Biological treatment method for sulfonic acid compound wastewater

Abstract

The invention discloses a biological treatment method for sulfonic acid compound wastewater, and belongs to the field of biological treatment of sulfonic acid compound wastewater. According to the treatment method, wastewater is sequentially subjected to activation and culture of a sulfonic acid compound degradation solid strain and wastewater biological treatment, the process is easy to operate and efficient in reaction, and sulfonic acid compounds can be degraded. According to the present invention, the sulfonic acid compound degradation bacterial agent is the microbial agent prepared from the Microbacterium esteraromaticum, and the Microbacterium esteraromaticum is preserved in the China General Microbiological Culture Collection Center (CGMCC) on July 25, 2024, and has the preservation number of CGMCC NO.31455; the device can be used for treating sulfonic acid compound wastewater such as o-cresol sulfonic acid, sodium p-toluenesulfonate or sodium dodecyl benzene sulfonate with the inlet water sulfonic acid compound concentration of 1000mg / L. The method disclosed by the invention is used for biologically enhancing a common biological method and widening the application range of biologically treating the sulfonic acid compound wastewater.

Description

Technical Field

[0001] The invention belongs to the field of biological treatment of sulfonic acid compound wastewater, and specifically relates to a biological treatment method for sulfonic acid compound wastewater. Background Art

[0002] Sulfonic acid compounds are a class of chemical substances that contain a sulfonic acid functional group (-SO3H) in their molecules. This functional group plays an important role in chemical reactions and can enhance the hydrophilicity, acidity and catalytic activity of the compound. Sulfonic acid compounds are widely used in organic synthesis, chemical analysis, medicine and industry.

[0003] It is convenient and quick to treat sulfonic acid compound wastewater by physical methods. The commonly used physical method in practical applications is activated carbon adsorption. However, studies have found that the adsorption capacity of activated carbon columns for sulfonic acid group compounds such as naphthalenesulfonic acid is low. This is because the surface of activated carbon contains a large number of alkaline groups, which repel the electron-withdrawing sulfonic acid groups, reducing the adsorption affinity, and the repulsion effect increases with the increase of sulfonic acid groups. Jia et al. used alkaline resin adsorption to remove 2-naphthalenesulfonic acid from water, and also found that the presence of sulfonic acid groups may be unfavorable to the adsorption of resins. Ozone method has been used to oxidize and degrade naphthalenesulfonic acid, and COD has been effectively removed, and biodegradability has been significantly increased, but the investment cost of ozone oxidation is relatively high.

[0004] There are few studies on biological treatment of sulfonic acid compound wastewater, which is mainly reflected in the fact that after sulfonic acid enters the cell, it causes DNA damage through the substitution of nitrogenated bases, inhibiting the growth and reproduction of microorganisms. In addition, sulfonic acid compound wastewater is usually difficult to biodegrade, such as 4-methylbenzenesulfonic acid BOD is less than 0.05. But there is no doubt that biological treatment has the lowest cost, and the current research on the biodegradation of sulfonic acid compounds has made certain progress. For example, C Juárez-Ramírez isolated and identified bacterial colonies that can degrade 4-aminonaphthalene-1-sulfonic acid, belonging to the genera Bacillus, Arthrobacter, Microbacterium, Nocardia and Oleomonas, making it possible to biodegrade sulfonic acid compound wastewater. However, the common biological method for treating sulfonic acid compound wastewater has the disadvantages of low influent concentration limit, unstable operation, and low degradation efficiency. Summary of the invention

[0005] The present invention aims at the problems existing in the prior art and discloses a biological treatment method for sulfonic acid compound wastewater, which can degrade sulfonic acid compounds. The method is a biological enhancement of the common biological method and broadens the application scope of biological treatment of sulfonic acid compound wastewater. In addition, the process is simple to operate and has high reaction efficiency. The sulfonic acid compound degradation bacterial agent is a microbial bacterial agent prepared by Microbacterium esters, which can treat sulfonic acid compound wastewater such as o-cresol sulfonic acid, sodium p-toluenesulfonate or sodium dodecylbenzenesulfonate with an influent sulfonic acid compound concentration of 1000 mg / L, and the COD degradation rate is higher than 90%.

[0006] The present invention is achieved in that:

[0007] A biological treatment method for sulfonic acid compound wastewater, characterized in that the biological treatment method comprises the following steps:

[0008] Step 1: Activation and cultivation of sulfonic acid compound degradation bacteria:

[0009] 1.1. Add 1-5‰ solid bacterial agent of sulfonic acid compound degradation bacteria, 0.5-1.5g / L glucose, tap water, pH 7-8, and culture in a culture expansion tank at 25-35℃ for 48h to activate the bacteria, DO 2-4mg / L.

[0010] 1.2. After the activation of the bacteria, the bacterial density is detected under a microscope. The activation culture is completed when the bacterial density reaches 1×109 CFU / mL.

[0011] Step 2: Biological treatment of wastewater:

[0012] 2.1. The wastewater containing sulfonic acid groups adjusted to pH 7-8 is passed into the biological treatment tank, the temperature is controlled at 25-35°C, the reaction time and dissolved oxygen are controlled, 10% activated cultured sulfonic acid compound degrading bacteria liquid is added to the biological treatment tank, and the sulfonic acid compound degrading bacteria are immobilized on the polyurethane filler.

[0013] 2.2. When the biological treatment system is started, the concentration of sulfonic acid compounds in the influent is less than 500 mg / L, or the COD is less than 2000 mg / L. During the first 1 to 3 days after the system is started, 300 to 500 mg / LCOD equivalent carbon source is added every day. No carbon source is added after 3 days.

[0014] 2.3. Load increase and full load: Increase the load in a gradient from 300 to 500 mg / L of sulfonic acid compound concentration or from 500 to 1000 mg / L of COD, with COD given priority. Replace 80% of the water in each batch until the influent load reaches the target influent sulfonic acid compound concentration. The full load influent sulfonic acid compound concentration can reach 1000 mg / L or the COD concentration can reach 3000 to 5000 mg / L.

[0015] Furthermore, the hydraulic retention time (HRT) is: when the influent sulfonic acid compound concentration is 300-500 mg / L, the HRT is 24-48 h; when the influent sulfonic acid compound concentration is 500-1000 mg / L, the HRT is 48-72 h.

[0016] Furthermore, the biological treatment system adopts an aerobic biological treatment process with a dissolved oxygen (DO) of 2 to 4 mg / L.

[0017] Furthermore, the solid bacterial agent of sulfonic acid compound degrading bacteria is characterized in that it is a microbial agent prepared by Bacillus esterificus, and the Bacillus esterificus is deposited in the General Microbiological Center of China Microorganism Culture Collection Administration, with a deposit number of CGMCC NO.31455 and a deposit date of July 25, 2024.

[0018] Furthermore, the implementation method of the sulfonic acid compound degrading bacteria and polyurethane filler immobilization is as follows: the sulfonic acid compound degrading bacteria agent is added into a reaction tank filled with 50-70% polyurethane filler in 2-3 batches at a dosage of 10%, and aerated culture is carried out at 25-35°C, and the residence time is controlled to be 48-72h.

[0019] Furthermore, after the COD degradation rate is greater than 85% and the COD degradation effect is stable for 5 to 10 days, the influent load is increased with a sulfonic acid compound concentration gradient of 300 to 500 mg / L or a COD concentration gradient of 500 to 1000 mg / L, with 80% of the water replaced each batch, until the influent load reaches the target influent sulfonic acid compound concentration of 1000 mg / L or the COD concentration of 3000 to 5000 mg / L.

[0020] Microbial deposit information of Microbacterium esteraromaticum:

[0021] Deposit date: July 25, 2024

[0022] Name of depository: China National Microbiological Culture Collection Administration General Microbiology Center

[0023] Deposit number: CGMCC NO.31455

[0024] Address of the depository: No. 3, Yard 1, Beichen West Road, Chaoyang District, Beijing

[0025] Classification name: Microbacterium esteraromaticum

[0026] The DNA sequence is shown in SEQ ID NO.1:

[0027] ggctcaggat gaacgctggc ggcgtgctta acacatgcaa gtcgaacgat gaagcccagc 60

[0028] ttgctgggtg gattagtggc gaacgggtga gtaacacgtg agcaacctgc ccctgactct 120

[0029] gggataagcg ctggaaacgg cgtctaatac tggatatgtc ccgtcaccgc atggtgtgcg 180

[0030] ggtggaaaga tttttcggtt ggggatgggc tcgcggccta tcagcttgtt ggtgaggtaa 240

[0031] tggctcacca aggcgtcgac gggtagccgg cctgagaggg tgaccggcca cactgggact 300

[0032] gagacacggc ccagactcct acgggaggca gcagtgggga atattgcaca atgggcggaa 360

[0033] gcctgatgca gcaacgccgc gtgagggatg acggccttcg ggttgtaaac ctcttttagc 420

[0034] agggaagaag cgagagtgac ggtacctgca gaaaaagcac cggctaacta cgtgccagca 480

[0035] gccgcggtaa tacgtagggt gcaagcgtta tccggaatta ttgggcgtaa agagctcgta 540

[0036] ggcggtctgt cgcgtctgct gtgaaatccc gaggctcaac ctcgggcttg cagtgggtac 600

[0037] gggcagacta gagtgcggta ggggagattg gaattcctgg tgtagcggtg gaatgcgcag 660

[0038] atatcaggag gaacaccgat ggcgaaggca gatctctggg ccgtaactga cgctgaggag 720

[0039] cgaaagggtg gggagcaaac aggcttagat accctggtag tccaccccgt aaacgttggg 780

[0040] aactagttgt ggggtccttt ccacggattc cgtgacgcag ctaacgcatt aagttccccg 840

[0041] cctggggagt acggccgcaa ggctaaaact caaaggaatt gacggggacc cgcacaagcg 900

[0042] gcggagcatg cggattaatt cgatgcaacg cgaagaacct taccaaggct tgacatacac 960

[0043] gagaacgggc cagaaatggt caactctttg gacactcgtg aacaggtggt gcatggttgt1020

[0044] cgtcagctcg tgtcgtgaga tgttgggtta agtcccgcaa cgagcgcaac cctcgttcta1080

[0045] tgttgccagc acgtaatggt gggaactcat gggatactgc cggggtcaac tcggaggaag1140

[0046] gtggggatga cgtcaaatca tcatgcccct tatgtcttgg gcttcacgca tgctacaatg1200

[0047] gccggtacaa tgggctgcga taccgtaagg tggagcgaat cccaaaaagc cggtcccagt1260

[0048] tcggattgag gtctgcaact cgacctcatg aagtcggagt cgctagtaat cgcagatcag1320

[0049] caacgctgcg gtgaatacgt tcccgggtct tgtacacacc gcccgtcaag tcatgaaagt1380

[0050] cggtaacacc tgaagccggt ggcctaaccc cttgtgggag ggagctgtcg aaggtggggat1440

[0051] cggtaattag gactaagtcg t 1461

[0052] The beneficial effects of the present invention compared with the prior art are:

[0053] 1. The present invention can treat sulfonic acid compound wastewater by a fully biological method, with good effect, low cost and no secondary pollution.

[0054] 2. The sulfonic acid compound degrading bacteria used in the present invention are formulated according to a unique exclusive degradation bacteria formula and can treat sulfonic acid compound wastewater. When the sulfonic acid compound concentration is 1000 mg / L, it can be efficiently biodegraded, and the organic matter degradation rate is higher than 90%.

[0055] 3. In the treatment method of the present invention, the wastewater is sequentially activated and cultured by solid bacteria for degradation of sulfonic acid compounds-wastewater biological treatment. The process is simple to operate and has efficient reaction, and can degrade sulfonic acid compounds. The sulfonic acid compound degradation bacterial agent in the present invention is a microbial agent prepared by Microbacterium esteraromaticum, which was deposited in the General Microbiological Center of the China Microbiological Culture Collection Administration Committee on July 25, 2024. The present invention can treat sulfonic acid compound wastewaters such as o-cresol sulfonic acid, sodium p-toluenesulfonate or sodium dodecylbenzenesulfonate with an influent sulfonic acid compound concentration of 1000 mg / L. The method of the present invention is a biological enhancement of the ordinary biological method, which broadens the scope of application of biological treatment of sulfonic acid compound wastewater. BRIEF DESCRIPTION OF THE DRAWINGS

[0056] Figure 1This is the colony morphology of Microbacterium esteraromaticum of the present invention. DETAILED DESCRIPTION

[0057] In order to make the purpose, technical solution and effect of the present invention clearer and more specific, the present invention is further described in detail by enumerating examples below. It should be noted that the specific implementation described here is only used to explain the present invention and is not used to limit the present invention.

[0058] A biological treatment method for sulfonic acid compound wastewater, characterized in that in the treatment method, the wastewater is sequentially activated and cultured with sulfonic acid compound degrading solid bacteria → biological treatment of wastewater, and the specific implementation scheme is as follows:

[0059] 1-5% sulfonic acid compound degrading bacteria, 1-1.5 g / L glucose, tap water, pH 7-8 are added, and the bacteria are activated by aeration (DO 2-4 mg / L) at 25-35° C. in a bacterial culture tank for 48 hours; the sulfonic acid compound degrading bacteria are microbial agents prepared from Microbacterium esters.

[0060] After the activation of the strain, the bacterial density was tested and the microscopic examination showed that it reached 1×10 9 CFU / mL is the completion of activation culture.

[0061] Adjust the pH of the wastewater to 7-8, the initial influent sulfonic acid compound concentration of the system is less than 500 mg / L, or the COD is less than 2000 mg / L, add 300-500 mg / LCOD equivalent carbon source every day for 3 days before the system is started, and no carbon source is added after 3 days; when the COD degradation rate is greater than 85%, the water is fed at a stable load for 5-10 days, and then the load is increased by a gradient of sulfonic acid compound concentration of 300-500 mg / L or COD500-1000 mg / L, with COD given priority, and 80% of the water is replaced each batch until the influent load reaches the target influent sulfonic acid compound concentration; the full load influent sulfonic acid compound concentration can reach 1000 mg / L or the COD concentration is 3000-5000 mg / L.

[0062] The implementation method of organic sulfonic acid compound degrading bacteria and polyurethane filler immobilization is as follows: the activated bacterial solution of organic sulfonic acid compound degrading bacteria is added into a reaction tank filled with 50-70% polyurethane filler in 2-3 batches at a dosage of 10%, and aerated culture is carried out at 25-35°C, and the residence time is controlled to be 48-72h.

[0063] The biological treatment process of organic sulfonic acid compounds can adopt aerobic biochemical process; sulfonic acid compound degradation bacteria and 50-70% polyurethane filler are inoculated in the aerobic reaction tank. The hydraulic retention time is: when the influent sulfonic acid compound concentration is 300-500 mg / L, HRT is 24-48h; when the influent sulfonic acid compound concentration is 500-1000 mg / L, HRT is 48-72h.

[0064] The following specific examples are given to describe the application of the biological treatment method for organic sulfonic acid compound wastewater: The experimental methods in the following embodiments, unless otherwise specified, are carried out in accordance with the technical conditions provided by the present invention.

[0065] The activation method of the solid bacterial agent of sulfonic acid compound degrading bacteria in the following embodiments is: adding 1‰ sulfonic acid compound degrading bacteria, 0.5g / L glucose, tap water, pH7-8, aeration culture at 25-35°C for 48h to activate the bacteria, DO2-4mg / L, to form an activated bacterial solution.

[0066] Example 1, o-cresol sulfonic acid biological treatment

[0067] The COD of wastewater from a certain project was 3100 mg / L, of which the concentration of o-cresol sulfonic acid was 1050 mg / L. 50% polyurethane filler was immobilized in the aerobic biological treatment pool and 5% sulfonic acid compound degrading bacteria were inoculated to activate the bacterial solution. The HRT was 72h. After 18 days of operation, the effluent was stable, with an effluent COD of 160-200 mg / L and a COD degradation rate of 94%. No sulfonic acid groups were detected by the colorimetric method.

[0068] Example 2: Sodium p-toluenesulfonate biological treatment

[0069] The COD of wastewater from a certain project was 3600 mg / L, of which the concentration of sodium p-toluenesulfonate was 980 mg / L. The aerobic biological treatment pool was immobilized with 50% polyurethane filler and inoculated with 5% sulfonic acid compound-degrading bacteria. The HRT was 48h. After 13 days of operation, the effluent was stable, with an effluent COD of 150-170 mg / L and a COD degradation rate of 95%. No sulfonic acid groups were detected by the colorimetric method.

[0070] Example 3: Biological treatment of sodium dodecylbenzene sulfonate

[0071] The COD of wastewater from a certain project was 4800 mg / L, of which sodium dodecylbenzene sulfonate was 1000 mg / L. 50% polyurethane filler was immobilized in the aerobic biological treatment pool and 5% sulfonic acid compound degradation bacteria were inoculated. The HRT was 72h. After 20 days of operation, the effluent was stable, with an effluent COD of 230-310 mg / L and a COD degradation rate of 93-95%. No sulfonic acid groups were detected by the colorimetric method.

[0072] The above description is only a preferred embodiment of the present invention. It should be pointed out that a person skilled in the art can make several improvements without departing from the principle of the present invention, and these improvements should also be regarded as within the protection scope of the present invention.

Claims

1. A Microbacterium esteraromaticum, characterized in that: It is deposited in the General Microbiology Center of China Microorganism Culture Collection Administration, with the deposit number: CGMCC NO.31455 and the deposit date of July 25, 2024.

2. The biological treatment method for sulfonic acid compound wastewater according to claim 1, characterized in that: A microbial agent for solid-degrading bacteria that produces sulfonic acid compounds prepared by Microbacterium esterificum.

3. A biological treatment method for sulfonic acid compound wastewater, characterized in that: Microbacterium esters is prepared into a sulfonic acid compound degradation bacterial agent, and then the sulfonic acid compound wastewater is treated by a biological treatment method. The specific steps are: Step 1: Activation and cultivation of sulfonic acid compound-degrading bacteria: Add 1-5‰ solid bacterial agent of sulfonic acid compound degradation bacteria, 0.5-1.5g / L glucose, tap water, add dilute sulfuric acid or liquid alkali to adjust the pH to 7-8, and culture in a culture expansion tank at 25-35℃ for 48h to activate the bacteria, DO2-4mg / L; after the bacteria are activated, the bacterial density is detected under a microscope, and the bacterial density reaches 1×10 9 CFU / mL is the completion of activation culture, and the activated bacterial solution of sulfonic acid compound-degrading bacteria after activation culture is obtained; Step 2: Biological treatment of wastewater: The pH of the wastewater containing sulfonic acid compounds is adjusted to 7-8, and passed into a biological treatment tank for biological treatment. The biological treatment tank is added with 10% activated bacterial solution of sulfonic acid compound-degrading bacteria after activation and cultivation in the above step 1, and the sulfonic acid compound-degrading bacteria are immobilized on a polyurethane filler. The wastewater can treat sulfonic acid compound concentrations of up to 1000 mg / L or COD concentrations of 3000-5000 mg / L.

4. The biological treatment method for sulfonic acid compound wastewater according to claim 3, characterized in that: The step 2 is specifically as follows: 2.

1. The wastewater containing sulfonic acid groups adjusted to pH 7-8 is passed into the biological treatment tank, the temperature is controlled at 25-35°C, the reaction time and dissolved oxygen are controlled, 10% activated cultured sulfonic acid compound degrading bacteria liquid is added to the biological treatment tank, and the sulfonic acid compound degrading bacteria are immobilized on the polyurethane filler; 2.

2. When the biological treatment system is started, the concentration of sulfonic acid compounds in the influent is less than 500 mg / L, or the COD is less than 2000 mg / L. During the first 1 to 3 days of the system startup, 300 to 500 mg / LCOD equivalent carbon source is added every day, and no carbon source is added after 3 days; 2.

3. Load increase and full load: Increase the load in a gradient from 300 to 500 mg / L of sulfonic acid compound concentration or from 500 to 1000 mg / L of COD, with COD given priority. Replace 80% of the water in each batch until the influent load reaches the target influent sulfonic acid compound concentration. The full load influent sulfonic acid compound concentration can reach 1000 mg / L or the COD concentration can reach 3000 to 5000 mg / L.

5. The biological treatment method for sulfonic acid compound wastewater according to claim 4, characterized in that: The solid bacterial agent for degrading sulfonic acid compounds is added in 2 to 3 batches at a dosage of 10% activated bacterial solution into a reaction tank filled with 50 to 70% polyurethane filler and aerated for 48 to 72 hours to solidify the bacteria; the amount of tap water is added according to the proportion of the solid bacterial agent for degrading sulfonic acid compounds, 1 kg of solid bacterial agent corresponds to 1 t of tap water.

6. The biological treatment method for sulfonic acid compound wastewater according to claim 4, characterized in that: The hydraulic retention time (HRT) of wastewater biological treatment is 300-500 mg / L. HRT 24 ~ 48h; influent sulfonic acid compound concentration is 500 ~ 1000mg / L, HRT 48 ~ 72h.

7. The biological treatment method for sulfonic acid compound wastewater according to claim 4, characterized in that: The biological treatment in step 2 adopts an aerobic process, the dissolved oxygen (DO) is 2-4 mg / L, and the reaction temperature is 25-35°C.

8. The biological treatment method for sulfonic acid compound wastewater according to claim 4, characterized in that: When the system is started up and the biological treatment is conducted in a biological treatment pool, the concentration of sulfonic acid compounds in the influent is less than 500 mg / L, or the COD is less than 2000 mg / L. On the first to third days after the system is started up, 300 to 500 mg / LCOD equivalent carbon source is added every day, and no carbon source is added after three days. The water is increased in a gradient from 300 to 500 mg / L of sulfonic acid compound concentration or from 500 to 1000 mg / L of COD, with COD being given priority. 80% of the water is replaced each batch until the influent load reaches the target influent sulfonic acid compound concentration. The influent sulfonic acid compound concentration at full load can reach 1000 mg / L or the COD concentration is 3000 to 5000 mg / L.

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