CN103771650A - Method for treating coal gasification wastewater - Google Patents
Method for treating coal gasification wastewater Download PDFInfo
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- CN103771650A CN103771650A CN201210404170.7A CN201210404170A CN103771650A CN 103771650 A CN103771650 A CN 103771650A CN 201210404170 A CN201210404170 A CN 201210404170A CN 103771650 A CN103771650 A CN 103771650A
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Abstract
The invention discloses a method for treating coal gasification wastewater. The method comprises steps of: (1) lime softening by first adding lime milk to the coal gasification wastewater to conduct chemical precipitation on calcium salt and magnesium salt with the lime milk, standing the precipitation and filtering an supernatant; (2) ozone oxidation by sending the wastewater filtered in the step (1) into an ozone oxidation device for treatment; (3) MBBR treatment by sending the wastewater subjected to ozone oxidation into an MBBR for treatment; (4) coarse filtration; (5) continuous membrane filtration or ultrafiltration; (6) reverse osmosis; and (7) multi-effect evaporation by conducting multi-effect evaporation on the concentrate obtained by reverse osmosis treatment, and further crystallizing the concentrate obtained by multi-effect evaporation. The method of the invention can effectively remove the main pollutants such as COD, ammonia nitrogen and chroma in coal gasification wastewater, can also greatly reduce the salt content of the wastewater, ensure the efficient and long-term running of the double membranes, and achieve zero discharge of coal gasification wastewater.
Description
Technical field
The present invention relates to field of waste water treatment, be specifically related to a kind for the treatment of process of coal gasification waste water.
Background technology
Coal is the main fossil energy of China, and in recent years, gasification industry development is rapid.But gasification is the industry of high pollution, long, complex process of the cycle of operation, produces dirty link many, and poisonous and harmful mostly, and the waste water water yield especially producing is large, it is heavy to pollute, and is difficult to qualified discharge and reuse.Water resources and water environmental problems have become the bottleneck of restriction gasification industry development, seek the waste water treatment process that treatment effect is better, technology stability is stronger, working cost is lower, realize the target of wastewater zero discharge, become an urgent demand of gasification industry development.In the relevant policies of country, also explicitly call in key industrys such as iron and steel, electric power, chemical industry, coals and promote cycling utilization of wastewater, strive for waste water and discharge less or zero release.
(coal water slurry) waste water that coal high-temperature gasification technique produces is mainly flyash gasified water, and pollutant kind is many, and most organic pollutant hard degradation.The saltiness of high-temperature gasification technique waste water is 1000～2000mg/L, the calcium ions and magnesium ions that contains higher concentration, and wherein calcium salt content is 300～500mg/L, and magnesium salts content is higher than 10mg/L, and pH value is 7.0～8.0.At present, high-temperature gasification technique waste water adopts SBR treatment process more, water outlet generally can meet emission request, but exist water outlet saltiness is high, contain higher concentration calcium ions and magnesium ions and part heavy metal etc., be difficult to recycle, corrode follow-up advanced treatment device, and be difficult to reach emission standard, be substantially difficult to carry out waste water recycling.
CN200910177228.7 discloses a kind for the treatment of process of coal gasification waste water, this method adopts the combination process flow process of oil removal-coagulation-adjusting-one-level bio-contact oxidation-bioelectrochemistry reaction-two stage biological catalytic oxidation-catalytic oxidation treatment, and COD, ammonia nitrogen and colourity in waste water are reached to certain treatment effect.But this method is not more efficiently removed for other pollutents in waste water, the problem that especially in waste water, saltiness is high does not effectively solve.
CN200910143563.5 discloses a kind of coal chemical wastewater treating technique, utilize air supporting-Fenton reaction-activated sludge process-ultrafiltration-reverse osmosis-evaporative crystallization combination process to process coal gasification waste water, this method is added active carbon powder in active sludge, improve reaction effect, can realize the standard of " zero release ".But this method need to add Fenton reagent, increase cost, make the saltiness in waste water increase simultaneously, be unfavorable for follow-up two film reactions, increase burden also to follow-up two film reactions.
CN201019114056.9 provides a kind of novel process for the treatment of coal gasification wastewater with active coke, utilize activated coke to carry out first paragraph adsorption treatment and remove most COD, suspended substance and colourity, after adsorption treatment, water outlet enters immobilized microorganism-anaerobic biofilter (hereinafter to be referred as I-AF) and immobilized microorganism-aerobic aeration biological filter (hereinafter to be referred as I-BAF) system is carried out a biological disposal upon, remove most ammonia-nitrogen and COD in waste water, through I-AF+I-BAF water outlet after treatment, more further utilize activated coke to carry out degree of depth second segment adsorption treatment.This method can effectively be removed COD, ammonia nitrogen, the colourity in waste water, and water outlet can reach emission standard.But this method only reaches certain treatment effect to COD, ammonia nitrogen, colourity, other pollutents in waste water are not more efficiently removed, especially to organic pollutant complexity, difficult degradation in coal gasification waste water, saltiness is high all effectively not to be solved, and can not meet current environmental requirement.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind for the treatment of process of coal gasification waste water.The inventive method both can efficiently remove coal gasification waste water process in the principal pollutant such as COD, ammonia nitrogen and colourity, can greatly reduce the saltiness in waste water simultaneously, guarantee the efficient and long-time running of two films to realize the zero release of coal gasification waste water.
The treatment process of coal gasification waste water of the present invention comprises following seven processing units:
(1) lime is softening, first, to feeding lime breast in coal gasification waste water, makes calcium salt, magnesium salts and milk of lime generation chemical precipitation in waste water, staticly settles rear filtering supernatant;
(2) ozone oxidation, the waste water after step (1) is filtered enters ozone-oxidizing device processing;
(3) MBBR processes, and enters into MBBR process through the waste water of ozone oxidation;
(4) coarse filtration processing, carries out coarse filtration through MBBR waste water after treatment;
(5) continuous membrane filter or ultrafiltration, the waste water after step (4) is filtered enters continuous membrane filter or ultrafiltration system processing;
(6) reverse-osmosis treated, step (5) waste water after treatment enters reverse osmosis system processing, and the pure water obtaining through reverse-osmosis treated is for the circulating cooling make-up water of coal gasifying process;
(7) multiple-effect evaporation,, the concentrated solution that reverse-osmosis treated is obtained carries out multiple-effect evaporation, and the concentrated solution further multiple-effect evaporation being obtained carries out crystallization treatment.
In the present invention, during the lime of step (1) is softening, input milk of lime can directly adopt saturated milk of lime, also can prepare with industrial unslaked lime; Controlling the pH value of waste water after mixing is 8.5～10.0.Within the scope of this pH, calcium salt, magnesium salts in coal gasification waste water react with milk of lime generation chemical precipitation, effectively reduce water hardness.
In the present invention, the ozone-oxidizing device of step (2) adopts reaction tower or contact-oxidation pool, and ozone oxidation agent is provided by the ozone generating-device outside treatment unit.The dosage of ozone oxidation agent is 20～40mg/L waste water; The hydraulic detention time of waste water in reaction tower or oxidation pond is 10～20min.Ozone oxidation can effectively be removed COD, reduces colourity, improves the biodegradability of waste water, for follow-up biochemical reaction does good pre-treatment simultaneously.In the present invention, the removal of coal gasification waste water COD after ozone oxidation can reach 50wt%～70wt%, more than chroma removal rate can reach 80wt %, and the pollutent such as phenols, cyanogen is also had to certain removal effect.
In the present invention, the described MBBR of step (3) is MBBR, mainly comprises entering of the mechanical, electrical magnet valve of micro-pore aeration, programmable controller program Controlling System control water and air, the adding than being 30%～50% of reactor volume of filler.By add the suspending carrier of some amount in reactor, improve biomass and biological species in reactor, thereby improve the processing efficiency of reactor.Because packing density is close to water, so in aeration, be complete admixture with water, the environment of microorganism growth is gas, liquid, solid three-phase.Collision and the shearing action of carrier in water, makes air bubble more tiny, has increased the utilization ratio of oxygen.In addition, inside and outside each carrier, all there is different biological species, some anerobes of growth inside or double oxygen bacterium, outside has been bacteria, each like this carrier is a microreactor, nitration reaction and anti-nitration reaction is existed simultaneously, thereby improved treatment effect.
In the present invention, the coarse filtration processing of step (4) can be selected conventional filter plant, as more medium filter, sand-bed filter, drift sand strainer, millipore filter etc.The backwashing period of filtration treatment is 24～48h, and working pressure is 0.1～0.5MPa.By waste water is carried out to filtration treatment, meet into the requirement of ultrafiltration and reverse osmosis system processing.
In the present invention, the continuous membrane filter (CMF) that step (5) is described or ultrafiltration (UF) be well known to those skilled in the art membrane separating method.CMF is the membrane filtration technique of processing unit centered by high resistance to crocking hollow-fibre membrane; particular design efficient automatically controlled cleaning system and can realize hollow-fibre membrane do not shut down to on-line cleaning; thereby accomplish to process continuously water is uninterrupted; guarantee produce efficiently, carry out continuously, for good pre-treatment is done in reverse osmosis.Ultra-filtration membrane can be removed virus, macromolecular substance, colloid and microorganism.
In the present invention, the described reverse-osmosis treated of step (6) adopts one or more levels reverse osmosis system.In the present invention, preferably adopt three grades of reverse osmosiss, the pure water part that first-stage reverse osmosis obtains recycles as circular water replenishing, concentrated solution part enters two-pass reverse osmosis, the pure water part of two-pass reverse osmosis recycles as circular water replenishing, concentrated solution part enters three grades of reverse osmosiss, the pure water part of three grades of reverse osmosiss recycles as circular water replenishing, and concentrated solution part enters multiple-effect evaporation.
In the present invention, the condensed water that the described multiple-effect evaporation of step (7) obtains reclaims, and its concentrated solution further carries out crystallization treatment.Multiple-effect evaporation can be transformed into gaseous state from liquid state by the various volatile organic matters in water, and is again converted into liquid state after heat exchange.
The present invention has following beneficial effect:
(1) the present invention adopts that lime is softening carries out pre-treatment, calcium salt, magnesium salts in water is reacted, reduction water hardness with milk of lime generation chemical precipitation.Simultaneously, the softening adjusting of lime pH is 8.5～10.0, because ozone oxidation oxidation effectiveness under alkaline condition is better, be conducive to produce more hydroxyl radical free radical OH, and the wastewater pH of lime after softening is just in time under suitable alkaline condition, needn't regulate pH, can realize efficient ozone oxidation effect, improve the clearance of COD and the biodegradability of waste water.PH value in ozone oxidation process with oxidation carry out on a declining curvely, its reason is that oxidation operation becomes small molecular organic acid aldehyde material; The optimum operation pH scope of MBBR is that the too low microbial film of 6.0～9.0, pH easily comes off, the too high meeting of pH decomposer micelle, and through ozone oxidation, not only the biodegradability of waste water has improved, the pH of waste water drops to below 9.0 naturally simultaneously, can directly enter MBBR reaction, not need to regulate again pH.
(2) to adopt the object of ozone oxidation be not to make mineralization of organic material completely in the present invention, and object is in removing part pollutent, improves the biodegradability of waste water, and therefore oxidization time is short, and consumption is few.And ozone is extremely strong oxygenant, and it is different from the reactions such as flocculation, fenton, can decompose voluntarily in the short period of time, there is no secondary pollution, has avoided Xiang Shuizhong to add a large amount of oxidant cost high, and there is secondary pollution and increase the problem of saltiness.
(3) the present invention combines ozone oxidation with MBBR, and the water B/C ratio after ozone oxidation is improved, and guarantees that the COD of MBBR water outlet is reduced to below 50mg/L, reduces the load to follow-up pair of film, extends two film work-ing life.The load of MBBR processing is simultaneously high, does not need sludge reflux and backwashing equipment, and sludge yield is low, has reduced sludge disposal expense.
(4) adopt combination process flow process of the present invention both can effectively remove traditional coal gasification waste water process in the principal pollutant such as COD, ammonia nitrogen, also greatly reduce saltiness in water outlet simultaneously, reach the standard of country about coal gasification waste water zero release.The clear water rate of recovery of the present invention's coal gasification waste water after treatment can reach more than 90%, can be used as boiler replenishing water in coal gasifying process, recirculated water and is reused.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of a kind of coal gasification waste water treatment process of the present invention.
Wherein: 1-lime is softening, 2-ozone oxidation, 3-MBBR processes, 4-filtration treatment, 5-continuous membrane filter or ultrafiltration, 6-reverse-osmosis treated, 7-multiple-effect evaporation.
Embodiment
Below the inventive method specific embodiment is elaborated.In the present invention, wt% is massfraction.
Adopt the combination process flow process of the inventive method accompanying drawing 1 to process certain coal gasification waste water.Waste water quality is as follows: pH is that 7.3, COD is 961mg/L, and ammonia nitrogen is 141.49 mg/L, and Ca2+ is 426.23 mg/L, and Mg2+ is 12.52mg/L, and total salinity is 1525.92 mg/L, and B/C ratio is: 0.27.The wastewater treatment water yield is 1000L, and main experimental device formation, operational conditions and the treatment effect of each processing unit are in table 1.
The main processing unit of table 1 embodiment 1 forms and treatment effect
Effluent quality after treatment: COD is 40mg/L, and ammonia nitrogen is 3.91mg/L, Ca
2+for 6.33mg/L, Mg
2+for 0.98mg/L, total salinity is 25mg/L, reclaims water yield 937L.
Adopt the combination process flow process of the inventive method accompanying drawing 1 to process certain coal gasification waste water.Waste water quality is for as follows: pH is 7.6, and COD is 3326mg/L, and ammonia nitrogen is 208.19 mg/L, Ca
2+for 369.83mg/L, Mg
2+for 12.14mg/L, total salinity is 1553.6 mg/L, and B/C is 0.21.
Adopt method of the present invention, above-mentioned waste water is carried out to combined treatment test.The wastewater treatment water yield is 1000L, and main experimental device formation, operational conditions and the treatment effect of each processing unit are in table 1.
The main processing unit of table 2 embodiment 2 forms and treatment effect
Effluent quality after treatment: COD is 37mg/L, and ammonia nitrogen is 4.28mg/L, Ca
2+for 3.17mg/L, Mg
2+for 0.21mg/L, total salinity is 15.09mg/L, reclaims water yield 918L.
Claims (10)
1. a treatment process for coal gasification waste water, comprises following seven processing units:
(1) lime is softening, first, to feeding lime breast in coal gasification waste water, makes calcium salt, magnesium salts and milk of lime generation chemical precipitation in waste water, staticly settles rear filtering supernatant;
(2) ozone oxidation, the waste water after step (1) is filtered enters ozone-oxidizing device processing;
(3) MBBR processes, and enters into MBBR process through the waste water of ozone oxidation;
(4) coarse filtration processing, carries out coarse filtration through MBBR waste water after treatment;
(5) continuous membrane filter or ultrafiltration, the waste water after step (4) is filtered enters continuous membrane filter or ultrafiltration system processing;
(6) reverse-osmosis treated, step (5) waste water after treatment enters reverse osmosis system processing, and the pure water obtaining through reverse-osmosis treated is for the circulating cooling make-up water of coal gasifying process;
(7) multiple-effect evaporation, the concentrated solution that reverse-osmosis treated is obtained carries out multiple-effect evaporation, and the concentrated solution further multiple-effect evaporation being obtained carries out crystallization treatment.
2. in accordance with the method for claim 1, it is characterized in that: during the lime of step (1) is softening, input milk of lime directly adopts saturated milk of lime or prepares with industrial unslaked lime.
3. according to the method described in claim 1 or 2, it is characterized in that: during the lime of step (1) softens, controlling the pH value of waste water after mixing is 8.5～10.0.
4. in accordance with the method for claim 1, it is characterized in that: the ozone-oxidizing device of step (2) adopts reaction tower or contact-oxidation pool, and ozone oxidation agent is provided by the ozone generating-device outside treatment unit.
5. according to the method described in claim 1 or 4, it is characterized in that: the dosage of ozone oxidation agent is 20～40mg/L waste water, the hydraulic detention time of waste water in reaction tower or oxidation pond is 10～20min.
6. in accordance with the method for claim 1, it is characterized in that: the described MBBR of step (3) is MBBR, mainly comprises entering of the mechanical, electrical magnet valve of micro-pore aeration, programmable controller program Controlling System control water and air.
7. according to the method described in claim 1 or 6, it is characterized in that: in the MBBR described in step (3), filler adds than being 30%～50% of reactor volume.
8. in accordance with the method for claim 1, it is characterized in that: more medium filter, sand-bed filter, drift sand strainer or millipore filter are selected in the coarse filtration processing of step (4), the backwashing period of filtration treatment is 24～48h, and working pressure is 0.1～0.5MPa.
9. it is characterized in that in accordance with the method for claim 1: the described reverse-osmosis treated of step (6) adopts one or more levels reverse osmosis system.
10. in accordance with the method for claim 1, it is characterized in that: the condensed water that the described multiple-effect evaporation of step (7) obtains reclaims, and its concentrated solution further carries out crystallization treatment.
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| CN114590975A (en) * | 2022-04-06 | 2022-06-07 | 成都硕特科技股份有限公司 | Zero-discharge treatment method and treatment system for phenol-containing coal gas wastewater |
| CN114590975B (en) * | 2022-04-06 | 2023-04-25 | 成都硕特科技股份有限公司 | Zero-emission treatment method and treatment system for phenolic gas-containing wastewater |
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