CN203960003U - Process system for the treatment of high gravity fermentation class or chemosynthesis class pharmacy waste water - Google Patents

Abstract

The utility model discloses the process system for the treatment of high gravity fermentation class or chemosynthesis class pharmacy waste water, it is characterized in that: the hydrolysis acidification pool (1), up-flow anaerobic sludge blanket (UASB) reactor (2), first carrier fluidized bed (3), activated sludge tank (4), Second support fluidized-bed (5), settling tank (6), Fenton (Fenton) reaction tank (7), ozone oxidation pond (8), the rear biochemistry pool (9) that comprise mutual configuration.It is COD, the ammonia nitrogen in the art breading waste water of core that the utility model adopts " acidication+UASB+ is carrier fluidized bed+biochemistry of Fenton oxidation+catalytic ozonation+afterwards ", efficient biochemical system and advanced catalytic oxidation technique are mutually combined, organic pollution materials in fast degradation sewage, make inlet COD concentration up to 20000mg/L, ammonia nitrogen during up to 600mg/L, final outflow water COD, ammonia nitrogen reach respectively 120mg/L, below 15mg/L, reach and surpass emission standard, being specially adapted to the processing of high gravity fermentation class pharmacy waste water.

Description

Process system for treating high-concentration fermentation or chemical synthesis pharmaceutical wastewater

technical field

The utility model relates to a process system for treating industrial waste water, in particular to a process system for treating high-concentration fermentation, chemical synthesis and pharmaceutical waste water.

Background technique

According to incomplete statistics, there are currently more than 4,000 domestic enterprises engaged in pharmaceutical production and research, producing more than 10,000 kinds of raw materials with an annual output of nearly one million tons (t), and the research and development of related new drugs is also continuously developing. in progress. Although the total production value of the pharmaceutical industry only accounts for about 1.6% of the country, its wastewater discharge accounts for more than 2%. According to statistics, the annual discharge of wastewater from the pharmaceutical industry reaches 2.5×10 ⁸ t, the chemical oxygen demand is about 1.51×10 ⁵ t, and the annual average treatment rate is less than 30%.

The high-concentration organic wastewater produced in the pharmaceutical process mainly includes antibiotic production wastewater, synthetic drug production wastewater, and washing water and flushing wastewater in the production process of various preparations. Among them, fermentation and chemical synthesis pharmaceuticals are the focus of pollution control in the pharmaceutical industry And difficulties, in the production process of the pharmaceutical industry, due to the complex composition of raw materials, the composition of wastewater is complex. The characteristics of pharmaceutical wastewater are as follows: ①The volume and quality of pharmaceutical wastewater change with the change of production process, and most of them are discharged intermittently, resulting in uneven drainage water quality and large changes in water quality and quantity. ②The organic components contained are complex and changeable, contain many heterocyclic and refractory substances, have strong inhibition to microorganisms, high toxicity, deep color and high salt content. ③ The content of organic matter is extremely high, usually the range of COD is 20000-50000mg/L, and the water quality is slightly acidic, which is a typical high-concentration organic wastewater. Therefore, it is urgent to find a treatment method for the efficient degradation of pharmaceutical wastewater, so as to realize the comprehensive and stable discharge of wastewater discharged from enterprises.

At home and abroad, the combination of materialization and biology is still the main treatment method. Such as membrane separation technology, anaerobic-aerobic combination technology, hydrolytic acidification + contact oxidation, upflow anaerobic sludge bed (UASB) reactor + sequencing batch activated sludge process (SBR), upflow sludge bed- Filter (UBF) + cycle activated sludge method (CASS), etc., with the "GB21903-2008 Fermentation Pharmaceutical Industry Water Pollutant Discharge Standard" and "GB21904-2008 Chemical Synthesis Pharmaceutical Industry Water Pollutant Discharge Standard" Implementation, the combination of physicochemical and biological processes cannot meet the requirements, and advanced treatment becomes necessary, which increases the cost of pharmaceutical wastewater treatment. Environmental protection requirements have become an important factor restricting the further development of many biopharmaceutical manufacturers. Traditional methods have deficiencies in treatment efficiency, secondary pollution, and treatment costs. It is difficult to achieve up-to-standard discharge of pharmaceutical wastewater, and due to deficiencies in design, operation management, etc., wastewater treatment systems have large engineering investment, high operating costs, and technical problems. The process is complicated and the purification efficiency is not high.

Utility model content

The technical problem to be solved by the utility model is the treatment process system of industrial wastewater, especially to provide a process system for treating high-concentration fermentation, chemical synthesis and pharmaceutical wastewater, and solve the problems of purification efficiency and treatment cost in the above-mentioned prior art. The treatment system can quickly degrade the organic pollutants in the sewage, so that the final effluent COD and ammonia nitrogen can reach below 200mg/L and 15mg/L respectively, reaching and exceeding the discharge standard, especially suitable for fermentation, chemical synthesis, Wastewater treatment in biochemical, pharmaceutical and other fields.

The technical problem to be solved by the utility model is achieved through the following technical solutions:

A process system for treating high-concentration fermentation or chemical synthesis pharmaceutical wastewater, including mutually configured hydrolytic acidification tanks, upflow anaerobic sludge bed (UASB) reactors, first carrier fluidized beds, activated sludge tanks, The second carrier fluidized bed, sedimentation tank, Fenton reaction tower, ozone oxidation tank, post-biochemical tank. The mutual configuration refers to interconnection through water pipelines and pumps.

The hydrolytic acidification tank is provided with a heating rod.

The front end of the upflow anaerobic sludge bed (UASB) reactor is provided with a pipeline mixer to add phosphorus and alkali;

The inside of the upflow anaerobic sludge bed (UASB) reactor is provided with a water distributor, a three-phase separator, and several sampling ports; the sampling ports are arranged along the height direction of the reactor,

The reactor is equipped with a pneumatic diaphragm pump for internal circulation.

The first carrier fluidized bed and the second carrier fluidized bed are provided with suspended fillers. The main material of the suspended filler is high-density polyethylene (HDPE), with a nominal diameter of 25±2mm, a nominal length of 10±1mm, and a bulk density of the carrier filler: 98(±1)kg/m ³ .

The filling rate of the suspended filler in the first carrier fluidized bed and the second carrier fluidized bed is 20-60%.

The residence time of the hydrolytic acidification tank is 5-20h; the residence time of the upflow anaerobic sludge bed (UASB) reactor is 20-100h; the residence time of 1# carrier fluidized bed, activated sludge tank, and 2# carrier fluidized bed 20-50h; residence time of sedimentation tank 2-8h; residence time of Fenton (Fenton) reaction tower 2-6h; residence time of ozone oxidation tank 1-5h, residence time of post-biochemical tank 6-20h.

An aeration device is provided at the bottom of the first carrier fluidized bed, the activated sludge tank, and the second carrier fluidized bed; the aeration device communicates with the aeration equipment.

The sedimentation tank communicates with the first carrier fluidized bed through an air stripping device. The Fenton (Fenton) reaction tank is connected with the ozone oxidation tank by a lift pump;

The ozone oxidation pools are several pools connected in series or in parallel. The ozone oxidation pool is connected with an ozone generator. The ozone oxidation tank is connected with a tail gas destruction device;

The ozone oxidation tank is filled with a loaded transition metal ion catalyst with a volume ratio of 20%-100%. The loaded transition metal ion catalyst is an ozone oxidation catalyst, which can be activated carbon, silica gel, ceramsite, zeolite, molecular sieve, and aluminum oxide. One or more compounding compositions of Fe, Cu, Mn, Co, Pd, Ni, Mn are loaded as active components; the main material of the suspended filler is high-density polyethylene.

The utility model adopts the above-mentioned technical scheme, and compared with the prior art, it has the following characteristics and advantages:

1. This combined process system is based on the combined process equipment using "hydrolytic acidification + UASB + carrier fluidized bed + Fenton oxidation + ozone catalytic oxidation + post-biochemical" as the core to treat COD and ammonia nitrogen in pharmaceutical wastewater, so that the concentration of COD in the influent can reach as high as 20,000mg /L and ammonia nitrogen up to 600mg/L, the final effluent COD and ammonia nitrogen reach below 100mg/L and 15mg/L respectively, reaching the "GB21903-2008 Fermentation Pharmaceutical Industry Water Pollutant Discharge Standard" and "GB21904-2008 Chemical Synthesis Pharmaceutical Industry According to the discharge standard stipulated in the Industrial Water Pollutant Discharge Standard, the cost of medication after process treatment is about 10 yuan per ton of water.

2. This combined process system can quickly degrade the organic pollutants in the sewage, so that the final effluent COD and ammonia nitrogen can reach below 200mg/L and 15mg/L respectively, reaching the discharge standard stipulated in GB8978-1996 "Comprehensive Wastewater Discharge Standard", especially It is used in the treatment of wastewater in the fields of fermentation, chemical synthesis, biochemical, pharmaceutical, and other fields.

3. The utility model has a high COD removal rate. Under the action of the loaded transition metal ion catalyst, it produces a comprehensive and intense oxidation reaction to remove or decompose and transform highly refractory COD components, thereby achieving the purpose of COD removal.

4. The carrier fluidized bed system adopts a unique suspended filler, which is conducive to the growth of microorganisms that degrade refractory organic matter. The biological flora is rich and the effluent water quality is good.

5. The utility model has the advantages of small floor area, short construction period, low operating cost, low processing cost, and obvious economic and social benefits.

Description of drawings

Below in conjunction with accompanying drawing, the utility model is further described.

Fig. 1 is a process flow diagram of the utility model

Fig. 2 is the structural representation of the utility model process system

Figure 3-1 is a schematic diagram of the structure of the utility model suspension packing

Figure 3-2 is a side view of Figure 3-1

In the figure: 1-hydrolytic acidification tank, 2-upflow anaerobic sludge bed (UASB) reactor, 3-first carrier fluidized bed, 4-activated sludge tank, 5-second carrier fluidized bed, 6 -Sedimentation tank, 7-Fenton (Fenton) reaction tank, 8-ozone oxidation tank, 9-post-biochemical tank, 10-heating rod, 11-pipeline mixer, 12-water distributor, 13-three-phase separator, 14-several sampling ports, 15-pneumatic diaphragm pump, 16-aeration device, 17-aeration equipment, 18-air lift device, 19-suspension packing, 20-outer ring, 21-inner ring, 22-diameter Directional ribs, 23-small fins, 24-radial radiation fins, 25-connecting ribs, 26-chamber, 27-lift pump, 28-ozone generator, 29-exhaust gas destruction device.

Detailed ways

The process system for treating high-concentration fermentation or chemical synthesis pharmaceutical wastewater as shown in Figure 1, Figure 2, and Figure 3: includes a hydrolytic acidification tank 1 configured with water pipelines and pumps, and an upflow anaerobic sludge bed (UASB) reactor 2, first carrier fluidized bed 3, activated sludge tank 4, second carrier fluidized bed 5, sedimentation tank 6, Fenton (Fenton) reaction tank 7, ozone oxidation tank 8, biochemical tank 9. Heating rod 10, pipe mixer 11, water distributor 12, three-phase separator 13, several sampling ports 14, pneumatic diaphragm pump 15, aeration device 16, aeration device 17, air lift device 18, suspended filler 19 , outer ring 20, inner ring 21, radial ribs 22, small fins 23, radial radiation fins 24, connecting ribs 25, chamber 26, lift pump 27, ozone generator 28, exhaust gas destruction device 29.

The specific process steps of this system and the functions of each section of equipment are as follows:

(1) Wastewater, such as pharmaceutical wastewater, is pumped into the hydrolytic acidification tank 1 by a metering pump, and the hydrolytic acidification tank is provided with a heating rod 10 to keep the inlet water temperature at about 30° C., and the wastewater is treated first. The water delivery hydrolysis acidification tank plays the role of adjusting the quality and quantity of incoming water and reducing the impact on the subsequent processing units. The organic matter in the wastewater is initially degraded in the hydrolysis acidification tank, and the macromolecular organic matter is decomposed into small molecular organic matter, which can improve the subsequent biochemical treatment. efficiency;

(2) The effluent of the above-mentioned hydrolytic acidification tank 1 enters the upflow anaerobic sludge bed (UASB) reactor 2. The characteristics and advantages of the upflow anaerobic sludge bed (UASB) reactor are mainly reflected in the formation of granular sludge, so that the reaction The sludge concentration in the reactor is greatly increased, so the hydraulic retention time is greatly shortened; at the same time, a three-phase separator 13 is installed in the upflow anaerobic sludge bed (UASB) reactor, which saves the sedimentation tank, so the structure is simpler .

If there is a lack of phosphorus in the waste water, a pipeline mixer can be set before the UASB reactor 2 to throw 11 to add supplementary phosphorus; at the same time, alkali can be added in time according to needs, such as NaOH, to ensure that the upflow anaerobic sludge bed (UASB ) The reactor 2 is at the most suitable pH value, which is convenient for maintaining a stable reaction environment for the anaerobic methanogens in the reactor.

In this system, the upflow anaerobic sludge bed (UASB) reactor 2 is provided with a number of sampling ports 14 arranged along the height direction of the reactor, which is convenient for observation and sampling of sludge. In order to enhance the contact between sludge and waste water, the reactor is provided with an air-operated diaphragm pump 15 for internal circulation, which effectively speeds up the reaction rate. After the above treatment, most of the COD of the wastewater in the UASB reactor is removed.

(3) The effluent from the above-mentioned upflow anaerobic sludge bed (UASB) reactor enters the first carrier fluidized bed 3, the activated sludge tank 5, and the second carrier fluidized bed in order to remove organic matter and ammonia nitrogen respectively. The carrier fluidized bed adopts suspended filler 19, which floats with the water flow in the reaction tank under the disturbance of the blower aeration device 16, so that the carrier fluidized bed has higher sludge concentration and higher density than traditional biochemical process equipment. In a uniform fluidized state, the attached growth of microorganisms can reach a high biomass, and the biological concentration in the reaction tank can reach 2 to 4 times that of the traditional suspended growth activated sludge process, up to 8 to 12g/L, and the degradation efficiency is therefore Multiplied, so as to obtain better purification effect. This process section adopts two-stage carrier fluidized bed to fully balance the contradiction between processing load and project investment, and reduces the dosage of suspended biological filler.

(4) The effluent of the above-mentioned carrier fluidized bed enters the sedimentation tank 6 for mud-water separation. The sedimentation tank adopts a vertical flow sedimentation tank. In the vertical flow sedimentation tank, the sewage flows vertically from top to bottom, and the suspended matter settles into the tank In the conical sedimentation bucket at the bottom, the clarified water flows out from the surrounding overflow weir around the pool. The advantage of the vertical flow sedimentation tank is that it occupies a small area and is easy to discharge mud. Part of the sludge passes through the air lift device and returns to the front-end first carrier fluidized bed 3 to maintain the concentration of suspended sludge in the system.

(5) After the pharmaceutical wastewater is treated by the first carrier fluidized bed 3, the activated sludge tank 4, and the second carrier fluidized bed biochemical 5, most of the organic matter is treated, and the remaining organic matter that is difficult to degrade has been difficult to pass through biochemical treatment. For further degradation, advanced treatment must be carried out.

A certain amount of sulfuric acid, hydrogen peroxide, and ferrous sulfate are added to the effluent of the sedimentation tank, and the oxidation reaction is first carried out in a Fenton reaction tank. The Fenton oxidation method will generate a large number of hydroxyl radicals (OH) in the reaction. It is a very active and non-selective species. Its oxidation potential is 2.8V and its oxidation ability is very strong. It can trigger the oxidation of most organic substances in aqueous solution. reduction reaction. However, the Fenton method alone needs to consume a large amount of acid and alkali substances, and will generate a large amount of sludge. Therefore, in order to take into account the effect of advanced treatment and operating costs, this process system reduces the reagent dosage of Fenton oxidation treatment, appropriately increases the COD value of the effluent, and introduces the effluent to the ozone oxidation tank 8 for ozone catalytic oxidation treatment. The ozone catalytic oxidation process is currently recognized as an advanced technology for treating high-concentration, refractory organic wastewater. The feature of this technology is that the ozone oxidant can effectively generate and increase free radicals in the reaction system under the action of the newly developed loaded transition metal ion catalyst. As a result, a comprehensive and intense oxidation reaction is produced to remove or decompose and transform highly refractory COD components. The ozone catalytic oxidation reaction does not need to be carried out under high temperature and high pressure, and can meet the reaction requirements under normal conditions, and obtain high oxidation treatment efficiency.

(6) The above-mentioned oxidized effluent enters the post-biochemical tank for aerobic biochemical treatment. After the wastewater is oxidized, the biodegradability of the wastewater is improved, and the aerobic biochemical treatment of the wastewater can further remove the organic matter in the wastewater, and the required cost is also very low.

Trial operation example 1 of this combined process system

A pharmaceutical company in Guangdong is an important yeast production base in China. In the production process of yeast, waste molasses is used as raw material. After being utilized by yeast, a large amount of high-concentration and high-color organic wastewater is discharged. The wastewater is divided into primary separation wastewater, secondary separation wastewater, and tertiary separation wastewater. It is composed of various flushing wastewater, etc. In order to meet the environmental protection requirements of the country, the wastewater needs to be treated.

The experimental conditions are as follows:

The amount of pharmaceutical wastewater treated in this experiment is 20L/h, the COD is about 20000mg/L, the pH value is between 4 and 5, and the ammonia nitrogen is 100-600mg/L. The residence time of hydrolytic acidification tank 1 is 10h; the residence time of upflow anaerobic sludge bed (UASB) reactor 2 is 70h, the circulation flow rate is 180-300L/h, the dosage of phosphoric acid is 180mg/L; the first carrier fluidized bed 3 residence time 45h, activated sludge tank 4 residence time 45h, second carrier fluidized bed 4 residence time 34h; sedimentation tank 6 residence time 4h, sludge return flow 20-80L/h; Fenton (Fenton) reaction tank 7 residence time 4h , the dosage of sulfuric acid and ferrous sulfate is 2000mg/L, the dosage of hydrogen peroxide is 1200mg/L; the residence time of ozone oxidation tank 8 is 1h, and the dosage of ozone is 200mg/L; the residence time of post-biochemical tank 9 is 10h. Multiple groups of experiments were taken to measure COD and ammonia nitrogen in the effluent of each unit. The COD data of the effluent of each unit is shown in Table 1. The effluent of ammonia nitrogen can reach below 15mg/L. After calculation, the cost of chemical consumption is about 10 yuan per ton of water.

Table 1: Data unit mg/L of effluent COD of each unit

Experiments show that: according to the water quality characteristics of pharmaceutical wastewater, the combined process of this system "hydrolytic acidification + UASB + carrier fluidized bed + Fenton oxidation + ozone catalytic oxidation + post-biochemical" is used as the core to treat pharmaceutical wastewater. After 5L/h high-concentration fermentation The continuous flow test of pharmaceutical wastewater has made the influent COD concentration as high as 20000mg/L and ammonia nitrogen as high as 600mg/L, and the final effluent COD and ammonia nitrogen are respectively below 100mg/L and 15mg/L. Water Pollutant Discharge Standard" and "GB21904-2008 Chemical Synthesis Pharmaceutical Industry Water Pollutant Discharge Standard" stipulated in the discharge standard, the chemical consumption cost of the process is about 10 yuan per ton of water. The advantage of this process is that it combines an efficient biochemical system with an advanced catalytic oxidation process. It is of great significance to explore a combined process system for treating high-concentration fermentation or chemical synthesis pharmaceutical wastewater.

The above-mentioned embodiments are only one of the selected specific implementations of the present utility model, and are not intended to limit the implementations. For those skilled in the art, other changes in different forms can also be made on the basis of the above description. The obvious changes and substitutions derived therefrom shall be included in the protection scope of the present utility model.

Claims (9)

1. A process system for treating high-concentration fermentation or chemical synthesis pharmaceutical wastewater, which is characterized in that it includes a hydrolytic acidification tank (1), an upflow anaerobic sludge bed reactor (2), and a second First carrier fluidized bed (3), activated sludge tank (4), second carrier fluidized bed (5), sedimentation tank (6), Fenton reaction tank (7), ozone oxidation tank (8), post-biochemical Pool (9). the 2. The process system for treating high-concentration fermentation or chemical synthesis pharmaceutical wastewater according to claim 1, characterized in that: the hydrolysis acidification tank (1) is provided with a heating rod (10). the 3. The process system for treating high-concentration fermentation or chemical synthesis pharmaceutical wastewater according to claim 1, characterized in that: the front end of the upflow anaerobic sludge bed reactor (2) is provided with a pipeline mixer (11), the inside is provided with water distributor (12), three-phase separator (13), some sampling ports (14); said upflow type anaerobic sludge bed reactor (2) is provided with pneumatic diaphragm pump ( 15). the 4. The process system for treating high-concentration fermentation or chemical synthesis pharmaceutical wastewater according to claim 1, characterized in that: the first carrier fluidized bed (3), activated sludge tank (4), An aeration device (16) is provided at the bottom of the second carrier fluidized bed (5); the aeration device (16) communicates with the aeration device (17). the 5. The process system for treating high-concentration fermentation or chemical synthesis pharmaceutical wastewater according to claim 1, characterized in that: the sedimentation tank (6) is fluidized with the first carrier through an air stripping device (18) The beds (3) are connected. the 6. The process system for treating high-concentration fermentation or chemical synthesis pharmaceutical wastewater according to claim 1, characterized in that: the first carrier fluidized bed (3), the second carrier fluidized bed (5 ) is provided with a suspended filler (19); the suspended filler (19) includes an outer ring (20), an inner ring (21), radial ribs (22), small fins (23), radial radiation Fins (24); the outer ring (20) and the inner ring (21) are connected by two vertically intersecting radial ribs (21); between the outer ring and the inner ring There are connecting ribs (25); multiple chambers (26) are formed between the outer ring and the inner ring; the radial radiation fins (24) are arranged at intervals outside the outer ring (20) On the surface: the small fins (23) are arranged at intervals on the outer surface of the inner ring (21). the 7. The process system for treating high-concentration fermentation or chemical synthesis pharmaceutical wastewater according to claim 1, characterized in that: the Fenton reaction tank (7) and the ozone oxidation tank (8) pass through the lift pump ( 27) Connect. the 8. The process system for treating high-concentration fermentation or chemical synthesis pharmaceutical wastewater according to claim 1, characterized in that: the ozone oxidation pool (8) is a plurality of pools connected in series or in parallel; Oxidation pond (8) is connected with ozone generator (28); Described ozone oxidation pond (8) is connected with tail gas destruction device (29). the 9. The process system for treating high-concentration fermentation or chemical synthesis pharmaceutical wastewater according to claim 1, characterized in that: the mutual configuration refers to interconnection through water pipelines and pumps. the