CN111994881A - Sulfuric acid recovery method and system - Google Patents
Sulfuric acid recovery method and system Download PDFInfo
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- CN111994881A CN111994881A CN202011068271.2A CN202011068271A CN111994881A CN 111994881 A CN111994881 A CN 111994881A CN 202011068271 A CN202011068271 A CN 202011068271A CN 111994881 A CN111994881 A CN 111994881A
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/90—Separation; Purification
- C01B17/905—Removal of organic impurities
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/88—Concentration of sulfuric acid
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/90—Separation; Purification
- C01B17/901—Recovery from spent acids containing metallic ions, e.g. hydrolysis acids, pickling acids
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- C05—FERTILISERS; MANUFACTURE THEREOF
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Abstract
The invention provides a sulfuric acid recovery method, which can be conveniently used for the recovery treatment of sulfuric acid waste liquid in the semiconductor industry, and has the advantages of low production cost, low energy consumption and good recovery and utilization effects; the method comprises the steps of treating the high-concentration semiconductor industrial sulfuric acid waste liquid containing 50-60% of sulfuric acid by using a distillation principle and a rectification and fractionation two-stage process, wherein during rectification, hydrogen peroxide impurities in the sulfuric acid waste liquid can oxidize organic impurities to degrade the organic matters, and when the hydrogen peroxide cannot be completely oxidized and degraded, the oxidation and degradation are carried out through an oxidation tower, so that double removal of the organic matters and the hydrogen peroxide impurities is realized; during fractionation, because the boiling point of metal salt impurities is high, the metal salt impurities are left at the bottom of the heater after fractionation, the metal salt impurities are removed through slag discharge, and the mass fraction of the recovered concentrated sulfuric acid reaches 92.5 percent, and the recovered concentrated sulfuric acid is industrial-grade sulfuric acid which can be directly sold.
Description
Technical Field
The invention relates to the technical field of treatment and recovery of sulfuric acid waste liquid, in particular to the technical field of treatment and recovery of sulfuric acid waste liquid in semiconductor manufacturing industry, and specifically relates to a sulfuric acid recovery method and a sulfuric acid recovery system.
Background
Sulfuric acid is an important industrial raw material, a large amount of sulfuric acid waste liquid is generated in the industrial production process, if the sulfuric acid is directly discharged, the ecological environment is influenced, and the waste of sulfuric acid resources is also caused, so that the sulfuric acid waste liquid needs to be treated before being discharged; at present, the method for treating the sulfuric acid waste liquid mainly comprises a neutralization precipitation method, a high-temperature cracking method and the like, wherein the neutralization precipitation method is generally used for treating the sulfuric acid waste liquid with relatively low sulfuric acid concentration, such as the sulfuric acid waste liquid with the mass fraction of 10%, and when the sulfuric acid waste liquid with higher concentration and the mass fraction of more than 30% is treated by the neutralization precipitation method, dilution is needed firstly, so that the treatment is inconvenient, and the production cost is increased; the high-temperature cracking method, such as the method for producing sulfuric acid by the high-temperature cracking of alkylation waste sulfuric acid with the publication number of CN106744716A, needs to crack at the temperature of 1000-1100 ℃, and has high energy consumption; the method is not effectively applicable to the treatment of the sulfuric acid waste liquid generated in the semiconductor manufacturing industry, and the sulfuric acid waste liquid generated in the semiconductor manufacturing industry is generally 50% of high-concentration sulfuric acid waste liquid and contains a small amount of impurities including hydrogen peroxide, metal salts and organic matters.
Disclosure of Invention
Aiming at the defects of inconvenient treatment, high production cost, large energy consumption and inapplicability to treatment and recycling of the sulfuric acid waste liquid in the semiconductor industry, the invention provides a sulfuric acid recycling method which can be conveniently used for the recycling treatment of the sulfuric acid waste liquid in the semiconductor industry, and has low production cost, low energy consumption and good recycling effect.
The invention adopts the following technical scheme: a sulfuric acid recovery method is characterized in that: which comprises the following steps of,
step 1: a rectifying tower which is provided with a negative pressure device and is connected with the inlet end of a reboiling circulation loop is adopted to carry out rectifying preconcentration on sulfuric acid waste liquid with the mass fraction of 50-60% and the mass fraction of impurities of 2-3% at 180-190 ℃, the pressure of the negative pressure device is-10 KPa-15 KPa, and sulfuric acid preconcentration liquid and dilute sulfuric acid fraction are obtained;
step 2: carrying out oxidative degradation on the sulfuric acid preconcentrate by adopting an oxidation tower connected with the outlet end of the reboiling circulation loop;
and step 3: and (3) fractionating and purifying the sulfuric acid preconcentrated solution after oxidative degradation by adopting a fractionating column connected with a quartz heater, wherein the heating temperature of the quartz heater is 285 ℃ during fractionation, so that concentrated sulfuric acid with the mass fraction of 92.5% and recycled dilute sulfuric acid are obtained, and the recycled dilute sulfuric acid flows back to the rectifying tower.
It is further characterized in that:
in the step 2, potassium permanganate or potassium dichromate is used as an oxidant in the oxidation tower, or active carbon is used as an adsorbent;
in the step 1, ammonia water is introduced after the dilute sulfuric acid fraction is condensed, and then the dilute sulfuric acid fraction is filtered by an RO reverse osmosis membrane.
A sulfuric acid recovery system is characterized in that: it includes the head tank that connects in order, be equipped with vacuum device's rectifying column, oxidation column and fractionating column, reation kettle and RO reverse osmosis membrane are connected in order to the top of rectifying column, the rectifying column with be equipped with reboiling circulation circuit between the oxidation column, the quartz heater is connected to the fractionating column, the top export of fractionating column with the rectifying column intercommunication.
It is further characterized in that:
the reboiling circulation loop comprises a reboiler and a vapor-liquid separation tank, wherein an outlet of the reboiler is communicated with an inlet of the vapor-liquid separation tank, a bottom outlet of the vapor-liquid separation tank and a bottom outlet of the rectifying tower are converged and then connected with an inlet of the reboiler, a top outlet of the vapor-liquid separation tank is communicated with the rectifying tower, and a side outlet of the vapor-liquid separation tank is communicated with the oxidation tower;
the gas evaporation pipeline of the quartz heater is provided with a precise filter screen, and the bottom of the gas evaporation pipeline is provided with a slag discharge port;
the negative pressure device is a vacuum pump;
a preheater is arranged between the raw material tank and the rectifying tower;
a high-level tank and a balance bottle are arranged between the oxidation tower and the fractionating column;
the shell passes of the rectifying tower, the preheater and the vapor-liquid separation tank are all made of glass lining materials, and the tube passes of the preheater and the reboiler are all made of silicon carbide materials.
The method has the beneficial effects that the distillation principle is utilized, and the rectification and fractionation two-stage process is adopted to treat the semiconductor industrial sulfuric acid waste liquid with higher concentration and the sulfuric acid content of 50-60%, the rectification and fractionation temperature is below 300 ℃, so that the energy consumption is effectively reduced; during rectification, hydrogen peroxide impurities in the sulfuric acid waste liquid can oxidize organic impurities to degrade the organic matters, and the hydrogen peroxide cannot be oxidized and degraded completely through the oxidation tower, so that the organic matters and the hydrogen peroxide impurities are removed; during fractionation, because the boiling point of metal salt impurities is high, the metal salt impurities are left at the bottom of the heater after fractionation, and are removed through slag discharge, so that the purification of concentrated sulfuric acid is realized, the process is simple, the treatment is convenient, the production cost is low, the mass fraction of the recovered concentrated sulfuric acid reaches 92.5 percent, and the recovered concentrated sulfuric acid is industrial-grade sulfuric acid which can be directly sold, and the recycling effect is good.
Dilute sulfuric acid fractions generated in the rectification are neutralized by ammonia water and are filtered by an RO reverse osmosis membrane to obtain ammonium sulfate which can be recycled for agricultural fertilizers, and the recycled dilute sulfuric acid generated in the fractionation flows back to the rectification tower, so that the recycling effect can be further improved, and the sulfuric acid in the sulfuric acid waste liquid can be fully recycled; sour water vapor containing sulfur that the vapour-liquid knockout drum produced is retrieved to the rectifying column, can further improve the sulphuric acid concentration of sulphuric acid preconcentration, guarantees the recycle of 92.5% industrial grade sulphuric acid, and the maximize realizes no sulphuric acid and discharges, the environmental protection.
Drawings
FIG. 1 is a process flow diagram of the recovery process of the present invention.
FIG. 2 is a schematic diagram of the recycling system of the present invention.
Detailed Description
The invention is further illustrated by the following figures and examples:
as shown in fig. 1, the present invention provides a sulfuric acid recovery method, which comprises the steps of,
step 1: a rectifying tower provided with a negative pressure device and connected with the inlet end of a reboiling circulation loop is adopted to carry out rectifying preconcentration on sulfuric acid waste liquid with the mass fraction of 50-60% and the mass fraction of impurities of 2-3% at 180-190 ℃, and the pressure is-10 KPa-15 KPa, so as to obtain sulfuric acid preconcentration liquid and dilute sulfuric acid fraction; by utilizing a distillation principle and adopting reduced pressure distillation and a reboiling circulation loop, a sulfuric acid preconcentration liquid with the mass fraction of sulfuric acid reaching 80-85% and a dilute sulfuric acid fraction with the mass fraction of sulfuric acid being 0.6-0.8% can be obtained, and the reduced pressure distillation can reduce energy consumption, save energy and protect environment; the impurities are hydrogen peroxide and Fe2(SO4)3、CuSO4And NiSO4When metal salts and toluene, alcohols or ketone organic matters are subjected to vacuum rectification, hydrogen peroxide can react with the organic matters to realize double removal of hydrogen peroxide and partial/all organic matters; 0.6 to 0.8 percent of dilute sulfuric acid fraction is condensed and then is introduced with ammonia water, and then is filtered by an RO reverse osmosis membrane, preferably, the molar ratio of the ammonia water to the dilute sulfuric acid fraction is 2:1, and ammonium sulfate obtained by filtering after the ammonia water and the dilute sulfuric acid fraction are subjected to neutralization reaction can be recycled for agricultural fertilizers, so that the recycling effect is further improved, and resources are saved.
Step 2: the sulfuric acid pre-concentrated solution is subjected to oxidative degradation by adopting an oxidation tower connected with the outlet end of the reboiling circulation loop, potassium permanganate or potassium dichromate is adopted as an oxidant in the oxidation tower, or activated carbon is adopted as an adsorbent, the oxidant can be selectively used for oxidative degradation according to different types of organic matters, or the organic matter impurities are further removed by activated carbon adsorption, so that the impurity removing effect and the purity of sulfuric acid recovery are improved.
And step 3: and (3) fractionating and purifying the sulfuric acid preconcentrated solution after oxidative degradation by adopting a fractionating column connected with a quartz heater, wherein the temperature of the quartz heater is 285 ℃ during fractionation, so that concentrated sulfuric acid with the mass fraction of 92.5% and recycled dilute sulfuric acid with the mass fraction of 10% -15% are obtained, and the recycled dilute sulfuric acid flows back to the rectifying tower.
The distillation principle is utilized, and a rectification and fractionation two-stage process is adopted to treat the semiconductor industrial sulfuric acid waste liquid with higher concentration and the sulfuric acid content of 50-60%, wherein the rectification and fractionation temperature is below 300 ℃, so that the energy consumption is effectively reduced; during rectification, hydrogen peroxide impurities in the sulfuric acid waste liquid can oxidize organic impurities to degrade the organic matters, and the hydrogen peroxide cannot be oxidized and degraded completely through the oxidation tower, so that the organic matters and the hydrogen peroxide impurities are removed; during fractionation, because the boiling point of metal salt impurities is high, the metal salt impurities are left at the bottom of the heater after fractionation, and are removed through slag discharge, so that the purification of concentrated sulfuric acid is realized, the process is simple, the treatment is convenient, the production cost is low, the mass fraction of the recovered concentrated sulfuric acid reaches 92.5 percent, and the recovered concentrated sulfuric acid is industrial-grade sulfuric acid which can be directly sold, and the recycling effect is good.
As shown in fig. 2, a sulfuric acid recovery system comprises a raw material tank 1, a rectifying tower 4 provided with a negative pressure device, an oxidation tower 9 and a fractionating column 15 which are connected in sequence, wherein the negative pressure device is a vacuum pump; the top of the rectifying tower 4 is sequentially connected with a reaction kettle 5 and an RO reverse osmosis membrane 6, a reboiling circulation loop is arranged between the rectifying tower 4 and the oxidation tower 9 and comprises a reboiler 7 and a vapor-liquid separation tank 8, an outlet 702 of the reboiler 7 is communicated with an inlet 801 of the vapor-liquid separation tank 8, a bottom outlet 804 of the vapor-liquid separation tank 8 and a bottom outlet 404 of the rectifying tower 4 are converged and then connected with an inlet 701 of the reboiler 7, a top outlet 802 of the vapor-liquid separation tank 8 is communicated with the rectifying tower 4, a side outlet 803 of the vapor-liquid separation tank 8 is communicated with the oxidation tower 9, and the reboiling circulation loop can improve the preconcentration effect and ensure the purity of concentrated sulfuric acid purified by fractionation; preferably, the top outlet 802 of the vapor-liquid separation tank 8 is communicated with the second inlet 403 at the lower part of the rectifying tower 4, so that the sulfuric acid-containing water vapor entering from the lower part of the rectifying tower can exchange heat with the sulfuric acid waste liquid and the recycled dilute sulfuric acid mixed liquid entering from the upper part of the rectifying tower, the sulfuric acid concentration of the sulfuric acid preconcentrate can be further improved, and the recycling of 92.5 percent industrial-grade sulfuric acid is ensured.
The fractionating column 15 is connected with the quartz heater 12, a gas evaporation pipeline of the quartz heater 12 is provided with a precise filter screen 14, the bottom of the gas evaporation pipeline is provided with a slag discharge port, metal salt impurities are discharged through a slag discharge valve 13 at the slag discharge port, the precise filter screen 14 can intercept a small amount of metal ions carried by concentrated sulfuric acid steam foam, and the metal ions return to the quartz heater and are discharged from the slag discharge port at the bottom of the quartz heater, so that the impurity removal effect and the sulfuric acid recovery purity are further improved, and the quartz heater is high-temperature resistant, good in insulating property and long in service life; the top outlet 1501 of the fractionating column 15 is communicated with the rectifying tower 4, and the recycled dilute sulfuric acid generated during fractionation can flow back to the rectifying tower, so that the recycling effect is further improved, and the sulfuric acid in the sulfuric acid waste liquid is fully recycled.
A preheater 3 is arranged between the raw material tank 1 and the rectifying tower 4, preferably, as shown in figure 2, an outlet pipeline 16 of the preheater 3 and an outlet pipeline 17 at the top of the fractionating column are converged and then connected with a first inlet 401 at the upper part of the rectifying tower 4, so that the reasonability of pipeline arrangement can be improved, and the occupied space and the production cost can be reduced; a high-level tank 10 and a balance bottle 11 are arranged between the oxidation tower 9 and the fractionating column 15, as shown in figure 2, an outlet 901 of the oxidation tower 9 is sequentially connected with the high-level tank 10 and the balance bottle 11, an outlet 1101 of the balance bottle 11 is communicated with a condensation pipe 1503 of the fractionating column 15, and the high-level tank and the balance bottle can control the liquid entering the fractionating column to keep constant flow rate and automatically add liquid.
The shell passes of the rectifying tower 4, the preheater 3 and the vapor-liquid separation tank 8 are all glass lining materials, and the glass lining materials are resistant to strong acid, so that the service life of the rectifying tower can be prolonged; the tube passes of the preheater 3 and the reboiler 7 are made of silicon carbide materials, and the silicon carbide tubes are high-temperature resistant, corrosion resistant, fast in heat conduction and good in heat and shock resistance.
The working principle is as follows: as shown in fig. 1 and 2, a sulfuric acid waste liquid with a sulfuric acid mass fraction of 50-60% is conveyed from a raw material tank 1 to a preheater 3 through a pump 2, is preheated, is mixed with recycled dilute sulfuric acid flowing out from an outlet 1501 at the top of a fractionating column 15, and then enters a rectifying tower 4 with a vacuum pump arranged therein for reduced pressure distillation, wherein hydrogen peroxide can react with organic matters during reduced pressure distillation, so that hydrogen peroxide and partial/all organic matters are removed; and (3) performing reduced pressure distillation, feeding dilute sulfuric acid fraction obtained by a reboiling circulation loop into a reaction kettle 5 to perform neutralization reaction with introduced ammonia water, and filtering and recovering the dilute sulfuric acid fraction by an RO reverse osmosis membrane 6 to obtain ammonium sulfate for preparing agricultural fertilizers.
The sulfuric acid pre-concentrated solution obtained by reduced pressure distillation and a reboiling circulation loop enters an oxidation tower 9 for oxidation degradation or adsorbent adsorption to further remove organic impurities, then stably enters a fractionating column 15 through a high-level tank 10 and a balance bottle 11, the concentrated sulfuric acid steam and the water vapor obtained by the quartz heater 12 enter the fractionating column 15 again and are separated from the sulfuric acid preconcentration liquid which is discharged from the oxidation tower 9 and is removed with hydrogen peroxide and organic impurities after acid-acid heat exchange condensation, so that a concentrated sulfuric acid finished product with the mass fraction of 92.5 percent and recycled dilute sulfuric acid with the mass fraction of 10 to 15 percent are obtained, 92.5 percent of the concentrated sulfuric acid finished product is recovered from a bottom outlet 1502 of the fractionating column 15 and is industrial-grade sulfuric acid which can be directly sold, and the recycled dilute sulfuric acid flows back to the rectifying tower 4 from a top outlet 1501 of the fractionating column 15 for secondary treatment.
Example 1
A rectifying tower provided with a negative pressure device and connected with the inlet end of a reboiling circulation loop is adopted to rectify and preconcentrate sulfuric acid waste liquid with 50 mass percent of sulfuric acid and 2 mass percent of impurities at 180 ℃, wherein the impurities are hydrogen peroxide and metal salt (Fe)2(SO4)3、CuSO4) Reacting hydrogen peroxide with organic matters (ketone and toluene) under the pressure of-10 KPa to partially remove the organic matters so as to obtain a sulfuric acid preconcentration solution with the mass fraction of sulfuric acid of 80 percent and a dilute sulfuric acid fraction of 0.6 percent; and (3) condensing dilute sulfuric acid fraction with the mass fraction of 0.6% of sulfuric acid, introducing ammonia water, and filtering by adopting an RO reverse osmosis membrane to obtain ammonium sulfate for preparing agricultural fertilizers.
Oxidizing and degrading the sulfuric acid preconcentrated solution with the sulfuric acid mass fraction of 80% by using potassium permanganate in an oxidation tower to remove toluene.
Fractionating and purifying the sulfuric acid preconcentrated solution from which hydrogen peroxide and organic impurities are removed by adopting a fractionating column connected with a quartz heater, wherein the temperature of the quartz heater is 285 ℃ during fractionation, obtaining 92.5% by mass of concentrated sulfuric acid and 10% by mass of recycled dilute sulfuric acid, refluxing the recycled dilute sulfuric acid to a rectifying tower, discharging metal salt from a slag discharge port at the bottom of the quartz heater, and recovering 528 kg of 92.5% by mass of concentrated sulfuric acid from one ton of sulfuric acid waste liquid with the mass fraction of 50% according to the calculation of the actually treated sulfuric acid waste liquid.
Example 2
A rectifying tower provided with a negative pressure device and connected with the inlet end of a reboiling circulation loop is adopted to rectify and preconcentrate sulfuric acid waste liquid with the mass fraction of 60 percent and the mass fraction of 2.5 percent of impurities at 190 ℃, wherein the impurities are hydrogen peroxide and metal salt (Fe)2(SO4)3、CuSO4And NiSO4) And ketone organic matters are mixed, the pressure is-15 KPa, hydrogen peroxide reacts with the ketone organic matters to realize double removal, and sulfuric acid pre-concentrated solution with the mass fraction of sulfuric acid of 85 percent and dilute sulfuric acid fraction of 0.8 percent are obtained; and (3) condensing dilute sulfuric acid fraction with the mass fraction of 0.8% of sulfuric acid, introducing ammonia water, and filtering by adopting an RO reverse osmosis membrane to obtain ammonium sulfate for preparing agricultural fertilizers.
Fractionating and purifying sulfuric acid preconcentrated solution which flows into the oxidation tower and is removed with hydrogen peroxide and organic matter impurities by adopting a fractionating column connected with a quartz heater, wherein the temperature of the quartz heater is 285 ℃ during fractionation, obtaining concentrated sulfuric acid with the mass fraction of 92.5% and recycled dilute sulfuric acid with the mass fraction of 15%, refluxing the recycled dilute sulfuric acid to the rectifying tower, discharging metal salt from a slag discharge port at the bottom of the quartz heater, and recycling 635% sulfuric acid waste liquid to obtain 635 kg of concentrated sulfuric acid with the mass fraction of 92.5% according to the measurement and calculation of the actually processed sulfuric acid waste liquid.
Example 3
A rectifying tower provided with a negative pressure device and connected with the inlet end of a reboiling circulation loop is adopted to rectify and preconcentrate sulfuric acid waste liquid with 55 mass percent of sulfuric acid and 3 mass percent of impurities at 185 ℃, and the impurities are hydrogen peroxide and metal salt (Fe)2(SO4)3、CuSO4、NiSO4) Reacting hydrogen peroxide with organic matters (ketones and alcohols) under the pressure of-13 KPa to partially remove the organic matters so as to obtain sulfuric acid preconcentration liquid with the sulfuric acid mass fraction of 82% and dilute sulfuric acid fraction of 0.7%; and (3) condensing a dilute sulfuric acid fraction with the mass fraction of 0.7% of sulfuric acid, introducing ammonia water, and filtering by adopting an RO reverse osmosis membrane to obtain ammonium sulfate for preparing agricultural fertilizers.
Oxidizing and degrading the sulfuric acid preconcentrated solution with 82% of sulfuric acid mass fraction in an oxidation tower by using potassium dichromate to remove alcohol organic matters.
Fractionating and purifying the sulfuric acid preconcentrated solution from which hydrogen peroxide and organic impurities are removed by adopting a fractionating column connected with a quartz heater, wherein the temperature of the quartz heater is 285 ℃ during fractionation, obtaining 92.5% by mass of concentrated sulfuric acid and 12.5% by mass of recycled dilute sulfuric acid, refluxing the recycled dilute sulfuric acid to a rectifying tower, discharging metal salt from a slag discharge port at the bottom of the quartz heater, and recycling 580 kg of 92.5% by mass of concentrated sulfuric acid from one ton of sulfuric acid waste liquid with the mass fraction of 55% according to the measurement and calculation of the actually treated sulfuric acid waste liquid.
Claims (10)
1. A sulfuric acid recovery method is characterized in that: which comprises the following steps of,
step 1: a rectifying tower which is provided with a negative pressure device and is connected with the inlet end of a reboiling circulation loop is adopted to carry out rectifying preconcentration on sulfuric acid waste liquid with the mass fraction of 50-60% and the mass fraction of impurities of 2-3% at 180-190 ℃, the pressure of the negative pressure device is-10 KPa-15 KPa, and sulfuric acid preconcentration liquid and dilute sulfuric acid fraction are obtained;
step 2: carrying out oxidative degradation on the sulfuric acid preconcentrate by adopting an oxidation tower connected with the outlet end of the reboiling circulation loop;
and step 3: and (3) fractionating and purifying the sulfuric acid preconcentrated solution after oxidative degradation by adopting a fractionating column connected with a quartz heater, wherein the heating temperature of the quartz heater is 285 ℃ during fractionation, so that concentrated sulfuric acid with the mass fraction of 92.5% and recycled dilute sulfuric acid are obtained, and the recycled dilute sulfuric acid flows back to the rectifying tower.
2. A sulfuric acid recovery process according to claim 1, characterized in that: in the step 2, the oxidation tower adopts potassium permanganate or potassium dichromate as an oxidant, or adopts activated carbon as an adsorbent.
3. A sulfuric acid recovery process according to claim 1, characterized in that: in the step 1, ammonia water is introduced after the dilute sulfuric acid fraction is condensed, and then the dilute sulfuric acid fraction is filtered by an RO reverse osmosis membrane.
4. A recovery system for use in a sulfuric acid recovery process according to any one of claims 1 to 3, characterized in that: it includes the head tank that connects in order, be equipped with vacuum device's rectifying column, oxidation column and fractionating column, reation kettle and RO reverse osmosis membrane are connected in order to the top of rectifying column, the rectifying column with be equipped with reboiling circulation circuit between the oxidation column, the quartz heater is connected to the fractionating column, the top export of fractionating column with the rectifying column intercommunication.
5. A sulfuric acid recovery system according to claim 4, wherein: the reboiling circulation loop comprises a reboiler and a vapor-liquid separation tank, the outlet of the reboiler is communicated with the inlet of the vapor-liquid separation tank, the bottom outlet of the vapor-liquid separation tank and the bottom outlet of the rectifying tower are connected with the inlet of the reboiler after confluence, the top outlet of the vapor-liquid separation tank is communicated with the rectifying tower, and the side outlet of the vapor-liquid separation tank is communicated with the oxidation tower.
6. A sulfuric acid recovery system according to claim 4, wherein: the gas evaporation pipeline of the quartz heater is provided with a precise filter screen, and the bottom of the gas evaporation pipeline is provided with a slag discharge port.
7. A sulfuric acid recovery system according to claim 4, wherein: the negative pressure device is a vacuum pump.
8. A sulfuric acid recovery system according to claim 5, wherein: a preheater is arranged between the raw material tank and the rectifying tower.
9. A sulfuric acid recovery system according to claim 4, wherein: a high-level tank and a balance bottle are arranged between the oxidation tower and the fractionating column.
10. A sulfuric acid recovery system according to claim 8, wherein: the shell passes of the rectifying tower, the preheater and the vapor-liquid separation tank are all made of glass lining materials, and the tube passes of the preheater and the reboiler are all made of silicon carbide materials.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3956373A (en) * | 1973-08-20 | 1976-05-11 | Standard Oil Company | Process for sulfuric acid purification |
| CN101200439A (en) * | 2006-12-13 | 2008-06-18 | 北京清华紫光英力化工技术有限责任公司 | Novel comprehensive utilization technique of industrial waste sulfuric acid |
| CN104129762A (en) * | 2013-05-01 | 2014-11-05 | 联仕电子化学材料股份有限公司 | Preparation method and preparation system of high-purity sulfuric acid solution |
| CN210065174U (en) * | 2019-05-23 | 2020-02-14 | 胡平 | Concentrated recovery system of dilute sulfuric acid |
| CN111573629A (en) * | 2020-05-29 | 2020-08-25 | 盛隆资源再生（无锡）有限公司 | Recovery treatment method of sulfuric acid waste acid |
-
2020
- 2020-10-08 CN CN202011068271.2A patent/CN111994881A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3956373A (en) * | 1973-08-20 | 1976-05-11 | Standard Oil Company | Process for sulfuric acid purification |
| CN101200439A (en) * | 2006-12-13 | 2008-06-18 | 北京清华紫光英力化工技术有限责任公司 | Novel comprehensive utilization technique of industrial waste sulfuric acid |
| CN104129762A (en) * | 2013-05-01 | 2014-11-05 | 联仕电子化学材料股份有限公司 | Preparation method and preparation system of high-purity sulfuric acid solution |
| CN210065174U (en) * | 2019-05-23 | 2020-02-14 | 胡平 | Concentrated recovery system of dilute sulfuric acid |
| CN111573629A (en) * | 2020-05-29 | 2020-08-25 | 盛隆资源再生（无锡）有限公司 | Recovery treatment method of sulfuric acid waste acid |
Non-Patent Citations (1)
| Title |
|---|
| R.拉曼编著, 化学工业出版社 * |
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