CN111333485B - Treatment method of diketene production wastewater - Google Patents

Treatment method of diketene production wastewater Download PDF

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CN111333485B
CN111333485B CN202010180515.XA CN202010180515A CN111333485B CN 111333485 B CN111333485 B CN 111333485B CN 202010180515 A CN202010180515 A CN 202010180515A CN 111333485 B CN111333485 B CN 111333485B
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CN111333485A (en
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王国军
王益挺
施红杰
施海洪
钟永波
沈海军
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Ningbo Wanglong Tech Co ltd
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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
    • C07C45/42—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrolysis
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
    • C05F5/00—Fertilisers from distillery wastes, molasses, vinasses, sugar plant or similar wastes or residues, e.g. from waste originating from industrial processing of raw material of agricultural origin or derived products thereof
    • C05F5/006—Waste from chemical processing of material, e.g. diestillation, roasting, cooking
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    • C07—ORGANIC CHEMISTRY
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    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/083—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid anhydrides
    • C07C51/087—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid anhydrides by hydrolysis
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    • C07—ORGANIC CHEMISTRY
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    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
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    • 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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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
    • C07C51/46—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation by azeotropic distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C51/50—Use of additives, e.g. for stabilisation
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    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract

The application discloses a treatment method of diketene production wastewater, which obtains CO by hydrolysis2Acetone, water, low molecular weight sodium polyacrylate/acetic acid coating, etc., and collecting CO via escape method2And distilling to collect acetone, concentrating and azeotroping to remove water, destroying low molecular weight sodium polyacrylate/acetic acid coating and separating out acetic acid, wherein the organic matters in the residual low molecular weight sodium polyacrylate, diketene high polymer, sodium dodecyl benzene sulfonate and the like in the system have high concentration and are easy to ferment, the fermented gas is used as a heat source, solid residues are used as fertilizers, waste liquid is comprehensively treated, various effective components are recovered, resources are fully utilized, and environmental pollution is reduced.

Description

Treatment method of diketene production wastewater
Technical Field
The invention relates to a method for treating wastewater from diketene production.
Background
Diketene, also known as diketene, is colorless or yellowish liquid, has strong pungent odor, has high chemical activity and excellent reaction performance in organic synthesis due to the fact that the structure of the diketene contains two double bonds and has high unsaturation, is an important intermediate and acetylating agent in the organic synthesis, and is widely used in the industries of medicine, pesticides, dyes, food and the like.
The acetic acid cracking method is a commonly used method for producing diketene, and the production process of the acetic acid cracking method comprises the following steps: acetic acid is heated and vaporized, mixed with a phosphate aqueous solution catalyst and fed into a preheating section together for preheating, the preheated ketene is fed into a cracking furnace for cracking and dehydration to generate ketene and water, and the ketene after cooling and separation is fed into a rear section for normal pressure absorption and polymerization to generate crude diketene. The rectification and purification of the crude product of diketene is an essential process, about 10 percent of residues, namely rectification residues, are generated in the rectification process, the rectification residues contain a certain amount of diketene, acetic anhydride, diketene high polymer and other substances, and the residues have high viscosity and pungent smell.
If the waste is directly treated by landfill or incineration, the environment is seriously polluted and resources in residues are wasted. The research on the treatment method of the diketene production wastewater has certain application value.
Disclosure of Invention
The invention aims to provide a method for treating wastewater from diketene production, which comprehensively treats waste liquid, recovers various effective components, fully utilizes resources and reduces environmental pollution.
The technical purpose of the invention is realized by the following technical scheme:
a treatment method of diketene production wastewater comprises the following steps:
(1) hydrolysis
Mixing rectification residues and waste liquid generated by preparing diketene by an acetic acid cracking method to obtain waste water to be treated; adding water into the waste water to be treated,EDTA disodium, low molecular weight sodium polyacrylate and sodium dodecyl sulfate are stirred to react at room temperature, and CO generated in the reaction is collected2Until the reaction is free of CO2Generating;
according to the mass, the using amount ratio of the wastewater to be treated, water, EDTA disodium, low molecular weight sodium polyacrylate and sodium dodecyl sulfate is 1: 1.5-2.5: 0.01-0.02: 0.24-0.28: 0.04-0.06;
(2) separation of acetone
Distilling the slurry obtained by the step (1), wherein the distillation temperature is 42-48 ℃, and the distilled gas is collected into an acetone receiving tank after condensation treatment;
(3) dewatering
Concentrating the slurry obtained by the step (2) until the residual liquid in the slurry is 1/5-1/3 of the total amount of the liquid before concentration, wherein the concentration pressure is 0.10-0.15 MPa, and the concentration temperature is 80-90 ℃; placing the concentrated slurry into a reaction tower, introducing butyl acetate, heating to an azeotropic state, condensing the gas obtained by azeotropic distillation, and then performing ester-water separator, wherein the butyl acetate obtained after ester-water separation is circularly introduced into the reaction tower for dehydration;
(4) separation of acetic acid
Cooling the slurry obtained by the treatment in the step (3) to room temperature, adding ether, adjusting the pH value of the system to 5.5-6.0, stirring and reacting for 10-20 min at room temperature, and performing solid-liquid separation to obtain solid residues and a treatment solution; distilling the treatment liquid at the distillation temperature of 28-32 ℃, condensing the distilled gas, collecting the condensed gas into an ether receiving tank, distilling the treatment liquid again at the secondary distillation temperature of 95-105 ℃ until no ether is distilled out, and collecting the condensed gas into an acetic acid receiving tank;
according to the mass, the dosage ratio of the pulp obtained by the step (3) to the ether is 1: 0.2-0.4;
(5) post-treatment
Collecting and mixing all solid residues generated in the step (4), and putting the mixture into a fermentation tank for fermentation treatment.
Preferably, the method comprises the following steps:
(1) hydrolysis
Mixing rectification residues and waste liquid generated by preparing diketene by an acetic acid cracking method to obtain waste water to be treated; adding water, EDTA disodium, low molecular weight sodium polyacrylate and sodium dodecyl sulfate into wastewater to be treated, stirring for reaction at room temperature, and collecting CO generated by the reaction2Until the reaction is free of CO2Generating;
according to the mass percentage, the dosage ratio of the waste water to be treated, the water, the EDTA disodium, the low molecular weight sodium polyacrylate and the sodium dodecyl sulfate is 1:2.0:0.02:0.25: 0.05;
(2) separation of acetone
Distilling the slurry obtained by the step (1), wherein the distillation temperature is 45 ℃, and collecting distilled gas into an acetone receiving tank after condensation treatment;
(3) dewatering
Concentrating the serous fluid obtained by the step (2) until the residual liquid in the serous fluid is 1/4 of the total liquid amount before concentration, wherein the concentration pressure is 0.12MPa and the concentration temperature is 85 ℃; placing the concentrated slurry into a reaction tower, introducing butyl acetate, heating to an azeotropic state, condensing the gas obtained by azeotropic distillation, and then performing ester-water separator, wherein the butyl acetate obtained after ester-water separation is circularly introduced into the reaction tower for dehydration;
(4) separation of acetic acid
Cooling the slurry obtained by the treatment in the step (3) to room temperature, adding ether, adjusting the pH of the system to 5.6, stirring and reacting for 15min at room temperature, and carrying out solid-liquid separation to obtain solid residues and a treatment solution; distilling the treated liquid at 30 deg.C, collecting the distilled gas into ether receiving tank, distilling off ether at 100 deg.C, and collecting the gas into acetic acid receiving tank;
according to the mass, the dosage ratio of the pulp obtained by the step (3) and the diethyl ether is 1: 0.3;
(5) post-treatment
Collecting and mixing all solid residues generated in the step (4), and putting the mixture into a fermentation tank for fermentation treatment.
Preferably, in the step (4), fly ash is added while adding ether, and the mass ratio of the ether to the fly ash is 1: 0.05-0.10.
Preferably, step (5) comprises the steps of:
collecting and mixing all solid residues generated in the step (4), putting into a fermentation tank, adding biogas residues and vinasse waste liquid, performing electric fermentation treatment, collecting gas discharged by fermentation, standing the fermented liquid for 2-4 hr, and discharging supernatant; according to the mass, the using amount ratio of the solid residues, the biogas residues and the vinasse waste liquid is 2-4: 0.8-1.2: 50;
the electric fermentation is carried out in the electric fermentation tank, the electrolytic fermentation tank is a fermentation tank provided with a plate electrode, graphite is an anode, zinc is a cathode, a zinc plate is laid at the bottom of the fermentation tank, a graphite strip is placed in the fermentation tank, the zinc plate and the graphite strip are connected with a battery through electric wires, and the battery is a 36V battery.
The technical effects of the invention are mainly reflected in the following aspects: hydrolyzing the rectification residue and the waste liquid to obtain acetic acid, acetone, carbon dioxide and solid residues, separating and recovering the acetic acid, the acetone, the carbon dioxide and the solid residues, comprehensively treating the waste liquid, recovering various effective components, fully utilizing resources and reducing environmental pollution; the method is specifically completed by the following steps:
hydrolyzing the diketene and acetic anhydride in the residue waste liquid into acetic acid, acetone and CO by a hydrolysis step2Hydrolysis involves mainly the following reactions: CH (CH)2COCH2CO+H2O→CH3COCH3+CO2，CH3COOOCCH3+H2O→2CH3COOH，(CH2CO)n+H2O→CH3COCH3+CH3COOH+CO2(n≤4)；
In the hydrolysis step of the present application, hydrolysis produces acetic acid, acetone and CO2When the hydrolysis reaction is carried out, the low-molecular-weight sodium polyacrylate (Mw of 2000-5000) swells and disperses in the system, acetic acid is attracted by the low-molecular-weight sodium polyacrylate and surrounds the low-molecular-weight sodium polyacrylate to form a coating insoluble in water, the concentration of the acetic acid in the hydrolysis system is reduced, the pH value is adjusted to 7-8, and CO is absorbed2The forward direction of hydrolysis is promoted, and the hydrolysis is accelerated; in thatWhile the acetone content of the system is continuously increased, because the sodium polyacrylate with low molecular weight is insoluble in the acetone, the sodium dodecyl benzene sulfonate and the coating are combined, so that the damage of a solvent to the coating is reduced, the coating is uniformly dispersed in a hydrolysis system, the possibility of coating residues such as diketene high polymer and the like and the solvent is reduced, and the difficulty of later separation is reduced; in the research process, the existence and concentration of partial heavy metal ions have certain influence on the hydrolysis step of the method, so that the batch-to-batch difference is caused, and the problem is solved by adopting a method of chelating the heavy metal in the EDTA disodium salt;
the hydrolyzed system comprises water, acetone and CO2Coating, ketene dimer and sodium dodecylbenzenesulfonate, etc., and collecting CO by escaping2And distilling at 42-48 ℃ to collect acetone; compared with the method for distilling acetone from an acetone and acetic acid mixed system, the method for distilling acetone has the advantages that the existence of acetic acid is not detected, and the content of acetone is greatly improved, because in the prior art, although the boiling point (118 ℃) of acetic acid is high, a certain amount of acetic acid still can be volatilized when the acetic acid is distilled at 42-48 ℃, and the amount of acetic acid is difficult to separate from acetone; the acetic acid is coated outside the low molecular weight sodium polyacrylate molecules to form a coating, and the coating is not damaged by distillation at 42-48 ℃, so that the acetic acid is not evaporated along with the acetone volatile substance, and the quality of the separated acetone is improved;
separation of CO2The system of the acetone and the water, the coating, the diketene high polymer, the sodium dodecyl benzene sulfonate and the like are firstly concentrated to remove a large amount of solvent, and then a small amount of solvent in the system is removed by an azeotropic method, the former is economical and rapid, the operation is convenient, the latter has good water removal effect, the combination of the two methods can improve the production efficiency, reduce the production cost, and the dehydration rate is obviously superior to the prior art, thereby providing possibility for the recycling of the acetic acid; in the prior art, water can only be removed through the latter, because water and acetic acid are simultaneously distilled out when the water is directly removed through a concentration mode, so that the waste of the acetic acid is caused; the dehydrated system is treated by ethyl ether and pH adjustment, the acetic acid in the coating is separated out, and the acetic acid is respectively recovered by secondary evaporationEther and acetic acid are collected, and the collected acetic acid has high yield and content; almost all the residues are low molecular weight sodium polyacrylate, diketene high polymer and sodium dodecyl benzene sulfonate, and the organic matter concentration in the residues is high, thereby being beneficial to the fermentation of the residues;
in the acetic acid separation step, the fly ash is added while the ether is added, and the fly ash is utilized to wrap the low molecular weight sodium polyacrylate and the diketene high polymer, so that the separation is accelerated, and nutrients are provided for subsequent fermentation; the hydrolysis step is not added, so that the influence of the fly ash on the acting force of the acetic acid coated outside the low molecular weight sodium polyacrylate and the low molecular weight sodium polyacrylate in the previous steps is reduced, and the normal operation of the previous steps is ensured;
the fermented gas can be used as energy for heating, the fermented dregs can be used as fertilizer, and the method is adopted to treat wastewater, comprehensively treat, consume by self production and realize green production.
Detailed Description
Example 1: a treatment method of diketene production wastewater comprises the following steps:
(1) hydrolysis
Mixing rectification residues and waste liquid generated by preparing diketene by an acetic acid cracking method to obtain waste water to be treated; adding water, EDTA disodium, low molecular weight sodium polyacrylate and sodium dodecyl sulfate into wastewater to be treated, stirring for reaction at room temperature, and collecting CO generated by the reaction2Until the reaction is free of CO2Generating;
according to the mass percentage, the dosage ratio of the waste water to be treated, the water, the EDTA disodium, the low molecular weight sodium polyacrylate and the sodium dodecyl sulfate is 1:2.0:0.02:0.25: 0.05;
(2) separation of acetone
Distilling the slurry obtained by the step (1), wherein the distillation temperature is 45 ℃, and collecting distilled gas into an acetone receiving tank after condensation treatment;
(3) dewatering
Concentrating the serous fluid obtained by the step (2) until the residual liquid in the serous fluid is 1/4 of the total liquid amount before concentration, wherein the concentration pressure is 0.12MPa and the concentration temperature is 85 ℃; placing the concentrated slurry into a reaction tower, introducing butyl acetate, heating to an azeotropic state, condensing the gas obtained by azeotropic distillation, and then performing ester-water separator, wherein the butyl acetate obtained after ester-water separation is circularly introduced into the reaction tower for dehydration;
(4) separation of acetic acid
Cooling the slurry obtained by the treatment in the step (3) to room temperature, adding ether, adjusting the pH of the system to 5.6, stirring and reacting for 15min at room temperature, and carrying out solid-liquid separation to obtain solid residues and a treatment solution; distilling the treated liquid at 30 deg.C, collecting the distilled gas into ether receiving tank, distilling off ether at 100 deg.C, and collecting the gas into acetic acid receiving tank;
according to the mass, the dosage ratio of the pulp obtained by the step (3) and the diethyl ether is 1: 0.3;
(5) post-treatment
Collecting and mixing all solid residues generated in the step (4), placing into a fermentation tank, adding biogas residues and distiller's grains waste liquid, performing electric fermentation treatment, collecting gas discharged by fermentation, standing the fermented liquid for 3hr, and discharging supernatant; according to the mass, the dosage ratio of the solid residues, the biogas residues and the vinasse waste liquid is 3:1.0: 50;
the electric fermentation is carried out in the electric fermentation tank, the electrolytic fermentation tank is a fermentation tank provided with a plate electrode, graphite is an anode, zinc is a cathode, a zinc plate is laid at the bottom of the fermentation tank, a graphite strip is placed in the fermentation tank, the zinc plate and the graphite strip are connected with a battery through wires, and the battery is a 36V battery.
Example 2: a treatment method of diketene production wastewater comprises the following steps:
(1) hydrolysis
Mixing rectification residues and waste liquid generated by preparing diketene by an acetic acid cracking method to obtain waste water to be treated; adding water, EDTA disodium, low molecular weight sodium polyacrylate and sodium dodecyl sulfate into wastewater to be treated, stirring for reaction at room temperature, and collecting CO generated by the reaction2Until the reaction is free of CO2Generating;
according to the mass percentage, the dosage ratio of the waste water to be treated, the water, the EDTA disodium, the low molecular weight sodium polyacrylate and the sodium dodecyl sulfate is 1:1.5:0.01:0.24: 0.04;
(2) separation of acetone
Distilling the slurry obtained by the step (1), wherein the distillation temperature is 42 ℃, and collecting distilled gas into an acetone receiving tank after condensation treatment;
(3) dewatering
Concentrating the serous fluid obtained by the step (2) until the residual liquid in the serous fluid is 1/3 of the total liquid amount before concentration, wherein the concentration pressure is 0.15MPa and the concentration temperature is 80 ℃; placing the concentrated slurry into a reaction tower, introducing butyl acetate, heating to an azeotropic state, condensing the gas obtained by azeotropic distillation, and then performing ester-water separator, wherein the butyl acetate obtained after ester-water separation is circularly introduced into the reaction tower for dehydration;
(4) separation of acetic acid
Cooling the slurry obtained by the treatment in the step (3) to room temperature, adding ether, adjusting the pH of the system to 5.5, stirring and reacting for 10min at room temperature, and carrying out solid-liquid separation to obtain solid residues and a treatment solution; distilling the treated liquid at 28 deg.C, collecting the distilled gas into ether receiving tank, distilling off ether at 95 deg.C, and collecting the gas into acetic acid receiving tank;
according to the mass, the dosage ratio of the pulp obtained by the step (3) and the diethyl ether is 1: 0.2;
(5) post-treatment
Collecting and mixing all solid residues generated in the step (4), placing into a fermentation tank, adding biogas residues and distiller's grains waste liquid, performing electric fermentation treatment, collecting gas discharged by fermentation, standing the fermented liquid for 2hr, and discharging supernatant; according to the mass, the dosage ratio of the solid residues, the biogas residues and the vinasse waste liquid is 2:0.8: 50;
the electric fermentation is carried out in the electric fermentation tank, the electrolytic fermentation tank is a fermentation tank provided with a plate electrode, graphite is an anode, zinc is a cathode, a zinc plate is laid at the bottom of the fermentation tank, a graphite strip is placed in the fermentation tank, the zinc plate and the graphite strip are connected with a battery through wires, and the battery is a 36V battery.
Example 3: a treatment method of diketene production wastewater comprises the following steps:
(1) hydrolysis
Mixing rectification residues and waste liquid generated by preparing diketene by an acetic acid cracking method to obtain waste water to be treated; adding water, EDTA disodium, low molecular weight sodium polyacrylate and sodium dodecyl sulfate into wastewater to be treated, stirring for reaction at room temperature, and collecting CO generated by the reaction2Until the reaction is free of CO2Generating;
according to the mass percentage, the dosage ratio of the waste water to be treated, the water, the EDTA disodium, the low molecular weight sodium polyacrylate and the sodium dodecyl sulfate is 1:2.5:0.02:0.28: 0.06;
(2) separation of acetone
Distilling the slurry obtained by the step (1), wherein the distillation temperature is 48 ℃, and collecting distilled gas into an acetone receiving tank after condensation treatment;
(3) dewatering
Concentrating the serous fluid obtained by the step (2) until the residual liquid in the serous fluid is 1/5 of the total liquid amount before concentration, wherein the concentration pressure is 0.10MPa and the concentration temperature is 90 ℃; placing the concentrated slurry into a reaction tower, introducing butyl acetate, heating to an azeotropic state, condensing the gas obtained by azeotropic distillation, and then performing ester-water separator, wherein the butyl acetate obtained after ester-water separation is circularly introduced into the reaction tower for dehydration;
(4) separation of acetic acid
Cooling the slurry obtained by the treatment in the step (3) to room temperature, adding ether, adjusting the pH of the system to 6.0, stirring and reacting for 20min at room temperature, and carrying out solid-liquid separation to obtain solid residues and a treatment solution; distilling the treated liquid at 32 deg.C, collecting the distilled gas into ether receiving tank, distilling off ether at 105 deg.C, and collecting the gas into acetic acid receiving tank;
according to the mass, the dosage ratio of the pulp obtained by the step (3) and the diethyl ether is 1: 0.4;
(5) post-treatment
Collecting and mixing all solid residues generated in the step (4), placing into a fermentation tank, adding biogas residues and distiller's grains waste liquid, performing electric fermentation treatment, collecting gas discharged by fermentation, standing the fermented liquid for 4hr, and discharging supernatant; according to the mass, the dosage ratio of the solid residues, the biogas residues and the vinasse waste liquid is 4:1.2: 50;
the electric fermentation is carried out in the electric fermentation tank, the electrolytic fermentation tank is a fermentation tank provided with a plate electrode, graphite is an anode, zinc is a cathode, a zinc plate is laid at the bottom of the fermentation tank, a graphite strip is placed in the fermentation tank, the zinc plate and the graphite strip are connected with a battery through wires, and the battery is a 36V battery.
Example 4: a method for treating wastewater from diketene production, which is different from example 1 in that step (4) is replaced by the following method:
cooling the slurry obtained by the treatment in the step (3) to room temperature, adding diethyl ether and fly ash, adjusting the pH of the system to 5.6, stirring and reacting for 15min at room temperature, and carrying out solid-liquid separation to obtain solid residues and a treatment solution; distilling the treated liquid at 30 deg.C, collecting the distilled gas into ether receiving tank, distilling off ether at 100 deg.C, and collecting the gas into acetic acid receiving tank;
according to the mass, the dosage ratio of the slurry obtained by the step (3) to the ether is 1:0.3, and the mass ratio of the ether to the fly ash is 1: 0.05.
Example 5: a method for treating wastewater from diketene production, which is different from example 1 in that step (4) is replaced by the following method:
cooling the slurry obtained by the treatment in the step (3) to room temperature, adding diethyl ether and fly ash, adjusting the pH of the system to 5.6, stirring and reacting for 15min at room temperature, and carrying out solid-liquid separation to obtain solid residues and a treatment solution; distilling the treated liquid at 30 deg.C, collecting the distilled gas into ether receiving tank, distilling off ether at 100 deg.C, and collecting the gas into acetic acid receiving tank;
according to the mass, the dosage ratio of the slurry obtained by the step (3) to the ether is 1:0.3, and the mass ratio of the ether to the fly ash is 1: 0.10.
Example 6: a method for treating wastewater from diketene production, which is different from example 1 in that step (5) is replaced by the following method:
collecting and mixing all solid residues generated in the step (4), mixing the solid residues, water and isopropanol according to the mass ratio of 1:0.5:1.0, stirring and mixing for 10min, filtering, performing fermentation treatment on a filter cake, and concentrating the filtrate to remove the solvent to obtain a mixture; mixing the mixture with water according to a ratio of 1:0.2, stirring and mixing for 10min, filtering, drying a filter cake to obtain low-molecular-weight sodium polyacrylate, concentrating the filtrate to remove the solvent, and performing fermentation treatment;
adding biogas residue and distiller's grains waste liquid into the treated solid residue, performing electric fermentation, collecting gas discharged from fermentation, standing the fermented liquid for 3hr, and discharging supernatant; according to the mass, the dosage ratio of the solid residues, the biogas residues and the vinasse waste liquid is 3:1.0: 50;
the electric fermentation is carried out in the electric fermentation tank, the electrolytic fermentation tank is a fermentation tank provided with a plate electrode, graphite is an anode, zinc is a cathode, a zinc plate is laid at the bottom of the fermentation tank, a graphite strip is placed in the fermentation tank, the zinc plate and the graphite strip are connected with a battery through wires, and the battery is a 36V battery.
Example 7: a method for treating diketene production wastewater is different from example 1 in that step (5) is replaced by the following method:
collecting and mixing all solid residues generated in the step (4), mixing the solid residues, water and isopropanol according to the mass ratio of 1:0.8:1.5, stirring and mixing for 20min, filtering, performing fermentation treatment on a filter cake, and concentrating the filtrate to remove the solvent completely to obtain a mixture; mixing the mixture with water according to a ratio of 1:0.4, stirring and mixing for 20min, filtering, drying a filter cake to obtain low-molecular-weight sodium polyacrylate, concentrating the filtrate to remove the solvent, and performing fermentation treatment;
adding biogas residue and distiller's grains waste liquid into the treated solid residue, performing electric fermentation, collecting gas discharged from fermentation, standing the fermented liquid for 3hr, and discharging supernatant; according to the mass, the dosage ratio of the solid residues, the biogas residues and the vinasse waste liquid is 3:1.0: 50;
the electric fermentation is carried out in the electric fermentation tank, the electrolytic fermentation tank is a fermentation tank provided with a plate electrode, graphite is an anode, zinc is a cathode, a zinc plate is laid at the bottom of the fermentation tank, a graphite strip is placed in the fermentation tank, the zinc plate and the graphite strip are connected with a battery through wires, and the battery is a 36V battery.
Example 8: a method for treating wastewater from diketene production, which is different from example 1 in that step (5) is replaced by the following method:
collecting and mixing all solid residues generated in the step (4), putting into a fermentation tank, adding biogas residues and distiller's grains waste liquid, performing aeration fermentation treatment, collecting gas discharged by fermentation, standing the fermented liquid for 3hr, and discharging supernatant; the dosage ratio of the solid residue, the biogas residue and the vinasse waste liquid is 3:1.0:50 by mass.
Comparative example 1: a treatment method of diketene production wastewater comprises the following steps:
(1) hydrolysis
Mixing rectification residues and waste liquid generated by preparing diketene by an acetic acid cracking method to obtain waste water to be treated; adding water into the wastewater to be treated, and stirring and reacting at room temperature for 12 hr;
according to the mass, the dosage ratio of the wastewater to be treated to the water is 1: 2.0;
(2) separation of acetone
Distilling the slurry obtained by the step (1), wherein the distillation temperature is 45 ℃, and collecting distilled gas into an acetone receiving tank after condensation treatment;
(3) dewatering
Concentrating the serous fluid obtained by the step (2) until the residual liquid in the serous fluid is 1/4 of the total liquid amount before concentration, wherein the concentration pressure is 0.12MPa and the concentration temperature is 85 ℃; placing the concentrated slurry into a reaction tower, introducing butyl acetate, heating to an azeotropic state, condensing the gas obtained by azeotropic distillation, and then performing ester-water separator, wherein the butyl acetate obtained after ester-water separation is circularly introduced into the reaction tower for dehydration;
(4) separation of acetic acid
Cooling the slurry obtained by the treatment in the step (3) to room temperature, adding ether, adjusting the pH of the system to 5.6, stirring and reacting for 15min at room temperature, and carrying out solid-liquid separation to obtain solid residues and a treatment solution; distilling the treated liquid at 30 deg.C, collecting the distilled gas into ether receiving tank, distilling off ether at 100 deg.C, and collecting the gas into acetic acid receiving tank;
according to the mass, the dosage ratio of the pulp obtained by the step (3) and the diethyl ether is 1: 0.3;
(5) post-treatment
Collecting and mixing all solid residues generated in the step (4), placing into a fermentation tank, adding biogas residues and distiller's grains waste liquid, performing electric fermentation treatment, collecting gas discharged by fermentation, standing the fermented liquid for 3hr, and discharging supernatant; according to the mass, the dosage ratio of the solid residues, the biogas residues and the vinasse waste liquid is 3:1.0: 50;
the electric fermentation is carried out in the electric fermentation tank, the electrolytic fermentation tank is a fermentation tank provided with a plate electrode, graphite is an anode, zinc is a cathode, a zinc plate is laid at the bottom of the fermentation tank, a graphite strip is placed in the fermentation tank, the zinc plate and the graphite strip are connected with a battery through wires, and the battery is a 36V battery.
Comparative example 2: a treatment method of diketene production wastewater comprises the following steps:
(1) hydrolysis
Mixing rectification residues and waste liquid generated by preparing diketene by an acetic acid cracking method to obtain waste water to be treated; adding water into the wastewater to be treated, and stirring and reacting at room temperature for 12 hr;
according to the mass, the dosage ratio of the wastewater to be treated to the water is 1: 2.0;
(2) separation of acetone
Distilling the slurry obtained by the step (1), wherein the distillation temperature is 45 ℃, and collecting distilled gas into an acetone receiving tank after condensation treatment;
(3) dewatering
Placing the slurry obtained by the treatment in the step (2) into a reaction tower, introducing butyl acetate, heating to an azeotropic state, condensing the gas obtained by azeotropic distillation, and then carrying out an ester-water separator, wherein the butyl acetate obtained after the ester-water separation is circularly introduced into the reaction tower for dehydration;
(4) separation of acetic acid
Cooling the slurry obtained by the treatment in the step (3) to room temperature, and filtering to obtain liquid which is acetic acid;
(5) post-treatment
Collecting and mixing all solid residues generated in the step (4), placing into a fermentation tank, adding biogas residues and distiller's grains waste liquid, performing electric fermentation treatment, collecting gas discharged by fermentation, standing the fermented liquid for 3hr, and discharging supernatant; according to the mass, the dosage ratio of the solid residues, the biogas residues and the vinasse waste liquid is 3:1.0: 50;
the electric fermentation is carried out in the electric fermentation tank, the electrolytic fermentation tank is a fermentation tank provided with a plate electrode, graphite is an anode, zinc is a cathode, a zinc plate is laid at the bottom of the fermentation tank, a graphite strip is placed in the fermentation tank, the zinc plate and the graphite strip are connected with a battery through wires, and the battery is a 36V battery.
Performance testing
8407kg of diketene and 10209kg of acetic anhydride are mixed to be used as mother liquor to be tested, 50kg of mother liquor to be tested is taken as an original sample to be processed according to an embodiment or a comparative example, and the hydrolysis rate, the recovery rate of acetone and acetic acid, the content and other performances in the processing process are tested.
Hydrolysis rate (%) — actual yield m1 of acetone or acetic acid after hydrolysis/theoretical yield m0 × 100% of acetone or acetic acid after hydrolysis; recovery (%) — amount of acetone or acetic acid recovered m 2/actual yield of acetone or acetic acid after hydrolysis m1 × 100%; the solvent content was determined by gas chromatography.
TABLE 1
Figure BDA0002412372530000121
TABLE 2
Figure BDA0002412372530000131
The above are only typical examples of the present invention, and besides, the present invention may have other embodiments, and all the technical solutions formed by equivalent substitutions or equivalent changes are within the scope of the present invention as claimed.

Claims (5)

1. A treatment method of diketene production wastewater is characterized by comprising the following steps:
(1) hydrolysis
Mixing rectification residues and waste liquid generated by preparing diketene by an acetic acid cracking method to obtain waste water to be treated; adding water, EDTA disodium, low molecular weight sodium polyacrylate and sodium dodecyl sulfate into wastewater to be treated, stirring for reaction at room temperature, and collecting CO generated by the reaction2Until the reaction is free of CO2Generating;
according to the mass, the using amount ratio of the wastewater to be treated, water, EDTA disodium, low molecular weight sodium polyacrylate and sodium dodecyl sulfate is 1: 1.5-2.5: 0.01-0.02: 0.24-0.28: 0.04-0.06;
(2) separation of acetone
Distilling the slurry obtained by the step (1), wherein the distillation temperature is 42-48 ℃, and the distilled gas is collected into an acetone receiving tank after condensation treatment;
(3) dewatering
Concentrating the slurry obtained by the step (2) until the residual liquid in the slurry is 1/5-1/3 of the total amount of the liquid before concentration, wherein the concentration pressure is 0.10-0.15 MPa, and the concentration temperature is 80-90 ℃; placing the concentrated slurry into a reaction tower, introducing butyl acetate, heating to an azeotropic state, condensing the gas obtained by azeotropic distillation, introducing the gas into an ester-water separator, and circularly introducing the butyl acetate obtained by ester-water separation into the reaction tower for dehydration;
(4) separation of acetic acid
Cooling the slurry obtained by the treatment in the step (3) to room temperature, adding ether, adjusting the pH value of the system to 5.5-6.0, stirring and reacting for 10-20 min at room temperature, and performing solid-liquid separation to obtain solid residues and a treatment solution; distilling the treatment liquid at the distillation temperature of 28-32 ℃, condensing the distilled gas, collecting the condensed gas into an ether receiving tank, distilling the treatment liquid again at the secondary distillation temperature of 95-105 ℃ until no ether is distilled out, and collecting the condensed gas into an acetic acid receiving tank;
according to the mass, the dosage ratio of the slurry obtained by the step (3) to the ether is 1: 0.2-0.4;
(5) post-treatment
Collecting and mixing all solid residues generated in the step (4), and putting the mixture into a fermentation tank for fermentation treatment.
2. The method for treating diketene production wastewater as claimed in claim 1, which is characterized by comprising the following steps:
(1) hydrolysis
Mixing rectification residues and waste liquid generated by preparing diketene by an acetic acid cracking method to obtain waste water to be treated; adding water, EDTA disodium, low molecular weight sodium polyacrylate and sodium dodecyl sulfate into wastewater to be treated, stirring for reaction at room temperature, and collecting CO generated by the reaction2Until the reaction is free of CO2Generating;
according to the mass percentage, the dosage ratio of the wastewater to be treated, water, EDTA disodium, low molecular weight sodium polyacrylate and sodium dodecyl sulfate is 1:2.0:0.02:0.25: 0.05;
(2) separation of acetone
Distilling the slurry obtained by the step (1), wherein the distillation temperature is 45 ℃, and collecting distilled gas into an acetone receiving tank after condensation treatment;
(3) dewatering
Concentrating the serous fluid obtained by the step (2) until the residual liquid in the serous fluid is 1/4 of the total liquid amount before concentration, wherein the concentration pressure is 0.12MPa and the concentration temperature is 85 ℃; placing the concentrated slurry into a reaction tower, introducing butyl acetate, heating to an azeotropic state, condensing the gas obtained by azeotropic distillation, introducing the gas into an ester-water separator, and circularly introducing the butyl acetate obtained by ester-water separation into the reaction tower for dehydration;
(4) separation of acetic acid
Cooling the slurry obtained by the treatment in the step (3) to room temperature, adding ether, adjusting the pH of the system to 5.6, stirring and reacting for 15min at room temperature, and carrying out solid-liquid separation to obtain solid residues and a treatment solution; distilling the treated liquid at 30 deg.C, collecting the distilled gas into ether receiving tank, distilling off ether at 100 deg.C, and collecting the gas into acetic acid receiving tank;
according to the mass, the dosage ratio of the slurry obtained by the step (3) to the ether is 1: 0.3;
(5) post-treatment
Collecting and mixing all solid residues generated in the step (4), and putting the mixture into a fermentation tank for fermentation treatment.
3. The method for treating diketene production wastewater as claimed in claim 1, wherein fly ash is added while diethyl ether is added in step (4), and the mass ratio of diethyl ether to fly ash is 1: 0.05-0.10.
4. The method for treating diketene production wastewater as claimed in claim 1, wherein the step (5) comprises the following steps:
collecting and mixing all solid residues generated in the step (4), putting into a fermentation tank, adding biogas residues and vinasse waste liquid, performing electric fermentation treatment, collecting gas discharged by fermentation, standing the fermented liquid for 2-4 hr, and discharging supernatant; according to the mass, the using amount ratio of the solid residues, the biogas residues and the vinasse waste liquid is 2-4: 0.8-1.2: 50;
the electric fermentation is carried out in the electric fermentation tank, the electrolytic fermentation tank is a fermentation tank provided with a plate electrode, graphite is an anode, zinc is a cathode, a zinc plate is laid at the bottom of the fermentation tank, a graphite strip is placed in the fermentation tank, the zinc plate and the graphite strip are connected with a battery through electric wires, and the battery is a 36V battery.
5. The method for treating wastewater from diketene production according to claim 1, wherein the solid residue produced in step (4) is subjected to the following treatment before fermentation treatment:
mixing the solid residues, water and isopropanol according to the mass ratio of 1: 0.5-0.8: 1.0-1.5, stirring and mixing for 10-20 min, filtering, performing fermentation treatment on a filter cake, and concentrating the filtrate to remove the solvent completely to obtain a mixture; mixing the mixture with water according to the ratio of 1: 0.2-0.4, stirring and mixing for 10-20 min, filtering, drying filter cakes to obtain low-molecular-weight sodium polyacrylate, concentrating the filtrate to remove the solvent, and then performing fermentation treatment.
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