CN-118954805-B - DSD acid oxidation wastewater treatment method and application thereof

Abstract

The invention relates to the technical field of water treatment, in particular to a DSD acid oxidation wastewater treatment method which comprises the steps of wastewater extraction, macroporous resin adsorption, iron-carbon micro-electrolysis and MVR evaporation concentration, wherein DNS in water is extracted through an extractant, back-extracted water is returned to a DNS reduction working section to prepare DSD acid, the product yield is improved, the macroporous resin adsorption is used for enriching the residual DNS, the eluted DNS can be directly sleeved on reduction to prepare DSD acid, the comprehensive removal rate of CODCr in the first two steps is 90-95%, the iron-carbon micro-electrolysis is advanced, the color of effluent is colorless and transparent, the color of the CODCr is below 100mg/L, the MVR concentration is used for preparing high-quality salt, and the distilled water is used for S2 resin desorption or DSD preparation process, so that the treatment difficulty of DSD acid oxidation wastewater is effectively solved.

Inventors

• JU PENGPENG
• YANG YANG
• LIU JUNQI
• LIANG BING
• LIU SHUOLEI

Assignees

• 河北深茂新材料科技有限公司

Dates

Publication Date

20260508

Application Date

20240304

Claims (2)

1. 1. The DSD acid oxidation wastewater treatment method is characterized by comprising the following steps of: S1, extracting waste water, namely extracting acid oxidation waste water by using an extracting agent to obtain primary waste water and an oil phase, and then carrying out reverse extraction on the oil phase to obtain DNS concentrate, and recovering the DNS concentrate for preparing DSD acid in a DNS reduction section; S2, macroporous resin adsorption, namely adsorbing the primary wastewater by macroporous resin to obtain secondary wastewater, and desorbing the macroporous resin by using a desorbing agent to recover DNS; s3, performing iron-carbon micro-electrolysis, namely performing micro-electrolysis treatment on the secondary wastewater by using iron-carbon, and then treating the micro-electrolyzed wastewater by using an inorganic adsorbent to obtain tertiary wastewater; S4, MVR evaporation concentration, namely performing MVR evaporation concentration on the three-stage wastewater to obtain high-quality salt, wherein the distilled water is used in the S2 resin desorption or DSD preparation process; The components of the extractant comprise an organic amine extractant or an ether extractant, the components of the extractant also comprise an alcohol extractant or a phosphate extractant, the components of the extractant also comprise other extractants, the other extractants comprise at least one of toluene, gasoline, kerosene, sulfonated kerosene and carbon tetrachloride, the organic amine extractant or the ether extractant, the alcohol extractant or the phosphate extractant and the other extractants respectively have the volume ratio of 2-6:1-3:1-7, the ether extractant comprises at least one of diisopropyl ether, ethylhexyl ether and 9-alkenyl-12-hydroxyoctadecanoate polyoxyethylene ether-10, the phosphate extractant comprises at least one of hexyl phosphate di (2-ethylhexyl) ester, dioctyl phosphate and tributyl phosphate, the alcohol extractant comprises at least one of isoamyl alcohol, sec-octyl alcohol, isooctyl alcohol and n-octyl alcohol, and the organic amine extractant is at least one ammonium salt of tri-Xin Guiwan tertiary amine, quaternary amine, trioctylamine and dodecyl tertiary amine; The macroporous resin is macroporous weak-base anion exchange resin, wherein the macroporous weak-base anion exchange resin comprises at least one of styrene series, phenolic series and acrylic series, the adsorption temperature in S2 is 0-50 ℃, and the flow rate of wastewater passing through the macroporous resin is 0.25-5BV/h; the extraction temperature in the S1 is 20-50 ℃, the extraction pH value is 1-6, the back extraction temperature is 20-60 ℃, and the back extraction pH value is 8-12; The desorption agent for desorption in the step S2 is water or dilute alkali, the flow rate of the desorption agent is 0.5-6BV/h, the consumption of the desorption agent is 2-15BV, and the desorption temperature is 60-100 ℃; The iron-carbon is a mixture of iron matter and activated carbon or an iron-carbon filler obtained by sintering iron, carbon and metal catalysts thereof, wherein the mass ratio of the iron matter to the activated carbon in the iron-carbon is 0.1-0.5:1-2, hydrogen peroxide is also introduced in the micro-electrolysis treatment process, and the hydrogen peroxide introduction amount accounts for 0.05-2% of the mass of the secondary wastewater.
2. 2. The use of the treatment method according to claim 1, characterized in that the treatment method is used for the treatment of at least one of DSD acid oxidation wastewater, sulphonation wastewater in the preparation of DSD acid or reduction wastewater.

Description

DSD acid oxidation wastewater treatment method and application thereof Technical Field The invention relates to the technical field of water treatment, in particular to a DSD acid oxidation wastewater treatment method and application thereof. Background DSD acid (4, 4 '-diaminostilbene-2, 2' -disulfonic acid) is an important dye intermediate. The production process includes sulfonating ① p-nitrotoluene (PNT) with fuming sulfuric acid to obtain p-nitrotoluene ortho-sulfonic acid (NTS), catalytic oxidation of ② NTS to obtain 4,4 '-dinitrostilbene-2, 2' -disulfonic acid (DNS acid), and catalytic hydrogenation reduction of ③ DNS acid with iron powder to obtain DSD acid. In the process, about 20t of waste water is produced for producing each ton of DSD acid products, and the waste water contains a large amount of developed organic matters containing sulfonic groups and nitro groups, a large amount of salts such as Cl -, red SO 42- and the like, and a large amount of waste acid, intermediate products, byproducts and the like, SO that the waste water has very high CODCr value (more than or equal to 20000 mg/L), chromaticity (more than or equal to 15000 times) and salt content, and the waste water is seriously polluted and is harmful to human health if the waste water is directly discharged without treatment. However, organic matters contained in the DSD acid wastewater have high water solubility, are difficult to remove by adopting a traditional flocculation method, and meanwhile, the high salinity characteristic of the DSD acid wastewater causes that the wastewater is possibly subjected to biochemical treatment after being diluted by a large amount of clear water, so that the wastewater is one of the most difficult chemical wastewater at present. Chinese patent CN113603264A discloses a treatment method of waste water in a DNS acid reduction section, which carries out flocculation and diazotization coupling reaction on the waste water to achieve the aim of removing water-soluble 2, 4-diaminobenzene sodium sulfonate in the waste water, and simultaneously generates water-insoluble azo compounds to improve the recycling utilization rate of the waste water, but the method is only suitable for the waste water in the reduction section and has poor treatment effect on the waste water in the oxidation section and the waste water in the comprehensive section. Chinese patent CN1156407C discloses treatment and recycling of 4,4 '-dinitrostilbene-2, 2' -disulfonic acid production wastewater, wherein the wastewater is adsorbed by using a macroporous weak base anion exchange resin fixed bed, adsorbed water is nearly colorless, CODCr is reduced from 13000-18000mg/L to 1000mg/L, but the CODCr content is still higher. Disclosure of Invention In order to solve the technical problems, the invention firstly provides a DSD acid oxidation wastewater treatment method which mainly comprises complexation extraction, resin adsorption and multi-effect concentration. The main idea is to recycle valuable intermediate DNS sodium salt (4, 4 '-dinitrostilbene-2, 2' -disulfonic acid sodium salt) in the wastewater, simultaneously and effectively remove COD and chromaticity, and the treated wastewater is evaporated by MVR to produce by-product anhydrous sodium sulphate, thereby generating economic benefit, and the distilled water is recycled for reaction, so that the recycling degree of the wastewater is improved. Further, the DSD acid oxidation wastewater treatment method comprises the following steps: S1, extracting waste water, namely extracting acid oxidation waste water by using an extracting agent to obtain primary waste water and an oil phase, and then carrying out reverse extraction on the oil phase to obtain DNS concentrate, and recovering the DNS concentrate for preparing DSD acid in a DNS reduction section; S2, macroporous resin adsorption, namely adsorbing the primary wastewater by macroporous resin to obtain secondary wastewater, and desorbing the macroporous resin by using a desorbing agent to recover DNS; s3, performing iron-carbon micro-electrolysis, namely performing micro-electrolysis treatment on the secondary wastewater by using iron-carbon, and then treating the micro-electrolyzed wastewater by using an inorganic adsorbent to obtain tertiary wastewater; S4, MVR evaporation concentration, namely performing MVR evaporation concentration on the three-stage wastewater to obtain high-quality salt, wherein the distilled water is used in the S2 resin desorption or DSD preparation process. Further, the components of the extractant comprise at least one of organic amine extractant, alcohol extractant, ester extractant, phosphate extractant, sulfoxide extractant, ether extractant and other extractant. Further, the organic amine extractant includes, but is not limited to, at least one of tri Xin Guiwan-tertiary amine (N235), trialkylmethylamine, quaternary ammonium salt, didecylamine, trioctylamine, trinonyl amine, dodecyl tertiary amine,