CN109735850A - A kind of method of pickling iron and steel and water circulation use - Google Patents
A kind of method of pickling iron and steel and water circulation use Download PDFInfo
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- CN109735850A CN109735850A CN201811625290.3A CN201811625290A CN109735850A CN 109735850 A CN109735850 A CN 109735850A CN 201811625290 A CN201811625290 A CN 201811625290A CN 109735850 A CN109735850 A CN 109735850A
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- acid
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- 238000005554 pickling Methods 0.000 title claims abstract description 88
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910001868 water Inorganic materials 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 49
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 19
- 239000010959 steel Substances 0.000 title claims abstract description 19
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 82
- 238000004519 manufacturing process Methods 0.000 claims abstract description 22
- 239000010935 stainless steel Substances 0.000 claims abstract description 15
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 15
- 238000002161 passivation Methods 0.000 claims abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 94
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 21
- 238000005260 corrosion Methods 0.000 claims description 17
- 230000007797 corrosion Effects 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 11
- 239000010802 sludge Substances 0.000 claims description 10
- -1 m-nitro, m-nitrobenzene sodium Chemical compound 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 9
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 8
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 8
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000004571 lime Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims description 6
- 238000005273 aeration Methods 0.000 claims description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 6
- 238000001223 reverse osmosis Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 239000008235 industrial water Substances 0.000 claims description 5
- 239000005416 organic matter Substances 0.000 claims description 5
- 238000000108 ultra-filtration Methods 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- 229940031098 ethanolamine Drugs 0.000 claims description 4
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 4
- 229960004011 methenamine Drugs 0.000 claims description 4
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 3
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 3
- GADGMZDHLQLZRI-VIFPVBQESA-N N-(4-aminobenzoyl)-L-glutamic acid Chemical compound NC1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 GADGMZDHLQLZRI-VIFPVBQESA-N 0.000 claims description 3
- 229960004050 aminobenzoic acid Drugs 0.000 claims description 3
- 235000013922 glutamic acid Nutrition 0.000 claims description 3
- 239000004220 glutamic acid Substances 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 230000008929 regeneration Effects 0.000 claims description 3
- 238000011069 regeneration method Methods 0.000 claims description 3
- 239000000837 restrainer Substances 0.000 claims description 3
- 239000011775 sodium fluoride Substances 0.000 claims description 3
- 235000013024 sodium fluoride Nutrition 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 235000010288 sodium nitrite Nutrition 0.000 claims description 3
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012964 benzotriazole Substances 0.000 claims description 2
- 238000011953 bioanalysis Methods 0.000 claims description 2
- 230000003851 biochemical process Effects 0.000 claims description 2
- 238000011109 contamination Methods 0.000 claims description 2
- 238000001514 detection method Methods 0.000 claims description 2
- 238000012554 master batch record Methods 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 238000006065 biodegradation reaction Methods 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000005406 washing Methods 0.000 abstract description 15
- 229910000975 Carbon steel Inorganic materials 0.000 abstract description 14
- 239000010962 carbon steel Substances 0.000 abstract description 14
- 238000004064 recycling Methods 0.000 abstract description 9
- 239000010865 sewage Substances 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 239000003595 mist Substances 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 3
- 239000008237 rinsing water Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 56
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 238000011084 recovery Methods 0.000 description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 239000010963 304 stainless steel Substances 0.000 description 5
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000013589 supplement Substances 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 150000003852 triazoles Chemical class 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 244000061176 Nicotiana tabacum Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
It is passivated field in carbon steel surface acid-washing and acid-washing stainless steel, there are several environmental issues that must face: 1, production process generates a large amount of acid mist；2, workpiece rinse water processing difficulty is big, realizes that the investment of Treated sewage reusing and operating cost are high；3, the recycling of spent acid is difficult.The invention proposes a kind of methods of pickling iron and steel and rinsing water circulation use, the pickling that can be used for carbon steel can be used for the acid wash passivation of stainless steel, waste acid recycling is realized while can be realized with a low cost rinse water and be recycled, on the basis of ensuring production efficiency and product quality, environmental risk is greatly lowered.
Description
Technical field
The invention belongs to environmental protection and the field of metal processing, the in particular to water circulation use of pickling iron and steel and acid recovery side
Method.
Background technique
It is processed into steel production enterprise and using steel the enterprise of product, it usually needs pickling is carried out to steel surface and is removed
Rust just can be carried out the surface treatment such as subsequent passivation, phosphatization, plating.Generally use the strong acid such as hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid
Property solution to steel surface oxide layer remove, it is especially more universal with hydrochloric acid or sulfuric acid.
Ordinary carbon steel is high-efficient using hydrochloric acid cleaning, surface not dust, does not need generally to heat acid, but production process meeting
There is a large amount of acid mist to generate, acid mist corrodes production facility and influences producers' health, needs at the sour gas of Wind Volume
Reason system is collected neutralisation treatment.It repeatedly carries out the ferrous ion of enriched in the pickling solution of workpiece pickling and supplement,
Decline production efficiency, it has to carry out aging acid solution and scrap processing, can will be added concentrated hydrochloric acid in Ageing solution, then to acid solution into
Row freezing and crystallizing realizes the separation and the regeneration of acid of frerrous chloride.But use the workpiece rinse water and gas after chlorohydric acid pickling
It collects to neutralize and contains a large amount of chloride ion in water, be difficult to remove by simple and easy method, industrial water is made to be difficult to realize reach
Mark discharge or Treated sewage reusing.
Acid wash passivation is carried out to stainless steel using nitric acid, hydrofluoric acid is added, in nitric acid generally to improve production efficiency.Nitre
Acid+hydrofluoric acid production technology has several environmental issues that must face: 1, production process generates a large amount of tobacco；2, workpiece rinses
Contain a large amount of nitric acid rhizosphere fluorine ion in water, wastewater treatment difficulty is big, realizes that the investment of Treated sewage reusing and operating cost are high；3,
The recycling of spent acid is difficult, and general to recycle nitration mixture using vacuum distillation or roasting technique, equipment investment is big, energy consumption is high.
Carbon steel is generally required and heated to acid solution using the pre- pickling of sulfuric acid using sulfuric acid washing or to stainless steel, and
Workpiece surface is easy dust, and someone adds sodium chloride, hydrogen peroxide in sulfuric acid to improve the production efficiency of sulfuric acid.
Above method all only solves the problems, such as some aspect, it is difficult to from production efficiency, substrate adaptability, investment, fortune
Row cost, environmental protection etc. systematicness solve the problems, such as.
The present inventor proposes a kind of pickling iron and steel new method, that is, meets the quality of production and efficiency of workpiece, and realize acid
Recycle the recycling with rinse water.
Summary of the invention
1, technical problem to be solved:
It is difficult in existing pickling iron and steel from production efficiency, substrate adaptability, investment, operating cost, environmental protection etc. systematicness
It solves the problem of that existing acid washing method can only solve some aspect, and can not accomplish to reduce acid cleaning process acid mist
It generates；It is realized with a low cost the recycling of workpiece rinse water after pickling；Realize the recycling and recycling of spent acid.
2, technical solution:
It uses sulfuric acid for production acid, promotor and corrosion inhibiter is added and is passed through air or ozone and controls suitable temperature, i.e.,
Can be used for carrying out steel surface acid pickling and rust removing can also be used for carrying out acid wash passivation to stainless steel.
Sulfuric acid concentration is weight percentage 15-45%, and most suitable concentration is 25-40%.The temperature of pickling solution is 25-
85 °C, optimum temperature is 40-60 °C.
Promotor can be the inorganic salts containing halogen and nitrogenous inorganic salts or organic matter forms.Such as sodium fluoride, chlorination
Sodium, calcium chloride, sodium bromide, potassium bromide, potassium iodide, sodium nitrate, calcium nitrate, sodium nitrite, m-nitro, m-nitrobenzene sulfonic acid
One or more of compositions of the substances such as sodium, NSC 71042, p-aminobenzoic acid, glutamic acid.The addition of promotor
Amount is pickling solution weight percent 0.5%-10%, and optimum range is 3%-5%.
Restrainer can be by containing methenamine, hydrazine hydrate, 1,4 diacetylene alcohol, ethanol amine, triethanolamine, benzene a pair of horses going side by side
One or more of compositions of the substances such as triazole.Additive amount is pickling solution weight percent 0.01%-1%, and optimum range is
0.05%-0.5%。
To air or ozone is passed through in acid solution, can be realized using any of following methods: by aeration plate, aeration
Pipe or Wen Qiuli mixing, be filled in the container of sulfuric acid solution to air or ozone pressurization again will be in container containing oxygen or ozone
The sulfuric acid method that flows back to entrained gas in the medium disclosed liquid of pickling tube.According to the volume of sulfuric acid solution, be added oxygen or
The amount of ozone is 1-10mg/L.
The rinse water of pickling workpiece realizes industrial water zero-emission by method provided by the invention.
Rinse water can be with direct circulation reuse after lime precipitation；When there are COD in organic contamination, rinse water for workpiece surface
When not meeting recycle water standard with indexs such as ammonia nitrogens, the reuse up to standard after the water of lime neutralization precipitation is by biochemical treatment；Work as life
When changing the TDS of the water accumulation of processing more than recycle water standard, carried out by ultrafiltration+reverse osmosis water to after part or all of biochemistry
Processing, clear water direct reuse after processing, concentrated water are used for the preparation of sulfuric acid solution.
The biochemical process of use can be anaerobism, anoxic, aerobic isoreactivity sludge, bioanalysis, MBR etc. be able to achieve it is organic
The biodegradable single technique of object or process combination.
The used spent acid of pickling and most of additive are realized by method provided by the invention and are recycled.
Acid solution is done into spent acid after iron concentration is more than 80g/L in acid solution by iron concentration in detection pickling solution
Regeneration treatment.The concentrated sulfuric acid is added in spent acid makes sulfuric acid concentration reach 50% or more, and acid solution is cooled to 10 °C hereinafter, making acid
Sludge settling precipitation is washed, sulfuric acid and additive containing a small amount of metal ion are with clear liquid circulating and recovering.
3, the utility model has the advantages that
It increases substantially the production efficiency of pickling, avoid workpiece surface dust.It is greatly reduced and is made using nitric acid or chlorohydric acid pickling
At acid mist.
Workpiece is from after pickling tube taking-up, advanced acid recovery pond, then carry out countercurrent rinsing, rinse water neutralizes through lime, precipitating,
Industrial water zero-emission is realized in reuse after filtering.
The spent acid of multiple pickling workpiece is added after the concentrated sulfuric acid and is cooled to 5 °C hereinafter, containing the pickling of a large amount of ferrous sulfate
Sludge crystalline deposit, is separately disposed after filters pressing, and pressing filtering liquid continues to precipitate, and supernatant is avoided as production sulfuric acid direct reuse
Acid is scrapped.
Detailed description of the invention
Fig. 1 is pickling-rinsing process flow chart of the invention.
Specific embodiment
Below by solution preparation steps, process flow and embodiment, the present invention is described in detail.
1, solution is configured in the following order:
Configure sulfuric acid solution sulfuric acid content 15-45%
Promotor 0.5-10% is added
Corrosion inhibiter 0.01-1% is added
Oxygen or ozone are passed through to solution and are heated to 35 °C --- 85 °C
The pickling time of workpiece 1-70 minutes
Pickling in above-mentioned solution is put the workpiece in, the specific pickling time of workpiece needs the material according to steel-iron components, in acid solution
The temperature of sulfuric acid concentration and acid solution determines.
Process description
Iron and steel parts to be cleaned are first put into the pickling tube for having configured sulfuric acid solution, after surface oxide layer removal is clean, workpiece
It is taken out immediately after being put into acid recovery pond, after being rinsed in order into washing 1, washing 2, washing 3, workpiece enters next work
Sequence is such as electroplated, phosphatization.If workpiece is stainless steel, steam blowing is used after directly finally being cleaned with tap water or reverse osmose pure-water,
Make surface passivation with heated-air drying.
The carbon steel thicker for oxide skin or the stainless steel for being difficult to oxide film dissolving can use the method for pickling twice,
First the acid of multiple pickling workpiece is impregnated, make workpiece surface oxide skin largely remove, then by workpiece eo-acid into
Row cleaning, to improve production efficiency.
In addition to using 2 pickling, the key factor for improving production efficiency is addition promotor, corrosion inhibiter, is led in acid solution
Enter oxygen or ozone, control acid liquor temperature and sulfuric acid concentration.
Sulfuric acid concentration general control is in 15-45%, optimum concentration range 25-40%.Acid liquor temperature can make at 25-85 °C
With optimum temperature range is 40-60 °C.
Acid pickling promotor is made of the inorganic salts containing halogen and nitrogenous inorganic salts or organic matter.Such as sodium fluoride, chlorination
Sodium, calcium chloride, sodium bromide, potassium bromide, potassium iodide, sodium nitrate, calcium nitrate, sodium nitrite, m-nitro, m-nitrobenzene sulfonic acid
One or more of compositions of the substances such as sodium, NSC 71042, p-aminobenzoic acid, glutamic acid.The addition of promotor
Amount is pickling solution weight percent 0.5%-10%, and optimum range is 3%-5%.
Restrainer can be by containing methenamine, hydrazine hydrate, 1,4 diacetylene alcohol, ethanol amine, triethanolamine, benzene a pair of horses going side by side
One or more of compositions of the substances such as triazole.
To air or ozone is passed through in acid solution, can be realized using any of following methods: by aeration plate, aeration
Pipe or Wen Qiuli mixing, be filled in the container of sulfuric acid solution to air or ozone pressurization again will be in container containing oxygen or ozone
The sulfuric acid method that flows back to entrained gas in the medium disclosed liquid of pickling tube.
It is mixed into air or ozone in sulfuric acid solution, under the synergistic effect of above-mentioned promotor, pickling will be increased substantially
Efficiency.It is such as added without in the case that promotor is not also passed through air, 25% sulfuric acid solution, in the case where 60 °C, pickling carbon steel needs
1 hour, 304 stainless steel of pickling can not be cleaned 20 hours surfaces.Promotor, 25% sulfuric acid solution, the case where 60 °C is added
Under, pickling carbon steel needs 30 minutes, and 304 stainless steel of pickling needs 3 hours or more.Promotor is added, is passed through air, 25% sulfuric acid
Solution, in the case where 60 °C, pickling carbon steel needs 10 minutes, and 304 stainless steel of pickling needs 1-2 hours.Promotor is added, is passed through
Ozone, 25% sulfuric acid solution, in the case where 60 °C, pickling carbon steel only needs 1 minute, and 304 stainless steel of pickling only needs 35 minutes.
According to the volume of sulfuric acid solution, the amount that oxygen or ozone is added is 1-10mg/L.
The purpose that corrosion inhibiter is added is to prevent acid solution to work while improving to carbon steel and stainless steel surface pickling efficiency
The excessive erosion of part substrate.It is such as added without corrosion inhibiter, promotor is only added, is passed through ozone, 25% sulfuric acid solution, 60 °C the case where
Under, pickling carbon steel only needs 1 minute, to the corrosion rate 0.5mm/h of substrate, if the operation control time is improper, easily to base
Material causes excessive erosion, after corrosion inhibiter is added, is down to 0.03mm/h to the corrosion rate of carbon steel base material hereinafter, to 304 stainless base steels
The corrosion rate of material is down to 0.002mm/h or less by 0.036mm/h.Corrosion inhibiter can be by containing methenamine, hydrazine hydrate, 1,4
One or more of compositions of the substances such as diacetylene alcohol, ethanol amine, triethanolamine, benzotriazole, additive amount are pickling solution
Weight percent 0.01%-1%, optimum range are 0.1%-0.3%.
After workpiece is by the cleaning of above-mentioned sulfuric acid washing solution, rinsing process is entered back into behind acid recovery pond.The acid in acid recovery pond
Liquid timing is with being pumped back to pickling tube, to supplement the acid solution that workpiece surface is taken out of, the insufficient liquid level in acid recovery pond it is corresponding periodically by
Wash the water supplement in No. 1 pond.
After the acid solution of pickling tube is used for multiple times, to prevent pickling efficiency from declining, when acid solution ferrous ions concentration is more than
When 80g/L, the acid solution pump that more pickling sludge is contained in bottom is discharged into spent acid collecting pit, is added to the acid in sour reuse tank
Pickling tube, and No. 1 water in acid recovery pond, ultra filtering reverse osmosis concentrated water, washing water are successively refilled into pickling tube, until pickling tube reaches
Work the subsequent continuous production of liquid level.
The concentrated sulfuric acid is added in spent acid collecting pit, makes in spent acid collecting pit that sulfuric acid concentration is up to 50% or more, by spent acid Chi Zhonghan
There is the sulfuric acid of ferrous sulfate to be pumped into cooling sedimentation basin, acid solution is stood and is cooled to 10 °C hereinafter, there will be a large amount of sulfur acid
Ferrous pickling sludge settling is precipitated, and iron concentration is down to 20g/L hereinafter, to be discharged into acid recovery tank spare in supernatant sulfuric acid.
The circulation process of rinse water is as follows:
Treated sewage reusing --- --- washing 2 --- washing 1 --- wastewater collection of washing 3
--- neutralization precipitation --- biochemistry --- Treated sewage reusing
Water after countercurrent rinsing flows into wastewater collection pond three times, after the processing of lime neutralization precipitation is added, most of sulfate radical with
The sludge formed after the precipitated filters pressing of metal ion, which is taken away, separately to be disposed, and clear water carries out biochemical treatment, passes through microbial degradation steel
The by-product etc. that the organic matter and additive that iron surface spot carries are generated by reaction, COD, ammonia nitrogen etc. refer to after biochemical treatment
It is stand-by that the water that mark reaches Treated sewage reusing standard is discharged into Treated sewage reusing pond.Due to being added to promotor and corrosion inhibiter in pickling solution,
Contain inorganic salt and other material in promotor and corrosion inhibiter, long-continued production there will be part TDS be enriched in rinse water and possibility
Make TDS >=1000mg/L, influence reuse water quality, handled using part water of the ultrafiltration+reverse osmosis process to reuse pool, is located
Pure water after reason is discharged into washing 3, improves rinsing water quality, the common configuration pickling solution of acid in concentrated water that treated and sour reuse tank
Realization recycles.For protect ultrafiltration+reverse osmosis unit, should first to reuse water addition soda ash be sufficiently stirred by most of calcium from
It just can enter ultrafiltration+reverse osmosis unit after son precipitating removal.Due to the removing of iron containing sludge in system and neutralization precipitation sludge
Removing will cause the loss of a small amount of promotor and corrosion inhibiter, and need to only do appropriate supplement can maintain line balancing.
Since pickling solution is in heating work state, systematic water evaporation will be caused to be lost, evaporation water section passes through
Gas condensation is recycled after collecting, and insufficient section fills into tap water from No. 3 ponds of washing, forms watering balance.
According to the above technical scheme, industrial water zero-emission, spent acid zero-emission are realized, and increases substantially production efficiency.
Before method provided by the invention can be used for steel surface cleaning, acid-washing stainless steel passivation, pre-electroplating treatment, phosphatization
The fields such as processing.
Embodiment 1
Pickling solution is prepared by sulfuric acid 35%, promotor 8%, corrosion inhibiter 0.5%, air and pickling is molten is passed through in pickling solution
Liquid temperature is controlled to 60 °C.The 304 stainless steel material pickling to surface black, stainless steel surface exposes silvery white after pickling 35 minutes
Color base body.316L stainless steel material pickling to surface black, stainless steel surface exposes silvery white matrix after pickling 50 minutes.
Embodiment 2
Pickling solution is prepared by sulfuric acid 28%, promotor 5%, corrosion inhibiter 1%, air is passed through in pickling solution and by pickling solution
Temperature computer heating control is to 40 °C.Pickling is carried out to the carbon steel of surface black, steel surface exposes silvery white matrix within 5 minutes.
Embodiment 3
Certain anchor chain factory largely uses the carbon steel wire rod of diameter 6-12mm, first carries out acid pickling and rust removing before carrying out anchor chain processing, uses
Hydrochloric acid pickling process.Because containing hydrochloric acid in rinse water, after being neutralized with lime, generate largely containing the brine waste of calcium chloride,
Zero-emission difficult to realize.
All emptied to by hydrochloric acid in pickling tube, sour pool size be it is 3 meters long, 2.5 wide, 2.5 deep, 12 cubes of dischargeable capacity
Rice.Pickling solution, 40 ° of computer heating control pickling solution temperature are prepared by 25% sulfuric acid, 3% promotor, 0.5% corrosion inhibiter in sour pond
C is mixed ozone with pickling solution through venturi mixer with acid-proof pump, and ozone intake is 30g/ hours.1 ton of every batch of or so
Steel disk round wires material 2.5-5 minutes surface derustings in pickling tube are clean, enter subsequent processing after rinsing is dry and process.
Rinse water recycling and waste acid recycling are realized after carrying out technological transformation in the present inventive method.
Embodiment 4
Certain stainless-steel pipe factory, the stainless steel pipes such as mass production 304,316L carry out the acid wash passivation of product before factory.It is former
Using nitric acid+hydrofluoric acid process route, reuse after being neutralized with lime to poaching wastewater generates 1000 tons of pickling dirts every year
In addition mud has disposition of entrusting outside spent acid.
It is realized after progress technological transformation in the present inventive method and rinses water circulation use and acid recovery, at the no longer outer committee of spent acid
It sets.
Embodiment more than original text is merely illustrative of the invention's technical idea, and protection model of the invention cannot be limited with this
Enclose, it is all according to the technical idea provided by the invention, any changes made on the basis of the technical scheme each falls within guarantor of the present invention
Within the scope of shield.The technology that the present invention is not directed to can be realized by existing technology.
Claims (10)
1. a kind of method of pickling iron and steel and water circulation use, it is characterised in that: use sulfuric acid for production acid, promotor is added
With corrosion inhibiter and be passed through air or ozone and control suitable temperature, can be used to carry out acid pickling and rust removing to steel surface also to can be used
In to stainless steel progress acid wash passivation.
2. according to the method described in claim 1, the 15-45% it is characterized by: sulfuric acid concentration is weight percentage, most suitable
Concentration is 25-40%, and the temperature of pickling solution is 25-85 °C, and optimum temperature is 40-60 °C.
3. according to the method described in claim 1, it is characterized by: promotor can be inorganic salts containing halogen and nitrogenous
Inorganic salts or organic matter composition, be sodium fluoride, sodium chloride, calcium chloride, sodium bromide, potassium bromide, potassium iodide, sodium nitrate, calcium nitrate,
Sodium nitrite, m-nitro, m-nitrobenzene sodium sulfonate, NSC 71042, p-aminobenzoic acid, glutamic acid substance
The additive amount of one or more composition, promotor is pickling solution weight percent 0.5%-10%, and optimum range is 3%-5%.
4. according to the method described in claim 1, it is characterized by: restrainer can by containing methenamine, hydrazine hydrate,
1, one or more of compositions of 4 diacetylene alcohol, ethanol amine, triethanolamine, benzotriazole substance, additive amount are pickling solution weight
Percentage 0.01%-1% is measured, optimum range is 0.05%-0.5%.
5. according to the method described in claim 1, it is characterized by: can be used following to air or ozone is passed through in acid solution
Any of method realizes: by aeration plate, aeration tube or Wen Qiuli mixing, to be filled with sulfuric acid to air or ozone pressurization molten
The sulfuric acid containing oxygen or ozone in container is flowed back into entrained gas in the medium disclosed liquid of pickling tube again in the container of liquid
Method, according to the volume of sulfuric acid solution, the amount that oxygen or ozone is added is 1-10mg/L.
6. according to the method for claim 1, it is characterized by: the rinse water of pickling workpiece is real by method provided by the invention
Existing industrial water zero-emission.
7. according to the method described in claim 7, it is characterized by: rinse water can be with direct circulation reuse after lime precipitation；
When workpiece surface is not there are when the indexs such as COD and ammonia nitrogen meet recycle water standard in organic contamination, rinse water, through in lime and heavy
The water in shallow lake passes through reuse up to standard after biochemical treatment；When the TDS that the water of biochemical treatment accumulates is more than recycle water standard, pass through ultrafiltration
+ it is reverse osmosis to it is part or all of it is biochemical after water handle, clear water direct reuse after processing, concentrated water is matched for sulfuric acid solution
System.
8. according to the method described in claim 8, it is characterized by: the biochemical process used can be anaerobism, anoxic, aerobic etc.
Activated sludge process, bioanalysis, MBR etc. are able to achieve the single technique or process combination of organic matter biodegradation.
9. according to the method described in claim 1, it is characterized by: the used spent acid of pickling and most of additive are by the present invention
The method of offer, which is realized, to be recycled.
10. according to the method described in claim 10, it is characterized by: working as acid solution by iron concentration in detection pickling solution
After middle iron concentration is more than 80g/L, acid solution is done into acid regeneration processing, the concentrated sulfuric acid is added in spent acid reaches sulfuric acid concentration
50% or more, and acid solution is cooled to 10 °C hereinafter, pickling sludge settling is precipitated, the sulfuric acid containing a small amount of metal ion and add
Add agent with clear liquid circulating and recovering.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111003844A (en) * | 2019-12-26 | 2020-04-14 | 泰州市科源水处理有限公司 | Treatment process for simultaneously treating various industrial waste acids with different components |
| CN112553612A (en) * | 2020-12-31 | 2021-03-26 | 中船重工西安东仪科工集团有限公司 | Synchronous pickling passivation method for stainless steel parts |
| CN114369780A (en) * | 2022-01-13 | 2022-04-19 | 湖北汉唐电力器材有限公司 | Hot galvanizing process for power iron accessory and photovoltaic solar bracket |
| CN115572965A (en) * | 2022-10-19 | 2023-01-06 | 常州广利管路系统科技有限公司 | A kind of chromium-free passivation solution and the method for applying it to passivate copper-tin alloy coating of petroleum casing |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111003844A (en) * | 2019-12-26 | 2020-04-14 | 泰州市科源水处理有限公司 | Treatment process for simultaneously treating various industrial waste acids with different components |
| CN112553612A (en) * | 2020-12-31 | 2021-03-26 | 中船重工西安东仪科工集团有限公司 | Synchronous pickling passivation method for stainless steel parts |
| CN112553612B (en) * | 2020-12-31 | 2023-08-08 | 中船重工西安东仪科工集团有限公司 | Synchronous pickling and passivating method for stainless steel parts |
| CN114369780A (en) * | 2022-01-13 | 2022-04-19 | 湖北汉唐电力器材有限公司 | Hot galvanizing process for power iron accessory and photovoltaic solar bracket |
| CN115572965A (en) * | 2022-10-19 | 2023-01-06 | 常州广利管路系统科技有限公司 | A kind of chromium-free passivation solution and the method for applying it to passivate copper-tin alloy coating of petroleum casing |
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