CN102320697A - Desulfuration process for chromate waste water - Google Patents

Desulfuration process for chromate waste water Download PDF

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Publication number
CN102320697A
CN102320697A CN201110144574A CN201110144574A CN102320697A CN 102320697 A CN102320697 A CN 102320697A CN 201110144574 A CN201110144574 A CN 201110144574A CN 201110144574 A CN201110144574 A CN 201110144574A CN 102320697 A CN102320697 A CN 102320697A
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CN
China
Prior art keywords
waste water
tail gas
chromate waste
absorption tower
chromate
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Pending
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CN201110144574A
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Chinese (zh)
Inventor
袁代建
高波
魏全
杨菲
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Chongqing Minfeng Chemical Co Ltd
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Chongqing Minfeng Chemical Co Ltd
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Priority to CN201110144574A priority Critical patent/CN102320697A/en
Publication of CN102320697A publication Critical patent/CN102320697A/en
Pending legal-status Critical Current

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Abstract

The invention relates to the processing of an industrial three-waste product, in particular to a desulfuration process for chromate waste water, which comprises the following steps: sulfur tail gas is cooled and washed after being dedusted firstly; the pH value of the chromate waste water is adjusted to 2 to 3; the sulfur tail gas and the chromate waste water react in an absorption tower; alkali liquor and flocculating agent is added in reacted liquid in the absorption tower and then chromium hydroxide is separated out through deposition; and the tail gas which comes from the absorption tower is desulfurized thoroughly through a double alkali method. Proven by a test, the processing process of the chromate waste water is simple, so that the chromate waste water pollution and sulfur waste gas pollution can be solved simultaneously merely through one process, the device investment is less, the energy consumption is low, and the national requirements of energy conservation and emission reduction can be met; and moreover, the process is adaptable, so that both high-concentration chromate waste water and low-concentration chromate waste water can be processed.

Description

The chromate waste water sulfur removal technology
Technical field
The present invention relates to the processing of industry " three wastes " product, be specifically related to the chromate waste water sulfur removal technology.
Background technology
Chromate waste water is often referred to and contains Cr 6+Waste water, for chromium salt production enterprise, it mainly comes from the wash-down water that the chromium slag leaches water and production site, and the waste water of some workshop section, the output of these waste water is huge, wherein Cr 6+Content also sizable.Because Cr 6+Can in animal and plant body, enrichment also understand the serious harm human health, therefore must be to containing Cr 6+Waste water is effectively administered.The national environmental protection law regulation, Cr in the discharge water 6+<0.5 mglitre, standard is compared therewith, Cr in all chromium salt production enterprise disused chrome waters 6+All surpass state specified standards, therefore administering disused chrome water is a very urgent task.
Chromium salt production enterprise produces a large amount of sulfur-containing smoke gas in the process of roasting material simultaneously, and boiler also produces a large amount of sulfur-containing smoke gas in the production process in addition, and the sulfur-containing smoke gas environmental pollution is bigger, is the arch-criminal who causes acid rain.
At the existing Cr that contains 6+In the treatment process of waste water, distillation method of enrichment processing power is very limited, bad adaptability, only be applicable to concentration of treatment height and impurity seldom contain Cr 6+Rinse water, to containing Cr in a large number 6+The relatively low waste water of concentration can't be handled, and the facility investment of ion exchange method is big, complex technical process, and its resin and soda acid consumption are big, and electrodialysis and reverse osmosis law technology are difficult for grasping, and energy consumption is big.Processing for sulfur-containing smoke gas also is bigger environmental protection input of enterprise in addition, independent flue gas need be set usually handle workshop section.
Summary of the invention
The objective of the invention is to overcome above-mentioned deficiency, provide that a kind of technology is simple, flexibility is strong, can solve the treatment process that chromate waste water and sulphur-containing exhaust gas pollute simultaneously.
To achieve these goals, the present invention provides a kind of chromate waste water sulfur removal technology, includes following steps:
A carries out dedusting, cooling and washing with boiler exhaust gas, obtains clean SO 2Tail gas;
B will contain Cr 6+Waste water inject circulatory pool, and the pH value of regulating waste water is 2~3;
C obtains SO with steps A 2Tail gas is sent into the sulfurous gas absorption tower from the bottom, with the Cr that contains after the step B processing 6+Waste water is sent into the sulfurous gas absorption tower from top, make SO 2Tail gas with contain Cr 6+Following reaction takes place:
Na 2Cr 2O 7+3SO 2+H 2O=2Cr(OH)SO 4+Na 2SO 4
D handles step C the Cr that obtains 3+Waste water mix with sodium hydroxide, regulating pH value is 7~9, the Cr of free state 3+Become the chromium hydroxide of indissoluble, reaction equation is following:
Cr(OH)SO 4+2NaOH=Cr(OH) 3+Na 2SO 4
E adds flocculation agents such as SEPIGEL 305 in step D reacted solution, make solution pass through the inclined tube sedimentation then, comes out chromium hydroxide is settlement separate, obtains supernatant liquid;
F, with among the step B from the sulfurous gas absorption tower tail gas discharged, adopt two alkaline process to carry out desulfurization, the absorption tower tail gas discharged respectively with Na 2CO 3Reaction generates Na with NaOH 2SO 3Back emptying, its reaction equation is following:
Na 2CO 3+SO 2=Na 2SO 3+CO 2
2NaOH+SO 2=Na 2SO 3+H 2O
Na 2SO 3+SO 2+H 2O=2NaHSO 3
As preferred version, consider to also have the chromium hydroxide that do not settle down of part in the supernatant liquid in the step e, therefore with the supernatant liquid that obtains in the step e, pass through the inclined tube sedimentation once more, isolate chromium hydroxide wherein, liquids recovery utilization or efflux.
As preferred version, in order to save the input of NaOH, simultaneously also in order to prevent unsettled Na 2SO 3Decompose the Na that generates in the step F 2SO 3With the calcium hydroxide emulsion reaction, regeneration NaOH, the CaSO of generation 3After stirring oxidation, generate gypsum.
Chromate waste water sulfur removal technology of the present invention has following advantage: 1, and the Processing Equipment less investment that technology is simple, a technology can solve chromate waste water and sulphur-containing exhaust gas pollution simultaneously, energy consumption is low, meets the requirement of national energy-saving and emission-reduction; 2, flexibility is strong, and chromate waste water that not only can treatment of high concentration also can be handled the chromate waste water of lower concentration.
Embodiment
A kind of chromate waste water sulfur removal technology is characterized in that including following steps:
A obtains tail gas or coal firing boiler tail gas with the sulfide containing material roasting and cools off and wash, and obtains SO 2Tail gas;
B will contain Cr 6+Waste water inject circulatory pool, through adding sulphuric acid soln the pH value of waste water is adjusted to 2~3;
C obtains SO with steps A 2Tail gas is sent into the sulfurous gas absorption tower from the bottom, with the Cr that contains after the step B processing 6+Waste water is sent into the sulfurous gas absorption tower from top, make SO 2Tail gas with contain Cr 6+Following reaction takes place:
Na 2Cr 2O 7+ 3SO 2+ H 2O=2Cr (OH) SO 4+ Na 2SO 4, this moment, the specific absorption of S reached as high as 80%;
D handles step C the Cr that obtains 3+Waste water mix with sodium hydroxide, regulating pH value is 7~9, the Cr of free state 3+Become the chromium hydroxide of indissoluble, reaction equation is following:
Cr(OH)SO 4+2NaOH=Cr(OH) 3+Na 2SO 4
E adds flocculation agents such as SEPIGEL 305 in step D reacted solution, make solution pass through the inclined tube sedimentation then, comes out Cr in the supernatant liquid that obtains with chromium hydroxide is settlement separate 6+Content be lower than 0.02 mg/litre, the supernatant liquid that obtains is passed through the inclined tube sedimentation once more, isolate chromium hydroxide wherein, liquids recovery utilization or efflux;
F, with among the step B from the sulfurous gas absorption tower tail gas discharged, adopt two alkaline process to carry out desulfurization, the absorption tower tail gas discharged respectively with Na 2CO 3Reaction generates Na with NaOH 2SO 3Back emptying, its reaction equation is following:
Na 2CO 3+SO 2=Na 2SO 3+CO 2
2NaOH+SO 2=Na 2SO 3+H 2O
Na 2SO 3+SO 2+H 2O=2NaHSO 3
This moment, the specific absorption of sulphur can reach 97%, the Na that reaction generates 2SO 3With the calcium hydroxide emulsion reaction, regeneration NaOH, the CaSO of generation 3After stirring oxidation, generate gypsum.
Above-described only is part preferred implementation of the present invention, should be pointed out that for a person skilled in the art, under the prerequisite that does not break away from treatment process of the present invention, can also make some improvement, and these also should be regarded as protection scope of the present invention.

Claims (3)

1. chromate waste water sulfur removal technology is characterized in that including following steps:
Boiler is obtained tail gas carry out dedusting, cooling and washing, obtain SO 2Tail gas;
To contain Cr 6+Waste water inject circulatory pool, and the pH value of waste water is adjusted to 2~3;
Steps A is obtained SO 2Tail gas is sent into the sulfurous gas absorption tower from the bottom, with the Cr that contains after the step B processing 6+Waste water is sent into sulfurous gas absorption tower, SO from top 2Tail gas with contain Cr 6+React;
D handles step C the Cr that obtains 3+Waste water mix with sodium hydroxide, regulating pH value is 7~9, the Cr of free state 3+Become the chromium hydroxide of indissoluble;
E adds flocculation agents such as SEPIGEL 305 in step D reacted solution, make solution pass through the inclined tube sedimentation then, comes out chromium hydroxide is settlement separate, obtains supernatant liquid;
F, with among the step B from the sulfurous gas absorption tower tail gas discharged, adopt two alkaline process to carry out desulfurization, the absorption tower tail gas discharged respectively with Na 2CO 3Reaction generates Na with NaOH 2SO 3Back emptying.
2. chromate waste water sulfur removal technology according to claim 1 is characterized in that: the supernatant liquid that obtains in the step e, pass through the inclined tube sedimentation once more, and isolate chromium hydroxide wherein, liquids recovery utilization or efflux.
3. chromate waste water sulfur removal technology according to claim 1 is characterized in that: the Na that generates in the step F 2SO 3With the calcium hydroxide emulsion reaction, regeneration NaOH, the CaSO of generation 3After stirring oxidation, generate gypsum.
CN201110144574A 2011-05-31 2011-05-31 Desulfuration process for chromate waste water Pending CN102320697A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102795726A (en) * 2012-08-27 2012-11-28 武汉钢铁(集团)公司 Method and apparatus for treating chromium-containing wastewater by means of sintering flue gas
CN102935327A (en) * 2012-11-23 2013-02-20 四川省安县银河建化(集团)有限公司 Method for removing sulfur dioxide in tail gas from industrial kiln and method for comprehensively utilizing tail gas from industrial kiln
CN103288236A (en) * 2013-05-27 2013-09-11 山东三维石化工程股份有限公司青岛分公司 Treatment method for salt-containing wastewater

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Publication number Priority date Publication date Assignee Title
JPS6283090A (en) * 1985-10-08 1987-04-16 Kurita Water Ind Ltd Treatment of waste water containing chromium
CN1406882A (en) * 2001-09-12 2003-04-02 攀枝花世纪行实业发展有限公司 Process for treating acid waste water for depositing vanadium
CN1803655A (en) * 2006-01-04 2006-07-19 四川安县银河建化集团有限公司 Reclaiming and utilizing method of sulfuric acid production wastewater
CN1994929A (en) * 2006-12-29 2007-07-11 中国人民解放军后勤工程学院环境保护科学研究所 High-concentration chromium-containing wastewater resource treatment method
CN101200328A (en) * 2007-11-01 2008-06-18 华侨大学 Process for treating electroplating mixed wastewater by air oxidation method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6283090A (en) * 1985-10-08 1987-04-16 Kurita Water Ind Ltd Treatment of waste water containing chromium
CN1406882A (en) * 2001-09-12 2003-04-02 攀枝花世纪行实业发展有限公司 Process for treating acid waste water for depositing vanadium
CN1803655A (en) * 2006-01-04 2006-07-19 四川安县银河建化集团有限公司 Reclaiming and utilizing method of sulfuric acid production wastewater
CN1994929A (en) * 2006-12-29 2007-07-11 中国人民解放军后勤工程学院环境保护科学研究所 High-concentration chromium-containing wastewater resource treatment method
CN101200328A (en) * 2007-11-01 2008-06-18 华侨大学 Process for treating electroplating mixed wastewater by air oxidation method

Non-Patent Citations (2)

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韩百光: "含铬电镀废水与硫酸厂尾气综合治理的试验研究", 《武汉师范学院学报(自然科学版)》, no. 01, 31 March 1983 (1983-03-31) *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102795726A (en) * 2012-08-27 2012-11-28 武汉钢铁(集团)公司 Method and apparatus for treating chromium-containing wastewater by means of sintering flue gas
CN102795726B (en) * 2012-08-27 2013-12-25 武汉钢铁(集团)公司 Method and apparatus for treating chromium-containing wastewater by means of sintering flue gas
CN102935327A (en) * 2012-11-23 2013-02-20 四川省安县银河建化(集团)有限公司 Method for removing sulfur dioxide in tail gas from industrial kiln and method for comprehensively utilizing tail gas from industrial kiln
CN102935327B (en) * 2012-11-23 2015-07-01 四川省银河化学股份有限公司 Method for removing sulfur dioxide in tail gas from industrial kiln and method for comprehensively utilizing tail gas from industrial kiln
CN103288236A (en) * 2013-05-27 2013-09-11 山东三维石化工程股份有限公司青岛分公司 Treatment method for salt-containing wastewater
CN103288236B (en) * 2013-05-27 2014-12-24 山东三维石化工程股份有限公司青岛分公司 Treatment method for salt-containing wastewater

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Application publication date: 20120118