CN102363820B - Reutilization method of chromium-containing leather production sludge - Google Patents
Reutilization method of chromium-containing leather production sludge Download PDFInfo
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Abstract
The invention relates to a reutilization method of chromium-containing leather production sludge. The method comprises steps that: the chromium-containing leather production sludge is dissolved by using acid, and is hydrolyzed; the obtained material is filtered, and a filtrate is used for producing a chrome tanning agent; the filter residue is used for producing a chromium-containing retanning agent, such that a secondary environmental pollution problem caused by filter residue produced during the reutilization of the chromium-containing leather production sludge is completely solved. When the filtrate is used for producing the chrome tanning agent, a powdery chrome tanning agent is produced.
Description
Technical field
The invention belongs to the clearer production technology in a kind of tanning industry, particularly relate to a kind of reutilization method of chromium-containing leather production sludge, with the problem of the mud contaminate environment that produces in the thorough solution leather production.
Background technology
The mud that produces in the leather production causes severe contamination to environment.It all is with after the acid dissolving that present existing process hides chromium-bearing sludge is recycled scheme, through filtering, filtrate is mixed with the chrome tanning agent that process hides is used, but the filter residue after filtering is not all processed.The main component of filter residue is scurf hydrolytic residue and inorganic salt precipitate, and itself still for containing chromium solid waste thing, does not recycle, and will cause secondary pollution to environment.Eliminate the filter residue secondary pollution, realize the utilization of filter residue, thoroughly solve the problem of the mud contaminate environment that produces in the leather production, become the important technical problem that tanning industry needs to be resolved hurrily.
Summary of the invention
The present invention is directed to above-mentioned the deficiencies in the prior art, recycle scheme in conjunction with existing process hides chromium-bearing sludge, when filtrate recycle prepares chrome tanning agent, analysis filter residue composition is also utilized, realized that whole reclaiming system produces without secondary environmental pollution, thoroughly solved the problem of filter residue secondary pollution environment.
The technical scheme that technical solution problem of the present invention is taked is: a kind of reutilization method of chromium-containing leather production sludge, comprise that the process hides chromium-bearing sludge with acid dissolving, is hydrolyzed again, then filter and with filtrate for the production of chrome tanning agent; Also comprise filter residue for the production of containing chromium retanning agent, the problem of the filter residue Re-pollution environment that is produced during with thorough solution process hides chromium-bearing sludge reuse; Described is to produce chrome tanning powder with filtrate for the production of chrome tanning agent.
Described reutilization method of chromium-containing leather production sludge comprises that the recovery of process hides chromium-bearing sludge, sour dissolving, hydrolysis, filtration, filtrate recycle are produced chrome tanning powder and filter residue reuse production contains chromium retanning agent, wherein:
⑴ process hides chromium-bearing sludge reclaims: tannery is just tanned waste water through fine filtering and precipitates to reclaim namely obtains the process hides chromium-bearing sludge, and its chromium sesquioxide content is greater than 8wt%, and total solids level is greater than 30 wt%, and calcium hydroxide content is less than 2 wt%;
⑵ acid dissolving, hydrolysis: under whipped state, it is that the mass ratio of process hides chromium-bearing sludge and dilute sulphuric acid is 1～3:1 in 40%～60% the dilute sulphuric acid that the process hides chromium-bearing sludge that reclaims is put into concentration, after process hides contains leather mud input, slowly be warming up to 60～90 ℃, stir, be hydrolyzed 2～4 hours;
⑶ filter: be cooled to 30～50 ℃, filter, get filtrate and filter residue;
⑷ filtrate recycle is produced chrome tanning powder: sodium dichromate is put in the filtration step ⑶ gained filtrate, and input amount is 14%～45% of process hides chromium-bearing sludge quality, then drips β-amylose solution and carries out reduction reaction and make chromium slurry solution; Wherein part chromium slurry solution carries out spraying drying between 150～170 ℃, gets the chrome tanning powder that process hides is used;
⑸ filter residue reuse is produced and contained chromium retanning agent: the resulting part chromium slurry of reduction reaction solution mixes with synthetic tanning agent in the lump among filtration step ⑶ gained filter residue and the filtrate recycle production chrome tanning powder step ⑷, chromium slurry solution: filter residue: the mass ratio of synthetic tanning agent is 6:0.3～1:3～3.5, be blended under 40～50 ℃ and carry out through clarifixator, then between 150～170 ℃, carry out spraying drying, get the chromium retanning agent that contains that process hides uses.
As a kind of preferred, described filtration adopts plate-and-frame filter press to filter.
As a kind of preferred, described synthetic tanning agent is the condenses of phenol sulfonic acid and formaldehyde, and its structural formula is
N=1～3 wherein; Or be the condenses of sulfone and phenol sulfonic acid and formaldehyde, its structural formula is
Or
Or be the sulfonated bodies of sulfone, its structural formula is
As a kind of preferred, the technological process that reduction reaction among the described filtrate recycle production chrome tanning powder step ⑷ makes chromium slurry solution is: after dropping into sodium dichromate in the filtrate, slowly be warmed up to 90～100 ℃, insulated and stirred 2 hours, then be cooled to 80～85 ℃, the dropping mass content is 50% the β-amylose aqueous solution, the quality of the β-amylose aqueous solution that drips is 50% of sodium dichromate input quality, time for adding approximately 1 hour, hexavalent chrome reduction is become trivalent chromium, 95～100 ℃ of insulated and stirred 1 hour, then cool to 40～60 ℃ after being added dropwise to complete, detect control sexavalent chrome residual volume and be no more than 2mg/kg, namely make chromium slurry solution.
The present invention compares with general process hides chromium-bearing sludge reusing plan, and reuse is thorough, and the filter residue that produces in the reuse process has also been carried out sufficient utilization, makes it have use value, has avoided simultaneously containing the problem of chromium filter residue secondary pollution environment.
Embodiment
Embodiment 1:
It is to dissolve in 55% the dilute sulphuric acid that 680kg concentration is put in the gradation of 2000kg process hides chromium-bearing sludge, then slowly is warmed up to and stirs hydrolysis 4 hours between 80～90 ℃, cools to 30～40 ℃ and gets filtrate 2620kg and filter residue 60kg through filter presss.
The sodium dichromate of 280kg is put in the 2620kg filtrate of gained, then slowly be warmed up between 90～100 ℃, and 90～100 ℃ of insulated and stirred 2 hours, insulation cools to 80～85 ℃ after finishing, and to drip mass content be 50% β-amylose aqueous solution 140kg, drip approximately and finished in 1 hour, hexavalent chrome reduction is become trivalent chromium, after being added dropwise to complete between 95～100 ℃ insulated and stirred 1 hour, detect control sexavalent chrome residual volume and be no more than 2mg/kg, then cool between 40～60 ℃, namely get chromium slurry solution 3000kg.
Getting 2640kg chromium slurry solution carries out spraying drying and gets the chrome tanning powder that process hides is used between 150～170 ℃ of inlet temperature; 360kg chromium slurry solution and 60kg filter residue and structural formula are in addition
Phenol sulfonic acid and the condenses 180kg of formaldehyde drop in the lump in the clarifixator, at 40～50 ℃ of intimate mixing after 30 minutes, between 150～170 ℃ of inlet temperature, carry out spraying drying and get the chromium retanning agent that contains that process hides uses.
Embodiment 2:
It is to dissolve in 55% the dilute sulphuric acid that 1000kg concentration is put in the gradation of 2000kg process hides chromium-bearing sludge, then slowly is warmed up to and stirs hydrolysis 3 hours between 70～80 ℃, cools to 40～50 ℃ and gets filtrate 2940kg and filter residue 60kg through filter presss.
The sodium dichromate of 350kg is put in the 2940kg filtrate of gained, then slowly be warmed up between 90～100 ℃, and 90～100 ℃ of insulated and stirred 2 hours, insulation cools to 80～85 ℃ after finishing, and to drip mass content be 50% β-amylose aqueous solution 170kg, drip approximately and finished in 1 hour, hexavalent chrome reduction is become trivalent chromium, after being added dropwise to complete between 95～100 ℃ insulated and stirred 1 hour, detect control sexavalent chrome residual volume and be no more than 2mg/kg, then cool between 40～60 ℃, namely get approximately 3460kg of chromium slurry solution.
Getting 2660kg chromium slurry solution carries out spraying drying and gets the chrome tanning powder that process hides is used between 150～170 ℃ of inlet temperature; 800kg chromium slurry solution and 60kg filter residue and structural formula are in addition
Sulfone and the condenses 450kg of phenol sulfonic acid and formaldehyde drop in the lump in the clarifixator, at 40～50 ℃ of intimate mixing after 30 minutes, between 150～170 ℃ of inlet temperature, carry out spraying drying and get the chromium retanning agent that contains that process hides uses.
Embodiment 3:
It is to dissolve in 55% the dilute sulphuric acid that 2000kg concentration is put in the gradation of 2000kg process hides chromium-bearing sludge, then slowly is warmed up to and stirs hydrolysis 3 hours between 60～70 ℃, cools to 40～50 ℃ and gets filtrate 3940kg and filter residue 60kg through filter presss.
The sodium dichromate of 900kg is put in the 3940kg filtrate of gained, then slowly be warmed up between 90～100 ℃, and 90～100 ℃ of insulated and stirred 2 hours, after insulation is finished 80～85 ℃ of cooling to drip mass content be 50% β-amylose aqueous solution 450kg, drip approximately and finished in 1 hour, hexavalent chrome reduction is become trivalent chromium, after being added dropwise to complete between 95～100 ℃ insulated and stirred 1 hour, detect control sexavalent chrome residual volume and be no more than 2mg/kg, then cool between 40～60 ℃, namely get approximately 5290kg of chromium slurry solution.
Getting 4290kg chromium slurry solution carries out spraying drying and gets the chrome tanning agent pulvis that process hides is used between 150～170 ℃ of inlet temperature; 1000kg chromium slurry solution and 60kg filter residue and structural formula are in addition
The sulfonated bodies 580kg of sulfone drop into together in the clarifixator, at 40～50 ℃ of intimate mixing after 30 minutes, between 150～170 ℃ of inlet temperature, carry out spraying drying and get the chromium retanning agent that contains that process hides uses.
Embodiment 4:
Wherein synthetic tanning agent adopts structural formula to be
Phenol sulfonic acid and the condenses of formaldehyde, add-on is 190kg, all the other are identical with embodiment 1.
Embodiment 5:
Wherein synthetic tanning agent adopts structural formula to be
Phenol sulfonic acid and the condenses of formaldehyde, add-on is 210kg, all the other are identical with embodiment 1.
Embodiment 6:
Wherein synthetic tanning agent adopts structural formula to be
Sulfone and the condenses of phenol sulfonic acid and formaldehyde, add-on is 400kg, all the other are identical with embodiment 2.
Embodiment 7:
Wherein synthetic tanning agent adopts structural formula to be
The sulfonated bodies of sulfone, add-on is 500 kg, all the other are identical with embodiment 3.
Claims (4)
1. reutilization method of chromium-containing leather production sludge comprises that the process hides chromium-bearing sludge with the acid dissolving, is hydrolyzed again, then filter and with filtrate for the production of chrome tanning agent; It is characterized in that, comprise also that with filter residue for the production of containing chromium retanning agent, described is to produce chrome tanning powder with filtrate for the production of chrome tanning agent; Concrete steps comprise that the recovery of process hides chromium-bearing sludge, sour dissolving, hydrolysis, filtration, filtrate recycle are produced chrome tanning powder and filter residue reuse production contains chromium retanning agent, wherein:
⑴ process hides chromium-bearing sludge reclaims: tannery is just tanned waste water through fine filtering and precipitates to reclaim namely obtains the process hides chromium-bearing sludge, and its chromium sesquioxide content is greater than 8wt%, and total solids level is greater than 30 wt%, and calcium hydroxide content is less than 2 wt%;
⑵ acid dissolving, hydrolysis: under whipped state, it is that the mass ratio of process hides chromium-bearing sludge and dilute sulphuric acid is 1～3:1 in 40%～60% the dilute sulphuric acid that the process hides chromium-bearing sludge that reclaims is put into concentration, after the process hides chromium-bearing sludge drops into, slowly be warming up to 60～90 ℃, stir, be hydrolyzed 2～4 hours;
⑶ filter: be cooled to 30～50 ℃, filter, get filtrate and filter residue;
⑷ filtrate recycle is produced chrome tanning powder: sodium dichromate is put in the filtration step ⑶ gained filtrate, and input amount is 14%～45% of process hides chromium-bearing sludge quality, then drips β-amylose solution and carries out reduction reaction and make chromium slurry solution; Wherein part chromium slurry solution carries out spraying drying between 150～170 ℃, gets the chrome tanning powder that process hides is used;
⑸ filter residue reuse is produced and contained chromium retanning agent: the resulting part chromium slurry of reduction reaction solution mixes with synthetic tanning agent in the lump among filtration step ⑶ gained filter residue and the filtrate recycle production chrome tanning powder step ⑷, chromium slurry solution: filter residue: the mass ratio of synthetic tanning agent is 6:0.3～1:3～3.5, be blended under 40～50 ℃ and carry out through clarifixator, then between 150～170 ℃, carry out spraying drying, get that process hides uses contain chromium retanning agent.
2. reutilization method of chromium-containing leather production sludge as claimed in claim 1 is characterized in that: the filtration of described filtration employing plate-and-frame filter press.
3. reutilization method of chromium-containing leather production sludge as claimed in claim 1, it is characterized in that: described synthetic tanning agent is the condenses of phenol sulfonic acid and formaldehyde:
N=1～3 wherein; Perhaps be the condenses of sulfone and phenol sulfonic acid and formaldehyde:
Or
Perhaps be the sulfonated bodies of sulfone:
Or
4. reutilization method of chromium-containing leather production sludge as claimed in claim 1, it is characterized in that: the technological process that the reduction reaction among the described filtrate recycle production chrome tanning powder step ⑷ makes chromium slurry solution is: after dropping into sodium dichromate in the filtrate, slowly be warmed up to 90～100 ℃, insulated and stirred 2 hours, then be cooled to 80～85 ℃, the dropping mass content is 50% the β-amylose aqueous solution, the quality of the β-amylose aqueous solution that drips is 50% of sodium dichromate input quality, time for adding approximately 1 hour, hexavalent chrome reduction is become trivalent chromium, after being added dropwise to complete 95～100 ℃ of insulated and stirred 1 hour, then cool to 40～60 ℃, detect control sexavalent chrome residual volume and be no more than 2mg/kg, namely make chromium slurry solution.
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102965455B (en) * | 2012-10-29 | 2014-05-07 | 浙江特力再生资源有限公司 | Method for preparing basic chromium sulfate tanning liquor by using tanning chromium sludge |
| CN103014191B (en) * | 2012-12-13 | 2014-11-05 | 四川大学 | Method for recovering collagen and chromium salts from chromium-containing scrap leather residues |
| CN103352092A (en) * | 2012-12-24 | 2013-10-16 | 山东华升化工科技有限公司 | Method for preparation of chrome tanning agent and combined production of vitamin K3 through using chromium-rich sludge |
| CN103351089A (en) * | 2012-12-24 | 2013-10-16 | 山东华升化工科技有限公司 | Method for preparing autoalkalization chromium tanning agent through utilizing leather making chromium-rich sludge |
| CN104310733A (en) * | 2014-11-05 | 2015-01-28 | 北京泛博化学股份有限公司 | Method and device for recycling chromium-containing sludge |
| CN104609683B (en) * | 2014-12-12 | 2016-10-05 | 浙江工商大学 | A kind of renovation process of chrome tanning Heavy Metals in Sludge chromium |
| CN104498648B (en) * | 2014-12-17 | 2016-05-18 | 四川大学 | A kind of method of preparing chrome tanning agent from chroming waste liquor |
| CN107099623B (en) * | 2017-03-08 | 2019-04-12 | 四川大学 | A kind of microwave-assisted method for preparing chrome tanning agent using Vitamin K3 production waste liquid |
| CN108315509B (en) * | 2018-01-23 | 2020-07-24 | 山东华升化工科技有限公司 | Method for preparing chrome tanning agent by using sodium hydrosulfite |
| CN109879559A (en) * | 2019-04-16 | 2019-06-14 | 陕西科技大学 | A kind of de- chromium device and its dechromium method of chromium-bearing sludge chemical extraction |
| CN110540354B (en) * | 2019-08-20 | 2022-04-05 | 中国皮革制鞋研究院有限公司 | Resource recycling process for materialized sludge in leather making industry |
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| CN1034187A (en) * | 1988-01-16 | 1989-07-26 | 广西河池师范专科学校 | Comprehensive treatment of tanning sewage by sulfuric acid process |
| CN1220174A (en) * | 1997-12-19 | 1999-06-23 | 李振亚 | Process for recovery of waste chromium liquid |
| CN102167482A (en) * | 2011-01-19 | 2011-08-31 | 陕西科技大学 | Method for extracting Cr3+ and Fe3+ from tannery sludge |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1034187A (en) * | 1988-01-16 | 1989-07-26 | 广西河池师范专科学校 | Comprehensive treatment of tanning sewage by sulfuric acid process |
| CN1220174A (en) * | 1997-12-19 | 1999-06-23 | 李振亚 | Process for recovery of waste chromium liquid |
| CN102167482A (en) * | 2011-01-19 | 2011-08-31 | 陕西科技大学 | Method for extracting Cr3+ and Fe3+ from tannery sludge |
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