Pharmaceutical wastewater treatment method

Abstract

The invention relates to the technical field of water treatment, in particular to a pharmaceutical wastewater treatment method. The pharmaceutical wastewater treatment method comprises the following steps: adjusting the pH value of raw water to be acidic, adding an agent, controlling the pH value of a reaction system to be acidic, and carrying out reaction treatment to obtain effluent meeting wastewater discharge requirements; the raw water is to-be-treated pharmaceutical wastewater; the agent comprises an iron source, a carbon-based nano material and hydrogen peroxide, and the iron source contains ferrous ions; the molar ratio of ferrous ions in the added iron source to hydrogen peroxide is 1: (1-4). When the pharmaceutical wastewater is treated by adopting the method disclosed by the invention, the types and the content of impurities in the wastewater can be effectively reduced, particularly toxic and harmful substances such as organic halides, anilines, nitrobenzenes, phenols and benzaldehydes can be effectively removed, the COD (Chemical Oxygen Demand) content of the wastewater and the acute toxicity and the genetic toxicity of luminous bacteria are effectively reduced, and the biochemical degradability of the wastewater is improved.

Description

Technical Field

[0001] The present application relates to the field of water treatment technology, and in particular to a method for treating pharmaceutical wastewater. Background Art

[0002] Chemical synthetic drugs refer to raw materials that are made from simpler compounds or natural products with certain basic structures through a series of reaction processes and have preventive, therapeutic and diagnostic effects on the human body. With the development of organic chemistry, pharmacology and chemical industry, chemical synthetic drugs have developed rapidly, and their varieties, output, output value, etc. have occupied a leading position in the pharmaceutical industry. There are thousands of chemical synthetic drugs used clinically in the world.

[0003] However, due to the long synthesis process, many reaction steps, and the final product only accounting for 5%-15% of the total raw materials, the production process of chemical synthetic drugs will produce very serious waste gas, waste water, waste residue and other pollution. Among them, pharmaceutical wastewater has the following characteristics: most of them contain biotoxic substances that are difficult to degrade and inhibit the growth of microorganisms, have high chromaticity, contain a large amount of organic solvents (such as benzene, aliphatic compounds, ammonia nitrogen, esters, alcohols, sulfides, etc.), contain salt, starch, metal ions, antibiotic residues and other wastes, solid suspended substance (SS), chemical oxygen demand (COD), dichromate oxidizability index (COD Cr ), high biochemical oxygen demand (BOD) concentration, large fluctuations in water quality, high toxicity and difficulty in biodegradation. Traditional biological treatment technology has poor treatment effects on it. Conventional water quality indicators are difficult to meet the increasingly stringent wastewater discharge requirements, and the residual concentration of toxic and harmful substances such as antibiotics in the effluent is high, posing a high biological risk to the receiving water body. Summary of the invention

[0004] In view of the shortcomings of the prior art mentioned above, the present invention provides a method for treating pharmaceutical wastewater to solve the technical problems such as the poor treatment effect of the above-mentioned traditional biological treatment technology, the difficulty of conventional water quality indicators in meeting the increasingly stringent wastewater discharge requirements, and the high residual concentration of toxic and harmful substances such as antibiotics in the effluent, which brings higher biological risks to the receiving water body.

[0005] To achieve the above objectives, the scheme of this application is as follows:

[0006] The present invention provides a method for treating pharmaceutical wastewater, which comprises the following steps:

[0007] The pH of the raw water is adjusted to acidic, a reagent is added, and the pH of the reaction system is controlled to be acidic, and the reaction treatment obtains effluent that meets the wastewater discharge requirements;

[0008] The raw water is pharmaceutical wastewater to be treated;

[0009] The agent comprises an iron source, a carbon-based nanomaterial and hydrogen peroxide, wherein the iron source contains ferrous ions;

[0010] The molar ratio of the ferrous ions in the added iron source to the hydrogen peroxide is 1:1-4.

[0011] It should be noted that, in the present application, the iron source includes but is not limited to: ferrous sulfate, ferrous chloride, ferrous nitrate, hydrate of ferrous sulfate, hydrate of ferrous chloride, hydrate of ferrous nitrate.

[0012] In the present application, the carbon-based nanomaterial may include at least one of carbon nanoparticles, amorphous carbon, carbon nanospheres, carbon nanotubes, porous carbon, carbon nanosheets, molecular sieves, zeolites, and the like.

[0013] Optionally, the pharmaceutical wastewater is wastewater generated during the production process of chemical synthetic drugs.

[0014] Optionally, the chemically synthesized drug is ciprofloxacin or its derivatives.

[0015] In the present application, ciprofloxacin or its derivatives are prepared by condensing 2,4-dichloro-5-fluoroacetophenone with dimethyl carbonate (or diethyl carbonate), ethoxymethylenating with triethyl orthoformate, aminated with cyclopropylamine, and finally cyclizing and piperazine substitution.

[0016] Optionally, the raw water meets at least one of the following indicators (A1)-(A4):

[0017] (A1) Impurity Type

[0018] There are at least 14 halogenated organic compounds;

[0019] There are at least 48 non-halogenated organic compounds;

[0020] (A2) Chemical oxygen demand ≥ 700 mg / L;

[0021] (A3) The relative inhibition rate of luminescent bacteria is ≥75%.

[0022] (A4) Genotoxicity ≥60 mg / L.

[0023] In this application, the pharmaceutical wastewater of ciprofloxacin or its derivatives includes halogenated organic matter and non-halogenated organic matter, 14 kinds of halogenated organic matter, including chlorinated organic acid, brominated organic acid, chlorinated aniline, bromine-containing heterocycle, chlorinated heterocycle, chlorinated ketone, brominated alkane and chlorinated alkane, etc. There are 48 non-halogenated organic species, including organic acid, aniline, phenol, heterocyclic compound, ketone, alkane, alkene, alcohol, etc., among which chlorinated organic acid accounts for 40%-45% of the mass content of total impurities, chlorinated ketone accounts for 8%-15% of the mass content of total impurities, and alkane accounts for 30%-35% of the mass content of total impurities.

[0024] Optionally, the wastewater discharge requirements include the following indicators (B1):

[0025] (B1) Chemical oxygen demand ≤ 500 mg / L.

[0026] Optionally, the effluent meets at least one of the following indicators (C1)-(C4):

[0027] (C1) Impurity types and contents

[0028] No more than 3 halogenated organic compounds;

[0029] No more than 19 non-halogenated organic substances;

[0030] (C2) Chemical oxygen demand ≤ 300 mg / L;

[0031] (C3) Relative inhibition rate of luminous bacteria ≤ -20%;

[0032] (C4) Genotoxicity ≤180μg / L.

[0033] In this application, the chemical oxygen demand is tested using the potassium dichromate method.

[0034] Optionally, the relative inhibition rate of luminescent bacteria is tested using a luminescent bacteria method.

[0035] Optionally, genotoxicity is tested using the umu genotoxicity test.

[0036] Optionally, the molar ratio of the ferrous ion to the hydrogen peroxide is 1:2-4., preferably 1:2.5-3.5.

[0037] Optionally, in the reaction system, the concentration of the ferrous ions is 0.025-0.035 mol / L.

[0038] Optionally, the mass ratio of the hydrogen peroxide to the chemical oxygen demand of the wastewater to be treated is 2-4:1, preferably 2.5-4:1.

[0039] Optionally, in the reaction system, the concentration of the carbon-based nanomaterial is 200-450 mg / L, preferably 350-420 mg / L.

[0040] Optionally, the reaction duration is 1-2 hours.

[0041] As described above, the pharmaceutical wastewater treatment method of the present application has the following beneficial effects:

[0042] The method of the present application is used to treat pharmaceutical wastewater, which can effectively reduce the types and contents of impurities in the wastewater, and in particular can effectively remove toxic and harmful substances such as organic halides, anilines, nitrobenzenes, phenols, and benzaldehydes.

[0043] The method of the present application is used to treat pharmaceutical wastewater, which can effectively reduce the COD content of the wastewater, the acute toxicity and genetic toxicity of luminous bacteria, and improve the biodegradability of the wastewater. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the structures shown in these drawings without paying creative work.

[0045] Figure 1 is the total organic carbon (TOC) removal rate, UV 254 Removal rate and ciprofloxacin hydrochloride (CPFX) removal rate test result graph, the ordinate represents the removal rate;

[0046] Figure 2 is the total organic carbon (TOC) removal rate, UV 254 Removal rate and ciprofloxacin hydrochloride (CPFX) removal rate test result graph;

[0047] Figure 3 Total organic carbon (TOC) removal rate, UV 254 Removal rate and ciprofloxacin hydrochloride (CPFX) removal rate test results chart. DETAILED DESCRIPTION

[0048] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0049] An embodiment of the present invention provides a method for treating pharmaceutical wastewater, wherein the pharmaceutical wastewater is wastewater generated in the production process of a chemical synthetic drug, and the chemical synthetic drug is ciprofloxacin or its derivatives; the method comprises the following steps:

[0050] The pH of the raw water is adjusted to acidic, a reagent is added, and the pH of the reaction system is controlled to be acidic, and the reaction treatment obtains effluent that meets the wastewater discharge requirements;

[0051] The raw water is pharmaceutical wastewater to be treated;

[0052] The agent comprises an iron source, a carbon-based nanomaterial and hydrogen peroxide, wherein the iron source contains ferrous ions;

[0053] The molar ratio of ferrous ions in the added iron source to hydrogen peroxide is 1:1-4.

[0054] The raw water meets at least one of the following indicators (A1)-(A4):

[0055] (A1) Impurity Type

[0056] There are at least 14 halogenated organic compounds;

[0057] There are at least 48 non-halogenated organic compounds;

[0058] (A2) Chemical oxygen demand ≥ 700 mg / L;

[0059] (A3) The relative inhibition rate of luminescent bacteria is ≥75%.

[0060] (A4) Genotoxicity ≥ 60 mg / L;

[0061] Wastewater discharge requirements include the following indicators (B1):

[0062] (B1) Chemical oxygen demand ≤ 500 mg / L;

[0063] The effluent meets at least one of the following criteria (C1)-(C4):

[0064] (C1) Impurity types and contents

[0065] No more than 3 halogenated organic compounds;

[0066] No more than 19 non-halogenated organic substances;

[0067] (C2) Chemical oxygen demand ≤ 300 mg / L;

[0068] (C3) Relative inhibition rate of luminous bacteria ≤ -20%;

[0069] (C4) Genotoxicity ≤180μg / L.

[0070] In the following description, numerous details are discussed to provide a more thorough explanation of embodiments of the present invention; however, it is apparent to one skilled in the art that embodiments of the present invention may be practiced without these specific details.

[0071] (I) Optimizing the amount of carbon-based nanomaterials

[0072] 1.1 A method for treating ciprofloxacin pharmaceutical wastewater, the specific steps are as follows:

[0073] The pH of ciprofloxacin pharmaceutical wastewater (before treatment) was adjusted to 3.5, and ferrous sulfate heptahydrate, carbon-based nanomaterial carbon nanospheres (commercially available) and hydrogen peroxide were added to the ciprofloxacin pharmaceutical wastewater to obtain a reaction system in which the concentration of ferrous sulfate heptahydrate was 0.025 mol / L, the concentration of carbon nanospheres was 500 mg / L and the concentration of hydrogen peroxide was 0.10 mol / L, and the reaction was stirred for 1 hour.

[0074] 1.2 Several portions of ciprofloxacin pharmaceutical wastewater (from the same source as 1.1) were treated in the same manner as 1.1, except that the concentration of the carbon-based nanomaterials was adjusted to 400 mg / L, 300 mg / L, 200 mg / L, 100 mg / L and 0 mg / L, respectively.

[0075] Detect the total organic carbon (TOC) content, UV 254 and ciprofloxacin hydrochloride (CPFX) content, and calculated the total organic carbon (TOC) removal rate, UV 254 The removal rate and ciprofloxacin hydrochloride (CPFX) removal rate are shown in Figure 1 shown.

[0076] Depend on Figure 1 It can be seen that the total organic carbon (TOC) removal rate and UV 254 The removal rates of total organic carbon (TOC), UV 254 When the concentration of carbon-based nanomaterials was 400 mg / L, the removal rate of total organic carbon (TOC), UV 254 The removal rate of ciprofloxacin hydrochloride (CPFX) increased to 53.1%, 84.4% and 100%, respectively, which were 13.6%, 9.1% and 4.2% higher than those of the reaction system without carbon nanospheres. When the amount of carbon nanospheres added continued to increase to a concentration of 500 mg / L, the improvement in the water purification effect was not obvious.

[0077] (II) Optimizing the dosage of ferrous ions

[0078] 2.1 A method for treating ciprofloxacin pharmaceutical wastewater, the specific steps are as follows:

[0079] The pH of ciprofloxacin pharmaceutical wastewater (before treatment) was adjusted to 3.5, and ferrous sulfate heptahydrate, carbon-based nanomaterials (commercially available) and hydrogen peroxide were added to the ciprofloxacin pharmaceutical wastewater to obtain a molar ratio of ferrous ions to hydrogen peroxide (i.e., n(Fe 2 + ): n(H 2 O 2 )) is 1:12, the concentration of carbon-based nanomaterials is 400 mg / L and the concentration of hydrogen peroxide is 0.10 mol / L, and the reaction is stirred for 1 hour.

[0080] 2.2 The molar ratio of ferrous ions to hydrogen peroxide (i.e. n(Fe 2+ ): n(H 2 O 2 Several portions of ciprofloxacin pharmaceutical wastewater (from the same source as 2.1) were treated in the same manner as 2.1, except that the ratio of the wastewater to the reaction mixture was adjusted to 1:8, 1:4, 1:3, 1:1, and 1:1 respectively.

[0081] Detect the total organic carbon (TOC) content, UV 254 and ciprofloxacin hydrochloride (CPFX) content, and calculated the total organic carbon (TOC) removal rate, UV 254 The removal rate and ciprofloxacin hydrochloride (CPFX) removal rate are shown in Figure 2 shown.

[0082] like Figure 2 As shown, the molar ratio of ferrous ion to hydrogen peroxide (i.e., n(Fe 2+ ): n(H 2 O 2 )) When the ratio was adjusted from 1:12 to 1:3, after stirring for 1 hour, the removal rate of total organic carbon (TOC), UV 254 The removal rates of Fe and ciprofloxacin hydrochloride (CPFX) were increased from 38.1%, 81.7% and 95.3% to 52.8%, 84.0% and 100%, respectively. 2+ As the dosage continued to increase, the total organic carbon (TOC) removal rate and UV 254 The removal rate of ciprofloxacin hydrochloride (CPFX) did not increase but decreased. Obviously, 1:3 is the optimal molar ratio of ferrous ion to hydrogen peroxide (i.e., n(Fe 2+ ): n(H 2 O 2 )).

[0083] (III) Optimizing the dosage of hydrogen peroxide

[0084] 3.1 A method for treating ciprofloxacin pharmaceutical wastewater, the specific steps are as follows:

[0085] The pH of ciprofloxacin pharmaceutical wastewater (before treatment) was adjusted to 3.5, and ferrous sulfate heptahydrate, carbon-based nanomaterials (commercially available) and hydrogen peroxide were added to the ciprofloxacin pharmaceutical wastewater to obtain a carbon-based nanomaterial concentration of 400 mg / L, a ferrous ion concentration of 0.033 mol / L, and a mass ratio of hydrogen peroxide to the chemical oxygen demand of the wastewater to be treated (i.e., m(H 2 O 2 :COD)) in the reaction system of 0.5:1, and stir the reaction for 1 hour.

[0086] 3.2 The mass ratio of hydrogen peroxide to the chemical oxygen demand of the wastewater to be treated (i.e. m(H 2 O 2 Several portions of ciprofloxacin pharmaceutical wastewater (from the same source as 3.1) were treated in the same manner as 3.1, except that the ratio of carbon dioxide to water was 1:1, 2:1, 2.5:1, 3:1, and 4:1 respectively.

[0087] Detect the total organic carbon (TOC) content, UV 254 and ciprofloxacin hydrochloride (CPFX) content, and calculated the total organic carbon (TOC) removal rate, UV 254 The removal rate and ciprofloxacin hydrochloride (CPFX) removal rate are shown in Figure 3 shown.

[0088] like Figure 3 As shown in the figure, when the mass ratio of hydrogen peroxide to the chemical oxygen demand of the wastewater before treatment is small, that is, the amount of hydrogen peroxide added is small, the total organic carbon (TOC) removal rate and UV 254 The removal rates of total organic carbon (TOC), UV 254 The removal rate of total organic carbon (TOC), UV removal rate and ciprofloxacin hydrochloride (CPFX) removal rate gradually increased. When the dosage of hydrogen peroxide increased to a mass ratio of 3:1 with the chemical oxygen demand of the wastewater before treatment, if the dosage of hydrogen peroxide continued to increase, the removal rate of total organic carbon (TOC), UV 254 The removal rate of ciprofloxacin hydrochloride (CPFX) did not change significantly or decreased instead of increasing. Obviously, the optimal mass ratio of hydrogen peroxide addition to the chemical oxygen demand of the wastewater before treatment is 3:1.

[0089] (IV) Reaction under optimal conditions

[0090] Example 1

[0091] The pH of ciprofloxacin pharmaceutical wastewater (before treatment) was adjusted to 3.5, and ferrous sulfate heptahydrate, carbon nanospheres (commercially available) and hydrogen peroxide were added to the ciprofloxacin pharmaceutical wastewater to obtain a carbon-based nanomaterial concentration of 400 mg / L, a ferrous ion concentration of 0.033 mol / L, and a mass ratio of hydrogen peroxide to the chemical oxygen demand of the wastewater before treatment (i.e., m(H 2 O 2 :COD)) in a reaction system of 3:1, and stir the reaction for 1 hour.

[0092] Comparative Example 1

[0093] Ciprofloxacin pharmaceutical wastewater (from the same source as in Example 1) was treated in the same manner as in Example 1 except that no carbon nanospheres were added.

[0094] Comparative Example 2

[0095] Ciprofloxacin pharmaceutical wastewater (from the same source as in Example 1) was treated in the same manner as in Example 1, except that iron powder was used instead of ferrous sulfate heptahydrate.

[0096] Performance Testing

[0097] The types and peak areas of impurities such as chlorinated organic acids, brominated organic acids, chlorinated anilines, bromine-containing heterocyclic substances, chlorinated heterocyclic substances, chlorinated ketones, brominated alkanes, chlorinated alkanes, etc., organic acids, anilines, phenols, heterocyclic compounds, ketones, alkanes, alkenes, alcohols, other non-halogenated organic substances, etc. before and after treatment in Example 1 and Comparative Examples 1-2 were detected by gas chromatography-mass spectrometry. The results are shown in Table 1 (Fenton effluent refers to the wastewater after treatment in Comparative Example 1, iron powder Fenton refers to the wastewater after treatment in Comparative Example 2, and carbon-based nanomaterial Fenton refers to the wastewater after treatment in Example 1, and the peak area reflects the concentration of each substance.

[0098] Table 1 Test results

[0099]

[0100] As shown in Table 1, 62 substances were detected in the ciprofloxacin pharmaceutical wastewater before treatment. After being treated by each Fenton system, the abundance and concentration of the substance peaks in the ciprofloxacin pharmaceutical wastewater were significantly reduced. Among them, after being treated by comparative example 1, the total peak area of ​​the system decreased by about 98.5%, and only 28 substances were detected, including 6 halogenated organics and 22 non-halogenated organics; after being treated by comparative example 2, the total peak area of ​​the system decreased by 97.0%, and 28 substances were detected after treatment, including 4 halogenated organics and 24 non-halogenated organics; and embodiment 1 had the best wastewater treatment effect, with a total peak area decrease of 98.6%, and only 22 substances were detected, of which only 3 halogenated organics were detected. The results show that the method of the present application for treating ciprofloxacin pharmaceutical wastewater can effectively reduce the types and impurity contents of impurities in wastewater, especially can effectively remove toxic and harmful substances such as organic halides, anilines, nitrobenzenes, phenols, benzaldehydes, etc.

[0101] The chemical oxygen demand (COD) of the wastewater before and after treatment in Example 1 and Comparative Examples 1-2 was measured by potassium dichromate method, and the results are shown in Table 2;

[0102] The ratio of biochemical oxygen demand to chemical oxygen demand (BOD) of the wastewater before and after treatment in Example 1 and Comparative Examples 1-2 was measured. 5 / COD index), the specific test method is as follows: According to HJ 505-2009 Water Quality Five-Day Biochemical Oxygen Demand (BOD 5 ) Determination of BOD by dilution and inoculation method 5 , then follow the BOD 5 / COD index = formula BOD 5 ÷COD is calculated, and the results are shown in Table 2;

[0103] The luminescent bacteria method was used to detect the acute toxicity EC50 of the wastewater before and after treatment in Example 1 and Comparative Examples 1-2 and the relative inhibition rate of luminescent bacteria at 100% wastewater concentration. The results are shown in Table 2.

[0104] The umu genetic toxicity test method (ie, SOS / umu test method) was used to detect the genetic toxicity of the wastewater before and after treatment in Example 1 and Comparative Examples 1-2. The results are shown in Table 2.

[0105] Table 2 Test results

[0106]

[0107] As shown in Table 2, the COD of ciprofloxacin pharmaceutical wastewater before treatment was 743.6 mg / L. After treatment with each Fenton system, the COD of the wastewater was significantly reduced. After treatment with Comparative Example 1, Comparative Example 2 and Example 1, the COD of ciprofloxacin pharmaceutical wastewater was reduced to 338.0 mg / L, 368.8 mg / L and 294.4 mg / L, respectively, and the BOD 5 / COD index is increased from 0.25 before treatment to 0.43, 0.30 and 0.45 respectively, acute toxicity EC50 is increased from 28.8% before treatment to 100%, luminous bacteria relative inhibition rate of 100% wastewater concentration is reduced from 79.4% before treatment to -12.7%, 23.2% and -32.0% respectively, genetic toxicity is reduced from 66.6mg / L before treatment to 242.7ug / L, 446.4ug / L and 160.4ug / L respectively, and genetic toxicity reduction rate exceeds 99%. Obviously, the method of the present application has the best treatment effect on ciprofloxacin pharmaceutical wastewater. The result shows that the method of the present application is used to treat pharmaceutical wastewater, which can effectively reduce the COD content of wastewater, the acute toxicity and genetic toxicity of luminous bacteria, and improve the biodegradability of wastewater.

[0108] The ciprofloxacin pharmaceutical wastewater (from the same source as in Example 1) was treated in the same manner as in Example 1 except that carbon nanoparticles, amorphous carbon, carbon nanotubes or porous carbon were used as carbon-based nanomaterials. The COD of the treated wastewater was ≤300 mg / L, and the BOD 5 / COD index increased to ≥0.42, acute toxicity EC50 reached 100%, the relative inhibition rate of luminous bacteria at 100% wastewater concentration was reduced to ≤-30.0%, and the genetic toxicity reduction rate was reduced to ≤165ug / L.

[0109] The above embodiments are merely illustrative of the principles and effects of the present invention, and are not intended to limit the present invention. Anyone familiar with the technology may modify or change the above embodiments without violating the spirit and scope of the present invention. Therefore, all equivalent modifications or changes made by a person of ordinary skill in the art without departing from the spirit and technical ideas disclosed by the present invention shall still be covered by the claims of the present invention.

Claims

1. A method for treating pharmaceutical wastewater, characterized in that: The following steps are involved: The pH of the raw water is adjusted to acidic, a reagent is added, and the pH of the reaction system is controlled to be acidic, and the reaction treatment obtains effluent that meets the wastewater discharge requirements; The raw water is pharmaceutical wastewater to be treated; The agent comprises an iron source, a carbon-based nanomaterial and hydrogen peroxide, wherein the iron source contains ferrous ions; The molar ratio of the ferrous ions in the added iron source to the hydrogen peroxide is 1:1-4.

2. The pharmaceutical wastewater treatment method according to claim 1, characterized in that: The pharmaceutical wastewater is wastewater generated during the production of chemical synthetic drugs.

3. The pharmaceutical wastewater treatment method according to claim 2, characterized in that: The chemically synthesized drug is ciprofloxacin or its derivatives.

4. The pharmaceutical wastewater treatment method according to claim 1, characterized in that: The raw water meets at least one of the following indicators (A1)-(A4): (A1) Impurity Type There are at least 14 halogenated organic compounds; There are at least 48 non-halogenated organic compounds; (A2) Chemical oxygen demand ≥ 700 mg / L; (A3) The relative inhibition rate of luminescent bacteria is ≥75%. (A4) Genotoxicity ≥60 mg / L.

5. The pharmaceutical wastewater treatment method according to claim 1, characterized in that: The wastewater discharge requirements include the following indicators (B1): (B1) Chemical oxygen demand ≤ 500 mg / L.

6. The pharmaceutical wastewater treatment method according to claim 1, characterized in that: The effluent meets at least one of the following indicators (C1)-(C4): (C1) Impurity types and contents No more than 3 halogenated organic compounds; No more than 19 non-halogenated organic substances; (C2) Chemical oxygen demand ≤ 300 mg / L; (C3) Relative inhibition rate of luminous bacteria ≤ -20%; (C4) Genotoxicity ≤180μg / L.

7. The pharmaceutical wastewater treatment method according to claim 1, characterized in that: In the reaction system, the concentration of the ferrous ions is 0.025-0.035 mol / L.

8. The pharmaceutical wastewater treatment method according to claim 7, characterized in that: The mass concentration ratio of the hydrogen peroxide to the chemical oxygen demand of the wastewater to be treated is 2-4:

1.

9. The pharmaceutical wastewater treatment method according to claim 1, characterized in that: In the reaction system, the concentration of the carbon-based nanocomposite material is 200-450 mg / L.

10. The pharmaceutical wastewater treatment method according to claim 1, characterized in that: The reaction time is 1-2 hours.

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