CN105461104A - Treatment process of concentrated salt wastewater produced by coal chemical industry - Google Patents
Treatment process of concentrated salt wastewater produced by coal chemical industry Download PDFInfo
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Abstract
A treatment process of concentrated salt wastewater produced by coal chemical industry is as below: the concentrated salt wastewater produced by coal chemical industry passes through a first security filter, and is supercharged and sent into a nanofiltration device; the water produced by the nanofiltration device is sent to a rear hydrogen ion exchanger for treatment, so that the zero hardness of the wastewater is less than 0.1ppm; the wastewater is sent into a decarbonization tower and subjected to negative pressure operation, so as to parse the carbon dioxide the in the wastewater; the outlet water from the decarbonization tower is supplemented with sodium hydroxide to adjust the pH value to an alkaline range and sent into a second security filter; the outlet water enters into a concentrated water reverse osmosis membrane device; and the generated fresh water is used for circulating water replenishment, and the generated high concentration brine is subjected to coal blending or evaporative crystallization, so as to ensure zero discharge of wastewater. The invention advantages of low investment, low operation cost and high recovery rate.
Description
Technical field
The invention belongs to a kind of technological method of strong brine reprocessing, the technology method of the strong brine reprocessing produced after relating in particular to a kind of coal chemical industrial waste water advanced treatment and reclamation.
Background technology
Coal Chemical Industry process coal is converted to gas, liquid and solid phase prod or half product, is then processed into the industry of chemical industry, energy product further.Comprise coking, gasification, gelatin liquefaction etc.
The Coal Chemical Industry of China is mainly distributed in the area of the coal resources relative abundance such as northwest at present, New Coal Chemical scope of the enterprise and water loss huge, ton product water consumption is more than ten tons, and year, water consumption was usually up to several ten million cubic metres.And the distribution of water resources in these areas is few, or be in the area that environment is comparatively responsive, because of ground, water environment capacity is very limited, environmental requirement enterprise productive life waste water maximum using or zero release, water resources and water environmental problems have become one of subject matter of restriction Developing Coal Chemical Industry.
It is large that coal chemical industrial waste water has the water yield often, water quality is complicated, containing a large amount of phenols, polycyclic aromatic hydrocarbons, heterocyclic, prussiate, oil and ammonia nitrogen etc., belong to used water difficult to degradate, usual employing physico-chemical pretreatment+biochemical treatment+biochemical tail water pre-treatment+membranous system desalination, the usual rate of recovery is no more than 70%, the strong brine of generation more than 30% is treated as the key of wastewater zero discharge, due to its saltiness high (usual TDS >=10000mg/l), organic concentration high (COD >=200mg/l), adopting conventional dense water reverse osmosis to process subject matter is further that film dirt is stifled serious, the rate of recovery not high (lower than 40%), cause total yield about 80%, also have an appointment 20% high strong brine need supporting evaporated crystallization device to realize wastewater zero discharge, because this unit capacity is large, energy consumption is high, cause plant investment large, running cost is high, the economic cost realizing wastewater zero discharge is huge, only has the treatment scale as far as possible reducing end evaporative crystallization, effectively could reduce scale wastewater treatment investment and working cost.Therefore, the reprocessing of strong brine and high efficiente callback become raising system total yield, reduce one of end evaporated crystallization device size investment and the key running processing costs.
Comprehensive above technique, for large-scale Coal Chemical Engineering Project, wastewater discharge is large, advanced treatment and reuse scale often go up kiloton/hour, from wastewater zero discharge angle, with high investment, the high cost expense of end evaporated crystallization device to be reduced as far as possible, only have the rate of recovery promoting leading portion further, reduce evaporative crystallization design scale; Solve environmental protection and the economic pressures of enterprise on the whole.
Summary of the invention
The object of the invention is to provide a kind of reduced investment, running cost low for coal chemical industrial waste water advanced treatment, and there is the dense salt waste water treatment process produced Coal Chemical Industry of high-recovery.
Treatment process of the present invention comprises the following steps:
(1) the dense salt waste water of Coal Chemical Industry generation is after lift pump supercharging, outlet conduit adds Scale inhibitors, after the first cartridge filter, again by entering nanofiltration device after the supercharging of nanofiltration topping-up pump, nanofiltration device produces the H-ion exchanger device that water send rear end, and dense water delivers to the softening settling pond reprocessing reuse of advanced treatment front end;
Nanofiltration (NF) is the molecular level isolation technique that its separatory membrane has nano level aperture, between reverse osmosis and micro-filtration.Nanofiltration membrane equally belongs to pressure-driven membrane separation technique with reverse osmosis, but its mass transport mechanism is different, general nanofiltration membrane is charged type (mostly being negative charge), not only controls by partial potential the separating behavior of inorganic salt, is also subject to the impact of potential gradient simultaneously.In flux one timing, the impressed pressure required for nanofiltration process is more much lower than reverse osmosis, and it has the interception capacity of 90% to the organism that relative molecular mass is greater than 300; Because nanofiltration membrane is with electric charge, by electrostatic interaction, can hinder polyvalent ion (particularly polyvalent cation) through, the most of hardness in waste water can be removed; Especially then very high to the salt rejection of multivalent anions, reach more than 95%; The rate of recovery of nanofiltration system is about more than 80%;
(2) nanofiltration produces water through H-ion exchanger process (employing weakly acidic cationic exchanger resin), makes waste water zero hardness lower than 0.1ppm;
(3) H-ion exchanger water outlet enters decarbonizing tower, by negative-pressure operation, the carbonic acid gas in waste water is parsed;
(4) decarbonizing tower water outlet enters intermediate pool, through hydro-oxidation sodium adjust ph be alkalescence, first after lift pump adherence pressure, enter the second cartridge filter, water outlet enters dense water reverse osmosis membrane apparatus again after reverse osmosis booster pump supercharging, the fresh water produced is back to circulating cooling make-up water, the high strong brine amount produced is few, can coal blending or evaporative crystallization, guarantees wastewater zero discharge.
Coal chemical industrial waste water of the present invention is the strong brine that biochemical tail water produces after advanced treatment and the process of film desalination system, in dense water, chemical oxygen demand (COD) (COD) is between 150-250mg/L, be mainly refractory organic compounds, total dissolved solid (TDS) is between 10000-15000mg/L.
As step (1) first cartridge filter and step (4) second cartridge filter adopt large flux, inner pressed strainer, design requirements intake pressure 0.3-0.6MPa, filtering accuracy 5um usually; Form is vertical cylinder, be made up of cylindrical shell and filter core, cylindrical shell material is SUS304, filter core material is that PP folds, its domestic production producer is more, as JSP-DJMF serial model No., the WX-L series of Shanghai Wei Xiu filter plant company limited production, the bright auspicious MRBA Series Filter etc. filtering production in Jiangsu that golden three yang edema process companies produce;
(membrane element is that U.S. GE produces to nanofiltration device as described in step (1), pollution-resistant, and model is DURASLJCKNF8040,), intake pressure 0.8-1.0Mpa, design membrane flux is 14-20LMH, system recoveries rate about 80%, the total ratio of desalinization 50 ~ 70% of system; The rejection of multivalent anions salt reaches more than 90%; The most of hardness in waste water can be removed.
H-ion exchanger as described in step (2) adopts weakly acidic cationic exchanger resin (usually to adopt more weak reactive group as carboxyl (-COOH base) etc., the Ca of this ion exchange resin only in commutative weak base
2+, Mg
2+deng, and for the Na in highly basic
+, K
+plasma cannot exchange, and concrete operations require water inlet normal temperature, intake pressure 0.2 ~ 0.4MPa, can following current or counter-current regeneration provide processing condition), all hardness relevant with basicity can be removed, go out the water hardness lower than 0.1ppm.Regeneration adopts regeneration of hydrochloric acid, and wide material sources, cost is low.
Negative pressure as described in step (3) maintains-0.1 ~-0.15MPa, and water outlet carbonic acid gas is less than 10ppm.
As described in step (4), dense water reverse osmosis membrane apparatus adopts the requirement of HERO running technology, and water inlet hydro-oxidation sodium adjust ph 9-11, intake pressure 2.0 ~ 2.4Mpa, membrane flux is 25 ~ 28L/m
2.h, the device rate of recovery can reach more than 90%.
Employing HERO running technology as above is as follows:
HERO is the abbreviation of HighEfficiencyReverseOsmosis.At present applying more widely abroad, is widely used in the manufacture of semicon industry high purity water, sea water desaltination, the industrial circles such as electric power plant circulating water water charging system, refinery oily(waste)water.But service condition at present is not at home also very universal.
Usual RO process operation PH is lower, and intaking by the primary and foremost purpose of acid adding reduction pH is reduce the tendency of calcium carbonate scaling in the dense water of RO, namely reduces bright Greer index [LSI], as LSIc=pHc-pHs < 0, and carbonate non-scaling, HERO technology is then contrary, in zero hardness, low alkalinity, the reverse osmosis process run under high pH value condition, it is a special case of RO technology, under high PH operating mode: organism keeps dissolved state, can not be adsorbed on membranous wall, and little organic physical efficiency is survived under high PH operating mode, also can not breed, under high PH operating mode, the solubleness of silicon can significantly increase, above feature well solves membranous system Organic pollutants, biological pollution, the problem of silicon fouling, RO system recoveries rate is increased, pollution problem (such as hardness is had at a high ph for preventing brackish water, basicity, iron, manganese etc.), pre-treatment adopts acidulous cation resin system and de-gassing vessel to remove these pollutents usually.
The dense water reverse osmosis unit that the present invention uses adopts HERO operation mechanism, feed water by reverse osmosis runs under zero hardness, low alkalinity, high ph-values condition, compare conventional reverse osmosis technology, have without organism with raw fouling, without features such as foulings, the rate of recovery of waste water is made to reach more than 90%, the rate of recovery of whole Waste Water Treatment can be promoted to more than 95%, greatly alleviates evaporative crystallization process treatment scale and the running cost of follow-up high strong brine.Compare traditional RO technique, HERO system only limits by osmolality, the rate of recovery reaches more than 90%, the dirt that there is not silicon, organism and biology is blocked up, few cleaning, water outlet can be used for circulating cooling make-up water or de-salted water feedwater, and concentrated water drainage is high-volume little, is easy to fully recovering or carries out evaporative crystallization further.
Compared to the prior art the present invention has following features:
1, biochemical tail water through pre-treatment and film desalination system (usually adopting ultrafiltration+reverse osmosis process) process after generation dense water, suspended substance in waste water, colloidal type, larger molecular organics etc. have been removed at leading portion, turbidity is lower, mainly organism and salt, directly can adopt nanofiltration device, utilize its membrane property to remove partial salts and most hardness, remove partial organic substances, COD clearance can reach 50%, improves the operation condition of strong brine process follow up device.
2, nanofiltration product water makes waste water be removed to zero hardness through weakly acidic cationic exchanger resin, and by adjustment pH value, adopt HERO operation condition, the rate of recovery of lifting system greatly, reduces size investment and the working cost of subsequent evaporation crystallization apparatus system.
3, present invention process compares conventional dense water reverse osmosis process, the rate of recovery significantly improves, and is promoted to 90% by 40%, and the rate of recovery of whole Waste Water Treatment can be promoted to 95%, below the high strong brine thus produced is few, and follow-up evaporated crystallization device scale and running cost are sent out and significantly reduced.
4, present invention process has simply, reduced investment, the rate of recovery are high, take up an area less, advantage that running cost is low, has good effect to enterprise implement factory effluent " zero release ".
Accompanying drawing explanation
Fig. 1 schematic flow sheet of the present invention.
Embodiment
Embodiment 1
(1) nanofiltration device
Dense water (the COD:150mg/L of biochemical tail water after advanced treatment and film desalination, TDS:10000mg/L, total hardness: 500mg/L) enter strong brine pond, through lift pump adherence pressure to 0.3MPa, by the first cartridge filter, be then pressurized to 0.8MPa through nanofiltration topping-up pump, nanofiltration device arrangement adopts one-level two sections of forms, often prop up container 6 membrane element series connection, membrane element is DURASLJCKNF8040, and design membrane flux is 18L/m
2.h, nanofiltration device produces the H-ion exchanger device that water (COD is 80mg/L, and hardness is 50mg/L, and yield is 80%) send rear end, and dense water delivers to the softening settling pond reprocessing reuse of advanced treatment front end;
(2) resin is except hard unit
Nanofiltration is produced water and is entered resin again except hard unit, and adopt H-ion exchanger (employing weakly acidic cationic exchanger resin), product water is normal temperature, pressure 0.2MPa, makes the total hardness in waste water be 0.084mg/L, incidentally removes part basicity simultaneously;
(3) decarburization unit
H-ion exchanger water outlet enters decarbonizing tower, passes through-0.1Mpa negative-pressure operation, removes the carbonic acid gas in water, makes CO in water
2residual volume is 10ppm;
(4) dense water reverse osmosis unit
Dense water after decarburization enters intermediate pool, through hydro-oxidation sodium adjust ph to 9, after water pump lifting pressure to 0.3MPa, enter the second cartridge filter, water outlet is pressurized to 2.0Mpa by reverse osmosis booster pump again, enters dense water reverse osmosis unit, design membrane flux 28L/m
2.h, controlling the rate of recovery is 90%, produce water water quality and reach reclaimed water reuse circulating cooling make-up water water quality requirement in " Code for design of industrial recirculating cooling water treatment " (GB50050-2007), and leading indicator COD:10mg/l, TDS:100mg/l, is better than the control overflow of water quality standard (COD≤30mg/l, TDS≤1000mg/l) in (GB50050-2007), as circulating cooling make-up water reuse, the high strong brine of generation send evaporated crystallization device.
Embodiment 2
(1) nanofiltration device
Dense water (the COD:200mg/L of biochemical tail water after advanced treatment and film desalination, TDS:12000mg/L, total hardness: 750mg/L) enter strong brine pond, through lift pump adherence pressure to 0.4MPa, by the first cartridge filter, then be pressurized to 0.9MPa through nanofiltration topping-up pump, design membrane flux is 16L/m
2.h, nanofiltration device produces the H-ion exchanger device that water (COD is 100mg/L, and total hardness is 75mg/L, and yield is 80%) send rear end, and dense water delivers to the softening settling pond reprocessing reuse of advanced treatment front end;
(2) resin is except hard unit
Nanofiltration is produced water and is entered resin again except hard unit, and adopt H-ion exchanger (employing weakly acidic cationic exchanger resin), products water is normal temperature, pressure 0.3MPa, makes total hardness in waste water lower than 0.092mg/L, simultaneously subsidiary removal part basicity;
(3) decarburization unit
H-ion exchanger water outlet enters decarbonizer, passes through the following negative-pressure operation of-0.12Mpa, removes the carbonic acid gas in water, make CO in water
2residual volume is 9.55ppm;
(4) dense water reverse osmosis unit
Dense water after decarburization enters intermediate pool, through hydro-oxidation sodium adjust ph to 10, after water pump lifting pressure to 0.4MPa, enter cartridge filter, be pressurized to 2.2Mpa by reverse osmosis booster pump again, enter dense water reverse osmosis unit, design membrane flux 26.5L/m
2.h, controlling the rate of recovery is 90%, produce water water quality and reach reclaimed water reuse circulating cooling make-up water water quality requirement in " Code for design of industrial recirculating cooling water treatment " (GB50050-2007), and leading indicator COD:15mg/l, TDS:120mg/l, is better than the control overflow of water quality standard (COD≤30mg/l, TDS≤1000mg/l) in (GB50050-2007), as circulating cooling make-up water reuse, the high strong brine of generation send evaporated crystallization device.
Embodiment 3
(1) nanofiltration device
Dense water (the COD:250mg/L of biochemical tail water after advanced treatment and film desalination, TDS:15000mg/L, total hardness: 1000mg/L) enter strong brine pond, through lift pump adherence pressure to 0.6MPa, by the first cartridge filter, then 1.0MPa is pressurized to through nanofiltration topping-up pump, design membrane flux is 14L/m2.h, nanofiltration device produces water, and (water outlet COD is 120mg/L, total hardness is 100mg/L, yield is 80%) send the H-ion exchanger device of rear end, dense water delivers to the softening settling pond reprocessing reuse of advanced treatment front end;
(2) resin is except hard unit
Nanofiltration is produced water and is entered resin again except hard unit, and through H-ion exchanger (employing weakly acidic cationic exchanger resin), product water is normal temperature, pressure 0.4MPa, makes the total hardness in waste water be 0.095mg/L, incidentally removes part basicity simultaneously;
(3) decarburization unit
H-ion exchanger water outlet enters decarbonizer, passes through the following negative-pressure operation of-0.15Mpa, removes the carbonic acid gas in water, make CO in water
2residual volume is less than 9.0ppm;
(4) dense water reverse osmosis unit
Dense water after decarburization enters intermediate pool, through hydro-oxidation sodium adjust ph to 10.5, after water pump lifting pressure to 0.6MPa, enter the second cartridge filter, be pressurized to 2.4Mpa by reverse osmosis booster pump again, enter dense water reverse osmosis unit, design membrane flux 25L/m
2.h, controlling the rate of recovery is 90%, produce water water quality and reach reclaimed water reuse circulating cooling make-up water water quality requirement in " Code for design of industrial recirculating cooling water treatment " (GB50050-2007), and leading indicator COD is lower than 20mg/l, TDS, lower than 150mg/l, is better than water quality standard in (GB50050-2007) (COD lower than 30mg/l, TDS lower than 1000mg/l), as circulating cooling make-up water reuse, the high strong brine of generation send evaporated crystallization device.
Claims (10)
1., to the dense salt waste water treatment process that Coal Chemical Industry produces, it is characterized in that comprising the steps:
(1) the dense salt waste water of Coal Chemical Industry generation is after lift pump supercharging, outlet conduit adds Scale inhibitors, after the first cartridge filter, again by entering nanofiltration device after the supercharging of nanofiltration topping-up pump, nanofiltration device produces the H-ion exchanger device that water send rear end, and dense water delivers to the softening settling pond reprocessing reuse of advanced treatment front end;
(2) nanofiltration produces water through H-ion exchanger process, makes waste water zero hardness lower than 0.1ppm;
(3) H-ion exchanger water outlet enters decarbonizing tower, by negative-pressure operation, the carbonic acid gas in waste water is parsed;
(4) decarbonizing tower water outlet enters intermediate pool, through hydro-oxidation sodium adjust ph be alkalescence, first after lift pump adherence pressure, enter the second cartridge filter, water outlet enters dense water reverse osmosis membrane apparatus again after reverse osmosis booster pump supercharging, the fresh water produced is back to circulating cooling make-up water, the high strong brine produced carries out coal blending or evaporative crystallization, guarantees wastewater zero discharge.
2. as claimed in claim 1 a kind of to Coal Chemical Industry produce dense salt waste water treatment process, it is characterized in that the dense salt waste water that Coal Chemical Industry produces is the strong brine that biochemical tail water produces after advanced treatment and the process of film desalination system, in dense water, chemical oxygen demand (COD) is between 150-250mg/L, and total dissolved solid is between 10000-15000mg/L.
3. as claimed in claim 1 a kind of to Coal Chemical Industry produce dense salt waste water treatment process, it is characterized in that step (1) first cartridge filter and step (4) second cartridge filter adopt large flux, inner pressed strainer, design requirements intake pressure 0.3-0.6MPa, filtering accuracy 5um; Form is vertical cylinder, is made up of cylindrical shell and filter core, and cylindrical shell material is SUS304, and filter core material is that PP folds.
4. as claimed in claim 3 a kind of to Coal Chemical Industry produce dense salt waste water treatment process, it is characterized in that step (1) first cartridge filter and step (4) second cartridge filter be golden three yang edema process companies produce JSP-DJMF serial model No., Shanghai Wei Xiu filter plant company limited produce WX-L series, Jiangsu bright auspicious filter produce MRBA Series Filter.
5. as claimed in claim 1 a kind of to Coal Chemical Industry produce dense salt waste water treatment process, it is characterized in that the intake pressure 0.8-1.0Mpa of the nanofiltration device described in step (1), design membrane flux is 14-20LMH.
6. as claimed in claim 5 a kind of to Coal Chemical Industry produce dense salt waste water treatment process, it is characterized in that the membrane element in the nanofiltration device described in step (1) is that U.S. GE produces, pollution-resistant, model is DURASLJCKNF8040.
7. as claimed in claim 1 a kind of to Coal Chemical Industry produce dense salt waste water treatment process, it is characterized in that the H-ion exchanger described in step (2) adopts weakly acidic cationic exchanger resin, concrete operations require water inlet normal temperature, intake pressure 0.2 ~ 0.4MPa, following current or counter-current regeneration.
8. as claimed in claim 1 a kind of to Coal Chemical Industry produce dense salt waste water treatment process, what it is characterized in that the H-ion exchanger described in step (2) goes out the water hardness lower than 0.1ppm.
9. as claimed in claim 1 a kind of to Coal Chemical Industry produce dense salt waste water treatment process, it is characterized in that the negative pressure described in step (3) maintains-0.1 ~-0.15MPa, water outlet carbonic acid gas is less than 10ppm.
10. as claimed in claim 1 a kind of to Coal Chemical Industry produce dense salt waste water treatment process, it is characterized in that the described dense water reverse osmosis membrane apparatus of described step (4) adopts HERO running technology, water inlet hydro-oxidation sodium adjust ph 9-11, intake pressure 2.0 ~ 2.4Mpa, membrane flux is 25 ~ 28L/m
2.h.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110092506A (en) * | 2019-05-28 | 2019-08-06 | 武汉江扬环境科技股份有限公司 | A kind of full-automatic desalinating process of RO concentrated water rich in barium strontium ion |
| CN110304752A (en) * | 2018-03-20 | 2019-10-08 | 宝武炭材料科技有限公司 | A kind of processing method being concentrated again for coking wastewater reverse osmosis concentrated water |
| CN112125433A (en) * | 2020-09-10 | 2020-12-25 | 黄河三角洲京博化工研究院有限公司 | Petrochemical wastewater reduction and concentration treatment process by full-membrane method |
| CN115259460A (en) * | 2022-08-02 | 2022-11-01 | 淮南矿业(集团)有限责任公司 | Method for treating brackish mine water of coal mine |
| CN115925152A (en) * | 2022-11-08 | 2023-04-07 | 中煤科工西安研究院(集团)有限公司 | Membrane chemical reaction equipment, coal mine water defluorination treatment system and process |
| CN117865422A (en) * | 2024-03-13 | 2024-04-12 | 杭州水处理技术研究开发中心有限公司 | Treatment process and system for softening high-salt negative hard wastewater and volatile organic compounds |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110304752A (en) * | 2018-03-20 | 2019-10-08 | 宝武炭材料科技有限公司 | A kind of processing method being concentrated again for coking wastewater reverse osmosis concentrated water |
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| CN117865422A (en) * | 2024-03-13 | 2024-04-12 | 杭州水处理技术研究开发中心有限公司 | Treatment process and system for softening high-salt negative hard wastewater and volatile organic compounds |
| CN117865422B (en) * | 2024-03-13 | 2024-05-28 | 杭州水处理技术研究开发中心有限公司 | Treatment process and system for softening high-salt negative hard wastewater and volatile organic compounds |
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Application publication date: 20160406 |