CN111825062A - Method for recovering waste sulfuric acid - Google Patents
Method for recovering waste sulfuric acid Download PDFInfo
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- CN111825062A CN111825062A CN202010735614.XA CN202010735614A CN111825062A CN 111825062 A CN111825062 A CN 111825062A CN 202010735614 A CN202010735614 A CN 202010735614A CN 111825062 A CN111825062 A CN 111825062A
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 200
- 239000002699 waste material Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 40
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 81
- 238000011084 recovery Methods 0.000 claims abstract description 47
- 238000001914 filtration Methods 0.000 claims abstract description 32
- 238000000605 extraction Methods 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 12
- 239000012074 organic phase Substances 0.000 claims abstract description 12
- 239000012535 impurity Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims description 48
- 239000012528 membrane Substances 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000000706 filtrate Substances 0.000 claims description 18
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 12
- 244000060011 Cocos nucifera Species 0.000 claims description 12
- 238000001471 micro-filtration Methods 0.000 claims description 12
- 238000001728 nano-filtration Methods 0.000 claims description 12
- 238000009835 boiling Methods 0.000 claims description 6
- 238000005341 cation exchange Methods 0.000 claims description 6
- 238000002485 combustion reaction Methods 0.000 claims description 6
- 239000012141 concentrate Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000000446 fuel Substances 0.000 claims description 6
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical group [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000003456 ion exchange resin Substances 0.000 claims description 6
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 6
- 239000012071 phase Substances 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 abstract description 6
- 238000005342 ion exchange Methods 0.000 abstract description 6
- 229910021645 metal ion Inorganic materials 0.000 abstract description 4
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 42
- 238000004821 distillation Methods 0.000 description 8
- 238000011085 pressure filtration Methods 0.000 description 8
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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Classifications
-
- 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
- C01B17/88—Concentration of sulfuric acid
-
- 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
-
- 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
- C01B17/904—Recovery from spent acids containing metallic ions, e.g. hydrolysis acids, pickling acids by ion-exchange
-
- 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
- C01B17/905—Removal of organic impurities
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a recovery method for waste sulfuric acid, which is based on a set of recovery device, wherein the recovery device comprises a filtering kettle, an extraction kettle, a rectification kettle I, a rectification kettle II, a cation exchange resin column, a concentration kettle and a double condenser; the method for recovering the waste sulfuric acid aims at the production process of preparing the p-nitrophenol by the chlorobenzene method, firstly, insoluble substances in the waste sulfuric acid are separated in a filtering mode, the residual organic substances in the waste sulfuric acid are extracted by benzene, an extracting agent is separated in a rectifying mode, and then, a sulfuric acid solution with higher purity is obtained by concentration after ion exchange; the invention creatively uses the extraction mode to strip the organic phase in the waste sulfuric acid from the waste sulfuric acid, then intercepts the metal ions in the solution through ion exchange, reduces the salt content in the solution to the minimum, realizes the filtration of impurities in the solution, and can repeatedly use the recovered waste sulfuric acid and the organic phase, thereby reducing the production cost, improving the economic benefit and having good practicability and application prospect.
Description
Technical Field
The invention relates to the technical field of waste acid recovery, in particular to a recovery method for waste sulfuric acid.
Background
Sulfuric acid has been widely used as a chemical product in various industries, such as chemical industry, petroleum industry, etc., and a large amount of dilute sulfuric acid is produced in the production process. In order to avoid pollution of dilute sulfuric acid to the environment, lime or other alkaline solutions are generally adopted for neutralization, but consumption of lime or other alkaline solutions is caused, and waste of sulfuric acid resources is caused, and concentration of waste sulfuric acid is beneficial to reducing consumption of substances such as lime and the like, recycling of sulfuric acid can be achieved, economic cost is increased, and a resource-saving society is constructed.
At present, the concentration treatment of dilute sulfuric acid in production mainly comprises the following methods: evaporating and eluting water at high temperature in a heating environment, or concentrating under reduced pressure in a heating process. However, since sulfuric acid has a strong corrosiveness, it is liable to corrode the concentration equipment, and the consumption rate of the concentration equipment is further increased under a high temperature condition, which will increase the maintenance and management costs of the concentration equipment. In addition, different industrial waste liquids contain dilute sulfuric acid to be recovered, and also contain other waste materials, for example, in the process of producing alkylate by a sulfuric acid method, isoparaffin and olefin generate alkylate under the catalysis of strong acid, and the reaction only contains waste sulfuric acid in the waste liquid, but also contains a small amount of unreacted isoparaffin, olefin and alkylate which is completely separated. The waste sulfuric acid solution from the pickling of the factory may also contain metal ions such as Fe 3+, Ni +, Cr 3+ and the like, and may also contain chlorine or other suspended matters. If the waste liquid is directly used for heating and concentrating, only the effect of concentrating sulfuric acid can be achieved, and the effect of increasing the purity of the sulfuric acid cannot be achieved.
In conclusion, the prior art has the problems that the equipment loss rate is high and the purity of the sulfuric acid cannot be improved in the process of heating and concentrating the sulfuric acid.
Disclosure of Invention
The invention aims to provide a method for recovering waste sulfuric acid, which aims to recover a high-purity and high-concentration sulfuric acid solution from the waste sulfuric acid, degrade the loss rate, improve the economic benefit and avoid environmental pollution.
The invention is realized by the following technical scheme:
a recovery method for waste sulfuric acid is based on a set of recovery device, the recovery device comprises a filtering kettle (1), an extraction kettle (2), a rectifying kettle I (3), a rectifying kettle II (4), a cation exchange resin column (5) and a concentration kettle (6), and double condensers (7) are connected to the rectifying kettle I (3), the rectifying kettle II (4) and the concentration kettle (6);
the method for recovering the waste sulfuric acid comprises the following steps:
1) filtering: transferring the solution containing the waste sulfuric acid into a filtering kettle, heating to 50-80 ℃, adding coconut shell activated carbon into the solution, stirring at a stirring speed of 500-800 r/min for 20-40 min, standing at a constant temperature for 10-30 min, performing filter pressing with a microfiltration membrane, performing filter pressing with a nanofiltration membrane, controlling the air pressure to be 0.2-0.5 Mpa, and collecting filtrate;
2) extraction: transferring the filtrate into an extraction kettle, cooling to 20-30 ℃, adding an extractant benzene into the filtrate, uniformly stirring at a stirring speed of 500-800 r/min, standing for layering, transferring an organic phase into a rectification I kettle, and transferring a water phase into a rectification II kettle;
3) rectifying: setting different heating temperature points according to the boiling point difference of benzene and other organic matters in the rectifying kettle I, stirring at a stirring speed of 500-1000 r/min, completely separating an extracting agent from other organic components, directly using high-boiling-point impurities at the bottom of the rectifying kettle as fuel for combustion, and recovering the extracting agent benzene;
heating the temperature of a rectification II kettle to 80-100 ℃, stirring at a stirring speed of 500-1000 r/min, collecting rectified light components, heating to 100-110 ℃ again, rectifying to remove water, and primarily concentrating the solution;
4) column passing: transferring the heavy rectification component in the rectification II kettle into a cation exchange resin column for cation exchange, recovering a sulfuric acid solution from the lower end of the resin column, and controlling the temperature of the column passing at 20-50 ℃;
5) concentrating: transferring the sulfuric acid solution after column passing into a concentration kettle, raising the temperature in the kettle to 100-150 ℃, rectifying to remove water and concentrate sulfuric acid, and controlling the rectifying temperature and the rectifying time according to the required concentration to obtain the recovered waste sulfuric acid.
As a preferable technical scheme, the mass percent of the coconut shell activated carbon added into the filtering kettle in the step 1 of the recovery method is 5-15%.
As a preferable technical scheme, in the recovery method, in the step 1, the membrane aperture of the microfiltration membrane is 500-800 nm, and the membrane aperture of the nanofiltration membrane is 50-250 nm.
As a preferable technical scheme, the mass percent of the extractant benzene added in the step 2 of the recovery method is 30-70%.
As a preferable technical scheme, the concentration of the primarily concentrated sulfuric acid solution in the rectifying II kettle in the step 3 of the recovery method is 30-50%.
Preferably, the cation exchange resin in step 4 of the recovery method is a hydrogen ion exchange resin.
Preferably, the concentration of the sulfuric acid solution finally recovered in step 5 of the recovery method is 50-80%.
The invention has the beneficial effects that: the method for recovering the waste sulfuric acid aims at the production process of preparing the p-nitrophenol by the chlorobenzene method, firstly, insoluble substances in the waste sulfuric acid are separated in a filtering mode, the residual organic substances in the waste sulfuric acid are extracted by benzene, an extracting agent is separated in a rectifying mode, and then, a sulfuric acid solution with higher purity is obtained by concentration after ion exchange; the invention creatively uses the extraction mode to strip the organic phase in the waste sulfuric acid from the waste sulfuric acid, then intercepts the metal ions in the solution through ion exchange, reduces the salt content in the solution to the minimum, realizes the filtration of impurities in the solution, and can repeatedly use the recovered waste sulfuric acid and the organic phase, thereby reducing the production cost, improving the economic benefit and having good practicability and application prospect.
Drawings
FIG. 1 is a schematic view of the overall structure of a recovery apparatus for waste sulfuric acid according to the present invention.
In the figure: 1. filtering the kettle; 2. an extraction kettle; 3. a rectifying kettle I; 4. a rectifying kettle II; 5. a cation exchange resin column; 6. a concentration kettle; 7. a double condenser.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
As shown in figure 1, the recovery method for the waste sulfuric acid is based on a set of recovery device, the recovery device comprises a filtering kettle 1, an extraction kettle 2, a rectification I kettle 3, a rectification II kettle 4, a cation exchange resin column 5 and a concentration kettle 6, and the rectification I kettle 3, the rectification II kettle 4 and the concentration kettle 6 are all connected with a double condenser 7;
the method for recovering the waste sulfuric acid comprises the following steps:
1) filtering: transferring the solution containing waste sulfuric acid into a filtering kettle, heating to 80 ℃, adding coconut shell activated carbon into the solution, stirring at a stirring speed of 800r/min for 40min, standing at a constant temperature for 30min, performing pressure filtration by using a microfiltration membrane, performing pressure filtration by using a nanofiltration membrane, controlling the air pressure to be 0.5Mpa, and collecting filtrate;
the mass percent of the coconut shell activated carbon added into the filtering kettle is 15 percent; the membrane aperture of the micro-filtration membrane is 500nm, and the membrane aperture of the nano-filtration membrane is 50 nm;
2) extraction: transferring the filtrate into an extraction kettle, cooling to 30 ℃, adding an extractant benzene into the filtrate, uniformly stirring at a stirring speed of 800r/min, standing for layering, transferring an organic phase into a first rectification kettle, and transferring a water phase into a second rectification kettle;
adding 70% of extractant benzene by mass percent;
3) rectifying: setting different heating temperature points according to the boiling point difference of benzene and other organic matters in the rectifying kettle I, stirring at a stirring speed of 1000r/min, completely separating an extracting agent from other organic components, directly using high-boiling-point impurities at the bottom of the rectifying kettle as fuel for combustion, and recovering the extracting agent benzene;
heating the temperature of a rectification II kettle to 100 ℃, stirring at a stirring speed of 1000r/min, collecting the rectified light components, heating to 110 ℃ again, rectifying to remove water, and primarily concentrating the solution;
the concentration of the sulfuric acid solution in the rectification II kettle after primary concentration is 50 percent;
4) column passing: transferring the heavy distillation components in the second distillation kettle into a hydrogen ion exchange resin column for cation exchange, recovering a sulfuric acid solution from the lower end of the resin column, and controlling the temperature of the column to be 50 ℃;
5) concentrating: transferring the sulfuric acid solution after passing through the column into a concentration kettle, raising the temperature in the kettle to 150 ℃, rectifying to remove water and concentrate sulfuric acid, and controlling the rectifying temperature and the rectifying time according to the required concentration to obtain the waste sulfuric acid with the recovery concentration of 80%.
Example 2
The present embodiment is different from embodiment 1 in that:
a recovery method for waste sulfuric acid is based on a set of recovery device, the recovery device comprises a filtering kettle 1, an extraction kettle 2, a rectifying I kettle 3, a rectifying II kettle 4, a cation exchange resin column 5 and a concentration kettle 6, and double condensers 7 are connected to the rectifying I kettle 3, the rectifying II kettle 4 and the concentration kettle 6;
the method for recovering the waste sulfuric acid comprises the following steps:
1) filtering: transferring the solution containing waste sulfuric acid into a filtering kettle, heating to 50 ℃, adding coconut shell activated carbon into the solution, stirring at a stirring speed of 800r/min for 20min, standing at a constant temperature for 10min, performing pressure filtration by using a microfiltration membrane, performing pressure filtration by using a nanofiltration membrane, controlling the air pressure to be 0.2Mpa, and collecting filtrate;
the mass percent of the coconut shell activated carbon added into the filtering kettle is 5 percent; the membrane aperture of the micro-filtration membrane is 800nm, and the membrane aperture of the nano-filtration membrane is 250 nm;
2) extraction: transferring the filtrate into an extraction kettle, cooling to 20 ℃, adding an extractant benzene into the filtrate, uniformly stirring at a stirring speed of 500r/min, standing for layering, transferring an organic phase into a first rectification kettle, and transferring a water phase into a second rectification kettle;
adding 30 percent of extractant benzene by mass percent;
3) rectifying: setting different heating temperature points according to the boiling point difference of benzene and other organic matters in the rectifying kettle I, stirring at a stirring speed of 500r/min, completely separating an extracting agent from other organic components, directly using high-boiling-point impurities at the bottom of the rectifying kettle as fuel for combustion, and recovering the extracting agent benzene;
heating the temperature of a rectification II kettle to 80 ℃, stirring at a stirring speed of 500r/min, collecting the rectified light components, heating to 100 ℃ again, rectifying to remove water, and primarily concentrating the solution;
the concentration of the sulfuric acid solution in the rectification II kettle after primary concentration is 30 percent;
4) column passing: transferring the heavy distillation components in the second distillation kettle into a hydrogen ion exchange resin column for cation exchange, recovering a sulfuric acid solution from the lower end of the resin column, and controlling the temperature of the column passing at 20 ℃;
5) concentrating: transferring the sulfuric acid solution after passing through the column into a concentration kettle, raising the temperature in the kettle to 100 ℃, rectifying to remove water and concentrate sulfuric acid, and controlling the rectifying temperature and the rectifying time according to the required concentration to obtain waste sulfuric acid with the recovery concentration of 50%.
Example 3
The present embodiment is different from embodiments 1 and 2 in that:
a recovery method for waste sulfuric acid is based on a set of recovery device, the recovery device comprises a filtering kettle 1, an extraction kettle 2, a rectifying I kettle 3, a rectifying II kettle 4, a cation exchange resin column 5 and a concentration kettle 6, and double condensers 7 are connected to the rectifying I kettle 3, the rectifying II kettle 4 and the concentration kettle 6;
the method for recovering the waste sulfuric acid comprises the following steps:
1) filtering: transferring the solution containing waste sulfuric acid into a filtering kettle, heating to 60 ℃, adding coconut shell activated carbon into the solution, stirring at a stirring speed of 800r/min for 30min, standing at a constant temperature for 20min, performing pressure filtration by using a microfiltration membrane, performing pressure filtration by using a nanofiltration membrane, controlling the air pressure to be 0.3Mpa, and collecting filtrate;
the mass percent of the coconut shell activated carbon added into the filtering kettle is 10 percent; the membrane aperture of the micro-filtration membrane is 600nm, and the membrane aperture of the nano-filtration membrane is 100 nm;
2) extraction: transferring the filtrate into an extraction kettle, cooling to 25 ℃, adding an extractant benzene into the filtrate, uniformly stirring at a stirring speed of 600r/min, standing for layering, transferring an organic phase into a first rectification kettle, and transferring a water phase into a second rectification kettle;
adding 50% of extractant benzene by mass percent;
3) rectifying: setting different heating temperature points according to the boiling point difference of benzene and other organic matters in the rectifying kettle I, stirring at a stirring speed of 800r/min, completely separating an extracting agent from other organic components, directly using high-boiling-point impurities at the bottom of the rectifying kettle as fuel for combustion, and recovering the extracting agent benzene;
heating the temperature of a rectification II kettle to 90 ℃, stirring at the stirring speed of 800r/min, collecting the rectified light components, heating to 105 ℃ again, rectifying to remove water, and primarily concentrating the solution;
the concentration of the sulfuric acid solution in the rectification II kettle after primary concentration is 40 percent;
4) column passing: transferring the heavy distillation components in the second distillation kettle into a hydrogen ion exchange resin column for cation exchange, recovering a sulfuric acid solution from the lower end of the resin column, and controlling the temperature of the column to be 40 ℃;
5) concentrating: transferring the sulfuric acid solution after passing through the column into a concentration kettle, raising the temperature in the kettle to 120 ℃, rectifying to remove water and concentrate sulfuric acid, and controlling the rectifying temperature and the rectifying time according to the required concentration to obtain waste sulfuric acid with the recovery concentration of 60%.
Example 4
The present embodiment is different from embodiments 1, 2, and 3 in that:
a recovery method for waste sulfuric acid is based on a set of recovery device, the recovery device comprises a filtering kettle 1, an extraction kettle 2, a rectifying I kettle 3, a rectifying II kettle 4, a cation exchange resin column 5 and a concentration kettle 6, and double condensers 7 are connected to the rectifying I kettle 3, the rectifying II kettle 4 and the concentration kettle 6;
the method for recovering the waste sulfuric acid comprises the following steps:
1) filtering: transferring the solution containing waste sulfuric acid into a filtering kettle, heating to 70 ℃, adding coconut shell activated carbon into the solution, stirring at a stirring speed of 800r/min for 25min, standing at a constant temperature for 25min, performing pressure filtration by using a microfiltration membrane, performing pressure filtration by using a nanofiltration membrane, controlling the air pressure to be 0.4Mpa, and collecting filtrate;
the mass percent of the coconut shell activated carbon added into the filtering kettle is 10 percent; the membrane aperture of the micro-filtration membrane is 700nm, and the membrane aperture of the nano-filtration membrane is 150 nm;
2) extraction: transferring the filtrate into an extraction kettle, cooling to 25 ℃, adding an extractant benzene into the filtrate, uniformly stirring at a stirring speed of 700r/min, standing for layering, transferring an organic phase into a first rectification kettle, and transferring a water phase into a second rectification kettle;
adding 60 percent of extractant benzene by mass percent;
3) rectifying: setting different heating temperature points according to the boiling point difference of benzene and other organic matters in the rectifying kettle I, stirring at a stirring speed of 800r/min, completely separating an extracting agent from other organic components, directly using high-boiling-point impurities at the bottom of the rectifying kettle as fuel for combustion, and recovering the extracting agent benzene;
heating the temperature of a rectification II kettle to 95 ℃, stirring at a stirring speed of 1000r/min, collecting the rectified light components, heating to 110 ℃ again, rectifying to remove water, and primarily concentrating the solution;
the concentration of the sulfuric acid solution in the rectification II kettle after primary concentration is 45 percent;
4) column passing: transferring the heavy distillation components in the second distillation kettle into a hydrogen ion exchange resin column for cation exchange, recovering a sulfuric acid solution from the lower end of the resin column, and controlling the temperature of the column passing at 35 ℃;
5) concentrating: transferring the sulfuric acid solution after passing through the column into a concentration kettle, raising the temperature in the kettle to 120 ℃, rectifying to remove water and concentrate sulfuric acid, and controlling the rectifying temperature and the rectifying time according to the required concentration to obtain waste sulfuric acid with the recovery concentration of 60%.
In the invention, the recovery method of the waste sulfuric acid aims at the production process of preparing p-nitrophenol by a chlorobenzene method, firstly, insoluble substances in the waste sulfuric acid are separated in a filtering mode, residual organic substances in the waste sulfuric acid are extracted by benzene, an extracting agent is separated in a rectifying mode, and then a sulfuric acid solution with higher purity is obtained by concentration after ion exchange; the invention creatively uses the extraction mode to strip the organic phase in the waste sulfuric acid from the waste sulfuric acid, then intercepts the metal ions in the solution through ion exchange, reduces the salt content in the solution to the minimum, realizes the filtration of impurities in the solution, and can repeatedly use the recovered waste sulfuric acid and the organic phase, thereby reducing the production cost, improving the economic benefit and having good practicability and application prospect.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (7)
1. A method for recovering waste sulfuric acid is characterized in that: the recovery method is based on a set of recovery device, the recovery device comprises a filtering kettle (1), an extraction kettle (2), a rectifying I kettle (3), a rectifying II kettle (4), a cation exchange resin column (5) and a concentration kettle (6), and double condensers (7) are connected to the rectifying I kettle (3), the rectifying II kettle (4) and the concentration kettle (6);
the method for recovering the waste sulfuric acid comprises the following steps:
1) filtering: transferring the solution containing the waste sulfuric acid into a filtering kettle, heating to 50-80 ℃, adding coconut shell activated carbon into the solution, stirring at a stirring speed of 500-800 r/min for 20-40 min, standing at a constant temperature for 10-30 min, performing filter pressing with a microfiltration membrane, performing filter pressing with a nanofiltration membrane, controlling the air pressure to be 0.2-0.5 Mpa, and collecting filtrate;
2) extraction: transferring the filtrate into an extraction kettle, cooling to 20-30 ℃, adding an extractant benzene into the filtrate, uniformly stirring at a stirring speed of 500-800 r/min, standing for layering, transferring an organic phase into a rectification I kettle, and transferring a water phase into a rectification II kettle;
3) rectifying: setting different heating temperature points according to the boiling point difference of benzene and other organic matters in the rectifying kettle I, stirring at a stirring speed of 500-1000 r/min, completely separating an extracting agent from other organic components, directly using high-boiling-point impurities at the bottom of the rectifying kettle as fuel for combustion, and recovering the extracting agent benzene;
heating the temperature of a rectification II kettle to 80-100 ℃, stirring at a stirring speed of 500-1000 r/min, collecting rectified light components, heating to 100-110 ℃ again, rectifying to remove water, and primarily concentrating the solution;
4) column passing: transferring the heavy rectification component in the rectification II kettle into a cation exchange resin column for cation exchange, recovering a sulfuric acid solution from the lower end of the resin column, and controlling the temperature of the column passing at 20-50 ℃;
5) concentrating: transferring the sulfuric acid solution after column passing into a concentration kettle, raising the temperature in the kettle to 100-150 ℃, rectifying to remove water and concentrate sulfuric acid, and controlling the rectifying temperature and the rectifying time according to the required concentration to obtain the recovered waste sulfuric acid.
2. A recovery process for spent sulfuric acid according to claim 1, characterized in that: in the recovery method, the mass percent of the coconut shell activated carbon added into the filtering kettle in the step 1 is 5-15%.
3. A recovery process for spent sulfuric acid according to claim 1, characterized in that: in the recovery method, in the step 1, the membrane aperture of the microfiltration membrane is 500-800 nm, and the membrane aperture of the nanofiltration membrane is 50-250 nm.
4. A recovery process for spent sulfuric acid according to claim 1, characterized in that: in the recovery method, the mass percent of the extractant benzene added in the step 2 is 30-70%.
5. A recovery process for spent sulfuric acid according to claim 1, characterized in that: in the recovery method, the concentration of the primarily concentrated sulfuric acid solution in the rectifying II kettle in the step 3 is 30-50%.
6. A recovery process for spent sulfuric acid according to claim 1, characterized in that: the cation exchange resin in the step 4 of the recovery method is hydrogen ion exchange resin.
7. A recovery process for spent sulfuric acid according to claim 1, characterized in that: the concentration of the sulfuric acid solution finally recovered in the step 5 of the recovery method is 50-80%.
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