CN103351089A - Method for preparing autoalkalization chromium tanning agent through utilizing leather making chromium-rich sludge - Google Patents
Method for preparing autoalkalization chromium tanning agent through utilizing leather making chromium-rich sludge Download PDFInfo
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- CN103351089A CN103351089A CN2012105650558A CN201210565055A CN103351089A CN 103351089 A CN103351089 A CN 103351089A CN 2012105650558 A CN2012105650558 A CN 2012105650558A CN 201210565055 A CN201210565055 A CN 201210565055A CN 103351089 A CN103351089 A CN 103351089A
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Abstract
The invention relates to a method for preparing an autoalkalization chromium tanning agent through utilizing leather making chromium-rich sludge. The method mainly aims at the recovery and utilization of leather making chromium-rich sludge generated through processing a chromium-containing waste liquid in a leather making tanning operation. The method comprises the following steps: acidifying the leather making chromium-rich sludge, filtering, compounding, injecting powder, adding an autoalkalization agent, and mixing to produce the autoalkalization tanning agent. The method is a most economic processing method, tanning agent products satisfying the market demands can be produced through the method, and the cycle use of heavy metal chromium in the leather making industry is realized, so secondary chromium pollution is eliminated, the gradation alkali extraction disadvantage in the leather making tanning process is simplified, and automatic alkali extraction is realized.
Description
Technical field
The invention belongs to a kind of production technology of utilization of waste as resource, mainly is the recycle for the rich chromium mud of process hides, solves the leather-making enterprises chromate waste water from the source to the pollution of environment, and creates certain society and economic benefit.
Background technology
China's chromium ore resource is relatively poorer, belong to the national strategy resource, the chromium resource waste is serious in the tanning industry, the rich chromium mud that present most of leather-making enterprises produces adopts to be stacked, landfill, the methods of disposal such as burning, real the realization do not recycled, and can't fundamentally solve rich chromium Heavy Metals in Sludge chromium to the pollution of environment yet; There is the part leather-making enterprises to begin to adopt and recycles Chrome Tanning Wastewater, Chrome Tanning Wastewater is carried out being back to after the simple process method of leather-making technology, but complicated component in the waste water, the technology controlling and process difficulty, it is stable that the quality product of leather goods is difficult to control, so can not get effective popularization.
Summary of the invention
The certainly alkalization chrome tanning agent product that the present invention develops mainly for the recycle of the rich chromium mud of the chromate waste water disposal generation of discharging in the leather industry tanning operation not only allows rich chromium mud turn waste into wealth, and has also thoroughly solved the problem of secondary pollution.Simplifying simultaneously needs gradation to put forward the drawback of alkali in the process hides tannery, realize that Automatic continuous carries alkali, has improved the labor force of leather-making enterprises in the tanning operation and has dropped into, and reduces production costs and guarantees to put forward the stability of alkali process.
Technical scheme of dealing with problems of the present invention is: a kind of method of utilizing the rich chromium mud of process hides to prepare the chrome tanning agent that certainly alkalizes comprises recovery and the utilization thereof of the process hides chromate waste water being disposed the rich chromium mud that produces; Also comprise the acidolysis of rich chromium mud process, filter, adjust, dust, add from basifier, for the production of the chrome tanning powder that certainly alkalizes; Also comprise solving in the process hides tannery needing gradation to put forward the drawback of alkali, realize automatic lifting alkali, improved the labor force of leather-making enterprises in the tanning operation and dropped into, reduce production costs and guarantee to put forward the stability of alkali process.
Described a kind of method of utilizing the rich chromium mud of process hides to prepare the chrome tanning agent that certainly alkalizes comprises that rich chromium mud reclaims, and acidifying is filtered, and adjusts, and two water washing technology of tan pulvis and filter residue are removed from office in the rear production of dusting, wherein:
(1) recovery of chromium-bearing sludge: the chromate waste water that leather-making enterprises tanning operation produces is through the alkali precipitation technical finesse, and filter pressing gets rich chromium mud, and wherein chromium sesquioxide content is greater than 8wt%, and solid content is greater than 25wt%, and iron level is less than 0.1wt%, without dyestuff impurity.
(2) acidifying: rich chromium mud is added in the reaction flask, do not opening the sulfuric acid (98wt%) that slowly drips the 25-40wt% of the chromium mud amount of giving money as a gift in the whipping process, notice that foam generates more violent, drip proper quantity of defoaming agent, prevent flash, acid drips at 2/3rds o'clock, slowly open and stir, continue to drip, the control temperature of reaction is no more than 60 ℃, after dripping acid, continue to stir acidifying 3-4 hour.
(3) filter: after rich chromium mud all dissolves, select suction filtration or press filtration mode to carry out filtration treatment, obtain filtrate and filter residue.
(4) adjust: after filtrate changes adjustment tank over to, be adjusted to suitable basicity and concentration, namely get the liquid chrome tanning agent.
(5) dust: the liquid chrome tanning agent is carried out spraying drying between 150-170 ℃, make chromium powder.
(6) the alkaline agent batch mixing is carried in interpolation: carry the 0.25-0.5 that the alkaline agent consumption is chromium powder chromium sesquioxide weight), after mixing, make from alkalizing the formula chrome tanning powder.
(7) processing of filter residue: filter residue is through two water washing technology, reach general industry solid waste discharge standard after, discharge.
(8) the described a kind of rich chromium mud preparation of process hides two water washing technology in the method for the chrome tanning agent that alkalizes of utilizing comprise, filter residue passes through first the sulfuric acid acid rinsing of PH=2-2.5, after the washings water outlet is limpid, pass into again the soda lye wash that is dissolved with sodium hydroxide of pH=11-12 between the washings water outlet pH=8-9, carry out deslagging.When wherein adopting pumping and filtering device, acid, neutralizing treatment hydromining carry out with top spraying drip washing mode, and acid, neutralizing treatment water directly pass in the pressure filter and washs when adopting filtering equipment.Feed liquid is sneaked in the filtrate behind the acid rinsing, and feed liquid enters the buck pond for recovering and recycles after the soda lye wash.
Specific implementation method
Example 1 is 360g(chromium sesquioxide content 8.69wt%, solid content 35wt%) the process hides chromium-bearing sludge is put in the reaction flask, slowly drip sulfuric acid 32g(98wt%), drip in case of necessity proper quantity of defoaming agent, prevent flash, when sulfuric acid drips 2/3rds, slowly open the pond, ground and stir, after sulfuric acid all drips, continue to stir, acidifying 3-4 hour, treat that chromium hydroxide all is converted into the sulfuric acid chrome liquor in the rich chromium mud, through after the press filtration, obtain filtrate and filter residue, (pH=2-2.5) thoroughly washs filter residue by sour water, and washings all changes in the filtrate, again in filter residue, pass into sodium hydroxide solution (pH=11-12), make secondary filtrate pH value bring up to 8-9(and filter late detection drain pipe filtrate pH value), filtrate all changes the buck pond for recovering over to, the cleaning filter residue.
Be that the filtrate 500g of 6.25wt% changes in the reaction flask with chromium content, ℃ insulation of intensification degree to 100, concentrated sampling detection chromium content 12.35wt% after two hours, PH=2.5, whole chromium slurries are changed over to transfer tank, the chromium slurry carries out spraying drying between 150-160 ℃, make chromium sesquioxide content 25.3wt%, and basicity 30% chrome tanning powder work in-process are 125g approximately.The chrome tanning powder work in-process are carried alkaline agent with oneself mix by the weight ratio of 3:1, fully behind the mixing, namely get the certainly alkalization chrome tanning powder (chromium sesquioxide content 19wt%) that process hides is used.
Example 2 is 360g(chromium sesquioxide content 8.69wt%, solid content 35wt%) the process hides chromium-bearing sludge is put in the reaction flask, slowly drip sulfuric acid 40g(98wt%), drip in case of necessity proper quantity of defoaming agent, prevent flash, when sulfuric acid drips 2/3rds, slowly opening the pond, ground stirs, after sulfuric acid all drips, continue to stir acidifying 3-4 hour, treat that chromium hydroxide all is converted into the sulfuric acid chrome liquor in the rich chromium mud, through behind the filter press, obtain filtrate and filter residue, (pH=2-2.5) thoroughly washs filter residue by sour water, washings all changes in the filtrate, in filter residue, pass into sodium hydroxide solution (pH=11-12) again, make secondary filtrate pH value bring up to 8-9(and filter late detection drain pipe filtrate pH value), filtrate all changes the recycle of alkali liquor pond over to, the cleaning filter residue, packed after, be put into general mud storeroom.
Filtrate (chromium sesquioxide content 6%) approximately 510g changes in the reaction flask, ℃ insulation of intensification degree to 100, concentrated sampling detection chromium content 12.5wt% after two hours, PH=2, whole chromium slurries are changed over to transfer tank, the chromium slurry carries out spraying drying between 150-160 ℃, make chromium sesquioxide content 25wt%, and basicity 25% chrome tanning powder work in-process are 125g approximately.The chrome tanning powder work in-process are carried alkaline agent with oneself mix by the weight ratio of 2:1, fully behind the mixing, namely get the certainly alkalization chrome tanning powder (chromium sesquioxide content 16.8wt%) that process hides is used.
Claims (4)
1. one kind is utilized the rich chromium mud preparation of process hides from the method for the chrome tanning agent that alkalizes, and it is characterized in that, comprises the recovery of rich chromium mud; And the acidifying of rich chromium mud, filter, composite, dust, add from basifier and mix, produce from alkalizing chrome tanning powder, in this method, also comprise the processing of press filtration filter residue, the secondary pollution in the chromium-bearing sludge treating processes is solved thoroughly.
2. as claimed in claim 1ly a kind ofly utilize the rich chromium mud preparation of process hides from the method for the chrome tanning agent that alkalizes, it is characterized in that, may further comprise the steps: the recovery of (1) chromium-bearing sludge: the chromate waste water of leather-making enterprises tanning operation discharging is through the alkali precipitation technical finesse, be pressed into rich chromium mud, require solid content greater than 25wt%, butt chromium trioxide content is greater than 15wt%, and iron level is less than 0.1wt%, without dyestuff impurity; (2) rich chromium mud acidifying: rich chromium mud is put in the reaction flask, do not opening the sulfuric acid (98%) that slowly drips the 25-40wt% of the chromium mud amount of giving money as a gift in the whipping process, foam generates more violently in the process, drips proper quantity of defoaming agent, prevents flash, acid drips at 2/3rds o'clock, slowly open and stir, continue to drip, drip sulfuric acid acid after, continue to stir acidifying 3-4 hour, the control of acidization temperature is no more than 60 ℃; (3) filter: rich chromium mud is selected suitable filtration unit after all dissolving, and carries out filtration treatment, obtains filtrate and filter residue; (4) adjust: after filtrate changes adjustment tank over to, basicity is adjusted to 20-40%, degree Beaume is adjusted to 48-52; (5) dust: adjust rear filtrate and between 150-200 ℃, dry to moisture content 6-10wt%, make chromium powder; (6) batch mixing: roll over chromium sesquioxide weight according to chromium powder: the ratio from basifier weight=2-4:1 is carried out batch mixing, after mixing, makes from alkalizing chrome tanning powder; (7) innoxious process for treating of filter residue: filter residue passes through first the sulfuric acid acid rinsing of PH=2-2.5, after the washings water outlet is limpid, pass into again the soda lye wash that is dissolved with sodium hydroxide of pH=11-12 between the washings water outlet pH=8-9, carry out deslagging, this waste residue Leaching meets general industry solid waste standard after testing.
3. a kind ofly as claimed in claim 2 utilize the rich chromium mud preparation of process hides from the method for the chrome tanning agent that alkalizes, it is characterized in that, used filtration unit, when adopting pumping and filtering device, acid, neutralizing treatment hydromining carry out with top spraying drip washing mode; Acid, neutralizing treatment water directly pass in the pressure filter and wash when adopting filtering equipment.
4. a kind ofly as claimed in claim 2 utilize the rich chromium mud preparation of process hides from the method for the chrome tanning agent that alkalizes, it is characterized in that, employed from basifier, for company's self-control, comprising: the composite mixture of one or more in magnesium oxide, calcium oxide, magnesiumcarbonate, calcium carbonate, metasilicate, phosphoric acid salt, formate, the oxalate.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2012105650558A CN103351089A (en) | 2012-12-24 | 2012-12-24 | Method for preparing autoalkalization chromium tanning agent through utilizing leather making chromium-rich sludge |
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| CN2012105650558A CN103351089A (en) | 2012-12-24 | 2012-12-24 | Method for preparing autoalkalization chromium tanning agent through utilizing leather making chromium-rich sludge |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103667545A (en) * | 2013-12-27 | 2014-03-26 | 山东华升化工科技有限公司 | Preparation method for preparing self-alkalization chrome tanning agent with chrome sludge |
| CN103695576A (en) * | 2013-12-27 | 2014-04-02 | 山东华升化工科技有限公司 | Composite automatic basifying agent for tanning leathers |
| CN104498648A (en) * | 2014-12-17 | 2015-04-08 | 四川大学 | Method for preparing chrome tanning agent from waste chrome tanning liquid |
| CN110540354A (en) * | 2019-08-20 | 2019-12-06 | 中国皮革制鞋研究院有限公司 | Resource recycling process for materialized sludge in leather making industry |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1302907A (en) * | 2000-12-08 | 2001-07-11 | 山东轻工业学院 | Process for preparing chrome tanning agent |
| RU2230794C1 (en) * | 2003-04-30 | 2004-06-20 | Санкт-Петербургский государственный университет технологии и дизайна | Exhausted chrome tanning solution regeneration method |
| CN102363820A (en) * | 2011-09-22 | 2012-02-29 | 兄弟科技股份有限公司 | Reutilization method of chromium-containing leather production sludge |
| CN102787182A (en) * | 2012-08-01 | 2012-11-21 | 四川大学 | Self-alkalization masking zirconium-aluminum-titanium complex tanning agent |
-
2012
- 2012-12-24 CN CN2012105650558A patent/CN103351089A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1302907A (en) * | 2000-12-08 | 2001-07-11 | 山东轻工业学院 | Process for preparing chrome tanning agent |
| RU2230794C1 (en) * | 2003-04-30 | 2004-06-20 | Санкт-Петербургский государственный университет технологии и дизайна | Exhausted chrome tanning solution regeneration method |
| CN102363820A (en) * | 2011-09-22 | 2012-02-29 | 兄弟科技股份有限公司 | Reutilization method of chromium-containing leather production sludge |
| CN102787182A (en) * | 2012-08-01 | 2012-11-21 | 四川大学 | Self-alkalization masking zirconium-aluminum-titanium complex tanning agent |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103667545A (en) * | 2013-12-27 | 2014-03-26 | 山东华升化工科技有限公司 | Preparation method for preparing self-alkalization chrome tanning agent with chrome sludge |
| CN103695576A (en) * | 2013-12-27 | 2014-04-02 | 山东华升化工科技有限公司 | Composite automatic basifying agent for tanning leathers |
| CN104498648A (en) * | 2014-12-17 | 2015-04-08 | 四川大学 | Method for preparing chrome tanning agent from waste chrome tanning liquid |
| CN110540354A (en) * | 2019-08-20 | 2019-12-06 | 中国皮革制鞋研究院有限公司 | Resource recycling process for materialized sludge in leather making industry |
| 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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Application publication date: 20131016 |