CN109665661B - Method for separating sulfuric acid, acetic acid and furfural from furfural wastewater - Google Patents

Method for separating sulfuric acid, acetic acid and furfural from furfural wastewater Download PDF

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CN109665661B
CN109665661B CN201910138126.8A CN201910138126A CN109665661B CN 109665661 B CN109665661 B CN 109665661B CN 201910138126 A CN201910138126 A CN 201910138126A CN 109665661 B CN109665661 B CN 109665661B
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acetic acid
furfural
acid
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tower
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CN109665661A (en
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郭志刚
唐印
雷林
刘朝慧
李旭初
李刚
王明权
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Sichuan Golden Elephant Sincerity Chemical Co Ltd
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
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    • C02F1/26—Treatment of water, waste water, or sewage by extraction
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    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
    • C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
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Abstract

The invention belongs to the technical field of chemical production, and particularly relates to a method for separating sulfuric acid, acetic acid and furfural from furfural wastewater, which is used for recovering sulfuric acid and dilute acetic acid and comprises the steps of enabling the wastewater to enter a first-stage homogeneous membrane electrodialyzer, obtaining a mixture A of sulfuric acid and acetic acid in an acid recovery chamber, and enabling the remainder in a treatment chamber to be a furfural aqueous solution; the mixture A is pumped to a treatment chamber of a second-stage homogeneous membrane electrodialyzer from an acid recovery chamber to separate sulfuric acid, and the sulfuric acid returns to a furfural reaction process; dilute acetic acid of sulfuric acid separated by the second-stage electrodialysis treatment chamber is pumped into a third-stage electrodialysis device treatment chamber, and the acetic acid is concentrated; the acetic acid after concentration enters the rectification extraction step to obtain pure acetic acid. The method for recovering the sulfuric acid and the high-purity acetic acid by electrodialysis coupling extraction rectification is economical and efficient, and is particularly suitable for wastewater with lower contents of the sulfuric acid and the acetic acid.

Description

Method for separating sulfuric acid, acetic acid and furfural from furfural wastewater
Technical Field
The invention belongs to the field of wastewater treatment in chemical production technology, and particularly relates to a device and a method for separating sulfuric acid, acetic acid and furfural from furfural wastewater, wherein the sulfuric acid and dilute acetic acid are recovered.
Background
At home and abroad, the hydrolysis of cellulose or the hydrolysis of xylose to prepare furfural mostly adopts sulfuric acid as a catalyst, and the hydrolysis liquid is neutralized by lime in the hydrolysis liquid by the traditional method so as to adapt to the requirement of fermentation liquid on the pH value. However, sulfuric acid cannot be recycled, and a large amount of calcium sulfate solid waste is difficult to treat. This method is not the optimal choice. Meanwhile, acetic acid which is a byproduct in the reaction solution is not recovered, so that resources are wasted, and environmental pollution is caused.
The current literature reports methods for recovering acetic acid from wastewater as follows: common distillation, azeotropic distillation, solvent extraction, esterification, and combinations thereof. The rectification method is generally suitable for recovering high-concentration acetic acid, the concentration of the acetic acid in the wastewater is relatively low, and the rectification method is not economical for the low-concentration acetic acid solution; the solvent extraction method and the esterification method have unsatisfactory effect on the recovery of low-concentration acetic acid and have low recovery rate. Because most of the waste water contains lower acetic acid, more economical and effective methods are always sought to recover the acetic acid from the waste water containing dilute acetic acid.
In the method for recovering acetic acid from the waste water containing dilute acetic acid in the patent CN101234959B, the method is characterized in that: the method comprises the steps of firstly treating and recovering the waste water containing dilute acetic acid by an electrodialysis method to obtain an extremely dilute solution of acetic acid with the concentration of less than 1000ppm, and then further removing and recovering the acetic acid in the residual extremely dilute solution by an anion exchange resin adsorption method to ensure that the concentration of the acetic acid in the finally discharged waste water is less than 50ppm, thereby obtaining a certain effect.
The patent 200110010166.1 furfural wastewater treatment method comprises the following steps: neutralizing furfural wastewater with alkaline substances, reacting organic acid in the wastewater with alkali to generate salt, and removing impurities through precipitation separation, wherein the pH value of the obtained wastewater liquid is controlled between 6 and 9; secondly, evaporating waste water by utilizing the waste heat of aldehyde steam discharged by a hydrolysis kettle in furfural production to concentrate waste water liquid, and discharging concentrated liquid when the solid content of the concentrated liquid reaches 20-35%; and thirdly, sending the obtained concentrated solution to a boiler for incineration, or preparing the finished product of acetic acid or acetate by known refining equipment. Certain effect is also obtained.
However, in the recovery of low-concentration acetic acid, the recovery rate is not high, and since the boiling point of acetic acid is only 118.1 ℃, which is close to the boiling point of water of 100 ℃, and the two are non-ideal systems, the economic benefit is affected by increasing a plurality of tower plates and consuming a large amount of heat energy to obtain high-purity acetic acid from the low-concentration dilute acetic acid solution, so that the method is only suitable for purifying crude acetic acid with small water content, and is not suitable for the low-concentration dilute acetic acid solution.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for separating sulfuric acid, dilute acetic acid and furfural from furfural wastewater, which is economic and efficient and is particularly suitable for wastewater with lower contents of sulfuric acid and acetic acid by using electrodialysis coupling extraction rectification to recover sulfuric acid and high-purity acetic acid.
The method for separating sulfuric acid, acetic acid and furfural from furfural wastewater in the invention for solving the technical problems comprises the following steps:
(1) the furfural wastewater enters a first-stage homogeneous membrane electrodialyzer to obtain a mixture A of sulfuric acid and acetic acid in an acid recovery chamber, and the remainder in a treatment chamber is a furfural aqueous solution;
(2) pumping the mixture A from an acid recovery chamber to a treatment chamber of a second-stage homogeneous membrane electrodialyzer to separate sulfuric acid, and returning the sulfuric acid to a furfural reaction process;
(3) dilute acetic acid of sulfuric acid separated by the second-stage electrodialysis treatment chamber is pumped into a third-stage electrodialysis device treatment chamber, and the acetic acid is concentrated; until the concentration of the concentrated acetic acid is 30 percent.
(4) The concentrated acetic acid enters a rectification extraction step to obtain pure acetic acid.
The first stage homogeneous membrane electrodialysis step is preceded by a pretreatment step, namely, a furfural reaction solution passes through a high-speed disc centrifuge to separate a solvent phase from a water phase. After the biomass hydrolysate is pretreated, the main components of the water phase part of the biomass hydrolysate are a small amount of furfural, sulfuric acid and organic acid (mainly acetic acid), and the components of the furfural wastewater water phase are 1-2% of sulfuric acid, 0.5-1% of acetic acid and 0.2-0.5% of furfural.
And the separated sulfuric acid enters a reverse osmosis membrane for further concentration and then returns to the furfural reaction process.
According to the difference of migration speed, different electrodialysis separation modes are adopted, and the homogeneous membrane electrodialyzer is subjected to anion separation in the device under the action of a direct current electric fieldAn acid recovery chamber is formed between the proton exchange membrane and the cation exchange layer, and a treatment chamber (a diluting chamber) is formed between the anion exchange membrane and the anion exchange layer. Furfural and acid solution (Furfural, H)2SO4HAc) into a processing chamber, and SO in the processing chamber under the action of an electric field4 2-、Ac-And the furfural passes through a cation exchange membrane and enters an acid recovery chamber, and the furfural is basically not ionized and remains in a treatment chamber, so that the aim of separating the furfural from the acid is fulfilled.
In the first stage acid recovery chamber, SO transferred from the process chamber4 2-、Ac-Combining with H + obtained from cation membrane water dissociation to obtain sulfuric acid and HAc, and feeding the mixed acid into second-stage electrodialyzer to separate sulfuric acid from acetic acid, and separating and recovering sulfuric acid.
The acid recovery chamber of the first-stage electrodialyzer is connected to the treatment chamber of the second-stage electrodialyzer, and the sulfuric acid obtained by the separation of the acid recovery chamber of the second-stage electrodialyzer; the feed liquid after the separation of the sulfuric acid is firstly pumped into a treatment chamber of a third-stage electrodialyzer for concentration of the acetic acid, and the concentrated acetic acid enters a rectification extraction step.
The first electrodialysis and the second electrodialysis are homogeneous membrane electrodialysis, the third electrodialysis is bipolar membrane electrodialysis, the operating voltage of the homogeneous membrane electrodialysis is constant voltage, and the operating voltage is 40-50 v.
The operating voltage of each stage of electrodialysis is as follows: the voltage of the first electrodialysis is 50v, the voltage of the second electrodialysis is 40v, and the voltage of the third electrodialysis is 50v, which are all operated under constant voltage.
In the invention, the acid recovery chamber of the first-stage homogeneous membrane electrodialyzer is connected to the treatment chamber of the second-stage homogeneous membrane electrodialyzer, and the sulfuric acid obtained by the acid recovery chamber of the homogeneous membrane electrodialyzer is directly recycled, wherein the concentration of the sulfuric acid is 5%; or concentrating the furfural product to 10% by using a reverse osmosis membrane to serve as a catalyst for furfural preparation reaction.
After the sulfuric acid separation of the second-stage electrodialyzer, the dilute acetic acid in the treatment chamber is pumped into the treatment chamber of the third-stage bipolar membrane electrodialyzer for acetic acid concentration, the space between the anion exchange membrane and the anion exchange layer of the bipolar membrane is called as the treatment chamber, and the anion exchange membrane and the bipolar membraneThe space between the cation exchange layers of the sexual membrane is called an acid recovery chamber, the acetic acid-containing wastewater is pumped into a treatment chamber by a pump, and Ac in the treatment chamber is under the action of an electric field-OH generated from the bipolar membrane passes through the anion exchange membrane from the treatment chamber into the acid recovery chamber-Entering the processing chamber to remove the residual H+Neutralizing the acetic acid in the treatment chamber to gradually remove the acetic acid, and recovering the Ac in the acid recovery chamber from the treatment chamber-And H from a bipolar membrane＋Gradually obtaining concentrated acetic acid aqueous solution, and when the concentration of the acetic acid in the acid recovery chamber reaches a certain degree (such as 30 percent), the acetic acid aqueous solution can be injected into the feed inlet of the extractive distillation tower.
Concentrating the diluted acetic acid to 30% by bipolar membrane electrodialysis, and extracting and rectifying by using a solvent to obtain the acetic acid with the purity of 99-99.8%.
The invention adopts a constant voltage operation mode, and the second stage adopts a slightly lower voltage, so that the acetate ion migration caused by overlarge driving force can be avoided, and the temperature rise of the circulating liquid can be controlled not to be too high. Thereby achieving the separation of sulfuric acid and acetic acid.
The rectification extraction step is extraction in a rectification tower; the rectifying tower is a continuous extraction rectifying tower, and the weight ratio of acetic acid to an extracting agent is 1: 2-4; the acetic acid concentration is 30 percent. Water is distilled from the top of the tower, and an acetic acid solvent mixture is obtained at the bottom of the tower. In the extraction and rectification process, feeding, solvent addition and recovery are continuously carried out.
The extractant adopts one or more than two of octanol, tributyl phosphate and methyl formamide. When the dosage is more than two, the optimized dosage mass ratio is 1: 1, or the ratio is 1: 1: 1.
in the step (4), the rectification extraction step is that the concentrated acetic acid enters the middle part of a continuous extraction rectification tower, a solvent is added into the upper part of the tower, water vapor evaporated from the top of the tower enters a compressor to be compressed and heated, and then returns to a heating vapor inlet of a reboiler of the extraction rectification tower; a discharge hole at the bottom of the extraction and rectification tower is connected to a feed inlet at the middle part of the desolventizing tower, acetic acid distilled from the top of the desolventizing tower enters an inlet of a condenser and is condensed to obtain 99-99.8% acetic acid, and the solvent obtained at the bottom of the tower returns to a feed inlet at the upper part of the extraction and rectification tower; a discharge hole at the bottom of the desolventizing tower is connected to an inlet of a material pump, and an outlet of the material pump is connected to a solvent feed hole at the upper part of the extraction and rectification tower, so that the solvent can be recycled; vapor at the top of the acetic acid extractive distillation tower enters a compressor to be compressed and heated, and then is connected to a vapor inlet of a reboiler at the bottom of the extractive distillation tower to be used as a heating source; the separated water is discharged from the lower part of the desolventizing tower.
And (3) beating the acetic acid in the acid recovery chamber of the third electrodialyzer to a feed inlet of an extractive distillation tower, and extracting by adopting continuous extractive distillation, wherein the extraction of the distillation tower is carried out by continuous extractive distillation, and the weight ratio of the 30% concentration acetic acid to the solvent is 1:2-4 during extraction.
According to the difference of physicochemical properties of two ions, the invention adopts a mode of adjusting voltage by a homogeneous membrane and a bipolar membrane electrodialyzer to separate sulfuric acid, acetic acid and furfural in the biomass hydrolysate, thereby achieving the purpose of separating sulfuric acid, acetic acid and furfural. And then different electrodialysis separation and staged separation modes are adopted according to different migration speeds.
The invention has the following beneficial effects:
A. the furfural wastewater treatment avoids the pollution to the environment caused by the conventional lime neutralization process.
B. Useful substances in waste water are for example: the sulfuric acid, the acetic acid and the furfural are recovered, and the economic benefit is obvious.
C. The sulfuric acid, the acetic acid and the furfural can be separated from the dilute solution by adopting homogeneous membrane and bipolar membrane electrodialysis, so that the effects of high efficiency and energy saving are achieved.
D. Compared with the conventional distillation method, the method for separating the sulfuric acid, the acetic acid and the furfural from the dilute solution saves energy by 70 percent or more by adopting homogeneous membrane and bipolar membrane electrodialysis and coupling solvent extraction rectification processes.
E. A small amount of water in the desolventizing tower is pumped out from the lower part of the tower, and the tower has three purposes, thereby saving equipment investment and energy consumption.
Drawings
FIG. 1 is a block diagram of a process flow of the present invention;
FIG. 2 is a schematic diagram of the principle of recovering acetic acid by bipolar membrane electrodialysis in accordance with the present invention;
FIG. 3 is a schematic diagram of a processing system according to the present invention;
FIG. 4 is a schematic diagram of the structure of the double-column extractive distillation employed in the present invention.
Wherein the labels in the figure are specifically:
1. the device comprises a pretreatment device, 2, a first-stage electrodialyzer (2-1, a first-stage acid recovery chamber, 2-2, a first-stage treatment chamber), 3, a second-stage electrodialyzer (3-1, a second-stage acid recovery chamber, 3-2, a second-stage treatment chamber), 4, a reverse osmosis device, 5, a furfural reaction device, 6, an extractive distillation device, 7, an extractive distillation tower, 8, a vapor-liquid separator, 9, a compressor, 10, a reboiler, 11, a desolventizing tower, 12, a condenser, 13, a reboiler, 14, a material pump, 15, a third-stage bipolar membrane electrodialyzer (15-1, a third-stage treatment chamber, 15-2, a third-group acid recovery chamber) and 16, a furfural fractionating tower.
Detailed Description
The invention will be further illustrated with reference to specific embodiments:
example 1
The method for separating sulfuric acid, acetic acid and furfural from furfural wastewater comprises the following steps:
(1) the furfural wastewater enters a first-stage homogeneous membrane electrodialyzer to obtain a mixture A of sulfuric acid and acetic acid in an acid recovery chamber, and the remainder in a treatment chamber is a furfural aqueous solution;
(2) pumping the mixture A from an acid recovery chamber to a treatment chamber of a second-stage homogeneous membrane electrodialyzer to separate sulfuric acid, and returning the sulfuric acid to a furfural reaction process;
(3) dilute acetic acid of sulfuric acid separated by the second-stage electrodialysis treatment chamber is pumped into a third-stage electrodialysis device treatment chamber, and the acetic acid is concentrated; until the concentration of the concentrated acetic acid is 30 percent.
(4) The concentrated acetic acid enters a rectification extraction step to obtain pure acetic acid.
According to the difference of migration speed, a staged separation mode is adopted, under the action of a direct current electric field, an acid recovery chamber is arranged between an anion exchange membrane and a cation exchange layer in the device, and a treatment chamber is arranged between the anion exchange membrane and the anion exchange layer. Furfural and acid solution (Furfural, H)2SO4HAc) into a treatment chamber, and under the action of an electric field, SO is in the treatment chamber4 2-、Ac-Across a cation exchange membraneAnd (4) entering an acid recovery chamber, and simultaneously, because the furfural is basically not ionized and is left in a treatment chamber, the aim of separating the furfural from the acid is fulfilled.
In the acid recovery chamber, SO transferred from the treatment chamber4 2-、Ac-Combined with H + from water dissociation from cation membrane to obtain H2SO4And HAc, and then the mixed acid is sent into a treatment chamber of a second-stage electrodialyzer to separate sulfuric acid from acetic acid. Sodium sulfate aqueous solution is prepared to be used as electrode water so as to reduce the resistance value of the electrode chamber water. The operation mode of constant voltage is adopted, so that the acetate ion migration caused by overlarge driving force can be avoided, and the temperature rise of the circulating liquid can be controlled not to be overhigh. Thereby achieving the separation of sulfuric acid and acetic acid. The concentration of the sulfuric acid obtained by homogeneous membrane electrodialysis separation is 5%, and the sulfuric acid can be further concentrated to 10% by using a reverse osmosis membrane and used as a catalyst for furfural preparation reaction. The operating voltage of the homogeneous membrane electrodialysis is 40v-50 v.
After the sulfuric acid of the second-stage electrodialyzer is separated, the dilute acetic acid in the treatment chamber is pumped into the treatment chamber of the third-stage bipolar membrane electrodialyzer for acetic acid concentration, the space between the anion exchange membrane and the anion exchange layer of the bipolar membrane is called a treatment chamber, the space between the anion exchange membrane and the cation exchange layer of the bipolar membrane is called an acid recovery chamber, the acetic acid-containing wastewater is pumped into the treatment chamber by a pump, and Ac in the treatment chamber is subjected to the action of an electric field-OH generated from the bipolar membrane passes through the anion exchange membrane from the treatment chamber into the acid recovery chamber-Entering the processing chamber to remove the residual H+Neutralizing the acetic acid in the treatment chamber to gradually remove the acetic acid, and recovering the Ac in the acid recovery chamber from the treatment chamber-And H from a bipolar membrane＋Gradually obtaining concentrated acetic acid aqueous solution, and when the concentration of the acetic acid in the acid recovery chamber reaches a certain degree (such as 30 percent), the acetic acid aqueous solution can be injected into the feed inlet of the extractive distillation tower.
Concentrating the diluted acetic acid to 30% by bipolar membrane electrodialysis, and extracting and rectifying by using a solvent to obtain the acetic acid with the purity of 99-99.8%.
The voltage of the homogeneous membrane electrodialysis is constant voltage, the operating voltage of the first stage of homogeneous membrane electrodialysis is 50v, the operating voltage of the second stage of homogeneous membrane electrodialysis is 40v, and the operating voltage of the third stage of bipolar membrane electrodialysis is 40 v.
The second-stage homogeneous membrane electrodialysis adopts a slightly lower voltage (40 v), only sulfuric acid ions pass through the second-stage homogeneous membrane electrodialysis, so that the acetic acid ion migration caused by overlarge driving force can be avoided, and the temperature rise of the circulating liquid can be controlled not to be too high. Thereby achieving the separation of sulfuric acid and acetic acid.
And (3) beating acetic acid in an acid recovery chamber of the third-stage bipolar membrane electrodialyzer to a feed inlet of an extractive distillation tower, and extracting by adopting continuous extractive distillation, wherein the extraction of the distillation tower is carried out by continuous extractive distillation, and the weight ratio of 30% acetic acid to the solvent is 1:2-4 during extraction. Water is distilled from the top of the tower, and an acetic acid solvent mixture is obtained at the bottom of the tower. In the extraction and rectification process, feeding, solvent addition and recovery are continuously carried out.
The concentration of the acetic acid obtained by homogeneous membrane electrodialysis separation is 30%, and the purity of the obtained acetic acid is 99.8% by adopting two-tower continuous extraction rectification for extraction; during extraction, the weight ratio of 30% acetic acid to the solvent is 1:4, and the extraction yield is 97%. The extractant is tributyl phosphate. The steam at the top of the extraction and rectification tower is compressed by a compressor and heated up and then is used as a heating source of a reboiler at the bottom of the tower.
The homogeneous anion exchange membrane in the homogeneous membrane electrodialysis system belongs to one of an electric drive membrane and an ion electro-migration membrane, is a polyethylene grafted polystyrene quaternary ammonium type strong-basicity anion exchange membrane, and can only selectively allow SO in a solution to be contained under the action of an external direct current electric field force4 2-、CH3COO-The anions pass through and the permeation of the cations and the furfural is blocked. SO (SO)4 2-And CH3COO-The physical and chemical properties of the ions are greatly different, and since sulfuric acid is a strong acid and acetic acid is a weak acid, the ionization degree of sulfuric acid is 0.113 and the ionization degree of acetic acid is 0.00133 at a concentration of 0.1mol of aqueous solution, the physical and chemical properties are greatly different. The strong base type ion exchange resin can selectively permeate anions, and the permeability order is HSO4 -＞NO3 -＞CL-＞HCO3＞-H2PO4 -＞HCOOH-＞-CH3COO-From which HSO can be seen4 -The transmission rate is much higher than CH3COO-。
The continuous extractive distillation adopts double-tower operation, the first tower is an extractive distillation tower, separated materials continuously enter the tower from the middle part of the tower, and the solvent is continuously added at the part close to the top of the tower. The water in the extractive distillation tower is distilled out from the tower top, and the acetic acid and the solvent are discharged from the tower bottom and enter a solvent recovery tower. And compressing, pressurizing and heating the steam distilled from the tower top by a compressor, and taking the steam as a heat source of a reboiler of the rectifying tower. In the solvent recovery tower, acetic acid and solvent can be separated, acetic acid component is distilled out from the top of the tower, and the solvent is distilled out from the bottom of the tower and circularly returned to the extraction and rectification tower.
The bottom discharge hole of the extraction and rectification tower is connected to the middle feed inlet of the desolventizing tower, the top outlet of the desolventizing tower is connected to a condenser, and the obtained acetic acid has the purity of 99-99.8%; the discharge hole at the bottom of the desolventizing tower is connected to the inlet of the material pump, and the outlet of the material pump is connected to the solvent feed hole at the upper part of the extraction and rectification tower, so that the solvent can be recycled. The separated water is extracted from the lower part of the tower. The solvent recovery rate was 98.5%.
Example 2
Other contents, as in example 1, a process for separating sulfuric acid, acetic acid and furfural from furfural wastewater, comprising the steps of:
(1) a pretreatment step: and (3) separating the solvent phase from the water phase by the furfural reaction solution through a high-speed disc centrifuge. The furfural reaction solution is separated from a solvent phase and a water phase through a high-speed disc centrifuge, wherein the components in the water phase comprise 1% of sulfuric acid, 0.8% of acetic acid and 0.3% of furfural. According to the difference of physicochemical properties of two ions of sulfuric acid and acetic acid, the separation of sulfuric acid, acetic acid and furfural is achieved by adopting homogeneous membrane electrodialysis and a mode of controlling membrane to voltage.
(2) The furfural wastewater enters a first-stage homogeneous membrane electrodialyzer to obtain a mixture A of sulfuric acid and acetic acid in an acid recovery chamber, and the remainder in a treatment chamber is a furfural aqueous solution;
(3) pumping the mixture A from an acid recovery chamber to a treatment chamber of a second-stage homogeneous membrane electrodialyzer to separate sulfuric acid, and returning the sulfuric acid to a furfural reaction process;
(4) dilute acetic acid of sulfuric acid separated by the second-stage electrodialysis treatment chamber is pumped into a third-stage electrodialysis device treatment chamber, and the acetic acid is concentrated; until the concentration of the concentrated acetic acid is 30 percent.
(5) The concentrated acetic acid enters a rectification extraction step to obtain pure acetic acid.
Concentrating the diluted acetic acid to 30% by bipolar membrane electrodialysis, and extracting and rectifying by using a solvent to obtain the acetic acid with the purity of 99-99.8%.
The voltage of the homogeneous membrane electrodialysis is constant voltage, and the operating voltage is 40-50 v.
The first stage operating voltage is 50v, the second stage operating voltage is 40v, and the third stage operating voltage is 40 v.
The second stage adopts a slightly lower voltage (40 v), only sulfuric acid ions pass through the second stage, so that the acetic acid ion migration caused by overlarge driving force can be avoided, and the temperature rise of the circulating liquid can be controlled not to be too high. Thereby achieving the separation of sulfuric acid and acetic acid.
The concentration of the acetic acid obtained by homogeneous membrane electrodialysis separation is 30%, the acetic acid in the acid recovery chamber of the third electrodialyzer is pumped to the feed inlet of the extractive distillation tower, and two-tower continuous extractive distillation is adopted for extraction, so that the purity of the obtained acetic acid is 99.8%; during extraction, the weight ratio of 30% acetic acid to the solvent is 1:4, and the extraction yield is 94%. The extractant adopts tributyl phosphate. The steam at the top of the extraction and rectification tower is compressed by a compressor and heated up and then is used as a heating source of a reboiler at the bottom of the tower. Water is distilled from the top of the tower, and an acetic acid solvent mixture is obtained at the bottom of the tower. In the extraction and rectification process, feeding, solvent addition and recovery are continuously carried out.
The bottom discharge hole of the extraction and rectification tower is connected to the middle feed inlet of the desolventizing tower, the top outlet of the desolventizing tower is connected to a condenser, and the obtained acetic acid has the purity of 99-99.8%; the discharge hole at the bottom of the desolventizing tower is connected to the inlet of the material pump, and the outlet of the material pump is connected to the solvent feed hole at the upper part of the extraction and rectification tower, so that the solvent can be recycled. The separated water is extracted from the lower part of the tower. The solvent recovery rate was 98.5%.
Example 3
Other contents, as in example 1, a process for separating sulfuric acid, acetic acid and furfural from furfural wastewater, comprising the steps of:
(1) a pretreatment step: and (4) separating the solvent phase from the water phase by the furfural reaction solution through a high-speed disc centrifuge. The furfural reaction solution is separated from a solvent phase and a water phase by a high-speed disc centrifuge, wherein the water phase comprises 1.5% of sulfuric acid, 0.8% of acetic acid and 0.3% of furfural. According to the difference of physicochemical properties of two ions of sulfuric acid and acetic acid, the separation of sulfuric acid, acetic acid and furfural is achieved by adopting homogeneous membrane electrodialysis and a mode of controlling membrane to voltage.
(2) The furfural wastewater enters a first-stage homogeneous membrane electrodialyzer to obtain a mixture A of sulfuric acid and acetic acid in an acid recovery chamber, and the remainder in a treatment chamber is a furfural aqueous solution;
(3) pumping the mixture A from an acid recovery chamber to a treatment chamber of a second-stage homogeneous membrane electrodialyzer to separate sulfuric acid;
(4) the separated sulfuric acid enters a reverse osmosis membrane for further concentration and then returns to the furfural reaction process; the concentration of the sulfuric acid obtained by homogeneous membrane electrodialysis separation is 5%, and the sulfuric acid can be further concentrated to 10% by using a reverse osmosis membrane and used as a catalyst for furfural preparation reaction.
(5) Dilute acetic acid of sulfuric acid separated by the second-stage electrodialysis treatment chamber is pumped into a third-stage electrodialysis device treatment chamber, and the acetic acid is concentrated; until the concentration of the concentrated acetic acid is 30 percent.
(6) The concentrated acetic acid enters a rectification extraction step to obtain pure acetic acid.
The voltage of the homogeneous membrane electrodialysis is constant voltage, and the operating voltage is 40-50 v. Concentrating the diluted acetic acid to 30% by bipolar membrane electrodialysis, and extracting and rectifying by using a solvent to obtain the acetic acid with the purity of 99-99.8%.
The first stage operating voltage is 50v, the second stage operating voltage is 40v, and the third stage operating voltage is 40 v.
Acetic acid in an acid recovery chamber of the third-stage electrodialyzer is pumped to a feed inlet of an extractive distillation tower, and two-tower continuous extractive distillation is adopted for extraction, so that the purity of the obtained acetic acid is 99.8%; during extraction, the weight ratio of the 30 percent acetic acid to the solvent is 1:4, and the extraction yield is 97.8 percent. The extractant is octanol/tributyl phosphate 1/1. The steam at the top of the extraction and rectification tower is compressed by a compressor and heated up and then is used as a heating source of a reboiler at the bottom of the tower. Water is distilled from the top of the tower, and an acetic acid solvent mixture is obtained at the bottom of the tower. In the extraction and rectification process, feeding, solvent addition and recovery are continuously carried out.
The bottom discharge hole of the extraction and rectification tower is connected to the middle feed inlet of the desolventizing tower, the top outlet of the desolventizing tower is connected to a condenser, and the obtained acetic acid has the purity of 99-99.8%; the discharge hole at the bottom of the desolventizing tower is connected to the inlet of the material pump, and the outlet of the material pump is connected to the solvent feed hole at the upper part of the extraction and rectification tower, so that the solvent can be recycled. The separated water is extracted from the lower part of the tower. The solvent recovery rate was 98.5%.
Example 4
Otherwise, as in example 3, the furfural reaction solution was passed through a high-speed disk centrifuge to separate the solvent phase from the aqueous phase, which consisted of 2% sulfuric acid, 0.5% acetic acid, and 0.2% furfural.
According to the difference of physicochemical properties of two ions of sulfuric acid and acetic acid, the separation of sulfuric acid and acetic acid can be achieved by adopting homogeneous membrane electrodialysis and a mode of controlling membrane to voltage. According to the difference of migration speed, a staged separation mode is adopted, under the action of a direct current electric field, a treatment chamber is called between an anion exchange membrane and a cation exchange layer in the device, and an acid recovery chamber is called between the anion exchange membrane and the cation exchange layer. Furfural and acid solution (Furfural, H)2SO4HAc) into a processing chamber, and SO in the processing chamber under the action of an electric field4 2-、Ac-And the furfural passes through an anion exchange membrane and enters an acid recovery chamber, and the furfural is basically not ionized and remains in a treatment chamber, so that the aim of separating furfural from acid is fulfilled. In the acid recovery chamber, SO transferred from the treatment chamber4 2-、Ac-Combining with H + obtained by water dissociation from cation membrane to obtain HCl and HAc, and feeding the mixed acid into another electrodialyzer to separate sulfuric acid from acetic acid. Sodium sulfate aqueous solution is prepared to be used as electrode water so as to reduce the resistance value of the electrode chamber water. The operation mode of constant voltage is adopted, so that the acetate ion migration caused by overlarge driving force can be avoided, and the temperature rise of the circulating liquid can be controlled not to be overhigh. Thereby achieving the separation of sulfuric acid, acetic acid and furfural.
The concentration of the sulfuric acid obtained by homogeneous membrane electrodialysis separation is 5%, and the sulfuric acid can be further concentrated to 10% by using a reverse osmosis membrane and used as a catalyst for furfural preparation reaction. The operating voltage of homogeneous membrane electrodialysis is 50-40 v.
The acetic acid obtained by the homogeneous membrane electrodialysis separation enters a bipolar membrane electrodialysis, the concentration of the concentrated acetic acid is 30%, and the purity of the obtained acetic acid is 99.8% by adopting two-tower continuous extraction and rectification for extraction; during extraction, the weight ratio of 30% acetic acid to the solvent is 1:3, and the extraction yield is 94%. The steam at the top of the extraction and rectification tower is compressed by a compressor and heated up and then is used as a heating source of a reboiler at the bottom of the tower. The extractant is octanol/tributyl phosphate 1/1.
The acetic acid recovery for the different extractants is shown in the following table:
Figure 112606DEST_PATH_IMAGE001
example 5
Otherwise as in example 3, where the weight ratio of 30% strength acetic acid to solvent is 1:2, the extractant (solvent) is octanol: tributyl phosphate: methylformamide = 1: 1.
the device for separating sulfuric acid, acetic acid and furfural from furfural wastewater is provided with a furfural reaction device, a first-stage electrodialyzer, a second-stage electrodialyzer, a third-stage electrodialyzer, a furfural fractionating tower and a rectification extraction device, wherein the first-stage electrodialyzer is provided with a first-stage acid recovery chamber and a first-stage treatment chamber, the second-stage electrodialyzer is provided with a second-stage acid recovery chamber and a second-stage treatment chamber, the third-stage electrodialyzer is provided with a third-stage acid recovery chamber and a third-stage treatment chamber, the first-stage treatment chamber is connected with the furfural fractionating tower, the first-stage acid recovery chamber is connected with the second-stage treatment chamber, the second-stage acid recovery chamber is connected with the third-stage treatment chamber, the third-stage acid recovery chamber is connected with the rectification extraction device, and an acetic acid solution enters the rectification extraction device for extraction and concentration; the second-stage acid recovery chamber is connected with a furfural reaction device, and the sulfuric acid aqueous solution enters the furfural reaction device for recycling.
A reverse osmosis membrane device is also arranged between the acid recovery chamber of the second-stage electrodialyzer and the furfural reaction device, and the reverse osmosis membrane device is respectively connected with the second-stage acid recovery chamber and the furfural reaction device. The separated sulfuric acid enters a reverse osmosis membrane for further concentration and then returns to the furfural reaction process for recycling.
The mixture is pumped from the acid recovery chamber of the first-stage electrodialyzer to the treatment chamber of the second-stage electrodialyzer to separate out sulfuric acid, and the sulfuric acid returns to the furfural reaction device for reaction and reuse. And concentrating the feed liquid after the sulfuric acid is separated by third-stage electrodialysis, and performing rectification extraction to obtain the acetic acid. The third-stage electrodialyzer is a bipolar membrane electrodialyzer.
The treatment system is also provided with a pretreatment device which is connected with one end of the treatment chambers of the first group of electrodialysers. The pretreatment device is a disk centrifuge. In the pretreatment, furfural reaction liquid passes through a high-speed disc centrifuge to separate a solvent phase from a water phase.
The extraction and rectification device comprises an extraction and rectification tower, a vapor-liquid separator, a compressor, a reboiler, a desolventizing tower, a condenser, a reboiler and a material pump, wherein the third-stage acid recovery chamber is connected with the middle part of the extraction and rectification tower, the top end of the extraction and rectification tower is connected with the vapor-liquid separator, the bottom end of the extraction and rectification tower is connected with one end of the reboiler I, and the other end of the reboiler I is connected with one side of the bottom of the extraction and rectification tower to form a circulating ring; vapour and liquid separator and reboiler I pass through the compressor and link into an organic whole, reboiler I still is connected with the desolventizing tower, desolventizing tower top is connected with the condenser, reboiler II is connected with extraction rectification tower top one side to material pump one end, and the material pump other end is connected with desolventizing tower bottom and reboiler II respectively, and II one ends of reboiler are connected with desolventizing tower bottom one side. The devices can be connected through pipelines.
The first-stage electrodialyzer and the second-stage electrodialyzer are homogeneous membrane electrodialyzers, and the third-stage electrodialyzer is a bipolar membrane electrodialyzer. The devices or the devices can be connected through pipelines.
The concentrated acetic acid enters the middle part of the continuous extractive distillation tower, a solvent is added into the upper part of the continuous extractive distillation tower, and water vapor evaporated from the top of the continuous extractive distillation tower enters a compressor to be compressed and heated and then returns to a reboiler of the continuous extractive distillation tower to heat a vapor inlet; a discharge hole at the bottom of the extraction and rectification tower is connected to a feed inlet at the middle part of the desolventizing tower, acetic acid distilled from the top of the desolventizing tower enters an inlet of a condenser and is condensed to obtain 99-99.8% acetic acid, and a solvent obtained at the bottom of the tower returns to a feed inlet at the upper part of the extraction and rectification tower; a discharge hole at the bottom of the desolventizing tower is connected to an inlet of a material pump, and an outlet of the material pump is connected to a solvent feed hole at the upper part of the extraction and rectification tower, so that the solvent can be recycled; the vapor at the top of the acetic acid extractive distillation tower enters a compressor to be compressed and heated, and is connected to a vapor inlet of a reboiler at the bottom of the extractive distillation tower to be used as a heating source.
The discharge hole at the bottom of the desolventizing tower is connected to the inlet of the material pump, and the outlet of the material pump is connected to the solvent feed hole at the upper part of the extraction and rectification tower, so that the solvent can be recycled. The vapor at the top of the acetic acid extractive distillation tower enters a compressor to be compressed and heated, and then is connected to a vapor inlet of a reboiler at the bottom of the extractive distillation tower to be used as a heating source.
While the foregoing shows and describes the fundamental principles and principal features of the invention, together with the advantages thereof, the foregoing embodiments and description are illustrative only of the principles of the invention, and various changes and modifications can be made therein without departing from the spirit and scope of the invention, which will fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (6)

1. A method for separating sulfuric acid, acetic acid and furfural from furfural wastewater is characterized by comprising the following steps: the method comprises the following steps:
(1) the furfural wastewater enters a first-stage homogeneous membrane electrodialyzer to obtain a mixture A of sulfuric acid and acetic acid in an acid recovery chamber, and the remainder in the treatment chamber is a furfural aqueous solution;
(2) pumping the mixture A from an acid recovery chamber to a treatment chamber of a second-stage electrodialyzer to separate sulfuric acid, and returning the sulfuric acid to a furfural reaction process;
(3) dilute acetic acid of the sulfuric acid separated by the second-stage electrodialysis treatment chamber is pumped into a third-stage electrodialysis device treatment chamber, and the acetic acid is concentrated;
(4) the acetic acid after concentration enters a rectification extraction step to obtain pure acetic acid;
the first-stage homogeneous membrane electrodialysis step in the step (1) is preceded by a pretreatment step, namely, a furfural reaction solution passes through a high-speed disc centrifuge to separate a solvent phase from a water phase; the components of the wastewater water phase are 1-2% of sulfuric acid, 0.5-1% of acetic acid and 0.2-0.5% of furfural;
the rectification extraction step is extraction in a rectification tower; the rectifying tower is a continuous extraction rectifying tower, and the weight ratio of acetic acid to an extracting agent is 1: 2-4; the concentration of the acetic acid is 30 percent;
the rectification extraction step is that the concentrated acetic acid enters the middle part of a continuous extraction rectification tower, a solvent is added into the upper part of the tower, water vapor evaporated from the top of the tower enters a compressor to be compressed and heated, and then returns to a heating vapor inlet of a reboiler of the extraction rectification tower; a discharge hole at the bottom of the extraction and rectification tower is connected to a feed inlet at the middle part of the desolventizing tower, acetic acid distilled from the top of the desolventizing tower enters an inlet of a condenser and is condensed to obtain acetic acid, and a solvent obtained at the bottom of the tower returns to a feed inlet at the upper part of the extraction and rectification tower; a discharge hole at the bottom of the desolventizing tower is connected to an inlet of a material pump, and an outlet of the material pump is connected to a solvent feed hole at the upper part of the extraction and rectification tower, so that the solvent can be recycled; vapor at the top of the acetic acid extractive distillation tower enters a compressor to be compressed and heated, and then is connected to a vapor inlet of a reboiler at the bottom of the extractive distillation tower to be used as a heating source; the separated water is discharged from the lower part of the desolventizing tower.
2. The method for separating sulfuric acid, acetic acid and furfural from furfural wastewater according to claim 1, characterized in that: and the separated sulfuric acid enters a reverse osmosis membrane for further concentration and then returns to the furfural reaction process.
3. The method for separating sulfuric acid, acetic acid and furfural from furfural wastewater according to claim 1, characterized in that: the acid recovery chamber of the first-stage electrodialyzer is connected to the treatment chamber of the second-stage electrodialyzer, and the acid recovery chamber of the second-stage electrodialyzer separates the obtained sulfuric acid.
4. The method for separating sulfuric acid, acetic acid and furfural from furfural wastewater according to claim 1, characterized in that: the first-stage electrodialysis and the second-stage electrodialysis are homogeneous membrane electrodialysis, the third-stage electrodialysis is bipolar membrane electrodialysis, the operating voltage of the homogeneous membrane electrodialysis is constant voltage, and the operating voltage is 40-50 v.
5. The method for separating sulfuric acid, acetic acid and furfural from furfural wastewater according to claim 1, characterized in that: the operating voltage of each stage of electrodialysis is as follows: the voltage of the first electrodialysis stage is 50v, the voltage of the second electrodialysis stage is 40v, and the voltage of the third electrodialysis stage is 50 v.
6. The method for separating sulfuric acid, acetic acid and furfural from furfural wastewater according to claim 1, characterized in that: the extractant is one or more than two of octanol, tributyl phosphate and methyl formamide.
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