the purity of more than 80% or a resorcinol crude product with the purity of more than 85%, and the method for obtaining the semi-finished product with the purity of more than 80% or 85% by rectifying only can greatly reduce the requirement on the number of theoretical plates of a rectifying tower, so the method is not difficult to realize industrially.
(2) The invention can combine rectification and crystallization, firstly, the pyrocatechol crude product with the purity of more than 80 percent, the hydroquinone crude product with the purity of more than 80 percent or the resorcinol crude product with the purity of more than 85 percent are extracted from the gasified phenol residues through rectification, and the requirement on the rectification condition is not high; the benzenediol monomer product with the purity of more than 99 percent can be obtained after one-step solvent crystallization, filtration and drying, the finished product yield is high, the added value is high, the condition of the whole separation and purification process is mild, the operation is simple, the production cost is low, and the method has important significance for realizing resource utilization of gasified phenol residues, changing waste into valuable and improving the economic benefit of enterprises.
(3) Compared with patents US4239921(A) and CN102643169A, the invention adopts aromatic hydrocarbon with higher boiling point, and can heat and dissolve the crude product of benzenediol at higher temperature, thereby increasing the dissolving capacity of the solvent and reducing the volatilization loss of the solvent, and the use of polar solvents such as alcohol, ketone, ester and the like can improve the dissolving capacity of the polar benzenediol, reduce the solvent proportion and save the energy consumption of solvent recovery. Further, since the polar solvent has a high dissolving ability, a solvent having a slightly lower boiling point can be selected as necessary.
(4) The three benzenediol isomers (catechol, resorcinol and hydroquinone) can be crystallized and purified by adopting the mixed solvent provided by the invention with the same proportion, so that different solvents are avoided when different monomers are purified, the quantity of equipment (such as a tower, a storage tank and the like) required by solvent recovery is saved, and the equipment investment and the production cost are reduced.
In conclusion, the embodiment of the invention can separate and purify the benzenediol monomer products (such as resorcinol, catechol and hydroquinone) with the purity of more than 99 percent, increases the dissolving capacity of the solvent, reduces the volatilization loss of the solvent, reduces the solvent proportion, saves the energy consumption of solvent recovery, reduces the investment of production equipment, has mild conditions in the whole separation and purification process, simple operation and low production cost, and improves the economic benefit.
In order to more clearly show the technical scheme and the technical effects provided by the present invention, the method for separating and purifying isomers of benzenediol provided by the embodiments of the present invention is described in detail by the following specific examples.
The analytical instruments and methods used in the following examples were as follows: gas chromatograph align 7890B GC, capillary column HJ-5, column length 60m, column diameter 0.32mm, film thickness 0.5 μm; the FID detector is kept at 120 ℃ for 15min, then is heated to 200 ℃ at 10 ℃/min, and is heated to 280 ℃ at 15 ℃/min for 10 min.
Example 1
A method for separating and purifying hydroquinone isomers, which is used for separating and purifying hydroquinone monomers from certain gasified phenol residues purchased in the market, wherein the components of the gasified phenol residues are shown in the following table 1:
TABLE 1
| Composition of gasified phenol slag | Content/wt% |
| Catechol | 31.4 |
| Resorcinol | 25.1 |
| Hydroquinone | 16.8 |
| 4-Methylcatechol | 16.2 |
| Benzoic acid | 3.0 |
| 2-naphthol | 1.5 |
| 2-methylquinoline | 1.3 |
| Trimethylphenol | 0.4 |
| 5-Indenols | 1.6 |
| Ethylbenzenediol | 2.7 |
The method for separating and purifying the isomers of benzenediol may comprise the steps of:
step A1, rectification: performing reduced pressure distillation on 20kg of the gasified phenol residues, performing 10kPa absolute pressure on the top of the tower, fixing the reflux ratio of 30 theoretical plates of the distillation tower to 20, collecting catechol at 100 ℃ of cooling medium at the top of the tower, collecting resorcinol at 100 ℃ of cooling medium at the top of the tower, collecting hydroquinone at 150 ℃ of cooling medium at the top of the tower, collecting catechol crude products containing more than 82.8 wt% of catechol (the main impurities are respectively methyl benzenediol, benzoic acid, 2-methyl quinoline, trimethylphenol and 5-indanol, the contents are respectively 5.4 wt%, 5.6 wt%, 2.5 wt%, 0.7 wt% and 3.0 wt%) at the top of the tower, collecting hydroquinone crude products containing more than 80.5 wt% of hydroquinone (the main impurities are respectively resorcinol and 2-naphthol, the contents are respectively 8.7 wt% and 10.8 wt%) at the top of the tower are 207 to 210 ℃, and (3) when the temperature of the tower top is within the range of 201-204 ℃, obtaining a resorcinol crude product containing resorcinol above 86.1 wt% (the main impurities are hydroquinone, 2-naphthol and ethyl benzenediol respectively, and the contents are 7.1 wt%, 1.2 wt% and 5.6 wt% respectively).
Step A2, adding 60g of mixed solvent (the mixed solvent is formed by mixing ethylbenzene and methyl isobutyl carbinol (abbreviated as MIBC) according to the mass ratio of 3: 1) into 100g of the crude catechol, heating to completely dissolve the materials, slowly cooling to 30 ℃ for crystallization, keeping for 2 hours, performing suction filtration and separation to obtain 47g of filter cake, and performing vacuum drying on the filter cake at 100 ℃ to obtain 39g of pure catechol product. Through detection: the catechol content of the pure catechol product was 99.9 wt%.
Example 2
A method for separating and purifying diphenol isomers, which is used for separating and purifying diphenol monomers from gasified phenol residues in embodiment 1 of the invention, can comprise the following steps:
step B1 was the same as step A1 of inventive example 1.
And step B2, adding 80g of cumene solvent into 100g of the catechol crude product, heating to completely dissolve the material, slowly cooling to 50 ℃ for crystallization, keeping for 2 hours, performing suction filtration separation to obtain 75g of filter cake, and performing vacuum drying on the filter cake at 100 ℃ to obtain 64g of pure catechol product. Through detection: the catechol content of the pure catechol product was 99.9 wt%.
Example 3
A method for separating and purifying diphenol isomers, which is used for separating and purifying diphenol monomers from gasified phenol residues in embodiment 1 of the invention, can comprise the following steps:
step C1 was the same as step A1 of inventive example 1.
And step C2, adding 100g of ethylbenzene solvent into 100g of the catechol crude product, heating to completely dissolve the material, slowly cooling to 80 ℃ for crystallization, keeping for 2 hours, performing suction filtration and separation to obtain 48g of filter cake, and then performing vacuum drying on the filter cake at 100 ℃ to obtain 41g of pure catechol product. Through detection: the catechol content of the pure catechol product was 99.9 wt%.
Example 4
A method for separating and purifying diphenol isomers, which is used for separating and purifying diphenol monomers from gasified phenol residues in embodiment 1 of the invention, can comprise the following steps:
step D1 was the same as step A1 of inventive example 1.
And D2, adding 150g of n-butanol solvent into 100g of the hydroquinone crude product, heating to completely dissolve the material, slowly cooling to 30 ℃ for crystallization, keeping for 2 hours, performing suction filtration separation to obtain 46g of filter cake, and then performing vacuum drying on the filter cake at 120 ℃ to obtain 39g of pure hydroquinone product. Through detection: the hydroquinone content of the pure hydroquinone product is 99.5 wt%.
Example 5
A method for separating and purifying diphenol isomers, which is used for separating and purifying diphenol monomers from gasified phenol residues in embodiment 1 of the invention, can comprise the following steps:
step E1 was the same as step A1 of inventive example 1.
And E2, adding 180g of methyl isobutyl ketone (abbreviated as MIBK) solvent into 100g of the hydroquinone crude product, heating to completely dissolve the material, slowly cooling to 50 ℃ for crystallization, keeping for 2 hours, performing suction filtration and separation to obtain 27g of filter cake, and then performing vacuum drying on the filter cake at 120 ℃ to obtain 23g of pure hydroquinone product. Through detection: the hydroquinone content of the pure hydroquinone product is 99.7 wt%.
Example 6
A method for separating and purifying diphenol isomers, which is used for separating and purifying diphenol monomers from gasified phenol residues in embodiment 1 of the invention, can comprise the following steps:
step F1 was the same as step A1 of inventive example 1.
Step F2, adding 400g of a mixed solvent (the mixed solvent is formed by mixing ethylbenzene and methyl isobutyl carbinol (abbreviated as MIBC) according to a mass ratio of 3: 1) into 100g of the crude hydroquinone, heating to completely dissolve the materials, slowly cooling to 50 ℃ for crystallization, keeping for 2 hours, performing suction filtration to separate 59g of filter cake, and then performing vacuum drying on the filter cake at 170 ℃ to obtain 49g of a pure hydroquinone product. Through detection: the hydroquinone content of the pure hydroquinone product is 99.3 wt%.
Example 7
A method for separating and purifying diphenol isomers, which is used for separating and purifying diphenol monomers from gasified phenol residues in embodiment 1 of the invention, can comprise the following steps:
step G1 was the same as step A1 of inventive example 1.
Step G2, adding 500G of mixed solvent (which is formed by mixing hemimellitene and isobutanol according to the mass ratio of 4: 1) into 100G of the hydroquinone crude product, heating to completely dissolve the material, slowly cooling to 70 ℃ for crystallization, keeping for 2 hours, carrying out suction filtration and separation to obtain 44G of filter cake, and then carrying out vacuum drying on the filter cake at 170 ℃ to obtain 38G of pure hydroquinone product. Through detection: the hydroquinone content of the pure hydroquinone product is 99.7 wt%.
Example 8
A method for separating and purifying diphenol isomers, which is used for separating and purifying diphenol monomers from gasified phenol residues in embodiment 1 of the invention, can comprise the following steps:
step H1 was the same as step A1 of inventive example 1.
Step H2, adding 120g of a mixed solvent (the mixed solvent is formed by mixing ethylbenzene and methyl isobutyl carbinol (abbreviated as MIBC) according to a mass ratio of 3: 1) into 100g of the crude resorcinol, heating to completely dissolve the materials, slowly cooling to 30 ℃ for crystallization, keeping for 2 hours, performing suction filtration and separation to obtain 49g of a filter cake, and then performing vacuum drying on the filter cake at 120 ℃ to obtain 41g of a pure resorcinol product. Through detection: the resorcinol content of the pure resorcinol product was 99.1 wt%.
Example 9
A method for separating and purifying diphenol isomers, which is used for separating and purifying diphenol monomers from gasified phenol residues in embodiment 1 of the invention, can comprise the following steps:
step I1 was the same as step A1 of inventive example 1.
Step I2, adding 135g of mixed solvent (the mixed solvent is formed by mixing pseudocumene and n-butyl acetate according to the mass ratio of the pseudocumene to the n-butyl acetate of 3.5: 1) into 100g of the resorcinol crude product, heating to completely dissolve the material, slowly cooling to 40 ℃ for crystallization, keeping for 2 hours, performing suction filtration and separation to obtain 47g of filter cake, and then performing vacuum drying on the filter cake at 120 ℃ to obtain 39g of pure resorcinol product. Through detection: the resorcinol content of the pure resorcinol product was 99.1 wt%.
Example 10
A method for separating and purifying diphenol isomers, which is used for separating and purifying diphenol monomers from gasified phenol residues in embodiment 1 of the invention, can comprise the following steps:
step J1 was the same as step A1 of inventive example 1.
Step J2, adding 150g of a mixed solvent (the mixed solvent is formed by mixing m-xylene and methyl isobutyl ketone (abbreviated as MIBK) according to a mass ratio of 4: 1) into 100g of the crude resorcinol, heating to completely dissolve the materials, slowly cooling to 60 ℃ for crystallization, keeping for 2 hours, performing suction filtration and separation to obtain 21g of a filter cake, and then performing vacuum drying on the filter cake at 150 ℃ to obtain 17g of a pure resorcinol product. Through detection: the resorcinol content of the pure resorcinol product was 99.2 wt%.
Examples 1 to 10 summary of information
The information of the above examples 1 to 10 is summarized as shown in the following Table 2:
TABLE 2
The mixed solvent with the same formula (the mixed solvent is formed by mixing ethylbenzene and methyl isobutyl carbinol (abbreviated as MIBC) according to the mass ratio of 3: 1) is used in the above example 1, the above example 6 and the above example 8, which shows that the crude catechol, the crude hydroquinone and the crude resorcinol can be crystallized and purified completely by using the mixed solvent with the same formula, thus saving the number of equipment for recovering the solvent, simplifying the operation flow and reducing the production cost.
In conclusion, the embodiment of the invention can separate and purify the benzenediol monomer products (such as resorcinol, catechol and hydroquinone) with the purity of more than 99 percent, increases the dissolving capacity of the solvent, reduces the volatilization loss of the solvent, reduces the solvent proportion, saves the energy consumption of solvent recovery, reduces the investment of production equipment, has mild conditions in the whole separation and purification process, simple operation and low production cost, and improves the economic benefit.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims. The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (9)
1. A method for separating and purifying isomers of benzenediol, comprising:
at least one of the catechol crude product, the hydroquinone crude product or the resorcinol crude product is crystallized and purified by adopting a solvent crystallization method as follows:
(1) mixing the catechol crude product with a first organic solvent, wherein the dosage of the first organic solvent is 0.6-1.0 times of the total mass of the catechol crude product, heating to completely dissolve the material, the crystallization temperature is 30-80 ℃, performing solid-liquid separation after crystallization to remove the solution to obtain a filter cake, and performing vacuum drying on the filter cake at the melting point to obtain a pure catechol product with the content of more than 99%; the first organic solvent is an aromatic hydrocarbon solvent or a mixed solvent;
(2) mixing the hydroquinone crude product with a second organic solvent, wherein the dosage of the second organic solvent is 1.5-5.0 times of the total mass of the hydroquinone crude product, heating to completely dissolve the material, the crystallization temperature is 30-70 ℃, performing solid-liquid separation after crystallization to remove the solution to obtain a filter cake, and performing vacuum drying on the filter cake at the melting point to obtain a pure hydroquinone product with the content of more than 99%; the second organic solvent is a polar solvent or a mixed solvent;
(3) mixing the resorcinol crude product with a third organic solvent, wherein the using amount of the third organic solvent is 1.2-1.5 times of the total mass of the resorcinol crude product, heating to completely dissolve the material, the crystallization temperature is 30-60 ℃, performing solid-liquid separation after crystallization to remove the solution to obtain a filter cake, and performing vacuum drying on the filter cake at the melting point to obtain a pure resorcinol product with the content of more than 99%; the third organic solvent is a mixed solvent;
the mixed solvent is formed by mixing an aromatic hydrocarbon solvent and a polar solvent according to the mass ratio of the aromatic hydrocarbon to the polar solvent being 3-4: 1.
2. The method for separating and purifying diphenol isomers of claim 1, wherein the aromatic hydrocarbon solvent is benzene solvent with a boiling point of 136-176 ℃.
3. The method for separating and purifying diphenol isomers of claim 1 or 2, wherein the polar solvent is selected from the group consisting of alcohols having a boiling point of 105-176 ℃, ketones having a boiling point of 105-176 ℃ and esters having a boiling point of 105-176 ℃.
4. The method for separating and purifying diphenol isomers of claim 3, wherein said alcohols are at least one of n-butanol, iso-butanol, methyl iso-butyl carbinol, n-pentanol, iso-pentanol, n-hexanol, n-heptanol, 2-heptanol; the ketone is at least one of methyl isobutyl ketone and cyclohexanone; the esters are at least one of n-butyl acetate, isobutyl acetate, n-amyl acetate and isoamyl acetate.
5. The method for separating and purifying diphenol isomers of claim 1 or 2, wherein the aromatic hydrocarbon solvent is at least one of ethylbenzene, xylene isomers, trimethylbenzene isomers, cumene, propylbenzene and methylethylbenzene isomers.
6. The method for separating and purifying isomers of hydroquinone as claimed in claim 1 or 2, wherein the gasified phenol residue is rectified to obtain a crude catechol having a purity of 80% or more, a crude hydroquinone having a purity of 80% or more, or a crude resorcinol having a purity of 85% or more; and then crystallizing and purifying at least one of the catechol crude product, the hydroquinone crude product or the resorcinol crude product by a solvent crystallization method.
7. The method for separating and purifying diphenol isomers of claim 1 or 2, wherein the method is used for separating and purifying diphenol monomers from a feedstock comprising diphenol mixture.
8. The method for separating and purifying isomers of benzenediol as claimed in claim 1 or 2, wherein the method is used for purifying crude benzenediol produced by chemical synthesis.
9. The method for separating and purifying isomers of benzenediol as claimed in claim 1 or 2, wherein the method is used for separating and purifying benzenediol monomers from gasified phenol residues.
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|---|---|---|---|---|
| CN115043710A (en) * | 2022-05-31 | 2022-09-13 | 武汉华尔生物科技有限公司 | Method for purifying high-purity hydroquinone |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4308110A (en) * | 1979-10-09 | 1981-12-29 | Sumitomo Chemical Company Limited | Process for separation and purification of dihydric phenols |
| CA1115733A (en) * | 1979-12-27 | 1982-01-05 | Hirohiko Nambu | Method for recovering resorcinol |
| CS221373B1 (en) * | 1981-12-08 | 1983-04-29 | Zdenek Kvapil | Method of isolation of the pyrocatechine and its homologues from phenol mixtures |
| JPH10151301A (en) * | 1996-11-26 | 1998-06-09 | Mitsui Chem Inc | Method for separating or purifying material from mixed solution by crystallization |
| CN1450986A (en) * | 1999-01-25 | 2003-10-22 | 罗狄亚化学公司 | Method and installation for separating and purifying diphenols in the phenol and phenol derivatives industry |
| CN101054340A (en) * | 2007-05-31 | 2007-10-17 | 上海华谊丙烯酸有限公司 | Method of separating and purifying o/p-dihydroxy benzene prepared by phenol hydroxylation |
| CN101225025A (en) * | 2008-02-13 | 2008-07-23 | 上海华谊丙烯酸有限公司 | Method for separating catechol/hydroquinone from phenol hydroxylation reaction solution |
| CN101412662A (en) * | 2007-10-16 | 2009-04-22 | 江苏扬农化工集团有限公司 | Method for preparing p-dihydroxy benzene |
| CN101479223A (en) * | 2006-06-29 | 2009-07-08 | 罗地亚管理公司 | Process for preparing purified hydroquinone |
| US20110064950A1 (en) * | 2007-12-19 | 2011-03-17 | Jean-Claude Masson | Method for preparing purified pyrocatechol |
| CN106986751A (en) * | 2017-05-25 | 2017-07-28 | 北京石油化工学院 | A kind of method that crude phenols are extracted from carbolic oil |
| CN110944968A (en) * | 2019-10-29 | 2020-03-31 | 上海应用技术大学 | Method for recovering catechol from o-ethoxyphenol reaction liquid |
| CN111592447A (en) * | 2020-06-12 | 2020-08-28 | 内蒙古盛唐国际蒙医药研究院有限公司 | Resorcinol preparation method |
| CN112110796A (en) * | 2020-09-16 | 2020-12-22 | 内蒙古格林特制药有限责任公司 | Resorcinol refining method and concentration distillation equipment |
| CN112679320A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Process for preparing resorcinol and hydroquinone |
-
2021
- 2021-12-16 CN CN202111547845.9A patent/CN114163310A/en active Pending
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4308110A (en) * | 1979-10-09 | 1981-12-29 | Sumitomo Chemical Company Limited | Process for separation and purification of dihydric phenols |
| CA1115733A (en) * | 1979-12-27 | 1982-01-05 | Hirohiko Nambu | Method for recovering resorcinol |
| CS221373B1 (en) * | 1981-12-08 | 1983-04-29 | Zdenek Kvapil | Method of isolation of the pyrocatechine and its homologues from phenol mixtures |
| JPH10151301A (en) * | 1996-11-26 | 1998-06-09 | Mitsui Chem Inc | Method for separating or purifying material from mixed solution by crystallization |
| CN1450986A (en) * | 1999-01-25 | 2003-10-22 | 罗狄亚化学公司 | Method and installation for separating and purifying diphenols in the phenol and phenol derivatives industry |
| CN101479223A (en) * | 2006-06-29 | 2009-07-08 | 罗地亚管理公司 | Process for preparing purified hydroquinone |
| CN101054340A (en) * | 2007-05-31 | 2007-10-17 | 上海华谊丙烯酸有限公司 | Method of separating and purifying o/p-dihydroxy benzene prepared by phenol hydroxylation |
| CN101412662A (en) * | 2007-10-16 | 2009-04-22 | 江苏扬农化工集团有限公司 | Method for preparing p-dihydroxy benzene |
| US20110064950A1 (en) * | 2007-12-19 | 2011-03-17 | Jean-Claude Masson | Method for preparing purified pyrocatechol |
| CN101225025A (en) * | 2008-02-13 | 2008-07-23 | 上海华谊丙烯酸有限公司 | Method for separating catechol/hydroquinone from phenol hydroxylation reaction solution |
| CN106986751A (en) * | 2017-05-25 | 2017-07-28 | 北京石油化工学院 | A kind of method that crude phenols are extracted from carbolic oil |
| CN112679320A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Process for preparing resorcinol and hydroquinone |
| CN110944968A (en) * | 2019-10-29 | 2020-03-31 | 上海应用技术大学 | Method for recovering catechol from o-ethoxyphenol reaction liquid |
| CN111592447A (en) * | 2020-06-12 | 2020-08-28 | 内蒙古盛唐国际蒙医药研究院有限公司 | Resorcinol preparation method |
| CN112110796A (en) * | 2020-09-16 | 2020-12-22 | 内蒙古格林特制药有限责任公司 | Resorcinol refining method and concentration distillation equipment |
Non-Patent Citations (2)
| Title |
|---|
| 李小娜;尹秋响;陈巍;王静康;高海见;: "溶剂对对苯二酚晶体晶习的影响", 化工学报, no. 03, pages 480 - 485 * |
| 杜亚平;: "苯二酚的开发与生产进展", 上海化工, no. 03, pages 19 - 24 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115043710A (en) * | 2022-05-31 | 2022-09-13 | 武汉华尔生物科技有限公司 | Method for purifying high-purity hydroquinone |
| CN115043710B (en) * | 2022-05-31 | 2024-03-12 | 武汉华尔生物科技有限公司 | Purification method of high-purity hydroquinone |
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