CN103288232B - Resourceful treatment apparatus and method for waste liquid of chlorohydric acid pickling of steel - Google Patents
Resourceful treatment apparatus and method for waste liquid of chlorohydric acid pickling of steel Download PDFInfo
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- CN103288232B CN103288232B CN201310133517.3A CN201310133517A CN103288232B CN 103288232 B CN103288232 B CN 103288232B CN 201310133517 A CN201310133517 A CN 201310133517A CN 103288232 B CN103288232 B CN 103288232B
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 329
- 239000002699 waste material Substances 0.000 title claims abstract description 136
- 238000005554 pickling Methods 0.000 title claims abstract description 126
- 239000007788 liquid Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 49
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 30
- 239000010959 steel Substances 0.000 title claims abstract description 30
- 238000004821 distillation Methods 0.000 claims abstract description 47
- 239000000701 coagulant Substances 0.000 claims abstract description 45
- 239000012452 mother liquor Substances 0.000 claims abstract description 44
- 239000007787 solid Substances 0.000 claims abstract description 43
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 36
- WNQQFQRHFNVNSP-UHFFFAOYSA-N [Ca].[Fe] Chemical compound [Ca].[Fe] WNQQFQRHFNVNSP-UHFFFAOYSA-N 0.000 claims abstract description 26
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 18
- 239000001110 calcium chloride Substances 0.000 claims abstract description 18
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 18
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 18
- MHKWSJBPFXBFMX-UHFFFAOYSA-N iron magnesium Chemical compound [Mg].[Fe] MHKWSJBPFXBFMX-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 79
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 55
- 229910052742 iron Inorganic materials 0.000 claims description 40
- 238000006116 polymerization reaction Methods 0.000 claims description 29
- 239000011259 mixed solution Substances 0.000 claims description 28
- 229940045641 monobasic sodium phosphate Drugs 0.000 claims description 20
- 238000002425 crystallisation Methods 0.000 claims description 17
- 239000012530 fluid Substances 0.000 claims description 16
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 16
- 239000001488 sodium phosphate Substances 0.000 claims description 16
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 16
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 16
- 230000008025 crystallization Effects 0.000 claims description 15
- 238000013019 agitation Methods 0.000 claims description 14
- 238000000998 batch distillation Methods 0.000 claims description 14
- 230000003647 oxidation Effects 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 239000003381 stabilizer Substances 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 29
- 239000002351 wastewater Substances 0.000 description 24
- 238000005406 washing Methods 0.000 description 21
- 239000001045 blue dye Substances 0.000 description 12
- 235000019219 chocolate Nutrition 0.000 description 12
- 239000000975 dye Substances 0.000 description 12
- 239000001046 green dye Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000007792 gaseous phase Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 235000021110 pickles Nutrition 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940067573 brown iron oxide Drugs 0.000 description 1
- ZTFMLZCQQJOKPS-UHFFFAOYSA-J calcium iron(2+) tetrachloride Chemical compound [Fe+2].[Cl-].[Ca+2].[Cl-].[Cl-].[Cl-] ZTFMLZCQQJOKPS-UHFFFAOYSA-J 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- -1 iron ion Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention discloses a resourceful treatment apparatus and method for waste liquid of chlorohydric acid pickling of steel. At present, a conventional pickling waste liquid treatment method has the disadvantages of high requirements of treatment equipment, high treatment cost, inadequate recovery and the like. According to the invention, salt-added distillation technology is employed for recovery of high-concentration hydrochloric acid, and distillation mother liquor is used to prepare a liquid polyferric sulfate coagulant. The method comprises the following steps: adding a calcium chloride or magnesium chloride solid into the waste liquid of chlorohydric acid pickling, carrying out atmospheric distillation, removing excess acidity and recovering high-concentration hydrochloric acid; and then adding an oxidizing agent and a stabilizing agent into the distillation mother liquor with stirring, carrying out a reaction at normal temperature and normal pressure for 1 h and carrying out standing for curing for 24 h so as to obtain a liquid calcium-iron or magnesium-iron composite coagulant product. The invention has the following advantages: production process is simple, investment is little, recovery of hydrochloric acid and preparation of the polyferric sulfate coagulant can be synchronously carried out, zero discharge of waste liquid of pickling of steel is realized, the purposes of reuse of resources and treatment of waste with waste are achieved, and both an environmental value and an economic value are obtained.
Description
Technical field
The invention belongs to spent pickle liquor recycling field, be specifically related to a kind of device and method of steel hydrochloric acid pickling waste liquor recycling treatment.
Background technology
The coming years China per capita iron and steel consumption will continue soaring, the downstream industry maintenance growths such as building machinery, steel processing industry can be further developed.Acid cleaning process is a link important in the steel course of processing, and metal pickling discharging of waste liquid amount also will promote to some extent.Hydrochloric acid, sulfuric acid as clean-out system topmost in acid cleaning process, chlorohydric acid pickling because of stripping effect make base iron loss comparatively sulfuric acid to be widely used less, therefore at present acid washing rolled steel substantially based on chlorohydric acid pickling technique.Containing a large amount of residual hydrochloric acid and metallic iron ion in steel hydrochloric acid pickling waste liquor, be classified as Hazardous wastes both at home and abroad at present to manage, and strict restriction has been done to ferric remains discharge, iron emission standard as total in America and Europe is strict controlled in below 10mg/L, the provincial standard " pickling waste waters discharges total concentration of iron limit value " (DB 33/844-2011) economized of the Zhejiang Province, China also total iron emission limit set of strict regulation, at 2-10mg/L, performs the special standard of 2mg/L for Taihu Lake basin.The acid content of spent pickle liquor is at 5-10%, and total iron content, generally at 50-150g/L, arbitrarily discharges will cause high risks to water ecological environment if do not add process.
Spent pickle liquor treatment process conventional at present has traditional neutralisation and application technology as the second resource.Tradition neutralisation due to processing cost high, precipitating sludge is disposed the drawback such as difficult and is eliminated by most enterprises.And the resource treatment techniques such as high-temperature roasting method, evaporative crystallization method, ion exchange method, membrane processing method, evaporative distillation method are favored by enterprise deeply.High-temperature roasting method is high due to the economic worth reclaiming hydrochloric acid and brown iron oxide, is used by large iron and steel enterprise industrialization, but the method front-end investment is large, equipment and processing requirement strict.Evaporative crystallization method processing cost is low, but after crystallization treatment, exterior liquid ferric remains content cannot be up to standard.The utilization of ion exchange method and membrane processing method, also by the restriction of high density iron level, easily causes resin and fouling membrane.Evaporative distillation method has the advantages such as equipment is simple, processing cost is low, deeply favors by small-sized iron and steel enterprise, but during to hydrochloride waste evaporative distillation, can run into hydrochloric acid-water azeotrope obstacle, causes reclaiming concentration of hydrochloric acid not high, reclaims the shortcomings such as not thorough.
Distillation with adding salts technology can change hydrochloric acid-aqueous vapor liquid profile of equilibrium, improves and reclaims concentration of hydrochloric acid.Meanwhile, a large amount of ferrous components in waste liquid can be used for preparing liquid coagulating agent, salt add the polymerization degree that can improve iron, improve coagulation effect.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of steel hydrochloric acid pickling effluent resource treatment unit and method are provided.
A kind of steel hydrochloric acid pickling effluent resource of the present invention treatment unit, comprises waste liquid tank, heat exchanger, distillation tower, condenser, washing tower, absorption flow container, reclaims hydrochloric acid container for storing liquid and stirred reactor;
Whipping appts is provided with in described waste liquid tank, the discharge port of waste liquid tank is connected with the opening for feed of distillation tower, the still liquid discharge port of distillation tower is connected with the opening for feed of stirred reactor, the top gaseous phase outlet of distillation tower is connected with the inlet mouth of condenser, the condensate outlet of condenser respectively with the opening for feed reclaiming hydrochloric acid container for storing liquid, the bottom inlet mouth of washing tower connects, the liquid outlet of washing tower is connected with absorption flow container fluid inlet, the top of washing tower is provided with spray header, spray header is connected with the liquid outlet absorbing flow container by pump, input of column pipeline is connected with heat exchanger respectively with distillation tower gaseous phase outlet pipeline.
A kind of steel hydrochloric acid pickling effluent resource of the present invention treatment process, the method comprises the following steps:
Step one. in hydrochloric acid pickling waste liquor, add solid calcium chloride or magnesium chloride, at ambient pressure batch distillation operation is carried out to hydrochloric acid pickling waste liquor;
Get hydrochloric acid pickling waste liquor and be placed in still kettle, add solid calcium chloride or magnesium chloride, the add-on of solid is 0.75-1.25mol/L.Add thermal distillation, condensed fluid collection amount to be distillated and hydrochloride waste add volume ratio for (3 ~ 4): when 10, stop distillation;
Step 2. in evaporated mother liquor, add oxygenant sodium chlorate, stablizer sodium phosphate or SODIUM PHOSPHATE, MONOBASIC under agitation, carry out at normal temperatures and pressures being oxidized, polyreaction;
In hydrochloric acid pickling waste liquor evaporated mother liquor after processing to step one, thin up prevents crystallization, in hydrochloric acid pickling waste liquor evaporated mother liquor, stablizer sodium phosphate or SODIUM PHOSPHATE, MONOBASIC is added under constantly stirring, in stablizer and hydrochloric acid pickling waste liquor, the mol ratio of iron level is 0.075-0.1, drip mode with solution and add oxygenant sodium chlorate, sodium chlorate, in sodium chlorate and hydrochloric acid pickling waste liquor, the mol ratio of iron level is 0.18, and controlling mixed solution oxidation time is 1 h;
Step 3. slaking
Mixed solution in step 2 is left standstill slaking 24 h, namely obtain liquid polymerization calcium iron, magnesium iron compound coagulant.
The beneficial effect that the present invention has:
The present invention adopts distillation with adding salts technology, adds calcium chloride, vapor liquid equilibrium curve that magnesium chloride can change hydrochloric acid-water, improves distilling effect.Liquid polymerization calcium chloride iron, magnesium iron are a kind of NEW TYPE OF COMPOSITE inorganic coagulants, and the interpolation of calcium, magnesium can improve the extent of polymerization of poly-ferric chloride, and calcium, magnesium ion can play charge neutrality and sedimentation screen catches effect, improves coagulation effect.It is simple that the present invention has production technique, and the advantage of less investment, synchronously realizes HCl recovery and prepare Polyferric Sulfate coagulating agent, can realize the zero release of acid washing rolled steel waste liquid.The hydrochloric acid simultaneously reclaimed and the new composite coagulant of preparation all have higher economic worth, can reach the object of resource reusing, the treatment of wastes with processes of wastes against one another, have environmental value and economic worth concurrently.
Accompanying drawing explanation
Fig. 1 is device schematic diagram of the present invention.
Embodiment
As shown in Figure 1, the device of a kind of steel hydrochloric acid pickling waste liquor of the present invention recycling treatment, comprises waste liquid tank, heat exchanger, distillation tower, condenser, washing tower, absorption flow container, reclaims hydrochloric acid container for storing liquid and stirred reactor;
Whipping appts is provided with in described waste liquid tank, the discharge port of waste liquid tank is connected with the opening for feed of distillation tower, the still liquid discharge port of distillation tower is connected with the opening for feed of stirred reactor, the top gaseous phase outlet of distillation tower is connected with the inlet mouth of condenser, the condensate outlet of condenser respectively with the opening for feed reclaiming hydrochloric acid container for storing liquid, the bottom inlet mouth of washing tower connects, the liquid outlet of washing tower is connected with absorption flow container fluid inlet, the top of washing tower is provided with spray header, spray header is connected with the liquid outlet absorbing flow container by pump, input of column pipeline is connected with heat exchanger respectively with distillation tower gaseous phase outlet pipeline.
Embodiment 1
Step one. in hydrochloric acid pickling waste liquor, add solid calcium chloride, at ambient pressure batch distillation operation is carried out to hydrochloric acid pickling waste liquor;
Get hydrochloric acid pickling waste liquor and be placed in still kettle, add solid calcium chloride, the add-on of solid is 1mol/L.Add thermal distillation, condensed fluid collection amount to be distillated and hydrochloride waste add volume ratio when being 3:10, stop distillation;
Step 2. in evaporated mother liquor, add oxygenant sodium chlorate, stablizer sodium phosphate under agitation, carry out at normal temperatures and pressures being oxidized, polyreaction;
In hydrochloric acid pickling waste liquor evaporated mother liquor after processing to step one, thin up prevents crystallization, in hydrochloric acid pickling waste liquor evaporated mother liquor, stablizer sodium phosphate is added under constantly stirring, in stablizer and hydrochloric acid pickling waste liquor, the mol ratio of iron level is 0.075, drip mode with solution and add oxygenant sodium chlorate, sodium chlorate, in sodium chlorate and hydrochloric acid pickling waste liquor, the mol ratio of iron level is 0.18, and controlling mixed solution oxidation time is 1 h;
Step 3. slaking
Mixed solution in step 2 is left standstill slaking 24 h, namely obtain liquid calcium iron compound coagulant.
Reuse hydrochloric acid and chocolate liquid polymerization calcium iron compound coagulant product is obtained by this embodiment.Reclaim the hydrochloric acid 300kg/t of 22.3%, meet the requirement of acid washing rolled steel technique clean-out system.The polymerization calcium iron compound coagulant prepared to containing 50mg/L direct black dyes, Reactive green dyes, acid blue dye simulated wastewater chroma removal rate is respectively 95%, 85%, 60%, is that the chroma removal rate of the actual dying of 500 is 85% to colourity.
Embodiment 2
Step one. in hydrochloric acid pickling waste liquor, add solid calcium chloride, at ambient pressure batch distillation operation is carried out to hydrochloric acid pickling waste liquor;
Get hydrochloric acid pickling waste liquor and be placed in still kettle, add solid calcium chloride, the add-on of solid is 0.75mol/L.Add thermal distillation, condensed fluid collection amount to be distillated and hydrochloride waste add volume ratio when being 3.5:10, stop distillation;
Step 2. in evaporated mother liquor, add oxygenant sodium chlorate, stablizer sodium phosphate under agitation, carry out at normal temperatures and pressures being oxidized, polyreaction;
In hydrochloric acid pickling waste liquor evaporated mother liquor after processing to step one, thin up prevents crystallization, in hydrochloric acid pickling waste liquor evaporated mother liquor, stablizer sodium phosphate is added under constantly stirring, in stablizer and hydrochloric acid pickling waste liquor, the mol ratio of iron level is 0.09, drip mode with solution and add oxygenant sodium chlorate, sodium chlorate, in sodium chlorate and hydrochloric acid pickling waste liquor, the mol ratio of iron level is 0.18, and controlling mixed solution oxidation time is 1 h;
Step 3. slaking
Mixed solution in step 2 is left standstill slaking 24 h, namely obtain liquid calcium iron compound coagulant.
By the pickling waste waters process of this embodiment 10% content of hydrochloric acid, obtain reuse hydrochloric acid and chocolate liquid polymerization calcium iron compound coagulant product.Reclaim the hydrochloric acid 350kg/t of 21.0%, meet the requirement of steel iron acid cleaning process clean-out system.The polymerization calcium iron compound coagulant prepared to containing 50mg/L direct black dyes, Reactive green dyes, acid blue dye simulated wastewater chroma removal rate is respectively 93%, 85%, 50%, is that the chroma removal rate of the actual dying of 500 is 80% to colourity.
Embodiment 3
Step one. in hydrochloric acid pickling waste liquor, add solid calcium chloride, at ambient pressure batch distillation operation is carried out to hydrochloric acid pickling waste liquor;
Get hydrochloric acid pickling waste liquor and be placed in still kettle, add solid calcium chloride, the add-on of solid is 1.25mol/L.Add thermal distillation, condensed fluid collection amount to be distillated and hydrochloride waste add volume ratio when being 4:10, stop distillation;
Step 2. in evaporated mother liquor, add oxygenant sodium chlorate, stablizer sodium phosphate under agitation, carry out at normal temperatures and pressures being oxidized, polyreaction;
In hydrochloric acid pickling waste liquor evaporated mother liquor after processing to step one, thin up prevents crystallization, in hydrochloric acid pickling waste liquor evaporated mother liquor, stablizer sodium phosphate is added under constantly stirring, in stablizer and hydrochloric acid pickling waste liquor, the mol ratio of iron level is 0.1, drip mode with solution and add oxygenant sodium chlorate, sodium chlorate, in sodium chlorate and hydrochloric acid pickling waste liquor, the mol ratio of iron level is 0.18, and controlling mixed solution oxidation time is 1 h;
Step 3. slaking
Mixed solution in step 2 is left standstill slaking 24 h, namely obtain liquid calcium iron compound coagulant.
By the pickling waste waters process of this embodiment to 10% content of hydrochloric acid, obtain reuse hydrochloric acid and chocolate liquid polymerization calcium iron compound coagulant product.Reclaim the hydrochloric acid 400kg/t of 21.8%, meet the requirement of acid washing rolled steel technique clean-out system.The polymerization magnesium iron compound coagulant prepared to containing 50mg/L direct black dyes, Reactive green dyes, acid blue dye simulated wastewater chroma removal rate is respectively 93%, 83%, 55%, is that the chroma removal rate of the actual dying of 500 is 85% to colourity.
Embodiment 4
Step one. in hydrochloric acid pickling waste liquor, add solid calcium chloride, at ambient pressure batch distillation operation is carried out to hydrochloric acid pickling waste liquor;
Get hydrochloric acid pickling waste liquor and be placed in still kettle, add solid calcium chloride, the add-on of solid is 0.75mol/L.Add thermal distillation, condensed fluid collection amount to be distillated and hydrochloride waste add volume ratio when being 3:10, stop distillation;
Step 2. in evaporated mother liquor, add oxygenant sodium chlorate, stablizer SODIUM PHOSPHATE, MONOBASIC under agitation, carry out at normal temperatures and pressures being oxidized, polyreaction;
In hydrochloric acid pickling waste liquor evaporated mother liquor after processing to step one, thin up prevents crystallization, in hydrochloric acid pickling waste liquor evaporated mother liquor, stablizer SODIUM PHOSPHATE, MONOBASIC is added under constantly stirring, in stablizer and hydrochloric acid pickling waste liquor, the mol ratio of iron level is 0.075, drip mode with solution and add oxygenant sodium chlorate, sodium chlorate, in sodium chlorate and hydrochloric acid pickling waste liquor, the mol ratio of iron level is 0.18, and controlling mixed solution oxidation time is 1 h;
Step 3. slaking
Mixed solution in step 2 is left standstill slaking 24 h, namely obtain liquid calcium iron compound coagulant.
By the pickling waste waters process of this embodiment 10% content of hydrochloric acid, obtain reuse hydrochloric acid and chocolate liquid polymerization calcium iron compound coagulant product.Reclaim the hydrochloric acid 300kg/t of 22.3%, meet the requirement of acid washing rolled steel technique clean-out system.The polymerization calcium iron compound coagulant prepared to containing 50mg/L direct black dyes, Reactive green dyes, acid blue dye simulated wastewater chroma removal rate is respectively 92%, 86%, 53%, is that the chroma removal rate of the actual dying of 500 is 83% to colourity.
Embodiment 5
Step one. in hydrochloric acid pickling waste liquor, add solid calcium chloride, at ambient pressure batch distillation operation is carried out to hydrochloric acid pickling waste liquor;
Get hydrochloric acid pickling waste liquor and be placed in still kettle, add solid calcium chloride, the add-on of solid is 1mol/L.Add thermal distillation, condensed fluid collection amount to be distillated and hydrochloride waste add volume ratio when being 3.5:10, stop distillation;
Step 2. in evaporated mother liquor, add oxygenant sodium chlorate, stablizer SODIUM PHOSPHATE, MONOBASIC under agitation, carry out at normal temperatures and pressures being oxidized, polyreaction;
In hydrochloric acid pickling waste liquor evaporated mother liquor after processing to step one, thin up prevents crystallization, in hydrochloric acid pickling waste liquor evaporated mother liquor, stablizer SODIUM PHOSPHATE, MONOBASIC is added under constantly stirring, in stablizer and hydrochloric acid pickling waste liquor, the mol ratio of iron level is 0.08, drip mode with solution and add oxygenant sodium chlorate, sodium chlorate, in sodium chlorate and hydrochloric acid pickling waste liquor, the mol ratio of iron level is 0.18, and controlling mixed solution oxidation time is 1 h;
Step 3. slaking
Mixed solution in step 2 is left standstill slaking 24 h, namely obtain liquid calcium iron compound coagulant.
By the pickling waste waters process of this embodiment 10% content of hydrochloric acid, obtain reuse hydrochloric acid and chocolate liquid polymerization calcium iron compound coagulant product.Reclaim the hydrochloric acid 350kg/t of 22.8%, meet the requirement of acid washing rolled steel technique clean-out system.The polymerization calcium iron compound coagulant prepared to containing 50mg/L direct black dyes, Reactive green dyes, acid blue dye simulated wastewater chroma removal rate is respectively 94%, 83%, 52%, is that the chroma removal rate of the actual dying of 500 is 85% to colourity.
Embodiment 6
Step one. in hydrochloric acid pickling waste liquor, add solid calcium chloride, at ambient pressure batch distillation operation is carried out to hydrochloric acid pickling waste liquor;
Get hydrochloric acid pickling waste liquor and be placed in still kettle, add solid calcium chloride, the add-on of solid is 1.25mol/L.Add thermal distillation, condensed fluid collection amount to be distillated and hydrochloride waste add volume ratio when being 4:10, stop distillation;
Step 2. in evaporated mother liquor, add oxygenant sodium chlorate, stablizer SODIUM PHOSPHATE, MONOBASIC under agitation, carry out at normal temperatures and pressures being oxidized, polyreaction;
In hydrochloric acid pickling waste liquor evaporated mother liquor after processing to step one, thin up prevents crystallization, in hydrochloric acid pickling waste liquor evaporated mother liquor, stablizer SODIUM PHOSPHATE, MONOBASIC is added under constantly stirring, in stablizer and hydrochloric acid pickling waste liquor, the mol ratio of iron level is 0.1, drip mode with solution and add oxygenant sodium chlorate, sodium chlorate, in sodium chlorate and hydrochloric acid pickling waste liquor, the mol ratio of iron level is 0.18, and controlling mixed solution oxidation time is 1 h;
Step 3. slaking
Mixed solution in step 2 is left standstill slaking 24 h, namely obtain liquid calcium iron compound coagulant.
By the pickling waste waters process of this embodiment 10% content of hydrochloric acid, obtain reuse hydrochloric acid and chocolate liquid polymerization calcium iron compound coagulant product.Reclaim the hydrochloric acid 400kg/t of 21.2%, meet the requirement of acid washing rolled steel technique clean-out system.The polymerization calcium iron compound coagulant prepared to containing 50mg/L direct black dyes, Reactive green dyes, acid blue dye simulated wastewater chroma removal rate is respectively 91%, 82%, 50%, is that the chroma removal rate of the actual dying of 500 is 82% to colourity.
Embodiment 7
Step one. in hydrochloric acid pickling waste liquor, add solid magnesium chloride, at ambient pressure batch distillation operation is carried out to hydrochloric acid pickling waste liquor;
Get hydrochloric acid pickling waste liquor and be placed in still kettle, add solid magnesium chloride, the add-on of solid is 0.75mol/L.Add thermal distillation, condensed fluid collection amount to be distillated and hydrochloride waste add volume ratio when being 3:10, stop distillation;
Step 2. in evaporated mother liquor, add oxygenant sodium chlorate, stablizer sodium phosphate under agitation, carry out at normal temperatures and pressures being oxidized, polyreaction;
In hydrochloric acid pickling waste liquor evaporated mother liquor after processing to step one, thin up prevents crystallization, in hydrochloric acid pickling waste liquor evaporated mother liquor, stablizer sodium phosphate is added under constantly stirring, in stablizer and hydrochloric acid pickling waste liquor, the mol ratio of iron level is 0.075, drip mode with solution and add oxygenant sodium chlorate, sodium chlorate, in sodium chlorate and hydrochloric acid pickling waste liquor, the mol ratio of iron level is 0.18, and controlling mixed solution oxidation time is 1 h;
Step 3. slaking
Mixed solution in step 2 is left standstill slaking 24 h, namely obtain liquid magnesium iron compound coagulant.
By the pickling waste waters process of this embodiment to 10% content of hydrochloric acid, obtain reuse hydrochloric acid and chocolate liquid polymerization calcium iron compound coagulant product.Reclaim the hydrochloric acid 400kg/t of 22.8%, meet the requirement of acid washing rolled steel technique clean-out system.The polymerization magnesium iron compound coagulant prepared to containing 50mg/L direct black dyes, Reactive green dyes, acid blue dye simulated wastewater chroma removal rate is respectively 93%, 83%, 55%, is that the chroma removal rate of the actual dying of 500 is 85% to colourity.
Embodiment 8
Step one. in hydrochloric acid pickling waste liquor, add solid magnesium chloride, at ambient pressure batch distillation operation is carried out to hydrochloric acid pickling waste liquor;
Get hydrochloric acid pickling waste liquor and be placed in still kettle, add solid magnesium chloride, the add-on of solid is 1mol/L.Add thermal distillation, condensed fluid collection amount to be distillated and hydrochloride waste add volume ratio when being 3.5:10, stop distillation;
Step 2. in evaporated mother liquor, add oxygenant sodium chlorate, stablizer sodium phosphate under agitation, carry out at normal temperatures and pressures being oxidized, polyreaction;
In hydrochloric acid pickling waste liquor evaporated mother liquor after processing to step one, thin up prevents crystallization, stablizer sodium phosphate is added in hydrochloric acid pickling waste liquor evaporated mother liquor under constantly stirring, in stablizer and hydrochloric acid pickling waste liquor, the mol ratio of iron level is 0.09, drip mode with solution and add oxygenant sodium chlorate, sodium chlorate, in sodium chlorate and hydrochloric acid pickling waste liquor, the mol ratio of iron level is 0.18, and controlling mixed solution oxidation time is 1 h;
Step 3. slaking
Mixed solution in step 2 is left standstill slaking 24 h, namely obtain liquid magnesium iron compound coagulant.
By the pickling waste waters process of this embodiment to 10% content of hydrochloric acid, obtain reuse hydrochloric acid and chocolate liquid polymerization calcium iron compound coagulant product.Reclaim the hydrochloric acid 300kg/t of 22.5%, meet the requirement of acid washing rolled steel technique clean-out system.The polymerization magnesium iron compound coagulant prepared to containing 50mg/L direct black dyes, Reactive green dyes, acid blue dye simulated wastewater chroma removal rate is respectively 91%, 81%, 55%, is that the chroma removal rate of the actual dying of 500 is 82% to colourity.
Embodiment 9
Step one. in hydrochloric acid pickling waste liquor, add solid magnesium chloride, at ambient pressure batch distillation operation is carried out to hydrochloric acid pickling waste liquor;
Get hydrochloric acid pickling waste liquor and be placed in still kettle, add solid magnesium chloride, the add-on of solid is 1.25mol/L.Add thermal distillation, condensed fluid collection amount to be distillated and hydrochloride waste add volume ratio when being 4:10, stop distillation;
Step 2. in evaporated mother liquor, add oxygenant sodium chlorate, stablizer sodium phosphate under agitation, carry out at normal temperatures and pressures being oxidized, polyreaction;
In hydrochloric acid pickling waste liquor evaporated mother liquor after processing to step one, thin up prevents crystallization, in hydrochloric acid pickling waste liquor evaporated mother liquor, stablizer sodium phosphate is added under constantly stirring, in stablizer and hydrochloric acid pickling waste liquor, the mol ratio of iron level is 0.1, drip mode with solution and add oxygenant sodium chlorate, sodium chlorate, in sodium chlorate and hydrochloric acid pickling waste liquor, the mol ratio of iron level is 0.18, and controlling mixed solution oxidation time is 1 h;
Step 3. slaking
Mixed solution in step 2 is left standstill slaking 24 h, namely obtain liquid magnesium iron compound coagulant.
By the pickling waste waters process of this embodiment to 10% content of hydrochloric acid, obtain reuse hydrochloric acid and chocolate liquid polymerization calcium iron compound coagulant product.Reclaim the hydrochloric acid 400kg/t of 20.4%, meet the requirement of acid washing rolled steel technique clean-out system.The polymerization magnesium iron compound coagulant prepared to containing 50mg/L direct black dyes, Reactive green dyes, acid blue dye simulated wastewater chroma removal rate is respectively 92%, 81%, 53%, is that the chroma removal rate of the actual dying of 500 is 82% to colourity.
Embodiment 10
Step one. in hydrochloric acid pickling waste liquor, add solid magnesium chloride, at ambient pressure batch distillation operation is carried out to hydrochloric acid pickling waste liquor;
Get hydrochloric acid pickling waste liquor and be placed in still kettle, add solid magnesium chloride, the add-on of solid is 1.25mol/L.Add thermal distillation, condensed fluid collection amount to be distillated and hydrochloride waste add volume ratio when being 4:10, stop distillation;
Step 2. in evaporated mother liquor, add oxygenant sodium chlorate, stablizer SODIUM PHOSPHATE, MONOBASIC under agitation, carry out at normal temperatures and pressures being oxidized, polyreaction;
In hydrochloric acid pickling waste liquor evaporated mother liquor after processing to step one, thin up prevents crystallization, in hydrochloric acid pickling waste liquor evaporated mother liquor, stablizer SODIUM PHOSPHATE, MONOBASIC is added under constantly stirring, in stablizer and hydrochloric acid pickling waste liquor, the mol ratio of iron level is 0.075, drip mode with solution and add oxygenant sodium chlorate, sodium chlorate, in sodium chlorate and hydrochloric acid pickling waste liquor, the mol ratio of iron level is 0.18, and controlling mixed solution oxidation time is 1 h;
Step 3. slaking
Mixed solution in step 2 is left standstill slaking 24 h, namely obtain liquid magnesium iron compound coagulant.
By the pickling waste waters process of this embodiment to 10% content of hydrochloric acid, obtain reuse hydrochloric acid and chocolate liquid polymerization calcium iron compound coagulant product.Reclaim the hydrochloric acid 400kg/t of 20.8%, meet the requirement of acid washing rolled steel technique clean-out system.The polymerization magnesium iron compound coagulant prepared to containing 50mg/L direct black dyes, Reactive green dyes, acid blue dye simulated wastewater chroma removal rate is respectively 91%, 81%, 54%, is that the chroma removal rate of the actual dying of 500 is 83% to colourity.
Embodiment 11
Step one. in hydrochloric acid pickling waste liquor, add solid magnesium chloride, at ambient pressure batch distillation operation is carried out to hydrochloric acid pickling waste liquor;
Get hydrochloric acid pickling waste liquor and be placed in still kettle, add solid magnesium chloride, the add-on of solid is 1mol/L.Add thermal distillation, condensed fluid collection amount to be distillated and hydrochloride waste add volume ratio when being 3.5:10, stop distillation;
Step 2. in evaporated mother liquor, add oxygenant sodium chlorate, stablizer SODIUM PHOSPHATE, MONOBASIC under agitation, carry out at normal temperatures and pressures being oxidized, polyreaction;
In hydrochloric acid pickling waste liquor evaporated mother liquor after processing to step one, thin up prevents crystallization, in hydrochloric acid pickling waste liquor evaporated mother liquor, stablizer SODIUM PHOSPHATE, MONOBASIC is added under constantly stirring, in stablizer and hydrochloric acid pickling waste liquor, the mol ratio of iron level is 0.1, drip mode with solution and add oxygenant sodium chlorate, sodium chlorate, in sodium chlorate and hydrochloric acid pickling waste liquor, the mol ratio of iron level is 0.18, and controlling mixed solution oxidation time is 1 h;
Step 3. slaking
Mixed solution in step 2 is left standstill slaking 24 h, namely obtain liquid magnesium iron compound coagulant.
By the pickling waste waters process of this embodiment to 10% content of hydrochloric acid, obtain reuse hydrochloric acid and chocolate liquid polymerization calcium iron compound coagulant product.Reclaim the hydrochloric acid 350kg/t of 22.5%, meet the requirement of acid washing rolled steel technique clean-out system.The polymerization magnesium iron compound coagulant prepared to containing 50mg/L direct black dyes, Reactive green dyes, acid blue dye simulated wastewater chroma removal rate is respectively 93%, 81%, 53%, is that the chroma removal rate of the actual dying of 500 is 81% to colourity.
Embodiment 12
Step one. in hydrochloric acid pickling waste liquor, add solid magnesium chloride, at ambient pressure batch distillation operation is carried out to hydrochloric acid pickling waste liquor;
Get hydrochloric acid pickling waste liquor and be placed in still kettle, add solid magnesium chloride, the add-on of solid is 0.75mol/L.Add thermal distillation, condensed fluid collection amount to be distillated and hydrochloride waste add volume ratio when being 3:10, stop distillation;
Step 2. in evaporated mother liquor, add oxygenant sodium chlorate, stablizer SODIUM PHOSPHATE, MONOBASIC under agitation, carry out at normal temperatures and pressures being oxidized, polyreaction;
In hydrochloric acid pickling waste liquor evaporated mother liquor after processing to step one, thin up prevents crystallization, in hydrochloric acid pickling waste liquor evaporated mother liquor, stablizer SODIUM PHOSPHATE, MONOBASIC is added under constantly stirring, in stablizer and hydrochloric acid pickling waste liquor, the mol ratio of iron level is 0.09, drip mode with solution and add oxygenant sodium chlorate, sodium chlorate, in sodium chlorate and hydrochloric acid pickling waste liquor, the mol ratio of iron level is 0.18, and controlling mixed solution oxidation time is 1 h;
Step 3. slaking
Mixed solution in step 2 is left standstill slaking 24 h, namely obtain liquid magnesium iron compound coagulant.
By the pickling waste waters process of this embodiment to 10% content of hydrochloric acid, obtain reuse hydrochloric acid and chocolate liquid polymerization calcium iron compound coagulant product.Reclaim the hydrochloric acid 300kg/t of 21.5%, meet the requirement of acid washing rolled steel technique clean-out system.The polymerization magnesium iron compound coagulant prepared to containing 50mg/L direct black dyes, Reactive green dyes, acid blue dye simulated wastewater chroma removal rate is respectively 92%, 82%, 53%, is that the chroma removal rate of the actual dying of 500 is 84% to colourity.
Claims (1)
1. a steel resource treatment method for hydrochloric acid pickling waste liquor, is characterized in that the method comprises the following steps:
Step one. in hydrochloric acid pickling waste liquor, add solid calcium chloride or magnesium chloride, at ambient pressure batch distillation operation is carried out to hydrochloric acid pickling waste liquor;
Get hydrochloric acid pickling waste liquor and be placed in still kettle, add solid calcium chloride or magnesium chloride, the add-on of solid is 0.75-1.25mol/L; Add thermal distillation, when condensed fluid collection amount to be distillated and hydrochloride waste add volume ratio for (3 ~ 4) ︰ 10, stop distillation;
Step 2. in evaporated mother liquor, add oxygenant sodium chlorate, stablizer sodium phosphate or SODIUM PHOSPHATE, MONOBASIC under agitation, carry out at normal temperatures and pressures being oxidized, polyreaction;
In hydrochloric acid pickling waste liquor evaporated mother liquor after processing to step one, thin up prevents crystallization, in hydrochloric acid pickling waste liquor evaporated mother liquor, stablizer sodium phosphate or SODIUM PHOSPHATE, MONOBASIC is added under constantly stirring, in stablizer and hydrochloric acid pickling waste liquor, the mol ratio of iron level is 0.075-0.1, drip mode with solution and add oxygenant sodium chlorate, in sodium chlorate and hydrochloric acid pickling waste liquor, the mol ratio of iron level is 0.18, and controlling mixed solution oxidation time is 1h;
Step 3. slaking
Mixed solution in step 2 is left standstill slaking 24h, namely obtains liquid polymerization calcium iron, magnesium iron compound coagulant.
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| CN103938216B (en) * | 2014-05-08 | 2016-03-30 | 武汉钢铁(集团)公司 | The reuse method of metallurgical industry alkali cleaning removal of impurities waste water |
| CN105293439A (en) * | 2015-10-27 | 2016-02-03 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for recycling hydrochloric acid from titanium slag leaching waste fluid |
| CN107352778A (en) * | 2017-07-24 | 2017-11-17 | 淄博明奇净水材料有限公司 | A kind of sludge drainage bactericide |
| CN112978994A (en) * | 2021-02-25 | 2021-06-18 | 南京农业大学 | Method for treating stainless steel pickling wastewater and synchronously synthesizing secondary iron mineral |
| CN114671421B (en) * | 2022-04-29 | 2023-10-10 | 中国科学院过程工程研究所 | Method and system for preparing ferric phosphate by utilizing ferric acid pickling waste liquid resource |
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