CN106745886A - Free acid and metallic salt separator in industrial waste acid - Google Patents
Free acid and metallic salt separator in industrial waste acid Download PDFInfo
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- CN106745886A CN106745886A CN201611186764.XA CN201611186764A CN106745886A CN 106745886 A CN106745886 A CN 106745886A CN 201611186764 A CN201611186764 A CN 201611186764A CN 106745886 A CN106745886 A CN 106745886A
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- acid
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- water
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- storage tank
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- 239000002253 acid Substances 0.000 title claims abstract description 195
- 239000002440 industrial waste Substances 0.000 title claims abstract description 53
- 150000003839 salts Chemical class 0.000 title claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 89
- 239000011347 resin Substances 0.000 claims abstract description 83
- 229920005989 resin Polymers 0.000 claims abstract description 83
- 238000000926 separation method Methods 0.000 claims abstract description 49
- 238000003860 storage Methods 0.000 claims abstract description 43
- 239000002699 waste material Substances 0.000 claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 claims abstract description 24
- 238000010612 desalination reaction Methods 0.000 claims abstract description 22
- 239000012267 brine Substances 0.000 claims abstract description 16
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 16
- 239000000919 ceramic Substances 0.000 claims description 13
- 229910000975 Carbon steel Inorganic materials 0.000 claims description 12
- 239000010962 carbon steel Substances 0.000 claims description 12
- -1 sour batch box (T3) Substances 0.000 claims description 9
- 239000004743 Polypropylene Substances 0.000 claims description 8
- 229920001155 polypropylene Polymers 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 6
- 239000004800 polyvinyl chloride Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 3
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 3
- 239000011152 fibreglass Substances 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- 238000004140 cleaning Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 34
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 18
- 230000008569 process Effects 0.000 abstract description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 6
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 6
- 238000005272 metallurgy Methods 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 description 11
- 238000001514 detection method Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- 229920006351 engineering plastic Polymers 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 238000004064 recycling Methods 0.000 description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 230000003020 moisturizing effect Effects 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 238000006396 nitration reaction Methods 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000000502 dialysis Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 235000021110 pickles Nutrition 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 235000010215 titanium dioxide Nutrition 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 235000010269 sulphur dioxide Nutrition 0.000 description 2
- 239000004291 sulphur dioxide Substances 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 241001269238 Data Species 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000009614 chemical analysis method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 229910052571 earthenware Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 244000144985 peep Species 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/22—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the construction of the column
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/008—Control or steering systems not provided for elsewhere in subclass C02F
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The present invention relates to industrial waste acid processing equipment field; it is especially a kind of to single industrial waste acid or various industry mixing spent acid are applicable; it is easy to free acid and metallic salt separator in the industrial waste acid of acid/salt separation in the spent acid of industrial scale; including sour batch box, brine waste storage tank, water batch box and desalination spent acid storage tank; also include sour adsorbing separation resin column; sour batch box is connected with sour adsorbing separation resin column one end, and the water batch box is connected with the sour adsorbing separation resin column other end；Wherein, the acid solution in sour batch box is after sour adsorbing separation resin column first via brine waste storage tank is flowed into, and then, production water or pure water in the water batch box after sour adsorbing separation resin column via being flowed into desalination spent acid storage tank.The present invention is applied to various industries such as chemical industry, metallurgy after producing and using the single or mixed acid such as sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid, phosphoric acid, among the handling process of the similar spent acid of the substantial amounts of metalline class of output.
Description
Technical field
The present invention relates to free acid in industrial waste acid processing equipment field, especially a kind of industrial waste acid and metallic salt point
From device.
Background technology
Various industries such as chemical industry, metallurgy are produced during producing and using sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid, phosphoric acid etc.
Go out the similar spent acid of a large amount of metalline classes, the such as Waste Sulfuric Acid of sulfate process titanium dioxide, hydrometallurgy (electrolysis) Industrial Output, useless electricity
Solution liquid；The waste hydrochloric acid of titanium tetrachloride, titanium white chloride, titanium sponge and chlor-alkali industry；Stainless steel, steel, the plating of aluminium foil industry, pickling
The Waste Sulfuric Acid of link output, Waste Sulfuric Acid/hydrochloric acid nitration mixture, waste hydrochloric acid/waste nitric acid nitration mixture；Waste phosphoric acid of sulphur dioxide of phosphor chemical industry output etc.
Deng.Due to free acid and metallic salt containing higher concentration in these industrial waste acids, larger threat is caused to environment.Simultaneously
Due to the presence of a large amount of metallic salts in industrial waste acid, cause the direct recycling of metallic salt in industrial waste acid and spent acid
Difficulty is larger.
The handling process of industrial waste acid comparative maturity is at present：1) neutralisation:Acid pickle is added into alkaline matter (such as stone
Ash, salkali waste) acid-base neutralization is carried out, liquid PH 6~9 after neutralizing is adjusted, air can be passed through if necessary carries out forced aeration, improves
Neutralization precipitation thing condenses speed and structure, and neutralizing disposed slurry carries out separation of solid and liquid, and filter residue slag input is stacked, filtrate heel row up to standard
Put；2) waste acid concentration method：Using traditional heating evaporation technique, acid pickle is concentrated, with acid-spending strength and temperature
Improve, the reduction of solubility of the substantial amounts of metallic salt in acid can crystallize precipitation in spent acid, be concentrated into after finite concentration by
Necessary separation of solid and liquid, except the metallic salt of precipitation of decrystallizing, obtains certain density gelled acid, and metallic salt is most of in acid
It is removed, the gelled acid can return to factory and fresh acid collocation is used.3) diffusion dialysis embrane method.
The handling process of above-mentioned three kinds of acid pickles exists at aspects such as investment, operating cost, environmentally friendly secondary pollution, safety
Larger problem：1) neutralisation treatment industrial waste acid, there is not a large amount of free acids and metallic salt for having economic worth completely in spent acid
It is utilized, while adding substantial amounts of alkaline matter to neutralize, the filter residue of output several times volume causes secondary environmental pollution；2) give up
Sour concentration method processes spent acid, and the solution pollution of industrial waste acid and recycling are played a positive role, but the commercial plant is built
If input is huge, operating cost and high cost, simultaneously because being mingled with substantial amounts of metallic salt in industrial waste acid, disappear in concentration link
Heat consumption, crystallization are separated out and block heat-exchanger rig, cause enrichment facility to run difficult；3) diffusion dialysis embrane method：With development in science and technology,
Diffusive dialysis method is being produced as a trial on a small quantity in German commercialization, in recent years domestic some producers, the equipment maximum processing capability
It is 5~20M3/ d, because treating capacity is small, membrane lifetime is short, and easy aging breakage, the excessively low reason of cost performance, limitation industrial production is used.
For substantial amounts of free acid in industrial waste acid and metallic salt and the research of specific resin characterization of adsorption differentiation, open
Send a kind of industrial waste acid resin adsorption method acid/salt separating technology efficiently, inexpensive；In combination with the Adsorption and desorption of resin
The features such as characteristic, method of operation, develop supporting system and device.The technique and corollary apparatus and above-mentioned three kinds of industrial waste acids
Handling process compares, with the obvious advantage at aspects such as investment, operation stability, cost, safety coefficients.
The content of the invention
It is equal to single industrial waste acid or various industry mixing spent acid that the technical problems to be solved by the invention are to provide one kind
Applicable, it is easy to free acid and metallic salt separator efficiently, inexpensive in the spent acid of industrial scale.
The technical solution adopted for the present invention to solve the technical problems is：Free acid and metallic salt are separated in industrial waste acid
Device, including sour batch box, brine waste storage tank, water batch box and desalination spent acid storage tank, also including sour adsorbing separation resin column,
The sour batch box is connected with sour adsorbing separation resin column one end, and the water batch box connects with the sour adsorbing separation resin column other end
It is logical；Wherein, the acid solution in sour batch box is after sour adsorbing separation resin column first via brine waste storage tank is flowed into, then, institute
Production water or pure water in water batch box are stated via being flowed into desalination spent acid storage tank after sour adsorbing separation resin column.
It is further, including produces water/pure water storage tank, the production water/pure water storage tank is connected with water batch box.
It is further, including preliminary clearning acceptable material acid storage tank, the preliminary clearning acceptable material acid storage tank and acid metering
Bucket connection.
It is further that the sour adsorbing separation resin column is by resin column, the resin being arranged in resin column, setting
Moisturizing plate in resin column upper and lower ends, the water cap being arranged between moisturizing plate and resin column and it is arranged at the moisturizing
End cap on plate is constituted.
It is further that the making material of the resin column, end cap and moisturizing plate is polypropylene or polyvinyl chloride or glass
Glass steel or carbon steel polypropylene lining or carbon steel lining PO or carbon steel lining acid-resisting rubber or carbon steel lining F4.
It is further that the making material of the water cap is polypropylene or polyvinyl chloride or ABS.
It is further, including the PLC control devices for realizing automatically controlling, the acid solution and production water or pure water
Flow direction be controlled by PLC control devices.
It is further, including original sour preliminary clearning system, the original sour preliminary clearning system and preliminary clearning acceptable material
Acid storage tank is connected.
Be further that the equipment of original sour preliminary clearning system is precipitation apparatus, filter press, tubular filter, ceramics it is micro-
Hole filter or cartridge filter.
It is further that the material of the resin set in the sour adsorbing separation resin column is acid retardance resinoid.
The beneficial effects of the invention are as follows：Industrial waste acid after separating acid of the present invention, salt, can directly return as needed
Go back to factory to utilize, recycled after also can carrying out concentrate treatment using conventional waste acid concentration technique, to increase the reuse number of spent acid
Amount；Industrial waste acid can efficiently solve conventional waste acid concentration dress after resin adsorption method acid/salt separates technical finesse purification
Put the direct equipment for using the industrial waste acid without acid/salt treatment to bring blocking, the thermal efficiency is low, equipment abrasion is serious, acid yield
The problems such as low, plant running and maintenance cost high；By the recycling of spent acid, sour resource is both effectively saved, at reduction
Secondary pollution of the reason spent acid to environment, while the metal salt solution separated contains a small amount of free acid, the difficulty of its treatment
To be greatly lowered with expense, and the possibility for recycling will increase.The present invention is applied to various industries such as chemical industry, metallurgy in life
Produce and using sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid, the single or mixed acid such as phosphoric acid after, the substantial amounts of metalline class of output it is similar
Among the handling process of spent acid.
Brief description of the drawings
Fig. 1 is apparatus structure schematic diagram of the invention.
Fig. 2 is the structural representation of sour adsorbing separation resin column of the invention.
Marked in figure：Production water/pure water storage tank T1, preliminary clearning acceptable material acid storage tank T2, sour batch box T3, water metering
Bucket T4, desalination spent acid storage tank T5, brine waste storage tank T6, production water/pure water delivery pump P1, preliminary clearning raw material acid delivery pump P2,
Resin column enters sour pump P3, resin column intake pump P4, desalination spent acid delivery pump P5, brine waste delivery pump P6, sour adsorbing separation tree
Fat post R, resin column R1, end cap R2, water distributing plate R3, water cap R4, resin R5, control valve V (1,2,3,4,5,6,7,8) were ensured public security
Filter F (1,2), production water system 1, original sour preliminary clearning system 2, flow direction control valve (3,4).
Specific embodiment
The present invention is further described below in conjunction with the accompanying drawings.
Free acid and metallic salt separator in industrial waste acid as shown in Figure 1 and Figure 2, including sour batch box T3, saliferous
Waste water storage tank T6, water batch box T4 and desalination spent acid storage tank T5, also including sour adsorbing separation resin column R, the sour batch box T3
Connected with sour adsorbing separation resin column R one end, the water batch box T4 is connected with the sour adsorbing separation resin column R other ends；Wherein,
Acid solution in sour batch box T3 after sour adsorbing separation resin column R first via being flowed into brine waste storage tank T6, then, the water
Production water or pure water in batch box T4 after sour adsorbing separation resin column R via being flowed into desalination spent acid storage tank T5.
Present invention may apply to various industries such as chemical industry, metallurgy, producing and using sulfuric acid, nitric acid, hydrochloric acid, hydrogen fluorine
Acid, phosphoric acid etc. is single or mixed acid during, the treatment of the similar spent acid of a large amount of metalline classes of output.Such as sulfuric acid process titanium
In vain, the Waste Sulfuric Acid, waste electrolyte of hydrometallurgy (electrolysis) Industrial Output；Titanium tetrachloride, titanium white chloride, titanium sponge and chlor-alkali industry
Waste hydrochloric acid；Stainless steel, steel, the plating of aluminium foil industry, the Waste Sulfuric Acid of pickling link output, Waste Sulfuric Acid/hydrochloric acid nitration mixture, abraum salt
Acid/waste nitric acid nitration mixture；The waste phosphoric acid of sulphur dioxide of phosphor chemical industry output.Compared with traditional processing scheme, technical advantage of the invention is bright
It is aobvious, refer to following table：
General, when actually used, in order to ensure the separating effect in later stage, can select to set up original sour preliminary clearning system
2, the original sour preliminary clearning system 2 is connected with preliminary clearning acceptable material acid storage tank T2, first to consolidating for being mingled with raw material spent acid
Body suspension, is pre-processed (preliminary clearning) using solid-liquid separation process and equipment.Wherein, comparative maturity and the solid-liquid of practicality point
Separating process and equipment are included but is not limited to：Precipitation apparatus, filter press, tubular filter, ceramic capillary filter, cartridge filter
(also referred to as accurate filter) etc..What is recommended is two or more Processes and apparatus strings of above-mentioned solid-liquid separation process and equipment
Connection treatment, first-selected scheme is precipitation apparatus+filter press+ceramic capillary filter；And in this link, sedimentation time, filter cloth choosing
Type, the selection of ceramic capillary aperture are and its always, a large amount of field datas show, the sedimentation time is not less than 10 hours, 758 encryptions
Type filter cloth, the earthenware of 30 micron pore sizes should be first-selection；By temperature in normal temperature between 60 degree, and by sedimentation in 10 hours
The acidproof engineering plastic pump of industrial waste acid upper clear supernate is continuously transported to the filter press of recommendation, ceramic capillary filter in order
It is interior, by the industrial waste acid of filtration treatment by detecting up to after requiring, it is placed in preliminary clearning acceptable material acid storage tank (T2)
Stand-by, underproof spent acid returns to precipitation apparatus and processes again untill qualified.
It is as shown in Figure 1 by the qualified industrial waste acid after above-mentioned pre-decontamination steps, preliminary clearning raw material acid can be used
Delivery pump P2 is transported in sour batch box T3.In course of conveying, for resin bed is not blocked up by suspension in acid in ensuring resin column
Plug failure, cartridge filter (F2) is added between conveying pump discharge and resin column (bed) acid inlet, filter core aperture according to 0.1~
10 microns of considerations, it is first-selected 1~5 micron；Enter in sour batch box by the spent acid of cartridge filter, specifically enter acid metering by PLC
Opening/stop and accordingly for flowmeter controlling pump is set by the liquid level gauge/gravitometer being arranged on sour batch box or on pipeline
The ON/OFF of valve is realized.Same principle and step, production water/pure water delivery pump that industry water/pure water is passed through into supply mains
P1 is transported in water batch box T4 from production water/pure water storage tank T1, can be according to the specific water quality situation determination of production water/pure water
The no cartridge filter (F1) for installing same type additional.
Enter sour pump P3 with resin column to enter spent acid after preliminary clearning from sour adsorbing separation resin column R bottoms, spent acid is under
Supreme free acid is adsorbed by resin during sour adsorbing separation resin column R, and brine waste is from sour adsorbing separation resin
The discharge of post R tops, water batch box T4 and brine waste storage tank are sequentially entered by the switching of flow direction control valve (3,4) and valve
Deposited in T6 stand-by.The desalination waste water of early stage discharge is few containing free acid and metallic salt quantity, into water batch box, the later stage
Contain a small amount of free acid and substantial amounts of metallic salt in the waste water of discharge, the effluent part is entered into brine waste storage tank T6.
The sour adsorbing separation resin column R of industrial waste acid turnover of certain volume, after resin bed absorption free acid reaches saturation, stops
Stop into acid, pushed up the production water/pure water in water batch box from sour adsorbing separation resin column R by pipeline with resin column intake pump P4
Portion's inlet is squeezed into sour adsorbing separation resin column R, and production water/pure water will be set during from top to bottom resin bed is passed through
Fat absorption free acid drip washing be desorbed, from sour adsorbing separation resin column R bottoms discharge, successively, by flow direction control valve (3,
4) and valve switching sequentially enter sour batch box T3 and desalination spent acid storage tank T5 in deposit stand-by；What is adsorbed in resin is free
After sour drip washing is basically completed, stop water inlet.Early stage discharge contains substantial amounts of free acid and metallic salt except spent acid, is counted into acid
Reprocessed in measuring tank T3, a small amount of metallic salt and substantial amounts of free acid, the part spent acid are contained in the desalination spent acid of later stage discharge
Enter into desalination spent acid storage tank T5.Wherein, the resin of sour adsorbing separation resin column R fillings can select to be a kind of as needed
Or various kinds of resin, filling mode can be the filling of single kind resin or the mixing of various kinds of resin filling；Wherein resin kind
The selection of class is more crucial, the including but not limited to more representative strong basic type anion-exchange resin with quarternary amine functional group,
The acid retardance resinoid such as strongly acidic cation-exchange.
Above-mentioned step is repeated, allows industrial waste acid and production water/pure water alternately to pass in and out sour adsorbing separation resin column R successively,
Free acid and slaine are separated by Adsorption and desorption in industrial waste acid, become two kinds of liquid difference of desalination spent acid and brine waste
It is stored in desalination spent acid storage tank T5 and brine waste storage tank T6.If desired obtain free acid and metallic salt divides to a greater extent
From the desalination spent acid that will can be obtained is raw material, is repeated the above steps, and carries out secondary resin adsorption and separates.Industrial reality should
To realize double treatment in, must be by two covering device series operations.With reference to practical experience, free acid in desalination spent acid
50~95% (free acid yields) before measuring as separation, the residual quantity of metallic salt be before separating 50~95% (slaine goes
Except rate), treatment is per M3Industrial waste acid, processing cost and cost are relatively low：The quantity consumed for producing water/pure water is about
0.5~2M3；The consumption of industrial electro is about 0.5~3 KWH.Industrial waste acid by two systems series connection treatment after, industrial waste acid
The accumulative rate of recovery of middle free acid is 30~80%, and the accumulative clearance of metallic salt is up to 70~99%.
In order to sour adsorbing separation resin column R has more preferably anticorrosion ability and separating effect, such side can be selected
Case：The sour adsorbing separation resin column R by resin column R1, the resin R5 being arranged in resin column R1, be arranged at resin column
The water distributing plate R3 of body R1 upper and lower ends, the water cap R4 being arranged between water distributing plate R3 and resin column R1 and it is arranged at the cloth
End cap R2 on water plate R3 is constituted.Wherein, the making material of the resin column R1, end cap R2 and water distributing plate R3 be polypropylene or
Polyvinyl chloride or fiberglass or carbon steel polypropylene lining or carbon steel lining PO or carbon steel lining acid-resisting rubber or carbon steel lining F4.The water cap R4
Making material be polypropylene or polyvinyl chloride or ABS.The sour adsorbing separation resin column R surfaces are provided with peep hole or regard
Mirror, to facilitate operation and resin replacement.In addition, in order to realize control of industrialization, preferably setting up the PLC for realizing automatically controlling
The flow direction of control device, the acid solution and production water or pure water is controlled by PLC control devices.Using PLC control devices
Control, the detection and control of the volume/flow/weight by passing in and out sour adsorbing separation resin column R to spent acid and production water/pure water
System, selectively sour batch box, water batch box, purification after spent acid storage tank, production water/pure water storage tank, desalination spent acid storage tank,
Liquid level detection device, Weight detecting device are set in the equipment such as desalination waste water storage tank or flow detection is set on corresponding pipeline
Device, opens/stops and control valve V1~8 ON/OFF continuously to transport realizing system according to the corresponding pump of programme-control of PLC settings
OK.
Embodiment
First, it is mingled with the substantial amounts of colloid for exceeding 100 microns, solid suspension impurity in original industrial waste acid.
Firstly the need of carry out be industrial waste acid pretreatment (preliminary clearning), using separation of solid and liquid work as described in the present invention
Skill and equipment, this implementation are compared first using four sets of plan, are expressed as follows：
Scheme one, using 40m2Filter press+5m2Ceramic capillary filter combined treatment process and equipment, wherein press filtration machine filter
Cloth selects domestic conventional 758AB ciphering types, and 30 microns of ceramic capillary filter micropore filter element size selection uses generic engineering plastics
Pump continuous feed 8 hours, is suspended with solid suspension residual quantity in GB gravimetric method detection filtrate, and laser particle analyzer detection
Thing particle diameter, chemical method analysis filtrate free acid, metal salt concentration are as a result as follows：
Scheme two, using 100m3Gravity settling basin (ensuring to settle for 12 hours)+40m2Filter press+5m2Ceramic capillary is filtered
Device combined treatment process and equipment, wherein canvas press cloth select domestic conventional 758AB ciphering types, ceramic capillary filter micropore
30 microns of filter core size selection, with generic engineering plastics pump continuous feed 8 hours, detection method was ibid, as a result as follows：
Scheme three, using 100m3Gravity settling basin (ensuring to settle for 12 hours)+5m2Ceramic capillary filter Combined Treatment work
Skill and equipment, 30 microns of ceramic capillary filter micropore filter element size selection, with generic engineering plastics pump continuous feed 8 hours,
Detection method is ibid, as a result as follows：
Scheme four, using 200m3Gravity settling basin (ensuring to settle for 24 hours)+40m2Filter press combined treatment process and set
Standby, wherein canvas press cloth selects domestic conventional 758AB ciphering types, with generic engineering plastics pump continuous feed 8 hours, detection side
Method is ibid, as a result as follows：
The preliminary clearning Processes and apparatus configuration of four kinds of scheme industrial waste acids in above-described embodiment 1, due to handling process and sets
Standby selection is different, and the pretreating effect of industrial waste acid is also not quite similar, but can meet post-order process, described treatment substantially
Colloid, solid suspension residual quantity are by no more than 0.3 g/l, the colloidal impurity of residual, solid suspension in acceptable industrial spent acid
Particle diameter is not more than 100 microns of index.Four kinds of schemes are preferably scheme and second use 100m3Gravity settling basin (ensures that 12 is small
When settle)+40m2Filter press+5m2Ceramic capillary filter combined treatment process and equipment.
2nd, the industrial waste acid using the scheme two in above-mentioned technique after preliminary clearning is processed, carries out industrial waste acid middle reaches
From acid and the adsorbing separation of slaine, detailed is described as follows：
The equipment of selection is respectively 3m for disposal ability3/hr、5m3/hr、8m3The complexes of/hr, wherein the acid for configuring
Cartridge filter (F1 and F2) with water chooses 5 microns of filter core aperture；The diameter (D) and height of sour adsorbing separation resin column R
(H) ratio D/H is 0.6~(1.3：1)；Desorption water is production water；The volume ratio of production water and spent acid is (1~1.3)：1；
The desalination spent acid and brine waste excluded using engineering plastic pump continuous feed 8 hours, collection system, using chemical analysis method
Two kinds of production fluid compositions are analyzed, data are as follows：
From the above results, the industrial waste acid of several typical compositions industrial scale complete set of equipments treatment under, work
, 83~85%, the clearance of slaine is 82~85% for acid recovering rate of dissociating in industry spent acid
3rd, using in above-mentioned steps two by the industrial waste acid after a free acid and metallic salt separating treatment, according to
Mode and same complete set of equipments described in embodiment 2 are processed once again, and ibid, data are as follows for analysis method：
From the above results, using identical industry and equipment, the industrial waste acid to by a hypo acid, salt separate is carried out
Separate again, in second separation process, under the rate of recovery of free acid and the clearance of metallic salt slightly have in industrial waste acid
Drop：, 80~83%, the clearance of metallic salt is 79~83% for free acid recovering rate in separating postindustrial spent acid for the second time；And
After separating twice, the accumulative rate of recovery of free acid is in 65~73%, and the accumulative clearance of metallic salt in industrial waste acid
96~99% have been reached, and the desalination spent acid and Low acid produced in such processing procedure of series connection once or twice
Brine waste can be to carry out direct recycling.
Claims (10)
1. free acid and metallic salt separator in industrial waste acid, including sour batch box (T3), brine waste storage tank (T6), water
Batch box (T4) and desalination spent acid storage tank (T5), it is characterised in that：Including sour adsorbing separation resin column (R), the sour batch box
(T3) connect with sour adsorbing separation resin column (R) one end, the water batch box (T4) and acid adsorbing separation resin column (R) other end
Connection；
Wherein, the acid solution in sour batch box (T3) after sour adsorbing separation resin column (R) first via being flowed into brine waste storage tank
(T6), then, the production water or pure water in the water batch box (T4) after sour adsorbing separation resin column (R) via being flowed into desalination
In spent acid storage tank (T5).
2. free acid and metallic salt separator in industrial waste acid as claimed in claim 1, it is characterised in that：Including production
Water/pure water storage tank (T1), the production water/pure water storage tank (T1) is connected with water batch box (T4).
3. free acid and metallic salt separator in industrial waste acid as claimed in claim 1, it is characterised in that：Including pre- net
Chemical combination lattice raw material acid storage tank (T2), the preliminary clearning acceptable material acid storage tank (T2) connects with sour batch box (T3).
4. free acid and metallic salt separator in the industrial waste acid as described in claim 1,2 or 3, it is characterised in that：Institute
State sour adsorbing separation resin column (R) by resin column (R1), the resin (R5) being arranged in resin column (R1), be arranged at resin
The water distributing plate (R3) of cylinder (R1) upper and lower ends, the water cap (R4) being arranged between water distributing plate (R3) and resin column (R1) and
The end cap (R2) being arranged on the water distributing plate (R3) is constituted.
5. free acid and metallic salt separator in industrial waste acid as claimed in claim 4, it is characterised in that：The resin
The making material of cylinder (R1), end cap (R2) and water distributing plate (R3) is polypropylene or polyvinyl chloride or fiberglass or carbon steel lining poly- third
Alkene or carbon steel lining PO or carbon steel lining acid-resisting rubber or carbon steel lining F4.
6. free acid and metallic salt separator in industrial waste acid as claimed in claim 4, it is characterised in that：The water cap
(R4) making material is polypropylene or polyvinyl chloride or ABS.
7. free acid and metallic salt separator in the industrial waste acid as described in claim 1,2 or 3, it is characterised in that：Bag
Include for realizing the PLC control devices that automatically control, the flow direction of the acid solution and production water or pure water is entered by PLC control devices
Row control.
8. free acid and metallic salt separator in industrial waste acid as claimed in claim 3, it is characterised in that：Including original
Sour preliminary clearning system (2), the original sour preliminary clearning system (2) connects with preliminary clearning acceptable material acid storage tank (T2).
9. free acid and metallic salt separator in industrial waste acid as claimed in claim 8, it is characterised in that：Original acid is pre-
The equipment of cleaning system (2) is precipitation apparatus, filter press, tubular filter, ceramic capillary filter or cartridge filter.
10. free acid and metallic salt separator in the industrial waste acid as described in claim 1,2 or 3, it is characterised in that：Institute
It is acid retardance resinoid to state the material of the resin (R5) set in sour adsorbing separation resin column (R).
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| CN201611186764.XA CN106745886A (en) | 2016-12-20 | 2016-12-20 | Free acid and metallic salt separator in industrial waste acid |
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| CN109305656A (en) * | 2018-09-29 | 2019-02-05 | 济宁亿佳环保科技有限公司 | A kind of processing equipment of industrial sulphuric acid potassium by-product hydrochloric acid |
| CN109336289A (en) * | 2018-11-14 | 2019-02-15 | 浙江中达特钢股份有限公司 | A kind of recovery and treatment method of acid pickle |
| CN110776060A (en) * | 2019-12-02 | 2020-02-11 | 湖州优蓝新材料有限公司 | A modular waste acid purifier |
| CN113149248A (en) * | 2021-01-19 | 2021-07-23 | 中基(海南)科技有限公司 | Green electroplating wastewater recycling treatment process |
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| CN113149248A (en) * | 2021-01-19 | 2021-07-23 | 中基(海南)科技有限公司 | Green electroplating wastewater recycling treatment process |
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