CN114031509A - Preparation method of o-aminophenol - Google Patents
Preparation method of o-aminophenol Download PDFInfo
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- CN114031509A CN114031509A CN202111427669.5A CN202111427669A CN114031509A CN 114031509 A CN114031509 A CN 114031509A CN 202111427669 A CN202111427669 A CN 202111427669A CN 114031509 A CN114031509 A CN 114031509A
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- aminophenol
- liquid
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- water
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- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 20
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 230000007935 neutral effect Effects 0.000 claims abstract description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 14
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000004811 liquid chromatography Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000006396 nitration reaction Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 2
- RZXZXSFKKFUEEI-UHFFFAOYSA-N [O-][N+](C(C=CC=C1)=C1Cl)=O.Cl Chemical compound [O-][N+](C(C=CC=C1)=C1Cl)=O.Cl RZXZXSFKKFUEEI-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- SHUIDGXTJAQFJO-UHFFFAOYSA-N 2-aminophenol;sulfuric acid Chemical compound [O-]S([O-])(=O)=O.[NH3+]C1=CC=CC=C1O.[NH3+]C1=CC=CC=C1O SHUIDGXTJAQFJO-UHFFFAOYSA-N 0.000 description 1
- SCFXRRMXMMHURF-UHFFFAOYSA-N 2-nitrophenol;sodium Chemical compound [Na].OC1=CC=CC=C1[N+]([O-])=O SCFXRRMXMMHURF-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- CKRZKMFTZCFYGB-UHFFFAOYSA-N N-phenylhydroxylamine Chemical compound ONC1=CC=CC=C1 CKRZKMFTZCFYGB-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 230000017105 transposition Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C239/00—Compounds containing nitrogen-to-halogen bonds; Hydroxylamino compounds or ethers or esters thereof
- C07C239/08—Hydroxylamino compounds or their ethers or esters
- C07C239/10—Hydroxylamino compounds or their ethers or esters having nitrogen atoms of hydroxylamino groups further bound to carbon atoms of unsubstituted hydrocarbon radicals or of hydrocarbon radicals substituted by halogen atoms or by nitro or nitroso groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of o-aminophenol, which comprises the following steps: (1) the preparation method of the o-aminophenol comprises the steps of taking water, nitrobenzene and sulfuric acid as raw materials, adding a catalyst, preparing an initial reaction solution under the condition of introducing hydrogen, carrying out solid-liquid separation on the initial reaction solution, taking a solid matter as the catalyst, and reusing the solid matter in S1, taking a liquid matter as a mixture solution, and adjusting the pH of the mixture solution to be neutral by using an alkaline matter.
Description
Technical Field
The invention relates to the field of organic synthesis, and particularly relates to a preparation method of o-aminophenol.
Background
Ortho-aminophenol (OPA) is an important chemical intermediate, and is widely applied to the fields of dyes, medicines, printing industry and the like. The process for preparing o-aminophenol by the traditional process comprises the steps of carrying out low-temperature nitration on phenol to obtain a mixture of p-nitrophenol and o-nitrophenol, and carrying out hydrogenation reduction (at high temperature and high pressure) after separation to obtain o-aminophenol. The method has the disadvantages that the safety of the nitration process cannot be guaranteed, a part of tar is generated in addition to a certain amount of p-nitrophenol generated in the nitration process, the yield is low, the product purity is unstable, the environmental protection is difficult to treat, and the cost is high.
At present, the domestic market adopts o-nitrophenol and liquid alkali to hydrolyze under the conditions of high temperature and high pressure to obtain o-nitrophenol sodium, the o-nitrophenol is obtained by acidification, and the o-aminophenol is obtained by high temperature and high pressure hydrogenation reduction. The defect is that the hydrolysis and reduction steps must be carried out at high temperature and high pressure, a large amount of waste brine is generated, although the purity of the product can be achieved, the environment-friendly treatment cost is high, the product has certain influence on pharmacy because the o-nitro chlorobenzene raw material contains chlorine, and the integral synthesis cost is relatively high.
Disclosure of Invention
In order to solve the defects of the prior art, the preparation method of the o-aminophenol comprises the following steps:
s1: taking water, nitrobenzene and sulfuric acid as raw materials, adding a catalyst, and preparing an initial reaction solution under the condition of introducing hydrogen;
s2: carrying out solid-liquid separation on the initial reaction solution, wherein the solid matter is a catalyst and is used in S1 again, and the liquid matter is a mixture solution;
s3: adjusting the pH of the mixture solution to be neutral by using an alkaline substance;
s4: carrying out solid-liquid separation on the neutralized mixture solution of S3 to obtain solid o-aminophenol and liquid ammonium sulfate aqueous solution;
s5: concentrating the ammonium sulfate aqueous solution separated from S4 to obtain solid ammonium sulfate and liquid water;
s6: the water obtained in S5 was recovered in S1 and recycled as a raw material.
Preferably, the catalyst described in S1 is Pt-c, and the equivalent diameter of the catalyst particles is 0.01mm to 10.0 mm.
Preferably, the operating pressure of hydrogen in S1 is 0.3-0.5 MPa.
Preferably, the ratio of nitrobenzene to sulfuric acid to water in S1 is 1: 1.05: 20-30.
Preferably, the basic substance in S3 is liquid ammonia.
Has the advantages that:
(1) compared with the prior art, the preparation method of o-aminophenol provided by the invention has the advantages that nitrobenzene is used for replacing o-nitrochlorobenzene chloride, high-pressure hydrolysis and high-temperature high-pressure reduction are not needed, the reaction condition is mild, the operation process is simple, and the safety is high.
(2) The preparation method of o-aminophenol provided by the invention has the advantages of high production efficiency and high productivity, reduces the cost of products and increases the overall benefit. The purity of the product obtained by liquid chromatography is more than 99 percent, and the product quality is relatively stable.
(3) According to the preparation method of o-aminophenol provided by the invention, the raw material does not contain organic chlorine, so that the produced o-aminophenol does not contain chlorine and all reaches the drug grade standard.
(4) According to the preparation method of o-aminophenol provided by the invention, the ammonium sulfate aqueous solution is concentrated, and the obtained water is used as a raw material for repeated recycling, so that the utilization rate of the raw material is improved, the raw material cost is reduced, and the preparation method is green and environment-friendly.
Drawings
FIG. 1 is a process flow diagram for the preparation of ortho-aminophenols;
FIG. 2 is a liquid chromatogram of ortho-aminophenol.
Detailed Description
For the purpose of enhancing the understanding of the present invention, the present invention will be further described in detail with reference to the following examples and the accompanying drawings, which are only used for explaining the present invention and are not to be construed as limiting the scope of the present invention.
Firstly, preparing o-aminophenol:
the specifications of the raw material samples for the preparation of the ortho-aminophenol are shown in the following table:
the preparation method comprises the following steps:
s1, taking water, nitrobenzene and sulfuric acid as raw materials, adding a catalyst Pt-c, and introducing hydrogen, wherein the operating pressure of the hydrogen is 0.3-0.5Mpa, the nitrobenzene, the hydrogen and the water are subjected to hydrogenation reduction reaction to generate phenylhydroxylamine, the o-aminophenol sulfate is generated through sulfuric acid transposition, and the o-aminophenol and the ammonium sulfate are obtained through ammonia water neutralization;
s2, separating the solid and the liquid in the S1, adding the separated Pt-c into S1 for continuous reaction, wherein the equivalent diameter of the Pt-c is 0.01mm-10.0mm, introducing hydrogen, the operating pressure of the hydrogen is 0.3-0.5MPa, and the liquid obtained after separation is a mixture solution;
s3, adjusting the pH value of the mixture solution to be neutral by using liquid ammonia;
s4, separating the solid and the liquid of the neutralized mixture solution of S3 to obtain solid o-aminophenol and liquid ammonium sulfate aqueous solution;
s5, concentrating the liquid ammonium sulfate aqueous solution separated from the S4 to obtain solid ammonium sulfate, and recovering the solid ammonium sulfate, wherein the liquid is water;
s6, recycling the water obtained in S5 to S1 as raw materials.
The quality of the obtained product is shown in the following table:
| product name | Quality (g) |
| Ortho-aminophenols | 110.38 |
| Ammonium sulfate | 234 |
Purity detection of di-and o-aminophenols
The detection method comprises the following steps: liquid chromatography
The obtained chromatogram is shown in fig. 2, the information of the chromatogram is analyzed, and the analysis result is shown in the following table:
| peak number | Retention time | Peak height | Peak area | Content (wt.) |
| 1 | 3.442 | 1020.887 | 4619.700 | 0.1223 |
| 2 | 5.159 | 175.152 | 1190.555 | 0.0315 |
| 3 | 5.301 | 149.790 | 1063.359 | 0.0282 |
| 4 | 5.810 | 277.140 | 10927.769 | 0.2893 |
| 5 | 6.727 | 397861.906 | 3750893.500 | 99.3065 |
| 6 | 8.878 | 419.000 | 5015.200 | 0.1328 |
| 7 | 11.262 | 29.609 | 575.500 | 0.0152 |
| 8 | 11.963 | 76.732 | 1617.505 | 0.0428 |
| 9 | 12.563 | 66.610 | 1058.503 | 0.0280 |
| 10 | 18.132 | 3.667 | 127.300 | 0.0034 |
| Total of | / | 400080.491 | 3777088.891 | 100.00 |
From the above table, it is understood that the purity of the prepared p-anisidine is 99.3065%.
The preparation method of o-aminophenol uses nitrobenzene to replace o-nitrochlorobenzene chloride, does not need high-pressure hydrolysis, does not need high-temperature high-pressure reduction, and has mild reaction conditions, simple operation process and high safety.
The production efficiency is high, the productivity is high, the cost of the product is reduced, and the overall benefit is increased. The purity of the product obtained by liquid chromatography is more than 99 percent, and the product quality is relatively stable. As the raw materials do not contain organic chlorine, the produced o-aminophenol does not contain chlorine and all reaches the drug grade standard. By concentrating the ammonium sulfate aqueous solution, the obtained water is used as a raw material for repeated recycling, the utilization rate of the raw material is improved, the raw material cost is reduced, and the method is green and environment-friendly.
As a further improvement, the above-mentioned is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. The preparation method of the o-aminophenol is characterized by comprising the following specific steps:
s1: taking water, nitrobenzene and sulfuric acid as raw materials, adding a catalyst, and preparing an initial reaction solution under the condition of introducing hydrogen;
s2: carrying out solid-liquid separation on the initial reaction solution, wherein the solid matter is a catalyst and is used in S1 again, and the liquid matter is a mixture solution;
s3: adjusting the pH of the mixture solution to be neutral by using an alkaline substance;
s4: carrying out solid-liquid separation on the neutralized mixture solution of S3 to obtain solid o-aminophenol and liquid ammonium sulfate aqueous solution;
s5: concentrating the ammonium sulfate aqueous solution separated from S4 to obtain solid ammonium sulfate and liquid water;
s6: the water obtained in S5 was recovered in S1 and recycled as a raw material.
2. The method according to claim 1, wherein the catalyst in S1 is Pt-c, and the equivalent diameter of the catalyst particles is 0.01mm-10.0 mm.
3. The process according to claim 1, wherein the operating pressure of hydrogen in S1 is 0.3-0.5 MPa.
4. The method for preparing o-aminophenol according to claim 1, wherein the ratio of nitrobenzene, sulfuric acid and water in S1 is 1: 1.05: 20-30.
5. The method according to claim 1, wherein the basic substance in S3 is liquid ammonia.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111427669.5A CN114031509A (en) | 2021-11-26 | 2021-11-26 | Preparation method of o-aminophenol |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111427669.5A CN114031509A (en) | 2021-11-26 | 2021-11-26 | Preparation method of o-aminophenol |
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| CN114031509A true CN114031509A (en) | 2022-02-11 |
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| CN202111427669.5A Pending CN114031509A (en) | 2021-11-26 | 2021-11-26 | Preparation method of o-aminophenol |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4885389A (en) * | 1987-06-08 | 1989-12-05 | Industrial Technology Research Institute | Process for manufacturing p-aminophenol |
| CN112812025A (en) * | 2021-01-13 | 2021-05-18 | 江苏普洛德化学科技有限公司 | Preparation process of p-aminophenol |
-
2021
- 2021-11-26 CN CN202111427669.5A patent/CN114031509A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4885389A (en) * | 1987-06-08 | 1989-12-05 | Industrial Technology Research Institute | Process for manufacturing p-aminophenol |
| CN112812025A (en) * | 2021-01-13 | 2021-05-18 | 江苏普洛德化学科技有限公司 | Preparation process of p-aminophenol |
Non-Patent Citations (4)
| Title |
|---|
| 刘竹青 等: "硝基苯加氢制对氨基苯酚 Pt／C 催化性能研究", 《精细化工》, vol. 23, no. 6, 31 December 1998 (1998-12-31), pages 37 - 39 * |
| 化学工业部人事教育司，化学工业部教育培训中心组织编写: "《有机化学反应2》", vol. 7, 30 June 1997, 北京：化学工业出版社, pages: 170 * |
| 姚蒙正等编著: "《精细化工产品合成原理》", vol. 7, 31 March 2000, 北京：中石化出版社, pages: 437 * |
| 尹春凯 等: "Pt／C 催化剂催化硝基苯加氢制对氨基苯酚工艺过程剖析", 《工业催化》, vol. 8, no. 5, 30 September 2000 (2000-09-30), pages 13 - 17 * |
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