阅读说明：本技术 钝化除臭药剂环保性能评价及其废液处理方法 (Environment-friendly performance evaluation of passivation deodorizing agent and waste liquid treatment method thereof ) 是由 马和旭 程彬彬 程晓东 宫超 王刚 陈明翔 江龙武 程梦婷 于 2020-05-20 设计创作，主要内容包括：本发明提供了一种钝化除臭药剂环保性能评价方法,通过对药剂进行污染因子剖析,有机物去除效率评价,硝化效率评价以及细胞活力评价,对钝化除臭药剂进行分析,以指导企业对药剂进行合理选择。同时本发明还提供了所选择药剂废液的处理方法,根据对药剂的分析选择环保型药剂或一般型药剂,避开非环保型药剂,以使其废液可通过处理达到排放标准。并给出了相应的废液处理方法,使得处理过程更优,更经济。本发明为企业在药剂的选择使用及后续废液处理上提供了有力的技术支持。(The invention provides an environmental protection performance evaluation method for a passivation and deodorization medicament, which analyzes the passivation and deodorization medicament by analyzing a pollution factor of the medicament, evaluating the removal efficiency of organic matters, evaluating the nitrification efficiency and evaluating the cell activity so as to guide an enterprise to reasonably select the medicament. The invention also provides a method for treating the waste liquid of the selected medicament, which selects the environment-friendly medicament or the general medicament according to the analysis of the medicament and avoids the non-environment-friendly medicament so that the waste liquid can reach the discharge standard through treatment. And a corresponding waste liquid treatment method is provided, so that the treatment process is more excellent and more economic. The invention provides powerful technical support for the selection and the use of medicaments and the subsequent waste liquid treatment for enterprises.)

1. A method for evaluating the environmental protection performance of a passivation deodorizing agent is characterized by comprising the following steps:

s1 pollution factor analysis for inspecting the concentration of each pollution factor in the passivation and deodorization medicament, including water quality analysis and metal ion analysis, and dividing the pollution factors into good and bad according to the analysis result of the metal ion;

s2, evaluating the removal efficiency of organic matters, inspecting the COD removal rate before and after the activated sludge reaction, and classifying the COD removal rate into good and poor according to the COD removal rate result;

s3 nitration efficiency evaluation for investigating the ammonia nitrogen removal rate before and after nitration reaction, and dividing the ammonia nitrogen removal rate into a good type and a bad type according to the ammonia nitrogen removal rate result;

and S4 cell viability evaluation for inspecting the survival and death number of the nitrifying bacteria cells, calculating the living cell rate, and classifying the living cell rate into a good type and a poor type according to the living cell rate result.

2. The evaluation method according to claim 1, further comprising:

s5, classifying the passivation and deodorization agents, wherein the classification process comprises the following steps: if the results of pollution factor analysis, S2 organic matter removal efficiency evaluation, S3 nitrification efficiency evaluation and S4 cell viability evaluation in S1 are all good, the passivation and deodorization medicament is an environment-friendly passivation and deodorization medicament; if the analysis result of the pollution factors in the S1 is poor, or the results of the S2 organic matter removal efficiency evaluation, the S3 nitrification efficiency evaluation and the S4 cell viability evaluation are all poor, the medicament is a non-environment-friendly medicament; the rest is general type passivation deodorant.

3. The evaluation method according to claim 1 or 2, wherein the water quality analysis in step S1 includes general water pollutant items with emission limits and organic nitrogen, total phosphorus, ORP, TOC, TC analysis indexes.

4. The evaluation method according to claim 1 or 2, wherein the evaluation of the removal efficiency of S2 organic substances is carried out by shaking table shaking method under the following test conditions: the temperature is 15-30 ℃, the rotating speed is 100-200 rpm, and the reaction time is 24-96 h; the adding amount of activated sludge MLSS is 5000-20000 mg/L, and the ratio of sludge MLVSS to MLSS is 0.5-0.8; the adding concentration of the medicament is 500 mg/L-2000 mg/L calculated by COD.

5. The method according to claim 1 or 2, wherein the COD removal rate in S2 is determined by taking 60% of the blank removal rate as a reference standard, and is higher than 60% of the blank removal rate, so that the evaluation result of the organic matter removal efficiency is good, otherwise, the evaluation result is poor.

6. The method according to claim 1 or 2, wherein the nitrification efficiency in S3 is evaluated by shaking table shaking under the following test conditions: the temperature is 25-35 ℃, the rotating speed is 100-200 rpm, and the reaction time is 2-24 h.

7. The evaluation method according to claim 1 or 2, wherein the nitrification efficiency is determined by taking 60% of the removal rate of the blank sample as a reference standard, and is higher than 60% of the removal rate of the blank sample, so that the nitrification efficiency evaluation result is good, otherwise, the nitrification efficiency evaluation result is poor.

8. The method according to claim 1 or 2, wherein the evaluation of cell viability in S4 is based on the evaluation of nitrification efficiency, and the cell viability is evaluated to be good if the viable cell rate is higher than 45% and poor if the viable cell rate is lower than 45% by comparing the survival and death numbers of nitrifying bacteria cells.

9. The method according to claim 1 or 2, wherein the cell viability evaluation procedure in S4 is:

a. preparing trypan blue mother liquor:

b. preparing a cell suspension;

c. and (3) slice making and dyeing: uniformly mixing the cell suspension with trypan blue solution with the mass fraction of 0.1% -0.8% in a volume ratio of 7: 1-10: 1;

d. microscopic observation: dead cells were stained visibly blue, while live cells were colorless and transparent;

e. cell counting: live and dead cells were counted separately within 3 minutes;

f. counting the cell viability: the viable cell rate (%) = the number of viable cells/the total number of cells × 100%.

10. A method for treating waste liquid of a passivation and deodorization medicament is characterized by comprising the following steps:

s6, deodorizing by using the environment-friendly passivation and deodorization agent or the general passivation and deodorization agent as described in any one of claims 2 to 9 to obtain waste liquid of the environment-friendly passivation and deodorization agent or the general passivation and deodorization agent;

s7, performing demulsification flocculation, oil separation, air flotation and two-stage biochemistry on the waste liquid of the environment-friendly passivation and deodorization agent, wherein the two-stage biochemistry is primary A/O biochemistry and secondary BAF biochemistry;

s8 for the treatment of general type waste liquid of deactivating and deodorizing agent, a hydrolysis acidification unit is added before the first-stage A/O biochemical treatment in the step S7, and a high-stage oxidation unit is added before the second-stage BAF biochemical treatment.

11. The process of claim 10, wherein a post-phosphorus removal unit is added after the secondary BAF biochemical treatment if the total phosphorus concentration is higher than 1 mg/L.

12. The method according to claim 10, wherein the advanced oxidation in S8 includes two types, ozone catalytic oxidation and/or hypochlorous acid advanced oxidation, and the residence time of ozone catalytic oxidation and/or hypochlorous acid advanced oxidation is 1-8 h.

13. The treatment method of claim 10, wherein the demulsification flocculation is carried out by adding a demulsifying agent, polyaluminium chloride and polyacrylamide into water, stirring and mixing, and then adding into a regulating reservoir together with the waste liquid; based on the volume of the waste liquid, the dosage of the demulsifier is 10 mg/L-200 mg/L, the dosage of the polyaluminium chloride is 20 mg/L-300 mg/L, and the dosage of the polyacrylamide is 3 mg/L-20 mg/L.

14. The treatment method according to claim 10, wherein the air flotation is a two-stage air flotation, one stage is a cavitation air flotation, and the second stage is a dissolved air pressurization air flotation.

15. The process according to claim 10, characterized in that the hydrolytic acidification residence time is comprised between 6 and 20 hours.

16. The process of claim 10, wherein the A/O biochemical treatment comprises an aerobic section and an anoxic section, wherein the aerobic section is in front of the anoxic section, the anoxic section is behind the aerobic section, the residence time of the aerobic section is 20-40 h, and the anoxic section is 3-10 h.

17. The process of claim 10, wherein the secondary BAF biochemical residence time is 4 to 24 hours.

18. The treatment method of claim 11, wherein the post-dephosphorization treatment unit comprises two-stage dephosphorization, and 34mg/L to 980mg/L ferric chloride and 10mg/L to 700mg/L calcium hydroxide are added in the first-stage dephosphorization; and adding 10-300 mg/L ferric chloride and 4-200 mg/L calcium hydroxide into the secondary phosphorus removal.

Technical Field

The invention relates to an environmental protection performance evaluation method of a passivation deodorizing agent and a waste liquid treatment method thereof, belonging to the technical field of environmental protection.

Background

The medicament wastewater generated by passivation and deodorization is always a great problem in the shutdown and overhaul period of a refinery plant, and due to the characteristics of high COD (chemical oxygen demand), high organic nitrogen, high organic phosphorus, complex chemical components, difficult biodegradation and the like, a sewage treatment field is easy to impact, the effluent of the sewage treatment field in a light person is not up to standard, the active sludge is poisoned or dead in a severe person, and the biological activity in a short period is difficult to recover. Moreover, petroleum and chemical plants increasingly use high-sulfur crude oil (containing more than 1% of sulfur), the quality is increasingly poor, the requirements on safety and environmental protection are increasingly high, more devices are inevitably used for passivation and deodorization operation during shutdown and maintenance, and the passivation and deodorization agents in the current market are various, so that the selection of the environment-friendly, pollution-free and biodegradable 'green' passivation and deodorization agent becomes vital.

CN201210077149 provides a deodorizing and passivating double-effect cleaning agent for oil refining devices, wherein hydroxy phosphonic acid compounds of a deodorant are preferably hydroxy ethylidene diphosphonic acid (HEDP), and HEDP has stable properties and is not easy to decompose under common conditions, especially, C-P chemical bonds are very firm and difficult to biochemically treat, and COD and total phosphorus exceed standards. The chemical often appears in circulating water agents, the concentration of the chemical is 1-10 mg/L as a scale inhibitor, the concentration of the chemical is 10-50 mg/L as a corrosion inhibitor, and the concentration of the chemical as a cleaning agent is up to 1000-2000 mg/L, aiming at the wastewater, Huckgwang of Hunan Tan university adopts more complicated treatment means such as scrap iron micro-electrolysis, Fenton oxidation, sodium hypochlorite oxidation and the like in the experimental research on the treatment process of the HEDP pre-copper plating wastewater. In addition, the passivator and the active component of the medicament both adopt tetramethylolsulfuric acid (THPS), and the evaluation of THPS green performance by Xinqing of Wuhan university indicates that THPS belongs to environment-friendly green biocide at low concentration, has good biodegradability, but has obvious inhibition effect on organisms in sewage when the concentration exceeds 10mg/L, and plays a role of biocide. Therefore, the deodorizing and passivating double-effect cleaning agent provided by CN201210077149 is safe and convenient without heating, meets the discharge standard that COD is less than or equal to 1300mg/L after compound treatment, but cannot ensure that no influence is generated on biochemical units of a sewage treatment field, and particularly does not contain advanced oxidation units.

CN 20121039460 discloses a ferrous sulfide passivating cleaning agent, which comprises: sodium bicarbonate, sodium hypochlorite, tetrasodium ethylene diamine tetraacetate (EDTA-tetrasodium), potassium ferrate, surfactant and water, which are novel efficient multifunctional passivation treating agents integrating oxidation, adsorption, coagulation aiding, sterilization, disinsection and deodorization, but the used tetrasodium ethylene diamine tetraacetate (EDTA-tetrasodium) has poor biodegradability, and at present, the EDTA is limited to use in some washing products according to the national regulations of the European Union because of the environmental protection problem; the chemical is added with about 1.5 percent of sodium dodecyl benzene sulfonate by mass fraction, the chemical is controversial internationally, wherein branched AES has poor biodegradability and is forbidden by many countries, linear LAS has good biodegradability, but the foaming phenomenon of water caused by the branched AES affects the reoxygenation rate and the oxygenation degree of the water, and finally the activity of microorganisms is affected; the Alkylphenol Polyoxyethylene Ether (APE) with the mass fraction of about 0.5 percent is added into the medicament, the biodegradation of the APE is poor, the use of the APE is forbidden or limited in many countries and regions, and the use of the APE is forbidden in Chinese washing powder national standard GB/T13171-2004.

CN201910314143 discloses a passivation deodorizing cleaning agent suitable for sulfur-containing gas fields, which comprises potassium ferrate, hydrogen peroxide, N-methyldiethanolamine, 1- (2-aminoethyl) -2-benzyl-imidazoline quaternary ammonium salt, isothiazolinone, amino trimethylene phosphonic acid and water. Wherein the N-Methyldiethanolamine (MDEA) is a difficultly degradable organic compound; the amino trimethylene phosphonic Acid (ATP), the 1- (2-aminoethyl) -2-benzyl-imidazoline quaternary ammonium salt and the isothiazolinone have weak degradation capability and need long-term domestication, and in addition, the three substances are rich in organic nitrogen and organic phosphorus, so that the exceeding of the total nitrogen and the total phosphorus in a sewage treatment plant is easily caused.

CN201610712970 discloses an environment-friendly high-efficiency ferrous sulfide passivator. The preparation process of the detergent is characterized in that more than ten chemicals are added, wherein the added disodium ethylene diamine tetraacetate (EDTA-disodium) is very poor in biodegradability like tetrasodium ethylene diamine tetraacetate (EDTA-tetrasodium) in patent CN 20121039460, and some countries of European Union such as Switzerland washing product associations of the countries of European Union have already passed a decision, do not allow washing products to contain EDTA components, and are mainly worried about the problem of environmental hazard after a large amount of EDTA components are used and discharged; sulfonated lignin added into the corrosion inhibitor is proved to be good in the paper of lignin biodegradation and application research progress, and the lignin biodegradation is always a hot spot and a difficult problem in the world research.

At present, passivation deodorizing agents sold on the market are various in types and complex in components, and some environment-friendly agents emerge with the improvement of the environment-friendly concept, but only a plurality of environment-friendly components are added in the agent formula, so that the biodegradability and the standard discharge are not elaborated in the field of wastewater treatment. From the prior patents, the environment-friendly medicament has the defects of more or less components which are difficult to biodegrade, rich organic nitrogen and rich organic phosphorus.

As mentioned above, the passivation deodorant in the market is various in types, different in chemical components and structures, and the deodorizing function of the passivation deodorant is considered more by the medicament, so that the damage to the environment is ignored, and the means and the method for subsequent environmental protection treatment are not considered. Many passivation deodorants have the defects of more components difficult to biodegrade, more organic nitrogen and more organic phosphorus, and a reasonable and effective judgment method aiming at the agent is lacked. At present, an application enterprise of the passivation deodorant is lack of cognition on medicament wastewater generated by passivation and deodorization operation. Or the sewage is discharged to a sewage treatment field or is blindly put into a tank for caching, the former is easy to cause serious impact on the sewage treatment field, and the latter occupies the tank capacity for a long time, so that the method is not a fundamental method for solving the problem.

Disclosure of Invention

Aiming at the defects of the prior art, the first purpose of the invention is to provide an environmental protection performance evaluation method for a passivation and deodorization medicament, which is used for representing the biodegradation capacity of the passivation and deodorization medicament and the harm to water microorganisms so as to provide guidance for enterprises in selecting the passivation and deodorization medicament. Meanwhile, the invention also aims to provide a method for treating waste liquid according to the evaluation result of the passivation deodorizing agent.

The invention provides a method for evaluating the environmental protection performance of a passivation deodorizing agent, which comprises the following steps:

s1 pollution factor analysis for inspecting the concentration of each pollution factor in the passivation and deodorization medicament, including water quality analysis and metal ion analysis, and dividing the pollution factors into good and bad according to the analysis result of the metal ion;

s2, evaluating the removal efficiency of organic matters, inspecting the COD removal rate before and after the activated sludge reaction, and classifying the COD removal rate into good and poor according to the COD removal rate result;

s3 nitration efficiency evaluation for investigating the ammonia nitrogen removal rate before and after nitration reaction, and dividing the ammonia nitrogen removal rate into a good type and a bad type according to the ammonia nitrogen removal rate result;

and S4 cell viability evaluation for inspecting the survival and death number of the nitrifying bacteria cells, calculating the living cell rate, and classifying the living cell rate into a good type and a poor type according to the living cell rate result.

The evaluation method further comprises the following steps:

s5, classifying the passivation and deodorization agents by the following method: if the results of pollution factor analysis, S2 organic matter removal efficiency evaluation, S3 nitrification efficiency evaluation and S4 cell viability evaluation in S1 are all good, the passivation and deodorization medicament is an environment-friendly passivation and deodorization medicament; if the analysis result of the pollution factors in the S1 is poor, or the results of the S2 organic matter removal efficiency evaluation, the S3 nitrification efficiency evaluation and the S4 cell viability evaluation are all poor, the medicament is a non-environment-friendly medicament; the rest is general type passivation deodorant.

And S1, analyzing the metal ions by adopting microwave digestion/inductively coupled plasma mass spectrometry.

The metal ion analysis focuses on the concentration of heavy metals such as manganese, chromium, lead, arsenic, mercury, and the like, which have emission limits or high biotoxicity. If the concentration of the heavy metal with the emission limit exceeds the standard, the evaluation result is poor, otherwise, the evaluation result is good.

The water quality analysis includes a conventional water contaminant project with emission limits and other contaminant projects. The conventional water pollutant items with emission limits include pH, COD, BOD₅Ammonia nitrogen, total nitrogen, salt content, conductivity, nitrate nitrogen, sulfide and the like; the other water contaminant items include organic nitrogen, total phosphorus, ORP, TOC, TC, and the like.

The organic nitrogen, the total phosphorus and the ORP are pollutant items which are very easy to ignore in water quality analysis, and the fact that the organic nitrogen or the total phosphorus are too high means that the passivation deodorant contains a large amount of organic matters containing nitrogen and phosphorus, and the organic matters are generally complex in structure and difficult to biodegrade; if the ORP value is high, the passivation deodorant contains a large amount of oxidant, and if the passivation operation is incomplete, the high ORP can generate a biocidal effect on microorganisms in a biochemical unit; the TOC and TC are also important indexes of the water quality analysis of the invention, and it has been found that individual organic compounds can be detected by the TOC and TC, but the COD is zero by a potassium dichromate method, such as strong filter, which is often found in a passivation deodorant as an efficient oxidant.

If the concentration of pollution factors such as ammonia nitrogen, organic nitrogen, total phosphorus and the like is high, the biochemical performance evaluation is focused, and advanced oxidation and postpositive phosphorus removal are added in the waste liquid treatment method with poor biochemical performance.

S2, the organic matter removal efficiency evaluation is that the passivation and deodorization agent is prepared into wastewater with corresponding proportion, and the removal rate of COD before and after the reaction is inspected by an activated sludge method.

The shaking table oscillation method is adopted in the organic matter removal efficiency evaluation test. The operation method comprises the following steps: selecting a specially-made conical bottle of a shaker, firstly determining the volume of a prepared solution, wherein the volume of the prepared solution should not exceed the capacity 2/3 of the conical bottle, then determining the adding amount of activated sludge, a diluting solution and a medicament by calculation, then adding the activated sludge and the diluting solution into the conical bottle, then adding the medicament, quickly adjusting the pH to 6-9, and adding a carbon source, a nitrogen source and a phosphorus source into part of samples as supplements. Meanwhile, a blank test is set, namely, no medicament is added, and nutrients are supplemented. And standing the prepared sample, taking a small amount of supernatant, filtering the supernatant by using filter paper, measuring COD (chemical oxygen demand), then placing the supernatant into a shaker oscillator, and carrying out oscillation reaction according to set temperature, time and rotating speed. After the reaction is finished, the mixture is also kept stand, a small amount of supernatant is taken and filtered by filter paper, and then COD is measured and compared with indexes before the reaction.

The shaking table oscillation method test conditions are as follows: the temperature is 15-30 ℃, the rotating speed is 100-200 rpm (revolutions per minute), and the reaction time is 24-96 hours; the adding amount of the activated sludge is controlled to be 5000-20000 mg/L of MLSS, and the ratio of MLVSS to MLSS of the sludge is 0.5-0.8; the adding concentration of the medicament is 500 mg/L-2000 mg/L (calculated by COD). The COD of the pure passivator can be zero, and nutrients are required to be supplemented, wherein a carbon source is glucose, a nitrogen source is urea or ammonium chloride, and a phosphorus source is monopotassium phosphate or dipotassium phosphate; the diluted solution adopts distilled water or deionized water; the alkaline pH regulator adopts sodium hydroxide or potassium hydroxide, and the acidic pH regulator adopts sulfuric acid or hydrochloric acid.

The COD removal rate is 60 percent of the blank sample removal rate as a reference standard, and is higher than 60 percent of the blank sample removal rate, the evaluation result of the organic matter removal efficiency is good, otherwise, the evaluation result is poor; the blank sample is glucose solution with the same concentration.

The nitrification efficiency in S3 refers to the ammonia nitrogen degradation amount of unit sludge in unit time, the nitrification efficiency evaluation also adopts a shaking table oscillation method, and the operation is simply expressed as follows: selecting a special conical flask, determining the volume of a reaction solution, and inoculating a nitrifying bacteria agent, wherein the inoculation amount is 10-30% of the reaction volume; diluting the medicament by 1-100 times with distilled water, adding the medicament into a conical flask to a scale mark (the controlled volume corresponds to the scale mark), and setting a blank sample, wherein the blank sample is not added with the medicament and is replaced by the distilled water; adding a certain amount of ammonium chloride or urea, and controlling the initial concentration of ammonia nitrogen to be 30-100 mg/L; adjusting the initial pH of the reaction system to be about 7.5-8.5 by using sodium bicarbonate, and properly supplementing the alkalinity by using the sodium bicarbonate in the test process; the prepared erlenmeyer flask is put into a shaker. The test conditions were: the temperature is 25-35 ℃, the rotating speed is 100-200 rpm (revolutions per minute), and the reaction time is 2-24 h; and measuring pH and ammonia nitrogen after the reaction is finished, and comparing the measured pH and ammonia nitrogen with indexes before the reaction to obtain the ammonia nitrogen removal rate, namely the nitration efficiency. And the nitrification efficiency evaluation is that the single nitrifying bacteria is adopted to investigate the ammonia nitrogen removal rate before and after the medicament is prepared into the wastewater nitrification reaction. The nitration efficiency takes 60% of the removal rate of the blank sample as a reference standard, and is higher than 60% of the removal rate of the blank sample, so the nitration efficiency evaluation result is good, otherwise, the nitration efficiency evaluation result is poor.

The nitrifying bacteria used for evaluation are different from decarbonizing microorganisms (bacteria, actinomycetes and fungi) in various types and strong in adaptability, are very sensitive to the external environment and the water quality of a water body, show obvious difference in nitrification rate for different types of passivation and deodorization agents with different concentrations, and are very suitable for representing the biological toxicity of the agent wastewater. Further, the nitrifying agent is preferably the nitrifying agent used in the embodiment of patent CN201010510855, and additionally, the novacin biological synergist 5805 (product code 7579190-.

The evaluation of cell viability described in S4 was based on the evaluation of nitrification efficiency, and the survival and death numbers of nitrifying bacterial cells were compared. If the living cell rate is higher than 45%, the cell viability evaluation result is good, and if the living cell rate is lower than 45%, the cell viability evaluation result is poor.

Because the deodorizing and passivating agents with different types and different concentrations have different influence degrees on nitrifying bacteria and different dead and alive numbers of cells, the biological toxicity of the agent wastewater on microorganisms represented by the nitrifying bacteria can be further characterized on a microscopic level. The cell viability evaluation adopts a staining elimination method, and the action mechanism is as follows: many acid dyes do not easily penetrate the plasma membrane of living cells into cells, but can penetrate dead cells to stain them, thereby identifying dead and living cells; trypan blue is a commonly used cell reactive dye, and is commonly used in assays for detecting the integrity of cell membranes and cell viability, where live cells are not stained blue, while dead cells are stained pale blue.

The cell viability evaluation operation method is simply expressed as follows:

a. preparing trypan blue mother liquor:

b. preparing a cell suspension;

c. and (3) slice making and dyeing: uniformly mixing the cell suspension with trypan blue solution with the mass fraction of 0.1% -0.8% in a volume ratio of 7: 1-10: 1;

d. microscopic observation: dead cells were stained visibly blue, while live cells were colorless and transparent;

e. cell counting: live and dead cells were counted separately within 3 minutes;

f. counting the cell viability: the viable cell rate (%) = the number of viable cells/the total number of cells × 100%.

The process for preparing the trypan blue mother solution in the step a comprises the following steps: weighing 2-8 g of trypan blue, adding double distilled water for grinding, then adding 100mL of distilled water, filtering by using filter paper, and storing at 2-6 ℃. When in use, the solution is diluted to 0.1 to 0.8 percent by PBS (phosphate buffered saline); the PBS buffer is one of buffers commonly used in biological laboratories, and has no specific formula. The invention provides a formula for reference, namely, 8.0g of NaCl, 0.2g of KCl and Na₂HPO₄·H₂O 1.56g ,KH₂PO₄0.2 g) is poured into a beaker filled with double distilled water, the glass rod is stirred and fully dissolved, then the solution is poured into a conical flask to accurately fix the volume to 1000ml, and the prepared PBS solution is obtained after shaking up.

Further, the preparation method of the cell suspension in the step b comprises the following steps: uniformly shaking the reaction solution, sucking 5-20 ml of solution into a centrifugal tube, digesting the solution for 30-100 minutes by using 0.1-0.5% trypsin solution, centrifuging the solution for 3-5 minutes at 1500-3000 rpm, discarding supernatant, washing the supernatant by using PBS (phosphate buffer solution), adding culture solution (balanced salt solution such as PBS) and carrying out heavy suspension to prepare cell suspension.

Furthermore, the cell counting in the step e should ensure that the total cell number of the bacterial suspension is not less than 104/ml, centrifugation is needed for re-culture when the number is small, and PBS culture solution is needed for dilution when the number is excessive, so as to finally ensure that the cell number is sufficient and the dispersion is good.

The invention provides a method for treating waste liquid of a passivation and deodorization medicament, which further comprises the following steps:

s6, deodorizing by using the environment-friendly passivation and deodorization agent or the general passivation and deodorization agent to obtain waste liquid of the environment-friendly passivation and deodorization agent or the general passivation and deodorization agent;

s7, treating the waste liquid of the environment-friendly passivation and deodorization agent by adopting conventional demulsification and flocculation, oil separation, air flotation and two-stage biochemistry, wherein the two-stage biochemistry is primary A/O biochemistry and secondary BAF biochemistry;

s8 for the treatment of general type waste liquid of deactivating and deodorizing agent, a hydrolysis acidification unit is added before the first-stage A/O biochemical treatment in the step S7, and a high-stage oxidation unit is added before the second-stage BAF biochemical treatment.

If the total phosphorus concentration is higher than 1mg/L, a post-phosphorus removal unit is added behind the secondary BAF biochemical unit.

The advanced oxidation in S8 includes two types of ozone catalytic oxidation and/or hypochlorous acid advanced oxidation, and the residence time of the ozone catalytic oxidation and/or hypochlorous acid advanced oxidation is 1-8 h. The concentration of the ozone for catalytic oxidation of the ozone is 20 mg/L-400 mg/L, and the volume space velocity is 0.5h^-1～2 h^-1The dosage of the hypochlorous acid in the hypochlorous acid advanced oxidation is 200 mg/L-3000 mg/L. The catalytic oxidation by ozone and the advanced oxidation by hypochlorous acid can further decompose refractory organic matters, so that the reaction rate and the biodegradability of wastewater are improved, and the subsequent standard-reaching treatment is facilitated; in addition, the catalytic oxidation of ozone has the characteristics of strong decomposition capability, short half-life period and no influence on subsequent biochemistry; the hypochlorous acid can remove ammonia nitrogen by oxidation and can decompose strong filter liquor. Therefore, the evaluation of the organic matter removal efficiency in S2 is poor, and ozone catalytic oxidation is preferred, and the evaluation of the nitrification efficiency in S3 is poor, and hypochlorous acid advanced oxidation is preferred.

The demulsification flocculation is to add a demulsifier, polyaluminium chloride (PAC) and Polyacrylamide (PAM) into water, stir and mix the mixture, and then add the mixture and waste liquid into an adjusting tank; based on the volume of the waste liquid, the dosage of the demulsifier is 10 mg/L-200 mg/L of the waste liquid, the dosage of PAC is 20 mg/L-300 mg/L of the waste liquid, and the dosage of PAM is 3 mg/L-20 mg/L of the waste liquid, wherein the demulsifier is a common demulsifying product on the market.

The air supporting be two-stage air supporting, the cavitation air supporting is adopted to the one-level, and the dissolved air pressurization air supporting is adopted to the second grade, through preceding breakdown of emulsion flocculation, the emulsified oil obtains the separation, through oil interceptor and air supporting pond, upper oil slick, dross, alum blossom etc. are collected and are got rid of.

The hydrolysis acidification effect is that macromolecule organic matters are hydrolyzed and acidified into micromolecule organic matters, the difficulty of subsequent two-stage biochemical treatment is reduced, and the retention time is generally 6-20 h.

The A/O biochemistry comprises an aerobic section and an anoxic section, wherein the aerobic section is arranged in front of the anoxic section, the detention time of the aerobic section of the A/O biochemistry is 20-40 h, and the detention time of the anoxic section is 3-10 h. After the aerobic section is aerated for a long time, micromolecular organic matters are decomposed into carbon dioxide and water, and ammonia nitrogen is converted into nitrate nitrogen and nitrite nitrogen through nitrification; the anoxic section carries out denitrification to remove total nitrogen and can also remove partial total phosphorus in the sewage; the biochemical retention time of the secondary BAF is 4-24 h, and the secondary BAF is used for further removing COD and has a filtering effect.

Further, the post-phosphorus removal treatment unit comprises two-stage phosphorus removal, wherein 34-980 mg/L ferric chloride and 10-700 mg/L calcium hydroxide are added in the first-stage phosphorus removal; and adding 10-300 mg/L ferric chloride and 4-200 mg/L calcium hydroxide into the secondary phosphorus removal. Adding excessive ferric chloride and calcium hydroxide into the primary phosphorus removal, and filtering; and (4) adding a small amount of ferric chloride and calcium hydroxide into the secondary phosphorus removal, and discharging the filtered water body after reaching the standard. The ferric chloride is acidic, the calcium hydroxide is alkaline, the ferric chloride and the calcium hydroxide are compounded according to a certain proportion to ensure that the pH of the liquid is neutral, and the subsequent effluent does not need to be subjected to pH adjustment.

Furthermore, the effluent after the treatment process meets the discharge standard, namely meets the requirements of the emission Standard of pollutants for the oil refining industry (GB 31570), namely COD is less than or equal to 60mg/L, ammonia nitrogen is less than or equal to 8mg/L, and total phosphorus is less than or equal to 1 mg/L.

According to the invention, the passivation and deodorization medicament is evaluated, so that enterprises can select the passivation and deodorization medicament according to the property of the passivation and deodorization medicament. The use of non-environment-friendly medicaments is avoided according to the analysis of the medicaments, so that the waste liquid can reach the discharge standard through treatment. The invention also provides a subsequent treatment method for the selected medicament waste liquid, and the treatment process can meet the discharge standard, and simultaneously, the treatment process is most economical, and the combination of treatment units is optimal. The invention provides powerful technical support for the selection and the use of medicaments and the subsequent waste liquid treatment for enterprises.

Compared with the prior art, the invention has the following advantages:

(1) the evaluation method provided by the invention is comprehensive, objective and systematic, wherein the pollutant factors are analyzed comprehensively and objectively to lay a foundation for subsequent evaluation, and the three methods of organic matter removal efficiency evaluation, nitrification efficiency evaluation, cell activity evaluation and the like provide a practical basis, so that the macroscopic phenomenon is inspected, and the microscopic change is captured. The basis of the method is that the evaluation of the organic matter removal efficiency depends on heterotrophic decarbonization bacteria, the evaluation of the nitrification efficiency depends on autotrophic nitrifying bacteria, the evaluation of the cell activity focuses on the death and the propagation of the cells, and the three are parallel, independent and mutually complementary.

(2) The invention provides a corresponding waste liquid treatment method while judging the environmental protection performance of the passivation and deodorization medicament, provides technical support for enterprises on the selection and use of the medicament and the subsequent waste liquid treatment, and simultaneously the difficulty degree of the waste liquid treatment method indirectly reflects the environmental protection performance of the medicament.

(3) The evaluation method provided by the invention is rapid and convenient, wherein the pollution factor analysis can be completely completed within five days, the COD and nitrification efficiency evaluation is synchronously carried out, a simple and efficient shaking table oscillation method is adopted, the cell activity evaluation only needs one day, and the total time does not exceed eight days, so that a complete evaluation result can be given.

(4) In the invention, the pollution factor analysis focuses on the conventional pollutant components which are easy to ignore, including organic nitrogen, total phosphorus, ORP, TOC, TC and the like, which can indirectly reflect the environmental protection performance of the medicament and is also a key focus index for subsequent biochemical evaluation.

(5) According to the invention, representative nitrifying bacteria are selected to carry out nitrification evaluation, and cell viability evaluation is carried out on the basis, so that the death, reproduction and life vitality of microbial cells are inspected, and the evaluation work is more rigorous and complete. The basis for establishing the cell viability evaluation is that the nitrobacteria are very sensitive to the external environment and the water quality of the water body, and are also important components of the microorganisms of the sewage biochemical unit, so that the method is very suitable for representing the inhibition degree and the toxicity influence of the medicament wastewater on the microorganisms on a microscopic level.

(6) The evaluation method provided by the invention has strong practicability and operability, can be used for carrying out an evaluation test in a laboratory, avoids the unpredictable influence caused by the fact that the medicament wastewater directly enters a sewage treatment field, and is also suitable for similar related fields, thereby having very good application value.

Additional features and advantages of the invention will be set forth in the detailed description which follows.

Drawings

FIG. 1 is a schematic diagram of the method for evaluating the environmental protection performance of the passivation deodorizing agent of the present invention;

FIG. 2 is a schematic view of the method for treating waste liquid of the passivation and deodorization chemicals of the present invention.

Detailed Description

The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.

Example 1

A certain passivation deodorizing agent is subjected to S1 pollution factor analysis, including metal ion analysis and water quality analysis, wherein the metal ion analysis adopts microwave digestion/inductive coupling plasma mass spectrometry, and the water quality analysis adopts a national standard method, which comprises the following specific steps:

TABLE 1 Water quality analysis results

Item	COD	BOD5	pH	Electrical conductivity of	TDS	Total hardness	SO4 2-	S2-
									Numerical value	15050	3310	5.69	7460	17400	1220	3210	3.1
Nitrate nitrogen	Nitrite nitrogen	Organic nitrogen	Ammonia nitrogen	Total nitrogen	TOC	TC	ORP	Total phosphorus
									51.5	0.25	247.8	22.5	322	6530	6560	58	2

Remarking: the unit of the electric conductivity is mu s/cm, the unit of the oxidation-reduction potential is mv, the pH is dimensionless, and the unit of other pollution factors is mg/L.

TABLE 2 analysis results of metal ions

Item	Ag	Al	As	B	Ba	Be	Bi	Ca
										—	3260	—	—	48.8	—	1.54	7740
Cd	Co	Cr	Cu	Fe	K	Li	Mg	Mn
									—	288	22.7	78.7	1260000	—	—	24100	8030
Mo	Na	Ni	Pb	Rb	Se	Sr	V	Zn
									—	—	150	41.7	—	68.3	317	110	963

Remarking: the unit μ g/L, "-" indicates no detection.

The pollution factor analysis result of the embodiment shows that the chemical agent COD, TOC, ORP, total phosphorus and total nitrogen are in a reasonable range, and the manganese ions in metal analysis are less, which indicates that the main body of the passivating agent is not potassium permanganate, other polluting metal ions are less, and the metal ion analysis result is good.

Further, evaluation of organic matter removal efficiency was performed in S2: adopting a shaking table oscillation method, setting the temperature to be 25 ℃, the rotating speed to be 150rpm, the reaction time to be 48h, controlling the volume of a conical flask special for the shaking table to be 600ml, controlling the reaction liquid to be 350ml, adding 200ml of activated sludge, controlling the MLSS to be about 10000mg/L and controlling the ratio of MLVSS to MLSS to be about 0.6; according to the pollution factor analysis, the COD concentration of the chemical agent is 15050mg/L, the adding amount is 24ml, about 126ml of distilled water is added, the COD of the finally prepared solution is about 1215mg/L, the carbon source, the nitrogen source and the phosphorus source do not need to be supplemented, and the pH does not need to be adjusted. Blank test active sludge dosage is 200ml, distilled water is 150ml, glucose is supplemented by 0.35g, ammonium chloride is 0.05g, and potassium dihydrogen phosphate is 0.05 g. And (3) detecting pH, ORP and COD before and after the reaction, wherein a water sample needs to be filtered before the COD is detected. The test result shows that the COD removal rate of the wastewater containing the medicament is as high as 69.6 percent, which is about 78 percent of the COD removal rate of the blank test, and the analysis result of the removal rate of the organic matters is good, which is shown in the table.

TABLE 3 COD removal test results

Remarking: COD unit is mg/L, oxidation-reduction potential unit mv, pH is dimensionless

Further, evaluation of nitrification efficiency of S3: adopting a shaking table oscillation method, setting the temperature to be 25 ℃, the rotating speed to be 150rpm, the reaction time to be 6 hours, controlling the volume of a conical flask special for the shaking table to be 600ml, controlling the volume of reaction liquid to be 200ml, inoculating a nitrifying agent which is used in the embodiment of the patent CN201010510855, wherein the inoculation amount is 15 percent of the volume of the reaction liquid, namely 30 ml; diluting the reagent by 20 times with distilled water, adding into a conical flask to 200ml of scale mark, wherein the COD of the solution is about 800mg/L, the ammonia nitrogen is about 1.1mg/L, and adding ammonium chloride to adjust the ammonia nitrogen to 50 mg/L; the initial pH of the reaction system was adjusted to about 8.0 with sodium bicarbonate and the pH was adjusted regularly during the experiment; and additionally arranging a blank sample, wherein the only difference is that no medicament is added and distilled water is used instead. And measuring ammonia nitrogen after the reaction is finished, and comparing the measured ammonia nitrogen with the indexes before the reaction to obtain the reagent nitrification efficiency of 91.2 percent, the blank sample nitrification efficiency of 95.8 percent and the reagent nitrification efficiency of 95.2 percent of the blank sample nitrification efficiency. The evaluation result of the nitrification efficiency was good.

Further, the cell viability of S4 was evaluated by the following operating method:

a. preparation of 4% trypan blue mother liquor: 4g of trypan blue was weighed, ground with a small amount of double distilled water, and then 100mL of distilled water was added, filtered with filter paper, and stored at 3 ℃. When used, PBS buffer (NaCl 8.0g, KCl 0.2g, Na)₂HPO₄·H₂O 1.56g ,KH₂PO₄0.2g, prepared by diluting double distilled water to 1000 ml) to 0.4%;

b. preparing a cell suspension: 10ml of each solution of the reaction solution at the initial stage of the nitrification efficiency evaluation test and after the reaction is finished is taken and put into a centrifuge tube, after being digested for 50 minutes by 0.3 percent trypsin liquid, the centrifuge tube is centrifuged for 4 minutes at 2000rpm, the supernatant is discarded, the culture solution is added after being washed by PBS liquid, and the cell suspension is prepared by resuspension.

c. And (3) slice making and dyeing: the cell suspension was mixed well with 0.4% trypan blue solution at 8: 1.

d. Microscopic observation: dead cells were stained visibly blue, while live cells were colorless and transparent;

e. cell counting: live and dead cells were counted separately within 3 minutes;

f. counting the cell viability: the viable cell rate (%) = the number of viable cells/the total number of cells × 100%.

As shown in the table below, by examining the cell viability before and after the nitrification reaction, the total bacterial count and the viable bacterial count of the nitrifying bacteria both tend to increase, and with the increase of time, the tolerance of the nitrifying bacteria to the medicament is enhanced, and the cell viability is slightly increased.

TABLE 4 evaluation results of cell viability

Item

Time

Dilution factor

Total number of bacteria per unit area

Viable count per unit area

Actual total number of bacteria

Actual viable count

Cell viability

Medicament

0h

100000

174

102

7.73E+11

4.53E+11

58.6%

Medicament

6h

100000

209

147

9.28E+11

6.53E+11

70.3%

Pollution factor analysis shows that all indexes of the medicament are in a reasonable range, and the analysis result of metal ions is good; in the evaluation of the organic matter removal efficiency, the COD removal rate is 78% of that of the blank sample, and the evaluation result of the organic matter removal efficiency is good; the nitration efficiency is 95.2% of that of the blank sample, and the nitration efficiency evaluation result is good; the cell viability reaches up to 70.3 percent, and the cell viability evaluation result is good. Therefore, the passivation and deodorization medicament is judged to be an environment-friendly medicament.

The evaluation result shows that the medicament has good biodegradability and no influence on water microorganisms. The corresponding waste liquid treatment method is a conventional sewage treatment process, and comprises demulsification and flocculation, oil separation, air flotation, primary A/O biochemistry and secondary BAF biochemistry, and effluent reaches the standard and is discharged.

The normal passivation deodorizing agent can be diluted in a certain proportion when in use, and if the normal passivation deodorizing agent is diluted by 10 times, the treatment method of the waste liquid comprises demulsification and flocculation, oil separation, air flotation, A/O biochemistry and BAF biochemistry according to the water inlet sequence. Wherein the demulsifier adopts a Huanli BKL-1010 water-soluble demulsifier, the dosage is 120mg/L, the dosage of PAC is 140mg/L, and the dosage of PAM is 8 mg/L. The air floatation adopts two-stage air floatation of cavitation and dissolved air pressurization. The retention time of the A/O biochemical aerobic section is 30h, the retention time of the anoxic section is 6h, the retention time of the BAF biochemical treatment section is 14h, and the effluent quality of each unit is shown in the following table, wherein the medicament wastewater is mixed wastewater comprising the medicament and pollutants in the tower.

TABLE 5 quality of effluent from each unit

	COD	Ammonia nitrogen	Total phosphorus	Petroleum products
					Chemical waste liquid	2010	79	5.3	1012
Air-float water outlet	1853	67	2.1	15
					Water outlet of aerobic section	198	11.5	0.8	4.2
Oxygen-deficient section yielding water	75	6.3	0.4	3.5
					BAF pool effluent	42	3.7	0.1	1.1

According to the embodiment, the passivation and deodorization medicament is an environment-friendly medicament, the three evaluation results are good, and the standard discharge of medicament waste liquid can be met by adopting a conventional sewage treatment process.

Example 2

A certain passivation deodorizing agent is firstly subjected to pollution factor analysis, including metal ion analysis and water quality analysis, wherein the metal ion analysis adopts a microwave digestion/inductive coupling plasma mass spectrometry method, and the water quality analysis adopts a national standard method, which comprises the following specific steps:

TABLE 6 Water quality analysis results

Item	COD	BOD5	pH	Electrical conductivity of	TDS	Total hardness	SO4 2-	S2-
										21352	0	5.65	30300	47800	0	659	1.6
Nitrate nitrogen	Nitrite nitrogen	Organic nitrogen	Ammonia nitrogen	Total nitrogen	TOC	TC	ORP	Total phosphorus
									1.42	0	38.28	16.9	56.6	4360	4440	297	11700

Remarking: the unit of the electric conductivity is mu s/cm, the unit of the oxidation-reduction potential is mv, the pH is dimensionless, and the unit of other pollution factors is mg/L.

TABLE 7 analysis results of metal ions

Item	Ag	Al	As	B	Ba	Be	Bi	Ca
										16.8	1110	—	—	20.2	—	—	17600
Cd	Co	Cr	Cu	Fe	K	Li	Mg	Mn
									—	5450	535	—	2100000	—	—	375000	12200
Mo	Na	Ni	Pb	Rb	Se	Sr	V	Zn
									—	—	2550	27.6	—	41.7	147	640	10100

Remarking: the unit μ g/L, "-" indicates no detection.

The result of the pollution factor analysis of the embodiment shows that the chemical agent has high COD, high total phosphorus and less manganese ions in metal analysis, which indicates that the main body of the passivator is not potassium permanganate and other polluting metal ions are less, and the result of the metal ion analysis is good.

Further, the method for evaluating the organic matter removing efficiency was similar to that in example 1, except that the amount of the chemical added was 16.5ml, and about 133.5ml of distilled water was added, and that the COD of the prepared solution was 1115mg/L, the carbon source, the nitrogen source, and the phosphorus source were not supplemented, and the pH was not adjusted. The test result shows that the COD of the medicament wastewater is not removed but is increased to 1282mg/L, while the removal rate of the COD in the blank test is up to 87 percent, which is specifically shown in the following table.

TABLE 8 COD removal test results

Remarking: COD unit is mg/L, oxidation-reduction potential unit mv, pH is dimensionless

Further, the nitrification efficiency evaluation method is similar to that of example 1, except that the reagent is diluted by 25 times with distilled water, and then the reagent is added into a conical flask to the 300ml scale mark, at this time, the COD of the solution is about 884mg/L, the ammonia nitrogen is about 0.56mg/L, and ammonium chloride is added additionally to adjust the ammonia nitrogen of the solution to 50.2 mg/L. And measuring ammonia nitrogen after the reaction is finished, and comparing the measured ammonia nitrogen with the indexes before the reaction to obtain the product with the nitrification efficiency of 96.5 percent, the nitrification efficiency of a blank sample of 95.2 percent and the nitrification efficiency of the medicament of 101 percent of the nitrification efficiency of the blank sample.

Further, cell viability was evaluated by the same method as in example 1. As shown in the following table, the total bacterial count and the viable bacterial count of the nitrifying bacteria both increased, and the cell viability was always maintained at a high level.

TABLE 9 evaluation results of cell viability

Item

Time

Dilution factor

Total number of bacteria per unit area

Viable count per unit area

Actual total number of bacteria

Actual viable count

Cell viability

Medicament

0h

100000

165

132

7.33E+11

5.86E+11

80.0%

Medicament

6h

100000

229

178

1.02E+12

7.91E+11

77.7%

Pollution factor analysis shows that the analysis result of metal ions is good; COD is not removed in the organic matter removal efficiency evaluation, and the organic matter removal efficiency evaluation result is poor; the nitration efficiency is 101% of that of the blank sample; the nitrification efficiency evaluation result was good. The cell viability reaches 77.7 percent, and the cell viability evaluation result is good. Therefore, the deactivating deodorizing agent is judged to be a general type agent.

The evaluation result shows that the medicament has no biological toxicity, but contains complex organic matters and has high total phosphorus content. The corresponding waste liquid treatment method is a relatively complex sewage treatment process, and comprises demulsification flocculation, oil separation, air flotation, hydrolytic acidification, A/O biochemistry, ozone catalytic oxidation and secondary BAF biochemical treatment, wherein the total phosphorus concentration is still higher than 1mg/L after the BAF biochemical treatment, a postposition phosphorus removal unit is added, and the effluent reaches the standard and is discharged. Compared with the traditional treatment process, the method has the advantages that hydrolytic acidification treatment, intermediate ozone oxidation retreatment and postposition phosphorus removal are added, wherein ozone oxidation not only improves the biodegradability of wastewater and is convenient for BAF advanced treatment, but also converts organic phosphorus into inorganic phosphorus and is beneficial to postposition chemical phosphorus removal.

The normal passivation deodorizing agent can be diluted in a certain proportion when in use, and if the normal passivation deodorizing agent is diluted by 10 times, the treatment method of the waste liquid comprises demulsification and flocculation, oil separation, air floatation, hydrolytic acidification, A/O biochemistry, ozone catalytic oxidation, BAF biochemistry and postposition phosphorus removal according to the water inlet sequence. Wherein the demulsifier adopts Huali BKL-1010 water-soluble demulsifier, the dosage is 115mg/L, the PAC dosage is 145mg/L, the PAM dosage is 7mg/L, the air floatation adopts two-stage air floatation of cavitation and dissolved air pressurization, the hydrolytic acidification retention time is 14h, the A/O biochemical aerobic section retention time is 24h, the anoxic section retention time is 8h, the ozone catalytic oxidation retention time is 5h, the ozone concentration is 200mg/L, and the volume space velocity is 1h^-1The BAF biochemical treatment section stays for 18 hours, the post-phosphorus removal comprises two stages, wherein 600mg/L ferric chloride and 400mg/L calcium hydroxide are added in the first-stage phosphorus removal, and 200mg/L ferric chloride and 150mg/L calcium hydroxide are added in the second-stage phosphorus removal. The quality of the effluent of each unit is shown in the following table, wherein the medicament wastewater is mixed wastewater and is packagedIncluding the medicament itself and contaminants within the tower.

TABLE 10 quality of effluent from each unit

	COD	Ammonia nitrogen	Total phosphorus	Petroleum products
					Medicament wastewater	2425	80	1210	1023
Air-float water outlet	2216	68	321	16
					Water outlet of hydrolysis acidification section	1863	55	253	3.5
Water outlet of aerobic section	986	11.5	232	1.5
					Oxygen-deficient section yielding water	765	6.3	211	1.0
Ozone section water outlet	314	5.3	209	0.2
					BAF pool effluent	55	2.7	185	＜0.1
Postposition dephosphorization effluent	46	2.3	＜1	＜0.1

According to the embodiment, the passivation and deodorization medicament is a general medicament, the evaluation on the removal efficiency of organic matters is poor, the evaluation on the nitrification rate and the cell activity is good, and the medicament has no biotoxicity, and the standard discharge can be achieved only by adopting a complex sewage treatment process, so that the medicament is difficult to degrade organic matters and is rich in organic phosphorus.

Example 3

A certain passivation deodorizing agent is firstly subjected to pollution factor analysis, including metal ion analysis and water quality analysis, wherein the metal ion analysis adopts a microwave digestion/inductive coupling plasma mass spectrometry method, and the water quality analysis adopts a national standard method, which comprises the following specific steps:

TABLE 11 Water quality analysis results

Item	COD	BOD5	pH	Electrical conductivity of	TDS	Total hardness	SO4 2-	S2-
										14107	3562	6.61	20300	32500	0	1248	2.6
Nitrate nitrogen	Nitrite nitrogen	Organic nitrogen	Ammonia nitrogen	Total nitrogen	TOC	TC	ORP	Total phosphorus
									5.6	1.02	45.8	32.1	86.3	4360	2800	256	8650

Remarking: the unit of the electric conductivity is mu s/cm, the unit of the oxidation-reduction potential is mv, the pH is dimensionless, and the unit of other pollution factors is mg/L.

TABLE 12 analysis results of metal ions

Item	Ag	Al	As	B	Ba	Be	Bi	Ca
										0.889	—	—	72.5	4.57	—	—	1570
Cd	Co	Cr	Cu	Fe	K	Li	Mg	Mn
									—	—	—	—	137	72100	7.49	11900	2.68
Mo	Na	Ni	Pb	Rb	Se	Sr	V	Zn
									—	—	1.14	—	154	—	1.22	—	—

Remarking: the unit μ g/L, "-" indicates no detection.

The pollution factor analysis result of the embodiment shows that the total phosphorus of the agent is higher, COD, TOC, ORP and total nitrogen are in reasonable ranges, and manganese ions are fewer in metal analysis, which indicates that the main body of the passivating agent is not potassium permanganate, and other polluting metal ions are fewer, so that the metal ion analysis result is good.

Further, the organic matter removing efficiency evaluation method was similar to that in example 1, and the COD of the prepared solution was 1198 mg/L. The test result shows that the COD removal rate of the wastewater containing the medicament is as high as 68.1 percent and is about 76.3 percent of the COD removal rate of the blank test, and the details are shown in the following table.

TABLE 13 COD removal test results

Remarking: COD unit is mg/L, oxidation-reduction potential unit mv, pH is dimensionless

Further, the nitration efficiency evaluation method is similar to that of the example 1, the dilution times are the same, the COD of the prepared solution is about 890mg/L, and the ammonia nitrogen is 51 mg/L. And measuring ammonia nitrogen after the reaction is finished, and comparing the measured ammonia nitrogen with the indexes before the reaction to obtain the product with the nitrification efficiency of 32.8 percent, the nitrification efficiency of a blank sample of 94.4 percent and the nitrification efficiency of the medicament of 34.7 percent of the nitrification efficiency of the blank sample.

Further, cell viability was evaluated by the same method as in example 1. As shown in the following table, the total number of nitrifying bacteria and the number of viable bacteria both tended to decrease significantly, and the cell viability rate was decreasing.

TABLE 14 evaluation results of cell viability

Item

Time

Dilution factor

Total number of bacteria per unit area

Viable count per unit area

Actual total number of bacteria

Actual viable count

Cell viability

Medicament

0h

100000

133

62

5.91E+11

2.75E+11

46.6%

Medicament

6h

100000

85

22

3.77E+11

9.77E+10

25.9%

The pollution factor analysis result shows that the metal ion analysis result is good; in the evaluation of the organic matter removal efficiency, the COD removal rate is 76.3% of that of the blank sample, and the evaluation result of the organic matter removal efficiency is good; the nitration efficiency is 34.7% of the blank sample, and the nitration efficiency evaluation result is poor; the cell viability was only 25.9%, and the cell viability evaluation result was poor. Therefore, the deactivating deodorizing agent is judged to be a general type agent.

The evaluation result shows that the medicament has certain biological toxicity which is mainly reflected in the influence on the activity of nitrobacteria, and simultaneously contains complex organic matters and possibly contains rich organic phosphorus. The corresponding waste liquid treatment method is a relatively complex sewage treatment process, and comprises demulsification flocculation, oil removal, air flotation, hydrolytic acidification, A/O biochemistry, hypochlorous acid advanced oxidation, secondary BAF biochemical advanced treatment, total phosphorus concentration still higher than 1mg/L after BAF biochemical treatment, and a post-arranged phosphorus removal unit is added, so that the effluent reaches the standard and is discharged. Compared with the traditional treatment process, the method has the advantages that hydrolytic acidification pretreatment, hypochlorous acid oxidation retreatment in the middle link and postposition retreatment phosphorus removal are added, wherein the hypochlorous acid oxidation can remove ammonia nitrogen, convert organic phosphorus into inorganic phosphorus and simultaneously improve the biodegradability of wastewater.

The normal passivation deodorizing agent can be diluted in a certain proportion when in use, and if the dilution is 10 times, the treatment method of the waste liquid comprises demulsification and flocculation, oil separation, air flotation, A/O biochemistry, hypochlorous acid oxidation, BAF advanced treatment and postposition phosphorus removal according to the water inlet sequence. The demulsifier adopts Huali BKL-1010 water-soluble demulsifier, the dosage is 118mg/L, the dosage of PAC is 141mg/L, the dosage of PAM is 8mg/L, the air flotation adopts cavitation and dissolved air pressurization two-stage air flotation, the retention time of an acidified water stage is 8h, the retention time of an A/O biochemical aerobic section is 28h, the retention time of an anoxic section is 10h, the retention time of hypochlorous acid advanced oxidation is 6h, the dosage of hypochlorous acid is 1200mg/L, the retention time of a BAF advanced treatment section is 15h, the post-dephosphorization comprises two-stage dephosphorization, 580mg/L ferric chloride and 370mg/L calcium hydroxide are added in the first-stage dephosphorization, and 180mg/L ferric chloride and 145mg/L calcium hydroxide are added in the second-stage dephosphorization. The quality of the effluent of each unit is shown in the following table, wherein the medicament wastewater is mixed wastewater and comprises the medicament and pollutants in the tower.

Table 15 quality of each unit effluent

	COD	Ammonia nitrogen	Total phosphorus	Petroleum products
					Medicament wastewater	2023	81	896	1016
Air-float water outlet	1862	69	265	15
					Water outlet of hydrolysis acidification section	1693	65	258	7
Water outlet of aerobic section	345	58	245	1.8
					Oxygen-deficient section yielding water	215	55	186	1.1
Hypochlorous acid section effluent	92	4.3	181	0.3
					BAF pool effluent	56	1.2	175	＜0.1
Postposition dephosphorization effluent	50	0.5	＜1	＜0.1

According to the embodiment, the passivation and deodorization medicament is a general medicament, the organic matter removal efficiency evaluation is good, the nitrification rate and the cell activity evaluation are poor, the standard discharge can be achieved only by adopting a complex sewage treatment process, and the reason is that the medicament has an inhibition effect on the nitrification rate and is rich in organic phosphorus.

Example 4

A certain passivation deodorizing agent is firstly subjected to pollution factor analysis, including metal ion analysis and water quality analysis, wherein the metal ion analysis adopts a microwave digestion/inductive coupling plasma mass spectrometry method, and the water quality analysis adopts a national standard method, which comprises the following specific steps:

TABLE 16 Water quality analysis results

Item	COD	BOD5	pH	Electrical conductivity of	TDS	Total hardness	SO4 2-	S2-
										24365	1410	5.69	38700	63600	112	659	0
Nitrate nitrogen	Nitrite nitrogen	Organic nitrogen	Ammonia nitrogen	Total nitrogen	TOC	TC	ORP	Total phosphorus
									11.8	0.042	33.56	39.4	84.8	5420	5450	321	15500

Remarking: the unit of the electric conductivity is mu s/cm, the unit of the oxidation-reduction potential is mv, the pH is dimensionless, and the unit of other pollution factors is mg/L.

TABLE 17 results of metal ion analysis

Item	Ag	Al	As	B	Ba	Be	Bi	Ca
										—	23.2	4030	—	90.2	—	—	49700
Cd	Co	Cr	Cu	Fe	K	Li	Mg	Mn
									—	—	17.1	258	—	38200	457	20400	—
Mo	Na	Ni	Pb	Rb	Se	Sr	V	Zn
									—	13500000	291	—	—	—	234	108	380

Remarking: the unit μ g/L, "-" indicates no detection.

The result of the pollution factor analysis of the embodiment shows that the chemical agent has high COD and total phosphorus, and less manganese ions are generated in the metal analysis, which indicates that the main body of the passivating agent is not potassium permanganate, and other polluting metal ions are less, so that the result of the metal ion analysis is good.

Further, the evaluation method of the organic matter removing efficiency was similar to that in example 1, and the COD of the prepared solution was 1230 mg/L. The test result shows that the COD of the wastewater containing the medicament is not removed, the activated sludge is partially dead, the COD value does not decrease and inversely increases, and the removal rate of the COD in the blank test is 88.9 percent, which is shown in the following table.

TABLE 18 COD removal test results

Remarking: COD unit is mg/L, oxidation-reduction potential unit mv, pH is dimensionless

Further, the nitration efficiency evaluation method is similar to that of the example 1, the dilution times are the same, the COD of the prepared solution is about 885mg/L, and the ammonia nitrogen is 49.5 mg/L. And measuring ammonia nitrogen after the reaction is finished, and comparing the measured ammonia nitrogen with the indexes before the reaction to obtain the product with the nitrification efficiency of 15.6 percent, the nitrification efficiency of a blank sample of 93.9 percent and the nitrification efficiency of the medicament of 16.6 percent of the nitrification efficiency of the blank sample.

Further, cell viability was evaluated by the same method as in example 1. As shown in the following table, the total number of nitrifying bacteria and the number of viable bacteria were both reduced in a large scale, and the cell viability rate was significantly reduced.

TABLE 19 evaluation results of cell viability

Item

Time

Dilution factor

Total number of bacteria per unit area

Viable count per unit area

Actual total number of bacteria

Actual viable count

Cell viability

Medicament

0h

100000

92

32

4.09E+11

1.42E+11

34.7%

Medicament

6h

100000

43

7

1.91E+11

3.1E+10

16.3%

The pollution factor analysis result shows that the metal ion analysis result is good; COD is not removed in the organic matter removal efficiency evaluation, and the organic matter removal efficiency evaluation result is poor; the nitration efficiency is 16.6% of the blank sample, and the nitration efficiency evaluation result is poor; the cell viability was only 16.3%, and the cell viability evaluation result was poor. Therefore, the passivation deodorant agent is judged to be a non-environment-friendly agent.

The evaluation results show that the medicament has strong biological toxicity, which is reflected in the influence on both decarbonized microorganisms and nitrifying bacteria, and the biocidal effect is indeed existed through the verification of cell viability at a microscopic level. Aiming at the medicament wastewater, no corresponding sewage treatment process can achieve the standard discharge at the present stage, and in order to further clarify the harm, a complex sewage treatment process is adopted for experimental comparison, wherein the process comprises demulsification and flocculation, oil separation, air flotation, hydrolysis acidification, A/O biochemistry, ozone and hypochlorous acid two-stage oxidation, BAF advanced treatment and postposition phosphorus removal.

The normal passivation deodorizing agent can be diluted in a certain proportion when in use, and if the normal passivation deodorizing agent is diluted by 10 times, the treatment method of the waste liquid comprises demulsification and flocculation, oil separation, air floatation, hydrolytic acidification, A/O biochemistry, ozone and hypochlorous acid two-stage oxidation, BAF advanced treatment and postposition dephosphorization according to the water inlet sequence. Wherein the demulsifier adopts Huali BKL-1010 water-soluble demulsifier, the dosage is 130mg/L, the PAC dosage is 150mg/L, the PAM dosage is 10mg/L, the air floatation adopts two-stage air floatation of cavitation and dissolved air pressurization, the hydrolytic acidification retention time is 16h, the A/O biochemical aerobic section retention time is 30h, the anoxic section retention time is 12h, the ozone catalytic oxidation retention time is 8h, the ozone concentration is 250mg/L, and the volume space velocity is 1.2 h^-1The advanced oxidation retention time of hypochlorous acid is 4 hours, the adding amount of hypochlorous acid is 1500mg/L, the retention time of a BAF advanced treatment section is 16 hours, the post-phosphorus removal comprises two-stage phosphorus removal, 800mg/L ferric chloride and 550mg/L calcium hydroxide are added in the first-stage phosphorus removal, and 250mg/L ferric chloride and 180mg/L calcium hydroxide are added in the second-stage phosphorus removal. The quality of the effluent of each unit is shown in the following table, wherein the medicament wastewater is mixed wastewater and comprises the medicament and pollutants in the tower.

Table 20 quality of each unit effluent

	COD	Ammonia nitrogen	Total phosphorus	Petroleum products
					Medicament wastewater	2625	83	1580	1010
Air-float water outlet	2314	73	765	14
					Water outlet of hydrolysis acidification section	1966	68	653	12
Water outlet of aerobic section	1910	65	623	1.5
					Lack of oxygenSectional water outlet	1723	56	577	1.0
Ozone section water outlet	1453	51	550	0.8
					Hypochlorous acid section effluent	1395	13	521	0.4
BAF pool effluent	1318	10	502	＜0.1
					Postposition dephosphorization effluent	1316	9.8	353	＜0.1

According to the embodiment, the passivation and deodorization medicament is a non-environment-friendly medicament, the organic matter removal efficiency evaluation, the nitrification rate evaluation and the cell activity evaluation are very poor, the water quality is still poor after the complex sewage treatment process is adopted, and a great distance is reserved between the passivation and deodorization medicament and the standard discharge.

Example 5

A certain passivation deodorizing agent is firstly subjected to pollution factor analysis, including metal ion analysis and water quality analysis, wherein the metal ion analysis adopts a microwave digestion/inductive coupling plasma mass spectrometry method, and the water quality analysis adopts a national standard method, which comprises the following specific steps:

TABLE 21 Water quality analysis results

Item	COD	BOD5	pH	Electrical conductivity of	TDS	Total hardness	SO4 2-	S2-
										0	0	7.24	3540	1000	112	830	6.2
Nitrate nitrogen	Nitrite nitrogen	Organic nitrogen	Ammonia nitrogen	Total nitrogen	TOC	TC	Oxidation reduction potential	Total phosphorus
									3.3	0.21	10.29	19.7	33.5	545	586	687	5

Remarking: the unit of the electric conductivity is mu s/cm, the unit of the oxidation-reduction potential is mv, the pH is dimensionless, and the unit of other pollution factors is mg/L.

TABLE 22 analysis results of metal ions

Item	Ag	Al	As	B	Ba	Be	Bi	Ca
										—	98200	—	—	—	—	—	—
Cd	Co	Cr	Cu	Fe	K	Li	Mg	Mn
									47.3	14	—	—	2310	—	—	—	—
Mo	Na	Ni	Pb	Rb	Se	Sr	V	Zn
									25100	—	10400	—	—	—	115	3930	—

Remarking: the unit μ g/L, "-" indicates no detection.

The results of the pollution factor analysis of the embodiment show that the total phosphorus and the total nitrogen of the medicament are very low, the oxidation-reduction potential is as high as 687mv, and the metal analysis shows that the solution substance is simple, the concentration of each metal ion is very low, and the medicament is not the traditional potassium permanganate passivator. The chemical agent is characterized in that COD is zero, TOC is 545mg/L, which indicates that the chemical agent contains organic matters which cannot be oxidized by potassium dichromate, and the chemical agent is inferred to possibly contain oxidant strong filter. The analysis result of the metal ions was good.

Further, the method for evaluating the organic matter removing efficiency was similar to that of example 1, except that the amount of the chemical was 50ml, glucose was additionally added in an amount of 0.35g, and the reaction time was extended to 72 hours. Test results show that the COD removal rate of the wastewater of the reaction reagent in 48 hours is only 15.4 percent and is possibly related to that the ORP of the reaction liquid is still up to 256mv, the ORP of the reaction liquid is up to 195.8mv after the reaction time is prolonged to 72 hours, the corresponding COD removal rate is increased to 52.5 percent, the COD removal rate of a blank sample is up to 91.6 percent, and the removal rate of organic matters in 72 hours is 57.3 percent of that of the blank sample, which is shown in the table below.

TABLE 23 COD removal test results

Remarking: COD unit is mg/L, oxidation-reduction potential unit mv, pH is dimensionless

Further, the nitrification efficiency evaluation method was similar to that of example 1, and the chemical was diluted 20 times with distilled water to prepare a solution with COD of about 15mg/L and ammonia nitrogen of 49.6 mg/L. And measuring ammonia nitrogen after the reaction is finished, and comparing the measured ammonia nitrogen with the indexes before the reaction to obtain the product with the nitrification efficiency of only 18.6 percent, the nitrification efficiency of the blank sample of 94.5 percent and the nitrification efficiency of the medicament of 19.7 percent of the nitrification efficiency of the blank sample.

Further, cell viability was evaluated by the same method as in example 1. The results are shown in the following table, the total bacterial count of the nitrifying bacteria is in a descending trend, the number of living cells is slightly increased, and the cell viability rate is obviously increased, which indicates that the activity of the nitrifying bacteria begins to gradually recover after undergoing inhibition.

TABLE 24 evaluation results of cell viability

Item

Time

Dilution factor

Total number of bacteria per unit area

Viable count per unit area

Actual total number of bacteria

Actual viable count

Cell viability

Medicament

0h

100000

113

23

5.02E+11

1.02E+11

20.6%

Medicament

6h

100000

65

31

2.88E+11

1.38E+11

47.7%

Through the previous series of analysis and evaluation, the pollution factor analysis shows that the metal ion analysis result is good. The COD removal rate of 48h in the organic matter removal efficiency evaluation is lower, the COD removal rate of 72h is obviously improved, the organic matter removal efficiency is 57.3 percent of that of the blank sample, and the organic matter removal efficiency evaluation result is good; the nitrification efficiency was greatly affected, and was only 16.6% of the blank sample, and the result of the nitrification efficiency evaluation was poor. However, the cell viability is further verified to be in a gradually rising trend, the cell viability is increased to 47.7% after 6 hours and is more than 45%, which indicates that the high ORP value of the medicament influences the biochemical performance of the medicament in the initial stage, the ORP value is reduced along with the increase of the reaction time, the inhibition effect of the medicament on microorganisms begins to disappear, and the cell viability evaluation result is good. Therefore, the deactivating deodorizing agent is judged to be a general type agent.

As the agent is special, the sewage treatment is additionally provided with pretreatment, the whole process comprises acidic water regulation, demulsification and flocculation, oil removal, air flotation, A/O biochemistry, hypochlorous acid oxidation and BAF advanced treatment, and the effluent reaches the standard and is discharged. Therefore, compared with the traditional treatment process, the acidic water regulation and the hypochlorous acid oxidation in the intermediate link are added, wherein the acidic water contains the reducibility due to the sulfide, the ORP value of the medicament wastewater can be reduced, but the acidic water can bring extra ammonia nitrogen, the ammonia nitrogen can be removed by the hypochlorous acid oxidation, the strong filtrate can be decomposed, and the biodegradability of the sewage can be improved.

The normal passivation deodorizing agent can be diluted in a certain proportion when in use, and if the dilution is 10 times, the treatment method of the waste liquid comprises the steps of acidic water regulation, demulsification and flocculation, oil separation, air flotation, A/O biochemistry, hypochlorous acid oxidation and BAF advanced treatment according to the water inlet sequence. The ratio of the acid water to the medicament wastewater is 1:20, the demulsifier adopts a Huanli BKL-1010 water-soluble demulsifier, the adding amount is 128mg/L, the adding amount of PAC is 142mg/L, the adding amount of PAM is 8mg/L, the air flotation adopts cavitation and dissolved air pressurization two-stage air flotation, the retention time of an A/O biochemical aerobic section is 24h, the retention time of an anoxic section is 6h, the oxidation time of hypochlorous acid is 3h, the adding amount of hypochlorous acid is 1300mg/L, the retention time of a BAF advanced treatment section is 10h, the water quality of each unit is shown in the following table, wherein the medicament wastewater is mixed wastewater comprising medicament per se, pollutants in a tower and the acid water.

TABLE 25 quality of effluent from each unit

	COD	TOC	Ammonia nitrogen	Total phosphorus	Petroleum products
						Medicament wastewater	513	55	115	5.4	1016
Air-float water outlet	410	54.5	103	2.4	16
						Water outlet of aerobic section	188	54	75	0.9	4.4
Oxygen-deficient section yielding water	137	50	64	0.4	3.7
						Oxidation of hypochlorous acid	76	12	11	0.2	1.2
BAF pool effluent	42	5	5.6	0.1	0.5

According to the embodiment, the passivation deodorizing agent is a general agent, the organic matter removal efficiency evaluation is good after the reaction time is prolonged, the nitrification rate evaluation is poor, the cell viability evaluation shows that the nitrifying bacteria viability has an ascending trend, the standard discharge can be achieved by adopting a slightly special sewage treatment process, and the reason for the standard discharge is that the initial oxidation-reduction potential of the agent is high.