CN114315036A - Processing system of terpene resin waste water - Google Patents
Processing system of terpene resin waste water Download PDFInfo
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- CN114315036A CN114315036A CN202111660669.XA CN202111660669A CN114315036A CN 114315036 A CN114315036 A CN 114315036A CN 202111660669 A CN202111660669 A CN 202111660669A CN 114315036 A CN114315036 A CN 114315036A
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Images
Abstract
The invention provides a treatment system for terpene resin production wastewater, which comprises a physicochemical pretreatment system, a biochemical treatment system and a sludge treatment system, wherein the physicochemical pretreatment system comprises a plane grating, an oil separation tank, a water collection regulating tank, an iron-carbon reactor, a Fenton reactor, an electrode oxidizer and an inclined plate sedimentation tank, the biochemical treatment system comprises a hydrolysis acidification tank, a contact aerobic tank and a secondary sedimentation tank, and the sludge treatment system comprises a sludge concentration tank and a belt filter press.
Description
Technical Field
The invention relates to the technical field of industrial wastewater treatment, in particular to a treatment system for terpene resin production wastewater.
Background
The terpene resin is a general name of a polymer obtained by mainly using a dicyclic monoterpene compound as a raw material and carrying out cationic catalytic polymerization, has the advantages of light color, low odor, high hardness, high adhesion, good oxidation resistance and thermal stability, good compatibility and solubility and the like, and particularly has excellent compatibility, weather resistance and tackifying effect in hot sols such as EVA SIS systems, SBS systems and the like. The industrial production process includes the steps of using toluene or xylene as solvent, using alpha-pinene, beta-pinene, etc. in turpentine oil or tall oil as polymerizing monomer, cationic polymerizing in reactor at low temperature to obtain toluene solution of terpene resin, high temperature distilling to eliminate solvent toluene, un-polymerized monomer and low molecular weight polymer, and cooling to obtain solid terpene resin product. In the existing production technology, aluminum trichloride is used as a catalyst for polymerization reaction, and because the aluminum trichloride is insoluble in toluene and turpentine, after each reaction is completed, semi-finished terpene resin is washed with water, so that the aluminum trichloride is dissolved in water, and after the water and the semi-finished terpene resin are layered, the water is drained, so that the aluminum trichloride is removed, and the terpene resin toluene solution is obtained. And then distilling to remove toluene, and finally granulating, forming and packaging to obtain the terpene resin finished product.
A large amount of production wastewater can be generated in the production of terpene resin, the main components of the production wastewater comprise a large amount of organic pollutants such as resin, turpentine, ether, styrene, toluene and the like for inhibiting biochemistry and inorganic pollutants such as aluminum trichloride, boron trifluoride and the like, and the production wastewater can cause serious environmental pollution if being directly discharged without being treated.
Disclosure of Invention
The invention aims to provide a treatment system for terpene resin production wastewater.
In order to achieve the purpose, the treatment system for terpene resin production wastewater provided by the invention comprises a physicochemical pretreatment system, a biochemical treatment system and a sludge treatment system:
(1) materialization pretreatment system
The physicochemical pretreatment system comprises a plane grating, an oil separation tank, a water collecting regulation tank, an iron-carbon reactor, a Fenton reactor, an electrode oxidizer and an inclined plate sedimentation tank, terpene resin production wastewater enters the oil separation tank for treatment after intercepting large-particle floating objects by the plane grating, the wastewater is kept stand in the oil separation tank for a period of time, an upper layer of grease polymerization liquid returns to a workshop for recycling, and a lower layer of water phase is discharged into the water collecting regulation tank;
a wastewater lifting pump is arranged between the water collection regulating reservoir and the iron-carbon reactor, wastewater in the water collection regulating reservoir is injected into the iron-carbon reactor by the wastewater lifting pump to carry out micro-electrolytic oxidation reaction, the iron-carbon reactor is designed into a carbon steel lining rubber cylinder vertical structure, the iron-carbon reactor is provided with an acid adding device, the adding amount of acid liquor is controlled and metered by an online pH meter, and the pH value is controlled to be 3-4;
the effluent of the iron-carbon reactor automatically flows into a Fenton reactor, the Fenton reactor is designed to be a carbon steel lining rubber cylinder vertical structure, and FeSO is added into the Fenton reactor through metering4、H2O2The reagent completes the secondary oxidation reaction;
the effluent of the Fenton reactor automatically flows into an electrode oxidizer, and after the wastewater is oxidized by an electrode, scum is pushed by a scum scraper arranged at the upper part of the equipment and flows into a scum groove;
the effluent of the electrode oxidizer automatically flows into an inclined plate sedimentation tank, a dosing device is arranged on the inclined plate sedimentation tank, and solid-liquid separation is carried out on the wastewater by dosing lime milk, PAC, PAM and NaOH;
discharging the precipitated sludge subjected to iron-carbon reaction, Fenton reaction, electrode oxidation and inclined plate precipitation into a sludge concentration tank, and pumping the supernatant subjected to inclined plate precipitation into a biochemical treatment system after automatically flowing into an intermediate water tank;
(2) biochemical treatment system
The biochemical treatment system comprises a hydrolysis acidification tank, a contact aerobic tank and a secondary sedimentation tank, wherein elastic three-dimensional fillers are arranged in the hydrolysis acidification tank and the contact aerobic tank, and pretreated wastewater treated by the physicochemical pretreatment system is gathered in an intermediate water tank, pumped into the hydrolysis acidification tank and then sequentially flows through the contact aerobic tank and the secondary sedimentation tank;
(3) sludge treatment system
The sludge treatment system comprises a sludge concentration tank and a belt filter press, precipitated sludge discharged by the physicochemical pretreatment system and the biochemical treatment system is collected in the sludge concentration tank, the sludge concentration tank is designed into a vertical civil steel concrete structure, the precipitated sludge in the sludge concentration tank is injected into the belt filter press by a sludge delivery pump for sludge drying treatment, the dried sludge is transported outwards, and the filter press liquid flows back to the water collection regulating tank for circulation treatment.
Further, the HRT of the water collecting and adjusting tank is 15h to 20 h.
Furthermore, the treatment system for the terpene resin production wastewater also comprises an aeration device, and the aeration device is respectively connected with the water collection regulating tank, the iron-carbon reactor, the Fenton reactor, the electrode oxidizer and the contact aerobic tank through pipelines.
Further, an ultrasonic generator is arranged in the hydrolysis acidification tank.
Further, the sound energy density emitted by the ultrasonic generator is 4W/mL to 6W/mL.
Further, the processing time of the ultrasonic generator is 30min to 60 min.
Further, terpene resin waste water's processing system still includes discharges the inspection pond, discharge the inspection pond and set up at biochemical treatment system's end, two heavy pond supernatant flows into the spontaneous flow and discharges the inspection pond, discharge the inspection pond with through the tube coupling between the equalizing basin catchments, set up on this pipeline and surmount the backwash pump, detect that processing water quality is up to standard qualified emission, handle out of water not up to standard or salt concentration is too high then by surmounting the backwash pump backward flow to catchment equalizing basin, carry out materialization preliminary treatment and biochemical treatment again.
The invention has the beneficial effects that:
1. according to the invention, by combining the physicochemical pretreatment system and the biochemical treatment system, the treatment of the terpene resin production wastewater can be effectively completed, and the treated clear water completely meets the emission standard;
2. the hydrolysis acidification tank is internally provided with an ultrasonic generator, strong cavitation is generated by ultrasonic, a large number of micro bubbles are generated in sewage, the micro bubbles are instantaneously exploded, and strong hydraulic shearing force can be generated on a gas-liquid contact surface around the micro bubbles to destroy a sludge floc structure in the sewage.
Drawings
FIG. 1 is a schematic view showing the structure of a system for treating waste water from terpene resin production according to the present invention.
FIG. 2 is a graph of SCOD concentration versus time at different acoustic energy densities for example 2 of the present invention.
The invention is further explained with reference to the drawings and the embodiments.
Detailed Description
Example 1
The invention provides a treatment system for terpene resin production wastewater, which comprises a materialization pretreatment system, a biochemical treatment system and a sludge treatment system, and the specific steps are described with reference to fig. 1.
(1) Materialization pretreatment system
The materialization pretreatment system comprises a plane grid 1, an oil separation tank 2, a water collecting adjusting tank 3, an iron-carbon reactor 4, a Fenton reactor 5, an electrode oxidizer 6 and an inclined plate sedimentation tank 7, wherein the oil separation tank 2, the water collecting adjusting tank 3, the iron-carbon reactor 4, the Fenton reactor 5, the electrode oxidizer 6 and the inclined plate sedimentation tank 7 are sequentially connected through pipelines.
Terpene resin waste water discharges into catchment equalizing basin 3 after through oil interceptor 2 handles, and oil interceptor 2 front end sets up plane grid 1 and intercepts the large granule floater in the waste water, and the waste water stews for a period of time at oil interceptor 2, and upper grease polymerization liquid recycles in the workshop, and lower floor's aqueous phase discharges into catchment equalizing basin 3.
Considering the characteristics of uneven wastewater discharge, high wastewater salt concentration and the like, the HRT of the catchment regulating tank 3 is designed to be 15h (HRT, hydraulic retention time); a wastewater lifting pump 30 is arranged on a pipeline between the water collecting adjusting tank 3 and the iron-carbon reactor 4. The water collecting and adjusting tank is designed into a civil engineering reinforced concrete structure.
The wastewater in the water collecting and adjusting tank 3 is injected into the iron-carbon reactor 4 by the wastewater lift pump 30 to carry out micro-electrolysis oxidation reaction. The iron-carbon reactor 4 is designed as a carbon steel rubber lined cylindrical upright structure. And in consideration of the pH value suitable for the iron-carbon reaction, the acid liquor addition amount is measured by the online pH meter control acid adding device 40, and the pH value is controlled to be 3-4.
The effluent from the iron carbon reactor 4 automatically flows into the Fenton reactor 5. The fenton reactor 5 is designed as a carbon steel rubber lined cylindrical upright structure. FeSO is metered and added through dosing devices 51 and 524、H2O2The reagent completes the secondary oxidation reaction.
The effluent of the Fenton reactor 5 automatically flows into the electrode oxidizer 6. The electrode oxidizer 6 is designed into a horizontal flow type high-voltage pulse type, the body is made of PP anti-corrosion materials, scum is pushed by a scum scraper arranged on the upper part of the equipment and is collected into a scum trough, and sediments are discharged into a sludge concentration tank.
The electrode oxidation effluent automatically flows into an inclined plate sedimentation tank 7, the inclined plate sedimentation tank 7 is designed into two parts of dosing coagulation and inclined plate sedimentation, lime milk, PAC (polyaluminium chloride), PAM (polyacrylamide) and NaOH are dosed through dosing devices 71, 72, 73 and 74, and solid-liquid separation is carried out on the wastewater. The inclined plate sedimentation tank 7 is designed into a advection type carbon steel lining glue structure.
The precipitated sludge of the iron carbon reactor 4, the Fenton reactor 5, the electrode oxidizer 6 and the inclined plate sedimentation tank 7 are all discharged into a sludge concentration tank, and the supernatant of the inclined plate sedimentation tank 7 automatically flows into an intermediate water tank 8 and then is pumped into a biochemical treatment system.
(2) Biochemical treatment system
The biochemical treatment system comprises a hydrolysis acidification tank 9, a contact aerobic tank 10 and a secondary sedimentation tank 11. The biochemical treatment system is designed into a civil engineering reinforced concrete structure. Elastic three-dimensional fillers (polyolefin, phi 150mm) are arranged in the hydrolysis acidification tank 9 and the contact aerobic tank 10; a submersible stirrer 90 is arranged in the hydrolysis acidification tank 9. The pretreated wastewater treated by the materialized pretreatment system is gathered in an intermediate water tank 8, pumped into a hydrolytic acidification tank 9 and then sequentially flows through a contact aerobic tank 10 and a secondary sedimentation tank 11;
the supernatant in the secondary sedimentation tank 11 automatically flows into the discharge monitoring tank 12. The discharge monitoring pool 12 is designed into a civil-engineering reinforced concrete structure, the discharge monitoring pool 12 is connected with the water collecting adjusting pool 3 through a pipeline, the pipeline is provided with an overrunning reflux pump 13, qualified discharge is realized when the quality of the treated water reaches the standard, the treated water does not reach the standard or the salt concentration is too high, and the treated water flows back to the water collecting adjusting pool 3 through the overrunning reflux pump 13, and the steps are carried out again.
(3) Sludge treatment system
The sludge treatment system comprises a sludge concentration tank 14 and a belt filter press 15, precipitated sludge discharged by the materialization pretreatment system and the biochemical treatment system is collected in the sludge concentration tank 14, the sludge concentration tank 14 is designed into a vertical civil engineering steel concrete structure, the precipitated sludge in the sludge concentration tank 14 is injected into the belt filter press 15 by a sludge delivery pump 16 for sludge drying treatment, the dried sludge is transported outwards, and the pressure filtrate flows back to the water collection regulating tank for circular treatment.
Further, the treatment system for the terpene resin production wastewater further comprises an aeration device 17, wherein the aeration device 17 is respectively connected with the water collection regulating tank 3, the iron-carbon reactor 4, the Fenton reactor 5, the electrode oxidizer 7 and the contact aerobic tank 10 through pipelines. The aeration device 17 pre-aerates the wastewater to adjust the water quality and prevent sedimentation and sedimentation of the tank body.
The treatment system of the invention combines a physicochemical pretreatment system and a biochemical treatment system, can effectively complete the treatment of the terpene resin production wastewater, and the treated clear water completely meets the emission standard (see table 1).
TABLE 1 Water quality index before and after treatment
Wherein: SS represents suspended solid or suspended substance, BOD5Represents five days biochemical oxygen demand, and CODcr represents chemical oxygen demand.
Example 2
In this example, an ultrasonic generator was installed in the hydrolysis-acidification tank, and the other structure was the same as that of example 1.
The ultrasound generates strong cavitation, a large amount of micro bubbles are generated in the sewage, the micro bubbles are instantaneously exploded, strong hydraulic shearing force can be generated on a gas-liquid contact surface around the micro bubbles, and the sludge floc structure in the sewage is damaged. The main component of the sludge floc is extracellular polymer, which consists of two parts: the exterior is loose extracellular polymer and the interior is polymer tightly bound with microorganisms. In the experimental process, the ultrasonic action can reduce the average grain diameter of the sludge in the sewage from 80 to 100 microns to 6 to 9 microns in a short time, which shows that the ultrasonic cavitation has strong destructive capacity on sludge flocs, can rapidly destroy extracellular polymers loose outside the sludge, and is beneficial to the later hydrolysis acidification.
The process of ultrasonic sludge destruction can be equivalent to the process of converting COD in a solid phase of sludge into SCOD in a liquid phase, so that the destruction degree of the sludge can be judged by measuring the concentration of SCOD in the sewage. FIG. 2 shows the SCOD concentration with time under different acoustic energy densities, and it can be seen from FIG. 2 that the SCOD concentration changes more gradually in 30min to 60min when the acoustic energy density is 2W/mL to 3W/mL, for example, the SCOD concentration only increases from 80mg/L to 345mg/L when the acoustic energy density is 2W/mL; at an acoustic energy density of 2W/mL, the SCOD concentration increased only from 114mg/L to 450 mg/L. When the acoustic energy density is 4W/mL to 6W/mL, the change of the SCOD concentration is relatively quick within 30min to 60min, for example, when the acoustic energy density is 4W/mL, the SCOD concentration is increased from 610mg/L to 2100 mg/L; when the sound energy density is 5W/mL, the concentration of SCOD is increased from 650mg/L to 2354 mg/L; when the acoustic energy density is 6W/mL, the concentration of SCOD is increased from 680mg/L to 2401 mg/L; however, as the sonic energy density continues to increase, the SCOD concentration does not change significantly, e.g., when the sonic energy density is 10W/mL, the SCOD concentration increases from 685mg/L to 2430mg/L within 30min to 60min, with no significant increase compared to when the sonic energy density is 6W/mL. Therefore, in consideration of energy consumption, in the invention, the sound energy density of the ultrasonic pretreatment is controlled to be 4W/mL to 6W/mL, and the time is controlled to be 30min to 60 min.
Finally, it should be emphasized that the above-described preferred embodiments of the present invention are merely examples of implementations, rather than limitations, and that many variations and modifications of the invention are possible to those skilled in the art, without departing from the spirit and scope of the invention.
Claims (7)
1. The treatment system for the terpene resin production wastewater is characterized by comprising a materialization pretreatment system, a biochemical treatment system and a sludge treatment system:
(1) materialization pretreatment system
The physicochemical pretreatment system comprises a plane grating, an oil separation tank, a water collecting regulation tank, an iron-carbon reactor, a Fenton reactor, an electrode oxidizer and an inclined plate sedimentation tank, terpene resin production wastewater enters the oil separation tank for treatment after large-particle floating objects are intercepted by the plane grating, the wastewater is kept stand in the oil separation tank for a period of time, an upper layer of grease polymerization liquid returns to a workshop for recycling, and a lower layer of water phase is discharged into the water collecting regulation tank;
a wastewater lifting pump is arranged between the water collecting adjusting tank and the iron-carbon reactor, wastewater in the water collecting adjusting tank is injected into the iron-carbon reactor by the wastewater lifting pump to carry out micro-electrolytic oxidation reaction, the iron-carbon reactor is designed into a carbon steel lining rubber cylinder vertical structure, the iron-carbon reactor is provided with an acid adding device, the adding amount of acid liquor is controlled and metered by an online pH meter, and the pH value is controlled to be 3-4;
the effluent of the iron-carbon reactor automatically flows into a Fenton reactor, the Fenton reactor is designed into a carbon steel lining rubber cylinder vertical structure, and the Fenton reactor is added with FeSO through metering4、H2O2The reagent completes the secondary oxidation reaction;
the effluent of the Fenton reactor automatically flows into an electrode oxidizer, and after the wastewater is oxidized by an electrode, scum is pushed by a scum scraper arranged at the upper part of the equipment and flows into a scum groove;
the effluent of the electrode oxidizer automatically flows into an inclined plate sedimentation tank, a dosing device is arranged on the inclined plate sedimentation tank, and solid-liquid separation is carried out on the wastewater by dosing lime milk, PAC, PAM and NaOH;
discharging the precipitated sludge subjected to iron-carbon reaction, Fenton reaction, electrode oxidation and inclined plate precipitation into a sludge concentration tank, and pumping the supernatant subjected to inclined plate precipitation into a biochemical treatment system after automatically flowing into an intermediate water tank;
(2) biochemical treatment system
The biochemical treatment system comprises a hydrolysis acidification tank, a contact aerobic tank and a secondary sedimentation tank, wherein elastic three-dimensional fillers are arranged in the hydrolysis acidification tank and the contact aerobic tank, and pretreated wastewater treated by the physicochemical pretreatment system is gathered in an intermediate water tank, pumped into the hydrolysis acidification tank and then sequentially flows through the contact aerobic tank and the secondary sedimentation tank;
(3) sludge treatment system
The sludge treatment system comprises a sludge concentration tank and a belt filter press, precipitated sludge discharged by the physicochemical pretreatment system and the biochemical treatment system is collected in the sludge concentration tank, the sludge concentration tank is designed into a vertical civil steel concrete structure, the precipitated sludge in the sludge concentration tank is injected into the belt filter press by a sludge delivery pump for sludge drying treatment, the dried sludge is transported outwards, and the filter press liquid flows back to the water collection regulating tank for circulation treatment.
2. The treatment system for terpene resin production wastewater according to claim 1, wherein:
the HRT of the water collecting adjusting tank is 15-20 h.
3. The treatment system for terpene resin production wastewater according to claim 1, wherein:
the device also comprises an aeration device which is respectively connected with the water collecting adjusting tank, the iron-carbon reactor, the Fenton reactor, the electrode oxidizer and the contact aerobic tank through pipelines.
4. The treatment system for terpene resin production wastewater according to claim 1, wherein:
and an ultrasonic generator is arranged in the hydrolysis acidification tank.
5. The treatment system for terpene resin production wastewater according to claim 1, wherein:
the acoustic energy density emitted by the ultrasonic generator is 4W/mL to 6W/mL.
6. The treatment system for terpene resin production wastewater according to claim 5, wherein:
the processing time of the ultrasonic generator is 30min to 60 min.
7. The treatment system for terpene resin production wastewater according to claim 1, wherein:
still including discharging the inspection pond, discharge the inspection pond and set up at biochemical treatment system's end, two heavy pond supernatant flows automatically and gets into and discharge the inspection pond, discharge the inspection pond with connect through the pipeline between the equalizing basin that catchments, set up on this pipeline and surmount the backwash pump, detect that processing water quality is up to standard qualified emission, handle out of water not up to standard or salt concentration is too high then by surmounting the backwash pump backward flow to the equalizing basin that catchments, carry out materialization preliminary treatment and biochemical treatment again.
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