CN117658779A - Method for recycling resorcinol and m-aminophenol - Google Patents
Method for recycling resorcinol and m-aminophenol Download PDFInfo
- Publication number
- CN117658779A CN117658779A CN202211006848.6A CN202211006848A CN117658779A CN 117658779 A CN117658779 A CN 117658779A CN 202211006848 A CN202211006848 A CN 202211006848A CN 117658779 A CN117658779 A CN 117658779A
- Authority
- CN
- China
- Prior art keywords
- resorcinol
- aminophenol
- catalyst
- polymer
- extractant
- 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.)
- Pending
Links
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 title claims abstract description 194
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 title claims abstract description 158
- 229940018563 3-aminophenol Drugs 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 47
- 238000004064 recycling Methods 0.000 title description 5
- 229920000642 polymer Polymers 0.000 claims abstract description 37
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 238000000605 extraction Methods 0.000 claims description 21
- 239000000539 dimer Substances 0.000 claims description 17
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 15
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 230000007062 hydrolysis Effects 0.000 claims description 12
- 239000008346 aqueous phase Substances 0.000 claims description 11
- 239000012295 chemical reaction liquid Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 7
- 239000012074 organic phase Substances 0.000 claims description 4
- 239000002198 insoluble material Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 description 21
- 238000001816 cooling Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 229940018564 m-phenylenediamine Drugs 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- XAGCINKAXMIFCR-UHFFFAOYSA-N 3-(3-aminoanilino)phenol Chemical compound NC=1C=C(C=CC=1)NC=1C=C(C=CC=1)O XAGCINKAXMIFCR-UHFFFAOYSA-N 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- JSQGOXTYKZBABW-UHFFFAOYSA-N 3-(3-hydroxyanilino)phenol Chemical compound OC1=CC=CC(NC=2C=C(O)C=CC=2)=C1 JSQGOXTYKZBABW-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000012847 fine chemical Substances 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000000575 pesticide Substances 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- ZOWMOTNBNDXEFP-UHFFFAOYSA-N 3-(3-aminophenoxy)phenol Chemical compound NC1=CC=CC(OC=2C=C(O)C=CC=2)=C1 ZOWMOTNBNDXEFP-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 238000007500 overflow downdraw method Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- UNEATYXSUBPPKP-UHFFFAOYSA-N 1,3-Diisopropylbenzene Chemical compound CC(C)C1=CC=CC(C(C)C)=C1 UNEATYXSUBPPKP-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- ZAJAQTYSTDTMCU-UHFFFAOYSA-N 3-aminobenzenesulfonic acid Chemical compound NC1=CC=CC(S(O)(=O)=O)=C1 ZAJAQTYSTDTMCU-UHFFFAOYSA-N 0.000 description 1
- WUBBRNOQWQTFEX-UHFFFAOYSA-N 4-aminosalicylic acid Chemical compound NC1=CC=C(C(O)=O)C(O)=C1 WUBBRNOQWQTFEX-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229960004909 aminosalicylic acid Drugs 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000016614 betalains Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- -1 but not limited to Chemical compound 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- NIJJYAXOARWZEE-UHFFFAOYSA-N di-n-propyl-acetic acid Natural products CCCC(C(O)=O)CCC NIJJYAXOARWZEE-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000000814 tuberculostatic agent Substances 0.000 description 1
- MSRILKIQRXUYCT-UHFFFAOYSA-M valproate semisodium Chemical compound [Na+].CCCC(C(O)=O)CCC.CCCC(C([O-])=O)CCC MSRILKIQRXUYCT-UHFFFAOYSA-M 0.000 description 1
- 229960000604 valproic acid Drugs 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for recovering resorcinol and/or m-aminophenol, which comprises the following steps: the polymer produced in the resorcinol and/or m-aminophenol production process is subjected to a hydrolysis reaction in the presence of a catalyst selected from one or both of sulfuric acid and hydrochloric acid. The invention can obtain resorcinol and m-aminophenol with higher purity, and improves the utilization rate of raw materials and economic benefit.
Description
Technical Field
The invention belongs to the field of fine chemical engineering, and relates to a method for recycling resorcinol and m-aminophenol.
Background
Resorcinol is an important intermediate in fine chemical industry and is widely used in rubber, plastics, medicines, pesticides, dyes and other industries. Currently, the industrial methods for synthesizing resorcinol mainly comprise a benzene sulfonation alkali fusion method, a m-diisopropylbenzene oxidation method and a m-phenylenediamine hydrolysis method.
M-aminophenol is an important intermediate in fine chemical industry and is widely used in medicine, dye, pesticide and other industries. The method is used for preparing the antitubercular agent para-aminosalicylic acid in the medicine field, is used for preparing varieties such as bendiquat, betalain, valproic acid and the like in the pesticide field, is used for preparing dyes, azo dyes and fluorescent whitening agents in the dye field, and is also used as a dyeing raw material of fur and hair. The method for synthesizing the m-aminophenol comprises an m-aminobenzenesulfonic acid alkali fusion method and an m-phenylenediamine hydrolysis method.
In the production process of resorcinol and m-aminophenol, since phenols are heat-sensitive substances, the condensation polymerization side reaction of resorcinol, m-aminophenol and the like inevitably occurs in the high temperature reaction process, and a polymer is produced. The polymer can be recovered in the rectification or extraction process section of the finished product. The polymer contains a large amount of phenolic compounds, has high toxicity and can cause pollution when being directly discharged. However, the phenolic substances are extracted and purified in a complex process, so that the treatment is very difficult and the cost is high, and domestic manufacturers usually adopt a direct incineration method for treatment. But the incineration process still generates a large amount of toxic and harmful gases, which causes environmental pollution.
In the prior art, the resourceful application of the polymer in the production of resorcinol and m-aminophenol is synthetic phenolic resin, building materials, preparation additives, sealants, lubricants and the like. For example, in patent document CN109046246B, formaldehyde, a catalyst, an organic acid metal salt template precursor and the like are added into a reaction kettle for m-phenylenediamine hydrolysis byproducts, so that a nano metal oxide template precursor is formed, and the recycling of the polymer is realized. However, the treatment method does not realize the reutilization of a large amount of phenolic substances in the polymer, so that the resource waste is caused.
Accordingly, there is a need in the art for a process for recovering resorcinol and meta-aminophenol from a polymer in the production of resorcinol/meta-aminophenol.
Disclosure of Invention
The invention provides a method for recycling resorcinol and m-aminophenol by hydrolysis, which aims at the defects of the existing resource utilization technology in the production of resorcinol and m-aminophenol. The invention carries out reverse hydrolysis on the polymer, can obtain resorcinol and m-aminophenol with higher purity, and improves the utilization rate of raw materials and economic benefit.
In particular, the invention provides a process for recovering resorcinol and/or m-aminophenol, the process comprising: the polymer produced in the resorcinol and/or m-aminophenol production process is subjected to a hydrolysis reaction in the presence of a catalyst selected from one or both of sulfuric acid and hydrochloric acid.
In one or more embodiments, the catalyst is sulfuric acid.
In one or more embodiments, the molar ratio of catalyst to amino groups in the polymer in the hydrolysis reaction is from 1 to 2.5:1, preferably from 1.1 to 1.5:1.
In one or more embodiments, the catalyst is fed in an amount of 10 to 30wt% of the total catalyst and water feed in the hydrolysis reaction.
In one or more embodiments, the temperature of the hydrolysis reaction is 210 to 260 ℃, preferably 220 to 250 ℃.
In one or more embodiments, the polymer is selected from one or more of a polymer produced during the hydrolysis process to produce resorcinol and/or m-aminophenol, a dimer produced during the rectification of resorcinol and/or m-aminophenol, and an insoluble material recovered during the extraction of resorcinol and/or m-aminophenol.
In one or more embodiments, the method further comprises: and extracting the reaction liquid by using an extractant to obtain an organic phase containing resorcinol and an aqueous phase after resorcinol extraction.
In one or more embodiments, the method further comprises: after the pH of the aqueous phase after resorcinol extraction is adjusted to 7-8, m-aminophenol in the aqueous phase is extracted using an extractant.
In one or more embodiments, the extractant is selected from one or more of butyl acetate, ethyl acetate, and n-butanol, preferably butyl acetate.
In one or more embodiments, the extractant is used in an amount of 1 to 1.5 times, preferably 1.1.+ -. 0.1 times the volume of the solution to be extracted.
Detailed Description
So that those skilled in the art can appreciate the features and effects of the present invention, a general description and definition of the terms and expressions set forth in the specification and claims follows. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, and in the event of a conflict, the present specification shall control.
The theory or mechanism described and disclosed herein, whether right or wrong, is not meant to limit the scope of the invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
Herein, "comprising," "including," "containing," and similar terms are intended to cover the meaning of "consisting essentially of … …" and "consisting of … …," e.g., where "a comprises B and C" is disclosed herein, "a consisting of B and C" should be considered as having been disclosed herein.
In this document, all features such as values, amounts, and concentrations that are defined as ranges of values or percentages are for brevity and convenience only. Accordingly, the description of a numerical range or percentage range should be considered to cover and specifically disclose all possible sub-ranges and individual values (including integers and fractions) within the range.
Herein, unless otherwise specified, percentages refer to mass percentages, and proportions refer to mass ratios.
Herein, when embodiments or examples are described, it should be understood that they are not intended to limit the invention to these embodiments or examples. On the contrary, all alternatives, modifications, and equivalents of the methods and materials described herein are intended to be included within the scope of the invention as defined by the appended claims.
In this context, not all possible combinations of the individual technical features in the individual embodiments or examples are described in order to simplify the description. Accordingly, as long as there is no contradiction between the combinations of these technical features, any combination of the technical features in the respective embodiments or examples is possible, and all possible combinations should be considered as being within the scope of the present specification.
In the production process of resorcinol and m-aminophenol (including the processes of reaction, rectification, extraction, etc.), m-phenylenediamine, m-aminophenol, resorcinol, etc. as a raw material, intermediate or product inevitably undergoes polycondensation side reactions to produce a polymer (mainly a dimer). The invention uses sulfuric acid and/or hydrochloric acid as catalyst to hydrolyze the polymer produced in the resorcinol and/or m-aminophenol production process into resorcinol, m-aminophenol and other monomers, and further purifying to obtain high-purity resorcinol and m-aminophenol, thereby improving the raw material utilization rate and economic benefit.
The method for recovering resorcinol and/or m-aminophenol of the present invention comprises: the polymer produced in the resorcinol and/or m-aminophenol production process is subjected to a hydrolysis reaction in the presence of a catalyst selected from one or both of sulfuric acid and hydrochloric acid. Herein, unless otherwise indicated, a polymer refers to a polymer produced during resorcinol and/or m-aminophenol production.
The polymer to be hydrolyzed may be derived from polymers produced in various process steps (including reaction, rectification, extraction, etc.) in the production process of resorcinol and/or m-aminophenol, including, but not limited to, polymers produced in the production process of resorcinol and/or m-aminophenol by hydrolysis (e.g., m-phenylenediamine hydrolysis), dimers produced in the rectification of resorcinol and/or m-aminophenol, insoluble matters recovered in the extraction of resorcinol and/or m-aminophenol, etc., such as hydrolysis waste residues, rectification waste residues of resorcinol and m-aminophenol, etc. In some embodiments, the polymer is a dimer produced when rectifying resorcinol and m-aminophenol, optionally also including insoluble material recovered from extraction.
In the invention, the main components of dimers generated during rectification of resorcinol and m-aminophenol and insoluble matters generated during extraction and recovery are 3,3 '-diaminodiphenylamine, 3- (3-amino anilino) phenol, 3' -dihydroxydiphenylamine, 3 '-diaminodiphenyl ether, 3- (3-aminophenoxy) phenol and 3,3' -dihydroxydiphenyl ether, and the structures are shown in the following formulas a-f respectively:
in some embodiments, the major components of the polymers produced during resorcinol and/or meta-aminophenol production used in the present invention are 3,3 '-diaminodiphenylamine, 3- (3-aminoanilino) phenol, 3' -dihydroxydiphenylamine, 3 '-diaminodiphenyl ether, 3- (3-aminophenoxy) phenol, and 3,3' -dihydroxydiphenyl ether; preferably, the sum of the mass of 3,3 '-diaminodiphenylamine, 3- (3-aminoanilino) phenol and 3,3' -dihydroxydiphenylamine is more than 80%, for example 85%, 90%, 95% of the total mass of the polymer.
In some embodiments, the resorcinol and/or m-aminophenol produced in the process of the present invention comprises 3,3 '-diaminodiphenylamine, 3- (3-aminoanilino) phenol and 3,3' -dihydroxydiphenylamine, and the sum of the masses of 3,3 '-diaminodiphenylamine, 3- (3-aminoanilino) phenol and 3,3' -dihydroxydiphenylamine is 85 to 95% of the total mass of the polymer, wherein the mass fraction of 3,3 '-diaminodiphenylamine is preferably 30 to 35% of the total mass of the polymer, the mass fraction of 3- (3-aminoanilino) phenol is preferably 35 to 40% of the total mass of the polymer, and the mass fraction of 3,3' -dihydroxydiphenylamine is preferably 20 to 25% of the total mass of the polymer.
The present invention found that sulfuric acid (H) 2 SO 4 ) And/or hydrochloric acid (HCl) can be used as a catalyst to effectively catalyze the hydrolysis reaction of the polymer, and a cocatalyst is not needed to be used, so that the operation is simple and the catalyst is easy to obtain. The present invention preferably uses sulfuric acid as a catalyst, which is advantageous in improving the yields of resorcinol and m-aminophenol recovered.
The molar ratio of amino groups in the catalyst to polymer in the hydrolysis reaction may be in the range 1 to 2.5:1, preferably 1.1 to 1.5:1, for example 1.2:1, 1.3:1, 1.4:1. Controlling the molar ratio of the catalyst to the amino groups in the polymer within the aforementioned range is advantageous in improving the yields of resorcinol and m-aminophenol recovered. The amino content can be calculated by determining the content of each component in the polymer by liquid chromatography.
In the hydrolysis reaction, the catalyst may be fed in an amount of 10 to 30wt%, for example, 12wt%, 15wt%, 18wt%, 19wt%, 20wt%, 21wt%, 22wt%, 23wt%, 25wt% based on the total amount of the catalyst and water. In the hydrolysis reaction, the catalyst and water may be mixed with the polymer in the form of an aqueous catalyst solution (e.g., sulfuric acid solution, hydrochloric acid solution). The concentration of the aqueous catalyst solution (i.e., the amount of catalyst in the aqueous catalyst solution) may be 10 to 30wt%. Controlling the ratio of catalyst to water within the aforementioned range is advantageous for improving the yields of resorcinol and m-aminophenol recovered. When resorcinol alone is recovered, the concentration of the aqueous catalyst solution (e.g., sulfuric acid solution) is preferably 10wt%. In the case of recovering resorcinol and m-phenylenediamine, the concentration of the aqueous catalyst solution (e.g., sulfuric acid solution) is preferably 18 to 23% by weight, for example, 19% by weight, 20% by weight, 21% by weight, 22% by weight.
The temperature of the hydrolysis reaction may be 210-260 ℃, preferably 220-250 ℃, e.g. 230 ℃, 240 ℃. Preferably, a lower reaction temperature is adopted, which is favorable for reducing impurities and improving the yield. The reaction time may be from 1 to 15 hours, preferably from 2 to 10 hours, for example 2 hours, 4 hours, 6 hours. Controlling the reaction temperature and time within the aforementioned ranges is advantageous for improving the yields of resorcinol and m-aminophenol recovered.
After the hydrolysis reaction is completed, resorcinol can be extracted from the reaction solution by extraction. The extractant used for extracting resorcinol may be one or more selected from butyl acetate, ethyl acetate and n-butanol. Preferably, the resorcinol is extracted using butyl acetate, which is advantageous for increasing resorcinol yield. The extractant may be used in an amount of 1 to 1.5 times, preferably 1 to 1.2 times, for example 1.1 times, the volume of the solution to be extracted. Extracting the reaction liquid by using an extractant, distilling to recover the extractant of an organic phase, thus obtaining crude resorcinol, and rectifying the crude resorcinol under reduced pressure to obtain the finished resorcinol with the purity of 99.5%.
In addition to resorcinol, m-aminophenol can be recovered by the process of the present invention. After resorcinol in the reaction solution is extracted by using an extractant, m-aminophenol remains in the aqueous phase. M-aminophenol may be extracted from the aqueous phase after resorcinol extraction by extraction, for example, by adjusting the pH of the aqueous phase to 7-8 and then extracting with an extractant. The reagent used to adjust the pH may be aqueous ammonia. The extractant used for extracting the m-aminophenol may be one or more selected from butyl acetate, ethyl acetate and n-butanol. Preferably, butyl acetate is used to extract the meta-aminophenol, which is advantageous in improving the yield of meta-aminophenol. The extractant may be used in an amount of 1 to 1.5 times, preferably 1 to 1.2 times, for example 1.1 times, the volume of the solution to be extracted. Extracting m-aminophenol with extractant, distilling to recover organic phase extractant to obtain coarse m-aminophenol, and re-crystallizing with water to obtain m-aminophenol product with purity over 99%.
The invention has the following beneficial effects:
the invention improves the utilization ratio of raw materials in the resorcinol/m-aminophenol production process, reduces the quality of waste and generates economic benefit, and the invention has the advantages of high yield of the recovered resorcinol and m-aminophenol, high product purity, easy obtainment of catalyst, no need of using a cocatalyst and simple operation.
The invention will be further illustrated by means of specific examples. It should be understood that these examples are illustrative only and are not intended to limit the scope of the invention. The methods and reagents used in the examples are, unless otherwise indicated, conventional in the art.
In the examples, the dimer produced when rectifying resorcinol and m-aminophenol and the insoluble matter recovered in the extraction mainly comprise the compounds of the following formula a-f, wherein the total mass fraction of the compounds of the formula a, the compounds of the formula b and the compounds of the formula c is 85-95%, wherein the mass fraction of the compounds of the formula a is 30-35%, the mass fraction of the compounds of the formula b is 35-40%, the mass fraction of the compounds of the formula c is 20-25%, the mass fraction is relative to the total mass of the dimer and the insoluble matter.
In the embodiment, the amino content is calculated by adopting a liquid chromatography method through carrying out quantitative external standard on each dimer, and after the synthesis process is stable, the composition of each batch of extraction waste residue and rectification waste residue is basically consistent.
In examples 1, 3 and 4, the yields of resorcinol and meta-aminophenol were calculated using the following method: the total mole amount of resorcinol and m-aminophenol which can be converted by the theory of substances in the raw materials is recorded as n 1 The molar quantity of the resorcinol finished product obtained by actual conversion is recorded as n 2 The molar quantity of the m-aminophenol finished product obtained by actual conversion is recorded as n 3 Resorcinol yield = n 2 /n 1 *100%, m-aminophenol yield = n 3 /n 1 *100% of the total yield is the sum of resorcinol yield and m-aminophenol yield.
In example 2, the yield of resorcinol was calculated using the following method: the mol amount of resorcinol which can be converted by the theory of substances in the raw materials is recorded as n 1 The molar quantity of the resorcinol finished product obtained by actual conversion is recorded as n 2 Resorcinol yield = n 2 /n 1 *100％。
Example 1
Adding sulfuric acid solution with the concentration of 19% and dimer generated when rectifying resorcinol and m-aminophenol into a reaction kettle (the molar ratio of amino groups in sulfuric acid and dimer is 1.2:1), heating to 240 ℃ for reaction for 2 hours, cooling to normal temperature, extracting the reaction solution by butyl acetate with the volume of 1.2 times of the reaction solution, distilling the solvent to obtain crude resorcinol, and decompressing and rectifying the crude resorcinol to obtain finished resorcinol with the purity of 99.5%. The aqueous phase after resorcinol extraction was neutralized to pH 7.5 with ammonia and the m-aminophenol in the aqueous phase was extracted with 1.2 volumes of butyl acetate. Distilling to recover the extraction solvent, then continuously distilling to obtain crude m-aminophenol, heating and dissolving the crude m-aminophenol by pure water, cooling and crystallizing to obtain the finished m-aminophenol with the purity of more than 99%. The crystallization mother liquor contains a small amount of m-phenylenediamine and m-aminophenol and can be sleeved back to the hydrolysis process. The resorcinol yield was 45.0%, the m-aminophenol yield was 40.5% and the total yield was 85.5%.
Example 2
Adding sulfuric acid solution with the concentration of 10 percent, dimer generated during rectification of resorcinol and m-aminophenol and insoluble matters recovered during extraction into a reaction kettle (the molar ratio of sulfuric acid to amino groups in the dimer and insoluble matters is 1.2:1), heating to 240 ℃ for reaction for 4 hours, cooling to normal temperature, extracting the reaction liquid by adopting butyl acetate with the volume of 1.1 times of the reaction liquid, distilling and recovering the solvent, and carrying out reduced pressure rectification on crude resorcinol to obtain resorcinol products with the purity of up to 99.5 percent. The resorcinol yield was 88%.
Example 3
Adding a hydrochloric acid solution with the concentration of 20% and a dimer generated when rectifying resorcinol and m-aminophenol into a reaction kettle (the molar ratio of hydrochloric acid to amino in the dimer is 2.1:1), heating to 220 ℃ for reaction for 8 hours, cooling to normal temperature, extracting the reaction liquid by butyl acetate with the volume of 1.2 times of the reaction liquid, distilling the solvent to obtain crude resorcinol, and distilling the crude resorcinol under reduced pressure to obtain finished resorcinol (purity 99.5%). And (3) regulating the pH value of the extracted water phase to 7.5 by adopting ammonia water, cooling to normal temperature, extracting by adopting butyl acetate with the volume of 1.2 times of the volume of the reaction liquid, distilling and recovering the solvent to obtain crude m-aminophenol, heating and dissolving by adopting pure water, cooling and recrystallizing, and filtering and drying to obtain m-aminophenol with the purity of more than 99%. The resorcinol yield was 20.3% and the m-aminophenol yield was 55.4%.
Example 4
Adding hydrochloric acid solution with the concentration of 10 percent, dimer generated during rectification of resorcinol and m-aminophenol and insoluble matters recovered during extraction into a reaction kettle (the molar ratio of hydrochloric acid to amino groups in the dimer and insoluble matters is 2.2:1), heating to 220 ℃ for reaction for 15 hours, cooling to normal temperature, extracting the reaction liquid by adopting butyl acetate with the volume of 1.2 times of the reaction liquid, distilling the solvent to obtain crude resorcinol, and obtaining finished resorcinol (purity 99.5%) after reduced pressure distillation of the crude resorcinol, wherein the rectification slag is sleeved back to the hydrolysis process. And (3) regulating the pH value of the extracted water phase to 7.5 by adopting ammonia water, cooling to normal temperature, extracting by adopting butyl acetate with the volume of 1.2 times of the volume of the reaction liquid, distilling and recovering the solvent to obtain crude m-aminophenol, heating and dissolving by adopting pure water, cooling and recrystallizing, and filtering and drying to obtain m-aminophenol with the purity of more than 99%. The resorcinol yield was 30.6% and the m-aminophenol yield was 37.5%.
Claims (10)
1. A process for recovering resorcinol and/or m-aminophenol, the process comprising: the polymer produced in the resorcinol and/or m-aminophenol production process is subjected to a hydrolysis reaction in the presence of a catalyst selected from one or both of sulfuric acid and hydrochloric acid.
2. The method of claim 1, wherein the catalyst is sulfuric acid.
3. The process according to claim 1, wherein the molar ratio of catalyst to amino groups in the polymer in the hydrolysis reaction is 1-2.5:1, preferably 1.1-1.5:1.
4. The method of claim 1, wherein the catalyst is fed in an amount of 10 to 30wt% of the total catalyst and water fed in the hydrolysis reaction.
5. The method according to claim 1, wherein the temperature of the hydrolysis reaction is 210-260 ℃, preferably 220-250 ℃.
6. The method of claim 1, wherein the polymer is selected from one or more of a polymer produced during the hydrolysis process to produce resorcinol and/or m-aminophenol, a dimer produced during the rectification of resorcinol and/or m-aminophenol, and an insoluble material recovered during the extraction of resorcinol and/or m-aminophenol.
7. The method of claim 1, wherein the method further comprises: and extracting the reaction liquid by using an extractant to obtain an organic phase containing resorcinol and an aqueous phase after resorcinol extraction.
8. The method of claim 7, wherein the method further comprises: after the pH of the aqueous phase after resorcinol extraction is adjusted to 7-8, m-aminophenol in the aqueous phase is extracted using an extractant.
9. The process according to claim 7 or 8, wherein the extractant is selected from one or more of butyl acetate, ethyl acetate and n-butanol, preferably butyl acetate.
10. A method according to claim 7 or 8, characterized in that the extractant is used in an amount of 1-1.5 times, preferably 1.1 ± 0.1 times the volume of the solution to be extracted.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211006848.6A CN117658779A (en) | 2022-08-22 | 2022-08-22 | Method for recycling resorcinol and m-aminophenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211006848.6A CN117658779A (en) | 2022-08-22 | 2022-08-22 | Method for recycling resorcinol and m-aminophenol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117658779A true CN117658779A (en) | 2024-03-08 |
Family
ID=90062838
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211006848.6A Pending CN117658779A (en) | 2022-08-22 | 2022-08-22 | Method for recycling resorcinol and m-aminophenol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117658779A (en) |
-
2022
- 2022-08-22 CN CN202211006848.6A patent/CN117658779A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110818543A (en) | Novel method for efficiently synthesizing dibenzoyl methane | |
| CN110317138B (en) | Preparation method of tetramethylethylenediamine | |
| CN117209361B (en) | Bisphenol F preparation method | |
| CN111217684A (en) | Production method for improving yield of cyclohexanone | |
| CN117658779A (en) | Method for recycling resorcinol and m-aminophenol | |
| CN112142624A (en) | Method for synthesizing N, N' -diisopropylcarbodiimide by using oxygen as oxidant | |
| CN114685253A (en) | Preparation method of prothioconazole intermediate 3, 5-dichloro-2-pentanone | |
| CN112250600B (en) | Technological method for improving yield of N, N' -diisopropylcarbodiimide product | |
| CN112778158A (en) | Preparation method and application of alpha-sodium formyl-beta-formamido propionitrile | |
| CN111362807B (en) | Preparation method of 3-nitro-2-methylbenzoic acid | |
| JPH05271143A (en) | Production of cyclohexanone | |
| CN1616434A (en) | Method for producing 1,3-dimethyl -2-imidazolinone | |
| CA1096888A (en) | Benzine-1,3,5-tris-acetoxime and the process of making phloroglucinol therewith | |
| CN113929588B (en) | Method for synthesizing 4-aminomethylbenzoic acid | |
| CN116003224B (en) | Method for preparing resorcinol | |
| CN114605336B (en) | Post-treatment and waste water resource utilization method for synthesizing 4, 6-dihydroxypyrimidine | |
| CN114933541B (en) | Method for preparing 2-methylamino-5-chlorobenzophenone | |
| CN112079734B (en) | Preparation method of 4-chloro-2, 5-dimethoxyaniline | |
| CN101412676B (en) | Preparation of 2,4-binitro bromobenzene | |
| JPH04145040A (en) | Production of dipentaerythritol | |
| SK14342000A3 (en) | Process for the preparation of phenol | |
| CN116924360A (en) | Preparation method of ultraviolet absorber UV326 reducing agent | |
| JP2000297178A (en) | Method for recovering dimethyl terephthalate | |
| CN113402402A (en) | Method for recovering trans-p-aminocyclohexanol from low-concentration waste liquid | |
| CN116924890A (en) | Phenol bulk drug and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication |