CN111704541B - Method for treating wastewater generated in ambrotone preparation process - Google Patents
Method for treating wastewater generated in ambrotone preparation process Download PDFInfo
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- CN111704541B CN111704541B CN202010523270.6A CN202010523270A CN111704541B CN 111704541 B CN111704541 B CN 111704541B CN 202010523270 A CN202010523270 A CN 202010523270A CN 111704541 B CN111704541 B CN 111704541B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/06—Boron halogen compounds
- C01B35/068—Halogenated hydrides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/02—Fluorides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
Abstract
The invention relates to a method for treating wastewater generated in the preparation process of ambrotone, in particular to a method for separating fluorine-containing waste salt and sodium acetate from wastewater, which comprises the following steps: (1) Providing wastewater, wherein the wastewater contains fluorine-containing sodium salt and sodium acetate; (2) Adjusting the pH of the wastewater to 9.5-11 with alkali, crystallizing at 10-20 ℃, and centrifuging to obtain a crystalline solid; (3) Heating the crystallized solid obtained in the step (2) to 75-85 ℃, keeping the temperature for 120-170 minutes under the stirring condition, standing at 75-85 ℃, separating out the solid, and performing centrifugal separation to obtain the fluorine-containing sodium salt solid and clear liquid; (4) Adjusting pH of the clear liquid to 8.5-9 with acid, adding 0.1-2wt% of active carbon, heating to 85-95 deg.C, adjusting clear liquid concentration to 20-30 Baume degree with water, filtering, crystallizing the filtrate at 20-30 deg.C, and centrifuging to obtain solid crystal sodium acetate. The method can separate fluorine-containing waste salt and sodium acetate in the wastewater generated in the preparation process of ambrotone, reduce the cost of sewage treatment and improve the recycling of resources.
Description
Technical Field
The invention relates to the field of wastewater treatment, in particular to a method for treating wastewater generated in the preparation process of ambrotone.
Background
The ambrotone has costustoot and ambergris, has lasting fragrance and stable property, can be used as a spice or a fixative, and has the following chemical structural formula:
in the existing preparation method of ambrotone, the following method is often adopted for preparation, and the method comprises the following steps: 3-methyl-3-pentene-2-one synthesis, diene addition and cyclization. The diene addition reaction typically comprises the steps of reacting 3-methyl-3-penten-2-one with myrcene in the presence of a boron trifluoride catalyst and acetic anhydride, neutralizing a reaction liquid to be alkaline by using alkali, standing for layering, separating to obtain an organic phase and a waste water phase, wherein the separated waste water phase is waste water, and carrying out vacuum distillation on the organic phase to obtain the isopril saxolone. As the boron trifluoride catalyst is used in the diene addition process, the catalyst is neutralized and destroyed by liquid alkali after the catalysis is finished, the produced wastewater contains villiaumite and sodium acetate, and the mixture belongs to dangerous waste due to the villiaumite, so that most production enterprises do not have treatment qualification, units with the qualification are required to be found for treatment, great burden is brought to the production enterprises, and the dangerous waste causes certain harm to social environmental protection. Sodium acetate has very extensive application, however, the existing chemical synthesis of sodium acetate needs larger cost and resources, and the chemical synthesis of sodium acetate also can produce a lot of substances harmful to the environment, so if sodium acetate in the wastewater produced by the preparation of ambrotone is not recovered, not only sodium acetate is wasted in vain, but also the difficulty of the post-treatment of wastewater is increased, and the wastewater treatment cost is increased.
Therefore, there is a need in the art to develop a method for separating fluorine-containing waste salt and sodium acetate from wastewater generated in the preparation process of ambrotone, so as to reduce the cost of wastewater treatment, protect the environment and improve the recycling of resources.
Disclosure of Invention
The invention aims to provide a method for separating fluorine-containing waste salt and sodium acetate in wastewater generated in the preparation process of ambrotone, so that the sewage treatment cost is reduced, the environment is protected, and the resource recycling is improved.
One aspect of the present invention provides a method for separating fluorine-containing waste salt and sodium acetate from wastewater, the method comprising the steps of:
(1) Providing wastewater, wherein the wastewater contains fluorine-containing sodium salt and sodium acetate;
(2) Adjusting the pH of the wastewater to 9.5-11 by using alkali, then crystallizing at 10-20 ℃, and centrifuging to obtain a crystalline solid;
(3) Heating the crystallized solid obtained in the step (2) to 75-85 ℃, keeping the temperature for 120-170 minutes under the stirring condition, standing at 75-85 ℃, separating out the solid, and performing centrifugal separation to obtain the fluorine-containing sodium salt solid and clear liquid;
(4) Adjusting the pH of the clear liquid to 8.5-9 with acid, adding 0.1-2wt% of activated carbon, heating to 85-95 ℃, adjusting the concentration of the clear liquid to 20-30 Baume degrees with water, filtering, crystallizing the filtrate at 20-30 ℃, and centrifuging to obtain solid crystalline sodium acetate.
Preferably, the fluorine-containing sodium salt is selected from the group consisting of: sodium fluoride, sodium bifluorofenate, or a combination thereof.
Preferably, in the step (2), the alkali is sodium hydroxide.
Preferably, in the step (3), the temperature is kept for 140 to 160 minutes.
Preferably, in the step (4), the acid is acetic acid.
Preferably, in the step (4), the clear solution is adjusted to pH =8-8.5 with an acid.
Preferably, in the step (4), the amount of the activated carbon is 0.5 to 1.2wt%.
Preferably, in the step (4), the activated carbon is calculated by the weight of the clear liquid.
Preferably, the wastewater is prepared by the following method:
in the presence of a boron trifluoride catalyst and acetic anhydride, 3-methyl-3-pentenyl-2-one reacts with myrcene, reaction liquid is neutralized to be neutral by alkali, an organic phase and a wastewater phase are obtained by separation after standing and layering, and the separated wastewater phase is wastewater.
Preferably, the wastewater is prepared by the following method:
adding 3-methyl-3-pentene-2-one and more than half of acetic anhydride in the total amount into a container, stirring and mixing uniformly, adding a boron trifluoride catalyst, heating to 40-50 ℃, adding myrcene, adding the rest of acetic anhydride after the myrcene is added, and reacting for 8-10 hours at 40-50 ℃ with heat preservation; then neutralizing with alkali to neutrality, standing for layering, and separating to obtain an organic phase and a wastewater phase, wherein the separated wastewater phase is wastewater.
Preferably, the organic phase is distilled under reduced pressure, and the fractions at 120-130 deg.C under 1-3mmHg are collected to obtain the isopril saxolone.
Preferably, the wastewater is prepared by the following method:
370-400g of 3-methyl-3-pentene-2 ketone and 30-40g of acetic anhydride are mixed, 13-17g of boron trifluoride acetic acid solution with the mass concentration of 30-40% of catalyst is added, the temperature is raised to 40-50 ℃, 550-600g of myrcene is added in the temperature range, 15-25g of acetic anhydride is added after the addition of myrcene is finished, stirring and heat preservation reaction are carried out for 8-10 hours, after the reaction is finished, 80-90g of sodium hydroxide solution with the mass concentration of 13-17% is added into a reactant to be neutralized, an organic phase and a waste water phase are obtained by separation after standing and layering, and the separated waste water phase is waste water.
Preferably, the boron trifluoride catalyst is boron trifluoride acetic acid solution with the mass concentration of 32-38%.
Preferably, the wastewater is wastewater generated in the preparation method of ambrotone.
Preferably, the preparation of ambrotone is carried out by the following method, the method comprises the following steps of 3-methyl-3-penten-2-one synthesis, diene addition and cyclization, and the specific steps are as follows:
(a) 3-methyl-3-pentene-2 ketone synthesis: adding butanone into a strong acid solution, heating to 50-70 ℃, adding acetaldehyde at the temperature, stirring to react for 1-2 hours after the acetaldehyde is added, cooling to room temperature, adding alkali into the reaction product to neutralize to be neutral, recovering butanone, carrying out reduced pressure distillation, and collecting 40-60mHg 60-70 ℃ fraction to obtain 3-methyl-3-penten-2-one;
(b) Addition of diene: adding 3-methyl-3-pentene-2-one and more than half of acetic anhydride in the total amount into a container, stirring and mixing uniformly, adding a boron trifluoride catalyst, heating to 40-50 ℃, adding myrcene, adding the rest of acetic anhydride after the myrcene is added, and reacting for 8-10 hours at 40-50 ℃ with heat preservation; then neutralizing with alkali to neutrality, standing for layering, separating to obtain an organic phase and a wastewater phase, wherein the separated wastewater phase is wastewater, and the organic phase is subjected to reduced pressure distillation and collected at 1-3mmHg and the fraction at 120-130 ℃ to obtain isopril saxolone;
(c) Cyclization: adding 5-10% of the fraction obtained in the step (b) into an acid solution, heating to 70-80 ℃, continuously adding the rest fraction obtained in the step (b), preserving heat for 8-10 hours after adding, then adding alkali to neutralize to be neutral, standing to separate an organic phase, carrying out reduced pressure distillation, collecting 1-3mmHg to fractionate the fraction at 126-130 ℃, and obtaining the ambrotone.
Preferably, the wastewater is the wastewater generated in the diene addition process in the step (b).
Preferably, the strong acid solution in step (a) is a sulfuric acid solution with a mass concentration of 60-70%.
Preferably, in the step (a), the mass ratio of the acetaldehyde solution to the butanone solution to the sulfuric acid solution is 1.
Preferably, in the step (b), the boron trifluoride catalyst is a boron trifluoride acetic acid solution with the mass concentration of 32-38%.
Preferably, in the step (b), the weight ratio of the 3-methyl-3-penten-2-one to the boron trifluoride acetic acid solution with the mass concentration of 32-38%, acetic anhydride (total) and myrcene is 1.
Preferably, the base is sodium hydroxide or potassium hydroxide.
Preferably, the base is an alkaline solution.
Preferably, in step (a), the alkaline solution has a mass concentration of 20-30%.
Preferably, in step (b), the alkaline solution has a mass concentration of 10-15%.
Preferably, in step (c), the alkaline solution has a mass concentration of 10-15%.
Preferably, in the step (c), the acidic solution is a phosphoric acid solution with a mass concentration of 55-85%, and the weight ratio of the isoprilsalatrexone to the phosphoric acid solution is 1.
It is to be understood that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) may be combined with each other to form new or preferred embodiments. Not to be reiterated herein, but to the extent of space.
Detailed Description
In the invention, the inventor unexpectedly develops a method for separating fluorine-containing waste salt and sodium acetate in wastewater generated in the preparation process of ambrotone for the first time, the method can efficiently separate the fluorine-containing waste salt and the sodium acetate in the wastewater generated in the preparation process of ambrotone, avoid the danger caused by the fluorine-containing waste salt, greatly reduce the wastewater treatment cost and protect the environment, and the separated sodium acetate is crystalline sodium acetate, has the content consistent with the content range of the commercially available crystalline sodium acetate, and can be used for commercial application, thereby improving the recycling utilization of resources.
Term(s) for
Unless defined otherwise, 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.
As used herein, the terms "comprising," "including," and "containing" are used interchangeably and include not only open-ended definitions, but also semi-closed and closed-ended definitions. In other words, the term includes "consisting of … …" and "consisting essentially of … …".
As used herein, the term "fluorine-containing sodium salt" includes mixtures of a plurality of fluorine salts (e.g., sodium fluoride, sodium fluoroborate).
As used herein, the term "crystalline sodium acetate" is sodium acetate trihydrate, a commercially available crystalContent of sodium acetate (CH) 3 COONa·3H 2 O)/% is 58-60%.
Method for separating fluorine-containing waste salt and sodium acetate from wastewater
The invention provides a method for separating fluorine-containing waste salt and sodium acetate from wastewater, which comprises the following steps:
(1) Providing wastewater, wherein the wastewater contains fluorine-containing sodium salt and sodium acetate;
(2) Adjusting the pH of the wastewater to 9.5-11 by using alkali, then crystallizing at 10-20 ℃, and centrifuging to obtain a crystalline solid;
(3) Heating the crystallized solid obtained in the step (2) to 75-85 ℃, keeping the temperature for 120-170 minutes under the stirring condition, standing at 75-85 ℃, separating out the solid, and performing centrifugal separation to obtain the fluorine-containing sodium salt solid and clear liquid;
(4) Adjusting pH of the clear liquid to 8.5-9 with acid, adding 0.1-2wt% of activated carbon, heating to 85-95 deg.C, adjusting clear liquid concentration to 20-30 Baume degree with water, filtering, crystallizing filtrate at 20-30 deg.C, and centrifuging to obtain solid crystal sodium acetate.
Preferably, the fluorine-containing sodium salt is selected from the group consisting of: sodium fluoride, sodium bifluorofenate, or a combination thereof.
Preferably, in the step (2), the alkali is sodium hydroxide.
Preferably, in the step (3), the temperature is kept for 140 to 160 minutes.
Preferably, in the step (4), the acid is acetic acid.
Preferably, in the step (4), the clear solution is adjusted to pH =8-8.5 with an acid.
Preferably, in the step (4), the amount of the activated carbon is 0.5 to 1.2wt%.
Preferably, in the step (4), the activated carbon is based on the weight of the clear liquid.
In another preferred embodiment of the present invention, the wastewater is prepared by the following method:
in the presence of a boron trifluoride catalyst and acetic anhydride, 3-methyl-3-pentenyl-2-one reacts with myrcene, reaction liquid is neutralized to be neutral by alkali, an organic phase and a wastewater phase are obtained by separation after standing and layering, and the separated wastewater phase is wastewater.
Preferably, the wastewater is prepared by the following method:
adding 3-methyl-3-pentenyl-2-one and more than half of acetic anhydride into a container, stirring and mixing uniformly, adding a boron trifluoride catalyst, heating to 40-50 ℃, adding myrcene, adding the rest of acetic anhydride after the myrcene is added, and reacting for 8-10 hours at the temperature of 40-50 ℃; then neutralizing with alkali to neutrality, standing for layering, and separating to obtain an organic phase and a wastewater phase, wherein the separated wastewater phase is wastewater.
Preferably, the organic phase is distilled under reduced pressure, and the fractions at 120-130 deg.C under 1-3mmHg are collected to obtain the isopril saxolone.
Preferably, the wastewater is prepared by the following method:
370-400g of 3-methyl-3-pentene-2 ketone and 30-40g of acetic anhydride are mixed, 13-17g of boron trifluoride acetic acid solution with the mass concentration of 30-40% of catalyst is added, the temperature is raised to 40-50 ℃, 550-600g of myrcene is added in the temperature range, 15-25g of acetic anhydride is added after the addition of myrcene is finished, stirring and heat preservation reaction are carried out for 8-10 hours, after the reaction is finished, 80-90g of sodium hydroxide solution with the mass concentration of 13-17% is added into a reactant to be neutralized, an organic phase and a waste water phase are obtained by separation after standing and layering, and the separated waste water phase is waste water.
Preferably, the boron trifluoride catalyst is boron trifluoride acetic acid solution with the mass concentration of 32-38%.
Preferably, the preparation of ambrotone is carried out by the following method, the method comprises the following steps of 3-methyl-3-penten-2-one synthesis, diene addition and cyclization, and the specific steps are as follows:
(a) 3-methyl-3-pentene-2 ketone synthesis: adding butanone into a strong acid solution, heating to 50-70 ℃, adding acetaldehyde at the temperature, stirring to react for 1-2 hours after the acetaldehyde is added, cooling to room temperature, adding alkali into the reaction product to neutralize to be neutral, recovering butanone, carrying out reduced pressure distillation, and collecting 40-60mHg 60-70 ℃ fraction to obtain 3-methyl-3-penten-2-one;
(b) Addition of diene: adding 3-methyl-3-pentene-2-one and more than half of acetic anhydride in the total amount into a container, stirring and mixing uniformly, adding a boron trifluoride catalyst, heating to 40-50 ℃, adding myrcene, adding the rest of acetic anhydride after the myrcene is added, and reacting for 8-10 hours at 40-50 ℃ with heat preservation; then neutralizing with alkali to neutrality, standing for layering, separating to obtain organic phase and waste water phase, vacuum distilling the organic phase, and collecting 1-3mmHg distillate at 120-130 deg.C to obtain isopril saxolone.
(c) Cyclization: adding 5-10% of the fraction obtained in the step (b) into an acid solution, heating to 70-80 ℃, continuously adding the rest fraction obtained in the step (b), preserving heat for 8-10 hours after adding, then adding alkali to neutralize to be neutral, standing to separate an organic phase, carrying out reduced pressure distillation, collecting 1-3mmHg to fractionate the fraction at 126-130 ℃, and obtaining ambrotone;
preferably, the strong acid solution in step (a) is a sulfuric acid solution with a mass concentration of 60-70%.
Preferably, in the step (a), the mass ratio of the acetaldehyde to the butanone to the sulfuric acid solution is 1.
Preferably, in the step (b), the boron trifluoride catalyst is 32-38% by mass concentration of boron trifluoride acetic acid solution.
Preferably, in the step (b), the weight ratio of the 3-methyl-3-penten-2-one to the boron trifluoride acetic acid solution with the mass concentration of 32-38%, acetic anhydride (total) and myrcene is 1.
Preferably, the base is sodium hydroxide or potassium hydroxide.
Preferably, the base is an alkaline solution.
Preferably, in step (a), the alkaline solution has a mass concentration of 20-30%.
Preferably, in step (b), the alkaline solution has a mass concentration of 10-15%.
Preferably, in step (c), the alkaline solution is at a mass concentration of 10-15%.
Preferably, in the step (c), the acidic solution is a phosphoric acid solution with a mass concentration of 55-85%, and the weight ratio of the isoprilsalatrexone to the phosphoric acid solution is 1.
The main technical effects of the invention comprise:
1. the invention unexpectedly develops a method for separating fluorine-containing waste salt and sodium acetate in wastewater generated in the preparation process of ambrotone, the method can efficiently separate the fluorine-containing waste salt and the sodium acetate in the wastewater generated in the preparation process of ambrotone, avoids the danger caused by the fluorine-containing waste salt, greatly reduces the wastewater treatment cost, protects the environment, and can be used for commercial application because the separated sodium acetate is crystalline sodium acetate with the content consistent with the content range of the commercially available crystalline sodium acetate, thereby improving the recycling utilization of resources.
2. The method for separating the fluorine-containing waste salt and the crystallized sodium acetate from the wastewater generated in the preparation process of the ambrotone has simple process and is easy for industrial production.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Experimental procedures without specific conditions noted in the following examples, generally according to conventional conditions, or according to conditions recommended by the manufacturer. Unless otherwise indicated, percentages and parts are by weight.
Example 1: preparation of ambrotone
1. 3-methyl-3-pentene-2 ketone synthesis:
adding 322g of butanone into 98g of sulfuric acid solution with the weight concentration of 65%, heating to 60 ℃, adding 142g of acetaldehyde at the temperature, stirring for reacting for 2 hours after the acetaldehyde is added, cooling to room temperature, adding 172g of sodium hydroxide solution with the weight concentration of 30% into the reaction product for neutralizing to be neutral, recovering the butanone, carrying out reduced pressure distillation, collecting 40-60mmHg 60-70 ℃ fraction to obtain the 3-methyl-3-pentene-2 ketone, wherein the yield of the 3-methyl-3-pentene-2 ketone is 92.1%, and the purity is 98.9%.
2. Diene addition Process
386g of 3-methyl-3-pentene-2-ketone with the purity of 98.9 percent and 35g of acetic anhydride are added into a three-mouth reaction flask, after uniform stirring, 15.3g of boron trifluoride acetic acid solution with the mass concentration of 35 percent of catalyst is added, 579g of myrcene with the purity of 78 percent is added in the temperature range when the temperature is raised to 45 ℃, 20g of acetic anhydride is added after the addition of myrcene is finished, stirring and heat preservation are carried out for reaction for 9 hours, and the reaction is finished. Adding 85g of 15% sodium hydroxide solution with mass concentration into the reactant to neutralize to be neutral, standing for layering, and separating to obtain an organic phase and a wastewater phase, wherein the separated wastewater phase is wastewater (the wastewater contains fluorine-containing sodium salt and sodium acetate); vacuum distilling the organic phase, and collecting 1-3mmHg120-130 deg.C fraction to obtain isopril saxolone. The yield of the isopril saxolone is 91.6 percent, and the purity is 95.3 percent.
3. Cyclization step
Adding 45g of isopril saxolone into 19.7g of phosphoric acid solution with the mass concentration of 85%, heating to 75 ℃, continuously adding 598g of isopril saxolone, preserving heat for 9 hours after the addition is finished, then adding 238g of sodium hydroxide solution with the mass concentration of 10% for neutralization to neutrality, standing, separating out an organic phase, carrying out reduced pressure distillation, collecting 1-3mmHg, fractionating to 126-130 ℃ fraction, and obtaining the ambergris ketone.
The purity of the ambrotone prepared in example 1 was 92.6% with an overall yield of 92.8% calculated on butanone.
Example 2
The wastewater obtained in the "diene addition step (2)" of example 1 was treated to separate a fluorine-containing sodium salt and crystalline sodium acetate therefrom, and the specific steps were as follows:
(1) The wastewater obtained in the "diene addition step (2) in example 1 was adjusted to pH =10 with an aqueous sodium hydroxide solution, and then cooled to 15 ℃.
(2) Heating the crystallized solid obtained in the step 1 to 80 ℃, keeping the temperature for 150 minutes under the stirring condition, keeping the temperature and standing at 80 ℃, separating out the solid, performing centrifugal separation to obtain a fluorine-containing sodium salt solid and a clear liquid, and intensively collecting and post-treating the obtained fluorine-containing sodium salt solid, thereby avoiding the harm of the fluorine-containing sodium salt in the wastewater to the environment and greatly reducing the wastewater treatment cost;
(3) Transferring the clear liquid into a reaction kettle, adjusting the pH to be =8.8 by using acetic acid, adding 0.8wt% of activated carbon (based on the weight of the clear liquid), heating to 90 ℃, adjusting the concentration of the clear liquid to be 25 Baume degrees by using water, filtering, crystallizing the filtrate at 25 ℃, and centrifuging to obtain solid crystals, namely crystalline sodium acetate.
And (4) analyzing results:
the crystalline sodium acetate obtained in step (3) of this example was analyzed to find that the sodium acetate content of the crystalline sodium acetate was 58.6% (the crystalline sodium acetate was sodium acetate containing three water phases and has a chemical formula of CH) 3 COONa·3H 2 O, commercial sodium acetate content 58-60%).
Example 3
The wastewater obtained in the "diene addition step (2)" of example 1 was treated to separate a fluorine-containing sodium salt and crystalline sodium acetate therefrom, and the specific steps were as follows:
(1) The wastewater obtained in the "diene addition step (2)" of example 1 was adjusted to pH =10 with an aqueous sodium hydroxide solution, and then cooled to 15 ℃, crystallized, and centrifuged to obtain a crystalline solid.
(2) Heating the crystallized solid obtained in the step 1 to 70 ℃, keeping the temperature for 150 minutes under the stirring condition, keeping the temperature at 70 ℃ and standing, separating out the solid, performing centrifugal separation to obtain fluorine-containing sodium salt solid and clear liquid, and performing centralized collection and post-treatment on the obtained fluorine-containing sodium salt solid, thereby avoiding the harm of the fluorine-containing sodium salt in the wastewater to the environment and greatly reducing the wastewater treatment cost;
(3) Transferring the clear liquid into a reaction kettle, adjusting the pH to be =8.8 by using acetic acid, adding 0.8wt% of activated carbon (based on the weight of the clear liquid), heating to 90 ℃, adjusting the concentration of the clear liquid to be 25 Baume degrees by using water, filtering, crystallizing the filtrate at 25 ℃, and centrifuging to obtain solid crystals, namely crystalline sodium acetate.
And (4) analyzing results:
when the crystalline sodium acetate obtained in the step (3) of this example was analyzed, the content of sodium acetate in the crystalline sodium acetate was 56.3% (the crystalline sodium acetate was a sodium acetate containing three water molecules and having a chemical formula of CH3COONa 3H2O, and the content of commercially available sodium acetate was 58 to 60%).
Example 4
The wastewater obtained in the "diene addition step (2)" of example 1 was treated to separate a fluorine-containing sodium salt and crystalline sodium acetate therefrom, and the specific steps were as follows:
(1) The wastewater obtained in the "diene addition step (2)" of example 1 was adjusted to pH =10 with an aqueous sodium hydroxide solution, and then cooled to 15 ℃, crystallized, and centrifuged to obtain a crystalline solid.
(2) Heating the crystallized solid obtained in the step 1 to 90 ℃, keeping the temperature for 150 minutes under the stirring condition, keeping the temperature for standing at 90 ℃, separating out the solid, performing centrifugal separation to obtain a fluorine-containing sodium salt solid and a clear liquid, and intensively collecting and post-treating the obtained fluorine-containing sodium salt solid, thereby avoiding the harm of the fluorine-containing sodium salt in the wastewater to the environment and greatly reducing the wastewater treatment cost;
(3) Transferring the clear liquid into a reaction kettle, adjusting the pH to be =8.8 by using acetic acid, adding 0.8wt% of activated carbon (based on the weight of the clear liquid), heating to 90 ℃, adjusting the concentration of the clear liquid to be 25 Baume degrees by using water, filtering, crystallizing the filtrate at 25 ℃, and centrifuging to obtain solid crystals, namely crystalline sodium acetate.
And (4) analyzing results:
when the crystalline sodium acetate obtained in the step (3) of this example was analyzed, the content of sodium acetate in the crystalline sodium acetate was 57.3% (the crystalline sodium acetate was a sodium acetate containing three water molecules and having a chemical formula of CH3COONa 3H2O, and the content of commercially available sodium acetate was 58 to 60%).
Example 5
The wastewater obtained in the "diene addition step (2)" of example 1 was treated to separate a fluorine-containing sodium salt and crystalline sodium acetate therefrom, and the specific steps were as follows:
(1) The wastewater obtained in the "diene addition step (2) in example 1 was adjusted to pH =10 with an aqueous sodium hydroxide solution, and then cooled to 15 ℃.
(2) Heating the crystallized solid obtained in the step 1 to 80 ℃, keeping the temperature for 150 minutes under the stirring condition, keeping the temperature at 80 ℃, standing, separating out the solid, performing centrifugal separation to obtain fluorine-containing sodium salt solid and clear liquid, and performing centralized collection and post-treatment on the obtained fluorine-containing sodium salt solid, thereby avoiding the harm of the fluorine-containing sodium salt in the wastewater to the environment and greatly reducing the wastewater treatment cost;
(3) Transferring the clear liquid into a reaction kettle, adjusting the pH to be =8.8 by using acetic acid, adding 0.8wt% of activated carbon (based on the weight of the clear liquid), heating to 90 ℃, adjusting the concentration of the clear liquid to be 25 Baume degrees by using water, filtering, crystallizing the filtrate at 15 ℃, and centrifuging to obtain solid crystals, namely crystalline sodium acetate.
And (4) analyzing results:
the crystalline sodium acetate obtained in step (3) of this example was analyzed to show that the content of sodium acetate in the crystalline sodium acetate was 56.5% (the crystalline sodium acetate was sodium acetate containing three water molecules and having a chemical formula of CH3 COONa.3H2O, and the content of commercially available sodium acetate was 58-60%).
To summarize
Through the embodiments 1-5, it can be seen that the method of the present invention can effectively separate the fluorine-containing waste salt and sodium acetate in the wastewater generated in the preparation process of ambrotone through the combination of the specific preparation route and the specific process parameters, so as to avoid or reduce the pollution of the fluorine-containing sodium salt or reduce the treatment difficulty and cost of the wastewater. Example 2 the recovered crystalline sodium acetate content was in accordance with the commercial crystalline sodium acetate content range and was used for commercial applications.
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes or modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the appended claims of the present application.
Claims (1)
1. A method for separating fluorine-containing waste salt and sodium acetate from wastewater is characterized by comprising the following steps:
(1) Providing wastewater, wherein the wastewater contains fluorine-containing sodium salt and sodium acetate;
(2) Adjusting the pH of the wastewater to 9.5-11 by using alkali, then crystallizing at 10-20 ℃, and centrifuging to obtain a crystalline solid;
(3) Heating the crystallized solid obtained in the step (2) to 75-85 ℃, keeping the temperature for 120-170 minutes under the stirring condition, standing at 75-85 ℃, separating out the solid, and performing centrifugal separation to obtain the fluorine-containing sodium salt solid and clear liquid;
(4) Adjusting the pH of the clear liquid to 8.5-9 with acid, adding 0.1-2wt% of activated carbon, heating to 85-95 ℃, adjusting the concentration of the clear liquid to 20-30 Baume degrees with water, filtering, crystallizing the filtrate at 20-30 ℃, and centrifuging to obtain solid crystalline sodium acetate;
wherein the wastewater of the step (1) is prepared by the following method:
370-400g of 3-methyl-3-pentene-2 ketone and 30-40g of acetic anhydride are mixed, 13-17g of boron trifluoride acetic acid solution with the mass concentration of 30-40% of catalyst is added, the temperature is raised to 40-50 ℃, 550-600g of myrcene is added in the temperature range, 15-25g of acetic anhydride is added after the addition of myrcene is finished, stirring and heat preservation reaction are carried out for 8-10 hours, after the reaction is finished, 80-90g of sodium hydroxide solution with the mass concentration of 13-17% is added into a reactant to be neutralized, an organic phase and a waste water phase are obtained by separation after standing and layering, and the separated waste water phase is waste water.
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