CN109626429A - A kind of comprehensive treatment utilization method of the spent acid containing chromium - Google Patents
A kind of comprehensive treatment utilization method of the spent acid containing chromium Download PDFInfo
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- CN109626429A CN109626429A CN201811497720.8A CN201811497720A CN109626429A CN 109626429 A CN109626429 A CN 109626429A CN 201811497720 A CN201811497720 A CN 201811497720A CN 109626429 A CN109626429 A CN 109626429A
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- acid
- chromium
- comprehensive treatment
- value
- utilization method
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- 239000002253 acid Substances 0.000 title claims abstract description 113
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 62
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 61
- 239000011651 chromium Substances 0.000 title claims abstract description 61
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000000706 filtrate Substances 0.000 claims abstract description 48
- 229910052742 iron Inorganic materials 0.000 claims abstract description 47
- -1 iron ion Chemical class 0.000 claims abstract description 39
- 238000001556 precipitation Methods 0.000 claims abstract description 33
- 239000013078 crystal Substances 0.000 claims abstract description 27
- 238000001704 evaporation Methods 0.000 claims abstract description 24
- 230000008020 evaporation Effects 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 20
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 17
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 16
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 15
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims abstract description 14
- 238000012423 maintenance Methods 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 48
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 48
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 16
- 235000006408 oxalic acid Nutrition 0.000 claims description 15
- 230000001376 precipitating effect Effects 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- RMXTYBQNQCQHEU-UHFFFAOYSA-N ac1lawpn Chemical compound [Cr]#[Cr] RMXTYBQNQCQHEU-UHFFFAOYSA-N 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 19
- 239000002699 waste material Substances 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 11
- 238000012545 processing Methods 0.000 abstract description 9
- 238000003672 processing method Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 20
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 18
- 239000012065 filter cake Substances 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 11
- 229910020284 Na2SO4.10H2O Inorganic materials 0.000 description 9
- 235000011121 sodium hydroxide Nutrition 0.000 description 9
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 229910001430 chromium ion Inorganic materials 0.000 description 2
- 238000005097 cold rolling Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 210000002500 microbody Anatomy 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G37/00—Compounds of chromium
- C01G37/08—Chromium sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B15/00—Other processes for the manufacture of iron from iron compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Metallurgy (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Removal Of Specific Substances (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a kind of comprehensive treatment utilization methods of spent acid containing chromium.Contain sulfate radical and iron ion in the spent acid of this method processing, chromium spent acid pH value will be contained by, which including the following steps:, is adjusted to 1 ~ 3, and precipitation reaction, isolated ferrous precipitation and filtrate occur for acid adding and iron ion, and maintenance system pH value is 1 ~ 3 in sour adition process；By the cooling precipitated crystal of separating filtrate, sodium sulfate crystal and secondary filtrate is obtained by filtration；It is concentrated by evaporation secondary filtrate to obtain chromium sulfate.Processing method of the invention realizes the classification Resource recovery of acid, iron and chromium by gradually classification processing, avoid precipitated in existing processing method generation and resource that the secondary dangerous waste of bring is just burned after chromium recovery value it is not high the problems such as, the synthesis high value for realizing the spent acid containing chromium recycles, wherein the rate of recovery of iron is up to 95.0%, the rate of recovery of acid is up to 80.0%, the rate of recovery of chromium can be widely applied in the recovery processing of the spent acid containing chromium up to 90.5%.
Description
Technical field
The present invention relates to cold rolling or electroplating technology, the integrated treatment more particularly, to a kind of spent acid containing chromium is utilized
Method.
Background technique
In cold rolling industry and other pickling industries, there is a large amount of stainless steel to need pickling processes, contain difference in steel
The chromium of content enters in pickle liquor through pickling, if to comprehensively utilize these spent acid, it is necessary to chromium therein is separated,
Otherwise subsequent use will be seriously affected.The minimizing technology of chromium, which mainly uses, in existing spent acid adds alkali (caustic soda or stone
Ash) neutralize, by iron and chromium precipitating after filters pressing, dangerous waste filter cake burn, the disadvantages of this method are as follows: neutralize disposition need large quantities of lime and
The sediment of caustic soda, formation is more, and filter cake remarketing is costly, while effective ingredient is not utilized very well.It is another
The removing method of chromium is exactly direct progress incineration disposal in kind spent acid, directly burns the waste that will cause vast resources and the energy,
Processing cost is too high, is unfavorable for actual dangerous waste processing, be easy to cause secondary secondary dangerous waste.It is also disclosed correlation in the prior art
The method of Precipitation discloses in prior art CN106865729A and a kind of utilizes molten iron pretreatment desulfurizing Slag treatment weight containing chromium
The method of metallic wastewater first selects the magnetic material in desulfurization slag using magnetic separation in this method, using magnetic material by hexavalent chrome reduction
At trivalent chromium, iron tailings etc. is recycled to remove the trivalent chromium chemical precipitation of reduction treatment, the operation of this method is comparatively laborious, no
Adapt to actual production processing.
Therefore, the comprehensive treatment utilization method of a kind of spent acid containing chromium provided by the invention, will using the method for clean and environmental protection
Effective component therein recycles to form corresponding by-product, promotes comprehensive utilization value, and no secondary dangerous waste of correlation generates.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the defects and deficiency of chromium minimizing technology in existing spent acid, provide one kind
The comprehensive treatment utilization method of the spent acid containing chromium, this method are heavy by adjusting spent acid system pH and pH value of reaction system constant control
Form sediment separation chromium ion, and reprecipitation crystallizes to obtain sodium sulphate product, and then filters concentrated acid and obtain chromium sulfate, entire integrated conduct method
Easy to operate, no secondary dangerous waste generates, and realizes the high value comprehensive utilization of dangerous waste.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
A kind of comprehensive treatment utilization method of the spent acid containing chromium contains sulfate radical and iron ion in the spent acid, includes the following steps:
S1. it will contain chromium spent acid pH value and be adjusted to 1 ~ 3, precipitation reaction, isolated ferrous precipitation and filter occur for acid adding and iron ion
Liquid, maintenance system pH value is 1 ~ 3 during acid adding；
S2. by the cooling precipitated crystal of above-mentioned separating filtrate, filtering dries in the shade to obtain sodium sulfate crystal and secondary filtrate；
S3. it is concentrated by evaporation above-mentioned secondary filtrate to obtain chromium sulfate.
Comprehensive reutilization method of the invention changes burning disposal or direct burning disposal after original Direct precipitation
Processing method sediment is formed by chelated acid and iron to efficiently separate out iron ion by the way that sequestering power strong acid is added,
Acid, ferrous iron and chromium ion in spent acid are comprehensively utilized, reduces the waste of resource, reduces disposal costs, is improved
Economic value.
Chromium spent acid pH value will wherein be contained before acid adding be adjusted to 1 ~ 3 can accelerate iron ion and acid chelating production precipitating, make
It obtains entirely to react and be carried out to positive reaction direction, improve the utilization rate of iron.System pH is control in the reaction of entire precipitation of iron ions
Precipitation reaction equalization point processed realizes the key factor of iron efficiently separated, and maintenance system pH value is 1 ~ 3 in entire reaction system
It is the Direction of Reaction to maintain iron precipitation reaction, accelerates positive reaction, improve the utilization rate of iron.
The cooling precipitated crystal generation sodium sulphate of separating filtrate, preferably 30 DEG C -35 DEG C of cooling temperature.
Above-mentioned filtering dries in the shade to obtain sodium sulfate crystal to be sulfate crystal object Na2SO4。
It can reach 90% using the separation recovery efficiencies of the above-mentioned iron of preparation method of the invention, sour separation recovery efficiencies can
Reach 80%, the separation recovery efficiencies of chromium are up to 90%.
Preferably, pH value described in S1 is adjusted to 1 ~ 2, and system pH maintains 1 ~ 3.Such as pH value be adjusted to 1,1.5 or
2, system pH maintains 1,1.5,2 or 3.
Preferably, the addition speed control of the precipitating of acid adding described in S1 is system pH >=0.5 after being added.According to acidity
Speed is added in variation control, and the variation of excessive velocities acidity is too fast, and precipitating is too slow, and speed is too slow, and reaction efficiency is low.
Preferably, additional amount sour described in S1 is 1.05 ~ 1.2 times of the amount of the substance of iron ion.It such as can be 1.1
Or 1.2 times, sour additional amount control is conducive to control precipitation reaction speed, precipitates more complete.
Acid described in S1 is the mixed acid of citric acid, oxalic acid, acetic acid and EDTA, wherein citric acid, oxalic acid, acetic acid and EDTA
The mass ratio of the material be 4.5 ~ 5.5:1.5 ~ 2.5:1:1.Preferably 5:2:1:1.
Preferably, the pH value of spent acid containing chromium described in S1 adjust use concentration for 10 ~ 20% lye.
Preferably, system pH is maintained by the way that lye is added dropwise in S1, and wherein the concentration of lye is 5 ~ 20%.Concentration of lye is too
Height will affect acidity variation it is too fast, be unfavorable for the control of system pH, be easy to cause the acidity of precipitation reaction microbody system to change, shadow
Ring whole sedimentation effect.
Preferably, precipitation reaction time described in S1 is 20 ~ 40min.
Preferably, the condensed water being concentrated by evaporation in S3 can be used as Treated sewage reusing.The condensed water of evaporation and concentration of the invention
Particular content object is water and Determining Micro Acid, has the characteristics that middle water, can be used as Treated sewage reusing, realizes the totally enclosed type of spent acid ingredient
It recycles, the generation without secondary dangerous waste, there is economic and environment-friendly treatment effect.
Comprehensive treatment utilization method of the invention can be used for handling chromium content in 0.5 ~ 1.0% iron content Waste Sulfuric Acid, recycle
For the purity of the sodium sulphate arrived 94% or more, ferrous purity can reach 82% or more.
Compared with prior art, the beneficial effects of the present invention are:
The present invention provides a kind of comprehensive treatment utilization method of spent acid containing chromium, first presetting spent acid pH, acid adding are heavy in processing method
Shallow lake iron ion, then gradually crystallisation by cooling recycles sulfuric acid content, crystallization filtrate is finally concentrated to get chromium sulfate, by being gradually classified
Processing realizes the classification Resource recovery of acid, iron and chromium, avoids and burns bring after precipitating just chromium in existing processing method
The generation of secondary dangerous waste and the recovery value of resource it is not high the problems such as, realize the spent acid containing chromium synthesis high value recycling benefit
With wherein the rate of recovery of iron is up to 90%, and up to 80%, the rate of recovery of chromium can be widely applied to up to 90% containing chromium the sour rate of recovery
In the recovery processing of spent acid.
Detailed description of the invention
Fig. 1 is comprehensive reutilization flow chart of the invention.
Specific embodiment
The present invention is further illustrated With reference to embodiment, but embodiment the present invention is not done it is any
The restriction of form.Unless otherwise indicated, source chemicals used in the embodiment of the present invention are the source chemicals routinely bought.
The specific ingredient of the spent acid containing chromium in the embodiment of the present invention is as shown in table 1:
The main component and content of 1 spent acid containing chromium of table
Embodiment 1
A kind of comprehensive treatment utilization method of the spent acid containing chromium, as shown in Figure 1, including the following steps:
S1. it will contain chromium spent acid pH value and be adjusted to 1.5, precipitation reaction occurs for acid adding and iron ion, is stirred for 20min, mistake after acid adding
Filter isolated ferrous precipitation and filtrate, in sour adition process maintenance system pH value be 1.5, sour additional amount be spent acid in iron from
1.1 times of son, acid are the mixed acid of citric acid, oxalic acid, acetic acid and EDTA, wherein the substance of citric acid, oxalic acid, acetic acid and EDTA
Amount ratio be 5:2:1:1；
S2. above-mentioned separating filtrate is cooled down into precipitated crystal, secondary filter, filter cake dries in the shade to obtain sodium sulfate crystal Na2SO4.10H2O
With secondary filtrate；
S3. it is concentrated by evaporation above-mentioned secondary filtrate to obtain chromium sulfate CrSO4, it is poly- that the condensed water of evaporation and concentration can be back to production
It closes in aluminium chloride technique or is used for water in recycling.
Embodiment 2
A kind of comprehensive treatment utilization method of the spent acid containing chromium, includes the following steps:
S1. it will contain chromium spent acid pH value and be adjusted to 1, precipitation reaction occurs for acid adding and iron ion, is stirred for 20min after acid adding, filters
Isolated ferrous precipitation and filtrate, maintenance system pH value is 1 in sour adition process, and sour additional amount is iron ion in spent acid
1.1 times, sour addition speed control is system pH >=0.5 after being added, and acid is the mixing of citric acid, oxalic acid, acetic acid and EDTA
Acid, wherein the mass ratio of the material of citric acid, oxalic acid, acetic acid and EDTA are 4.5:2:1:1；
S2. above-mentioned separating filtrate is cooled down into precipitated crystal, secondary filter, filter cake dries in the shade to obtain sodium sulfate crystal Na2SO4.10H2O
With secondary filtrate；
S3. it is concentrated by evaporation above-mentioned secondary filtrate to obtain chromium sulfate CrSO4, it is poly- that the condensed water of evaporation and concentration can be back to production
Close in aluminium chloride technique or be used for recirculated water.
Embodiment 3
A kind of comprehensive treatment utilization method of the spent acid containing chromium, includes the following steps:
S1. it will contain chromium spent acid pH value and be adjusted to 3, precipitation reaction occurs for acid adding and iron ion, is stirred for 20min after acid adding, filters
Isolated ferrous precipitation and filtrate, maintenance system pH value is 3 in sour adition process, and sour additional amount is iron ion in spent acid
1.1 times, sour addition speed control is system pH >=0.5 after being added, and acid is the mixing of citric acid, oxalic acid, acetic acid and EDTA
Acid, wherein the mass ratio of the material of citric acid, oxalic acid, acetic acid and EDTA are 5:2.5:1:1；
S2. above-mentioned separating filtrate is cooled down into precipitated crystal, secondary filter, filter cake dries in the shade to obtain sodium sulfate crystal Na2SO4.10H2O
With secondary filtrate；
S3. it is concentrated by evaporation above-mentioned secondary filtrate to obtain chromium sulfate CrSO4, it is poly- that the condensed water of evaporation and concentration can be back to production
Close in aluminium chloride technique or be used for recirculated water.
Embodiment 4
A kind of comprehensive treatment utilization method of the spent acid containing chromium, includes the following steps:
S1. it uses concentration that will contain chromium spent acid pH value for 15% lye and is adjusted to 2, precipitation reaction occurs for acid adding and iron ion, adds
It is stirred for 20min after acid, is separated by filtration to obtain ferrous precipitation and filtrate, maintenance system pH value is 2 in sour adition process, and sour adds
Enter 1.1 times that amount is iron ion in spent acid, sour addition speed control is system pH >=0.5 after being added, and acid is citric acid, grass
The mixed acid of acid, acetic acid and EDTA, wherein the mass ratio of the material of citric acid, oxalic acid, acetic acid and EDTA are 5:2:1:1；
S2. above-mentioned separating filtrate is cooled down into precipitated crystal, secondary filter, filter cake dries in the shade to obtain sodium sulfate crystal Na2SO4.10H2O
With secondary filtrate；
S3. it is concentrated by evaporation above-mentioned secondary filtrate to obtain chromium sulfate CrSO4, it is poly- that the condensed water of evaporation and concentration can be back to production
Close in aluminium chloride technique or be used for recirculated water.
Embodiment 5
A kind of comprehensive treatment utilization method of the spent acid containing chromium, includes the following steps:
S1. it will contain chromium spent acid pH value and be adjusted to 1, precipitation reaction occurs for acid adding and iron ion, is stirred for 20min after acid adding, filters
Isolated ferrous precipitation and filtrate, maintenance system pH value is 1 in sour adition process, and sour additional amount is iron ion in spent acid
1.3 times, acid is the mixed acid of citric acid, oxalic acid, acetic acid and EDTA, wherein the amount of the substance of citric acid, oxalic acid, acetic acid and EDTA
Than for 4.5:2:1:1；
S2. above-mentioned separating filtrate is cooled down into precipitated crystal, secondary filter, filter cake dries in the shade to obtain sodium sulfate crystal Na2SO4.10H2O
With secondary filtrate；
S3. it is concentrated by evaporation above-mentioned secondary filtrate to obtain chromium sulfate CrSO4, it is poly- that the condensed water of evaporation and concentration can be back to production
Close in aluminium chloride technique or be used for recirculated water.
Embodiment 6
A kind of comprehensive treatment utilization method of the spent acid containing chromium, includes the following steps:
S1. it will contain chromium spent acid pH value and be adjusted to 1, precipitation reaction occurs for acid adding and iron ion, is stirred for 20min after acid adding, filters
Isolated ferrous precipitation and filtrate, maintenance system pH value is 1 in sour adition process, and sour additional amount is iron ion in spent acid
1.05 times, sour addition speed control is system pH >=0.5 after being added, and acid is the mixing of citric acid, oxalic acid, acetic acid and EDTA
Acid, wherein the mass ratio of the material of citric acid, oxalic acid, acetic acid and EDTA are 4.5:2:1:1；
S2. above-mentioned separating filtrate is cooled down into precipitated crystal, secondary filter, filter cake dries in the shade to obtain sodium sulfate crystal Na2SO4.10H2O
With secondary filtrate；
S3. it is concentrated by evaporation above-mentioned secondary filtrate to obtain chromium sulfate CrSO4, it is poly- that the condensed water of evaporation and concentration can be back to production
Close in aluminium chloride technique or be used for recirculated water.
Embodiment 7
A kind of comprehensive treatment utilization method of the spent acid containing chromium, includes the following steps:
S1. it will contain chromium spent acid pH value and be adjusted to 1, precipitation reaction occurs for acid adding and iron ion, is stirred for 20min after acid adding, filters
Isolated ferrous precipitation and filtrate, maintenance system pH value is 1 in sour adition process, and sour additional amount is iron ion in spent acid
1.2 again；
S2. above-mentioned separating filtrate is cooled down into precipitated crystal, secondary filter, filter cake dries in the shade to obtain sodium sulfate crystal Na2SO4.10H2O
With secondary filtrate；
S3. it is concentrated by evaporation above-mentioned secondary filtrate to obtain chromium sulfate CrSO4, it is poly- that the condensed water of evaporation and concentration can be back to production
Close in aluminium chloride technique or be used for recirculated water.
Embodiment 8
A kind of comprehensive treatment utilization method of the spent acid containing chromium, includes the following steps:
S1. it will contain chromium spent acid pH value with 10% lye and be adjusted to 1, precipitation reaction occurs for acid adding and iron ion, stirs again after acid adding
20min is mixed, is separated by filtration to obtain ferrous precipitation and filtrate, maintenance system pH value is 1 in sour adition process, and sour additional amount is useless
1.2 times of iron ion in acid；
S2. above-mentioned separating filtrate is cooled down into precipitated crystal, secondary filter, filter cake dries in the shade to obtain sodium sulfate crystal Na2SO4.10H2O
With secondary filtrate；
S3. it is concentrated by evaporation above-mentioned secondary filtrate to obtain chromium sulfate CrSO4, it is poly- that the condensed water of evaporation and concentration can be back to production
Close in aluminium chloride technique or be used for recirculated water.
Embodiment 9
A kind of comprehensive treatment utilization method of the spent acid containing chromium, includes the following steps:
S1. it will contain chromium spent acid pH value with 20% lye and be adjusted to 1, precipitation reaction occurs for acid adding and iron ion, stirs again after acid adding
20min is mixed, is separated by filtration to obtain ferrous precipitation and filtrate, maintenance system pH value is 1 in sour adition process, and sour additional amount is useless
1.2 times of iron ion in acid；
S2. above-mentioned separating filtrate is cooled down into precipitated crystal, secondary filter, filter cake dries in the shade to obtain sodium sulfate crystal Na2SO4.10H2O
With secondary filtrate；
S3. above-mentioned secondary filtrate is concentrated by evaporation to obtain chromium sulfate CrSO4, it is poly- that the condensed water of evaporation and concentration can be back to production
Close in aluminium chloride technique or be used for recirculated water.
Comparative example 1
A kind of processing of the spent acid containing chromium utilizes method, and lime is added to neutralize, by filters pressing after iron and chromium precipitating, at dangerous waste filter cake burning
Reason.
As a result it detects
The rate of recovery and product quality of the acid of embodiment and comparative example, iron and chromium are detected, wherein
The detection method of the rate of recovery of acid are as follows: acidometry in GB/T 10531-2016
The detection method of the rate of recovery of iron are as follows: ferrous measuring method in GB/T 44822018
The detection method of the rate of recovery of chromium: the measurement atomic absorption spectrophotometry HJ749-2015 of total chromium
Testing result is as shown in table 2.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention.For those of ordinary skill in the art, may be used also on the basis of the above description
To make other variations or changes in different ways.There is no necessity and possibility to exhaust all the enbodiments.It is all this
Made any modifications, equivalent replacements, and improvements etc., should be included in the claims in the present invention within the spirit and principle of invention
Protection scope within.
Claims (10)
1. a kind of comprehensive treatment utilization method of spent acid containing chromium, sulfate radical and iron ion are contained in the spent acid, which is characterized in that
Include the following steps:
S1. it will contain chromium spent acid pH value and be adjusted to 1 ~ 3, precipitation reaction, isolated ferrous precipitation and filter occur for acid adding and iron ion
Liquid, maintenance system pH value is 1 ~ 3 during acid adding；
S2. by the cooling precipitated crystal of above-mentioned separating filtrate, sodium sulfate crystal and secondary filtrate is obtained by filtration；
S3. it is concentrated by evaporation above-mentioned secondary filtrate to obtain chromium sulfate.
2. comprehensive treatment utilization method as described in claim 1, which is characterized in that pH value described in S1 is adjusted to 1 ~ 2, system pH
Value maintains 1 ~ 3.
3. comprehensive treatment utilization method as claimed in claim 1 or 2, which is characterized in that the addition speed of the precipitating of acid adding described in S1
Degree control is system pH >=0.5 after addition.
4. comprehensive treatment utilization method as claimed in claim 3, which is characterized in that sour additional amount described in S1 is iron ion
1.05 ~ 1.2 times of the amount of substance.
5. comprehensive treatment utilization method as described in claim 1, which is characterized in that acid described in S1 is citric acid, oxalic acid, acetic acid
With the mixed acid of EDTA, wherein the mass ratio of the material of citric acid, oxalic acid, acetic acid and EDTA are 4.5 ~ 5.5:1.5 ~ 2.5:1:1.
6. comprehensive treatment utilization method as described in claim 1, which is characterized in that the pH value of spent acid containing chromium described in S1, which is adjusted, to be used
The lye that concentration is 10 ~ 20%.
7. comprehensive treatment utilization method as described in claim 1, which is characterized in that system pH is by being added dropwise lye dimension in S1
It holds, wherein the concentration of lye is 5 ~ 20%.
8. comprehensive treatment utilization method as described in claim 1, which is characterized in that precipitation reaction time described in S1 be 20min ~
40min。
9. comprehensive treatment utilization method as described in claim 1, which is characterized in that during the condensed water being concentrated by evaporation in S3 can be used as
Water reuse.
10. comprehensive treatment utilization method as described in claim 1, which is characterized in that in the spent acid containing chromium chromium content be 0.5 ~
1.0%。
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| CN113023949A (en) * | 2021-03-17 | 2021-06-25 | 哈尔滨工业大学 | Method for removing hexavalent chromium through filtration and reinforcement by catalytic reduction coupling membrane |
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