Environmental performance evaluation of passivation deodorizing agent and its waste liquid treatment method

Abstract

The present invention provides a method for evaluating the environmental performance of a passivation deodorant agent. By analyzing the pollution factors of the agent, evaluating the organic matter removal efficiency, evaluating the nitrification efficiency and evaluating the cell viability, the passivation deodorant agent is analyzed to guide enterprises to make reasonable selections of the agent. At the same time, the present invention also provides a method for treating the waste liquid of the selected agent. According to the analysis of the agent, an environmentally friendly agent or a general agent is selected, and non-environmentally friendly agents are avoided, so that the waste liquid can be treated to meet the emission standards. A corresponding waste liquid treatment method is also provided to make the treatment process more optimal and more economical. The present invention provides strong technical support for enterprises in the selection and use of agents and subsequent waste liquid treatment.

Description

Technical Field

[0001] The invention relates to environmental protection performance evaluation of a passivation deodorizing agent and a waste liquid treatment method thereof, belonging to the technical field of environmental protection. Background Art

[0002] The pharmaceutical wastewater produced by passivation deodorization has always been a major problem faced by refineries during shutdown and maintenance. Because of its high COD (chemical oxygen demand), high organic nitrogen, high organic phosphorus, complex chemical composition, and difficulty in biodegradation, it is very easy to impact the sewage treatment plant. In the lightest case, the effluent of the sewage treatment plant does not meet the standards, and in the severest case, it causes activated sludge poisoning or death, and it is difficult to restore biological activity in the short term. In addition, petrochemical plants are increasingly using high-sulfur crude oil (sulfur content above 1%), and the quality is getting worse and worse. In addition, safety and environmental protection requirements are getting higher and higher. During the shutdown and maintenance period, more devices will inevitably use passivation deodorization operations. There are many types of passivation deodorization agents on the market. Therefore, it is very important to choose an environmentally friendly, pollution-free, and biodegradable "green" passivation deodorization agent.

[0003] CN201210077149 provides a deodorizing and passivating double-effect cleaning agent for oil refining equipment, wherein the hydroxyphosphonic acid compound of the deodorizing agent is preferably hydroxyethylidene diphosphonic acid (HEDP), and HEDP itself is stable in nature and is not easy to decompose under normal conditions, especially the C-P chemical bond is very strong, which is difficult to biochemically treat, and will cause COD and total phosphorus to exceed the standard. This chemical often appears in circulating water reagents, and is generally used as a scale inhibitor at a concentration of 1-10 mg / L, as a corrosion inhibitor, it is generally used at a concentration of 10-50 mg / L, and as a cleaning agent, its concentration is as high as 1000-2000 mg / L. For this wastewater, Hu Kewei of Xiangtan University adopted more complex treatment methods such as iron filings micro-electrolysis, Fenton oxidation, and sodium hypochlorite oxidation in the article "Experimental Study on Treatment Process of HEDP Pre-Copper Plating Wastewater". In addition, the agent's passivation agent and activation component both use tetrakis hydroxymethylsulfuric acid (THPS). Xin Qing of Wuhan University wrote in "Evaluation of THPS Green Performance" that THPS is an environmentally friendly green biocide at low concentrations and has good biodegradability, but when the concentration exceeds 10 mg / L, it has a significant inhibitory effect on organisms in sewage and acts as a biocide. Therefore, although the deodorizing and passivating dual-effect cleaning agent provided by CN201210077149 does not require heating, is safe and convenient, and meets the COD ≤1300 mg / L emission standard after compounding, it cannot guarantee that it will not affect the biochemical unit of the sewage treatment plant, especially the sewage treatment plant that does not contain an advanced oxidation unit.

[0004] CN201210397460 discloses a ferrous sulfide passivation cleaning agent, which includes: sodium bicarbonate, sodium hypochlorite, tetrasodium ethylenediaminetetraacetate (EDTA-tetrasodium), potassium ferrate, surfactant and water. It is a new type of high-efficiency multifunctional passivation treatment agent integrating oxidation, adsorption, coagulant, sterilization, insecticide and deodorization. However, the tetrasodium ethylenediaminetetraacetate (EDTA-tetrasodium) used in it has poor biodegradability. At present, due to environmental protection issues, some EU countries stipulate that EDTA is restricted in some cleaning products. The agent adds about 1.5% The mass fraction of sodium dodecylbenzene sulfonate is a controversial chemical internationally. The branched AES has poor biodegradability and has been banned in many countries. The straight-chain LAS has slightly better biodegradability, but the foaming phenomenon it causes in the water affects the reoxygenation rate and oxygenation degree of the water, and ultimately affects the activity of microorganisms. The agent contains about 0.5% mass fraction of alkylphenol polyoxyethylene ether (APE). APE has poor biodegradability and its use has been banned or restricted in many countries and regions. The Chinese national standard for laundry detergent GB / T13171-2004 also prohibits the use of APE.

[0005] CN201910314143 discloses a passivation deodorizing cleaning agent suitable for sulfur-containing gas fields, including potassium ferrate, hydrogen peroxide, N-methyldiethanolamine, 1-(2-aminoethyl)-2-benzyl-imidazoline quaternary ammonium salt, isothiazolinone, aminotri(methylenephosphonic acid) and water. The N-methyldiethanolamine (MDEA) is a difficult-to-degrade organic compound; the aminotri(methylenephosphonic acid) (ATP), 1-(2-aminoethyl)-2-benzyl-imidazoline quaternary ammonium salt and isothiazolinone have weak degradation capabilities and require long-term acclimatization. In addition, the three substances are rich in organic nitrogen and organic phosphorus, which can easily cause the total nitrogen and total phosphorus in the sewage treatment plant to exceed the standard.

[0006] CN201610712970 discloses an environmentally friendly and efficient ferrous sulfide passivator. During the preparation process, more than a dozen chemicals are added, among which the added disodium ethylenediaminetetraacetate (EDTA-disodium) is the same as the tetrasodium ethylenediaminetetraacetate (EDTA-tetrasodium) in patent CN201210397460, and its biodegradability is very poor. In some EU countries, such as Switzerland, its detergent association has passed a resolution not to allow detergent products to contain EDTA-like ingredients, mainly because of concerns about environmental hazards after large-scale use and discharge; the sulfonated lignin added to its corrosion inhibitor, Chen Lixiang clearly pointed out in the article "Progress in Research on Lignin Biodegradation and Its Applications" that the biodegradation of lignin has always been a global research hotspot and problem.

[0007] At present, there are many types of passivation deodorizing agents on the market with complex ingredients. With the improvement of environmental protection concepts, some environmentally friendly agents have also emerged, but only a few environmentally friendly ingredients are added to the agent formula, and their biodegradability and how to achieve standard discharge are not elaborated in detail from the perspective of wastewater treatment. From the existing patents, this type of environmentally friendly agent still has more or less disadvantages of more difficult biodegradable ingredients, rich in organic nitrogen, and rich in organic phosphorus.

[0008] As mentioned above, there are many types of passivation deodorants on the market, with different chemical compositions and structures. Such agents are more concerned with their deodorization function, but often ignore their destructive effects on the environment, and do not consider the means and methods of subsequent environmental protection treatment. Many passivation deodorants have the disadvantages of having many difficult-to-biodegrade components, much organic nitrogen, and much organic phosphorus, and lack a reasonable and effective evaluation method for the agent. At present, the companies that use passivation deodorants lack awareness of the pharmaceutical wastewater generated by passivation deodorization operations. They either discharge it to a sewage treatment plant or blindly cache it in tanks. The former is likely to cause serious impact on the sewage treatment plant, and the latter occupies tank capacity for a long time, which is not a fundamental solution to the problem. Summary of the invention

[0009] In view of the shortcomings of the prior art, the first purpose of the present invention is to provide a method for evaluating the environmental performance of a passivation deodorant, which is used to characterize the biodegradability of the passivation deodorant and the harm to water microorganisms, so as to provide guidance for enterprises in selecting passivation deodorants. At the same time, another purpose of the present invention is to provide a method for treating waste liquid of the passivation deodorant according to the evaluation results of the passivation deodorant.

[0010] The first aspect of the present invention is to provide a method for evaluating the environmental performance of a passivation deodorant, comprising the following steps:

[0011] S1 Pollution factor analysis is used to examine the concentration of each pollution factor in the passivation deodorization agent, including water quality analysis and metal ion analysis, and divides it into good and poor categories according to the metal ion analysis results;

[0012] S2 organic matter removal efficiency evaluation is used to examine the COD removal rate before and after the activated sludge reaction, and it is divided into good and poor categories according to the COD removal rate results;

[0013] S3 nitrification efficiency evaluation is used to examine the ammonia nitrogen removal rate before and after the nitrification reaction, and is divided into good and poor categories according to the ammonia nitrogen removal rate results;

[0014] S4 cell viability evaluation is used to examine the number of nitrifying bacteria cells that survive and die, calculate the viable cell rate, and divide them into good and poor categories based on the viable cell rate results.

[0015] The evaluation method further comprises:

[0016] S5 classifies the passivation deodorizing agents, and the classification method is: if the results of the pollution factor analysis in S1, the organic matter removal efficiency evaluation in S2, the nitrification efficiency evaluation in S3, and the cell viability evaluation in S4 are all good, then the passivation deodorizing agent is an environmentally friendly passivation deodorizing agent; and if the pollution factor analysis result in S1 is poor, or the results of the organic matter removal efficiency evaluation in S2, the nitrification efficiency evaluation in S3, and the cell viability evaluation in S4 are all poor, then the agent is a non-environmentally friendly agent; the rest are general passivation deodorizing agents.

[0017] Metal ion analysis as described in S1 was performed using microwave digestion / inductively coupled plasma mass spectrometry.

[0018] The metal ion analysis focuses on the concentration of heavy metals with emission limits or high biological toxicity, such as manganese, chromium, lead, arsenic, mercury, etc. If the concentration of heavy metals with emission limits exceeds the standard, the evaluation result is poor, otherwise it is good.

[0019] The water quality analysis includes conventional water pollutant items with emission limits and other pollutant items. The conventional water pollutant items with emission limits include pH, COD, BOD 5 , ammonia nitrogen, total nitrogen, salt content, conductivity, nitrate nitrogen, sulfide, etc.; other water pollutants include organic nitrogen, total phosphorus, ORP, TOC, TC, etc.

[0020] The organic nitrogen, total phosphorus and ORP are pollutants that are easily overlooked in water quality analysis. Too high organic nitrogen or total phosphorus means that the passivation deodorant contains a large amount of nitrogen- and phosphorus-containing organic matter, and these organic matter are usually complex in structure and difficult to biodegrade; a high ORP value indicates that the passivation deodorant contains a large amount of oxidant. If the passivation operation is not complete, the high ORP will have a killing effect on the microorganisms in the biochemical unit; the TOC and TC are also important indicators of the water quality analysis of the present invention. It has been found that individual organic compounds can be detected by TOC and TC, but they are zero when COD is measured by potassium dichromate method, such as strong filter essence, and strong filter essence as a high-efficiency oxidant often appears in passivation deodorants.

[0021] If the concentrations of pollutants such as ammonia nitrogen, organic nitrogen, and total phosphorus are high, the focus should be on the evaluation of their biochemical performance. For those with poor biochemical performance, the waste liquid treatment method should include advanced oxidation and post-phosphorus removal.

[0022] The organic matter removal efficiency evaluation described in S2 is to mix the passivation deodorizing agent with wastewater in corresponding proportions, and examine the COD removal rate before and after the reaction by the activated sludge method.

[0023] The organic matter removal efficiency evaluation test adopts the shaking table oscillation method. The operation method is as follows: select a special conical bottle for the shaking table oscillator, first determine the volume of the configured solution, the volume should not exceed 2 / 3 of the capacity of the conical bottle, and then determine the amount of activated sludge, dilution solution, and agent by calculation, then add activated sludge and dilution solution to the conical bottle, then add the agent, and quickly adjust the pH to 6-9. Some samples need to add carbon source, nitrogen source, and phosphorus source as supplements. At the same time, a blank test is set, that is, no agent is added, and nutrients are supplemented. After the configured sample is allowed to stand, a small amount of supernatant is taken and filtered with filter paper to measure COD, and then placed in a shaking table oscillator, and the oscillation reaction is carried out according to the set temperature, time, and speed. After the reaction is completed, it is also allowed to stand and a small amount of supernatant is taken and filtered with filter paper to measure COD, and the data is compared with the indicators before the reaction.

[0024] The test conditions of the shaking table oscillation method are as follows: temperature 15-30°C, speed 100-200 rpm (revolutions / minute), reaction time 24h-96h; activated sludge dosage is controlled at MLSS 5000-20000mg / L, the ratio of sludge MLVSS to MLSS is between 0.5 and 0.8; the agent dosage concentration is 500mg / L-2000mg / L (in terms of COD). The COD of pure passivator may be zero, and nutrients should be supplemented, including glucose as carbon source, urea or ammonium chloride as nitrogen source, and potassium dihydrogen phosphate or dipotassium hydrogen phosphate as phosphorus source; dilute solution uses distilled water or deionized water; alkaline pH regulator uses sodium hydroxide or potassium hydroxide, and acidic pH regulator uses sulfuric acid or hydrochloric acid.

[0025] The COD removal rate is based on 60% of the blank sample removal rate as a reference standard. If it is higher than 60% of the blank sample removal rate, the organic matter removal efficiency evaluation result is good, otherwise it is poor; the blank sample is a glucose solution of the same concentration.

[0026] The nitrification efficiency described in S3 refers to the amount of ammonia nitrogen degraded by unit sludge per unit time. The nitrification efficiency is also evaluated by the shaking table method, and its operation is simply described as follows: select a special conical flask, determine the volume of the reaction solution, and inoculate nitrifying bacteria with an inoculation amount of 10% to 30% of the reaction volume; dilute the agent 1 to 100 times with distilled water, and then add it to the conical flask to the scale line (the controlled volume corresponds to the scale line), and set up a blank sample without adding the agent, and use distilled water instead; add a certain amount of ammonium chloride or urea to control the initial concentration of ammonia nitrogen between 30 and 100 mg / L; use sodium bicarbonate to adjust the initial pH of the reaction system to about 7.5 to 8.5, and use sodium bicarbonate to supplement the alkalinity appropriately during the test; put the configured conical flask into a shaking table oscillator. The test conditions are: temperature 25-35°C, speed 100-200 rpm (revolutions / minute), reaction time 2h-24h; after the reaction, measure pH and ammonia nitrogen, and compare the data with the indicators before the reaction to obtain the ammonia nitrogen removal rate, that is, the nitrification efficiency. The nitrification efficiency evaluation uses a single nitrifying bacteria to examine the ammonia nitrogen removal rate before and after the nitrification reaction of the wastewater prepared by the agent. The nitrification efficiency is based on 60% of the blank sample removal rate as a reference standard. If it is higher than 60% of the blank sample removal rate, the nitrification efficiency evaluation result is good, otherwise it is poor.

[0027] The nitrifying bacteria used in this evaluation are different from decarbonization microorganisms (bacteria, actinomycetes, fungi) in that they are of many types and have strong adaptability. Nitrifying bacteria are very sensitive to the external environment and water quality, and have obvious differences in nitrification rates for different types and concentrations of passivation and deodorization agents. They are very suitable for characterizing the biological toxicity of pharmaceutical wastewater in the present invention. Further, the nitrifying bacteria agent is preferably the nitrifying bacteria agent used in the embodiment of patent CN201010510855. In addition, Novozymes Biosynergist 5805 (product code 7579190-552) or nitrifying bacteria agents with equivalent effects can be selected.

[0028] The cell viability evaluation described in S4 is based on the nitrification efficiency evaluation, and compares the number of surviving and dead nitrifying bacteria cells. If the viable cell rate is higher than 45%, the cell viability evaluation result is good, and if the viable cell rate is lower than 45%, the cell viability evaluation result is poor.

[0029] Since different types and concentrations of deodorizing agents have different effects on nitrifying bacteria, the number of dead and alive cells is also different, which can further characterize the biological toxicity of agent wastewater to microorganisms represented by nitrifying bacteria at the microscopic level. The cell viability evaluation adopts the dye exclusion method, and its mechanism of action is: many acid dyes cannot easily pass through the plasma membrane of living cells to enter the cells, but can penetrate into dead cells and color them, so as to distinguish dead and living cells; trypan blue is a commonly used cell activity dye, which is often used to detect the integrity of cell membranes and cell survival analysis. Its living cells will not be stained blue, while dead cells will be stained light blue.

[0030] The cell viability evaluation operation method is briefly described as follows:

[0031] a. Preparation of Trypan blue stock solution:

[0032] b. Prepare cell suspension;

[0033] c. Preparation and staining: Mix the cell suspension and 0.1% to 0.8% trypan blue solution in a volume ratio of 7:1 to 10:1.

[0034] d. Microscopic observation: Dead cells are stained in a distinct blue color, while living cells are colorless and transparent;

[0035] e. Cell counting: Count live cells and dead cells separately within 3 minutes;

[0036] f. Statistical analysis of cell viability: viable cell rate (%) = number of viable cells / total number of cells × 100%.

[0037] The process of preparing the trypan blue mother solution in step a is: weigh 2 to 8 g of trypan blue, grind it with double distilled water, then add 100 mL of distilled water, filter it with filter paper and store it at 2 to 6 ° C. When using, dilute it with PBS buffer (phosphate buffered saline) to 0.1% to 0.8%; the PBS buffer is one of the commonly used buffers in biological laboratories and has no specific formula. The present invention provides a formula for reference, that is, the drug (NaCl 8.0g, KCl 0.2g, Na 2 HPO 4 ·H 2 O 1.56g , KH 2 PO 4 0.2g) into a beaker filled with double distilled water, stir with a glass rod to fully dissolve, then pour the solution into a conical flask and accurately make up to 1000ml, shake well to form the prepared PBS solution.

[0038] Furthermore, the method for preparing the cell suspension described in step b is: the reaction solution is shaken evenly, and then 5 to 20 ml of the solution is aspirated into a centrifuge tube, digested with a trypsin solution with a mass fraction of 0.1% to 0.5% for 30 to 100 minutes, centrifuged at 1500 to 3000 rpm for 3 to 5 minutes, the supernatant is discarded, and then washed with PBS solution, culture medium (balanced salt solution such as PBS) is added, and the cell suspension is resuspended.

[0039] Furthermore, the cell count described in step e should ensure that the total cell number of the bacterial suspension is not less than 104 cells / ml. If the number is small, centrifugation and re-culture are required. If the number is too large, dilution with PBS culture medium is required to ultimately ensure that the number of cells is sufficient and well dispersed.

[0040] The second aspect of the present invention is to provide a method for treating waste liquid of a passivated deodorant agent, further comprising the following steps:

[0041] S6: using the aforementioned environmentally friendly passivation deodorizing agent or general passivation deodorizing agent to perform deodorizing treatment to obtain environmentally friendly passivation deodorizing agent waste liquid or general passivation deodorizing agent waste liquid;

[0042] S7 For the environmentally friendly passivation deodorization agent waste liquid, conventional demulsification flocculation, oil separation, air flotation, and two-stage biochemical treatment are used, wherein the two-stage biochemical treatment is a primary A / O biochemical treatment and a secondary BAF biochemical treatment;

[0043] S8 For the treatment of general passivation and deodorization agent waste liquid, a hydrolysis acidification unit is added before the primary A / O biochemical in the aforementioned S7 step, and an advanced oxidation unit is added before the secondary BAF biochemical.

[0044] If the total phosphorus concentration is higher than 1 mg / L, a post-phosphorus removal unit should be added after the secondary BAF biochemical unit.

[0045] The advanced oxidation described in S8 includes ozone catalytic oxidation and / or hypochlorous acid advanced oxidation. The residence time of ozone catalytic oxidation and / or hypochlorous acid advanced oxidation is 1h to 8h. The ozone concentration of the ozone catalytic oxidation is 20mg / L to 400mg / L, and the volume space velocity is 0.5h -1 ~2 hours -1 , the dosage of hypochlorous acid in the hypochlorous acid advanced oxidation is 200mg / L to 3000mg / L. The ozone catalytic oxidation and the hypochlorous acid advanced oxidation can further decompose the refractory organic matter, improve the reaction rate and the biodegradability of the wastewater, and facilitate the subsequent treatment to meet the standards; in addition, the ozone catalytic oxidation has the characteristics of strong decomposition ability, short half-life, and will not affect the subsequent biochemical; hypochlorous acid oxidation can remove ammonia nitrogen and decompose strong filter essence. Therefore, the organic matter removal efficiency of S2 is poorly evaluated, and ozone catalytic oxidation is preferred. The nitrification efficiency of S3 is poorly evaluated, and hypochlorous acid advanced oxidation is preferred.

[0046] The demulsification and flocculation is to add demulsifier, polyaluminium chloride (PAC) and polyacrylamide (PAM) into water, stir and mix, and then add them into a regulating tank together with waste liquid; based on the volume of waste liquid, the demulsifier dosage is 10mg / L to 200mg / L waste liquid, the PAC dosage is 20mg / L to 300mg / L waste liquid, and the PAM dosage is 3mg / L to 20mg / L waste liquid, wherein the demulsifier is a commonly used demulsification product on the market.

[0047] The flotation is a two-stage flotation, the first stage adopts vortex flotation, and the second stage adopts dissolved air pressurized flotation. Through the previous demulsification and flocculation, the emulsified oil is separated, and the upper floating oil, scum, alum flocs, etc. are collected and removed after passing through the oil separator and the flotation tank.

[0048] The hydrolysis and acidification is to hydrolyze and acidify macromolecular organic matter into small molecular organic matter, thereby reducing the difficulty of subsequent two-stage biochemical treatment. The residence time is generally 6h to 20h.

[0049] The A / O biochemical process includes an aerobic section and an anoxic section, wherein the aerobic section is in front and the anoxic section is in the back. The aerobic section of the A / O biochemical process has a retention time of 20h to 40h and the anoxic section has a retention time of 3h to 10h. After a long period of aeration in the aerobic section, small molecular organic matter is decomposed into carbon dioxide and water, and ammonia nitrogen is converted into nitrate nitrogen and nitrite nitrogen through nitrification; the anoxic section performs denitrification to remove total nitrogen, and can also remove part of the total phosphorus in the sewage; the secondary BAF biochemical retention time is 4h to 24h, which is used to further remove COD and also plays a filtering role.

[0050] Furthermore, the post-phosphorus removal treatment unit includes two-stage phosphorus removal, the first stage phosphorus removal adds 34mg / L~980mg / L ferric chloride and 10mg / L~700mg / L calcium hydroxide; the second stage phosphorus removal adds 10mg / L~300mg / L ferric chloride and 4mg / L~200mg / L calcium hydroxide. The first stage phosphorus removal adds excessive ferric chloride and calcium hydroxide, which need to be filtered; the second stage phosphorus removal adds a small amount of ferric chloride and calcium hydroxide, and the water body meets the discharge standards after filtration. The ferric chloride is acidic and the calcium hydroxide is alkaline. The two are compounded in a certain proportion to ensure that the liquid pH is neutral, and the subsequent effluent does not need to be pH adjusted.

[0051] Furthermore, after the above treatment process, the effluent meets the discharge standards, that is, meets the requirements of the "Petroleum Refining Industry Pollutant Emission Standard" (GB31570), that is, COD ≤ 60 mg / L, ammonia nitrogen ≤ 8 mg / L, and total phosphorus ≤ 1 mg / L.

[0052] The present invention evaluates the passivation deodorization agent so that enterprises can select the passivation deodorization agent according to its properties. According to the analysis of the agent, the use of non-environmentally friendly agents is avoided so that the waste liquid can meet the emission standards through treatment. The present invention also provides a subsequent treatment method for the selected agent waste liquid, and the treatment process can not only meet the emission standards, but also make the treatment process the most economical and the treatment unit combination optimal. The present invention provides strong technical support for enterprises in the selection and use of agents and the subsequent waste liquid treatment.

[0053] Compared with the prior art, the present invention has the following advantages:

[0054] (1) The evaluation method provided by the present invention is comprehensive, objective and systematic. The pollution factor analysis comprehensively and objectively analyzes the pollutant components of the agent, laying the foundation for subsequent evaluation. The three methods of organic matter removal efficiency evaluation, nitrification efficiency evaluation and cell viability evaluation provide factual basis, which not only examines macroscopic phenomena but also captures microscopic changes. The basis for establishing this method is that the evaluation of organic matter removal efficiency relies on heterotrophic decarbonization bacteria, the evaluation of nitrification efficiency relies on autotrophic nitrifying bacteria, and the evaluation of cell viability focuses on the life and death and reproduction of the cells themselves. The three are both parallel and independent and complement each other.

[0055] (2) The present invention not only evaluates the environmental performance of the passivation deodorization agent, but also provides a corresponding waste liquid treatment method, which provides technical support for enterprises in the selection and use of agents and subsequent waste liquid treatment. At the same time, the difficulty of the waste liquid treatment method also indirectly reflects the environmental performance of the agent.

[0056] (3) The evaluation method provided by the present invention is quick and convenient. The pollution factor analysis can be completed within five days. The COD and nitrification efficiency evaluations are carried out simultaneously, both using a simple and efficient shaking table method. The cell viability evaluation also takes only one day. The total time does not exceed eight days to provide a complete evaluation result.

[0057] (4) The present invention focuses on the conventionally overlooked pollutant components in the pollution factor analysis, including organic nitrogen, total phosphorus, ORP, TOC, TC, etc., which can indirectly reflect the environmental performance of the agent and are also the key indicators of subsequent biochemical evaluation.

[0058] (5) The present invention selects representative nitrifying bacteria to carry out nitrification evaluation, and on this basis, carries out cell viability evaluation to examine the life and death, reproduction and vitality of microbial cells, making the evaluation work more rigorous and complete. The basis for establishing the cell viability evaluation is that nitrifying bacteria are very sensitive to the external environment and water quality, and are also an important component of the microorganisms of the sewage biochemical unit. They are very suitable for characterizing the inhibition degree and toxicity of pharmaceutical wastewater on microorganisms at the microscopic level.

[0059] (6) The evaluation method of the present invention is highly practical and operable. The evaluation test can be carried out in the laboratory, which avoids the direct entry of pharmaceutical wastewater into the sewage treatment plant and brings unpredictable impacts. At the same time, the evaluation method can also be adapted to similar related fields and has very good application value.

[0060] Other features and advantages of the present invention will be described in detail in the following detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0061] Figure 1 A schematic diagram of the environmental performance evaluation method of the passivation deodorant agent of the present invention;

[0062] Figure 2 It is a schematic diagram of the passivation deodorization agent waste liquid treatment method of the present invention. DETAILED DESCRIPTION

[0063] The following non-limiting embodiments may enable a person skilled in the art to more fully understand the present invention, but are not intended to limit the present invention in any way.

[0064] Example 1

[0065] For a certain passivation deodorant, the S1 pollution factor analysis was first performed, including metal ion analysis and water quality analysis. The metal ion analysis was performed using microwave digestion / inductively coupled plasma mass spectrometry, and the water quality analysis was performed using the national standard method, as follows:

[0066] Table 1 Water quality analysis results

[0067] project COD <![CDATA[BOD 5 ]]> pH Conductivity TDS Total hardness <![CDATA[SO 4 2- ]]> <![CDATA[S 2- ]]> Numeric 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

[0068] Note: The unit of conductivity is μs / cm, the unit of redox potential is mv, pH is dimensionless, and the units of other pollution factors are mg / L.

[0069] Table 2 Metal ion analysis results

[0070] project 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 R Se Sr V Zn — — 150 41.7 — 68.3 317 110 963

[0071] Note: Unit: μg / L, “—” means not detected.

[0072] The pollution factor analysis results of this embodiment show that the COD, TOC, ORP, total phosphorus and total nitrogen of the agent are all within a reasonable range. The manganese ion in the metal analysis is relatively small, indicating that the main body of the passivating agent is not potassium permanganate, and other polluting metal ions are relatively small, and the metal ion analysis result is good.

[0073] Further, the removal efficiency of S2 organic matter was evaluated: the shaking table oscillation method was used, the temperature was set at 25°C, the speed was 150rpm, the reaction time was 48h, the volume of the conical flask dedicated to the shaking table was 600ml, the reaction solution was controlled at 350ml, of which 200ml of activated sludge was added, and its MLSS was about 10000mg / L, and the ratio of MLVSS to MLSS was about 0.6; according to the pollution factor analysis, the COD concentration of the agent itself was 15050mg / L, the dosage was 24ml, and about 126ml of distilled water was added. The final solution COD was about 1215mg / L, and the carbon source, nitrogen source, and phosphorus source did not need to be supplemented, and the pH did not need to be adjusted. The blank test activated sludge dosage was 200ml, distilled water was 150ml, and glucose 0.35g, ammonium chloride 0.05g, and potassium dihydrogen phosphate 0.05g were supplemented. The pH, ORP, and COD before and after the reaction were tested, and the water sample needed to be filtered before COD detection. The test results show that the COD removal rate of wastewater containing pharmaceuticals is as high as 69.6%, which is about 78% of the COD removal rate of the blank test. The analysis results of the organic matter removal rate are good, as shown in the table below.

[0074] Table 3 COD removal rate test results

[0075]

[0076] Note: COD is in mg / L, redox potential is in mv, pH is dimensionless

[0077] Further, S3 nitrification efficiency evaluation: using a shaking table oscillation method, setting the temperature to 25°C, the speed to 150rpm, the reaction time to 6h, the volume of the conical flask dedicated to the shaking table to 600ml, the reaction solution to be controlled at 200ml, inoculated with nitrifying bacteria, the nitrifying bacteria used in the embodiment of patent CN201010510855, and the inoculation amount to be 15% of the volume of the reaction solution, i.e. 30ml; the agent was diluted 20 times with distilled water, and then added to the conical flask to the 200ml mark, at which time the COD of the solution was about 800mg / L, and the ammonia nitrogen was about 1.1mg / L, and ammonium chloride was added to adjust the ammonia nitrogen of the solution to 50mg / L; sodium bicarbonate was used to adjust the initial pH of the reaction system to about 8.0, and the pH was adjusted regularly during the test; a blank sample was set, the only difference being that no agent was added, and distilled water was used instead. After the reaction, ammonia nitrogen was measured and compared with the index before the reaction. The nitrification efficiency of the reagent was 91.2%, while the nitrification efficiency of the blank sample was 95.8%. The nitrification efficiency of the reagent was 95.2% of the nitrification efficiency of the blank sample. The nitrification efficiency evaluation result was good.

[0078] Further, the S4 cell viability evaluation was performed as follows:

[0079] a. Prepare 4% trypan blue stock solution: weigh 4g trypan blue, add a small amount of double distilled water to grind, then add 100mL of distilled water, filter with filter paper and store at 3℃. When using, use PBS buffer (NaCl 8.0g, KCl 0.2g, Na 2 HPO 4 ·H 2 O 1.56g, KH 2 PO 4 0.2g, double distilled water to 1000ml) diluted to 0.4%;

[0080] b. Preparation of cell suspension: Take 10 ml of the reaction solution from the initial stage of the nitration efficiency evaluation test and after the reaction is completed, put them into a centrifuge tube, digest them with 0.3% trypsin solution for 50 minutes, centrifuge at 2000 rpm for 4 minutes, discard the supernatant, wash with PBS solution, add culture medium, and resuspend to make a cell suspension.

[0081] c. Preparation and staining: Mix the cell suspension and 0.4% trypan blue solution in a ratio of 8:1.

[0082] d. Microscopic observation: Dead cells are stained in a distinct blue color, while living cells are colorless and transparent;

[0083] e. Cell counting: Count live cells and dead cells separately within 3 minutes;

[0084] f. Statistical analysis of cell viability: viable cell rate (%) = number of viable cells / total number of cells × 100%.

[0085] As shown in the table below, by examining the cell viability before and after the nitrification reaction, the total number of nitrifying bacteria and the number of live bacteria showed an increasing trend. As time went on, the tolerance of nitrifying bacteria to the agent increased, and the cell viability also increased slightly.

[0086] Table 4 Cell viability evaluation results

[0087] project time Dilution multiple Total bacteria count per unit area Number of viable bacteria per unit area Actual total bacterial count Actual number of viable bacteria Cell viability Pharmacy 0h 100000 174 102 7.73E+11 4.53E+11 58.6% Pharmacy 6h 100000 209 147 9.28E+11 6.53E+11 70.3%

[0088] Pollution factor analysis shows that all indicators of the agent are within a reasonable range, and the metal ion analysis result is good; in the evaluation of organic matter removal efficiency, the COD removal rate is 78% of the blank sample, and the organic matter removal efficiency evaluation result is good; the nitrification efficiency is 95.2% of the blank sample, and the nitrification efficiency evaluation result is good; the cell viability is as high as 70.3%, and the cell viability evaluation result is good. Therefore, it is determined that the passivation deodorant is an environmentally friendly agent.

[0089] The overall evaluation results show that the agent has good biodegradability and has no effect on water microorganisms. The corresponding waste liquid treatment method is a conventional sewage treatment process, including demulsification flocculation, oil separation, flotation, primary A / O biochemical, secondary BAF biochemical, and the effluent meets the discharge standards.

[0090] Normal passivation and deodorization agents will be diluted at a certain ratio when used. Assuming a 10-fold dilution, the treatment methods for the above waste liquid include demulsification and flocculation, oil separation, flotation, A / O biochemical, and BAF biochemical in the order of water inlet. The demulsifier uses Huali BKL-1010 water-soluble demulsifier, with a dosage of 120 mg / L, PAC dosage of 140 mg / L, and PAM dosage of 8 mg / L. Flotation uses two-stage flotation of vortex concave and dissolved air pressurization. The residence time of the A / O biochemical aerobic section is 30 hours, the residence time of the anoxic section is 6 hours, and the residence time of the BAF biochemical treatment section is 14 hours. The water quality of the effluent from each unit is shown in the table below, where the pharmaceutical wastewater is mixed wastewater, including the pharmaceutical itself and pollutants in the tower.

[0091] Table 5 Water quality of each unit

[0092] COD Ammonia nitrogen Total Phosphorus Petroleum Pharmaceutical waste liquid 2010 79 5.3 1012 Air floats out of water 1853 67 2.1 15 Aerobic section effluent 198 11.5 0.8 4.2 Anoxic section effluent 75 6.3 0.4 3.5 BAF pool effluent 42 3.7 0.1 1.1

[0093] Through this embodiment, it can be known that the passivation deodorizing agent is an environmentally friendly agent, and the three evaluation results are all good. It can meet the discharge standards of the agent waste liquid by using conventional sewage treatment technology.

[0094] Example 2

[0095] For a certain passivation deodorant, the pollution factor analysis is first carried out, including metal ion analysis and water quality analysis. The metal ion analysis adopts microwave digestion / inductively coupled plasma mass spectrometry, and the water quality analysis adopts the national standard method, as follows:

[0096] Table 6 Water quality analysis results

[0097] project COD <![CDATA[BOD 5 ]]> pH Conductivity TDS Total hardness <![CDATA[SO 4 2- ]]> <![CDATA[S 2- ]]> 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

[0098] Note: The unit of conductivity is μs / cm, the unit of redox potential is mv, pH is dimensionless, and the units of other pollution factors are mg / L.

[0099] Table 7 Metal ion analysis results

[0100] project 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 R Se Sr V Zn — — 2550 27.6 — 41.7 147 640 10100

[0101] Note: Unit: μg / L, “—” means not detected.

[0102] The pollution factor analysis results of this embodiment show that the COD of the agent is high, the total phosphorus is high, and the manganese ion in the metal analysis is less, indicating that the main body of the passivating agent is not potassium permanganate, and other polluting metal ions are less, and the metal ion analysis results are good.

[0103] Further, the method for evaluating the removal efficiency of organic matter is similar to that of Example 1, except that the dosage of the reagent is 16.5 ml, about 133.5 ml of distilled water is added, the COD of the prepared solution is 1115 mg / L, the carbon source, nitrogen source, and phosphorus source do not need to be supplemented, and the pH does not need to be adjusted. The test results show that the COD of the pharmaceutical wastewater is not removed, but increased to 1282 mg / L, while the blank test COD removal rate is as high as 87%, as shown in the table below.

[0104] Table 8 COD removal rate test results

[0105]

[0106] Note: COD is in mg / L, redox potential is in mv, pH is dimensionless

[0107] Further, the nitrification efficiency evaluation method is similar to that of Example 1, except that the reagent is diluted 25 times with distilled water and then added to the conical flask to the 300 ml mark. At this time, the solution COD is about 884 mg / L, the ammonia nitrogen is about 0.56 mg / L, and ammonium chloride is added to adjust the ammonia nitrogen of the solution to 50.2 mg / L. After the reaction is completed, the ammonia nitrogen is measured and compared with the index before the reaction. It is found that the nitrification efficiency of the reagent is 96.5%, while the nitrification efficiency of the blank sample is 95.2%, and the nitrification efficiency of the reagent is 101% of the nitrification efficiency of the blank sample.

[0108] Further, the cell viability was evaluated in the same manner as in Example 1. As shown in the following table, the total number of nitrifying bacteria and the number of live bacteria both showed an increasing trend, and the cell viability was maintained at a high level.

[0109] Table 9 Cell viability evaluation results

[0110] project time Dilution multiple Total bacteria count per unit area Number of viable bacteria per unit area Actual total bacterial count Actual number of viable bacteria Cell viability Pharmacy 0h 100000 165 132 7.33E+11 5.86E+11 80.0% Pharmacy 6h 100000 229 178 1.02E+12 7.91E+11 77.7%

[0111] Pollution factor analysis 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 nitrification efficiency is 101% of the blank sample; the nitrification efficiency evaluation result is good. The cell viability is as high as 77.7%, and the cell viability evaluation result is good. Therefore, it is determined that the passivation deodorant is a general agent.

[0112] The overall evaluation results show that the agent has no biological toxicity, but contains complex organic matter and has a high total phosphorus content. The corresponding waste liquid treatment method is a relatively complex sewage treatment process, including demulsification and flocculation, oil separation, flotation, hydrolysis and acidification, A / O biochemical, ozone catalytic oxidation, and secondary BAF biochemical treatment. After BAF biochemical treatment, the total phosphorus concentration is still higher than 1 mg / L. A post-phosphorus removal unit is added, and the effluent meets the discharge standards. Compared with the traditional treatment process, hydrolysis and acidification treatment, intermediate ozone oxidation retreatment and post-phosphorus removal are added. Among them, ozone oxidation not only improves the biodegradability of wastewater, facilitates BAF deep treatment, but also converts organic phosphorus into inorganic phosphorus, which is beneficial to post-chemical phosphorus removal.

[0113] Normal passivation and deodorization agents will be diluted at a certain ratio when used. Assuming that the dilution is 10 times, the treatment methods for the above waste liquid include demulsification and flocculation, oil separation, flotation, hydrolysis and acidification, A / O biochemical, ozone catalytic oxidation, BAF biochemical, and post-phosphorus removal in the order of water inlet. The demulsifier uses Huali BKL-1010 water-soluble demulsifier, the dosage is 115mg / L, the PAC dosage is 145mg / L, the PAM dosage is 7mg / L, the flotation uses vortex concave and dissolved air pressurization two-stage flotation, the hydrolysis and acidification residence time is 14h, the A / O biochemical aerobic section residence time is 24h, the anoxic section residence time is 8h, the ozone catalytic oxidation residence time is 5h, the ozone concentration is 200mg / L, and the volume space velocity is 1 h -1 The residence time of the BAF biochemical treatment section is 18h. The post-phosphorus removal includes two stages. The first stage phosphorus removal adds 600mg / L ferric chloride and 400mg / L calcium hydroxide, and the second stage phosphorus removal adds 200mg / L ferric chloride and 150mg / L calcium hydroxide. The effluent quality of each unit is shown in the table below, among which the pharmaceutical wastewater is mixed wastewater, including the pharmaceutical itself and pollutants in the tower.

[0114] Table 10 Water quality of each unit

[0115] COD Ammonia nitrogen Total Phosphorus Petroleum Pharmaceutical wastewater 2425 80 1210 1023 Air floats out of water 2216 68 321 16 Hydrolysis acidification stage effluent 1863 55 253 3.5 Aerobic section effluent 986 11.5 232 1.5 Anoxic section effluent 765 6.3 211 1.0 Ozone section water 314 5.3 209 0.2 BAF pool effluent 55 2.7 185 ＜0.1 Post-phosphorus removal effluent 46 2.3 ＜1 ＜0.1

[0116] Through this embodiment, it can be seen that the passivation deodorizing agent is a general agent, the organic matter removal efficiency is poor, the nitrification rate and cell viability are good, and it has no biological toxicity. It uses a complex sewage treatment process to achieve standard discharge. The reason is that the organic matter in the agent itself is difficult to degrade and is rich in organic phosphorus.

[0117] Example 3

[0118] For a certain passivation deodorant, the pollution factor analysis is first carried out, including metal ion analysis and water quality analysis. The metal ion analysis adopts microwave digestion / inductively coupled plasma mass spectrometry, and the water quality analysis adopts the national standard method, as follows:

[0119] Table 11 Water quality analysis results

[0120] project COD <![CDATA[BOD 5 ]]> pH Conductivity TDS Total hardness <![CDATA[SO 4 2- ]]> <![CDATA[S 2- ]]> 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

[0121] Note: The unit of conductivity is μs / cm, the unit of redox potential is mv, pH is dimensionless, and the units of other pollution factors are mg / L.

[0122] Table 12 Metal ion analysis results

[0123] project 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 R Se Sr V Zn — — 1.14 — 154 — 1.22 — —

[0124] Note: Unit: μg / L, “—” means not detected.

[0125] The pollution factor analysis results of this embodiment show that the total phosphorus of the agent is high, COD, TOC, ORP, and total nitrogen are all within a reasonable range, and the manganese ion in the metal analysis is less, indicating that the main body of the passivator is not potassium permanganate, and other polluting metal ions are less, and the metal ion analysis result is good.

[0126] Furthermore, the method for evaluating the removal efficiency of organic matter is similar to that in Example 1, and the COD of the prepared solution is 1198 mg / L. The test results show that the COD removal rate of the wastewater containing the pharmaceutical agent is as high as 68.1%, which is about 76.3% of the COD removal rate of the blank test, as shown in the table below.

[0127] Table 13 COD removal rate test results

[0128]

[0129] Note: COD is in mg / L, redox potential is in mv, pH is dimensionless

[0130] Further, the nitrification efficiency evaluation method is similar to that of Example 1, with the same dilution multiple, and the COD of the prepared solution is about 890 mg / L, and the ammonia nitrogen is 51 mg / L. After the reaction is completed, the ammonia nitrogen is measured, and the data is compared with the index before the reaction, and the nitrification efficiency of the agent is 32.8%, while the nitrification efficiency of the blank sample is 94.4%, and the nitrification efficiency of the agent is 34.7% of the nitrification efficiency of the blank sample.

[0131] Furthermore, the cell viability was evaluated in the same manner as in Example 1. The results are shown in the following table. The total number of nitrifying bacteria and the number of live bacteria showed a significant decreasing trend, and the cell viability was decreasing.

[0132] Table 14 Cell viability evaluation results

[0133] project time Dilution multiple Total bacteria count per unit area Number of viable bacteria per unit area Actual total bacterial count Actual number of viable bacteria Cell viability Pharmacy 0h 100000 133 62 5.91E+11 2.75E+11 46.6% Pharmacy 6h 100000 85 22 3.77E+11 9.77E+10 25.9%

[0134] The results of the pollution factor analysis showed that the metal ion analysis results were good; the COD removal rate in the organic matter removal efficiency evaluation was 76.3% of the blank sample, and the organic matter removal efficiency evaluation result was good; the nitrification efficiency was 34.7% of the blank sample, and the nitrification efficiency evaluation result was poor; the cell viability was only 25.9%, and the cell viability evaluation result was poor. Therefore, it was determined that the passivation deodorant was a general agent.

[0135] The overall evaluation results show that the agent has certain biological toxicity, which is mainly reflected in the impact on the activity of nitrifying bacteria. It also contains complex organic matter and may be rich in organic phosphorus. The corresponding waste liquid treatment method is a relatively complex sewage treatment process, including demulsification and flocculation, oil separation, flotation, hydrolysis and acidification, A / O biochemistry, hypochlorous acid advanced oxidation, secondary BAF biochemical deep treatment, and the total phosphorus concentration is still higher than 1 mg / L after BAF biochemical treatment. A post-phosphorus removal unit is added to ensure that the effluent meets the discharge standards. Compared with the traditional treatment process, hydrolysis and acidification pretreatment, intermediate hypochlorous acid oxidation retreatment and post-phosphorus removal are added. Hypochlorous acid oxidation can remove ammonia nitrogen and convert organic phosphorus into inorganic phosphorus. At the same time, it can also improve the biodegradability of wastewater.

[0136] Normal passivation and deodorization agents will be diluted at a certain ratio when used. Assuming a 10-fold dilution, the treatment methods for the above waste liquid, in order of water inlet, include demulsification and flocculation, oil separation, flotation, A / O biochemistry, hypochlorous acid oxidation, BAF deep treatment, and post-phosphorus removal. The demulsifier uses Huali BKL-1010 water-soluble demulsifier, the dosage is 118mg / L, the PAC dosage is 141mg / L, the PAM dosage is 8mg / L, the flotation uses vortex concave and dissolved air pressurization two-stage flotation, the acidification stage residence time is 8h, the A / O biochemical aerobic stage residence time is 28h, the anoxic stage residence time is 10h, the hypochlorous acid advanced oxidation residence time is 6h, the hypochlorous acid dosage is 1200mg / L, the BAF deep treatment stage residence time is 15h, and the post-phosphorus removal includes two-stage phosphorus removal, the first-stage phosphorus removal adds 580mg / L of ferric chloride and 370mg / L of calcium hydroxide, and the second-stage phosphorus removal adds 180mg / L of ferric chloride and 145mg / L of calcium hydroxide. The effluent quality of each unit is shown in the table below, where the pharmaceutical wastewater is mixed wastewater, including the pharmaceutical itself and pollutants in the tower.

[0137] Table 15 Water quality of each unit

[0138] COD Ammonia nitrogen Total Phosphorus Petroleum Pharmaceutical wastewater 2023 81 896 1016 Air floats out of water 1862 69 265 15 Hydrolysis acidification stage effluent 1693 65 258 7 Aerobic section effluent 345 58 245 1.8 Anoxic section effluent 215 55 186 1.1 Hypochlorous acid section effluent 92 4.3 181 0.3 BAF pool effluent 56 1.2 175 ＜0.1 Post-phosphorus removal effluent 50 0.5 ＜1 ＜0.1

[0139] Through this embodiment, it can be seen that the passivation deodorizing agent is a general agent, with a good organic matter removal efficiency evaluation, and a poor nitrification rate and cell viability evaluation. It uses a complex sewage treatment process to achieve standard discharge. The reason is that the agent has an inhibitory effect on the nitrification rate and is rich in organic phosphorus.

[0140] Example 4

[0141] For a certain passivation deodorant, the pollution factor analysis is first carried out, including metal ion analysis and water quality analysis. The metal ion analysis adopts microwave digestion / inductively coupled plasma mass spectrometry, and the water quality analysis adopts the national standard method, as follows:

[0142] Table 16 Water quality analysis results

[0143] project COD <![CDATA[BOD 5 ]]> pH Conductivity TDS Total hardness <![CDATA[SO 4 2- ]]> <![CDATA[S 2- ]]> 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

[0144] Note: The unit of conductivity is μs / cm, the unit of redox potential is mv, pH is dimensionless, and the units of other pollution factors are mg / L.

[0145] Table 17 Metal ion analysis results

[0146] project 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 R Se Sr V Zn — 13500000 291 — — — 234 108 380

[0147] Note: Unit: μg / L, “—” means not detected.

[0148] The pollution factor analysis results of this embodiment show that the COD and total phosphorus of the agent are relatively high, and the manganese ions in the metal analysis are relatively low, indicating that the main body of the passivating agent is not potassium permanganate, and other polluting metal ions are relatively low, and the metal ion analysis results are good.

[0149] Furthermore, the method for evaluating the removal efficiency of organic matter is similar to that of Example 1, and the COD of the prepared solution is 1230 mg / L. The test results show that the COD of the wastewater containing the pharmaceutical agent is not removed, and the activated sludge is partially dead, and the COD value increases instead of decreases, while the COD removal rate of the blank test is 88.9%, as shown in the table below.

[0150] Table 18 COD removal rate test results

[0151]

[0152] Note: COD is in mg / L, redox potential is in mv, pH is dimensionless

[0153] Further, the nitrification efficiency evaluation method is similar to that of Example 1, with the same dilution multiple, and the COD of the prepared solution is about 885 mg / L, and the ammonia nitrogen is 49.5 mg / L. After the reaction is completed, the ammonia nitrogen is measured, and the data is compared with the indicators before the reaction, and it is found that the nitrification efficiency of the agent is only 15.6%, while the nitrification efficiency of the blank sample is 93.9%, and the nitrification efficiency of the agent is 16.6% of the nitrification efficiency of the blank sample.

[0154] Furthermore, the cell viability was evaluated in the same manner as in Example 1. The results are shown in the following table. The total number of nitrifying bacteria and the number of live bacteria were greatly reduced, and the cell viability decreased significantly.

[0155] Table 19 Cell viability evaluation results

[0156] project time Dilution multiple Total bacteria count per unit area Number of viable bacteria per unit area Actual total bacterial count Actual number of viable bacteria Cell viability Pharmacy 0h 100000 92 32 4.09E+11 1.42E+11 34.7% Pharmacy 6h 100000 43 7 1.91E+11 3.1E+10 16.3%

[0157] The results of pollution factor analysis showed that the metal ion analysis results were good; COD was not removed in the organic matter removal efficiency evaluation, and the organic matter removal efficiency evaluation result was poor; the nitrification efficiency was 16.6% of the blank sample, so the nitrification efficiency evaluation result was poor; the cell viability was only 16.3%, and the cell viability evaluation result was poor. Therefore, it was determined that the passivation deodorant was not an environmentally friendly agent.

[0158] The overall evaluation results show that the agent has strong biological toxicity, which is reflected in the impact on decarbonization microorganisms and nitrifying bacteria, and through the verification of cell activity at the microscopic level, it does have a killing effect. For the wastewater produced by this agent, there is currently no corresponding sewage treatment process that can achieve its discharge standards. In order to further clarify its hazards, a complex sewage treatment process is now used for experimental comparison, including demulsification flocculation, oil separation, flotation, hydrolysis acidification, A / O biochemistry, ozone and hypochlorous acid two-stage oxidation, BAF deep treatment, and post-phosphorus removal.

[0159] Normal passivation and deodorization agents will be diluted at a certain ratio when used. Assuming that the dilution is 10 times, the treatment methods for the above waste liquid include demulsification and flocculation, oil separation, flotation, hydrolysis and acidification, A / O biochemical, ozone and hypochlorous acid two-stage oxidation, BAF deep treatment, and post-phosphorus removal in the order of water inflow. The demulsifier uses Huali BKL-1010 water-soluble demulsifier, the dosage is 130mg / L, the PAC dosage is 150mg / L, the PAM dosage is 10mg / L, the flotation uses vortex concave and dissolved air pressurization two-stage flotation, the hydrolysis and acidification residence time is 16h, the A / O biochemical aerobic section residence time is 30h, the anoxic section residence time is 12h, the ozone catalytic oxidation residence time is 8h, the ozone concentration is 250mg / L, and the volume space velocity is 1.2 h -1 , the residence time of advanced hypochlorous acid oxidation is 4h, the dosage of hypochlorous acid is 1500mg / L, the residence time of BAF deep treatment section is 16h, and the post-phosphorus removal includes two-stage phosphorus removal, the first-stage phosphorus removal adds 800mg / L of ferric chloride and 550mg / L of calcium hydroxide, and the second-stage phosphorus removal adds 250mg / L of ferric chloride and 180mg / L of calcium hydroxide. The water quality of each unit effluent is shown in the table below, among which the pharmaceutical wastewater is mixed wastewater, including the pharmaceutical itself and the pollutants in the tower.

[0160] Table 20 Water quality of each unit

[0161] COD Ammonia nitrogen Total Phosphorus Petroleum Pharmaceutical wastewater 2625 83 1580 1010 Air floats out of water 2314 73 765 14 Hydrolysis acidification stage effluent 1966 68 653 12 Aerobic section effluent 1910 65 623 1.5 Anoxic section effluent 1723 56 577 1.0 Ozone section water 1453 51 550 0.8 Hypochlorous acid section effluent 1395 13 521 0.4 BAF pool effluent 1318 10 502 ＜0.1 Post-phosphorus removal effluent 1316 9.8 353 ＜0.1

[0162] Through this embodiment, it can be seen that the passivation deodorizing agent is a non-environmentally friendly agent. The evaluation of organic matter removal efficiency, nitrification rate and cell viability is very poor. After using a complex sewage treatment process, the water quality is still very poor and is still a long way from meeting the discharge standards.

[0163] Example 5

[0164] For a certain passivation deodorant, the pollution factor analysis is first carried out, including metal ion analysis and water quality analysis. The metal ion analysis adopts microwave digestion / inductively coupled plasma mass spectrometry, and the water quality analysis adopts the national standard method, as follows:

[0165] Table 21 Water quality analysis results

[0166] project COD <![CDATA[BOD 5 ]]> pH Conductivity TDS Total hardness <![CDATA[SO 4 2- ]]> <![CDATA[S 2- ]]> 0 0 7.24 3540 1000 112 830 6.2 Nitrate nitrogen Nitrite Nitrogen Organic nitrogen Ammonia nitrogen Total Nitrogen TOC TC Redox potential Total Phosphorus 3.3 0.21 10.29 19.7 33.5 545 586 687 5

[0167] Note: The unit of conductivity is μs / cm, the unit of redox potential is mv, pH is dimensionless, and the units of other pollution factors are mg / L.

[0168] Table 22 Metal ion analysis results

[0169] project 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 R Se Sr V Zn 25100 — 10400 — — — 115 3930 —

[0170] Note: Unit: μg / L, “—” means not detected.

[0171] The pollution factor analysis results of this embodiment show that the total phosphorus and total nitrogen of the agent are very low, but the redox potential is as high as 687mv. The metal analysis shows that the solution material is simple, and the concentration of each metal ion is very low. It is a non-traditional potassium permanganate passivator. The special feature of this agent is that the COD is zero, but the TOC is 545mg / L, indicating that it contains organic matter that cannot be oxidized by potassium dichromate. It is inferred that it may contain oxidant strong filter essence. The metal ion analysis result is good.

[0172] Further, the method for evaluating the organic matter removal efficiency is similar to that of Example 1, except that the dosage of the reagent is 50 ml, 0.35 g of glucose is additionally added, and the reaction time is extended to 72 h. The test results show that the COD removal rate of the reagent wastewater after 48 h of reaction is only 15.4%, which may be related to the fact that the ORP of the reaction solution is still as high as 256 mv. After extending the reaction time to 72 h, the ORP of the reaction solution will reach 195.8 mv, and the corresponding COD removal rate will rise to 52.5%, while the COD removal rate of the blank sample is as high as 91.6%, and the 72 h organic matter removal efficiency is 57.3% of the blank sample, as shown in the table below.

[0173] Table 23 COD removal rate test results

[0174]

[0175] Note: COD is in mg / L, redox potential is in mv, pH is dimensionless

[0176] Further, the nitrification efficiency evaluation method is similar to that of Example 1, the agent is diluted 20 times with distilled water, and the COD of the prepared solution is about 15 mg / L, and the ammonia nitrogen is 49.6 mg / L. After the reaction is completed, the ammonia nitrogen is measured, and the data is compared with the indicators before the reaction, and it is found that the nitrification efficiency of the agent is only 18.6%, while the nitrification efficiency of the blank sample is 94.5%, and the nitrification efficiency of the agent is 19.7% of the nitrification efficiency of the blank sample.

[0177] Further, the cell viability was evaluated in the same manner as in Example 1. As shown in the following table, the total number of nitrifying bacteria showed a downward trend, the number of live cells increased slightly, and the cell viability increased significantly, indicating that the activity of nitrifying bacteria began to gradually recover after being inhibited.

[0178] Table 24 Cell viability evaluation results

[0179] project time Dilution multiple Total bacteria count per unit area Number of viable bacteria per unit area Actual total bacterial count Actual number of viable bacteria Cell viability Pharmacy 0h 100000 113 23 5.02E+11 1.02E+11 20.6% Pharmacy 6h 100000 65 31 2.88E+11 1.38E+11 47.7%

[0180] Through the previous series of analysis and evaluation, the pollution factor analysis showed that the metal ion analysis results were good. In the evaluation of its organic matter removal efficiency, the COD removal rate at 48h was low, while the COD removal rate at 72h was significantly improved, and the organic matter removal efficiency was 57.3% of the blank sample, and the organic matter removal efficiency evaluation result was good; the nitrification efficiency was greatly affected, only 16.6% of the blank sample, and the nitrification efficiency evaluation result was poor. However, after further verification of cell viability, its cell viability showed a gradual upward trend. After 6h, the cell viability rose to 47.7%, which was greater than 45%, indicating that the high ORP value of the agent in the initial stage affected its biochemical performance. As the reaction time increased, the ORP value decreased, and its inhibitory effect on microorganisms began to disappear, and the cell viability evaluation result was good. Therefore, it was determined that the passivation deodorant was a general agent.

[0181] In view of the special nature of the agent, its sewage treatment has added pretreatment, which includes acidic water regulation, demulsification and flocculation, oil separation, flotation, A / O biochemical, hypochlorous acid oxidation, BAF deep treatment, and the effluent meets the discharge standards. Therefore, compared with the traditional treatment process, acidic water regulation and hypochlorous acid oxidation in the intermediate link are added. Acidic water can reduce the ORP value of the agent wastewater because of the reducing property of sulfide, but acidic water will bring additional ammonia nitrogen, while hypochlorous acid oxidation can remove ammonia nitrogen and decompose strong filter essence to improve the biodegradability of sewage.

[0182] Normal passivation and deodorization agents will be diluted at a certain ratio when used. Assuming a 10-fold dilution, the treatment methods for the above waste liquid, in order of water inlet, include acidic water adjustment, demulsification and flocculation, oil separation, flotation, A / O biochemical, hypochlorous acid oxidation, and BAF deep treatment. The ratio of acidic water to pharmaceutical wastewater is 1:20, the demulsifier uses Huali BKL-1010 water-soluble demulsifier, the dosage is 128 mg / L, the PAC dosage is 142 mg / L, the PAM dosage is 8 mg / L, the flotation adopts two-stage flotation of vortex concave and dissolved air pressurization, the A / O biochemical aerobic section residence time is 24h, the anoxic section residence time is 6h, the hypochlorous acid oxidation time is 3h, the hypochlorous acid dosage is 1300 mg / L, the BAF deep treatment section residence time is 10h, the water quality of the effluent from each unit is shown in the table below, among which the pharmaceutical wastewater is mixed wastewater, including the pharmaceutical itself, pollutants in the tower, and acidic water.

[0183] Table 25 Water quality of each unit

[0184] COD TOC Ammonia nitrogen Total Phosphorus Petroleum Pharmaceutical wastewater 513 55 115 5.4 1016 Air floats out of water 410 54.5 103 2.4 16 Aerobic section effluent 188 54 75 0.9 4.4 Anoxic section effluent 137 50 64 0.4 3.7 Hypochlorous acid oxidation 76 12 11 0.2 1.2 BAF pool effluent 42 5 5.6 0.1 0.5

[0185] Through this embodiment, it can be seen that the passivation deodorizing agent is a general agent. After extending the reaction time, the organic matter removal efficiency is evaluated to be good, and the nitrification rate is evaluated to be poor. However, the cell viability evaluation shows that the activity of nitrifying bacteria has an upward trend. It can achieve standard discharge by adopting a slightly special sewage treatment process. The reason is that the initial redox potential of the agent is relatively high.

Claims

1. A method for evaluating the environmental performance of a passivation deodorant, characterized in that: The steps include: S1 Pollution factor analysis is used to examine the concentration of each pollution factor in the passivation deodorant, including water quality analysis and metal ion analysis, and divides it into good and poor categories according to the metal ion analysis results; S2 organic matter removal efficiency evaluation is used to examine the COD removal rate before and after the activated sludge reaction, and it is divided into good and poor categories according to the COD removal rate results; S3 nitrification efficiency evaluation is used to examine the ammonia nitrogen removal rate before and after the nitrification reaction, and is divided into good and poor categories according to the ammonia nitrogen removal rate results; S4 cell viability evaluation is used to examine the number of nitrifying bacteria cells that survive and die, calculate the viable cell rate, and divide them into good and poor categories based on the viable cell rate results; S5 classifies the passivation deodorant, and the classification process is: if the results of the pollution factor analysis in S1, the organic matter removal efficiency evaluation in S2, the nitrification efficiency evaluation in S3, and the cell viability evaluation in S4 are all good, then the passivation deodorant is an environmentally friendly passivation deodorant; if the pollution factor analysis result in S1 is poor, or the results of the organic matter removal efficiency evaluation in S2, the nitrification efficiency evaluation in S3, and the cell viability evaluation in S4 are all poor, then the agent is a non-environmentally friendly agent; the rest are general passivation deodorants; The water quality analysis in step S1 includes conventional water pollutant items with emission limits and organic nitrogen, total phosphorus, ORP, TOC, and TC analysis indicators; the metal ion analysis focuses on the concentrations of heavy metals with emission limits or high biological toxicity such as manganese, chromium, lead, arsenic, and mercury. If the concentration of heavy metals with emission limits exceeds the standard, the evaluation result is poor, otherwise it is good; The organic matter removal efficiency evaluation in step S2 adopts the shaking table method; the COD removal rate in S2 takes 60% of the blank sample removal rate as the reference standard, and if it is higher than 60% of the blank sample removal rate, the organic matter removal efficiency evaluation result is good, otherwise it is poor; The nitrification efficiency evaluation in step S3 adopts a shaking table method; The nitrification efficiency is based on 60% of the blank sample removal rate as a reference standard. If it is higher than 60% of the blank sample removal rate, the nitrification efficiency evaluation result is good, otherwise it is poor. The cell viability evaluation in step S4 is to compare and examine the number of survival and death of nitrifying bacteria cells on the basis of nitrification efficiency evaluation. If the viable cell rate is higher than 45%, the cell viability evaluation result is good, and if the viable cell rate is lower than 45%, the cell viability evaluation result is poor. The experimental conditions of the shaking table method in step S2 are: temperature 15-30°C, rotation speed 100-200 rpm, reaction time 24h-96h; activated sludge dosage MLSS 5000-20000 mg / L, sludge MLVSS to MLSS ratio between 0.5 and 0.8; agent addition concentration, calculated as COD, is 500 mg / L-2000 mg / L; The shaking table method in step S3 has the following experimental conditions: temperature 25-35° C., rotation speed 100-200 rpm, and reaction time 2 h-24 h.

2. The evaluation method according to claim 1, characterized in that: The cell viability evaluation operation method described in S4 is: a. Preparation of Trypan blue stock solution: b. Prepare cell suspension; c. Preparation and staining: Mix the cell suspension with 0.1% to 0.8% trypan blue solution at a volume ratio of 7:1 to 10:

1. d. Microscopic observation: Dead cells are stained in a distinct blue color, while living cells are colorless and transparent; e. Cell counting: Count live cells and dead cells separately within 3 minutes; f. Statistical analysis of cell viability: viable cell rate (%) = number of viable cells / total number of cells × 100%.

3. A method for treating waste liquid of a passivation deodorant agent, characterized in that: The following steps are involved: S6 According to the environmental performance evaluation method of the passivation deodorant according to any one of claims 1 to 2, an environmentally friendly passivation deodorant or a general passivation deodorant is obtained; the environmentally friendly passivation deodorant or the general passivation deodorant is selected for deodorization treatment to obtain an environmentally friendly passivation deodorant waste liquid or a general passivation deodorant waste liquid; S7 For the environmentally friendly passivation deodorization agent waste liquid, demulsification flocculation, oil separation, air flotation, and two-stage biochemical treatment are used, wherein the two-stage biochemical treatment is a primary A / O biochemical treatment and a secondary BAF biochemical treatment; S8 For the treatment of general passivation and deodorization agent waste liquid, a hydrolysis acidification unit is added before the primary A / O biochemical in the aforementioned S7 step, and an advanced oxidation unit is added before the secondary BAF biochemical.

4. The processing method according to claim 3, characterized in that: If the total phosphorus concentration is higher than 1 mg / L after the secondary BAF biochemical treatment, add a post-phosphorus removal unit.

5. The processing method according to claim 3, characterized in that: The advanced oxidation described in S8 includes ozone catalytic oxidation and / or hypochlorous acid advanced oxidation. The residence time of ozone catalytic oxidation and / or hypochlorous acid advanced oxidation is 1 hour to 8 hours.

6. The processing method according to claim 3, characterized in that: The demulsification and flocculation is to add demulsifier, polyaluminium chloride and polyacrylamide into water, stir and mix, and then add them into a regulating tank together with waste liquid; based on the volume of waste liquid, the demulsifier dosage is 10mg / L-200mg / L, the polyaluminium chloride dosage is 20mg / L-300mg / L, and the polyacrylamide dosage is 3mg / L-20mg / L.

7. The processing method according to claim 3, characterized in that: The air flotation is a two-stage air flotation, the first stage adopts vortex air flotation, and the second stage adopts dissolved air pressurized air flotation.

8. The processing method according to claim 3, characterized in that: The hydrolysis and acidification residence time is 6h to 20h.

9. The processing method according to claim 3, characterized in that: The A / O biochemical process comprises an aerobic section and an anoxic section, wherein the aerobic section is in front and the anoxic section is in the back, the residence time of the aerobic section is 20h to 40h, and the residence time of the anoxic section is 3h to 10h.

10. The processing method according to claim 3, characterized in that: The secondary BAF biochemical retention time is 4h to 24h.

11. The processing method according to claim 4, characterized in that: The post-phosphorus removal treatment unit includes two-stage phosphorus removal, the first-stage phosphorus removal adds 34mg / L-980mg / L ferric chloride and 10mg / L-700mg / L calcium hydroxide; the second-stage phosphorus removal adds 10mg / L-300mg / L ferric chloride and 4mg / L-200mg / L calcium hydroxide.

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