CN113880223A

CN113880223A - Treating agent and method for producing sewage based on bulk drugs

Info

Publication number: CN113880223A
Application number: CN202111334879.XA
Authority: CN
Inventors: 李帅; 李墨爱; 尤新军
Original assignee: Individual
Current assignee: Individual
Priority date: 2021-11-11
Filing date: 2021-11-11
Publication date: 2022-01-04

Abstract

The invention belongs to the technical field of sewage treatment, and particularly relates to a treating agent and a treating method for sewage generated based on bulk drugs; the treating agent comprises the following components in percentage by weight: 20-30 parts of modified fly ash, 10-25 parts of polyacrylamide, 20-30 parts of persulfate and 15-20 parts of potassium ferrate. The fly ash is modified by ferrous sulfate and cobalt sulfate. So that the sewage treatment device can generate multiple catalytic effects in the sewage treatment process. The sewage treatment agent and the waterless treatment scheme have simple processes and CODcrBOD and NH₃The removal rate of-N is high.

Description

Treating agent and method for producing sewage based on bulk drugs

Technical Field

The invention belongs to the technical field of sewage treatment, and particularly relates to a treating agent and a method for producing sewage based on bulk drugs.

Background

Organic pollutant wastewater generated in the production process of the pharmaceutical industry is one of the recognized serious environmental pollution sources. The pharmaceutical industry has been put into one of 12 industries for major pollution control by national environmental protection planning, and the wastewater generated in the production process of pharmaceutical industry becomes the major factor in environmental pollution control. Moreover, with the adoption of more and more strict treatment requirements of the country on the environmental pollution, the national environmental protection department requires that all pharmaceutical enterprises start to execute the water pollutant emission standard of the pharmaceutical industry, and for the enterprises with water pollutants not reaching the standard, the environmental protection department shall charge the enterprises to stop production and settle.

In all product production lines of the whole pharmaceutical industry, the waste water produced by six types of pharmacy, such as fermentation pharmacy, extraction pharmacy, chemical synthesis pharmacy, bioengineering pharmacy, traditional Chinese medicine pharmacy and mixed preparation pharmacy, is mostly high-concentration ammonia nitrogen waste water. The existing treatment method aiming at the high ammonia nitrogen wastewater is not limited to three types of physical method, chemical method and biological method and combination thereof.

Wherein, the chemical synthesis medicines are mostly produced by adopting an intermittent process organization, the chemical reaction steps are multiple, the yield of the main raw materials is generally 60 to 80 percent, and the rest raw materials are all discharged in a form of 'three wastes'. The sources of the chemical synthesis pharmaceutical wastewater are as follows:

(1) process wastewater: mainly comprises centrifuge throwing filtration waste water, extractor layering waste water, distillation concentration condensed water, plate frame filter pressing waste water and the like. The wastewater has the characteristics of complex components, high pollutant content, more toxic substances, poor biodegradability, high salt content and the like.

(2) Washing wastewater: mainly used for cleaning wastewater discharged during various reaction kettles, centrifuges, filter presses, material barrels and pipelines, and also comprises washing water of mops and cleaning cloths, hand washing wastewater and the like. The wastewater discharge rule is indefinite, and the concentration changes greatly.

(3) And (3) other wastewater: mainly comprises vacuum unit drainage, waste gas absorption spray tower replacement drainage, and periodic replacement drainage of a cooling circulating water system, steam condensate water, initial rainwater, domestic sewage and the like. The concentration of the wastewater is not high, but the water quantity is larger.

CN104876295A is magnetized, modified, dried, activated and the like to prepare the organic composite denitrifier modified magnesium-aluminum-iron-water talc magnetic nano-adsorption material, and then the adsorption material is made into an adsorption rod and placed in an adsorption tower to treat high-concentration ammonia nitrogen in chemical wastewater. Has good development prospect in the treatment of high-concentration ammonia nitrogen wastewater. However, the industrial cost is high through complicated operation steps such as high-temperature preparation, magnetic separation and the like.

CN105110561A discloses a method for treating high ammonia nitrogen wastewater under a low dissolved oxygen condition, which comprises the following steps: (1) after the heterotrophic nitrifier is subjected to expanded culture, adding the heterotrophic nitrifier into activated sludge for acclimatization culture; (2) adding a part of the sludge subjected to acclimation culture in the step (1) into an A2/O pool, performing membrane hanging acclimation on a biological rotating disk together with high ammonia nitrogen wastewater until the attachment rate of the biological membrane reaches 10,000-30,000mg/L, discharging effluent into an A2/O pool, simultaneously introducing the high ammonia nitrogen wastewater into an A2/O pool, controlling the dissolved oxygen concentration in an aerobic pool of the A2/O pool to be 0.5-1.0mg/L, and discharging the effluent of the A2/O pool up to the standard. However, the method can add glucose into the muddy water mixture when the acclimatization culture conditions are strict and the wastewater can not meet the nutrition required by the growth of the microorganisms. The dosage of the glucose is adjusted according to the growth conditions of the wastewater and the microorganisms. The cost is increased, and the domestication success rate is limited by the waste water condition. Is not suitable for wide application.

CN106007265A discloses a method for deeply treating biochemical tail water of chemical pharmaceutical wastewater, which adopts a treatment mode of organically combining four processes, namely an enhanced coagulating sedimentation treatment process, a rapid filtration process, a catalytic ozone oxidation treatment process and a magnetic microsphere resin adsorption treatment process.

CN108033649A provides a pharmaceutical wastewater treatment method, mixing distilled water obtained after evaporation desalination of high-salinity pharmaceutical wastewater and supernatant obtained after coagulating sedimentation of low-salinity pharmaceutical wastewater, introducing the mixture into a neutralization tank, performing nitrification and denitrification reactions in an anoxic tank and an aerobic tank in sequence, and finally filtering the mixture through an MBR membrane group, so that COD and ammonia nitrogen in the pharmaceutical wastewater can be effectively degraded, the removal rate of the COD can reach more than 90%, and the removal rate of the ammonia nitrogen can reach more than 87%.

CN 109721155A is a florfenicol pharmaceutical wastewater nitrification and denitrification treatment method, belonging to the pharmaceutical wastewater treatment field. In the wastewater biochemical treatment system, the effluent of the anaerobic sedimentation tank and the effluent of the aerobic sedimentation tank flow back to enter the anoxic tank according to a proportion, and the internal circulation is realized by aerobic and anoxic, so that the nitrification and denitrification process is formed. The new process overcomes the defects of the existing biochemical treatment process, a nitrification and denitrification process is adopted in the wastewater biochemical treatment system, the effluent quality of the biochemical system is better and stable, and the nitrification and denitrification biochemical section formed by aerobic-anoxic has good removal rate on COD and ammonia nitrogen.

CN109879538A discloses a method for treating antibiotic pharmaceutical wastewater with high total nitrogen and high salt content, which comprises the following steps: introducing antibiotic pharmaceutical wastewater into a coagulation air flotation tank, adding a coagulant into the coagulation air flotation tank, and performing coagulation air flotation pretreatment; then introducing the mixture into a hydrolysis acidification tank with built-in filler for hydrolysis acidification treatment; then, introducing the wastewater into an intermittent anoxic/aerobic MBR reaction tank for advanced treatment, and directly discharging the treated effluent.

The invention patent application of CN107032495A discloses a biological treatment combined process for high-COD high-salinity pharmaceutical wastewater, which is characterized in that the water quality reaches the standard after the treatment of a regulating tank, an anaerobic hydrolysis tank, an anoxic/aerobic tank and a membrane biological tank in sequence. For high-COD high-salinity pharmaceutical wastewater, the combined process can effectively degrade COD, ammonia nitrogen and total nitrogen in the pharmaceutical wastewater in a higher salinity environment, the removal rate of the COD can reach more than 90%, the removal rate of the ammonia nitrogen reaches more than 85%, and the removal rate of the total nitrogen reaches more than 70%.

The invention patent application of CN105776740A discloses a treatment method and equipment for up-to-standard discharge of vitamin fermentation pharmaceutical wastewater, and the process comprises the following steps: the wastewater sequentially passes through a pretreatment unit, an anaerobic treatment unit taking an IC reactor as a core, a two-stage short-cut nitrification-denitrification and post-denitrification combined process (hereinafter referred to as a D/N/D unit) and an advanced treatment unit taking catalytic ozone oxidation as a core to gradually remove organic matters, ammonia nitrogen, total nitrogen, suspended matters, chromaticity and the like, so that the emission standard is reached.

CN110746046A discloses a wastewater treatment process for cephalosporin pharmacy, wherein cephalosporin wastewater sequentially passes through a mother liquor adjusting tank, an MVC evaporation system, a cooling crystallization dehydration unit, an anoxic denitrification tank, an aerobic nitrification tank, a sedimentation tank and other treatment units; the total nitrogen is reduced from 17000mg/l to 50mg/l and the COD is reduced from 72000mg/l to 8000mg/l by an MVC treatment unit; TDS is reduced from 78000mg/l to 200 mg/l.

CN110902828A discloses a comprehensive treatment process of high ammonia nitrogen wastewater, belonging to the technical field of chemical wastewater treatment. It comprises the following steps: (1) pretreating the high ammonia nitrogen wastewater, and carrying out nitration reaction on the pretreated effluent; the invention can effectively reduce the ammonia nitrogen concentration in the wastewater and simultaneously can synchronously purify the thiourea-containing organic wastewater.

The invention discloses a chemical wastewater purifying agent and a preparation method thereof, wherein the chemical wastewater purifying agent is prepared from the following raw materials in parts by weight: 5-10 parts of silicon dioxide aerogel, 2-8 parts of graphene oxide, 4-10 parts of zeolite powder, 1-5 parts of carbon fiber, 1-20 parts of solid hydrogel spheres and 5-6 parts of an enzyme-bacterium mixture. The high water-absorbing polymer resin with a certain shape fully absorbs water and swells to form solid hydrogel balls and is used as a carbon fiber carrier, the wastewater treatment agent is prepared in a bead string mode, and each bead string at least comprises one solid hydrogel ball capable of floating on the water surface and two solid hydrogel balls sinking into the water bottom, so that the wastewater treatment agent can be fully contacted with wastewater, and the wastewater treatment efficiency is greatly improved.

The ammonia nitrogen and COD concentration in the wastewater in the pharmaceutical industry are high, the ammonia nitrogen is an important factor causing water eutrophication, and the discharge amount is large, the components are complex, the toxicity is strong, the harm to the water environment is great, and the treatment difficulty is large. In the aspect of high-concentration ammonia nitrogen wastewater treatment, the technology development direction for treating the high-concentration ammonia nitrogen wastewater is ideal as long as the environmental treatment goal of high-efficiency denitrification and the environmental and economic benefit goals of energy conservation, consumption saving, secondary pollution avoidance and the like are pursued. Pharmaceutical wastewater has become one of the important pollution sources, and how to treat the wastewater is a problem of environmental protection at present.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide a treating agent for producing sewage based on bulk drugs. The second purpose of the invention is to provide a production method of the treating agent for producing sewage based on the bulk drugs. The third purpose of the invention is to provide an application of the treating agent in sewage. The treating agent method can effectively remove organic matters, salt, ammonia nitrogen and the like in the high-concentration pharmaceutical wastewater, and the treating method is simple to operate, stable to operate and high in practical engineering feasibility. In particular can effectively degrade COD and ammonia nitrogen in the pharmaceutical wastewater.

The technical scheme of the invention is as follows:

a treating agent for sewage generated based on bulk drugs comprises the following components in parts by weight:

20-30 parts of modified fly ash, 10-25 parts of polyacrylamide, 20-30 parts of persulfate and 15-20 parts of potassium ferrate.

Preferably, the treating agent comprises the following components in parts by weight: 25 parts of modified fly ash, 20 parts of polyacrylamide, 25 parts of persulfate and 20 parts of potassium ferrate.

Preferably, the persulfate is a composite salt formed by any one or more of sodium persulfate, ammonium persulfate, potassium persulfate and potassium hydrogen persulfate. Sodium persulfate is preferred

The preparation method of the modified fly ash comprises the following steps: dissolving a certain amount of ferrous sulfate and cobalt sulfate in deionized water, adding a certain amount of fly ash, fully and uniformly stirring, standing for precipitation, collecting the precipitate, and drying until no water is separated to obtain the modified fly ash.

Preferably, the weight ratio of the ferrous sulfate, the cobalt sulfate, the water and the fly ash is as follows: 0.02-0.05: 2-3: 1.

Preferably, the drying temperature is 100-115 DEG C

The second purpose of the invention is to provide a production method of the treating agent for producing sewage based on raw material medicines, which comprises the following steps:

step 1: 20-30 parts of modified fly ash, 10-25 parts of polyacrylamide, 20-30 parts of persulfate and 15-20 parts of potassium ferrate according to weight ratio; mixing;

step 2: mixing the powder, and grinding the powder uniformly to obtain the treating agent.

The third purpose of the invention is to provide an application of the treating agent in sewage. The method specifically comprises the following steps:

firstly, adding 1.0-1.8 kg of treating agent into sewage according to the amount of each liter of sewage;

secondly, adding hydrogen peroxide into the sewage according to the amount of 20-40 mg/L of the sewage per liter;

thirdly, stirring the sewage added with the hydrogen peroxide and the treating agent of the components for 40-60 minutes;

fourthly, stopping stirring, and standing the sewage for 30-60 minutes;

and fifthly, discharging the clean water after standing.

The invention has the technical effects that:

the invention combines the Fenton oxidation method, the persulfate oxidation method, the potassium ferrate oxidation method and the fly ash adsorption flocculation method to be applied to the sewage treatment. Particularly, the modified fly ash and the loaded ferrous sulfate provide a catalyst for Fenton oxidation, so that the efficiency of the Fenton oxidation is improved; loaded ferrous sulfate and Fe in cobalt sulfate²⁺And Co²⁺Catalyzing the oxidation of persulfate. Due to Fe²⁺Is adsorbed in the gaps of the fly ash, and reduces the influence on the oxidizing capability of the potassium ferrate. The fly ash and polyacrylamide fully adsorb, flocculate and precipitate the oxidized product, and improve COD, BOD and NH in the pharmaceutical sewage₃The removal rate of-N has a synergistic effect. The problem of harsh requirements on microbial treatment in the prior art is avoided.

Detailed Description

The invention is further illustrated by the following examples, which should be properly understood: the examples of the present invention are merely illustrative and not restrictive, and therefore, the present invention may be modified in a simple manner without departing from the scope of the invention as claimed.

In the following examples, various procedures and methods not described in detail are conventional methods well known in the art.

Modified fly ash: dissolving 400g of ferrous sulfate and 400g of cobalt sulfate in 30kg of deionized water, adding 20kg of fly ash, fully and uniformly stirring, standing for precipitation, collecting the precipitate, and drying at 110 ℃ until no water flows out to obtain modified fly ash; and (5) standby.

The production method of the treating agent comprises the following steps:

Example 1

Taking sewage generated by quantitative bulk drug production, and detecting that CODcr is 1864 mg/L; BOD is 525 mg/L; NH (NH)₃-N is 198 mg/L.

The sewage treatment step:

firstly, adding 1.0kg of treating agent into sewage according to the amount of each liter of sewage: 20 parts of modified fly ash, 10 parts of polyacrylamide, 20 parts of sodium persulfate and 15 parts of potassium ferrate;

secondly, adding hydrogen peroxide into the sewage according to the amount of 20mg/L of sewage per liter;

thirdly, stirring the sewage added with the hydrogen peroxide and the treating agent of the components for 60 minutes;

fourthly, stopping stirring, and standing the sewage for 60 minutes;

and fifthly, discharging the clean water after standing.

Example 2

Taking sewage generated in the production of quantitative raw material medicines, and detecting that CODcr is 8568 mg/L; the BOD is 2315 mg/L; NH (NH)₃-N was 225 mg/L.

The sewage treatment step:

firstly, adding 1.5kg of treating agent into sewage according to the amount of each liter of sewage: 25 parts of modified fly ash, 20 parts of polyacrylamide, 25 parts of sodium persulfate and 20 parts of potassium ferrate;

secondly, adding hydrogen peroxide into the sewage according to the amount of 30mg/L of sewage per liter;

fourthly, stopping stirring, and standing the sewage for 60 minutes;

and fifthly, discharging the clean water after standing.

Example 3

Taking sewage generated in the production of quantitative raw material medicines, and detecting that CODcr is 16548 mg/L; BOD is 4137 mg/L; NH (NH)₃-N is 859 mg/L.

The sewage treatment step:

firstly, adding 1.8kg of treating agent into sewage according to the amount of each liter of sewage: 30 parts of modified fly ash, 25 parts of polyacrylamide, 30 parts of sodium persulfate and 20 parts of potassium ferrate;

secondly, adding hydrogen peroxide into the sewage according to the amount of 40mg/L of sewage per liter;

fourthly, stopping stirring, and standing the sewage for 60 minutes;

and fifthly, discharging the clean water after standing.

Comparative example 1

The sewage treatment step:

firstly, adding a treating agent into sewage according to the dosage of 1.5kg per liter of sewage: 25 parts of fly ash (unmodified), 5 parts of ferrous sulfate, 5 parts of cobalt sulfate, 20 parts of polyacrylamide, 25 parts of sodium persulfate and 20 parts of potassium ferrate;

fourthly, stopping stirring, and standing the sewage for 60 minutes;

and fifthly, discharging the clean water after standing.

Comparative example 2

Taking sewage generated in the production of quantitative raw material medicines, and detecting that CODcr is 8568 mg/L; the BOD is 2315 mg/L; NH3-N was 225 mg/L.

The sewage treatment step:

secondly, stirring the sewage added with the treating agent of the components for 60 minutes;

step three, stopping stirring, and standing the sewage for 60 minutes;

and fourthly, discharging the clean water after standing.

Comparative example 3

Modified fly ash: dissolving 400g of ferrous sulfate in 30kg of deionized water, adding 20kg of fly ash, fully and uniformly stirring, standing for precipitation, collecting the precipitate, and drying at 110 ℃ until no water is separated to obtain the modified fly ash for later use.

The sewage treatment step:

firstly, adding 1.5kg of treating agent into sewage according to the amount of each liter of sewage: 25 parts of modified fly ash (without cobalt sulfate), 20 parts of polyacrylamide, 25 parts of sodium persulfate and 20 parts of potassium ferrate;

fourthly, stopping stirring, and standing the sewage for 60 minutes;

and fifthly, discharging the clean water after standing.

Verification enforcement

In order to verify the effect of the technical scheme of the invention. The sewage was treated according to the above examples, and then the quality of the treated water was measured, and the results are shown in Table 1.

As can be seen from the above table, the sewage of different concentrations in examples 1 to 3 was treated according to the method of the present inventionThe latter CODcr, BOD and NH₃The content of-N is significantly reduced. Particularly, the CODcr concentration of the high-concentration sewage in the embodiment 3 is about 2 times of that of the embodiment 2, the adding amount of the catalyst is not doubled, but the removal rate is still high, and the catalytic effect is good. The probability of contact between the high concentration and the modified fly ash is high, and the probability of adsorption and oxidation is high. In comparative example 1, the coal ash is not modified by ferrous sulfate and cobalt sulfate, and the removal rate is obviously reduced. In comparative example 2, hydrogen peroxide was not added, and fenton oxidation could not be achieved, but the removal rate could still reach 85%. In comparative example 3, only ferrous sulfate modified fly ash is used, and the removal rate effect is only about 80%, so that the cobalt sulfate plays a synergistic role in catalysis. As can be seen, the treating agent of the invention can treat high-concentration and low-concentration pharmaceutical sewage CODcr, BOD and NH₃The removal rate of N is high, and the treatment effect is better especially on low-concentration sewage.

Claims

1. The treating agent for sewage generated based on the raw material medicines is characterized by comprising the following components in parts by weight: 20-30 parts of modified fly ash, 10-25 parts of polyacrylamide, 20-30 parts of persulfate and 15-20 parts of potassium ferrate.

2. The treating agent according to claim 1, wherein the treating agent consists of the following components in parts by weight: 25 parts of modified fly ash, 20 parts of polyacrylamide, 25 parts of persulfate and 20 parts of potassium ferrate.

3. The treating agent according to claim 1, wherein the persulfate is a complex salt composed of any one or more of sodium persulfate, ammonium persulfate, potassium persulfate and oxone.

4. The treating agent according to claim 1, wherein the modified fly ash is prepared by a method comprising: dissolving a certain amount of ferrous sulfate and cobalt sulfate in deionized water, adding a certain amount of fly ash, fully and uniformly stirring, standing for precipitation, collecting the precipitate, and drying until no water is separated to obtain the modified fly ash.

5. The treating agent according to claim 4, wherein the weight ratio of the ferrous sulfate, the cobalt sulfate, the water and the fly ash in the preparation method of the modified fly ash is as follows: 0.02-0.05: 2-3: 1.

6. The treating agent according to claim 4, wherein the drying temperature in the preparation method of the modified fly ash is 100-115 ℃.

7. The process for producing a treating agent according to claim 1,

8. The use of the treatment agent of claim 1 in bulk drug produced wastewater,

fourthly, stopping stirring, and standing the sewage for 30-60 minutes;

and fifthly, discharging the clean water after standing.