CN105036090A - High-COD waste sulfuric acid recycling treatment process technology - Google Patents
High-COD waste sulfuric acid recycling treatment process technology Download PDFInfo
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- CN105036090A CN105036090A CN201510194558.2A CN201510194558A CN105036090A CN 105036090 A CN105036090 A CN 105036090A CN 201510194558 A CN201510194558 A CN 201510194558A CN 105036090 A CN105036090 A CN 105036090A
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- Prior art keywords
- sulfuric acid
- waste sulfuric
- evaporation
- concentration
- waste
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 192
- 239000002699 waste material Substances 0.000 claims abstract description 51
- 238000001704 evaporation Methods 0.000 claims abstract description 27
- 230000008020 evaporation Effects 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 16
- 238000004064 recycling Methods 0.000 claims abstract description 11
- 238000002203 pretreatment Methods 0.000 claims abstract description 7
- 230000003647 oxidation Effects 0.000 claims description 16
- 238000007254 oxidation reaction Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 7
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 238000003860 storage Methods 0.000 claims description 6
- 235000011149 sulphuric acid Nutrition 0.000 claims description 6
- 239000001117 sulphuric acid Substances 0.000 claims description 6
- 239000000498 cooling water Substances 0.000 claims description 5
- 230000008929 regeneration Effects 0.000 claims description 3
- 238000011069 regeneration method Methods 0.000 claims description 3
- 238000004042 decolorization Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 238000002156 mixing Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- 239000010815 organic waste Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000010811 mineral waste Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- -1 oxynitride Chemical compound 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
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- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Abstract
The invention discloses a high-COD waste sulfuric acid recycling treatment process technology which is characterized by comprising the following steps: a) pre-treatment of waste sulfuric acid; b) evaporation concentration; c) high-temperature oxidizing decoloring; and d) cooling of regenerated sulfuric acid. The technical units are combined in the invention so that COD in the waste sulfuric acid can be reduced effectively and meanwhile almost organic substances in the waste sulfuric acid can be removed, thereby recycling the waste sulfuric acid. The obtained sulfuric acid has a recyclable value. The process technology is less in equipment investment, is stable in operation, achieves considerable economic benefit and also solves the environment-protection problem.
Description
Technical field
The present invention relates to Waste Sulfuric Acid technical field of regeneration, particularly relate to a kind of high COD Waste Sulfuric Acid recycling treatment process technical field.
Background technology
In industrial production, Waste Sulfuric Acid is mainly derived from organic nitrated, sulfonation, esterification, alkylation, catalysis, the process such as drying process and titanium white production, pickling iron and steel and gas drying.Usually be divided into organic waste sulfuric acid and mineral waste sulfuric acid by impurity difference contained in Waste Sulfuric Acid, wherein organic waste sulfuric acid has accounted for more than 60% of overall proportion.
Organic waste sulfuric acid, because of the feature of high organic content and high COD, makes it be difficult to realize effective recycling by usual processing route.General evaporating and concentrating process, along with the carrying out of evaporation, sulfuric acid concentration improves constantly, and the oxidisability of sulfuric acid manifests gradually.Add that the hot environment of vaporizer inside makes most organism, especially larger molecular organics carbonization, sex change, cause sulfuric acid viscosity to increase, fouling of evaporator is serious simultaneously.
Pyrogenic process cracking technology is taked to regenerate organic waste sulfuric acid, the finished product sulfuric acid quality better of its regeneration, plant running is comparatively stable, but its high equipment investment cost and running cost be not suitable for the enterprise that China overwhelming majority produces spent acid, therefore popularize rate not high.
Thus, the technique that a kind of stable equipment operation, cost of investment and running cost are lower be organic waste vitriolization field in the urgent need to technology.
Summary of the invention
Based on the technical problem that background technology exists, the present invention proposes a kind of high COD Waste Sulfuric Acid recycling treatment process technology.Effectively can solve the problem that other processing unit fluctuation of service, cost of investment and running costs are higher at present.
The one high COD Waste Sulfuric Acid recycling treatment process technology that the present invention proposes, is characterized in that comprising following processing step:
A) Waste Sulfuric Acid pre-treatment: Waste Sulfuric Acid is introduced pretreatment pool, adds the superoxol of 30% concentration as pretreatment auxiliary agent, and stir 24h, mixing speed controls at 80r/min, and leaves standstill 24h, squeezes into evaporation feed reservoir afterwards wait for evaporation and concentrating with pump.
B) evaporation and concentrating: according to Waste Sulfuric Acid concentration, and target finished product sulfuric acid concentration, select rational evaporation and concentrating mode, sulphuric acid concentration be not less than 90% to concentration.
C) high temperature oxidation decolouring: be concentrated into after aimed concn until Waste Sulfuric Acid, introduce bleacher, add 65% nitric acid while hot as oxidation promoter, mixing speed controls at 30r/min, and passes into circulating cooling water management temperature of reaction, namely completes decolouring after reaction 1-2h.
D) black sulfuric acid cooling: the sulfuric acid after decolouring is introduced sulfuric acid cooling tank, is finished product black sulfuric acid after cooling, enters storage tank.
Effect of the present invention is after a) Waste Sulfuric Acid pre-treatment, partial organic substances is wherein by hydrogen peroxide oxidation, organic matter molecular mass reduces, along with the carrying out of evaporation in subsequent evaporation process, part organism can overflow with secondary steam, become can biochemical treatment solidifying water and reduce fouling of evaporator phenomenon, and Waste Sulfuric Acid viscosity obviously reduces after pre-treatment, good fluidity, is beneficial to the carrying out of subsequent evaporation process.
In addition, also there is a part of organism because molecular weight is larger, and by the sulfuric acid carbonization of high density, solidifying water cannot be entered with secondary steam, the strong oxidizer nitric acid added in c) high temperature oxidation decolorization can be separated out from sulfuric acid by gases such as effectively resolving into oxysulfide, oxynitride, carbonic acid gas, thus the quality of recycled product sulfuric acid is guaranteed.
Embodiment
The one high COD Waste Sulfuric Acid recycling treatment process technology that the present invention that the present invention proposes proposes, is characterized in that comprising following processing step:
A) Waste Sulfuric Acid pre-treatment: Waste Sulfuric Acid is introduced pretreatment pool, add the superoxol of 30% concentration as pretreatment auxiliary agent, dosage is 0.5-0.8 times of organic content in raw material Waste Sulfuric Acid, stir 24h, mixing speed controls at 80r/min, and leave standstill 24h, squeeze into evaporation feed reservoir with pump afterwards and wait for evaporation and concentrating.
B) evaporation and concentrating: according to Waste Sulfuric Acid concentration, and target finished product sulfuric acid concentration, select rational evaporation and concentrating mode, sulphuric acid concentration be not less than 90% to concentration.
C) high temperature oxidation decolouring: be concentrated into after aimed concn until Waste Sulfuric Acid, introduce bleacher, add 65% nitric acid while hot as oxidation promoter, dosage is 0.9-1.1 times of organic content in raw material Waste Sulfuric Acid, mixing speed controls at 30r/min, and pass into circulating cooling water management temperature of reaction between 200-230 DEG C, namely complete decolouring after reaction 1-2h.
D) black sulfuric acid cooling: the sulfuric acid after decolouring is introduced sulfuric acid cooling tank, is finished product black sulfuric acid after cooling, enters storage tank.
Below, by specific embodiment, technical scheme of the present invention is described in detail.
Embodiment 1
Waste Sulfuric Acid is introduced pretreatment pool, adds the superoxol of 30% concentration as pretreatment auxiliary agent, dosage is 0.6 times of organic content in raw material Waste Sulfuric Acid, stir 24h, mixing speed controls at 80r/min, and leaves standstill 24h, squeezes into evaporation feed reservoir afterwards wait for evaporation and concentrating with pump.According to Waste Sulfuric Acid concentration, and target finished product sulfuric acid concentration, select rational evaporation and concentrating mode, sulphuric acid concentration is not less than 90% to concentration.High temperature oxidation decolours: be concentrated into after aimed concn until Waste Sulfuric Acid, introduce bleacher, add 65% nitric acid while hot as oxidation promoter, dosage is 1 times of organic content in raw material Waste Sulfuric Acid, mixing speed controls at 30r/min, and pass into circulating cooling water management temperature of reaction between 200-230 DEG C, namely complete decolouring after reaction 1-2h.Sulfuric acid after decolouring is introduced sulfuric acid cooling tank, is finished product black sulfuric acid after cooling, enters storage tank.
Embodiment 2
Waste Sulfuric Acid is introduced pretreatment pool, adds the superoxol of 65% concentration as pretreatment auxiliary agent, dosage is 0.3 times of organic content in raw material Waste Sulfuric Acid, stir 24h, mixing speed controls at 80r/min, and leaves standstill 24h, squeezes into evaporation feed reservoir afterwards wait for evaporation and concentrating with pump.According to Waste Sulfuric Acid concentration, and target finished product sulfuric acid concentration, select rational evaporation and concentrating mode, sulphuric acid concentration is not less than 90% to concentration.High temperature oxidation decolours: be concentrated into after aimed concn until Waste Sulfuric Acid, introduce bleacher, add 60% nitric acid while hot as oxidation promoter, dosage is 1.1 times of organic content in raw material Waste Sulfuric Acid, mixing speed controls at 30r/min, and pass into circulating cooling water management temperature of reaction between 210-220 DEG C, namely complete decolouring after reaction 1-2h.Sulfuric acid after decolouring is introduced sulfuric acid cooling tank, is finished product black sulfuric acid after cooling, enters storage tank.
Embodiment 3
Waste Sulfuric Acid is introduced pretreatment pool, adds the perchloric acid of 70% concentration as pretreatment auxiliary agent, dosage is 0.1 times of organic content in raw material Waste Sulfuric Acid, stir 20h, mixing speed controls at 80r/min, and leaves standstill 30h, squeezes into evaporation feed reservoir afterwards wait for evaporation and concentrating with pump.According to Waste Sulfuric Acid concentration, and target finished product sulfuric acid concentration, select rational evaporation and concentrating mode, sulphuric acid concentration is not less than 90% to concentration.High temperature oxidation decolours: be concentrated into after aimed concn until Waste Sulfuric Acid, introducing bleaching tower sprays, and blast ozone-air mixt as oxidation promoter, ozone dosage is 0.5 times of organic content in raw material Waste Sulfuric Acid, and controls temperature of reaction (by changing the amount of the blasting realization of air) between 200-230 DEG C.Sulfuric acid after decolouring is introduced sulfuric acid cooling tank, is finished product black sulfuric acid after cooling, enters storage tank.
The above; be only the present invention's preferably embodiment; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to according to technical scheme of the present invention and inventive concept thereof and replace or change, all should be encompassed within protection scope of the present invention.
Claims (3)
1. a high COD Waste Sulfuric Acid recycling treatment process technology, is characterized in that comprising following processing step:
A) Waste Sulfuric Acid pre-treatment: Waste Sulfuric Acid is introduced pretreatment pool, adds a certain amount of pretreatment auxiliary agent, stirs 24h and leaves standstill 24h, squeezes into evaporation feed reservoir afterwards wait for evaporation and concentrating with pump;
B) evaporation and concentrating: according to Waste Sulfuric Acid concentration, and target finished product sulfuric acid concentration, select rational evaporation and concentrating mode, sulphuric acid concentration be not less than 90% to concentration.(the present invention be not suitable for aimed concn lower than 90% Waste Sulfuric Acid regeneration);
C) high temperature oxidation decolouring: be concentrated into after aimed concn until Waste Sulfuric Acid, introduces bleacher, adds oxidation promoter while hot, stir and control temperature of reaction, namely completes decolouring after reaction 1-2h;
D) black sulfuric acid cooling: the sulfuric acid after decolouring is introduced sulfuric acid cooling tank, is finished product black sulfuric acid after cooling, enters storage tank.
2. the high COD Waste Sulfuric Acid recycling treatment process technology according to claims 1, it is characterized in that described Waste Sulfuric Acid pre-treatment step comprises: Waste Sulfuric Acid is introduced pretreatment pool, add superoxol as pretreatment auxiliary agent, stir 24h, stirred rear standing 24h.
3. the high COD Waste Sulfuric Acid recycling treatment process technology according to claims 1, it is characterized in that described high temperature oxidation decolorization process comprises: after Waste Sulfuric Acid is concentrated into aimed concn, introduce bleacher, stir, add nitric acid while hot as oxidation promoter, simultaneously because level of response is violent, cooling water control temperature of reaction need be used, namely complete decolouring after reaction 1-2h, obtain finished product black sulfuric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510194558.2A CN105036090A (en) | 2015-04-23 | 2015-04-23 | High-COD waste sulfuric acid recycling treatment process technology |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510194558.2A CN105036090A (en) | 2015-04-23 | 2015-04-23 | High-COD waste sulfuric acid recycling treatment process technology |
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| Publication Number | Publication Date |
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| CN105036090A true CN105036090A (en) | 2015-11-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510194558.2A Pending CN105036090A (en) | 2015-04-23 | 2015-04-23 | High-COD waste sulfuric acid recycling treatment process technology |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105712903A (en) * | 2016-01-20 | 2016-06-29 | 山东兴辉化工有限公司 | Dimethyl sulfate residue treatment method |
| CN112357892A (en) * | 2020-10-12 | 2021-02-12 | 江苏荣信环保科技有限公司 | Sulfuric acid recovery treatment process in waste sulfuric acid containing various organic matters |
| CN112573488A (en) * | 2020-10-12 | 2021-03-30 | 江苏荣信环保科技有限公司 | Metal product surface waste sulfuric acid treatment process |
| CN112573489A (en) * | 2020-10-12 | 2021-03-30 | 江苏荣信环保科技有限公司 | Comprehensive treatment process for waste sulfuric acid sludge and waste sulfuric acid on surface of metal product |
| CN113003546A (en) * | 2021-03-08 | 2021-06-22 | 盛隆资源再生（无锡）有限公司 | Method for comprehensively utilizing high-COD waste sulfuric acid |
| CN114671413A (en) * | 2022-03-01 | 2022-06-28 | 王少昆 | A kind of technological process and equipment for dilute sulfuric acid evaporation concentration |
-
2015
- 2015-04-23 CN CN201510194558.2A patent/CN105036090A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105712903A (en) * | 2016-01-20 | 2016-06-29 | 山东兴辉化工有限公司 | Dimethyl sulfate residue treatment method |
| CN112357892A (en) * | 2020-10-12 | 2021-02-12 | 江苏荣信环保科技有限公司 | Sulfuric acid recovery treatment process in waste sulfuric acid containing various organic matters |
| CN112573488A (en) * | 2020-10-12 | 2021-03-30 | 江苏荣信环保科技有限公司 | Metal product surface waste sulfuric acid treatment process |
| CN112573489A (en) * | 2020-10-12 | 2021-03-30 | 江苏荣信环保科技有限公司 | Comprehensive treatment process for waste sulfuric acid sludge and waste sulfuric acid on surface of metal product |
| CN112573489B (en) * | 2020-10-12 | 2023-10-31 | 江苏荣信环保科技有限公司 | Comprehensive treatment process for waste sulfuric acid sludge and waste sulfuric acid on surface of metal product |
| CN113003546A (en) * | 2021-03-08 | 2021-06-22 | 盛隆资源再生（无锡）有限公司 | Method for comprehensively utilizing high-COD waste sulfuric acid |
| CN114671413A (en) * | 2022-03-01 | 2022-06-28 | 王少昆 | A kind of technological process and equipment for dilute sulfuric acid evaporation concentration |
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Application publication date: 20151111 |
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