CN103352092A - Method for preparation of chrome tanning agent and combined production of vitamin K3 through using chromium-rich sludge - Google Patents
Method for preparation of chrome tanning agent and combined production of vitamin K3 through using chromium-rich sludge Download PDFInfo
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- CN103352092A CN103352092A CN2012105652642A CN201210565264A CN103352092A CN 103352092 A CN103352092 A CN 103352092A CN 2012105652642 A CN2012105652642 A CN 2012105652642A CN 201210565264 A CN201210565264 A CN 201210565264A CN 103352092 A CN103352092 A CN 103352092A
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Abstract
The invention relates to a method for the preparation of a chrome tanning agent and the combined production of vitamin K3 through using chromium-rich sludge. The method comprises a step of purifying chromium-rich sludge generated in a leather making enterprise, and a step of combining with a waste liquid generated in the production of vitamin K3 to prepare the chrome tanning agent. The method solves a discharge problem of the waste liquid generated in the production of vitamin K3, and also well solves discharge and processing problems of chromium-containing solid dangerous wastes of the leather making enterprise.
Description
Technical field
The invention belongs to a kind of clean method for producing, relate to reuse method, especially the coproducing vitamin K of the rich chromium mud of a kind of leather industry
3The refuse reclamation technology of production makes the rich chromium mud of process hides, vitamin K
3Produce refuse and can all realize recycling production process hides chrome tanning agent.Solve the rich chromium mud of leather industry, vitamin K
3Produce the problem of environmental pollution of refuse.
Background technology
The monitoring management of state key industry heavy metals emission has been listed in tanning industry pollution of chromium discharging in.The research of present rich chromium mud mainly concentrates on the leather-making enterprises internal recycling and uses, and also has and sees that leather chemical industry enterprise contains chrome tanning agent and retanning agent product as single exploitation.But utilize the rich chromium sludge disposal of leather industry and coproduction K
3Preparation chrome tanning agent product solves two industry environment pollution problems simultaneously, still belongs to precedent.Economy solves industrial enterprise's environmental issue, breaks through the vein Economic Development Mode, is the technological breakthrough that we attempt walking out.
Summary of the invention
The present invention is directed to the problems referred to above, in conjunction with leather industry rich chromium sludge disposal technique and existing vitamin K
3Production technique proposes once to solve the method that two industry pollutents are turned waste into wealth, and has realized rich chromium mud, vitamin K
3Chrome waste liquid, vitamin K
3Being prepared in conjunction with utilization of three kinds of Hazardous wastess of solvent alcohol rectification residue meets the chrome tanning agent product that GB requires, and thoroughly solves the problem of environmental pollution of these three kinds of Hazardous wastess.
The technical scheme that technical solution problem of the present invention is taked is: a kind of rich chromium mud prepares chrome tanning agent coproducing vitamin K
3Method, comprise rich chromium mud being prepared into through operations such as oven dry, pulverizing, screenings to contain chromium hydroxide be main powder, and then it put into vitamin K
3Carry out initial action by dissolving, temperature control operation in the chrome waste liquid; Also be included under the certain temperature condition and add reductive agent and carry out secondary reaction, wherein sexavalent chrome Restore All is become trivalent, replace above-mentioned reductive agent with the ethanol refinery residue, solution ethanol refinery residue emission problem; The operation such as do finally by ageing, spray and make the commercial chromium tanning agent.
Described a kind of rich chromium mud prepares chrome tanning agent coproducing vitamin K
3Method, comprise that rich chromium sludge pretreatment becomes the chromium hydroxide powder; With above-mentioned powder and vitamin K
3Chrome waste liquid carries out initial action; Adding alcohol residue is made reductive agent and is carried out secondary reaction; The chrome liquor adjustment that at last above-mentioned steps is generated is re-dubbed chrome tanning agent.Wherein
(1) rich chromium sludge pretreatment: the chromium hydroxide powder chromium sesquioxide content 15-25wt% after requiring to process, particle order number is greater than 100 orders.
(2) the initial action stage: with chromium hydroxide powder and vitamin K
3Chrome waste liquid carries out the acid-base neutralisation reaction in proportion, then is warming up to 65-100 ℃ of insulation 3 hours, makes the organism generation redox reaction in the chrome waste liquid, and organism is fully decomposed.
(3) the secondary reaction stage: 70-95 ℃ of control temperature, drip alcohol residue reductive agent, carry out the secondary oxidation reduction reaction, and be incubated 1 hour, make the sexavalent chrome Restore All become trivalent chromium.
(4) adjusting reaction feed liquid chromium sesquioxide concentration is 12-15wt%, and basicity 30-40% is the liquid chrome tanning agent.After chrome tanning agent dusted the pulvis chrome tanning agent.
As a kind of preferred, described chromium hydroxide powder and vitamin K
3The technological process of producing the refuse step of reaction is: it is the vitamin K of 7.5wt% that the chromium hydroxide powder is added chromium sesquioxide content in the ratio of the ratio 1:2-5 of chromium content
3In the chrome waste liquid, prevent the foam flash, can add proper quantity of defoaming agent, then be warming up under the 65-100 ℃ of condition, be incubated 3 hours, temperature control begins to drip the rectification residue that ethanol concn is 10wt% to 70-95 ℃ again, and dripping quantity is vitamin K
3The 8-10wt% of chrome waste liquid weight, time for adding are controlled at 30-45 minute, and after being added dropwise to complete, temperature control is to 85-100 ℃, and insulated and stirred 1 hour does not develop the color with starch-kalium iodide reagent, prove that sexavalent chrome reacts completely after, be cooled to 45 ℃ of dischargings.
The present invention is producing vitamin K
3The time, in conjunction with having disposed the various waste liquids in the production process, also disposed simultaneously the rich chromium mud of leather industry Hazardous wastes, solve simultaneously the cycling and reutilization problem of three kinds of refuses of two industries, have very high environment and economy and be worth.
Embodiment:
Embodiment one:
With rich chromium mud 2000g(chromium sesquioxide content 5wt% wherein, moisture content 80wt%) in 105 ℃ of baking ovens, dry, with pulverizer with crushing material, cross 100 mesh sieves, obtain about scurf thing 20g, (detect chromium sesquioxide content 22%) about chromium hydroxide powder 450g, stand-by.
Get above chromium hydroxide powder and slowly add vitamin K
3Produce chrome waste liquid 1650g(chromium content 7.5wt%) in, add 2 of defoamers, be warming up to 65-70 ℃, be incubated 3 hours, begin to drip the rectification residue 165g that ethanol concn is 10wt%, rate of addition is 30 minutes, after being added dropwise to complete, is warming up to 90-95 ℃ of insulation 30 minutes, be warming up to 98-100 ℃ of insulation 30 minutes, guarantee that sexavalent chrome does not detect, be cooled to 45 ℃ of left and right sides dischargings, get the about 2000g(chromium sesquioxide of chrome tanning agent content 11% after the press filtration)
When this chrome tanning agent process hides was used, 90-92 ℃ of the shrinkage temperature of just tanning thickened rate 15%, became grain clear, and chrome tanned leather color turquoise is heavier.
Embodiment two:
Get the chromium hydroxide powder 450g that processes by method in the example one and slowly add vitamin K3 production chrome waste liquid 2000g(chromium content 7.5wt%) in, add 2 of defoamers, be warming up to 100 ℃, be incubated 1 hour, the sodium dichromate solution 41g that adds concentration 60wt%, be incubated again 2 hours, be cooled to 70 ℃, begin to drip the rectification residue 250g that ethanol concn is 10wt%, rate of addition is 45 minutes, after being added dropwise to complete, be warming up to 90-95 ℃ of insulation 1 hour, guarantee that sexavalent chrome does not detect, be cooled to 45 ℃ of left and right sides dischargings, get the about 2400g(chromium sesquioxide of chrome tanning agent content 11wt% after the press filtration).
When this chrome tanning agent process hides is used, shrinkage temperature 93-95 ℃, thicken rate 16%, become grain clear, chrome tanned leather color turquoise is more shallow.
Embodiment three:
Get the chromium hydroxide powder 450g that processes by method in the example one and slowly add vitamin K3 production chrome waste liquid 2000g(chromium content 7.5wt%) in, add 2 of defoamers, be warming up to 75 ℃, begin to drip the rectification residue 200g that ethanol concn is 10wt%, rate of addition is 40 minutes, after being added dropwise to complete, be warming up to 85-90 ℃ of insulation 3 hours, guarantee that sexavalent chrome does not detect, be cooled to 45 ℃ of left and right sides dischargings, get the about 2250g(chromium sesquioxide of chrome tanning agent content 11% after the press filtration).
When this chrome tanning agent process hides is used, shrinkage temperature 90-92 ℃, thicken rate 13%, yield of leather is high, becomes grain clear, and chrome tanned leather color turquoise is darker.
Claims (8)
1. a rich chromium mud prepares chrome tanning agent coproducing vitamin K
3Method, it is characterized in that, may further comprise the steps: the pretreatment of (1) rich chromium mud: the oven dry of rich chromium mud, by pulverizing chromium hydroxide is separated in the vibratory screening apparatus of 100 order numbers with scurf, then with the chromium hydroxide mixing, after the detection, for subsequent use; (2) and vitamin K
3Coproduction: with pretreated chromium hydroxide powder and vitamin K
3Produce the chrome waste liquid that produces and be added in proportion in the flask vitaminize K
3The ethanol refinery residue is participated in reaction as reductive agent in the production, is trivalent chromium with wherein sexavalent chrome Restore All, then adjusts basicity to specialized range, still aging for some time, is qualified chrome tanning agent.
2. a kind of rich chromium mud according to claim 1 prepares chrome tanning agent coproducing vitamin K
3Method, it is characterized in that described rich chromium mud is that the tannery chrome tanning process produces the hazardous solid waste that waste water produces through the alkali precipitation technology, its main butt effective constituent is chromium hydroxide.
3. a kind of rich chromium mud according to claim 1 prepares chrome tanning agent coproducing vitamin K
3Method, it is characterized in that, leather industry contained chromium hazardous solid waste and vitamin K
3The chrome waste liquid that produces in the production process carries out combination, and adds reductive agent under certain condition and react, and makes two kinds to contain the chromium refuse and all become the chrome tanning agent that can be reused for process hides.
4. a kind of rich chromium mud according to claim 3 prepares chrome tanning agent coproducing vitamin K
3Method, it is characterized in that described reductive agent is vitamin K
3Spirit solvent rectification residue in the production, principal character component are ethanol and S-WAT, and general alcohol concn is 8-12%, and S-WAT content is 10-15%.
5. a kind of rich chromium mud according to claim 3 prepares chrome tanning agent coproducing vitamin K
3Method, it is characterized in that, utilized simultaneously vitamin K
3The rich chromium mud of two kinds of by-product waste materials that produce in the production process and leather industry Hazardous wastes is used for chrome tanning agent production, and the solution vitamin K can sweep all before one
3The problem of disposal of pollutants and the discharging of leather industry heavy metal chromium.
6. a kind of rich chromium mud according to claim 5 prepares chrome tanning agent coproducing vitamin K
3Method, it is characterized in that described reaction mechanism is:
7. a kind of rich chromium mud according to claim 6 prepares chrome tanning agent coproducing vitamin K
3Method, it is characterized in that vitamin K
3Produce the chrome waste liquid that produces and filter out the 2-methyl isophthalic acid, the mixture of other products of 4-vitamin k4 for raw material excessive in the reaction (1) and after reacting.
8. a kind of rich chromium mud according to claim 6 prepares chrome tanning agent coproducing vitamin K
3Method, it is characterized in that reaction (2), (3) become chromic process for organic decomposition reaction in the chrome waste liquid is about to the sexavalent chrome Restore All, reaction (3) is for adding the reaction behind the ethanol refinery residue.
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| CN2012105652642A CN103352092A (en) | 2012-12-24 | 2012-12-24 | Method for preparation of chrome tanning agent and combined production of vitamin K3 through using chromium-rich sludge |
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| CN2012105652642A CN103352092A (en) | 2012-12-24 | 2012-12-24 | Method for preparation of chrome tanning agent and combined production of vitamin K3 through using chromium-rich sludge |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613133A (en) * | 2013-12-17 | 2014-03-05 | 四川省银河化学股份有限公司 | Method for treating naphthoquinone production liquid waste containing hexavalent chromium and vitamin K3 production wastewater and co-producing chromium oxide green |
| 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 |
| CN103694097A (en) * | 2013-12-26 | 2014-04-02 | 山东华升化工科技有限公司 | Method for preparing menadione co-production chrome tanning agent with chromium-enriched sludge |
| CN107099623A (en) * | 2017-03-08 | 2017-08-29 | 四川大学 | The method that a kind of utilization Vitamin K3 production waste liquid of microwave radiation technology prepares chrome tanning agent |
| CN109628665A (en) * | 2019-01-31 | 2019-04-16 | 云南省陆良和平科技有限公司 | One kind is with vitamin K3Waste liquid is the Chrome Tanning Liquor and preparation method thereof of raw material |
| CN109880944A (en) * | 2019-03-22 | 2019-06-14 | 四川大学 | A method of chrome tanning agent is prepared using Vitamin K3 production waste liquid |
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| CN101348425A (en) * | 2008-09-02 | 2009-01-21 | 山东大华广济生化工程有限公司 | Method for coproduction of chrome tanning agent and menadione |
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| 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 |
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| RO95096B1 (en) * | 1986-03-12 | 1988-08-31 | INSTITUTUL DE CERCETARE PIELARIE SI îNCALTAMINTE | Complex product for tanning and retunning skins |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613133A (en) * | 2013-12-17 | 2014-03-05 | 四川省银河化学股份有限公司 | Method for treating naphthoquinone production liquid waste containing hexavalent chromium and vitamin K3 production wastewater and co-producing chromium oxide green |
| CN103613133B (en) * | 2013-12-17 | 2015-09-02 | 四川省银河化学股份有限公司 | The method of waste liquid and vitamin K3 factory effluent co-production chromoxide green is produced in a kind of process containing chromic naphthoquinones |
| CN103694097A (en) * | 2013-12-26 | 2014-04-02 | 山东华升化工科技有限公司 | Method for preparing menadione co-production chrome tanning agent with chromium-enriched sludge |
| CN103694097B (en) * | 2013-12-26 | 2016-01-20 | 山东华升化工科技有限公司 | A kind ofly rich chromium mud is utilized to prepare the method for vitamin k4 coproduction chrome tanning agent |
| 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 |
| CN107099623A (en) * | 2017-03-08 | 2017-08-29 | 四川大学 | The method that a kind of utilization Vitamin K3 production waste liquid of microwave radiation technology prepares chrome tanning agent |
| 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 |
| CN109628665A (en) * | 2019-01-31 | 2019-04-16 | 云南省陆良和平科技有限公司 | One kind is with vitamin K3Waste liquid is the Chrome Tanning Liquor and preparation method thereof of raw material |
| CN109628665B (en) * | 2019-01-31 | 2022-01-18 | 云南省陆良和平科技有限公司 | Vitamin K3Chrome tanning liquid using waste liquid as raw material and preparation method thereof |
| CN109880944A (en) * | 2019-03-22 | 2019-06-14 | 四川大学 | A method of chrome tanning agent is prepared using Vitamin K3 production waste liquid |
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Application publication date: 20131016 |