CN1060816C - Method for comprehensive uses by dissolving chromium residue to eliminate toxicity - Google Patents
Method for comprehensive uses by dissolving chromium residue to eliminate toxicity Download PDFInfo
- Publication number
- CN1060816C CN1060816C CN98113225A CN98113225A CN1060816C CN 1060816 C CN1060816 C CN 1060816C CN 98113225 A CN98113225 A CN 98113225A CN 98113225 A CN98113225 A CN 98113225A CN 1060816 C CN1060816 C CN 1060816C
- Authority
- CN
- China
- Prior art keywords
- chromium
- barium
- liquid separation
- water
- bariumchloride
- Prior art date
- 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.)
- Expired - Lifetime
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 11
- 230000001988 toxicity Effects 0.000 title abstract 4
- 231100000419 toxicity Toxicity 0.000 title abstract 4
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 37
- 239000011651 chromium Substances 0.000 claims abstract description 37
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims abstract description 24
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims abstract description 24
- 229910001626 barium chloride Inorganic materials 0.000 claims abstract description 24
- 239000002893 slag Substances 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 238000000926 separation method Methods 0.000 claims abstract description 19
- 239000004568 cement Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- QFFVPLLCYGOFPU-UHFFFAOYSA-N barium chromate Chemical compound [Ba+2].[O-][Cr]([O-])(=O)=O QFFVPLLCYGOFPU-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012065 filter cake Substances 0.000 claims abstract description 14
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011449 brick Substances 0.000 claims abstract description 10
- 239000000047 product Substances 0.000 claims abstract description 10
- 229910052788 barium Inorganic materials 0.000 claims abstract description 9
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229940045511 barium chloride Drugs 0.000 claims description 21
- 239000000706 filtrate Substances 0.000 claims description 11
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 6
- 235000011132 calcium sulphate Nutrition 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000004744 fabric Substances 0.000 claims description 4
- 239000013505 freshwater Substances 0.000 claims description 4
- 230000002829 reductive effect Effects 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 238000005660 chlorination reaction Methods 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 239000001175 calcium sulphate Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000003643 water by type Substances 0.000 claims 1
- 229940083898 barium chromate Drugs 0.000 abstract description 3
- 230000008030 elimination Effects 0.000 abstract 1
- 238000003379 elimination reaction Methods 0.000 abstract 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 abstract 1
- 239000004576 sand Substances 0.000 abstract 1
- 238000005507 spraying Methods 0.000 abstract 1
- 239000004575 stone Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 239000003818 cinder Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Processing Of Solid Wastes (AREA)
Abstract
The present invention relates to a comprehensive application method for dissolving chromium slag to eliminate toxicity. A water wet method is adopted to pulverize chromium slag, and then, the pulverized chromium slag is soaked in clear water for more than 24 hours. After solid-liquid separation, barium chloride is added into filter liquor to generate barium chromate used for producing barium chrome yellow or barium chrome green. After filter cakes are washed through spraying, barium chloride is added to separate out residual hexavalent chrome residual in the filter cakes, and then, the filter cakes, cement, sand stone, barium carbonate and barium chloride are mixed and pressed into cement bricks. The method of the present invention can be used for effectively eliminating toxicity in chromium slag and has low treating cost, and products after toxicity elimination can be made into products with use value.
Description
The present invention relates to a kind of chromium pulp water and dissolve malicious comprehensive use.
Contain the water-soluble sexavalent chrome that is confirmed to be strong carcinogen in the waste residue that in chromium salt production, is discharged.Adopt of existing improvement method becomes trivalent chromium with hexavalent chrome reduction more, but long trivalent chromium of time one can be oxidized into sexavalent chrome again, so can not thoroughly remove poison.The disclosed improvement method of Chinese patent application " eliminating poison of chromium cinder comprehensive use " (application number 89104693.3) is: add an amount of dilute hydrochloric acid in pulverized chromium residue, the pH value of control material is between 6.5-7.5, treat in the alkaline matter and water-soluble sexavalent chrome and the water-soluble solution of most of solubility in acid sexavalent chrome in the chromium slag, solid-liquid separation, in filter residue, add bariumchloride and remove remaining water-soluble sexavalent chrome, directly discharge then or be used to make cement brick, in filtrate, add bariumchloride, make the yellow barium chromate product.This method detoxifying effect is reliable, but owing to need a large amount of hydrochloric acid, so the treatment cost height especially is difficult to wide popularization and application in no a large amount of abraum salt acid available area.
It is low to the purpose of this invention is to provide a kind of treatment cost, detoxifying effect good and administer after the resultant chromium pulp water that can be made into the product of use value dissolve malicious comprehensive use.
Main technical schemes of the present invention is: the water wet method is broken to the screen cloth of whole energy by at least 120 order/inches with the chromium ground-slag, and in clear water, soak them more than 24 hours, regularly stir the abundant stripping of water-soluble sexavalent chrome that makes in the chromium slag granule, carry out solid-liquid separation then and get filter cake and filtrate, in the solid-liquid separation process, filter cake is carried out stepless hydro-peening with fresh water, adding excess chlorination barium in the filter cake behind hydro-peening makes the sexavalent chrome that remains in the filter cake generate water-fast baryta yellow, slag after detoxifcation slurry is carried out solid-liquid separation once more, it is reusable to contain bariumchloride in the filtrate, filter residue and cement, sandstone, bariumchloride, the barium carbonate mixing is pressed into cement brick, wherein because the sexavalent chrome that contained trivalent chromium may slowly be oxidised with air in the filter residue, according to trivalent chromium content in the filter residue, the barium carbonate that adds should surpass theoretical amount more than one times, calcium sulphate content in the add-on of bariumchloride and the cement composition adapts, in the filtrate after the first time solid-liquid separation, add an amount of barium chloride solution, reaction generates the baryta yellow precipitation, after the solid-liquid separation filtrate returned that the broken operation of chromium ground-slag is used or discharging regularly, add an amount of sodium sulfate again after adding an amount of bariumchloride before the discharging, make chromium in the relief liquor, barium content allow compliance with emission standards.
The present invention adopts water wet pulverization chromium slag and long-time the immersion, can make the fully stripping of sexavalent chrome in the chromium slag, need not use hydrochloric acid again, has reduced treatment cost.In the making raw material of cement brick, barium carbonate, bariumchloride are arranged, calcium sulfate reaction in bariumchloride and the cement composition, prevent calcium sulfate and barium carbonate reaction consumes barium carbonate, because barium carbonate is slightly soluble in water and nontoxic, and the trivalent chromium in the chromium slag is slowly to be oxidized to sexavalent chrome, timely and the stable baryta yellow of barium carbonate reaction generation with regard to the sexavalent chrome energy that can guarantee to generate makes the cement brick property retention stable, thereby possesses use value like this.The present invention uses drum filter in solid-liquid separation, improved solid-liquid separation and washing effect, is convenient to further processing, thereby guarantees detoxifying effect.
The following stated embodiment describes the present invention in detail.
Embodiment 1
Elder generation's water wet method with the chromium ground-slag be broken to can be all screen cloth by 120 order/inches, and in clear water, soak them more than 24 hours, regularly stir the abundant stripping of water-soluble sexavalent chrome that makes in the chromium slag granule, carry out solid-liquid separation with drum filter then, simultaneously filter cake is carried out stepless hydro-peening with fresh water.In isolated filter cake, add excess chlorination barium solution, fully stir, make sexavalent chrome residual in the filter cake generate water-fast baryta yellow, slag slurry after the detoxifcation carries out solid-liquid separation with drum filter once more, then with filter residue and cement, sandstone, bariumchloride, barium carbonate mixes stirring, be pressed into cement brick, the amount of adding bariumchloride reaches the calcium sulfate in the energy completely consumed cement composition, adding barium carbonate is in order to eliminate the sexavalent chrome of the oxidized generation of trivalent chromium in the filter residue, so, add and surpass the barium carbonate of theoretical amount more than one times according to chromic content in the filter residue.Filtrate after the solid-liquid separation is clarified an amount of barium chloride solution of back adding for the first time, and reaction generates baryta yellow, and through sedimentation, solid-liquid separation gets the baryta yellow product after hydro-peening, drying, pulverizing, the selection by winnowing, also be the yellow barium chromate product.Wherein the liquid behind filtrate and the hydro-peening can return broken operation use of chromium ground-slag or discharging regularly.If discharging adds an amount of sodium sulfate behind an amount of bariumchloride of adding earlier again, to guarantee chromium, barium content allow compliance with emission standards in the relief liquor.
Embodiment 2
Through the water wet method with the chromium ground-slag be broken to can be all screen cloth by 300 order/inches.Other steps are identical with embodiment 1, with the baryta yellow dissolving with hydrochloric acid that reaction generates, add oxalic acid it is reduced into chromium sesquioxide, are processed into the chromium sesquioxide product that contains a small amount of bariumchloride, also are barium chrome green product.
Cement brick at embodiment 1,2 is made in the test, presses filter residue 100kg, cement 85kg, sandstone 243kg, bariumchloride 7kg, barium carbonate 1kg and an amount of fresh water, is pressed into cement brick after mixing, and makes 26 altogether, and every is 40 * 40 * 4 centimetres
3After 28 days, recording its ultimate compression strength is 28.5MPa.Containing sexavalent chrome in the fragment of brick is 1-1.4mg/kg, is significantly less than the 5mg/kg of national regulation, follows the tracks of through three months and detects no change.
Claims (4)
1, a kind of chromium pulp water dissolves malicious comprehensive use, it is characterized in that: the water wet method with the chromium ground-slag be broken to can be all screen cloth by at least 120 order/inches, and in clear water, soak them more than 24 hours, regularly stir the abundant stripping of water-soluble sexavalent chrome that makes in the chromium slag granule, carry out solid-liquid separation then and get filter cake and filtrate, in the solid-liquid separation process, with fresh water filter cake is carried out stepless hydro-peening, adding excess chlorination barium in the filter cake behind hydro-peening makes the sexavalent chrome that remains in the filter cake generate water-fast baryta yellow, slag after detoxifcation slurry is carried out solid-liquid separation once more, it is reusable to contain bariumchloride in the filtrate, filter residue and cement, sandstone, bariumchloride, barium carbonate mixes, be pressed into cement brick, wherein owing to contained trivalent chromium in the filter residue may slowly be become sexavalent chrome by aerochlorination, according to trivalent chromium content in the filter residue, the barium carbonate that adds, its add-on surpasses theoretical amount more than one times, calcium sulphate content in the add-on of bariumchloride and the cement composition adapts, in the filtrate after the first time solid-liquid separation, add an amount of barium chloride solution, reaction generates the baryta yellow precipitation, after the solid-liquid separation filtrate returned that the broken operation of chromium ground-slag is used or discharging regularly, add an amount of sodium sulfate again after adding an amount of bariumchloride before the discharging, make chromium in the relief liquor, barium content allow compliance with emission standards.
2, a kind of chromium pulp water according to claim 1 dissolves malicious comprehensive use, it is characterized in that: with after the baryta yellow washing that generates, dry, the selection by winnowing the baryta yellow product.
3, a kind of chromium pulp water according to claim 1 dissolves malicious comprehensive use, it is characterized in that: with the baryta yellow that generates with dissolving with hydrochloric acid after, add reductive agent it be reduced into chromium sesquioxide, be processed into the chromium sesquioxide product that contains a small amount of bariumchloride then.
4, dissolve malicious comprehensive use according to claim 1 or 2 or 3 described a kind of chromium pulp waters, it is characterized in that: the equipment that adopts during solid-liquid separation is drum filter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98113225A CN1060816C (en) | 1998-05-29 | 1998-05-29 | Method for comprehensive uses by dissolving chromium residue to eliminate toxicity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98113225A CN1060816C (en) | 1998-05-29 | 1998-05-29 | Method for comprehensive uses by dissolving chromium residue to eliminate toxicity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1201836A CN1201836A (en) | 1998-12-16 |
| CN1060816C true CN1060816C (en) | 2001-01-17 |
Family
ID=5222982
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98113225A Expired - Lifetime CN1060816C (en) | 1998-05-29 | 1998-05-29 | Method for comprehensive uses by dissolving chromium residue to eliminate toxicity |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1060816C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101112647A (en) * | 2007-06-26 | 2008-01-30 | 广州铬德工程有限公司 | Technics for expelling poison for chromic slag |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102189093B (en) * | 2010-03-09 | 2015-02-04 | 刘杰 | Method for detoxicating chromium residues and comprehensive utilization of detoxicated chromium residues |
| CN104230229A (en) * | 2014-08-26 | 2014-12-24 | 许冬梅 | Hollow building block brick prepared from detoxified chromium residue |
| CN110153156B (en) * | 2019-04-10 | 2021-09-28 | 东莞市珠江海咸水淡化研究所有限公司 | Non-toxic and recycling treatment process for barium slag |
| CN113633920B (en) * | 2021-09-15 | 2022-09-02 | 中国恩菲工程技术有限公司 | Chromium slag detoxification method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1038771A (en) * | 1989-07-05 | 1990-01-17 | 广州市东山区珠峰新技术开发研究所 | The eliminating poison of chromium cinder comprehensive use |
| CN1066296A (en) * | 1991-04-29 | 1992-11-18 | 广州市珠峰研究所 | Method for treatment of chromium slag for comprehensive toxicity removal |
-
1998
- 1998-05-29 CN CN98113225A patent/CN1060816C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1038771A (en) * | 1989-07-05 | 1990-01-17 | 广州市东山区珠峰新技术开发研究所 | The eliminating poison of chromium cinder comprehensive use |
| CN1066296A (en) * | 1991-04-29 | 1992-11-18 | 广州市珠峰研究所 | Method for treatment of chromium slag for comprehensive toxicity removal |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101112647A (en) * | 2007-06-26 | 2008-01-30 | 广州铬德工程有限公司 | Technics for expelling poison for chromic slag |
| CN101112647B (en) * | 2007-06-26 | 2010-10-27 | 广州普得环保设备有限公司 | Technics for expelling poison for chromic slag |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1201836A (en) | 1998-12-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: ZHONG LVGUANG Free format text: FORMER OWNER: GUANGZHOU CHROMIUM RESIDUE NEW TECHNOLOGY FOR TREATMENT ENGINEERING CO. Effective date: 20030509 |
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Effective date of registration: 20030509 Address after: 510170 Guangzhou Dongfeng Road Jiahe building 705 room 3 yuan Patentee after: Zhong Lvguang Address before: Tianhe District Yuanbei Xiang Po Xi Lu Zhongshan road car 510660 Guangdong city of Guangzhou province No. 27 Patentee before: Guangzhou Chromium Slag Treatment New Tech. Engineering Co. |
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Effective date of registration: 20090327 Address after: Guangzhou City, Yuexiu District Siyou new roads 111115 No. 1112 room Patentee after: Guangzhou Pude Environmental Protection Facility Co., Ltd. Address before: Guangzhou Dongfeng Road Jiahe building 705 room 3 yuan Patentee before: Zhong Lvguang |
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Denomination of invention: Method for comprehensive uses by dissolving chromium residue to eliminate toxicity Effective date of registration: 20121112 Granted publication date: 20010117 Pledgee: Societe Generale Bank, Limited by Share Ltd, Guangzhou branch Pledgor: Guangzhou Pude Environmental Protection Facility Co., Ltd. Registration number: 2012440000001 |
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Date of cancellation: 20130221 Granted publication date: 20010117 Pledgee: Societe Generale Bank, Limited by Share Ltd, Guangzhou branch Pledgor: Guangzhou Pude Environmental Protection Facility Co., Ltd. Registration number: 2012440000001 |
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| ASS | Succession or assignment of patent right |
Owner name: GUANGZHOU XINZHICHENG ENVIRONMENTAL PROTECTION TEC Free format text: FORMER OWNER: GUANGZHOU PUDE ENVIRONMENTAL PROTECTION FACILITY CO., LTD. Effective date: 20130522 |
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Free format text: CORRECT: ADDRESS; FROM: GUANGZHOU, GUANGDONG PROVINCE TO: 510600 GUANGZHOU, GUANGDONG PROVINCE |
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Effective date of registration: 20130522 Address after: 510600 Guangzhou, Yuexiu District, Temple Road, the right of the new layer on the ground floor, No. third, No. 90, No. 168 Patentee after: Guangzhou Xinzhicheng Environmental Protection Technology Machinery Equipment Co., Ltd. Address before: Room 111-115, No. 1112, Xin Xin Road, Yuexiu District temple, Guangzhou Patentee before: Guangzhou Pude Environmental Protection Facility Co., Ltd. |
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| CX01 | Expiry of patent term |
Granted publication date: 20010117 |
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