CN102139983A - Waste water treatment method and system - Google Patents
Waste water treatment method and system Download PDFInfo
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- CN102139983A CN102139983A CN 201110039308 CN201110039308A CN102139983A CN 102139983 A CN102139983 A CN 102139983A CN 201110039308 CN201110039308 CN 201110039308 CN 201110039308 A CN201110039308 A CN 201110039308A CN 102139983 A CN102139983 A CN 102139983A
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- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 111
- 238000000034 method Methods 0.000 claims abstract description 66
- 239000002351 wastewater Substances 0.000 claims abstract description 50
- 239000002253 acid Substances 0.000 claims abstract description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000012267 brine Substances 0.000 claims abstract description 23
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 23
- 150000003839 salts Chemical class 0.000 claims abstract description 18
- 238000002425 crystallisation Methods 0.000 claims abstract description 17
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- 238000001704 evaporation Methods 0.000 claims abstract description 15
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- 238000001556 precipitation Methods 0.000 claims description 21
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- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000003610 charcoal Substances 0.000 claims description 4
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- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
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- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 18
- 239000000126 substance Substances 0.000 abstract description 15
- 230000020477 pH reduction Effects 0.000 abstract description 2
- 230000002378 acidificating effect Effects 0.000 abstract 1
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- 230000005484 gravity Effects 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 208000005156 Dehydration Diseases 0.000 description 8
- 230000018044 dehydration Effects 0.000 description 8
- 238000006297 dehydration reaction Methods 0.000 description 8
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
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- 238000005516 engineering process Methods 0.000 description 5
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- 239000000463 material Substances 0.000 description 5
- 239000012452 mother liquor Substances 0.000 description 5
- 239000010865 sewage Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 235000011089 carbon dioxide Nutrition 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 238000007872 degassing Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 239000002455 scale inhibitor Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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Images
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- Removal Of Specific Substances (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention relates to a waste water treatment method and a system. The waste water treatment method comprises the following steps: (a) insoluble substance removal: removing insoluble substances in waste water to obtain clear water; (b) acidification: adding strong acid to clear water so as to adjust pH to be acidic and produce inorganic salt, and removing gas therein; (c) evaporation: carrying out evaporation so as to obtain distilled water and strong brine; and (d) crystallization: crystallizing strong brine in a crystallizer so as to obtain crystal salts of organic salts, wherein waste water contains NH4<+>. The invention also relates to a waste water treatment system which comprises an insoluble substance removal unit, a mixed unit, an evaporator and a crystallizer, wherein the insoluble substance removal unit is used for removing insoluble matters or suspended matter in waste water; (B) the mixed unit is used for for mixing waste water and sulfuric acid; (C) the evaporator is arranged at the lower section of the mixed unit and is communicated with the mixed unit; and (D) the crystallizer is used for crystallizing organic salts in the strong brine. The method and the system have simple flow and low cost and are convenient to operate.
Description
Technical field
The present invention relates to a kind of method of wastewater treatment and system, the treatment process and the system, the particularly treatment process of catalyst for coal liquefaction factory effluent and system of especially high salt, high ammonia nitrogen, low organic wastewater.
Background technology
Catalyst for coal liquefaction is generally Fe-series catalyst or nickel, molybdenum and cobalt class catalyzer, and wherein efficient with it, the cheap and oligosaprobic advantage of Fe-series catalyst becomes the emphasis of current research.With the Fe-series catalyst is example, and their preparation method makes catalyst prod by raw materials such as coal dust or coal slurry, iron cpds through operations such as thorough mixing reaction back, washing, filtration and dryings.
In the production process of catalyst for coal liquefaction, produced a large amount of waste water, because starting material and coal in producing make the sewage of discharging have ammonium persulfate content, high dissolved solids (TDS), low organism, the uncertain characteristics of sewage component proportions.Its water quality scope is: NH
4 +: 1.3-1.8%; S0
4 2-: 2-4.5%, TDS:3.5-7%.The most biodegradability of this type of high salt high ammonia-nitrogen wastewater is poor, Pollutant levels height, difficult degradation, is a big difficult point of coal system oil.
At present, the treatment process of catalyst production waste water mainly is divided into physico-chemical process and biochemical treatment process, traditional physico-chemical process has flocculent precipitation, blow-off method, vaporizing extract process, ion exchange method, reverse osmosis etc., the most energy consumption height of these class methods, the alkaline consumption height, running cost height, deficiency in economic performance, there is the secondary pollution problem, is difficult to satisfy the requirement of producing; For biochemical process, the NH in the catalyst production waste water
3-N mainly exists with the form of inorganic ammonium salt and free ammonia, and the concentration difference is very big, is difficult to the biological degradation (BOD of waste water
5Almost nil), so processing efficiency is low, drainage water is difficult to reach national specified discharge standard.
CN1948191A has proposed a kind of treatment process of chemical catalyst production waste water, it comprises flocculating comes unstuck except that suspended substance, reverse osmosis desalination, the embrane method ammonia nitrogen removal, dosing removes treating processess such as sodium salt, but this method need add poly-aluminium, polyacrylamide, lime, medicines such as sodium removing agent, and the consumption of membrane module in the operational process, make running cost higher, though technology proposes to reclaim thiamines to reduce cost, but because the uncertainty of waste water composition, thiamines cost recovery height, simultaneously, this method complicated operation, difficult in maintenance, therefore, above problem makes it be unfavorable for that enterprise produces utilization.
CN1611456A has proposed a kind of treatment process of petrochemical industry catalyst production waste water, its treating processes comprises the processing of oil removal sediment, PH adjusting, flocculation-air floating, acidification hydrolization, catalytic oxidation etc., but it is that COD concentration is 14000～32000mg/l that this method adopts the precondition of biochemical technology, for the catalyst production waste water incompatibility that lacks organic carbon source, therefore can not be used for the processing of catalyst for coal liquefaction waste water.
Therefore, for high salt, high ammonia nitrogen, low organic catalyst for coal liquefaction factory effluent, be difficult in the prior art to have that a kind of flow process is simple, cost is low, non-secondary pollution, the easy to operate and method and system can stably reaching standard handled.
Summary of the invention
The objective of the invention is for a kind of wastewater treatment method and system are provided.
An aspect of of the present present invention relates to a kind of method of wastewater treatment, may further comprise the steps:
A) insolubles is removed
Remove the insolubles in the waste water, obtain clear water;
B) add acid
In clear water, add strong acid,, produce inorganic salt, and remove gas wherein so that pH regulator is extremely acid;
C) evaporation
Evaporate, obtain distilled water and strong brine;
D) crystallization
Strong brine is carried out crystallization at crystallizer, to obtain the crystal salt of inorganic salt;
Wherein, waste water contains NH
4 +
Preferably, insolubles is removed and is undertaken by sedimentation and/or filtration, preferably adopts sedimentation and filtration simultaneously.
Preferably, sedimentation is undertaken by inclined plate sedimentation method, advection settling process, perpendicular stream settling process or spoke stream settling process, is preferably undertaken by the inclined plate sedimentation method.
Preferably, filter and to be selected from running sand filtration, mechanical filter, active carbon filtration, rotational flow grit chamber filters and the fiber filter method at least a, preferred running sand filtration.
Preferably, at first carry out sedimentation or precipitation, filter then.
Preferably, the NH in the waste water
4 +Concentration 〉=1000mg/L, preferred 〉=1500mg/L, more preferably 〉=3500mg/L, most preferably 〉=4000mg/L.
Preferably, the organic concentration≤200mg/L in the waste water, preferred≤180mg/L, more preferably≤150mg/L, most preferably≤130mg/L.
Preferably, waste water is the catalyst for coal liquefaction factory effluent.
Preferably, strong acid is selected from sulfuric acid, nitric acid, hydrochloric acid or at least two kinds mixture wherein, preferably sulfuric acid.
Preferably, inorganic salt comprise ammonium salt, the preferably sulfuric acid ammonium.
The present invention relates to a kind of Waste Water Treatment on the other hand, comprising:
A) insolubles is removed the unit, is used for removing the insolubles of waste water, has waterwater entrance;
B) mixed cell is positioned at insolubles and removes unitary downstream, and removes unit and acid with insolubles and jar be connected, and is used for waste water is mixed with strong acid from the acid jar;
C) vaporizer is positioned at the downstream of mixed cell and is connected with mixed cell, has C1) vapor outlet port and C2) the strong brine outlet;
D) crystallizer is communicated with the strong brine outlet of vaporizer, is used for the inorganic salt crystallization with strong brine.
Preferably, insolubles is removed the unit and is selected from least a in precipitation apparatus, the filtering system.
Preferably, precipitation apparatus is selected from inclined plate sedimentation equipment, advection sedimentation equipment, perpendicular stream settling apparatus, rotational flow grit chamber or spoke stream settling apparatus, preferred inclined plate sedimentation equipment.
Preferably, filtering system is selected from least a in running sand filtration system, mechanical filter, charcoal filter and the fabric filter, preferred quicksand filtering system.
Preferably, filtering system is in the downstream of precipitation apparatus.
Preferably, Waste Water Treatment of the present invention further comprises: deoxygenator is arranged on B) mixed cell and C) between the vaporizer.
Preferably, Waste Water Treatment is a catalyst for coal liquefaction production wastewater treatment system.
Preferably, crystallizer is the condensing crystal device.
Method and system flow process of the present invention is simple, cost is low, easy to operate.
Description of drawings
Fig. 1 is the schema of a kind of preferred implementation of the present invention.
Fig. 2 is the process schematic representation of a kind of preferred implementation of the present invention.
Fig. 3 is the crystallizer synoptic diagram of a kind of preferred implementation of the present invention.
Embodiment
In the present invention, " with ... link to each other " or " being connected to " or " connections ", both can be that the two directly links to each other, also can across common parts or device (for example valve, pump, interchanger etc.) links to each other or connection.
In the present invention, under the situation of not contradiction or conflict, all embodiment of the present invention, embodiment and feature can make up mutually.
In the present invention, all units, parts etc. both can be purchased, also can be according to content self-control disclosed by the invention.
In the present invention, for outstanding emphasis of the present invention, the omission that operation and unit, the parts of some routines are carried out, or only do simple the description.
The present invention relates to a kind of method of wastewater treatment, method may further comprise the steps:
A) insolubles is removed
Remove the insolubles (or suspended substance) in the waste water, obtain clear water;
B) add acid
In clear water, add strong acid,, produce inorganic salt, and remove gas wherein so that pH regulator is extremely acid;
C) evaporation
Evaporate, obtain distilled water and strong brine;
D) crystallization
Strong brine is carried out crystallization at crystallizer, to obtain the crystal salt of inorganic salt;
Wherein, waste water contains NH
4 +
Wherein, waste water contains NH
4 +
NH in the waste water
4 +Concentration 〉=1000mg/L, preferred 〉=1500mg/L, more preferably 〉=3500mg/L, most preferably 〉=4000mg/L.Preferably, the organic concentration≤200mg/L in the waste water, preferred≤180mg/L, more preferably≤150mg/L, most preferably≤130mg/L.NH
4 +Concentration is the free ammonia ionic quality that contains in the per volume of catalyst waste water, and unit is mg/L.
Preferably, the organic concentration in the waste water is 0～200mg/L, preferred 10～180mg/L, more preferably 15～150mg/L, most preferably 20～130mg/L; NH in the waste water
4 +Concentration 1000～30000mg/L, preferred 1500～25000mg/L, more preferably 3500～22000mg/L, most preferably 4000～20000mg/L.
Preferably, NH in the waste water
4 +Concentration 1000～30000mg/L, preferred 1500～25000mg/L, more preferably 3500～22000mg/L, most preferably 4000～20000mg/L; SO
4 2-Concentration 1000～50000mg/L, preferred 2500～45000mg/L, more preferably 4000～40000mg/L, most preferably 8000～33000mg/L; Dissolved solids concentration 5000～100000mg/L, preferred 8000～90000mg/L, more preferably 10000～80000mg/L, most preferably 12000～70000mg/L.
Preferably, waste water is the catalyst for coal liquefaction factory effluent.
Preferably, insolubles is removed and is undertaken by sedimentation and/or filtration, more preferably adopts sedimentation and filtration simultaneously.
Preferably, sedimentation is undertaken by inclined plate sedimentation method, advection settling process, perpendicular stream settling process or spoke stream settling process, is more preferably undertaken by the inclined plate sedimentation method.
Preferably, filter and to be selected from running sand filtration, mechanical filter, active carbon filtration, rotational flow grit chamber filters and the fiber filter method at least a, more preferably running sand filtration.Preferably at first carry out sedimentation or precipitation, filter then.
Preferably, strong acid is to be selected from sulfuric acid, nitric acid, hydrochloric acid or at least two kinds mixture wherein, preferably sulfuric acid.
Preferably, in step b), with pH regulator to pH3.5～7.5, preferred pH4～7, more preferably pH4.5～6.5, also more preferably pH5～6, most preferably pH5.3～5.7.
Preferably, in step b), add scale inhibitor, to prevent the fouling of inorganic salt in equipment.
Preferably, alkali and acid all can be added in the vaporizer, to reduce ammonia volatilization as far as possible.Acid is selected from sulfuric acid, nitric acid, hydrochloric acid or at least two kinds mixture wherein, preferably sulfuric acid.Acid preferably with in mixing tank, add sour identical.Alkali for example is NaOH, KOH or LiOH, preferred NaOH.
Preferably, the step d) crystallization adopts the condensing crystal method to carry out.Preferably, the mother liquor that crystallization produced in the step d) crystallization returns crystallizer and circulates.
Another aspect of the present invention relates to a kind of Waste Water Treatment, comprising:
A) insolubles is removed the unit, is used for removing the insolubles or the suspended substance of waste water, has waterwater entrance;
B) mixed cell is positioned at insolubles and removes unitary downstream, and is connected with insolubles removal unit and acid jar,
Be used for waste water with from acid jar strong acid mix;
C) vaporizer is positioned at the downstream of mixed cell and is connected with mixed cell, has C1) vapor outlet port and
C2) strong brine outlet;
D) crystallizer is communicated with the strong brine outlet of vaporizer, is used for the inorganic salt crystallization with strong brine.
Preferably, insolubles is removed the unit and is selected from least a in precipitation apparatus, the filtering system.
Preferably, precipitation apparatus is selected from inclined plate sedimentation equipment, advection sedimentation equipment, perpendicular stream settling apparatus, rotational flow grit chamber or spoke stream settling apparatus, more preferably inclined plate sedimentation equipment.
Preferably, filtering system is selected from least a in running sand filtration system, mechanical filter, charcoal filter and the fabric filter, more preferably running sand filtration system.
Preferably, filtering system is in the downstream of precipitation apparatus.
Preferably, crystallizer is the condensing crystal device.
According to the difference of wastewater treatment capacity and the processing power of single device, identical device of the present invention or system can connect or use side by side.For example can be in parallel two or more precipitation apparatus, filter plant.
As shown in Figure 1, Waste Water Treatment of the present invention comprises: precipitation apparatus 110, filtering system 120, mixing tank 150, vaporizer 160, crystallizer 180.
A kind of preferred embodiment in, treatment process of the present invention may further comprise the steps successively:
A. at first containing wastewater from catalyst is delivered to the pretreatment unit import by external pump pressure;
B. behind magnetic flow meter, enter the inclined plate sedimentation equipment 110 of two parallel connections, the top water outlet, bottom spoil disposal, spoil disposal enter the muddy water pond, and muddy water is delivered to follow-up sludge dewatering equipment and is handled;
C. inclined plate sedimentation equipment 110 water outlets gravity flow is pooled to running sand filtration system 120, and the backwash water that sand filtration produces is carried out mud-water separation through the high-speed rotational separator, and concentrated water discharge is to muddy water pond 112, and clear water is delivered to the sand filtration import;
D. the water outlet gravity flow after filtering through sand filtration enters clean water basin 130, drains into regulating tank 140 by three outer wet-pits again;
G. strong brine enters crystallizer 180 processing after promoting, and the slurry that the high density of generation contains ammonium sulfate pumps into the wet crystal salt of equipment for separating liquid from solid (for example, whizzer) 182 dehydration back formation, recycling.Produced simultaneously secondary steam after condensation as water of productive use.
Referring to figs. 1 through Fig. 3, preferred embodiment the step and the equipment of method of the present invention is described in detail according to a kind of below.
1. precipitation apparatus 110
Waste water at first enters precipitation apparatus 110.Waste water enters precipitation apparatus 110, to remove suspended substance macrobead or insolubles macrobead.For example, precipitation apparatus 110 is selected from inclined plate sedimentation equipment, advection sedimentation equipment, perpendicular stream settling apparatus, rotational flow grit chamber or spoke stream settling apparatus, preferred inclined plate sedimentation equipment.
A kind of preferred embodiment in, containing wastewater from catalyst water inlet enters inclined plate sedimentation equipment 110 after magnetic flow meter carries out flow metering.The suspended substance macrobead by inclined plate sedimentation equipment 110, utilizes the shallow layer settling principle to be removed earlier.Inclined plate sedimentation equipment 110 is middle part water inlet, top water outlet, bottom spoil disposal.Inclined plate sedimentation equipment is closed equipment, and the top water outlet compiles by rising pipe after via effluent weir discharges.Two inclined plate sedimentation equipment 110 in parallel draining gravity flows separately compile the running sand filtration system that enters.Preferably, inclined plate sedimentation equipment 110 bottom spoil disposals are provided with electrical ball valve, by the unlatching of regional robot control system(RCS) PLC control electrical ball valve.Preferably, stable for holding device, spoil disposal is alternately repeatedly finished.Spoil disposal enters the muddy water pond.
2. filtering system 120
Preferably, filtering system 120 is selected from least a in running sand filtration system, mechanical filter, charcoal filter and the fabric filter, preferred quicksand filtering system.Waste water after the filtration of system 120, enters clean water basin 130 after filtration.
A kind of preferred embodiment in, precipitation apparatus 110 water outlets gravity flows is pooled to the water inlet manifold of running sand filtration system 120, then on average enters three running sand filtration devices.The running sand filtration device also is a closed equipment, is top water inlet, top water outlet, and backwash water is also discharged on top.
Be pooled to the sand filtration outfall sewer through the water outlet after the sand filtration filtration, gravity flow enters clean water basin 130.
The gravity flow of sand filtration backwash water compiles the backwash water house steward, then enters header tank.The backwash water design discharge is 10% of a flooding velocity, and for reducing the device percentage of water loss, device configuration high-speed swirler reduces water displacement to carry dense backwash water emission concentration; Swirler is got the sand filtration backwash water by high-pressure hydraulic pump from header tank, through high-speed rotational carry dense after, the dense water spin current of eddy flow device device bottom pressure is disposed to the muddy water pond; Eddy flow clear water pressure is delivered to drift sand filtering system 120 water inlet manifolds.The backwash water gravity flow of header tank remainder enters muddy water pond 112.
3. vaporizer 160
See also accompanying drawing 2.
Preferably, salt kind method technology can avoid the dirt in the vaporizer 160 to produce, but still has the chance of fouling in heat exchanger 210.Preferably, contain enough calcium sulfate in the charging, so that the valid function of salt solution thickener.A kind of preferred embodiment in, consider therefore, standby heat exchanger and on-the-spot cleaning system (CIP) to be set the situations of slight foulings in the heat exchanger 210, but also to adopt anti-dirt deoxygenator (for example, disc type and annular).For example, heat exchanger 210 adopts the plate and frame interchanger.
Preferably, the hot distilled water that the salt solution thickener produces is with feeding preheating (for example, being preheating near the ebullient temperature), and the charging of preheating enters vaporizer 160 and concentrates (for example, about 6 times), keeps the proper content of calcium sulfate in the circulation strong brine by recycle pump.Preferably, native system adopts outside steam to evaporate, owing to be T shape road on the pipe, each round-robin steam output is very low; Consider the adding of salt kind in addition again, these design factors prolong the interval of cleaning.Preferably, alkali 320 and acid 316 (for example, sulfuric acid) all can be added in the vaporizer 160, to reduce ammonia volatilization (for example, the pH of operation operation is about 3～4) as far as possible.The steam that the evaporation back produces enters hot well tank after entering the cooling of first step water cooler, promotes into heat exchanger preheating catalyst feed water through pump.Preferably, condenser and hot well tank are controlled under little negative pressure by blowdown system and work.
Shown in Fig. 2 only is preferred embodiment a kind of, and waste water also can directly enter vaporizer 160 without heat exchanger 210 and deoxygenator 190 behind mixing tank 150.As preferred embodiment, behind deoxygenator 190, enter vaporizer 160 again.
4. crystallizer 180
As shown in Figure 3, crystallizer 180 comprises evaporating pot 184, heating chamber 186.
Enter the top shwoot of condensing crystal device 180 from the concentrated solution 310 (for example, about 90 ℃) of evaporization process.Preferably, feed temperature is controlled at 60～65 ℃ in the evaporating pot 184, and through heating chamber 186 heating, evaporation, crystallization, inorganic salt are all separated out with the form of solid substance, with transfering material pump dense salt slurry 304 is pumped into material feeder and arrive equipment for separating liquid from solid 182 (for example, whizzer) dehydration again.Solid substance water ratio after the dehydration is about 5%, recycles.
Mother liquor 308 returns condensing crystal device 180, continues evaporation, concentrated, crystallization, and no mother liquor effluxes.Secondary steam is through the water cooler condensation, and the water of condensation of generation can be made the native system water of productive use, and redundance inserts pipe network, can make water of productive use for other system.
Advantage of the present invention is can be with high salt, high ammonia nitrogen, low organic containing wastewater from catalyst after treatment, and recycle is all carried out in water outlet, and flow process simple, save cost, processing efficiency height.After treatment, ammonia-nitrogen content is dropped to less than 50mg/L by 10000mg/L in the water, COD is less than 100mg/L, TSS (Total Suspended Solids, total suspended matter) content is less than 15mg/L, and petroleum-type concentration is less than 1mg/L, and specific conductivity is less than 300 μ s/cm, water outlet can be used as elementary de-mineralized water and recycles after subsequent technique is further refining, efflux thereby accomplish not have waste water.The solid crystal salt that produces is mainly ammonium sulfate, and nitrogen content is up to 16%, through further can be used as agricultural ammonium sulfate recycling after the drying-granulating packing.Therefore, no matter in economic benefit, environmental benefit, productivity effect has all realized higher-value.
Embodiment
Embodiment all adopts Fig. 1 to carry out to Waste Water Treatment shown in Figure 3.
Embodiment 1
Present method is implemented according to following steps:
1) inclined plate sedimentation equipment
The containing wastewater from catalyst water inlet enters the inclined plate sedimentation equipment 110 of two parallel connections after magnetic flow meter carries out flow metering.The suspended substance macrobead by inclined plate sedimentation equipment 110, utilizes the shallow layer settling principle to be removed earlier.Inclined plate sedimentation equipment 110 is middle part water inlet, top water outlet, bottom spoil disposal.Inclined plate sedimentation equipment 110 is open type equipment, and the top water outlet compiles by rising pipe after via effluent weir discharges.Two inclined plate sedimentation equipment 110 in parallel draining gravity flows separately compile the running sand filtration system 120 that enters.Inclined plate sedimentation equipment 110 bottom spoil disposals are provided with electrical ball valve, by the unlatching of regional robot control system(RCS) PLC control electrical ball valve.Stable for holding device, spoil disposal is alternately repeatedly finished.Spoil disposal enters muddy water pond 112.
2) running sand filtration system 120
Inclined plate sedimentation equipment 110 water outlets gravity flow is pooled to the water inlet manifold of running sand filtration system 120, then on average enters three running sand filtration devices.The running sand filtration device also is an open type equipment, is top water inlet, top water outlet, and backwash water is also discharged on top.
Be pooled to the sand filtration outfall sewer through the water outlet after the sand filtration filtration, gravity flow enters clean water basin 130.
The gravity flow of sand filtration backwash water compiles the backwash water house steward, then enters header tank.The backwash water design discharge is 10% of a flooding velocity, and for reducing the device percentage of water loss, device configuration high-speed swirler reduces water displacement to carry dense backwash water emission concentration; Swirler is got the sand filtration backwash water by high-pressure hydraulic pump from header tank, through high-speed rotational carry dense after, the dense water spin current of eddy flow device device bottom pressure is disposed to the muddy water pond; Eddy flow clear water pressure is delivered to drift sand filtering system water inlet manifold.The backwash water gravity flow of header tank remainder enters the muddy water pond.
3) vaporizer 160
The hot distilled water that the salt solution thickener produces arrives feeding preheating near the ebullient temperature, and the charging of preheating enters vaporizer 160 and concentrates about 6 times, keeps the proper content of calcium sulfate in the dense water of circulation by recycle pump.Native system adopts outside steam to evaporate, owing to be T shape road on the pipe, each round-robin steam output is very low; Consider the adding of salt kind in addition again, these design factors prolong the interval of cleaning.Alkali and sulfuric acid all can be added in the vaporizer 160, and to reduce ammonia volatilization as far as possible, the pH of operation operation is about 3～4.The steam that the evaporation back produces enters hot well tank after entering the cooling of first step water cooler, promotes into heat exchanger preheating catalyst feed water through pump.Condenser and hot well tank are controlled under little negative pressure by blowdown system and work.
4) crystal system
Enter the top shwoot of condensing crystal jar from the concentrated solution (about～90 ℃) of evaporization process.Feed temperature is controlled at 60～65 ℃ in the evaporating pot 184, and through heating chamber 186 heating, evaporation, crystallization, inorganic salt are all separated out with the form of solid substance, with transfering material pump high concentration slurry is pumped into material feeder and arrives whizzer 182 dehydrations again.Solid substance water ratio after the dehydration is about 5%, is transported outside the factory by automobile and recycles.
Centrifuge mother liquor returns condensing crystal system 180, continues evaporation, concentrated, crystallization, and no mother liquor effluxes.Secondary steam is through the water cooler condensation, and the water of condensation of generation can be made the native system water of productive use, and redundance inserts pipe network, can make water of productive use for other system.
The water quality of catalyst for coal liquefaction factory effluent is: NH
4 +Concentration is that 10280mg/L, COD concentration are that 120mg/L, TSS concentration are 200mg/L.Above-mentioned sewage carries out pre-treatment through inclined plate sedimentation equipment and running sand filtration system earlier, removes part TSS, reduces to 110mg/L; Regulate about PH to 5.5 through mixing tank then, enter vaporizer, effluent COD concentration is 97mg/L, NH
4 +Concentration is 39.1mg/L, and TSS concentration is 7mg/L; Concentrated solution enters crystallizer again, the outward transport of dehydration back.
Embodiment 2
Step is identical with embodiment 1, and actual conditions sees below and table 1.
The water quality of catalyst for coal liquefaction factory effluent is: NH
4 +Concentration is that 4707mg/L, COD concentration are that 110mg/L, TSS concentration are 52mg/L.Above-mentioned sewage carries out pre-treatment through inclined plate sedimentation equipment and running sand filtration system earlier, removes part TSS, reduces to 26mg/L; Regulate about PH to 5.5 through mixing tank then, enter vaporizer, effluent COD concentration is 77mg/L, NH
4 +Concentration is 48.9mg/L, and TSS concentration is 7mg/L; Concentrated solution enters crystallizer again, the outward transport of dehydration back.
Embodiment 3
Step is identical with embodiment 1, and actual conditions sees below and table 1.
The water quality of catalyst for coal liquefaction factory effluent is: NH
4 +Concentration is that 18862mg/L, COD concentration are that 115mg/L, TSS concentration are 165mg/L.Above-mentioned sewage carries out pre-treatment through inclined plate sedimentation equipment and running sand filtration system earlier, removes part TSS, reduces to 105mg/L; Regulate about PH to 5.5 through mixing tank then, enter vaporizer, effluent COD concentration is 87mg/L, NH
4 +Concentration is 39.5mg/L, and TSS concentration is 6mg/L; Concentrated solution enters crystallizer again, the outward transport of dehydration back.
Embodiment 4 to 8
Step is identical with embodiment 1, and actual conditions sees Table 1.
Table 1
Certainly, the present invention also can have other embodiments, and the above is a preferred implementation of the present invention only, is not to be used for limiting protection scope of the present invention; Without departing from the spirit of the invention, those of ordinary skills are every to make various corresponding variations and modification according to content of the present invention, all belongs to the protection domain of claim of the present invention.
The reference numeral explanation
110 precipitation apparatus
112 muddy water ponds
120 filtration systems
130 clean water basin
140 regulating tanks
150 mixing tanks
152 acid jars
160 vaporizers
170 strong brine jars
180 crystallizers
182 equipment for separating liquid from solid
184 evaporating pots
186 heating chambers
190 deoxygenators
210 heat exchangers
302 steam
304 dense salt slurries
306 water of condensation
308 mother liquors
310 concentrated solutions
312 steam
314 distilled water
316 acid
318 CaSO
4
320 alkali
Claims (18)
1. method of wastewater treatment may further comprise the steps:
A) insolubles is removed
Remove the insolubles in the waste water, obtain clear water;
B) add acid
In described clear water, add strong acid,, produce inorganic salt, and remove gas wherein so that pH regulator is extremely acid;
C) evaporation
Evaporate, obtain distilled water and strong brine;
D) crystallization
Described strong brine is carried out crystallization at crystallizer, to obtain the crystal salt of described inorganic salt;
Wherein, described waste water contains NH
4 +
2. method according to claim 1, wherein, described a) insolubles is removed and is undertaken by sedimentation and/or filtration, preferably adopts sedimentation and filtration simultaneously.
3. method according to claim 2, wherein, described sedimentation is undertaken by inclined plate sedimentation method, advection settling process, perpendicular stream settling process or spoke stream settling process, is preferably undertaken by the inclined plate sedimentation method.
4. according to each described method of claim 2 to 3, wherein, described filtration is selected from running sand filtration, mechanical filter, active carbon filtration, rotational flow grit chamber filters and the fiber filter method at least a, preferred running sand filtration.
5. according to each described method of claim 2 to 4, wherein, at first carry out sedimentation or precipitation, filter then.
6. according to each described method of claim 1 to 5, wherein, the NH in the described waste water
4 +Concentration 〉=1000mg/L, preferred 〉=1500mg/L, more preferably 〉=3500mg/L, most preferably 〉=4000mg/L.
7. according to each described method of claim 1 to 6, wherein, the organic concentration≤200mg/L in the described waste water, preferred≤180mg/L, more preferably≤150mg/L, most preferably≤130mg/L.
8. according to each described method of claim 1 to 7, wherein, described waste water is the catalyst for coal liquefaction factory effluent.
9. according to each described method of claim 1 to 8, wherein, described strong acid is selected from sulfuric acid, nitric acid, hydrochloric acid or at least two kinds mixture wherein, preferably sulfuric acid.
10. according to each described method of claim 1 to 9, wherein, described inorganic salt comprise ammonium salt, the preferably sulfuric acid ammonium.
11. a Waste Water Treatment comprises:
A) insolubles is removed the unit, is used for removing the insolubles of waste water, has waterwater entrance;
B) mixed cell is positioned at described insolubles and removes unitary downstream, and removes unit and acid with described insolubles and jar be connected, and is used for described waste water is mixed with strong acid from described acid jar;
C) vaporizer is positioned at the downstream of described mixed cell and is connected with described mixed cell, has C1) vapor outlet port and C2) the strong brine outlet;
D) crystallizer is communicated with the strong brine outlet of described vaporizer, is used for the inorganic salt crystallization with strong brine.
12. Waste Water Treatment according to claim 11, wherein, described insolubles is removed the unit and is selected from least a in precipitation apparatus, the filtering system.
13. Waste Water Treatment according to claim 12, wherein, described precipitation apparatus is selected from inclined plate sedimentation equipment, advection sedimentation equipment, perpendicular stream settling apparatus, rotational flow grit chamber or spoke stream settling apparatus, preferred inclined plate sedimentation equipment.
14. Waste Water Treatment according to claim 12, wherein, filtering system is selected from least a in running sand filtration system, mechanical filter, charcoal filter and the fabric filter, preferred quicksand filtering system.
15. according to each described Waste Water Treatment of claim 12 to 14, wherein, described filtering system is in the downstream of described precipitation apparatus.
16. according to each described Waste Water Treatment of claim 11 to 15, further comprise: deoxygenator is arranged on described B) mixed cell and described C) between the vaporizer.
17. according to each described Waste Water Treatment of claim 11 to 16, wherein, described Waste Water Treatment is a catalyst for coal liquefaction production wastewater treatment system.
18. according to each described Waste Water Treatment of claim 11 to 16, wherein, described crystallizer is the condensing crystal device.
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| CN104193060A (en) * | 2014-08-29 | 2014-12-10 | 中国五环工程有限公司 | Multiple-effect evaporation technique and system for coal chemical industry device concentrated brine |
| CN105152377A (en) * | 2015-09-10 | 2015-12-16 | 神华集团有限责任公司 | Sewage purifying and recycling system |
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| CN112062375A (en) * | 2020-09-09 | 2020-12-11 | 青岛伊西欧普节能新技术有限公司 | Evaporation and crystallization integrated treatment device for pickle wastewater |
| CN113880339A (en) * | 2021-10-09 | 2022-01-04 | 福建省环境保护设计院有限公司 | Advanced treatment and recycling process for high-salinity industrial wastewater |
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Application publication date: 20110803 |