CN101407366B - Method for rapidly recycling chrome from chroming waste liquor by alkali precipitation - Google Patents
Method for rapidly recycling chrome from chroming waste liquor by alkali precipitation Download PDFInfo
- Publication number
- CN101407366B CN101407366B CN200810122128XA CN200810122128A CN101407366B CN 101407366 B CN101407366 B CN 101407366B CN 200810122128X A CN200810122128X A CN 200810122128XA CN 200810122128 A CN200810122128 A CN 200810122128A CN 101407366 B CN101407366 B CN 101407366B
- Authority
- CN
- China
- Prior art keywords
- precipitation
- waste liquor
- chromium
- chrome
- chroming waste
- 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 - Fee Related
Links
Abstract
The invention discloses a method for recovering chrome by the fast alkali precipitation of chrome tannage waste fluid, belonging to the clean production technology and recycling technology in the technical field of leather production. After the collection of chrome tannage waste fluid in the invention, the solid impurities are removed by filtering, with the temperature adjusted, magnesium oxide or other alkali matters are added; and after the full stirring and alkalization, little polyacrylamide or other flocculants are added for fast precipitation to remove supernatant liquor; and chromic hydroxide precipitate is obtained after further removing the water of the underlayer flocculent precipitate with a centrifuger. With the adoption of the method, the concentration of dichromium trioxide in the waste fluid can reduce to below 0.05g/l from 2-4g/l, the removal rate reaches over 97 percent, and the addition of the flocculants can realize the fast precipitation of chromic hydroxide in 20 minutes, the precipitation volume is lower than 15 percent of the total volume, and the precipitate has good hydrophobic nature and can be recovered conveniently. The method provides a new way for the precipitation and recycling of waste chrome liquor in a tanyard.
Description
Technical field
The invention belongs to the clearer production technology and the recycling technology of leather production technical field, particularly relate to the method that a kind of chroming waste liquor rapid precipitation reclaims chromium.
Background technology
Have more than 100 year historical chrome tanning, can give the good performance of leather because of it is the mainstream technology of leather tanning always, almost can't shake.The chrome tanning agent utilization ratio has only about 70% in the tannery of reality, and all the other chrome tanning agents of about 30% all are not utilized and enter in the waste water.Yet Chrome Tanning Wastewater is more unmanageable a kind of waste water in the tanning industry, wherein chromium sesquioxide content is up to 1～5g/l, and this high-concentration chromium-containing wastewater is as being directly emitted, not only polluted-water, harm humans health and ecotope also are the great wastings of resources simultaneously.
It is a kind of technology that cleans that useless chrome liquor is utilized again, and common useless chrome liquor reutilization technology mainly comprises dual mode: a kind of is the direct circulation method that is used for pickling or chrome tanning behind the separating impurity; A kind of is the indirect cycle method of dissolving, regenerate basic chromium sulfate by the precipitation absorption method again.
The indirect cycle method is common alkaline precipitation, oxidation style, ion exchange method, membrane permeation method etc.Comparatively speaking, alkaline precipitation is most widely used.The solubility product of chromium hydroxide is very little by (6 * 10
-31), be adjusted to 8-9 when adding the pH value of alkali with chroming waste liquor, just can form chromium hydroxide precipitation, vitriolization again after the recovery can obtain basic chromium sulfate, can be reused for chrome tanning.Conventional at present technology is that hydro-oxidation sodium is handled the chromium hydroxide precipitation that obtains, but this mode obtains the volume of chromium hydroxide precipitation and accounts for about 50% of waste liquid volume, therefore after the chroming waste liquor precipitation is complete, chromium hydroxide suspension to be squeezed into pressure-vessel with impeller pump, be pressed into plate-and-frame filter press press filtration (also available other special pumps are directly squeezed into pressure filter) with pressurized air again.This method need adopt filter press, and facility investment is higher, and labour intensity is big.In addition since this method to have obtained the chromium hydroxide precipitation particle very tiny, belong to cotton-shaped colloidal precipitation, sedimentation is very slow, hydrophobicity is poor, the ability of sticking is strong, so be attached on difficult drop-off on the filter cloth when press filtration, easily formation secondary pollution of washing when changing filter cloth.And chrome tanning liquid quality problem of unstable is reclaimed in existence.
Summary of the invention
The objective of the invention is in order to overcome the shortcoming and defect that prior art exists, and provide a kind of chromium hydroxide precipitation speed fast, the deposit seeds hydrophobicity is good, the method for a kind of rapidly recycling chrome from chroming waste liquor by alkali precipitation that cost recovery is low.
For achieving the above object, technical scheme of the present invention is, may further comprise the steps, and is wherein by weight raw materials used:
(1), remove solid substance impurity: chroming waste liquor removes by filter solid substance impurity at least 95% after collecting;
(2), alkalinisation treatment: will be heated at least 30 ℃ through the chroming waste liquor after step 1 is handled, and to add alkali and adjust PH be 8.0～9.5, and fully stirred 30～120 minutes;
(3), rapid subsidence: with adding flocculation agent and mixing in the chroming waste liquor after step 2 is handled, left standstill 20 minutes, make the chromium hydroxide sedimentation, and precipitation volume is less than 15% of solidliquid mixture cumulative volume; The chromium hydroxide molecule has just formed in step 2, but because the too little settling velocity of molecule is very slow, so what see is suspension, so the present invention adds flocculation agent, and precipitation could rapid subsidence so that the chromium hydroxide molecule forms macromole.
(4), reclaim: remove the clear liquid of handling the upper strata 60% that obtains solidliquid mixture through step 3, will remain clear liquid and precipitate floss injection whizzer and reclaim chromium hydroxide precipitation.
After the present invention collects chroming waste liquor, remove by filter solid substance impurity, attemperation, after alkaline matters such as adding magnesium oxide fully stir alkalization, add flocculation agent rapid subsidence such as a small amount of polyacrylamide, remove supernatant liquid, lower floor's flocks is further removed moisture with whizzer, has both got chromium hydroxide precipitation.Adopt in this method waste liquid chromium sesquioxide concentration to reduce to below the 0.05g/L by 2～4g/L, clearance is more than 97%, add flocculation agent and can realize rapid precipitation chromium hydroxide in 20 minutes, and precipitation volume is less than cumulative volume below 15%, and sedimentary hydrophobicity is good, and it is convenient to reclaim.This method provides a kind of new approach for tannery's useless chrome liquor precipitation reuse, the present invention is used for the cleaner production of process hides process, with the chromium that extracts after the chroming waste liquor precipitation process, again make chrome liquor and be back to use retanning system operation, can realize the closed circulation of chroming waste liquor, resultant leather quality is good simultaneously, does not have obvious influence with conventional chrome tanning, and product meets People's Republic of China's light industry standard.
As to such scheme further replenish and perfect, it is the mixture of magnesium oxide and calcium oxide that the preferred technical solution of the present invention also includes the alkali that adds in the described step 2, its addition is to add 1.3～2.0kg in every cubic metre of waste liquid, and fully stirs alkalization 30～120 minutes.
Described step 1 is carried out in grating tank, and grating tank coarse strainer mesh is not more than 1cm, and the fie screen mesh is not more than 1mm.
Described step 3 is carried out in line mixer, and described flocculation agent is a polyacrylamide, and its amount is added 3～20g for every cubic metre of chroming waste liquor.Certain flocculation agent of the present invention can also be polyacrylamide, poly aluminium chloride and Tai-Ace S 150 etc.
Described step 1 adds thermal effluent to 35 ℃～45 ℃ by the steam mode.Adding thermal effluent, to adopt type of heating to have a variety of, can electrically heated, hot water heating, steam heating etc.The heating here need be considered to dock with practice in factory, and actual tannery generally all adopts the Boiler Steam heating.If adopt electrically heated in addition, too big to equipment corrosion, adopt the hot water heating can bring more water, the present invention preferably adopts steam heating, and convenient, the temperature control scope is big.Generally speaking, the high more settling rate to chromium hydroxide of temperature is favourable, must cause power consumption serious but temperature is too high, and technical scheme of the present invention only needs that waste liquid is heated to 35 ℃-45 ℃ just can reach very fast settling rate, and the technology power consumption of comparing traditional still less.
Embodiment
Below by embodiment further introduction is done in invention.
Embodiment 1
A kind of chroming waste liquor rapid precipitation reclaims the method for chromium, may further comprise the steps, and is wherein by weight raw materials used:
(1) remove solid substance impurity: chroming waste liquor is introduced into grating tank to remove solid substance impurity after collecting, and requiring the coarse strainer mesh is 1cm, and the fie screen mesh is 1mm;
(2) alkalinisation treatment: the chrome liquor that will give up enters the alkalization device, adopts steam heating waste liquid to 30 ℃, and every cubic metre of waste liquid adds alkaline matter 2.0kg such as magnesium oxide and fully stirs alkalization 120 minutes;
(3) rapid precipitation: useless chrome liquor enters settling tank by flocculation agent mixings such as line mixer and a small amount of polyacrylamides, is deposited in rapid subsidence in 20 minutes, and precipitation volume is less than cumulative volume 15%;
(4) reclaim: remove settling tank upper strata 60% clear liquid, will remain clear liquid and precipitation floss and inject whizzer recovery chromium hydroxide precipitation.
Embodiment 2
A kind of chroming waste liquor rapid precipitation reclaims the method for chromium, may further comprise the steps, and is wherein by weight raw materials used:
(1) remove solid substance impurity: chroming waste liquor is introduced into grating tank to remove solid substance impurity after collecting, and requiring the coarse strainer mesh is 1cm, and the fie screen mesh is 1mm;
(2) alkalinisation treatment: the chrome liquor that will give up enters the alkalization device, adopts steam heating waste liquid to 35 ℃, and every cubic metre of waste liquid adds alkaline matter 1.8kg such as magnesium oxide and fully stirs alkalization 90 minutes;
(3) rapid precipitation: useless chrome liquor enters settling tank by flocculation agent mixings such as line mixer and a small amount of polyacrylamides, is deposited in rapid subsidence in 20 minutes, and precipitation volume is less than cumulative volume 15%;
(4) reclaim: remove settling tank upper strata 60% clear liquid, will remain clear liquid and precipitation floss and inject whizzer recovery chromium hydroxide precipitation.
Embodiment 3
A kind of chroming waste liquor rapid precipitation reclaims the method for chromium, may further comprise the steps, and is wherein by weight raw materials used:
(1) remove solid substance impurity: chroming waste liquor is introduced into grating tank to remove solid substance impurity after collecting, and requiring the coarse strainer mesh is 1cm, and the fie screen mesh is 1mm;
(2) alkalinisation treatment: the chrome liquor that will give up enters the alkalization device, adopts steam heating waste liquid to 40 ℃, and every cubic metre of waste liquid adds alkaline matter 1.5kg such as magnesium oxide and fully stirs alkalization 60 minutes;
(3) rapid precipitation: useless chrome liquor enters settling tank by flocculation agent mixings such as line mixer and a small amount of polyacrylamides, is deposited in rapid subsidence in 20 minutes, and precipitation volume is less than cumulative volume 15%;
(4) reclaim: remove settling tank upper strata 60% clear liquid, will remain clear liquid and precipitation floss and inject whizzer recovery chromium hydroxide precipitation.
Embodiment 4
A kind of chroming waste liquor rapid precipitation reclaims the method for chromium, may further comprise the steps, and is wherein by weight raw materials used:
(1) remove solid substance impurity: chroming waste liquor is introduced into grating tank to remove solid substance impurity after collecting, and requiring the coarse strainer mesh is 1cm, and the fie screen mesh is 1mm;
(2) alkalinisation treatment: the chrome liquor that will give up enters the alkalization device, adopts steam heating waste liquid to 45 ℃, and every cubic metre of waste liquid adds alkaline matter 1.3kg such as magnesium oxide and fully stirs alkalization 30 minutes;
(3) rapid precipitation: useless chrome liquor enters settling tank by flocculation agent mixings such as line mixer and a small amount of polyacrylamides, is deposited in rapid subsidence in 20 minutes, and precipitation volume is less than cumulative volume 15%;
(4) reclaim: remove settling tank upper strata 60% clear liquid, will remain clear liquid and precipitation floss and inject whizzer recovery chromium hydroxide precipitation.
Claims (4)
1. the method for a chroming waste liquor rapid precipitation recovery chromium is characterized in that, may further comprise the steps, and is wherein by weight raw materials used:
(1), remove solid substance impurity: chroming waste liquor removes by filter solid substance impurity at least 95% after collecting;
(2), alkalinisation treatment: will be heated at least 30 ℃ through the chroming waste liquor after step 1 is handled, and to add alkali and adjust pH be 8.0～9.5, described alkali is the mixture of magnesium oxide and calcium oxide, the mass ratio of its magnesium oxide and calcium oxide is 1: 0～1: 0.5, its addition is to add 1.3～2.0kg in every cubic metre of waste liquid, and fully stirs alkalization 30～120 minutes;
(3), rapid subsidence: with adding flocculation agent and mixing in the chroming waste liquor after step 2 is handled, left standstill 20 minutes, make the chromium hydroxide precipitation sedimentation, and precipitation volume is less than 15% of solidliquid mixture cumulative volume;
(4), recovery: remove the clear liquid of handling the upper strata 60% that obtains solidliquid mixture through step 3, with the residue clear liquid and the precipitation floss injection whizzer recovery chromium hydroxide precipitation of bottom.
2. chroming waste liquor rapid precipitation according to claim 1 reclaims the method for chromium, and it is characterized in that: described step 1 is carried out in grating tank, and grating tank coarse strainer mesh is not more than 1cm, and the fie screen mesh is not more than 1mm.
3. chroming waste liquor rapid precipitation according to claim 2 reclaims the method for chromium, and it is characterized in that: described step 3 is carried out in line mixer, and described flocculation agent is a polyacrylamide, and its amount is added 3～20g for every cubic metre.
4. chroming waste liquor rapid precipitation according to claim 3 reclaims the method for chromium, it is characterized in that: described step 1 adds thermal effluent to 35 ℃～45 ℃ by the steam mode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810122128XA CN101407366B (en) | 2008-10-28 | 2008-10-28 | Method for rapidly recycling chrome from chroming waste liquor by alkali precipitation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810122128XA CN101407366B (en) | 2008-10-28 | 2008-10-28 | Method for rapidly recycling chrome from chroming waste liquor by alkali precipitation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101407366A CN101407366A (en) | 2009-04-15 |
| CN101407366B true CN101407366B (en) | 2010-12-29 |
Family
ID=40570609
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810122128XA Expired - Fee Related CN101407366B (en) | 2008-10-28 | 2008-10-28 | Method for rapidly recycling chrome from chroming waste liquor by alkali precipitation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101407366B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101823802A (en) * | 2010-05-07 | 2010-09-08 | 海宁瑞星皮革有限公司 | Leather tanning wastewater chromium recovery unit |
| CN102381781B (en) * | 2011-09-22 | 2013-07-10 | 兄弟科技股份有限公司 | Process for recovering chromium in chrome tanned leather waste water |
| CN102381783A (en) * | 2011-09-30 | 2012-03-21 | 哈尔滨工业大学 | Processing system for changing chrome tanning wastewater into resource and processing technique thereof |
| CN103663765A (en) * | 2012-08-30 | 2014-03-26 | 浙江中辉皮草有限公司 | Treatment method of recycling fur chromium retanning liquid for plurality of times |
| CN103695970B (en) * | 2013-12-17 | 2017-01-18 | 陕西科技大学 | Method for processing chrome-containing tanned wastewater and recycling chrome metal |
| CN103693723B (en) * | 2013-12-27 | 2015-12-30 | 山东华升化工科技有限公司 | A kind of technique utilizing the rich chrome waste water of alkali precipitation process process hides |
| CN103922521B (en) * | 2014-05-07 | 2015-06-24 | 中国电建集团中南勘测设计研究院有限公司 | Method used for chrome tanning waste water treatment and chrome recovery |
| CN105523665B (en) * | 2016-01-12 | 2018-02-09 | 武汉森泰环保股份有限公司 | A kind of method that chromium is reclaimed from leather tanning wastewater |
-
2008
- 2008-10-28 CN CN200810122128XA patent/CN101407366B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101407366A (en) | 2009-04-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101407366B (en) | Method for rapidly recycling chrome from chroming waste liquor by alkali precipitation | |
| CN101648759B (en) | Recycling processing method for wastewater produced by processing stainless steel | |
| CN103011524B (en) | Recycling and processing method for printing and dyeing wastewater | |
| CN103755081B (en) | A kind of method that alkali decrement waste water resource reclaims terephthaldehyde's bronsted lowry acids and bases bronsted lowry | |
| CN105585194A (en) | Comprehensive utilization method of high-concentration waste saline water containing Na<+>, Ka<+>, NH<4+>, Cl<->, SO4<2-> and NO<3-> in coal chemical industry | |
| CN102849879A (en) | Treatment technology for recycling reverse osmosis concentrated water | |
| CN103073163B (en) | Treatment and sludge reduction device and method of de-sizing wastewater | |
| CN101423875A (en) | Process technology for recycling and reuse waste chrome liquor in retanning | |
| CN105523665A (en) | Method for recovering chromium from leather tanning waste water | |
| CN105399260A (en) | A reusing treatment method for regenerated waste water of power plant condensate fine treatment | |
| CN101863516B (en) | Method for recovering ferrite containing chromium and nickel in stainless steel pickling waste water sludge | |
| CN108793568A (en) | A kind of stainless steel cleaning containing acid wastewater zero discharge waste water unit equipment | |
| CN203602414U (en) | System for recovering silvering wastewater and silver | |
| CN109019987B (en) | Efficient recovery method of printing and dyeing wastewater | |
| CN115305574B (en) | Method for rapidly preparing whisker by using phosphogypsum and saline | |
| CN214060178U (en) | Silica gel effluent disposal system | |
| CN109054750A (en) | A kind of technique using garbage flying ash preparation deicing salt | |
| CN108751533A (en) | A kind of processing method of the acidic rinse waste water suitable for process of metal working | |
| JP5224380B2 (en) | Manufacturing method of low grade Ni recycled sludge | |
| CN209161509U (en) | A kind of salt refining system of electrolysis production chlorine and hydrogen | |
| CN108914136B (en) | Steel pipe galvanizing pretreatment process | |
| CN108083529A (en) | A kind of method that chromate waste water cooperates with processing with acid waste water | |
| CN208717127U (en) | A kind of pickling sludge resource processing apparatus | |
| CN203999643U (en) | A kind of recycling device of chroming waste liquor | |
| CN211470949U (en) | Near-zero drainage water softening system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: HUNAN LEAD LEATHER CO., LTD. Assignor: Wenzhou University Contract record no.: 2012430000082 Denomination of invention: Method for rapidly recycling chrome from chroming waste liquor by alkali precipitation Granted publication date: 20101229 License type: Exclusive License Open date: 20090415 Record date: 20120511 |
|
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20090415 Assignee: HUNAN LEAD LEATHER CO., LTD. Assignor: Wenzhou University Contract record no.: 2012430000082 Denomination of invention: Method for rapidly recycling chrome from chroming waste liquor by alkali precipitation Granted publication date: 20101229 License type: Exclusive License Record date: 20120511 |
|
| LICC | Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20101229 Termination date: 20131028 |