CN114715856A - Waste sulfuric acid recovery and disposal method - Google Patents

Waste sulfuric acid recovery and disposal method Download PDF

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CN114715856A
CN114715856A CN202210355631.XA CN202210355631A CN114715856A CN 114715856 A CN114715856 A CN 114715856A CN 202210355631 A CN202210355631 A CN 202210355631A CN 114715856 A CN114715856 A CN 114715856A
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sulfuric acid
waste sulfuric
solution
disposing
washing
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刘剑
姚世明
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Wuxi Riyue Water Treatment Co ltd
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
    • B01D15/20—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the conditioning of the sorbent material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
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  • Materials Engineering (AREA)
  • Water Treatment By Sorption (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
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Abstract

The invention relates to the field of waste sulfuric acid treatment processes, in particular to a waste sulfuric acid recovery and disposal method, which comprises the steps of diluting waste sulfuric acid, adding a catalyst, carrying out ultrasonic and stirring treatment for 5-20h under the condition of illumination, filtering, adding adsorption resin into filtrate, adsorbing for 20-25h, and adjusting the concentration after filtering to obtain recovered sulfuric acid.

Description

Waste sulfuric acid recovery and disposal method
Technical Field
The invention relates to the field of waste sulfuric acid treatment processes, in particular to a waste sulfuric acid recycling method.
Background
Sulfuric acid is one of the most basic chemical products, and is widely applied to industries such as pesticide and fertilizer, lead storage batteries, petrochemical industry, dyes, colored metallurgy, printing and dyeing and the like, the dye industry is used as an acid consumer, about 2 tons of sulfuric acid is needed for each ton of dyes, only about 10% of sulfuric acid is used as an effective replacement group to enter the reaction, and the rest most of the sulfuric acid is discharged as low-concentration dilute waste acid.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the technical problem, the invention provides a method for recovering and disposing waste sulfuric acid.
The adopted technical scheme is as follows:
a method for recovering and disposing waste sulfuric acid comprises the following steps:
diluting waste sulfuric acid, adding a catalyst, performing ultrasonic treatment and stirring treatment for 5-20h under the condition of illumination, filtering, adding an adsorption resin into filtrate, adsorbing for 20-25h, and performing concentration adjustment after filtering, wherein the concentration adjustment can be omitted, or the concentration of the sulfuric acid can be changed by adding water or decompressing and concentrating distilled water according to actual use requirements to obtain recovered sulfuric acid;
the preparation method of the catalyst comprises the following steps:
s1: mixing 3- (N-anilino) propyl trimethoxy silane, sodium metaaluminate, rare earth salt, a template agent, polyethylene glycol, sodium hydroxide and water, heating to 80-90 ℃, stirring for reaction for 8-10h, transferring to a hydrothermal crystallization reaction kettle for crystallization at 108-112 ℃ for 72-96h, performing suction filtration, washing, drying, and finally putting into a muffle furnace for calcination to obtain the rare earth doped molecular sieve;
s2: mixing maleic anhydride grafted polyvinyl alcohol, sodium alginate and water to obtain a mixed solution A, adding a rare earth doped molecular sieve and boric acid into a calcium chloride solution, stirring and mixing uniformly, adding a white rot fungus spore suspension to obtain a mixed solution B, dropwise adding the mixed solution B into the mixed solution A, continuously stirring to obtain a colloid, and freeze-drying the colloid at a low temperature.
Further, the waste sulfuric acid is generated in the production process of the anthraquinone dye, the color is 5500-6000 times, and the COD is 7000-8000mg/L, pH is 1.
Further, the pH value of the diluted waste sulfuric acid is 3-5.
Further, the rare earth salt is cerium nitrate and yttrium nitrate, and the mass ratio of the cerium nitrate to the yttrium nitrate is 1-5: 1-5.
Further, the mass ratio of the 3- (N-anilino) propyl trimethoxy silane to the sodium metaaluminate to the template agent is 20-30: 500-800: 1.
further, the template agent is tetrapropylammonium bromide and hexamethonium bromide, and the mass ratio is 1-3: 1.
Further, during calcination, the temperature is firstly preserved for 1-2h at the temperature of 350-.
Further, the preparation method of the maleic anhydride grafted polyvinyl alcohol comprises the following steps:
and (2) dropwise adding a DMSO solution of polyvinyl alcohol into a DMSO solution of maleic anhydride, reacting for 2-4h at 50-60 ℃, recovering to room temperature after the reaction is finished, washing the obtained product with acetone, and drying.
Further, the white rot fungus spore suspension contains 1.5-2.0 × 10 spores per ml6And (4) respectively.
Further, the preparation method of the adsorption resin comprises the following steps:
adding the D201 resin into an ion exchange column, washing with deionized water for 30-50min, repeatedly and alternately washing with 1-2mol/L NaOH solution and 1-2mol/L HCl solution which are 8-10 times of the weight of the D201 resin for 30-50min, finally washing the resin with deionized water to neutrality, and then soaking in sodium ethylene diamine tetracetate solution for 90-120 min.
The invention has the beneficial effects that:
the invention provides a method for recycling and disposing waste sulfuric acid, which can purify anthraquinone dye and other organic impurities in the waste sulfuric acid by utilizing the catalytic degradation and adsorption of a catalyst and resin, reduce the chroma, and can be used as a crude chemical raw material after the waste sulfuric acid is recycled, thereby not only reducing the processing cost of the waste sulfuric acid, but also fully utilizing sulfuric acid resources, and completely degrading the waste sulfuric acid into sulfate radicals, nitrate radicals and ammonium ions by embedding the catalyst obtained by fixing white rot fungi on a rare earth doped molecular sieve, and through the processes of addition, substitution, electron transfer and the like among the free radicals, the anthraquinone dye and the organic impurities, the white rot fungi can synthesize and secrete special enzymes, carry out efficient ring-opening degradation on xenobiotics and various aromatic compounds, and can improve the degradation efficiency by cooperating with the rare earth doped molecular sieve, the treated D201 resin has enhanced adsorption performance on nitrate ions and ammonium ions generated by degradation, can reduce the content of impurity ions in the recovered sulfuric acid, and improves the quality of the recovered sulfuric acid.
Detailed Description
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1:
a method for recovering and disposing waste sulfuric acid comprises the following steps:
diluting waste sulfuric acid which is produced in the production process of anthraquinone dye-reactive brilliant blue KN-R and has the chroma of 5820 times and the COD of 7553mg/L, pH of 1 with water until the pH value is 3, adding catalyst with the amount of 1g/L, treating with 300W ultrasonic wave under the irradiation of 250W metal halide lamp for 10h, filtering to obtain filtrate, adding D201 resin into ion exchange column, washing with deionized water for 40min, repeatedly washing with 10 times of 1mol/L NaOH solution and 1mol/L HCl solution of D201 type resin for 50min alternately, washing with deionized water to neutral, soaking in 1mol/L sodium ethylenediamine tetracetate solution for 100min, air drying at room temperature, adding into the filtrate, the resin dosage is 10g/L, after 25h of adsorption, filtration is carried out to obtain recovered sulfuric acid, and the recovered sulfuric acid is decompressed and concentrated to the volume before dilution;
the preparation method of the catalyst comprises the following steps:
30g of 3- (N-anilino) propyl trimethoxy silane, 600g of sodium metaaluminate, 0.1g of cerium nitrate, 0.1g of yttrium nitrate, 0.5g of tetrapropyl ammonium bromide, 0.5g of hexamethonium bromide, 5g of polyethylene glycol, 0.3g of sodium hydroxide and 5L of water are mixed, heated to 90 ℃, stirred and reacted for 10 hours, then transferred to a hydrothermal crystallization reaction kettle for crystallization at 110 ℃ for 96 hours, filtered, washed, dried at 80 ℃ for 10 hours, finally placed in a muffle furnace for heating to 380 ℃ for heat preservation for 1.5 hours, heated to 600 ℃ for heat preservation for 5 hours to obtain a rare earth doped molecular sieve, 22g of polyvinyl alcohol is dissolved in 550g of DMSO to obtain a polyvinyl alcohol solution, 49g of maleic anhydride is dissolved in 110g of DMSO to obtain a polyvinyl alcohol solutionDripping a polyvinyl alcohol solution into a maleic anhydride solution, reacting for 4 hours at 60 ℃, recovering the room temperature after the reaction is finished, washing the obtained product with acetone, drying for 10 hours at 80 ℃ to obtain 262g of maleic anhydride grafted polyvinyl alcohol, mixing 100g of maleic anhydride grafted polyvinyl alcohol with 20g of sodium alginate and 300mL of water to obtain a mixed solution A, adding 45g of rare earth doped molecular sieve and 2g of boric acid into 200mL of 2 wt% calcium chloride solution, stirring and mixing uniformly, adding 10mL of white rot fungus spore suspension, wherein each mL of the white rot fungus spore suspension contains 1.5 multiplied by 10 spores6And (4) obtaining a mixed solution B, dripping the mixed solution B into the mixed solution A, continuously stirring to obtain a colloid, and freeze-drying the colloid at a low temperature.
Example 2:
a method for recovering and disposing waste sulfuric acid comprises the following steps:
diluting waste sulfuric acid which is produced in the production process of anthraquinone dye-reactive brilliant blue KN-R and has the chroma of 5820 times and the COD of 7553mg/L, pH of 1 with water until the pH value is 5, adding catalyst with the dosage of 1g/L, under the irradiation of 250W metal halogen lamp, performing 300W ultrasonic treatment and stirring treatment for 20h, filtering to obtain filtrate, adding D201 type resin into ion exchange column, washing with deionized water for 50min, repeatedly washing with 2mol/L NaOH solution and 2mol/L HCl solution of 10 times of D201 type resin for 50min alternately, washing with deionized water to neutral, soaking in 1mol/L sodium ethylenediamine tetracetate solution for 120min, air drying at room temperature, adding into the filtrate, the resin dosage is 10g/L, after 25h of adsorption, filtration is carried out to obtain recovered sulfuric acid, and the recovered sulfuric acid is decompressed and concentrated to the volume before dilution;
the preparation method of the catalyst comprises the following steps:
30g of 3- (N-anilino) propyl trimethoxy silane, 800g of sodium metaaluminate, 0.1g of cerium nitrate, 0.1g of yttrium nitrate, 0.5g of tetrapropyl ammonium bromide, 0.5g of hexamethonium bromide, 5g of polyethylene glycol, 0.3g of sodium hydroxide and 5L of water are mixed, heated to 90 ℃, stirred and reacted for 10 hours, then transferred to a hydrothermal crystallization reaction kettle for crystallization at 112 ℃ for 96 hours, filtered, washed, dried at 80 ℃ for 10 hours, finally placed in a muffle furnace for heating to 380 ℃ for heat preservation for 2 hours, heated to 600 ℃ for heat preservation for 6 hours to obtain a rare earth doped molecular sieve, 22g of polyvinyl alcohol is dissolved in alcohol, and the rare earth doped molecular sieve is obtainedObtaining a polyvinyl alcohol solution in 550g DMSO (dimethylsulfoxide), dissolving 49g of maleic anhydride in 110g DMSO to obtain a maleic anhydride solution, dropwise adding the polyvinyl alcohol solution into the maleic anhydride solution, reacting at 60 ℃ for 4 hours, recovering the room temperature after the reaction is finished, washing the obtained product with acetone, drying at 80 ℃ for 10 hours to obtain 262g of maleic anhydride grafted polyvinyl alcohol, mixing 100g of maleic anhydride grafted polyvinyl alcohol with 20g of sodium alginate and 300mL of water to obtain a mixed solution A, adding 45g of rare earth doped molecular sieve and 2g of boric acid into 200mL of 2 wt% calcium chloride solution, stirring and uniformly mixing, adding 10mL of white rot fungus spore suspension, wherein each mL of the white rot fungus spore suspension contains 1.5 multiplied by 10 spores6And (4) obtaining a mixed solution B, dripping the mixed solution B into the mixed solution A, continuously stirring to obtain a colloid, and freeze-drying the colloid at a low temperature.
Example 3:
a method for recovering and disposing waste sulfuric acid comprises the following steps:
diluting waste sulfuric acid which is produced in the production process of anthraquinone dye-reactive brilliant blue KN-R and has the chroma of 5820 times and the COD of 7553mg/L, pH of 1 with water until the pH value is 4, adding catalyst with the amount of 0.5g/L, treating with 300W ultrasonic wave under the irradiation of 250W metal halide lamp for 5 hr, filtering to obtain filtrate, adding D201 type resin into ion exchange column, washing with deionized water for 30min, repeatedly washing with 1mol/L NaOH solution and 1mol/L HCl solution of 8 times of D201 type resin for 30min alternately, washing with deionized water to neutral, soaking in 1mol/L sodium ethylenediamine tetracetate solution for 90min, air drying at room temperature, adding into the filtrate, the resin dosage is 5g/L, after 20h of adsorption, filtration is carried out to obtain recovered sulfuric acid, and the recovered sulfuric acid is decompressed and concentrated to the volume before dilution;
the preparation method of the catalyst comprises the following steps:
20g of 3- (N-anilino) propyl trimethoxy silane, 500g of sodium metaaluminate, 0.1g of cerium nitrate, 0.1g of yttrium nitrate, 0.5g of tetrapropyl ammonium bromide, 0.5g of hexamethonium bromide, 5g of polyethylene glycol, 0.3g of sodium hydroxide and 5L of water are mixed, heated to 80 ℃, stirred and reacted for 8 hours, then transferred to a hydrothermal crystallization reaction kettle for crystallization at 108 ℃ for 72 hours, filtered, washed, dried at 80 ℃ for 10 hours, finally placed into a muffle furnace, heated to 350 ℃ for heat preservation for 1 hour, and heated to 350 ℃ for heat preservation for 1 hourHeating to 550 ℃, preserving heat for 4 hours to obtain a rare earth doped molecular sieve, dissolving 22g of polyvinyl alcohol in 550g of DMSO to obtain a polyvinyl alcohol solution, dissolving 49g of maleic anhydride in 110g of DMSO to obtain a maleic anhydride solution, dropwise adding the polyvinyl alcohol solution into the maleic anhydride solution, reacting at 50 ℃ for 2 hours, recovering the room temperature after the reaction is finished, washing the obtained product with acetone, drying at 80 ℃ for 10 hours to obtain 262g of maleic anhydride grafted polyvinyl alcohol, mixing 100g of maleic anhydride grafted polyvinyl alcohol with 20g of sodium alginate and 300mL of water to obtain a mixed solution A, adding 45g of rare earth doped molecular sieve and 2g of boric acid into 200mL of 2 wt% calcium chloride solution, stirring and uniformly mixing, adding 10mL of white rot fungus suspension, wherein each milliliter of the white rot fungus suspension contains 1.5 multiplied by 10 spores6And (4) obtaining a mixed solution B, dripping the mixed solution B into the mixed solution A, continuously stirring to obtain a colloid, and freeze-drying the colloid at a low temperature.
Comparative example 1:
substantially the same as in example 1 except that the spent sulfuric acid was not diluted with water, the catalyst was added directly.
Comparative example 2:
substantially the same as in example 1 except that no sonication was performed.
Comparative example 3:
essentially the same as in example 1, except that the catalyst was prepared without the addition of cerium nitrate and yttrium nitrate.
Comparative example 4:
essentially the same as example 1, except that no hexamethonium bromide was added, tetrapropylammonium bromide was used alone as the templating agent.
Comparative example 5:
substantially the same as in example 1 except that the maleic anhydride-grafted polyvinyl alcohol was replaced with polyvinyl alcohol.
Comparative example 6:
essentially the same as in example 1, except that no white rot fungus spore suspension was added.
Comparative example 7:
substantially the same as in example 1, except that the D201 type resin was added directly to the filtrate without treatment for adsorption.
And (3) performance testing:
the waste sulfuric acid is analyzed, a UV6100 ultraviolet visible spectrophotometer (Shanghai chromatography instrument Co., Ltd.) is adopted to carry out full-wave-band scanning, and the absorbance of the sample at 200-600nm is measured. According to Lambert-beer's law, when a beam of monochromatic light passes through a solution containing a dye, the absorbance A of the solution has the following relationship with the mass concentration C (mg/L) of a light-absorbing substance and the thickness b (cm) of an absorbing layer.
A＝abC
Wherein a is the solution absorptivity, L/(mg. cm).
The standard working curve equation of linear fitting is that A is 0.01657 rho, R2＝0.9999
Wherein A is the absorbance of the reactive brilliant blue KN-R, and rho is the mass concentration of the reactive brilliant blue KN-R, mg/L.
Calculating degradation rate according to a standard curve equation of concentration and absorbance, and respectively measuring absorbance A at the maximum absorption wavelength before and after the recovery and disposal of the waste sulfuric acid by using an ultraviolet-visible spectrophotometer0And A1Substituting the standard curve with the obtained value to calculate the mass concentration rho of the reactive brilliant blue KN-R corresponding to the value0And ρ1。
(1-rho) degradation rate1/ρ0)×100％
The waste sulfuric acids recovered in examples 1 to 3 and comparative examples 1 to 7 were examined, and the examination results are shown in the following table 1:
table 1:
Figure BDA0003582402220000091
from the above table 1, the invention provides a method for recovering and disposing waste sulfuric acid, which can purify anthraquinone dye and other organic impurities in the waste sulfuric acid through catalytic degradation and adsorption, reduce chromaticity, and make the waste sulfuric acid used as a crude chemical raw material after recovery, thereby reducing the treatment cost of the waste sulfuric acid and fully utilizing sulfuric acid resources.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (10)

1. A waste sulfuric acid recovery and disposal method is characterized in that after waste sulfuric acid is diluted, a catalyst is added, ultrasonic and stirring treatment is carried out for 5-20 hours under the condition of illumination, filtration is carried out, adsorption resin is added into filtrate, adsorption is carried out for 20-25 hours, and concentration adjustment is carried out after filtration to obtain recovered sulfuric acid;
the preparation method of the catalyst comprises the following steps:
s1: mixing 3- (N-anilino) propyl trimethoxy silane, sodium metaaluminate, rare earth salt, a template agent, polyethylene glycol, sodium hydroxide and water, heating to 80-90 ℃, stirring for reaction for 8-10h, transferring to a hydrothermal crystallization reaction kettle for crystallization at 108-112 ℃ for 72-96h, performing suction filtration, washing, drying, and finally putting into a muffle furnace for calcination to obtain the rare earth doped molecular sieve;
s2: mixing maleic anhydride grafted polyvinyl alcohol, sodium alginate and water to obtain a mixed solution A, adding a rare earth doped molecular sieve and boric acid into a calcium chloride solution, stirring and mixing uniformly, adding a white rot fungus spore suspension to obtain a mixed solution B, dropwise adding the mixed solution B into the mixed solution A, continuously stirring to obtain a colloid, and freeze-drying the colloid at a low temperature.
2. The method for recycling and disposing waste sulfuric acid as claimed in claim 1, wherein the waste sulfuric acid is produced in the production process of anthraquinone dye, and has a color value of 5500-6000 times, and a COD of 7000-8000mg/L, pH of 1.
3. The method for recovering and disposing waste sulfuric acid as claimed in claim 1, wherein the diluted waste sulfuric acid has a pH of 3 to 5.
4. The method for recovering and disposing the waste sulfuric acid as claimed in claim 1, wherein the rare earth salt is cerium nitrate and yttrium nitrate, and the mass ratio of the rare earth salt to the yttrium nitrate is 1-5: 1-5.
5. The method for recycling and disposing waste sulfuric acid as claimed in claim 1, wherein the mass ratio of the 3- (N-anilino) propyl trimethoxy silane to the sodium metaaluminate to the template agent is 20-30: 500-800: 1.
6. the method for recycling and disposing waste sulfuric acid as claimed in claim 1, wherein the template agent is tetrapropylammonium bromide and hexamethonium bromide, and the mass ratio is 1-3: 1.
7. the method as claimed in claim 1, wherein the temperature is maintained at 380 ℃ for 1-2h in the calcination process, and then the temperature is raised to 600 ℃ for 4-6h in the calcination process.
8. The method for recycling and disposing the waste sulfuric acid as claimed in claim 1, wherein the maleic anhydride grafted polyvinyl alcohol is prepared by the following method:
and (2) dropwise adding a DMSO solution of polyvinyl alcohol into a DMSO solution of maleic anhydride, reacting for 2-4h at 50-60 ℃, recovering to room temperature after the reaction is finished, washing the obtained product with acetone, and drying.
9. The method for recovering and disposing the waste sulfuric acid as claimed in claim 1, wherein the white rot fungi spore suspension contains spores of 1.5-2.0 x 10/ml6And (4) respectively.
10. The method for recovering and disposing the waste sulfuric acid as claimed in claim 1, wherein the preparation method of the adsorption resin is as follows:
adding the D201 resin into an ion exchange column, washing with deionized water for 30-50min, repeatedly and alternately washing with 1-2mol/L NaOH solution and 1-2mol/L HCl solution which are 8-10 times of the weight of the D201 resin for 30-50min, finally washing the resin with deionized water to neutrality, and then soaking in sodium ethylene diamine tetracetate solution for 90-120 min.
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CN115784171A (en) * 2022-11-23 2023-03-14 无锡日月水处理有限公司 Method for recovering and treating waste sulfuric acid

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