CN106745887A - Industrial waste acid removal of impurities recovery process - Google Patents
Industrial waste acid removal of impurities recovery process Download PDFInfo
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- CN106745887A CN106745887A CN201611187103.9A CN201611187103A CN106745887A CN 106745887 A CN106745887 A CN 106745887A CN 201611187103 A CN201611187103 A CN 201611187103A CN 106745887 A CN106745887 A CN 106745887A
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- 239000002253 acid Substances 0.000 title claims abstract description 151
- 239000002440 industrial waste Substances 0.000 title claims abstract description 79
- 239000012535 impurity Substances 0.000 title claims abstract description 47
- 238000011084 recovery Methods 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 57
- 239000011347 resin Substances 0.000 claims abstract description 40
- 229920005989 resin Polymers 0.000 claims abstract description 40
- 150000003839 salts Chemical class 0.000 claims abstract description 33
- 239000007787 solid Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000010521 absorption reaction Methods 0.000 claims abstract description 16
- 238000003795 desorption Methods 0.000 claims abstract description 14
- 238000000746 purification Methods 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000002351 wastewater Substances 0.000 claims abstract description 8
- 238000004587 chromatography analysis Methods 0.000 claims abstract description 6
- 239000002699 waste material Substances 0.000 claims description 55
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 52
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 42
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 22
- 239000000919 ceramic Substances 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 238000006396 nitration reaction Methods 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- 235000010215 titanium dioxide Nutrition 0.000 claims description 9
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 229910000831 Steel Inorganic materials 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 6
- 239000003957 anion exchange resin Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000010959 steel Substances 0.000 claims description 6
- 239000005030 aluminium foil Substances 0.000 claims description 5
- 238000005868 electrolysis reaction Methods 0.000 claims description 5
- 238000009854 hydrometallurgy Methods 0.000 claims description 5
- 238000007747 plating Methods 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 235000014676 Phragmites communis Nutrition 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 238000005341 cation exchange Methods 0.000 claims description 4
- 239000000084 colloidal system Substances 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 235000010269 sulphur dioxide Nutrition 0.000 claims description 4
- 239000004291 sulphur dioxide Substances 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 235000003140 Panax quinquefolius Nutrition 0.000 claims description 3
- 240000005373 Panax quinquefolius Species 0.000 claims description 3
- 230000002745 absorbent Effects 0.000 claims description 3
- 239000002250 absorbent Substances 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims 1
- 238000001556 precipitation Methods 0.000 description 9
- 238000000926 separation method Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 229920006351 engineering plastic Polymers 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 239000012267 brine Substances 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000000502 dialysis Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 235000021110 pickles Nutrition 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 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
- 239000011888 foil Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000001038 titanium pigment Substances 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
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 Electricity Or Magnetism (AREA)
Abstract
The invention belongs to chemical separating field, and in particular to a kind of industrial waste acid removal of impurities recovery process.The inventive method is comprised the following steps：A, preliminary clearning：Remove the solid impurity in industrial waste acid；B, absorption：The industrial waste acid for removing solid impurity is adsorbed by resin chromatography post, efflux is high-salt wastewater；C, desorption：Desorbed with the above-mentioned resin chromatography post of water wash again, efflux is less salt purification spent acid.The inventive method can effectively remove contained metallic salt impurity in industrial waste acid, so as to finally realize purifying industrial waste acid and utilize.
Description
Technical field
The invention belongs to chemical separating field, and in particular to a kind of industrial waste acid removal of impurities recovery process.
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 addition alkaline matter is carried out into acid
Alkali is neutralized, liquid PH 6~9 after regulation neutralization, and air can be passed through if necessary carries out forced aeration, improves the cohesion of neutralization precipitation thing
Speed and structure, neutralizing disposed slurry carries out separation of solid and liquid, and filter residue slag input is stacked, discharge after filtrate is up to standard.2) waste acid concentration method：
Using traditional heating evaporation technique, acid pickle is concentrated, it is substantial amounts of in spent acid with the raising of acid-spending strength and temperature
The reduction of solubility of the metallic salt in acid can crystallize precipitation, be concentrated into after finite concentration by necessary separation of solid and liquid, remove
Decrystallize the metallic salt of precipitation, obtains certain density gelled acid, and metallic salt major part is removed in acid, and the gelled acid can
Return to factory and fresh acid collocation is used.3) three kinds of 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, easy aging breakage, the excessively low reason of cost performance, and limiting its industrial production makes
With.
The content of the invention
The defect of industrial waste acid is processed for prior art, work is reclaimed the invention provides a kind of new industrial waste acid removal of impurities
Skill, wherein, described industrial waste acid includes：The Waste Sulfuric Acid of sulfate process titanium dioxide Industrial Output, waste electrolyte；Hydrometallurgy electrolysis row
The Waste Sulfuric Acid of industry output, waste electrolyte；The waste hydrochloric acid of titanium tetrachloride, titanium white chloride, titanium sponge and chlor-alkali industry；Stainless steel, steel
Waste Sulfuric Acid, Waste Sulfuric Acid/hydrochloric acid nitration mixture, the waste hydrochloric acid/waste nitric acid nitration mixture of iron, the plating of aluminium foil industry or pickling link output；Phosphatization
The waste phosphoric acid of work Industrial Output.Further, the industrial waste acid is at least in sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid or phosphoric acid
Kind.5~400 g/l of free acid content in the industrial waste acid, 1~120 g/l of metal salt concentration (in terms of metal simple-substance).
The technical problems to be solved by the invention are to provide a kind of industrial waste acid removal of impurities recovery process.The method includes following
Step：
A, preliminary clearning：Remove the solid impurity in industrial waste acid；
B, absorption：The industrial waste acid for removing solid impurity is adsorbed by resin chromatography post, efflux is high salt
Waste water；
C, desorption：Desorbed with the above-mentioned resin chromatography post of water wash again, efflux is less salt purification spent acid.
Specifically, in above method step a, described industrial waste acid includes：The Waste Sulfuric Acid of sulfate process titanium dioxide Industrial Output,
Waste electrolyte；Waste Sulfuric Acid, the waste electrolyte of hydrometallurgy electrolysis industry output；Titanium tetrachloride, titanium white chloride, titanium sponge and chlor-alkali
The waste hydrochloric acid of industry；Stainless steel, steel, the plating of aluminium foil industry or the Waste Sulfuric Acid of pickling link output, Waste Sulfuric Acid/hydrochloric acid nitration mixture,
Waste hydrochloric acid/waste nitric acid nitration mixture；The waste phosphoric acid of sulphur dioxide of phosphor chemical industry output.
Further, in above method step a, described industrial waste acid is sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid or phosphoric acid
In at least one；Wherein free acid content is 5~400 g/l, 1~120 g/l of metal salt concentration.
Preferably, in above method step a, glue contained by the industrial waste acid after the solid impurity removed in industrial waste acid
Body impurity, solid suspension are not more than 0.3g/L, and colloidal impurity, solid suspension particle diameter are not more than 100 microns.
Specifically, in above method step a, the solid impurity removed in industrial waste acid includes by the way of：It is heavy
Drop equipment, filter press, tubular filter, ceramic capillary filter or cartridge filter.
Preferably, in above method step a, the precipitation apparatus, filter press, tubular filter, ceramic capillary filter
Or cartridge filter is used alone or two or more superpositions are used.
Further, in above method step a, the mode that uses of solid impurity removed in industrial waste acid for：It is heavy
Drop groove, filter press, the superposition of ceramic capillary filter are used.
Further, in above method step a, using subsider sedimentation up to more than 10 hours, then added with being coated with 758
The filter press press filtration of close type filter cloth, is finally filtered with the tubular ceramic membrane of 30 micron pore sizes.
Preferably, in above method step b, the resin be the strong basic type anion-exchange resin with quarternary amine functional group,
At least one in strongly acidic cation-exchange.
Further, in above method step b, the strong basic type anion-exchange resin of described band quarternary amine functional group is Du
Sheng, a reed pipe wind instrumentA-32, described strongly acidic cation-exchange is D101 macroporous absorbent resins.
Preferably, in above method step b, resin loading and the volume ratio of single treatment industrial waste acid of chromatographic column are
1 ︰ 0.1~1.
Preferably, in above method step b, the diameter and height ratio of the chromatographic column are 0.15~5 ︰ 1.
Further, in above method step b, the column diameter is 100~3000mm, highly for 300~
25000mm。
Preferably, in above method step b, c, the trend of industrial waste acid is bottom in and top out during the absorption, water during desorption
Trend be upper entering and lower leaving；The flow velocity of absorption and desorption is 0.002~0.02 meter per second.
Preferably, in above method step b, c, each secondary control is by the industrial waste acid of chromatographic column and the volume ratio of water
It is 1 ︰ 0.5~2.
Preferably, in above method step b, the chromatographic column to the treating capacity of industrial waste acid for 0.1~30 cubic metre/
hr。
Preferably, in the above method, according to the demand that spent acid is purified to less salt, step b, c is repeated, number of repetition is
More than once.
The inventive method is high to industrial waste acid separative efficiency, separated and recovered by resin can make acid recovering rate for 60~
90%th, the clearance of slaine is 60~90%, and being separated and recovered by resin twice can make acid recovering rate be 60~80%, metal
The clearance of salt be 88~99%, gained acid in metallic salt impurity largely removed so that gained acid can in large quantities directly again
Utilize；The high-salt wastewater that removal of impurities link is produced simultaneously, comprising substantial amounts of metallic salt, its acid content is relatively low, is sunk using conventional
The recovery metallic salt of low cost by the method for shallow lake, so as to prevent and reduce the secondary pollution that industrial waste acid administers link.
Specific embodiment
For the method for active ingredient in existing recovery industrial waste acid, the present invention is directed to following industrial waste acid：Sulfuric acid process titanium
Waste Sulfuric Acid, the waste electrolyte of white Industrial Output；Waste Sulfuric Acid, the waste electrolyte of hydrometallurgy electrolysis industry output；Titanium tetrachloride, chlorine
Change the waste hydrochloric acid of titanium white, titanium sponge and chlor-alkali industry；The sulfur waste of stainless steel, steel, the plating of aluminium foil industry or pickling link output
Acid, Waste Sulfuric Acid/hydrochloric acid nitration mixture, waste hydrochloric acid/waste nitric acid nitration mixture；The waste phosphoric acid of sulphur dioxide of phosphor chemical industry output proposes a kind of technique spent acid
Removal of impurities recovery process.
Described industrial waste acid is at least one in sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid or phosphoric acid；Wherein free acid contains
It is 5~400 g/l to measure, 1~120 g/l of metal salt concentration.
Industrial waste acid removal of impurities recovery process, comprises the following steps：
A, preliminary clearning：Separation of solid and liquid removing colloidal impurity therein, solid are carried out to industrial waste acid using conventional method to hang
The solid matters such as float, make contained colloidal impurity, solid suspension no more than 0.3g/L in the liquid after separation of solid and liquid, and colloid
Impurity, solid suspension particle diameter are not more than 100 microns；
B, Adsorption and desorption：The qualified industrial waste acid of preliminary clearning, by being filled with the resin column (bed) of specific resin, spent acid
In metallic salt follow spent acid to be excluded from resin column (bed), into brine waste storage tank, the part is sour less, metalline
More high-salt wastewater；Add water the free acid drip washing of resin adsorption is got off, the part be containing sour more, metalline compared with
Few less salt purification spent acid.
In above method step a, the method for removing solid impurity in industrial waste acid is varied, can routinely use sedimentation
At least one in equipment, filter press, tubular filter, ceramic capillary filter, cartridge filter etc. carries out solid-liquid isolation method.
As conventional selection be precipitation apparatus+filter press, precipitation apparatus+filter press+tubular filter/ceramic capillary filter, sedimentation set
The various ways such as standby+tubular filter/ceramic capillary filter, filter press+tubular filter/ceramic capillary filter, pass through
Filter cloth material, aperture and area and tubular filter/ceramics to precipitation apparatus height, area, feed flow rate and filter press
Millipore filter/filter core of security filter aperture and the reasonable selection of area, it is postindustrial useless to reach and meet preliminary clearning treatment
Acid meets contained colloidal impurity, solid suspension and is not more than 0.3g/L, and colloidal impurity, solid suspension particle diameter are not more than 100
The quality requirement of micron.Further, above-mentioned solid-liquid separation process and equipment two or more series connection treatment, preferably precipitation apparatus
+ filter press+ceramic capillary filter.Preferably, solid impurity mode is in removing industrial waste acid：Precipitation apparatus sedimentation is small up to 10
When more than, the filter press press filtration that is coated with 758 ciphering type filter clothes, the tubular ceramic membrane filtering of 30 micron pore sizes.
In above method step b, the resin is the strong basic type anion-exchange resin with quarternary amine functional group, strong-acid type sun
At least one in ion exchange resin.Further, the strong basic type anion-exchange resin of described band quarternary amine functional group is
Du's sheng, a reed pipe wind instrumentA-32, described strongly acidic cation-exchange is D101 macroporous absorbent resins.
It will be understood by those skilled in the art that：As adsorption treatment, the acid of gained waste water are carried out after resin adsorption saturation again
Content is high and acid can not be reclaimed fully, so, when resin adsorption reaches saturation, drip washing need to be carried out to resin with water, drench
Wash gained and be restored acid；Then the resin after the cleaning is recycled to be adsorbed again or inhaled using new resin
It is attached, the suction that those skilled in the art can carry out next time according to actual conditions selection using the resin after new resin or drip washing
It is attached.In order to ensure the abundant absorption of acid, the waste water after absorption also can again be carried out second adsorption and desorption ensures that acid recovery is more thorough
Bottom.So, in order to ensure to be no more than the absorption maximum saturation value of resin, it is necessary to control the ratio of resin and industrial waste acid, control
The resin loading of chromatographic column is 1 ︰ 0.1~1 with the volume ratio of single treatment industrial waste acid.Further, in order to ensure absorption
Quality, it is that diameter and height ratio are 0.15~5 ︰ 1 with height relationships also to need to control the diameter of chromatographic column.Preferably, the color
Spectrum column diameter is 100~3000mm, is highly 300~25000mm.
In order to ensure fully absorption, the trend of industrial waste acid is bottom in and top out during the absorption, and flow velocity is 0.002~0.02
Meter per second.
In order to ensure fully desorption, it is 1 ︰ 0.5~2 to control by the industrial waste acid of chromatographic column and the volume ratio of water.Institute
The trend of water is upper entering and lower leaving when stating desorption, and flow velocity is 0.002~0.02 meter per second.
During by the once absorption of the inventive method and desorption, gained acid recovering rate is the removal of 60~90%, slaine
Rate is 60~90%.
Further, according to the different demands to industrial waste acid purification and impurity removal degree, removal slaine as much as possible can
Carry out multiple resin separating step.Often it is repeated once, spent acid is obtained further on the basis of previous purification and impurity removal
Purification；Adsorption-desorption will realize the purification and impurity removal rate 30~90% of industrial waste acid each time, and can use a set of resin
Column system repeats, it would however also be possible to employ a few set resin column Cascade Systems are realized.By the inventive method, resin is separated back twice
Receipts can make the clearance that acid recovering rate is 60~80%, slaine be 88~99%.
Further, chromatographic column can singly cover operation during absorption, can also cover series operation more.Two sets or many sets are used in series
When, per one-level spent acid charging can both be directly connected to previous stage spent acid discharging, can also connect previous stage spent acid discharging in
Between groove；And the production water/pure water feed per one-level can be used alone production water/pure water, it is possible to use containing after rear stage treatment
Salt waste water；Controlling different production water/pure water consumption and different brine waste quantum of output (namely each grade resins post suctions
Echo desorption operations, the different volumes ratio of control absorption spent acid/solution water suction) on the basis of, reach what spent acid depth acid/salt was separate
Treatment effect.
The less salt for obtaining purification spent acid is reclaimed by the inventive method can be used directly, can also add into new corresponding acid
Reused after adjustment less salt purification acid-spending strength, may also pass through after necessary concentration improves concentration and reuse.
With reference to embodiment, the present invention is further described, and industrial waste acid is with sulfuric acid method titanium pigment hydrolysis Waste Sulfuric Acid, no
Nitric acid+hydrofluoric acid the nitration mixture of steel industry, electric aluminum foil industry waste hydrochloric acid/waste phosphoric acid become rusty for typical case shows row, but therefore will
The protection domain of invention is limited among scope of embodiments.
Embodiment 1
The following is the more typical industrial waste acid analyze data of different industries, it can be seen that be mingled with original industrial waste acid
The substantial amounts of colloid for exceeding 100 microns, solid suspension impurity, are shown in Table 1.
Table 1
Firstly the need of carry out be industrial waste acid pretreatment (preliminary clearning), using solid-liquid separation process and equipment, this reality
Apply example to be compared using four sets of plan, be 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, as a result such as table 2 below：
Table 2
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 ibid, as a result such as table 3 below：
Table 3
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 ibid, as a result such as table 4 below：
Table 4
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 ibid, as a result such as table 5 below：
Table 5
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 substantially, makes treatment qualified
Colloid, solid suspension residual quantity are by no more than 0.3 g/l, the colloidal impurity of residual, solid suspension particle diameter in industrial waste acid
No more than 100 microns of index.Four kinds of schemes are preferably scheme two -- subsider, filter press, the superposition of ceramic capillary filter
Use, 100m3Gravity settling basin (ensuring to settle for 12 hours)+40m2Filter press+5m2Ceramic capillary filter combined treatment process
And equipment.
Embodiment 2
Using industrial waste acid of the scheme two in embodiment 1 after preliminary clearning is processed, industry is carried out according to present invention process
The adsorbing separation of free acid and slaine in spent acid, detailed is described as follows：
The equipment of selection is respectively 3m for disposal ability3/h、5m3/h、8m3/ h (treating capacity 3m3The corresponding resin fills of/h
It is 0.8m to measure3, treating capacity 5m3The corresponding resin fill amounts of/h are 1.2m3, treating capacity 8m3The corresponding resin fill amounts of/h are
1.5m3) complexes, wherein the acid for configuring and the cartridge filter of water choose 5 microns of filter core aperture；Using Du's sheng, a reed pipe wind instrumentA-32；The D/H of nucleus equipment resin column (bed) is 1 ︰ 1；Desorption water is production water；Production water and the ratio of spent acid are
1 ︰ 1；The desalination purification spent acid and brine waste excluded using engineering plastic pump continuous feed 8 hours, collection system, using chemistry
Analysis method is analyzed to two kinds of production fluid compositions, data such as table 6 below, 7：
Table 6
Table 7
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.
Embodiment 3
Using in embodiment 2 by the industrial waste acid after a free acid and metallic salt separating treatment, according to embodiment 2
Described in mode and same complete set of equipments process again once, analysis method ibid, data such as table 8 below, 9：
Table 8
Table 9
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, after separating twice, the accumulative rate of recovery of free acid is 65~73% in industrial waste acid, and metallic salt is tired
Meter clearance has reached 96~99%, and the desalination spent acid produced in such processing procedure of series connection once or twice
Can be to carry out direct recycling with the brine waste of Low acid, its purposes is not specifically noted herein.
General principle of the invention and principal character and advantage has been shown and described above.The technical staff of the industry should
Understand, the present invention is not limited to the above embodiments.Simply original of the invention is illustrated described in above-described embodiment and specification
The substantially parameter area of reason and equipment, without departing from the spirit and scope of the present invention, the present invention also has various change
And improvement, these changes and improvements are each fallen within scope of the claimed invention.The claimed scope of the invention is by appended
Claims and its equivalent thereof.
Claims (10)
1. industrial waste acid removal of impurities recovery process, it is characterised in that：Comprise the following steps：
A, preliminary clearning：Remove the solid impurity in industrial waste acid；
B, absorption：The industrial waste acid for removing solid impurity is adsorbed by resin chromatography post, efflux is high-salt wastewater；
C, desorption：Desorbed with the above-mentioned resin chromatography post of water wash again, efflux is less salt purification spent acid.
2. industrial waste acid removal of impurities recovery process according to claim 1, it is characterised in that：In step a, described Industry Waste
Acid includes：The Waste Sulfuric Acid of sulfate process titanium dioxide Industrial Output, waste electrolyte；The Waste Sulfuric Acid of hydrometallurgy electrolysis industry 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 or acid
Wash Waste Sulfuric Acid, Waste Sulfuric Acid/hydrochloric acid nitration mixture, the waste hydrochloric acid/waste nitric acid nitration mixture of link output；The waste phosphoric acid of sulphur dioxide of phosphor chemical industry output；
Further, described industrial waste acid is at least one in sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid or phosphoric acid；Wherein free acid contains
It is 5~400 g/l to measure, 1~120 g/l of metal salt concentration.
3. industrial waste acid removal of impurities recovery process according to claim 1 and 2, it is characterised in that：In step a, the removing
Colloidal impurity, solid suspension are not more than 0.3g/L contained by the industrial waste acid after solid impurity in industrial waste acid, and colloid is miscellaneous
Matter, solid suspension particle diameter are not more than 100 microns.
4. industrial waste acid removal of impurities recovery process according to claim 1, it is characterised in that：It is described to remove industry in step a
The mode that solid impurity in spent acid is used for：Subsider, filter press, the superposition of ceramic capillary filter are used；Further, adopt
Settled up to more than 10 hours with subsider, then with the filter press press filtration of 758 ciphering type filter clothes is coated with, finally use 30 micron pore sizes
Tubular ceramic membrane filtering.
5. industrial waste acid removal of impurities recovery process according to claim 1, it is characterised in that：In step a, the resin is band
At least one in strong basic type anion-exchange resin, the strongly acidic cation-exchange of quarternary amine functional group；Further, institute
The strong basic type anion-exchange resin of the band quarternary amine functional group for stating is Du's sheng, a reed pipe wind instrumentA-32, described strong-acid type cation is handed over
Resin is changed for D101 macroporous absorbent resins.
6. industrial waste acid removal of impurities recovery process according to claim 1, it is characterised in that：In step b, the resin of chromatographic column
Loading is 1 ︰ 0.1~1 with the volume ratio of single treatment industrial waste acid.
7. industrial waste acid removal of impurities recovery process according to claim 1, it is characterised in that：In step b, the chromatographic column
Diameter and height ratio are 0.15~5 ︰ 1；Further, the column diameter is 100~3000mm, highly for 300~
25000mm。
8. industrial waste acid removal of impurities recovery process according to claim 1, it is characterised in that：In step b, c, during the absorption
The trend of industrial waste acid is bottom in and top out, and the trend of water is upper entering and lower leaving during desorption；The flow velocity of absorption and desorption is 0.002~
0.02 meter per second.
9. industrial waste acid removal of impurities recovery process according to claim 1, it is characterised in that：In step b, c, each secondary control
It is 1 ︰ 0.5~2 by the industrial waste acid of chromatographic column and the volume ratio of water.
10. industrial waste acid removal of impurities recovery process according to claim 1, it is characterised in that：Spent acid is purified according to less salt
Demand, repeat step b, c, number of repetition is for more than once.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107311856A (en) * | 2017-08-13 | 2017-11-03 | 河南省煤气(集团)有限责任公司义马气化厂 | A kind of purification recovery system of acetic acid waste liquid |
| CN107311345A (en) * | 2017-07-28 | 2017-11-03 | 科海思（北京）科技有限公司 | A kind of waste acidity recovery method and apparatus |
| CN109553070A (en) * | 2018-12-17 | 2019-04-02 | 江苏诺斯特拉环保科技有限公司 | Waste hydrochloric acid recycles method of disposal |
| CN109824193A (en) * | 2019-02-01 | 2019-05-31 | 宁波市达济环境工程有限公司 | Alumina chemical industry Waste acid recovery technology |
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| CN116621136A (en) * | 2023-07-25 | 2023-08-22 | 杭州永洁达净化科技有限公司 | Phosphoric acid recovery process and system for phosphorus-containing polishing waste acid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999066084A1 (en) * | 1998-06-19 | 1999-12-23 | The Procter & Gamble Company | Process for separation of heavy metals from residues by use of ethylene-diamine-disuccinic acid (edds) complexant |
| CN101966400A (en) * | 2010-08-24 | 2011-02-09 | 上海西恩化工设备有限公司 | Method for separating inorganic acid and inorganic acid salt in waste acid |
| CN101992133A (en) * | 2009-08-24 | 2011-03-30 | 李冶强 | Method for processing and recycling waste acid |
| CN102839380A (en) * | 2011-06-23 | 2012-12-26 | 张家港凯纳信息技术有限公司 | Stainless steel cold rolling waste acid purification system |
-
2016
- 2016-12-20 CN CN201611187103.9A patent/CN106745887A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999066084A1 (en) * | 1998-06-19 | 1999-12-23 | The Procter & Gamble Company | Process for separation of heavy metals from residues by use of ethylene-diamine-disuccinic acid (edds) complexant |
| AU5082199A (en) * | 1998-06-19 | 2000-01-05 | Procter & Gamble Company, The | Process for separation of heavy metals from residues by use of ethylene-diamine-disuccinic acid (edds) complexant |
| CN101992133A (en) * | 2009-08-24 | 2011-03-30 | 李冶强 | Method for processing and recycling waste acid |
| CN101966400A (en) * | 2010-08-24 | 2011-02-09 | 上海西恩化工设备有限公司 | Method for separating inorganic acid and inorganic acid salt in waste acid |
| CN102839380A (en) * | 2011-06-23 | 2012-12-26 | 张家港凯纳信息技术有限公司 | Stainless steel cold rolling waste acid purification system |
Non-Patent Citations (1)
| Title |
|---|
| 张兆杰等: "《锅炉水处理技术》", 31 July 2003, 黄河水利出版社 * |
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| CN109553070A (en) * | 2018-12-17 | 2019-04-02 | 江苏诺斯特拉环保科技有限公司 | Waste hydrochloric acid recycles method of disposal |
| CN109824193A (en) * | 2019-02-01 | 2019-05-31 | 宁波市达济环境工程有限公司 | Alumina chemical industry Waste acid recovery technology |
| CN110040696A (en) * | 2019-04-29 | 2019-07-23 | 成都先进金属材料产业技术研究院有限公司 | Utilize the method for manganese chloride processing titanium dioxide waste acid by sulfuric acid process |
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