CN103288232A - 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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- CN103288232A CN103288232A CN2013101335173A CN201310133517A CN103288232A CN 103288232 A CN103288232 A CN 103288232A CN 2013101335173 A CN2013101335173 A CN 2013101335173A CN 201310133517 A CN201310133517 A CN 201310133517A CN 103288232 A CN103288232 A CN 103288232A
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- hydrochloric acid
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- pickling waste
- acid pickling
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 334
- 239000002699 waste material Substances 0.000 title claims abstract description 140
- 238000005554 pickling Methods 0.000 title claims abstract description 127
- 239000007788 liquid Substances 0.000 title claims abstract description 65
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 31
- 239000010959 steel Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000004821 distillation Methods 0.000 claims abstract description 94
- 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 83
- 229910052742 iron Inorganic materials 0.000 claims description 42
- 238000006116 polymerization reaction Methods 0.000 claims description 29
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 28
- ANFIEGWCRSNVFS-UHFFFAOYSA-N [Na].OCl(=O)=O Chemical compound [Na].OCl(=O)=O ANFIEGWCRSNVFS-UHFFFAOYSA-N 0.000 claims description 28
- 239000011259 mixed solution Substances 0.000 claims description 28
- 230000003647 oxidation Effects 0.000 claims description 28
- 238000007254 oxidation reaction Methods 0.000 claims description 28
- 238000005406 washing Methods 0.000 claims description 25
- 229940045641 monobasic sodium phosphate Drugs 0.000 claims description 20
- 238000002425 crystallisation Methods 0.000 claims description 17
- 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
- 239000000243 solution Substances 0.000 claims description 14
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 239000007792 gaseous phase Substances 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 5
- 241000282326 Felis catus Species 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 abstract description 18
- 238000011084 recovery Methods 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract 2
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 239000003381 stabilizer Substances 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 30
- 239000002351 wastewater Substances 0.000 description 24
- 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
- 150000003839 salts Chemical class 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- 235000021110 pickles Nutrition 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000004140 cleaning Methods 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
- 239000012528 membrane Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 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
- 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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 to rise, downstream industries such as building machinery keep increasing, the steel processing industry can be further developed.Acid cleaning process is important in a steel course of processing link, and metal pickling discharging of waste liquid amount also will promote to some extent.Hydrochloric acid, sulfuric acid are as topmost clean-out system in the acid cleaning process, and chlorohydric acid pickling makes basic iron loss will be widely used less than sulfuric acid because of the effect of peeling off, so present acid washing rolled steel is substantially based on chlorohydric acid pickling technology.Contain a large amount of residual hydrochloric acid and metallic iron ion in the steel hydrochloric acid pickling waste liquor, being classified as Hazardous wastes both at home and abroad at present manages, and strict restriction has been done in residual iron discharging, be strict controlled in below the 10mg/L as the total iron emission standard of America and Europe, China Zhejiang Province provincial standard " pickling waste waters discharges total concentration of iron limit value " (DB 33/844-2011) also strict regulation total iron emission limit set at 2-10mg/L, carried out 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 will not cause very big harm generally at 50-150g/L to water ecological environment if do not add the random discharging of processing.
Spent pickle liquor treatment process commonly used at present has traditional neutralisation and application technology as the second resource.The tradition neutralisation is owing to the processing cost height, and drawbacks such as precipitating sludge disposal difficulty are eliminated by most of enterprises.And 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 used by the industrialization of large-scale iron and steel enterprise owing to reclaim hydrochloric acid and the economic worth height of brown iron oxide, but this method front-end investment is big, equipment and processing requirement strictness.Evaporative crystallization method processing cost is low, but the residual iron level of exterior liquid can't be up to standard after the crystallization treatment.The utilization of ion exchange method and membrane processing method also is subjected to the restriction of high density iron level, easily causes resin and film to pollute.The evaporative distillation method has advantages such as equipment is simple, processing cost is low, favored by small-sized iron and steel enterprise, but during to the hydrochloride waste evaporative distillation, can run into hydrochloric acid-water azeotrope obstacle, and it is not high to cause reclaiming concentration of hydrochloric acid, reclaims shortcomings such as not thorough.
The distillation with adding salts technology can change hydrochloric acid-aqueous vapor liquid profile of equilibrium, improves and reclaims concentration of hydrochloric acid.Simultaneously, a large amount of ferrous components in the waste liquid can be used for preparing liquid coagulating agent, and the adding of salt can improve the polymerization degree of iron, improves 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;
Be provided with whipping appts in the 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 cat head 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 that reclaims the 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 that absorbs flow container by pump, and the input of column pipeline links to each other 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, this method may further comprise the steps:
Step 1. in hydrochloric acid pickling waste liquor, add solid calcium chloride or magnesium chloride, under normal pressure, hydrochloric acid pickling waste liquor is carried out the batch distillation operation;
Get hydrochloric acid pickling waste liquor and place still kettle, add solid calcium chloride or magnesium chloride, the add-on of solid is 0.75-1.25mol/L.Add thermal distillation, when waiting to distillate phlegma collecting amount and hydrochloride waste adding volume ratio for (3～4) ︰ 10, stop distillation;
Step 2. under agitation condition, in the distillation mother liquor, add oxygenant chloric acid sodium, stablizer sodium phosphate or SODIUM PHOSPHATE, MONOBASIC, carry out oxidation, polyreaction at normal temperatures and pressures;
Thin up prevents that crystallization from separating out in the hydrochloric acid pickling waste liquor distillation mother liquor after handling to step 1, under constantly stirring, in hydrochloric acid pickling waste liquor distillation mother liquor, add stablizer sodium phosphate or SODIUM PHOSPHATE, MONOBASIC, the mol ratio of iron level is 0.075-0.1 in stablizer and the hydrochloric acid pickling waste liquor, add oxygenant chloric acid sodium with the drips of solution add mode, sodium chlorate, the mol ratio of iron level is 0.18 in sodium chlorate and the hydrochloric acid pickling waste liquor, and control mixed solution oxidation time is 1 h;
Mixed solution in the 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 the distillation with adding salts technology, and adding calcium chloride, magnesium chloride can change the vapor liquid equilibrium curve of hydrochloric acid-water, improve 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 be brought into play charge neutrality and the precipitation net is caught effect, improve coagulation effect.It is simple that the present invention has production technique, and the advantage of less investment realizes the poly-iron coagulating agent of salt acid recovery and preparation synchronously, can realize the zero release of acid washing rolled steel waste liquid.The new composite coagulant of the hydrochloric acid of Hui Shouing and preparation all has higher economic value simultaneously, can reach the purpose of resource reusing, the treatment of wastes with processes of wastes against one another, has environmental value and economic worth concurrently.
Description of drawings
Fig. 1 is device synoptic 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;
Be provided with whipping appts in the 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 cat head 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 that reclaims the 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 that absorbs flow container by pump, and the input of column pipeline links to each other with heat exchanger respectively with distillation tower gaseous phase outlet pipeline.
Embodiment 1
Step 1. in hydrochloric acid pickling waste liquor, add solid calcium chloride, under normal pressure, hydrochloric acid pickling waste liquor is carried out the batch distillation operation;
Get hydrochloric acid pickling waste liquor and place still kettle, add solid calcium chloride, the add-on of solid is 1mol/L.Add thermal distillation, wait to distillate phlegma collecting amount and hydrochloride waste and add volume ratio when being 3 ︰ 10, stop distillation;
Step 2. under agitation condition, in the distillation mother liquor, add oxygenant chloric acid sodium, stablizer sodium phosphate, carry out oxidation, polyreaction at normal temperatures and pressures;
Thin up prevents that crystallization from separating out in the hydrochloric acid pickling waste liquor distillation mother liquor after handling to step 1, under constantly stirring, in hydrochloric acid pickling waste liquor distillation mother liquor, add the stablizer sodium phosphate, the mol ratio of iron level is 0.075 in stablizer and the hydrochloric acid pickling waste liquor, add oxygenant chloric acid sodium with the drips of solution add mode, sodium chlorate, the mol ratio of iron level is 0.18 in sodium chlorate and the hydrochloric acid pickling waste liquor, and control mixed solution oxidation time is 1 h;
Mixed solution in the step 2 is left standstill slaking 24 h, namely obtain liquid calcium iron compound coagulant.
Obtain reuse hydrochloric acid and chocolate liquid polymerization calcium iron compound coagulant product by this embodiment.Reclaim 22.3% hydrochloric acid 300kg/t, meet the requirement of acid washing rolled steel technology clean-out system.The polymerization calcium iron compound coagulant for preparing is respectively 95%, 85%, 60% to the direct black dyes that contains 50mg/L, active green dye, acid blue dye simulated wastewater chroma removal rate, is that the chroma removal rate of 500 actual dying is 85% to colourity.
Embodiment 2
Step 1. in hydrochloric acid pickling waste liquor, add solid calcium chloride, under normal pressure, hydrochloric acid pickling waste liquor is carried out the batch distillation operation;
Get hydrochloric acid pickling waste liquor and place still kettle, add solid calcium chloride, the add-on of solid is 0.75mol/L.Add thermal distillation, wait to distillate phlegma collecting amount and hydrochloride waste and add volume ratio when being 3.5 ︰ 10, stop distillation;
Step 2. under agitation condition, in the distillation mother liquor, add oxygenant chloric acid sodium, stablizer sodium phosphate, carry out oxidation, polyreaction at normal temperatures and pressures;
Thin up prevents that crystallization from separating out in the hydrochloric acid pickling waste liquor distillation mother liquor after handling to step 1, under constantly stirring, in hydrochloric acid pickling waste liquor distillation mother liquor, add the stablizer sodium phosphate, the mol ratio of iron level is 0.09 in stablizer and the hydrochloric acid pickling waste liquor, add oxygenant chloric acid sodium with the drips of solution add mode, sodium chlorate, the mol ratio of iron level is 0.18 in sodium chlorate and the hydrochloric acid pickling waste liquor, and control mixed solution oxidation time is 1 h;
Mixed solution in the step 2 is left standstill slaking 24 h, namely obtain liquid calcium iron compound coagulant.
Pickling waste waters by this embodiment 10% content of hydrochloric acid is handled, and obtains reuse hydrochloric acid and chocolate liquid polymerization calcium iron compound coagulant product.Reclaim 21.0% hydrochloric acid 350kg/t, meet the requirement that the steel ferrous acid is washed the technology clean-out system.The polymerization calcium iron compound coagulant for preparing is respectively 93%, 85%, 50% to the direct black dyes that contains 50mg/L, active green dye, acid blue dye simulated wastewater chroma removal rate, is that the chroma removal rate of 500 actual dying is 80% to colourity.
Step 1. in hydrochloric acid pickling waste liquor, add solid calcium chloride, under normal pressure, hydrochloric acid pickling waste liquor is carried out the batch distillation operation;
Get hydrochloric acid pickling waste liquor and place still kettle, add solid calcium chloride, the add-on of solid is 1.25mol/L.Add thermal distillation, wait to distillate phlegma collecting amount and hydrochloride waste and add volume ratio when being 4 ︰ 10, stop distillation;
Step 2. under agitation condition, in the distillation mother liquor, add oxygenant chloric acid sodium, stablizer sodium phosphate, carry out oxidation, polyreaction at normal temperatures and pressures;
Thin up prevents that crystallization from separating out in the hydrochloric acid pickling waste liquor distillation mother liquor after handling to step 1, under constantly stirring, in hydrochloric acid pickling waste liquor distillation mother liquor, add the stablizer sodium phosphate, the mol ratio of iron level is 0.1 in stablizer and the hydrochloric acid pickling waste liquor, add oxygenant chloric acid sodium with the drips of solution add mode, sodium chlorate, the mol ratio of iron level is 0.18 in sodium chlorate and the hydrochloric acid pickling waste liquor, and control mixed solution oxidation time is 1 h;
Mixed solution in the step 2 is left standstill slaking 24 h, namely obtain liquid calcium iron compound coagulant.
By this embodiment the pickling waste waters of 10% content of hydrochloric acid is handled, obtained reuse hydrochloric acid and chocolate liquid polymerization calcium iron compound coagulant product.Reclaim 21.8% hydrochloric acid 400kg/t, meet the requirement of acid washing rolled steel technology clean-out system.The polymerization magnesium iron compound coagulant for preparing is respectively 93%, 83%, 55% to the direct black dyes that contains 50mg/L, active green dye, acid blue dye simulated wastewater chroma removal rate, is that the chroma removal rate of 500 actual dying is 85% to colourity.
Embodiment 4
Step 1. in hydrochloric acid pickling waste liquor, add solid calcium chloride, under normal pressure, hydrochloric acid pickling waste liquor is carried out the batch distillation operation;
Get hydrochloric acid pickling waste liquor and place still kettle, add solid calcium chloride, the add-on of solid is 0.75mol/L.Add thermal distillation, wait to distillate phlegma collecting amount and hydrochloride waste and add volume ratio when being 3 ︰ 10, stop distillation;
Step 2. under agitation condition, in the distillation mother liquor, add oxygenant chloric acid sodium, stablizer SODIUM PHOSPHATE, MONOBASIC, carry out oxidation, polyreaction at normal temperatures and pressures;
Thin up prevents that crystallization from separating out in the hydrochloric acid pickling waste liquor distillation mother liquor after handling to step 1, under constantly stirring, in hydrochloric acid pickling waste liquor distillation mother liquor, add the stablizer SODIUM PHOSPHATE, MONOBASIC, the mol ratio of iron level is 0.075 in stablizer and the hydrochloric acid pickling waste liquor, add oxygenant chloric acid sodium with the drips of solution add mode, sodium chlorate, the mol ratio of iron level is 0.18 in sodium chlorate and the hydrochloric acid pickling waste liquor, and control mixed solution oxidation time is 1 h;
Mixed solution in the step 2 is left standstill slaking 24 h, namely obtain liquid calcium iron compound coagulant.
Pickling waste waters by this embodiment 10% content of hydrochloric acid is handled, and obtains reuse hydrochloric acid and chocolate liquid polymerization calcium iron compound coagulant product.Reclaim 22.3% hydrochloric acid 300kg/t, meet the requirement of acid washing rolled steel technology clean-out system.The polymerization calcium iron compound coagulant for preparing is respectively 92%, 86%, 53% to the direct black dyes that contains 50mg/L, active green dye, acid blue dye simulated wastewater chroma removal rate, is that the chroma removal rate of 500 actual dying is 83% to colourity.
Embodiment 5
Step 1. in hydrochloric acid pickling waste liquor, add solid calcium chloride, under normal pressure, hydrochloric acid pickling waste liquor is carried out the batch distillation operation;
Get hydrochloric acid pickling waste liquor and place still kettle, add solid calcium chloride, the add-on of solid is 1mol/L.Add thermal distillation, wait to distillate phlegma collecting amount and hydrochloride waste and add volume ratio when being 3.5 ︰ 10, stop distillation;
Step 2. under agitation condition, in the distillation mother liquor, add oxygenant chloric acid sodium, stablizer SODIUM PHOSPHATE, MONOBASIC, carry out oxidation, polyreaction at normal temperatures and pressures;
Thin up prevents that crystallization from separating out in the hydrochloric acid pickling waste liquor distillation mother liquor after handling to step 1, under constantly stirring, in hydrochloric acid pickling waste liquor distillation mother liquor, add the stablizer SODIUM PHOSPHATE, MONOBASIC, the mol ratio of iron level is 0.08 in stablizer and the hydrochloric acid pickling waste liquor, add oxygenant chloric acid sodium with the drips of solution add mode, sodium chlorate, the mol ratio of iron level is 0.18 in sodium chlorate and the hydrochloric acid pickling waste liquor, and control mixed solution oxidation time is 1 h;
Mixed solution in the step 2 is left standstill slaking 24 h, namely obtain liquid calcium iron compound coagulant.
Pickling waste waters by this embodiment 10% content of hydrochloric acid is handled, and obtains reuse hydrochloric acid and chocolate liquid polymerization calcium iron compound coagulant product.Reclaim 22.8% hydrochloric acid 350kg/t, meet the requirement of acid washing rolled steel technology clean-out system.The polymerization calcium iron compound coagulant for preparing is respectively 94%, 83%, 52% to the direct black dyes that contains 50mg/L, active green dye, acid blue dye simulated wastewater chroma removal rate, is that the chroma removal rate of 500 actual dying is 85% to colourity.
Embodiment 6
Step 1. in hydrochloric acid pickling waste liquor, add solid calcium chloride, under normal pressure, hydrochloric acid pickling waste liquor is carried out the batch distillation operation;
Get hydrochloric acid pickling waste liquor and place still kettle, add solid calcium chloride, the add-on of solid is 1.25mol/L.Add thermal distillation, wait to distillate phlegma collecting amount and hydrochloride waste and add volume ratio when being 4 ︰ 10, stop distillation;
Step 2. under agitation condition, in the distillation mother liquor, add oxygenant chloric acid sodium, stablizer SODIUM PHOSPHATE, MONOBASIC, carry out oxidation, polyreaction at normal temperatures and pressures;
Thin up prevents that crystallization from separating out in the hydrochloric acid pickling waste liquor distillation mother liquor after handling to step 1, under constantly stirring, in hydrochloric acid pickling waste liquor distillation mother liquor, add the stablizer SODIUM PHOSPHATE, MONOBASIC, the mol ratio of iron level is 0.1 in stablizer and the hydrochloric acid pickling waste liquor, add oxygenant chloric acid sodium with the drips of solution add mode, sodium chlorate, the mol ratio of iron level is 0.18 in sodium chlorate and the hydrochloric acid pickling waste liquor, and control mixed solution oxidation time is 1 h;
Mixed solution in the step 2 is left standstill slaking 24 h, namely obtain liquid calcium iron compound coagulant.
Pickling waste waters by this embodiment 10% content of hydrochloric acid is handled, and obtains reuse hydrochloric acid and chocolate liquid polymerization calcium iron compound coagulant product.Reclaim 21.2% hydrochloric acid 400kg/t, meet the requirement of acid washing rolled steel technology clean-out system.The polymerization calcium iron compound coagulant for preparing is respectively 91%, 82%, 50% to the direct black dyes that contains 50mg/L, active green dye, acid blue dye simulated wastewater chroma removal rate, is that the chroma removal rate of 500 actual dying is 82% to colourity.
Embodiment 7
Step 1. in hydrochloric acid pickling waste liquor, add the solid magnesium chloride, under normal pressure, hydrochloric acid pickling waste liquor is carried out the batch distillation operation;
Get hydrochloric acid pickling waste liquor and place still kettle, add the solid magnesium chloride, the add-on of solid is 0.75mol/L.Add thermal distillation, wait to distillate phlegma collecting amount and hydrochloride waste and add volume ratio when being 3 ︰ 10, stop distillation;
Step 2. under agitation condition, in the distillation mother liquor, add oxygenant chloric acid sodium, stablizer sodium phosphate, carry out oxidation, polyreaction at normal temperatures and pressures;
Thin up prevents that crystallization from separating out in the hydrochloric acid pickling waste liquor distillation mother liquor after handling to step 1, under constantly stirring, in hydrochloric acid pickling waste liquor distillation mother liquor, add the stablizer sodium phosphate, the mol ratio of iron level is 0.075 in stablizer and the hydrochloric acid pickling waste liquor, add oxygenant chloric acid sodium with the drips of solution add mode, sodium chlorate, the mol ratio of iron level is 0.18 in sodium chlorate and the hydrochloric acid pickling waste liquor, and control mixed solution oxidation time is 1 h;
Mixed solution in the step 2 is left standstill slaking 24 h, namely obtain liquid magnesium iron compound coagulant.
By this embodiment the pickling waste waters of 10% content of hydrochloric acid is handled, obtained reuse hydrochloric acid and chocolate liquid polymerization calcium iron compound coagulant product.Reclaim 22.8% hydrochloric acid 400kg/t, met the requirement of acid washing rolled steel technology clean-out system.The polymerization magnesium iron compound coagulant for preparing is respectively 93%, 83%, 55% to the direct black dyes that contains 50mg/L, active green dye, acid blue dye simulated wastewater chroma removal rate, is that the chroma removal rate of 500 actual dying is 85% to colourity.
Step 1. in hydrochloric acid pickling waste liquor, add the solid magnesium chloride, under normal pressure, hydrochloric acid pickling waste liquor is carried out the batch distillation operation;
Get hydrochloric acid pickling waste liquor and place still kettle, add the solid magnesium chloride, the add-on of solid is 1mol/L.Add thermal distillation, wait to distillate phlegma collecting amount and hydrochloride waste and add volume ratio when being 3.5 ︰ 10, stop distillation;
Step 2. under agitation condition, in the distillation mother liquor, add oxygenant chloric acid sodium, stablizer sodium phosphate, carry out oxidation, polyreaction at normal temperatures and pressures;
Thin up prevents that crystallization from separating out in the hydrochloric acid pickling waste liquor distillation mother liquor after handling to step 1, under constantly stirring, add the stablizer sodium phosphate in the hydrochloric acid pickling waste liquor distillation mother liquor, the mol ratio of iron level is 0.09 in stablizer and the hydrochloric acid pickling waste liquor, add oxygenant chloric acid sodium with the drips of solution add mode, sodium chlorate, the mol ratio of iron level is 0.18 in sodium chlorate and the hydrochloric acid pickling waste liquor, and control mixed solution oxidation time is 1 h;
Mixed solution in the step 2 is left standstill slaking 24 h, namely obtain liquid magnesium iron compound coagulant.
By this embodiment the pickling waste waters of 10% content of hydrochloric acid is handled, obtained reuse hydrochloric acid and chocolate liquid polymerization calcium iron compound coagulant product.Reclaim 22.5% hydrochloric acid 300kg/t, meet the requirement of acid washing rolled steel technology clean-out system.The polymerization magnesium iron compound coagulant for preparing is respectively 91%, 81%, 55% to the direct black dyes that contains 50mg/L, active green dye, acid blue dye simulated wastewater chroma removal rate, is that the chroma removal rate of 500 actual dying is 82% to colourity.
Embodiment 9
Step 1. in hydrochloric acid pickling waste liquor, add the solid magnesium chloride, under normal pressure, hydrochloric acid pickling waste liquor is carried out the batch distillation operation;
Get hydrochloric acid pickling waste liquor and place still kettle, add the solid magnesium chloride, the add-on of solid is 1.25mol/L.Add thermal distillation, wait to distillate phlegma collecting amount and hydrochloride waste and add volume ratio when being 4 ︰ 10, stop distillation;
Step 2. under agitation condition, in the distillation mother liquor, add oxygenant chloric acid sodium, stablizer sodium phosphate, carry out oxidation, polyreaction at normal temperatures and pressures;
Thin up prevents that crystallization from separating out in the hydrochloric acid pickling waste liquor distillation mother liquor after handling to step 1, under constantly stirring, in hydrochloric acid pickling waste liquor distillation mother liquor, add the stablizer sodium phosphate, the mol ratio of iron level is 0.1 in stablizer and the hydrochloric acid pickling waste liquor, add oxygenant chloric acid sodium with the drips of solution add mode, sodium chlorate, the mol ratio of iron level is 0.18 in sodium chlorate and the hydrochloric acid pickling waste liquor, and control mixed solution oxidation time is 1 h;
Mixed solution in the step 2 is left standstill slaking 24 h, namely obtain liquid magnesium iron compound coagulant.
By this embodiment the pickling waste waters of 10% content of hydrochloric acid is handled, obtained reuse hydrochloric acid and chocolate liquid polymerization calcium iron compound coagulant product.Reclaim 20.4% hydrochloric acid 400kg/t, meet the requirement of acid washing rolled steel technology clean-out system.The polymerization magnesium iron compound coagulant for preparing is respectively 92%, 81%, 53% to the direct black dyes that contains 50mg/L, active green dye, acid blue dye simulated wastewater chroma removal rate, is that the chroma removal rate of 500 actual dying is 82% to colourity.
Embodiment 10
Step 1. in hydrochloric acid pickling waste liquor, add the solid magnesium chloride, under normal pressure, hydrochloric acid pickling waste liquor is carried out the batch distillation operation;
Get hydrochloric acid pickling waste liquor and place still kettle, add the solid magnesium chloride, the add-on of solid is 1.25mol/L.Add thermal distillation, wait to distillate phlegma collecting amount and hydrochloride waste and add volume ratio when being 4 ︰ 10, stop distillation;
Step 2. under agitation condition, in the distillation mother liquor, add oxygenant chloric acid sodium, stablizer SODIUM PHOSPHATE, MONOBASIC, carry out oxidation, polyreaction at normal temperatures and pressures;
Thin up prevents that crystallization from separating out in the hydrochloric acid pickling waste liquor distillation mother liquor after handling to step 1, under constantly stirring, in hydrochloric acid pickling waste liquor distillation mother liquor, add the stablizer SODIUM PHOSPHATE, MONOBASIC, the mol ratio of iron level is 0.075 in stablizer and the hydrochloric acid pickling waste liquor, add oxygenant chloric acid sodium with the drips of solution add mode, sodium chlorate, the mol ratio of iron level is 0.18 in sodium chlorate and the hydrochloric acid pickling waste liquor, and control mixed solution oxidation time is 1 h;
Mixed solution in the step 2 is left standstill slaking 24 h, namely obtain liquid magnesium iron compound coagulant.
By this embodiment the pickling waste waters of 10% content of hydrochloric acid is handled, obtained reuse hydrochloric acid and chocolate liquid polymerization calcium iron compound coagulant product.Reclaim 20.8% hydrochloric acid 400kg/t, meet the requirement of acid washing rolled steel technology clean-out system.The polymerization magnesium iron compound coagulant for preparing is respectively 91%, 81%, 54% to the direct black dyes that contains 50mg/L, active green dye, acid blue dye simulated wastewater chroma removal rate, is that the chroma removal rate of 500 actual dying is 83% to colourity.
Embodiment 11
Step 1. in hydrochloric acid pickling waste liquor, add the solid magnesium chloride, under normal pressure, hydrochloric acid pickling waste liquor is carried out the batch distillation operation;
Get hydrochloric acid pickling waste liquor and place still kettle, add the solid magnesium chloride, the add-on of solid is 1mol/L.Add thermal distillation, wait to distillate phlegma collecting amount and hydrochloride waste and add volume ratio when being 3.5 ︰ 10, stop distillation;
Step 2. under agitation condition, in the distillation mother liquor, add oxygenant chloric acid sodium, stablizer SODIUM PHOSPHATE, MONOBASIC, carry out oxidation, polyreaction at normal temperatures and pressures;
Thin up prevents that crystallization from separating out in the hydrochloric acid pickling waste liquor distillation mother liquor after handling to step 1, under constantly stirring, in hydrochloric acid pickling waste liquor distillation mother liquor, add the stablizer SODIUM PHOSPHATE, MONOBASIC, the mol ratio of iron level is 0.1 in stablizer and the hydrochloric acid pickling waste liquor, add oxygenant chloric acid sodium with the drips of solution add mode, sodium chlorate, the mol ratio of iron level is 0.18 in sodium chlorate and the hydrochloric acid pickling waste liquor, and control mixed solution oxidation time is 1 h;
Mixed solution in the step 2 is left standstill slaking 24 h, namely obtain liquid magnesium iron compound coagulant.
By this embodiment the pickling waste waters of 10% content of hydrochloric acid is handled, obtained reuse hydrochloric acid and chocolate liquid polymerization calcium iron compound coagulant product.Reclaim 22.5% hydrochloric acid 350kg/t, meet the requirement of acid washing rolled steel technology clean-out system.The polymerization magnesium iron compound coagulant for preparing is respectively 93%, 81%, 53% to the direct black dyes that contains 50mg/L, active green dye, acid blue dye simulated wastewater chroma removal rate, is that the chroma removal rate of 500 actual dying is 81% to colourity.
Embodiment 12
Step 1. in hydrochloric acid pickling waste liquor, add the solid magnesium chloride, under normal pressure, hydrochloric acid pickling waste liquor is carried out the batch distillation operation;
Get hydrochloric acid pickling waste liquor and place still kettle, add the solid magnesium chloride, the add-on of solid is 0.75mol/L.Add thermal distillation, wait to distillate phlegma collecting amount and hydrochloride waste and add volume ratio when being 3 ︰ 10, stop distillation;
Step 2. under agitation condition, in the distillation mother liquor, add oxygenant chloric acid sodium, stablizer SODIUM PHOSPHATE, MONOBASIC, carry out oxidation, polyreaction at normal temperatures and pressures;
Thin up prevents that crystallization from separating out in the hydrochloric acid pickling waste liquor distillation mother liquor after handling to step 1, under constantly stirring, in hydrochloric acid pickling waste liquor distillation mother liquor, add the stablizer SODIUM PHOSPHATE, MONOBASIC, the mol ratio of iron level is 0.09 in stablizer and the hydrochloric acid pickling waste liquor, add oxygenant chloric acid sodium with the drips of solution add mode, sodium chlorate, the mol ratio of iron level is 0.18 in sodium chlorate and the hydrochloric acid pickling waste liquor, and control mixed solution oxidation time is 1 h;
Mixed solution in the step 2 is left standstill slaking 24 h, namely obtain liquid magnesium iron compound coagulant.
By this embodiment the pickling waste waters of 10% content of hydrochloric acid is handled, obtained reuse hydrochloric acid and chocolate liquid polymerization calcium iron compound coagulant product.Reclaim 21.5% hydrochloric acid 300kg/t, meet the requirement of acid washing rolled steel technology clean-out system.The polymerization magnesium iron compound coagulant for preparing is respectively 92%, 82%, 53% to the direct black dyes that contains 50mg/L, active green dye, acid blue dye simulated wastewater chroma removal rate, is that the chroma removal rate of 500 actual dying is 84% to colourity.
Claims (2)
1. the device of a steel hydrochloric acid pickling waste liquor 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;
It is characterized in that: be provided with whipping appts in the 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 cat head 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 that reclaims the 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 that absorbs flow container by pump, and the input of column pipeline links to each other with heat exchanger respectively with distillation tower gaseous phase outlet pipeline.
2. steel resource treatment method for hydrochloric acid pickling waste liquor is characterized in that this method may further comprise the steps:
Step 1. in hydrochloric acid pickling waste liquor, add solid calcium chloride or magnesium chloride, under normal pressure, hydrochloric acid pickling waste liquor is carried out the batch distillation operation;
Get hydrochloric acid pickling waste liquor and place still kettle, add solid calcium chloride or magnesium chloride, the add-on of solid is 0.75-1.25mol/L; Add thermal distillation, when waiting to distillate phlegma collecting amount and hydrochloride waste adding volume ratio for (3～4) ︰ 10, stop distillation;
Step 2. under agitation condition, in the distillation mother liquor, add oxygenant chloric acid sodium, stablizer sodium phosphate or SODIUM PHOSPHATE, MONOBASIC, carry out oxidation, polyreaction at normal temperatures and pressures;
Thin up prevents that crystallization from separating out in the hydrochloric acid pickling waste liquor distillation mother liquor after handling to step 1, under constantly stirring, in hydrochloric acid pickling waste liquor distillation mother liquor, add stablizer sodium phosphate or SODIUM PHOSPHATE, MONOBASIC, the mol ratio of iron level is 0.075-0.1 in stablizer and the hydrochloric acid pickling waste liquor, add oxygenant chloric acid sodium with the drips of solution add mode, sodium chlorate, the mol ratio of iron level is 0.18 in sodium chlorate and the hydrochloric acid pickling waste liquor, and control mixed solution oxidation time is 1 h;
Step 3. slaking
Mixed solution in the step 2 is left standstill slaking 24 h, namely obtain liquid polymerization calcium iron, magnesium iron compound coagulant.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103938216A (en) * | 2014-05-08 | 2014-07-23 | 武汉钢铁(集团)公司 | Reutilization method of metallurgical-industry alkali washing impurity-removal wastewater |
| 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 |
| CN114671421A (en) * | 2022-04-29 | 2022-06-28 | 中国科学院过程工程研究所 | Method and system for preparing iron phosphate by recycling iron-containing hydrochloric acid pickling waste liquid |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1373243A (en) * | 2001-12-31 | 2002-10-09 | 南昌大学 | Process for treating waste pickling liquid of hydrochloric acid by negative-pressure external-circulation evaporation-concentrating crystallization method |
| CN201433147Y (en) * | 2009-06-03 | 2010-03-31 | 江阴市宇洁环保科技有限公司 | Comprehensive recycling device of hydrochloric acid waste liquor |
| CN102351252A (en) * | 2011-07-06 | 2012-02-15 | 福建方明环保科技有限公司 | Method for producing flocculant utilizing waste steel pickler |
| CN102417162A (en) * | 2011-08-29 | 2012-04-18 | 浙江金壳生物化学有限公司 | Recycling method of hydrochloric acid-acetic acid waste liquid |
| CN203244811U (en) * | 2013-04-17 | 2013-10-23 | 浙江大学 | Device for resourceful treatment of steel hydrochloric acid pickle liquor |
-
2013
- 2013-04-17 CN CN201310133517.3A patent/CN103288232B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1373243A (en) * | 2001-12-31 | 2002-10-09 | 南昌大学 | Process for treating waste pickling liquid of hydrochloric acid by negative-pressure external-circulation evaporation-concentrating crystallization method |
| CN201433147Y (en) * | 2009-06-03 | 2010-03-31 | 江阴市宇洁环保科技有限公司 | Comprehensive recycling device of hydrochloric acid waste liquor |
| CN102351252A (en) * | 2011-07-06 | 2012-02-15 | 福建方明环保科技有限公司 | Method for producing flocculant utilizing waste steel pickler |
| CN102417162A (en) * | 2011-08-29 | 2012-04-18 | 浙江金壳生物化学有限公司 | Recycling method of hydrochloric acid-acetic acid waste liquid |
| CN203244811U (en) * | 2013-04-17 | 2013-10-23 | 浙江大学 | Device for resourceful treatment of steel hydrochloric acid pickle liquor |
Non-Patent Citations (1)
| Title |
|---|
| 隋洁等: "钢铁酸洗废液的资源化处理技术", 《工业用水与废水》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103938216A (en) * | 2014-05-08 | 2014-07-23 | 武汉钢铁(集团)公司 | Reutilization method of metallurgical-industry alkali washing impurity-removal wastewater |
| 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 |
| CN114671421A (en) * | 2022-04-29 | 2022-06-28 | 中国科学院过程工程研究所 | Method and system for preparing iron phosphate by recycling iron-containing hydrochloric acid pickling waste liquid |
| 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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