CN1948252A - Method of preparing methyl catechol using calcium nitrite as raw material - Google Patents
Method of preparing methyl catechol using calcium nitrite as raw material Download PDFInfo
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- CN1948252A CN1948252A CN 200610131622 CN200610131622A CN1948252A CN 1948252 A CN1948252 A CN 1948252A CN 200610131622 CN200610131622 CN 200610131622 CN 200610131622 A CN200610131622 A CN 200610131622A CN 1948252 A CN1948252 A CN 1948252A
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Abstract
The present invention relates to a method for preparing guaiacol by using calcium nitrite as raw material. Said method is characterized by that it includes the following steps: in a diazotization still adding o-aminoanisole into dilute sulfuric acid to make neutralization to obtain methyl ether sulfate, then drop-adding calcium nitrite solution to make diazotization reaction, separating out solid residue, feeding the diazotization solution into hydrolysis procedure to make hydrolysis reaction so as to obtain crude guaiacol, then feeding the obtained crude guaiacol into separation procedure; making the waste liquor be fed into copper sulfate recovery procedure and making the phenol water containing crude guaiacol be fed into phenol recovery procedure, making the phenol water be continuously adsorbed in adsorption tower with macroporous adsorbing resin, using sodium hydroxide solution to make elution, using sulfuric acid to acidify eluent to separate out crude guaiacol; mixing above-mentioned two crude guaiacols in a distillation still, making reduced pressure distillation to remove water content and impurity from crude guaiacol so as to obtain the invented guaiacol finished product.
Description
Technical Field
The invention relates to the field of chemistry, in particular to a method for preparing guaiacol by using calcium nitrite as a raw material. Guaiacol is mainly used for preparing calcium guaiacol sulfonate in the pharmaceutical industry; vanillin and artificial musk are prepared in the perfume industry.
Background
The existing guaiacol preparation method comprises the following steps: a diazotization step, wherein sodium nitrite and o-aminoanisole are used as raw materials in the diazotization step, and low-temperature diazotization reaction is carried out under acidic conditions to generate diazo liquid consisting of o-aminoanisole diazonium salt and sodium sulfate; b, a hydrolysis process, wherein the hydrolysis process is to carry out hydrolysis reaction on the diazo liquid under the catalysis of copper sulfate to generate guaiacol and sulfuric acid, and release nitrogen, and the guaiacol is taken out by water vapor in a water vapor distillation mode; c, a separation process, wherein the separation process is to perform standing separation on the evaporated mixture to obtain hydrolyzed crude phenol and phenol water, the phenol water is extracted by using benzene, the extracted crude phenol is obtained after the solvent benzene is recovered, and the extracted crude phenol and the hydrolyzed crude phenol are combined and rectified to obtain the finished product guaiacol; d, waste liquid recovery, wherein the waste liquid recovery process is that the catalytic effect of copper sulfate is reduced after hydrolysis reaction is carried out for a period of time, the boiling point of the solution is increased, large replacement treatment is required, after the temperature of the waste liquid obtained after large replacement is reduced, copper sulfate and sodium sulfate are greatly separated out in the form of mixed crystals, simultaneously, the coked substance generated by reaction is also changed into solid, the coked substance is taken out and burned, and the mixed crystals and the waste liquid are replaced by scrap iron to obtain the sponge copper and the acidic ferrous sulfate waste liquid.
The prior preparation method of guaiacol has the following defects: 1. in the hydrolysis process, along with the increase of the amount of sulfuric acid generated in the reaction, mixed crystals formed by sodium sulfate and a catalyst copper sulfate in the diazotization process are gradually separated out, so that the catalytic effect of the copper sulfate is gradually reduced, and the hydrolysis yield is influenced; 2. the copper sulfate in the large exchange waste liquid is difficult to separate from the generated sodium sulfate, the copper sulfate needs to be converted into copper or copper oxide for recycling, the operation cost is high, a large amount of ferrous sulfate waste liquid which is difficult to treat is generated, and about 0.5-0.6 ton of copper sulfate is consumed by each ton of guaiacol; 3. the guaiacol dissolved in the phenol water generated by hydrolysis is extracted by using benzene, 0.05-0.08 ton of benzene is consumed for each ton of guaiacol, 8-10 tons of steam is consumed for recovering the solvent, the COD value of the raffinate phase after benzene extraction is high and reaches 2000-4000 mg/L because of containing benzene and other organic matters, 10-12 tons of wastewater is generated for each ton of guaiacol, and the treatment cost is high.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for preparing guaiacol by using calcium nitrite as a raw material, which has the advantages of advanced preparation method, high yield of guaiacol, low cost, less pollution, environmental protection and safe preparation process.
The technical scheme for solving the technical problem is as follows:
a method for preparing guaiacol by using calcium nitrite as a raw material is characterized by sequentially comprising the following steps:
(a) diazotization step 1, wherein in the diazotization step 1,sulfuric acid and water are added into a diazotization kettle to be mixed into dilute sulfuric acid, anthranilic ether is added into the dilute sulfuric acid to neutralize the dilute sulfuric acid into methyl ether sulfate, then calcium nitrite solution is dripped into the dilute sulfuric acid to carry out diazotization reaction, the reaction temperature is 5-10 ℃, after the reaction reaches the end point, solid-liquid separation is carried out to separate out solid residue, and the clarified diazotized solution is sent into a hydrolysis step 2 to carry out hydrolysis reaction;
(b) a hydrolysis step 2, wherein in the hydrolysis step 2, a copper sulfate solution with the concentration of 30-35% is added into a hydrolysis kettle, stirring and heating are started to boil, diazo liquid is dripped into the copper sulfate solution for hydrolysis reaction, the reaction temperature is 102-106 ℃, water vapor carries out the crude guaiacol generated by the reaction out to enter a separation step 3, and the waste liquid which needs to be subjected to large exchange treatment after hydrolysis is sent to a copper sulfate recovery step 4;
(c) a separation step 3, wherein the oil phase hydrolyzed crude guaiacol separated by the phenol-water separator in the separation step 3 is directly sent to a distillation step 6, and the phenol water containing the crude guaiacol is sent to a phenol recovery step 5;
(d) a copper sulfate recovery process 4, wherein the copper sulfate recovery process 4 firstly cools the waste liquid to be subjected to the large change treatment in the hydrolysis process 2 to remove tar, then the waste liquid is sent into a neutralization kettle in the copper sulfate recovery process 4 to be added with calcium oxide to neutralize sulfuric acid generated in the hydrolysis process, solid-liquid separation is carried out when the concentration of the sulfuric acid at the neutralizationend is 3-5%, residues are separated out, and the filtrate is subjected to decoloration treatment by activated carbon and then returns to the hydrolysis process 2 for recycling;
(e) a phenol recovery step 5, wherein the phenol water containing the crude guaiacol in the separation step 3 is sent into an adsorption tower filled with macroporous adsorption resin for continuous adsorption in the phenol recovery step 5, and is eluted by 3-5% sodium hydroxide solution after saturation is reached, the temperature of the sodium hydroxide solution is 50-70 ℃, and the eluent is acidified by sulfuric acid to separate out the crude guaiacol;
(f) and a distillation step 6, mixing the oil phase hydrolyzed crude guaiacol separated in the separation step 3 and the crude guaiacol recovered in the phenol recovery step 5 in a distillation kettle of the distillation step 6, and removing water and impurities in the crude guaiacol by reduced pressure distillation to obtain a guaiacol finished product.
Compared with the existing preparation method, the method for preparing the guaiacol by using the calcium nitrite as the raw material has the following advantages:
1. calcium nitrite is adopted for diazotization reaction, no mixed crystal is formed in the hydrolysis process, the hydrolysis condition is improved, and the yield of guaiacol is improved by 2-3 percent.
2. Calcium nitrite is adopted for diazotization reaction, so that the hydrolysis catalyst copper sulfate is easy and convenient to recycle, and the copper sulfate consumption is reduced to 0.08-0.1 t/t from 0.5-0.6 t/t in the prior art.
3. The diazotization reaction is carried out by adopting calcium nitrite, the problem of a large amount of wastewater pollution generated in the process of treating the large change waste liquid is solved, the pollution control cost is reduced, and residues generated in the reaction process can be used as building materials, so that the environment protection is facilitated.
4. The macroporous adsorption resin is adopted to replace the crude guaiacol in the phenol water extracted and recovered by benzene in the prior art, so that the steam consumption of the product is reduced by 8-10 t/t.
5. Macroporous adsorption resin is adopted to replace crude guaiacol in the benzene extraction and recovery phenolic water in the prior art, so that COD of the prepared and discharged wastewater is reduced to 500-800 mg/L from 2000-4000 mg/L. The sewage treatment cost is low.
6. The macroporous adsorption resin is adopted to replace crude guaiacol in the benzene extraction and recovery phenol water in the prior art, so that the safety performance of the preparation process is improved, and the pollution of benzene to air and the harm to operators in the solvent recovery process are avoided.
Drawings
FIG. 1 is a process flow diagram of the method of the present invention for preparing guaiacol using calcium nitrite as raw material.
Detailed Description
The invention is further described below with reference to the figures and examples.
Referring to fig. 1, the reaction equation for diazotization is:
the reaction equation for hydrolysis is:
the copper sulfate recovery reaction equation is:
referring to fig. 1, the method for preparing guaiacol by using calcium nitrite as a raw material sequentially comprises the following steps:
diazotization step 1, wherein in the diazotization step 1, sulfuric acid and water are added into a diazotization kettle to be mixed into dilute sulfuric acid, anthranilic ether is added into the dilute sulfuric acid to neutralize the dilute sulfuric acid into methyl ether sulfate, then calcium nitrite solution is dripped into the dilute sulfuric acid to carry out diazotization reaction, the reaction temperature is 5-10 ℃, after the reaction reaches the end point, solid-liquid separation is carried out to separate out solid residue, and the clarified diazotized solution is sent into a hydrolysis step 2 to carry out hydrolysis reaction;
a hydrolysis step 2, wherein in the hydrolysis step 2, a copper sulfate solution with the concentration of 30-35% is added into a hydrolysis kettle, stirring and heating are started to boil, diazo liquid is dripped into the copper sulfate solution for hydrolysis reaction, the reaction temperature is 102-106 ℃, water vapor brings out crude guaiacol generated by the reaction into a separation step 3, the hydrolysis is carried out for a certain time, then the exchange treatment is carried out, and waste liquid of the exchange treatment is sent into a copper sulfate recovery step 4;
a separation step 3, wherein the oil phase hydrolyzed crude guaiacol separated by the phenol-water separator in the separation step 3 is directly sent to a distillation step 6, and the phenol water containing the crude guaiacol is sent to a phenol recovery step 5;
a copper sulfate recovery process4, wherein the copper sulfate recovery process 4 firstly cools the waste liquid subjected to the exchange treatment in the hydrolysis process 2 to remove tar, then the waste liquid is sent into a neutralization kettle in the copper sulfate recovery process 4 to be added with calcium oxide to neutralize sulfuric acid generated in the hydrolysis process, solid-liquid separation is carried out when the concentration of the sulfuric acid at the neutralization end is 3-5%, residues are separated out, and the filtrate is subjected to decoloration treatment by activated carbon and then returns to the hydrolysis process 2 for recycling;
a phenol recovery step 5, wherein the phenol water containing the crude guaiacol in the separation step 3 is sent into an adsorption tower filled with macroporous adsorption resin for continuous adsorption in the phenol recovery step 5, and is eluted by 3-5% sodium hydroxide solution after the saturation degree is reached, the temperature of the sodium hydroxide solution is 50-70 ℃, and the eluent is acidified by sulfuric acid to separate out the crude guaiacol;
and a distillation step 6, mixing the oil phase hydrolyzed crude guaiacol separated in the separation step 3 and the crude guaiacol recovered in the phenol recovery step 5 in a distillation kettle of the distillation step 6, and removing water and impurities in the crude guaiacol by reduced pressure distillation to obtain a guaiacol finished product.
Process material ratio (weight ratio) and technological parameters in method for preparing guaiacol by using calcium nitrite as raw material
Diazotization process 1:
preparing a calcium nitrite solution: ca (NO)2)2∶H2O＝60～65∶300
Preparing methyl ether sulfate: c7H9NO∶H2SO4∶H2O＝100∶105～110∶500
Diazotization reaction temperature: 5 to 10 DEG C
A hydrolysis step 2:
the concentration of copper sulfate is as follows: 30 to 35 percent
Hydrolysis reaction temperature: 102-106 deg.C
And (3) finishing the hydrolysis reaction: the content of sulfuric acid is 20-25%
Copper sulfate recovery step 4:
and (3) a neutralization end point: the content of sulfuric acid is 3-5%
Phenol recovery step 5:
concentration of sodium hydroxide solution: 3 to 5 percent
Temperature of sodium hydroxide solution: 50-70 ℃.
The chemical raw materials used in the invention are all commercial products, and are easy to obtain.
Claims (1)
1. A method for preparing guaiacol by using calcium nitrite as a raw material is characterized by sequentially comprising the following steps:
(a) diazotization step 1, wherein in the diazotization step 1, sulfuric acid and water are added into a diazotization kettle to be mixed into dilute sulfuric acid, anthranilic ether is added into the dilute sulfuric acid to neutralize the dilute sulfuric acid into methyl ether sulfate, then calcium nitrite solution is dripped into the dilute sulfuric acid to carry out diazotization reaction, the reaction temperature is 5-10 ℃, after the reaction reaches the end point, solid-liquid separation is carried out to separate out solid residue, and the clarified diazotized solution is sent into a hydrolysis step 2 to carry out hydrolysis reaction;
(b) ahydrolysis step 2, wherein in the hydrolysis step 2, a copper sulfate solution with the concentration of 30-35% is added into a hydrolysis kettle, stirring and heating are started to boil, diazo liquid is dripped into the copper sulfate solution for hydrolysis reaction, the reaction temperature is 102-106 ℃, water vapor carries out the crude guaiacol generated by the reaction out to enter a separation step 3, and the waste liquid which needs to be subjected to large exchange treatment after hydrolysis is sent to a copper sulfate recovery step 4;
(c) a separation step 3, wherein the oil phase hydrolyzed crude guaiacol separated by the phenol-water separator in the separation step 3 is directly sent to a distillation step 6, and the phenol water containing the crude guaiacol is sent to a phenol recovery step 5;
(d) a copper sulfate recovery process 4, wherein the copper sulfate recovery process 4 firstly cools the waste liquid to be subjected to the large change treatment in the hydrolysis process 2 to remove tar, then the waste liquid is sent into a neutralization kettle in the copper sulfate recovery process 4 to be added with calcium oxide to neutralize sulfuric acid generated in the hydrolysis process, solid-liquid separation is carried out when the concentration of the sulfuric acid at the neutralization end is 3-5%, residues are separated out, and the filtrate is subjected to decoloration treatment by activated carbon and then returns to the hydrolysis process 2 for recycling;
(e) a phenol recovery step 5, wherein the phenol water containing the crude guaiacol in the separation step 3 is sent into an adsorption tower filled with macroporous adsorption resin for continuous adsorption in the phenol recovery step 5, and is eluted by 3-5% sodium hydroxide solution after saturation is reached, the temperature of the sodium hydroxide solution is 50-70 ℃, and the eluent is acidified by sulfuric acid to separate out the crude guaiacol;
(f) and a distillation step 6, mixing the oil phase hydrolyzed crude guaiacol separated in the separation step 3 and the crude guaiacol recovered in the phenol recovery step 5 in a distillation kettle of the distillation step 6, and removing water and impurities in the crude guaiacol by reduced pressure distillation to obtain a guaiacol finished product.
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| CNB2006101316223A CN100372824C (en) | 2006-11-07 | 2006-11-07 | Method of preparing methyl catechol using calcium nitrite as raw material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104447189A (en) * | 2014-11-17 | 2015-03-25 | 武汉瑞阳化工有限公司 | New method for synthesizing naphthaline-series fluorine-containing intermediate 1-fluoronaphthalene |
| CN112661719A (en) * | 2020-12-22 | 2021-04-16 | 河北合佳医药科技集团股份有限公司 | Clean preparation process of aminothiazoly loximate |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1176959A (en) * | 1997-09-26 | 1998-03-25 | 吉化江城化工有限责任公司助剂厂 | Improved art for preparing guaiacol |
| CN1231441C (en) * | 2003-07-11 | 2005-12-14 | 上海欣晨新技术公司 | Process for continuous hydrolysis synthesis of guaiacol |
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2006
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104447189A (en) * | 2014-11-17 | 2015-03-25 | 武汉瑞阳化工有限公司 | New method for synthesizing naphthaline-series fluorine-containing intermediate 1-fluoronaphthalene |
| CN112661719A (en) * | 2020-12-22 | 2021-04-16 | 河北合佳医药科技集团股份有限公司 | Clean preparation process of aminothiazoly loximate |
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