CN104498648B - A kind of method of preparing chrome tanning agent from chroming waste liquor - Google Patents
A kind of method of preparing chrome tanning agent from chroming waste liquor Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/04—Mineral tanning
- C14C3/06—Mineral tanning using chromium compounds
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Abstract
The invention discloses a kind of method of preparing chrome tanning agent from chroming waste liquor, be characterized in that the method comprises the following steps: tanning finishes the useless chrome liquor of rear collection, make chromium precipitation with alkali, plate compression obtains chromium cake; Sulfuric acid solution chromium cake, cold filtration obtains filtrate, adjust pH? 2.0～2.5, separate and survey component chromium content with cation-exchange chromatography, according to sodium formate and sodium acetate cloudy, that neutral component content adds corresponding umber, dissolve, boil concentrated, make final solid content reach 50%. Cooling 1 hour, cation-exchange chromatography separated and surveys component chromium content, and according to cloudy, neutral component content difference, ageing reaction 4～7 days, makes the moon, neutral component reach 75～84%; Do 6 times of water dilutions, adjust pH? 3.8～4.0, place the above high positive electricity component 17～22% of cloudy, neutral component 40～50% ,+4 valencys 6 hours. It is simple, flexible that the present invention prepares chrome tanning agent technological operation from chroming waste liquor, and earning rate is high, and chrome tanning agent function admirable is applicable to a floor height shelves leather of ox, sheep, pigskin etc. and the tanning of two layers.
Description
Technical field
The present invention relates to a kind of method of preparing chrome tanning agent from chroming waste liquor, the heavy metal belonging in leather industry recyclesTechnical field.
Technical background
Chrome tanning is one of process for tanning the most general in existing leather industry, if adopt conventional chrome tanning process, the utilization rate of chromiumOnly have 65～80%, have 20～35% chromium not absorbed by rawhide and fix and remain in spent tan, in general spent tanChrome green concentration is up to 2～8g/L. In addition, chromium also has toxicity, and the toxicity of chromium mainly embodies by Cr VI, chromiumPollution meeting teratogenesis, cause gene mutation and carcinogenic. Consider the nothing of Chrome Tanning Wastewater from the angle of environmental protection and sustainable developmentEvilization, minimizing, recycling treatment are trends of the times. Therefore must take measures increases the utilization rate of chromium and reduces environmentPollution.
The processing of chroming waste liquor, the more ripe recovery method generally having been adopted at present mainly contains direct circulation and utilizes method and alkaliPrecipitation absorption method. Direct circulation utilize method normally chroming waste liquor reclaim and material supplementary after, then be applied to leather pickling,Tanning, but along with the increase of cycle-index causes adverse effect to leather quality, in addition, can cause the accumulation of liquid measure. AlkaliPrecipitation absorption method is that tanning finishes the useless chrome liquor of rear collection, adds alkali to adjust pH to 8～9 of useless chrome liquor, makes chromium precipitation, after leaving standstillCollection chromium precipitation, then obtain chromium cake through plate and frame filter press dehydration, with sulfuric acid dissolution chromium cake, filter to such an extent that reclaim chrome liquor for tanningOperation. Alkali precipitation absorption method is a kind of method of thorough recovery chromium, can be all heavy main to tanning, water squeezing etc. chromate waste waterShallow lake is recycled, and can realize in theory the zero-emission of chromate waste water. Along with the increasing of environmental requirement, a lot of tanneries adoptBy alkali precipitation absorption method processing waste water containing chrome, in the process of practical application, there are some problems, be mainly to reclaim chrome tanning agentTanning properties is unstable, the recovery chrome tanning agent tanning dark, different batches of tanning color exists color distortion, chrome greenUtilization rate is low, the soft and full property of leather is also poor, and tanning properties and commercial chromium tanning agent gap are larger, can only be used for tanning low gradeLeather and second layer leather, high value recycling that this has just limited chromium cake, becomes restriction tannery and realizes chromate waste water chromium resourceRecycle for a long time and the technical bottleneck of the zero-emission of chromium.
Classical chrome tanning theory thinks that the tanning properties of Chrome Tanning Liquor is by what determine forming of Chrome Tanning Liquor complex, and tannery firstThat chrome tanning agent permeates to intracutaneous, along with the interior boundary that adds part collagen carboxylic ions to enter chromic compound of carrying alkaline agent occurs crosslinkedThe tanning effect of sewing up. So in order to obtain good tanning properties, chrome tanning agent at the tanning initial stage with cloudy, neutral little moleculeComplex is main, has good permeance property; After its infiltration evenly, carry alkaline agent raising pH by adding, promote chromium hydrolysis to joinPoly-, the moon, neutral component are to positive electricity and high positive electricity constitutional changes, and electric charge raises, the large molecule of multinuclear increases, and is conducive to hand overConnection is closed, the shrinkage temperature high (more than 100 DEG C) of tanning, and finished leather is best in quality. But, for current recovery chrome tanning agentThe problem existing, adopts cation-exchange chromatography and constituent content method for measuring to detect its composition, when pH exists2.0～2.5 o'clock, cloudy, neutral component only account for 25～35% ,+1 valency and+divalent component 20～25% ,+3 valency components 18～28%,The above high positive electricity component 21～28% of+4 valencys. Visible, in the chromium sulfate fluid component of recovery, high positive electricity is more, cloudy, neutralComponent very little, is unfavorable for the infiltration of tanning initial stage chrome tanning agent, so the absorptivity of chromium is low, and alkaline-resisting ability is weak in the later stageCarry the easy surface conjunction of alkali and too much cause the leather problems such as color is darker. Therefore, be necessary to regulate and control sulfuric acid dissolution by chemical modificationChromium cake reclaims the structure composition of chrome liquor.
Masking agent is that one can make chrome liquor stability improve, and alkaline-resisting ability strengthens, and composition and character change, and can slow down againThe acid of the effect of tanning and salt thereof. For example micromolecular organic acid and salt thereof, comprise monocarboxylic acid and salt thereof, dicarboxylic acids andIts salt, hydroxycarboxylic acid and salt thereof, these little molecule organic ligands are added to the interior boundary's replacement shakiness that enters complex in sulfuric acid chrome liquorFixed water or acid group, thus composition, molecular size, electric charge and constituent content and the hydrated chromium complex ion of whole owse changedContent etc., change the tanning properties of owse. The tanning chemistry man of these aspect various countries has done much work, and achievement is distinguished.As Sichuan University of China is used little molecule organic ligand etc. and the preparation of chromium science, develop KMC series and covered from alkalization the chrome tanning of limitingAgent (Li Guoying, MOLECULE DESIGN and the development [J] of Zhang Mingrang .KMC series chrome tanning powder, leather science and workJourney, 1992,2 (1): 13-21); But relevant masking agent reclaim chroming waste liquor alkali precipitation chromium cake prepare aspect chrome tanning agent shouldLittle with research, especially cation-exchange chromatography and masking agent are combined to chrome tanning agent performance for regulating and controlling recoveryPatent research have not been reported.
Summary of the invention
The object of the invention is provides a kind of method of preparing chrome tanning agent from chroming waste liquor for the deficiencies in the prior art, itsFeature is by tanning chromate waste water alkali precipitation chromium cake sulfuric acid dissolution, removes by filter impurity and obtain the solution of chromium sulfate basic, adoptsThe component that detects filtrate with cation-exchange chromatography and constituent content method for measuring distributes, and selects sodium formate and sodium acetate as illiteracyThe agent of limiting is carried out modification to sulfuric acid chrome liquor, boils concentrated, old by cation-exchange chromatography and constituent content method for measuring regulation and controlChange reaction condition, thereby make to cover the appropriate chrome tanning agent that makes function admirable of effect of limiting.
The object of the invention is to be realized by following technology, wherein said raw material weight mark, except specified otherwise, is quality and dividesNumber.
From chroming waste liquor, prepare the method for chrome tanning agent:
(1) tanning is finished to the useless chrome liquor of rear collection, adjust pH to 8～9 of useless chrome liquor with alkali, make chromium precipitation, after leaving standstill, collectChromium precipitation, then obtain chromium cake through plate and frame filter press dehydration, its chromium cake moisture content is 65～75%, containing chrome green 9～12%;
(2) by 100 portions of chromium cakes, add water 20～25 parts, stir, when chromium cake moisture content is 65～70%, add dense sulphur at solution26～30 parts of acid; When chromium cake moisture content is 71～75%, add 20～25 parts of the concentrated sulfuric acids at solution; Be warming up to 60～75 DEG C,Stir hydrolysis 15～30 minutes; Then, being cooled to room temperature removes by filter impurity and obtains filtrate, the filtrate obtaining like thisChrome green concentration 65～75g/L, adjusts pH 2.0～2.5; Filtrate is carried out to component separation with cation-exchange chromatographyAnd measure component chromium content, cloudy, neutral component accounts for 25～35% ,+1 valency and+divalent component 20～25% ,+3 valency components 18～The above high positive electricity component 21～28% of 28% ,+4 valencys, above component distributes provides the ratio adding for next step masking agentFoundation;
(3) above-mentioned filtrate is transferred in reactor, when cloudy, neutral component is 25～30%, to add in filtrate sodium formate 1.5～1.5～2 parts of 2 parts, sodium acetate; When the moon, neutral component are 31～35%, in filtrate, add 2～3 parts of sodium formates, second0.5～1 part, acid sodium, stirring and dissolving under room temperature, boils concentrated 0.5～1 hour, when final solid content reaches 50%, stopsHeating, obtains concentrate, and cooling 1 hour, separate and survey component chromium content with cation-exchange chromatography, meet the moon, neutral groupPoint 45～65% ,+1 valency and+the above high positive electricity component 6 of divalent component 18～28% ,+3 valency component 11～16% ,+4 valencys～13％；
(4) treat that above-mentioned concentrate is cooling, transfer in fluid reservoir and at room temperature ageing reaction 4～7 days, when dense in step (3)Contracting liquid the moon, neutral component are 45～55%, and in 6～7 days ageing reaction time, cloudy, neutral component just can reach 75～84%,+ 1 valency and+divalent component 15～20% ,+3 valency components are less than 10%, when concentrate the moon in step (3), neutral component 56～65% time, ageing reaction 4～5 days, cloudy, neutral component reaches 75～84% ,+1 valency and+divalent component 15～20% ,+3 valency groupsDivide and be less than 10%; To reclaim 6 times of chrome tanning agent dilute with waters, adjust pH to 3.8～4.0 with NaOH, place 6 hours,Separate and survey component chromium content with cation-exchange chromatography, meet cloudy, neutral component and account for 40～50% ,+1 valency and+divalent component21～29% ,+3 valency component 5～9% ,+4 valencys are high positive electricity component 17～22% above, makes the chrome tanning agent of function admirable.
Described alkali is NaOH, magnesia, any in sodium carbonate.
From chroming waste liquor, prepare the chrome tanning agent that the method for chrome tanning agent prepares.
Chrome tanning agent is for the tanning of leather.
Performance test
1. adopting diphenyl carbazide spectrophotometry (GB-7466-87), test chrome tanning agent chrome green concentration is 130～160g/L。
2 adopt acid base titration method, and measuring chrome tanning agent basicity is 30～35%.
3 solid contents of measuring chrome tanning agent are 50～55%.
The present invention has the following advantages:
1. the alkali precipitation that the present invention is suitable for the waste liquid that tanning stage of straight chrome tanning technique produces reclaims, acid-soluble solution recycles,And the present invention can be to circulation primary, twice and repeatedly the chromium cake of chroming waste liquor move by the component of sulfuric acid dissolutionState monitoring, thus take suitable modified condition to obtain the more consistent chrome tanning agent of performance, and this method can ensure that the circulation of chromium cake is someThe performance of inferior rear recovery chrome tanning agent is still stable, for recycling for a long time of chroming waste liquor provides a kind of new technological means.
2. it is good that the present invention reclaims the chrome tanning agent tanning properties of preparation, replaces commercial chromium tanning agent to tan for main, and resultant leather quality canTo reach requirement, both can use separately also and can use with the collocation of commercial chromium tanning agent; Technological operation is simple, flexible, raw materialCheaply, earning rate is high; The rate of recovery of chromium is high, both contributed to the recycling of chroming waste liquor, has reduced again chromium to environmentPollute.
Detailed description of the invention
Below by embodiment, the present invention is specifically described, it is important to point out that the present embodiment is only for entering the present inventionRow further illustrates, and can not be interpreted as limiting the scope of the invention, and the person skilled in the art in this field can be according to upperState the content of invention and make some nonessential improvement and adjustment.
Embodiment 1:
A kind of method of preparing chrome tanning agent from the chroming waste liquor of cattle hide soft leather comprises the following steps:
(1) tanning finishes the useless chrome liquor of rear collection, adjusts the pH to 8 of useless chrome liquor with NaOH, makes chromium precipitation, after leaving standstill, collectsChromium precipitation, then obtain chromium cake through plate and frame filter press dehydration, survey chromium cake moisture content 65%, chrome green 12%.
(2) first take 100 portions of chromium cakes, then take 25 parts of water, in solution, add 30 parts of 98% the concentrated sulfuric acids, add and weigh upChromium cake, be warming up to 60 DEG C, stir hydrolysis 30 minutes. Then, be cooled to room temperature and remove by filter impurity and obtain filtrate,Survey filtrate chrome green concentration 75g/L, adjust the pH to 2.5 of filtrate. Separating and survey component chromium with cation-exchange chromatography containsAmount, cloudy, neutral component accounts for 25% ,+1 valency and+more than 26% ,+4 high positive electricity component of divalent component 25% ,+3 valency components24％。
(3) above-mentioned filtrate is transferred in reactor, in filtrate, is added 2 parts of masking agent sodium formates, 1.5 parts of sodium acetates,Stirring and dissolving under room temperature, boils concentrated 0.5 hour, and gained concentrate, surveys its final solid content 52%, and cooling 1 hour,Separate and survey component chromium content with cation-exchange chromatography, cloudy, neutral component 45% ,+1 valency and+divalent component 26% ,+3 valencysComponent 16%, the above high positive electricity component 13% of+4 valencys.
(4) treat that above-mentioned concentrate is cooling, transfer in fluid reservoir and at room temperature ageing reaction 7 days, divide with cation chromatographyFrom and survey component chromium content, cloudy, neutral component accounts for 75% ,+1 valency and+divalent component 20% ,+3 valency components 5%; To reclaim6 times of chrome tanning agent dilute with waters, adjust pH value of solution 3.8 with NaOH, place 6 hours, separate also with cation-exchange chromatographySurvey component chromium content, cloudy, neutral component accounts for 50% ,+1 valency and+divalent component 25% ,+3 valency component 7% ,+4 valencys are above highPositive electricity component 18%, makes the recovery chrome tanning agent of function admirable, and recording chrome green concentration is 130g/L, and basicity is30%, solid content is 50%.
Application example 1
Chrome tanning agent is back to use in the middle of the tanning of cattle hide soft leather, adopts chrome tanning process as follows:
Pickling: 40% 20 DEG C, water, 5% sodium chloride, 1.5% formic acid, turns 10 minutes, 1.8% sulfuric acid, 20% water dilution, turns 2Hour, pH2.5, bromocresol green checks outer 2/3 yellow.
Tanning: discharge opeing 20%, add chrome tanning agent 20%, turn 30 minutes, 1.8% sodium carbonate (1:10 dilution), gradation adds,60 minutes, interval, turns 7 hours. Final pH is 3.5, and 38 DEG C of water temperatures are stopped drum and spent the night, and turn 30 minutes inferior morning, goes out drumTake horse 24 hours.
1. adopt diphenyl carbazide spectrophotometry (GB-7466-87), the chrome green concentration of the useless chrome liquor of test: chromiumThe chrome green concentration 1600mg/L in waste liquid that tans, the absorptivity 75% of chromium;
2. leather boiling resistance; Leather base color and commercial chromium tanning agent tanning solid colour; Organoleptic properties: finished leather softness, plentiful,Elasticity is all consistent with the tanning of commercial chromium tanning agent.
Embodiment 2:
A kind of method of preparing chrome tanning agent from the chroming waste liquor of production kid gloves leather comprises the following steps:
(1) tanning finishes the useless chrome liquor of rear collection, adjusts the pH to 9 of useless chrome liquor with magnesia, makes chromium precipitation, after leaving standstill, collects chromiumPrecipitation, then obtain chromium cake through plate and frame filter press dehydration, survey chromium cake moisture content 75%, chrome green 9%
(2) first take 100 portions of chromium cakes, then take 20 parts of water, in solution, add 20 parts of 98% the concentrated sulfuric acids, add and weigh upChromium cake, be slowly warming up to 65 DEG C, stir hydrolysis 20 minutes. Then, being cooled to room temperature removes by filter impurity and obtainsFiltrate, surveys three oxidation two concentration 65g/L of filtrate, adjusts the pH to 2.0 of filtrate. Separate and survey group with cation-exchange chromatographyPoint chromium content, cloudy, neutral component 35% ,+1 valency and+more than 22% ,+4 high positive electricity group of divalent component 20% ,+3 valency componentsDivide 23%.
(3) above-mentioned filtrate is transferred in reactor, in filtrate, is added 2 parts of masking agent sodium formates, 0.5 part of sodium acetate,Stirring and dissolving under room temperature, boils concentrated 1 hour, and gained concentrate, surveys its final solid content 48%, cooling 1 hour, usesCation-exchange chromatography separates and surveys component chromium content, cloudy, neutral component 65% ,+1 valency and+divalent component 18% ,+3 valency groupsDivide 11% ,+4 valencys above high positive electricity component 6%.
(4) treat that above-mentioned concentrate is cooling, transfer in fluid reservoir and at room temperature ageing reaction 4 days, divide with cation chromatographyFrom and survey component chromium content, cloudy, neutral component accounts for 84% ,+1 valency and+divalent component 15% ,+3 valency components 1%; To reclaim6 times of chrome tanning agent dilute with waters, adjust pH value of solution to 4.0 with NaOH, place 6 hours, separate with cation-exchange chromatographyAnd survey component chromium content, cloudy, neutral component accounts for 45% ,+1 valency and+more than divalent component 26% ,+3 valency component 9% ,+4 valencysHigh positive electricity component 20%, makes the recovery chrome tanning agent of function admirable, and recording chrome green concentration is 160g/L, basicityBe 35%, solid content is 55%.
Application example 2
Chrome tanning agent is back to use in the middle of the tanning of kid gloves leather, adopts chrome tanning process as follows:
Pickling: 10% 25 DEG C, water, 3% sodium chloride, turns 5 minutes, and 0.2% mould inhibitor (1:3), turns 10 minutes, 0.9% formic acid(85%) (1:5 dilution), turns 10 minutes, and 0.9% sulfuric acid (1:10 dilution), turns 2 hours, pH2.5.
Tanning: add chrome tanning agent 25%, turn 60 minutes, 2.5% sodium carbonate (1:10 dilution), divides and add for 6 times, interval 60Minute, heating water temperature raising, makes interior temperature reach 40 DEG C, and final pH is 3.8, stops bulging spending the night, and turns 30 minutes inferior morning and goes out bulging takingHorse.
1. adopt diphenyl carbazide spectrophotometry (GB-7466-87), the chrome green concentration of the useless chrome liquor of test: chromiumThe chrome green concentration 1200mg/L in waste liquid that tans, the absorptivity 80% of chromium;
2. leather boiling resistance; Leather base color and commercial chromium tanning agent tanning solid colour; Organoleptic properties: finished leather softness, plentiful,Elasticity is all consistent with the tanning of commercial chromium tanning agent.
Embodiment 3:
A kind of method of preparing chrome tanning agent from the chroming waste liquor of production pig leather for making garment comprises the following steps:
(1) tanning finishes the useless chrome liquor of rear collection, adjusts the pH to 8.5 of useless chrome liquor with sodium carbonate, makes chromium precipitation, after leaving standstill, collectsChromium precipitation, then obtain chromium cake through plate and frame filter press dehydration, survey chromium cake moisture content 70%, chrome green 10%
(2) take 23 parts of water by chromium cake percentage by weight, in solution, add 26 parts of 98% the concentrated sulfuric acids, add 100 partsChromium cake, is slowly warming up to 75 DEG C, stirs hydrolysis 15 minutes. Then, being cooled to room temperature removes by filter impurity and is filteredLiquid, surveys the chrome green concentration 70g/L of filtrate, adjusts the pH to 2.3 of filtrate. Separate and survey group with cation-exchange chromatographyPoint chromium content, cloudy, neutral component accounts for 32% ,+1 valency and+more than 19% ,+4 high positive electricity of divalent component 21% ,+3 valency componentsComponent 28%.
(3) above-mentioned filtrate is transferred in reactor, in filtrate, added 2.0 parts of sodium formates, 1.3 parts of sodium acetates, room temperatureLower stirring and dissolving, boils concentrated 0.7 hour, and gained concentrate, surveys its final solid content 50%, and cooling 1 hour, with sunIon-exchange chromatography separates and measures component chromium content, cloudy, neutral component 55% ,+1 valency and+divalent component 23% ,+3 valency groupsDivide 11% ,+4 valencys above high positive electricity component 11%.
(4) treat that above-mentioned concentrate is cooling, transfer in fluid reservoir and at room temperature ageing reaction 6 days, use cation exchange lookSpectrum separates and surveys component chromium content, and cloudy, neutral component accounts for 80% ,+1 valency and+divalent component 17% ,+3 valency components 3%; WillReclaim 6 times of chrome tanning agent dilute with waters, adjust pH value of solution to 3.9 with NaOH, place 6 hours, separate with cation chromatographyAnd survey component chromium content, cloudy, neutral component accounts for 43% ,+1 valency and+more than divalent component 29% ,+3 valency component 7% ,+4 valencysHigh positive electricity component 21%, makes the recovery chrome tanning agent of function admirable, and recording chrome green concentration is 140g/L, basicityBe 33%, solid content is 52%.
Application example 3
Chrome tanning agent is back to use in the middle of the tanning of pig leather for making garment, the chrome tanning process of employing is as follows:
Pickling: 30% 25 DEG C, water, 6% sodium chloride, turns 20 minutes, and 0.2% formic acid (1:10 dilution), turns 30 minutes, 1.3%Sulfuric acid (1:10 dilution), turns 80 minutes, turns 1 hour and stops 1 hour, within every 1 hour, turns 5 minutes, turns 2 hours.
Tanning: chrome tanning agent 20%, turn 60 minutes, 0.5% sodium formate, turns 180 minutes, and 1.2% sodium acid carbonate divides six minor ticks20 minutes, terminal pH was that 3.8,50% water make interior temperature reach 50 DEG C, and 0.07% mould inhibitor, turns 4 hours, stopped drum and spent the night.Turn 30 minutes inferior morning, pH3.8, go out drum take horse leave standstill.
1. adopt diphenyl carbazide spectrophotometry (GB-7466-87), the chrome green concentration of the useless chrome liquor of test: chromiumThe chrome green concentration 1500mg/L in waste liquid that tans, the absorptivity 77% of chromium;
2. leather boiling resistance; Leather base color and commercial chromium tanning agent tanning solid colour; Organoleptic properties: finished leather softness, plentiful,Elasticity is all consistent with the tanning of commercial chromium tanning agent.
Claims (4)
1. from chroming waste liquor, prepare a method for chrome tanning agent, it is characterized in that the method comprises the following steps:
(1) tanning is finished to the useless chrome liquor of rear collection, adjust pH to 8～9 of useless chrome liquor with alkali, make chromium precipitation, collect chromium precipitation after leaving standstill, then obtain chromium cake through plate and frame filter press dehydration, its chromium cake moisture content is 65～75%, containing chrome green 9～12%;
(2) by 100 portions of chromium cakes, add water 20～25 parts, stir, when chromium cake moisture content is 65～70%, add 26～30 parts of the concentrated sulfuric acids at solution; When chromium cake moisture content is 71～75%, add 20～25 parts of the concentrated sulfuric acids at solution; Be warming up to 60～75 DEG C, stir hydrolysis 15～30min; Then, be cooled to room temperature and remove by filter impurity and obtain filtrate, the filtrate chrome green concentration 65～75g/L obtaining like this, adjusts pH 2.0～2.5; Filtrate is carried out component separation and measured component chromium content with cation-exchange chromatography, cloudy, neutral component accounts for 25～35%, + 1 valency and+divalent component 20～25%, + 3 valency components 18～28%, the above high positive electricity component 21～28% of+4 valencys, above component distributes provides foundation by the ratio adding for next step masking agent;
(3) above-mentioned filtrate is transferred in reactor, when the moon, neutral component are 25～30%, in filtrate, added 1.5～2 parts of sodium formates, 1.5～2 parts of sodium acetates; When the moon, neutral component are 31～35%, in filtrate, add 2～3 parts of sodium formates, 0.5～1 part of sodium acetate, stirring and dissolving under room temperature, boils concentrated 0.5～1 hour, when final solid content reaches 50%, stop heating, concentrate, cooling 1 hour, separate and survey component chromium content with cation-exchange chromatography, meet cloudy, neutral component 45～65%, + 1 valency and+the above high positive electricity component 6～13% of divalent component 18～28% ,+3 valency component 11～16% ,+4 valencys;
(4) treat that above-mentioned concentrate is cooling, transfer in fluid reservoir and at room temperature ageing reaction 4～7 days, when concentrate the moon, neutral component in step (3) are 45～55%, 6～7 days ageing reaction time, cloudy, neutral component just can reach 75～84%, + 1 valency and+divalent component 15～20%, + 3 valency components are less than 10%, concentrate the moon, neutral component are 56～65% time in the step (3), ageing reaction 4～5 days, cloudy, neutral component reaches 75～84% ,+1 valency and+divalent component 15～20% ,+3 valency components are less than 10%; To reclaim 6 times of chrome tanning agent dilute with waters, with NaOH tune pH to 3.8～4.0, place 6 hours, separate and survey component chromium content with cation-exchange chromatography, meet cloudy, neutral component and account for 40～50% ,+1 valency and+divalent component 21～29% ,+3 valency components 5～9%, + 4 valencys are high positive electricity component 17～22% above, makes the chrome tanning agent of function admirable;
Each raw material by weight above.
2. from chroming waste liquor, prepare as claimed in claim 1 the method for chrome tanning agent, it is characterized in that alkali is NaOH, magnesia, any in sodium carbonate.
3. from chroming waste liquor, prepare as claimed in claim 1 the chrome tanning agent that the method for chrome tanning agent prepares.
4. from chroming waste liquor, prepare as claimed in claim 3 the purposes of chrome tanning agent, it is characterized in that the tanning of chrome tanning agent for leather.
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| CN111747593A (en) * | 2020-07-01 | 2020-10-09 | 河北东明皮革有限公司 | Segmented circulating system for waste liquid of tanning preparation and tanning section and using method thereof |
| CN112094962B (en) * | 2020-09-11 | 2022-04-12 | 陕西科技大学 | Method for preparing chromium-containing hydrotalcite nano tanning agent by using chrome tanning waste liquid |
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| US3950131A (en) * | 1973-06-20 | 1976-04-13 | Hoffmann-Stafford Tanning Co. | Continuous method for reclaiming chromium hydroxide from spent chrome tanning liquors and re-use thereof in subsequent tanning |
| CZ302476B6 (en) * | 2008-07-25 | 2011-06-08 | Eurosound S. R. O. | Chemical-mechanical treatment process of wastewater from tannery shops |
| CN102363820B (en) * | 2011-09-22 | 2013-09-18 | 兄弟科技股份有限公司 | Reutilization method of chromium-containing leather production 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 |
| 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 |
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