CN101519701A - Recycling technology of polyhydroxyalkylphosphine and derivants thereof in leather tanning application - Google Patents

Recycling technology of polyhydroxyalkylphosphine and derivants thereof in leather tanning application Download PDF

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Publication number
CN101519701A
CN101519701A CN200810007506A CN200810007506A CN101519701A CN 101519701 A CN101519701 A CN 101519701A CN 200810007506 A CN200810007506 A CN 200810007506A CN 200810007506 A CN200810007506 A CN 200810007506A CN 101519701 A CN101519701 A CN 101519701A
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China
Prior art keywords
tanning
derivative
alkyl phosphine
polyhydroxy alkyl
leather
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CN200810007506A
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Chinese (zh)
Inventor
杨颖颙
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Solvay Hengchang Zhangjiagang Specialty Chemical Co Ltd
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Rhodia Hengchang Zhangjiagang Specialty Chemical Co Ltd
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Application filed by Rhodia Hengchang Zhangjiagang Specialty Chemical Co Ltd filed Critical Rhodia Hengchang Zhangjiagang Specialty Chemical Co Ltd
Priority to CN200810007506A priority Critical patent/CN101519701A/en
Priority to NZ587313A priority patent/NZ587313A/en
Priority to PCT/CN2009/000192 priority patent/WO2009105962A1/en
Priority to CN200980107007.0A priority patent/CN101965411B/en
Priority to AU2009218971A priority patent/AU2009218971B2/en
Publication of CN101519701A publication Critical patent/CN101519701A/en
Pending legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C14SKINS; HIDES; PELTS; LEATHER
    • C14CCHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C3/00Tanning; Compositions for tanning
    • C14C3/02Chemical tanning
    • C14C3/08Chemical tanning by organic agents

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)

Abstract

The invention relates to a recycling technology of polyhydroxyalkylphosphine and derivants thereof in leather tanning application, which comprises the steps of preparing the polyhydroxyalkylphosphine and the tanning initial liquid of a derivant tanning agent thereof; recycling tanning and applying the polyhydroxyalkylphosphine and the derivant tanning agent thereof; and adjusting the tanning agent, pH, a stabilizing agent and the residual liquid of a buffer reagent and ensuring no change of the leather tanning quality; and repeating the steps to lead bath liquid to be used indefinitely. The technology can lead the tanned bath liquid to be recycled indefinitely without sewage discharge, has simple process, low temperature, small energy consumption, is forehanded, environment-friendly and easy for control and the whole course detection in production, and can ensure the stability and consistency of the product.

Description

Polyhydroxy alkyl phosphine and derivative thereof be recycle utilization in leather tanning is used
Technical field
The present invention relates to a kind of polyhydroxy alkyl phosphine and derivative thereof recycle utilization in leather tanning is used, relate to the green technology of a kind of polyhydroxy alkyl phosphine and derivative thereof the method for Technology and working substance monitoring in the recycle process specifically.
Technical background
Leather industry is one of heavy polluted industry, particularly the leather tanning operation.Because most tanning agent all is the poisonous and harmful chemicals.The metal tanning agent is chrome tanning agent especially, become the main chemical of current leather tanning, every year, the consumption as the salt fundamental mode chromium sulphate of leather retanning agent reached 22,000-27,000 ton (amounting to arsenic), these heavy metals have only about half of being discharged (having part to handle landfill after the discharging), after leatherware rubbishization, entered environment in conjunction with absorption portion by leather, because the chromium sulphate very big tendency that oriented arsenic transforms under physical environment, thereby chrome tanning agent also becomes the No.1 contaminating chemicals of tanning industry.For minimizing chrome tanning agent discharging as much as possible, scientists has carried out studying extensively and profoundly.Duan Zhenji etc. have studied PCPA (acrylic resin) auxiliary tanning agent, improving chrome tanning agent absorbs so that reduce the chrome tanning agent use, Zhang Mingrang etc. have studied high-absorption chrome tanning agent etc., obtained very proud achievement though improve the utilization ratio technology of chrome tanning agent, but can't fundamentally solve chrome tanning agent to the injury of environment with to the potential hazard of human body.Simultaneously, also have numerous scientist's research and utilization chroming waste liquors to recycle technology, but because the restriction of all technical factors can't obtain popularization all the time in industrial production.Aldehyde tanning agent is another kind of widely used organic tanning agent.Formaldehyde once was widely used in the fur industry, but because its great volatility and poisonous and harmful are forbidden application by national strictness.Glutaraldehyde and derivative thereof have the tanning agent that unique tanning characteristic is still the frequent use of leather industry at present, but glutaraldehyde and derivative tanning agent thereof still exist to environment with to the injury of human body.The oxazolidine tanning agent is a novel class organic tanning agent, and LG-DOW company is quite dark to this research, but does not see its cycle applications report.The vegetable tanning agent tan leather is a fine environmental protection tannery, can recycle fully, but because its specific tanning characteristics, tanning can only be finished small portion kind leather demand separately.Polyhydroxy alkyl phosphine and derivative thereof and composite prod are the novel organic tanning agents of a class, have excellent tanning performance.But tanning agent in any case can not absorbed by leather fully, simultaneously, contains the materials such as salt that do not absorbed by leather in a large number in the tanning raffinate, if all these materials are discharged, not only environment is produced huge injury, and is huge material wastage.
Summary of the invention
The object of the present invention is to provide a kind of polyhydroxy alkyl phosphine and derivative recycle utilization in leather tanning is used thereof that economizes on resources and reduce environmental pollution.
The object of the present invention is achieved like this: a kind of polyhydroxy alkyl phosphine and derivative thereof be recycle utilization in leather tanning is used, and it comprises the steps:
A. the preparation of polyhydroxy alkyl phosphine and the initial liquid of derivative tanning agent tanning thereof:
1) added stablizer in the initial liquid of tanning, wherein stablizer is the mixture that comprises tensio-active agent, polyol, microcosmic salt, sanitas etc., and its consumption is that the 0.1-2% of pickling tare weight or the 0.1-3 grams per liter of tanning body lotion calculate;
2) added buffer reagent in the initial liquid of tanning, its consumption is the 0.1-3% of pickling tare weight or the 0.1-3 grams per liter of tanning body lotion;
3) contain one or more polyhydroxy alkyl phosphine and derivatives thereof in the initial liquid of tanning, concentration is the 1-5% of pickling tare weight or the 1-7 grams per liter of tanning body lotion;
B. polyhydroxy alkyl phosphine and derivative tanning agent circulation tanning thereof are used:
Add pickled skin in the initial liquid of tanning, rotate the 90-360 branch, gradation adds alkali, makes the pH of body lotion be increased to 5-7 gradually; Be rotated further the 60-360 branch; Go out skin; Skin that tanning is finished is through washing, enters step after the conventional tanning.Raffinate is measured polyhydroxy alkyl phosphine and derivatives concentration thereof in the tanning raffinate with the microtitration proofing box by iodine titration solution, analyzes to be adjusted to initial tanning agent content and to use acid pH to be adjusted between the 3-5;
C. in the above-mentioned body lotion of adjusting tanning agent and pH, add stablizer and the buffer reagent that 0-1/2 mentions in steps A; The raffinate of adjusting tanning agent, pH, stablizer and buffer reagent fully just can continue to use, and guarantees the leather tanning mass conservation; Repeat the purpose that this step can reach the unlimited use of body lotion.
Wherein, tensio-active agent can be dodecyl alcohol polyoxyethylene (9) ether (AEO-9) or other; Polyol can be white sugar, polyvinyl alcohol, poly-ethanol etc.; Microcosmic salt can be positive microcosmic salt, pyrophosphate salt, metaphosphate, hydrophosphate and derivative thereof.
Wherein, buffer reagent can be the mixture of formic acid, acetate and highly basic salt thereof, for example: the mixture of formic acid and sodium formiate
Wherein, wherein polyhydroxy alkyl phosphine and derivative thereof be Tetrakis hydroxymethyl phosphonium chloride and with the polymkeric substance of urea, four hydroxyethyl phosphorus chloride and with the polymkeric substance of urea, four hydroxypropyl phosphorus chloride and with the polymkeric substance of urea, four hydroxyl normal-butyl chlorination phosphorus and with the polymkeric substance of urea, four hydroxyl n-pentyl chlorination phosphorus and with the polymkeric substance of urea, tetra methylol sulfuric acid phosphorus and with the polymkeric substance of urea and/or four ethylene hydroxy sulfuric acid phosphorus and with the polymkeric substance of urea.
Wherein, the application acid can be one or more in sulfate of ammoniac, formic acid, acetic acid, lactic acid, hydrochloric acid, sulfuric acid, nitric acid, the phosphoric acid.
The present invention compared with prior art, this technology makes the tanning body lotion can recycle without sewage discharge indefinitely; And technology is simple, and temperature is low, and it is little to consume energy, and economical environment-protective is easy to control; Be easy to produce omnidistance the detection, ensure the product stable and consistent.
Embodiment
Further specify the present invention below in conjunction with embodiment
Embodiment 1: a kind of polyhydroxy alkyl phosphine and derivative thereof be recycle utilization in leather tanning is used
1. the preparation of polyhydroxy alkyl phosphine and the initial liquid of derivative tanning agent tanning thereof:
Added the mixture of stablizer dodecyl alcohol polyoxyethylene (9) ether (AEO-9), white sugar, pyrophosphate salt and sanitas in the initial liquid of tanning, its consumption is 0.1 of a pickling tare weight; Added the mixture of buffer reagent formic acid and sodium formiate in the initial liquid of tanning, its consumption is 3% of a pickling tare weight; Contain in the initial liquid of tanning Tetrakis hydroxymethyl phosphonium chloride and with the polymkeric substance of urea, concentration is 1% of pickling tare weight;
2. polyhydroxy alkyl phosphine and derivative tanning agent circulation tanning thereof are used:
Add pickled skin in the initial liquid of tanning, rotated 360 fens, gradation adds alkali, makes the pH of body lotion be increased to 5-7 gradually.Be rotated further 60 fens.Go out skin.Skin that tanning is finished is through washing, enters step after the conventional tanning.Raffinate is measured polyhydroxy alkyl phosphine and derivatives concentration thereof in the tanning raffinate with the microtitration proofing box by iodine titration solution, analyzes to be adjusted to initial tanning agent content and using sulfated ammonia pH is adjusted between the 3-5;
3. in the above-mentioned body lotion of adjusting tanning agent and pH, add 1/2 stablizer of in step 1, mentioning and buffer reagent; The raffinate of adjusting tanning agent, pH, stablizer and buffer reagent fully just can continue to use, and guarantees the leather tanning mass conservation; Repeat the purpose that this step can reach the unlimited use of body lotion.
Embodiment 2: a kind of polyhydroxy alkyl phosphine and derivative thereof be recycle utilization in leather tanning is used
1. the preparation of polyhydroxy alkyl phosphine and the initial liquid of derivative tanning agent tanning thereof:
Added the mixture of stablizer dodecyl alcohol polyoxyethylene (9) ether (AEO-9), polyvinyl alcohol, positive microcosmic salt and sanitas etc. in the initial liquid of tanning, its consumption is 2% of a pickling tare weight; Added the mixture of buffer reagent formic acid and sodium formiate in the initial liquid of tanning, its consumption is 0.1% of a pickling tare weight; Contain in the initial liquid of tanning four hydroxypropyl phosphorus chloride and with the polymkeric substance of urea, concentration is 5% of pickling tare weight;
2. polyhydroxy alkyl phosphine and derivative tanning agent circulation tanning thereof are used:
Add pickled skin in the initial liquid of tanning, rotated 90 fens, gradation adds alkali, makes the pH of body lotion be increased to 5-7 gradually.Be rotated further 360 fens.Go out skin.Skin that tanning is finished is through washing, enters step after the conventional tanning.Raffinate is measured polyhydroxy alkyl phosphine and derivatives concentration thereof in the tanning raffinate with the microtitration proofing box by iodine titration solution, analyzes to be adjusted to initial tanning agent content and to use formic acid pH to be adjusted between the 3-5;
3. the raffinate of adjusting just can continue to use, and guarantees the leather tanning mass conservation; Repeat the purpose that this step can reach the unlimited use of body lotion.
Embodiment 3: a kind of polyhydroxy alkyl phosphine and derivative thereof be recycle utilization in leather tanning is used
1. the preparation of polyhydroxy alkyl phosphine and the initial liquid of derivative tanning agent tanning thereof:
Added the mixture of stablizer dodecyl alcohol polyoxyethylene (9) ether (AEO-9), poly-ethanol, metaphosphate and sanitas etc. in the initial liquid of tanning, its consumption is 1% of a pickling tare weight; Added buffer reagent in the initial liquid of tanning, its consumption is 1.5% of a pickling tare weight; Contain in the initial liquid of tanning four hydroxyethyl phosphorus chloride and with the polymkeric substance of urea, concentration is 3% of pickling tare weight;
2. polyhydroxy alkyl phosphine and derivative tanning agent circulation tanning thereof are used:
Add pickled skin in the initial liquid of tanning, rotated 230 fens, gradation adds alkali, makes the pH of body lotion be increased to 5-7 gradually.Be rotated further 210 fens.Go out skin.Skin that tanning is finished is through washing, enters step after the conventional tanning.Raffinate is measured polyhydroxy alkyl phosphine and derivatives concentration thereof in the tanning raffinate with the microtitration proofing box by iodine titration solution, analyzes to be adjusted to initial tanning agent content and to use acetic acid pH to be adjusted between the 3-5;
3. in the above-mentioned body lotion of adjusting tanning agent and pH, add 1/4 stablizer of in step 1, mentioning and buffer reagent; The raffinate of adjusting tanning agent, pH, stablizer and buffer reagent fully just can continue to use, and guarantees the leather tanning mass conservation; Repeat the purpose that this step can reach the unlimited use of body lotion.
Embodiment 4: a kind of polyhydroxy alkyl phosphine and derivative thereof be recycle utilization in leather tanning is used
1. the preparation of polyhydroxy alkyl phosphine and the initial liquid of derivative tanning agent tanning thereof:
Added the mixture of stablizer dodecyl alcohol polyoxyethylene (9) ether (AEO-9), white sugar, hydrophosphate and sanitas etc. in the initial liquid of tanning, its consumption is 0.1 grams per liter of tanning body lotion; The mixture that has added buffer reagent formic acid and sodium formiate in the initial liquid of tanning, its consumption are 3 grams per liters of tanning body lotion; Contain in the initial liquid of tanning four hydroxyl normal-butyl chlorination phosphorus and with the polymkeric substance of urea, concentration is 1 grams per liter of tanning body lotion;
2. polyhydroxy alkyl phosphine and derivative tanning agent circulation tanning thereof are used:
Add pickled skin in the initial liquid of tanning, rotated 360 fens, gradation adds alkali, makes the pH of body lotion be increased to 5-7 gradually.Be rotated further 60 fens.Go out skin.Skin that tanning is finished is through washing, enters step after the conventional tanning.Raffinate is measured polyhydroxy alkyl phosphine and derivatives concentration thereof in the tanning raffinate with the microtitration proofing box by iodine titration solution, analyzes to be adjusted to initial tanning agent content and to use lactic acid pH to be adjusted between the 3-5;
3. in the above-mentioned body lotion of adjusting tanning agent and pH, add 1/2 stablizer of in step 1, mentioning and buffer reagent; The raffinate of adjusting tanning agent, pH, stablizer and buffer reagent fully just can continue to use, and guarantees the leather tanning mass conservation; Repeat the purpose that this step can reach the unlimited use of body lotion.
Embodiment 5: a kind of polyhydroxy alkyl phosphine and derivative thereof be recycle utilization in leather tanning is used
1. the preparation of polyhydroxy alkyl phosphine and the initial liquid of derivative tanning agent tanning thereof:
Added the mixture of stablizer dodecyl alcohol polyoxyethylene (9) ether (AEO-9), polyvinyl alcohol, positive microcosmic salt, pyrophosphate salt and sanitas etc. in the initial liquid of tanning, its consumption is 3 grams per liters of tanning body lotion; The mixture that has added buffer reagent formic acid and sodium formiate in the initial liquid of tanning, its consumption are 0.1 grams per liter of tanning body lotion; Contain in the initial liquid of tanning four hydroxyl n-pentyl chlorination phosphorus and with the polymkeric substance of urea, concentration is 7 grams per liters of tanning body lotion;
2. polyhydroxy alkyl phosphine and derivative tanning agent circulation tanning thereof are used:
Add pickled skin in the initial liquid of tanning, rotated 90 fens, gradation adds alkali, makes the pH of body lotion be increased to 5-7 gradually.Be rotated further 360 fens.Go out skin.Skin that tanning is finished is through washing, enters step after the conventional tanning.Raffinate is measured polyhydroxy alkyl phosphine and derivatives concentration thereof in the tanning raffinate with the microtitration proofing box by iodine titration solution, analyzes to be adjusted to initial tanning agent content and to use hydrochloric acid pH to be adjusted between the 3-5;
3. just can continue to use at the above-mentioned raffinate of adjusting, and guarantee the leather tanning mass conservation; Repeat the purpose that this step can reach the unlimited use of body lotion.
Embodiment 6: a kind of polyhydroxy alkyl phosphine and derivative thereof be recycle utilization in leather tanning is used
1. the preparation of polyhydroxy alkyl phosphine and the initial liquid of derivative tanning agent tanning thereof:
Added the mixture of stablizer dodecyl alcohol polyoxyethylene (9) ether (AEO-9), polyvinyl alcohol, poly-ethanol, tetra-sodium and sanitas etc. in the initial liquid of tanning, its consumption is 1.5 grams per liters of tanning body lotion; The mixture that has added buffer reagent phosphoric acid salt and hydrophosphate in the initial liquid of tanning, its consumption are 1.6 grams per liters of tanning body lotion; Contain in the initial liquid of tanning Tetrakis hydroxymethyl phosphonium chloride and with the polymkeric substance of urea and tetra methylol sulfuric acid phosphorus and with the polymkeric substance of urea, concentration is 4 grams per liters of tanning body lotion;
2. polyhydroxy alkyl phosphine and derivative tanning agent circulation tanning thereof are used:
Add pickled skin in the initial liquid of tanning, rotated 220 fens, gradation adds alkali, makes the pH of body lotion be increased to 5-7 gradually.Be rotated further 210 fens.Go out skin.Skin that tanning is finished is through washing, enters step after the conventional tanning.Raffinate is measured polyhydroxy alkyl phosphine and derivatives concentration thereof in the tanning raffinate with the microtitration proofing box by iodine titration solution, analyzes to be adjusted to initial tanning agent content and using sulfated pH is adjusted between the 3-5;
3. in the above-mentioned body lotion of adjusting tanning agent and pH, add 1/4 stablizer of in step 1, mentioning and buffer reagent; The raffinate of adjusting tanning agent, pH, stablizer and buffer reagent fully just can continue to use, and guarantees the leather tanning mass conservation; Repeat the purpose that this step can reach the unlimited use of body lotion.

Claims (8)

1, polyhydroxy alkyl phosphine and derivative thereof recycle utilization in leather tanning is used, it comprises the steps:
A. the preparation of polyhydroxy alkyl phosphine and the initial liquid of derivative tanning agent tanning thereof:
4) added stablizer in the initial liquid of tanning, wherein stablizer is the mixture that comprises tensio-active agent, polyol, microcosmic salt, sanitas, and its consumption is that the 0.1-2% of pickling tare weight or the 0.1-3 grams per liter of tanning body lotion calculate;
5) added buffer reagent in the initial liquid of tanning, its consumption is the 0.1-3% of pickling tare weight or the 0.1-3 grams per liter of tanning body lotion;
6) contain one or more polyhydroxy alkyl phosphine and derivatives thereof in the initial liquid of tanning, concentration is the 1-5% of pickling tare weight or the 1-7 grams per liter of tanning body lotion;
B. polyhydroxy alkyl phosphine and derivative tanning agent circulation tanning thereof are used:
Add pickled skin in the initial liquid of tanning, rotate 90-360min, gradation adds alkali, makes the pH of body lotion be increased to 5-7 gradually; Be rotated further 60-360min; Go out skin; Skin that tanning is finished is through washing, enters step after the conventional tanning; Raffinate is measured polyhydroxy alkyl phosphine and derivatives concentration thereof in the tanning raffinate with the microtitration proofing box by iodine titration solution, analyzes to be adjusted to initial tanning agent content and to use acid pH to be adjusted between the 3-5;
C. in the above-mentioned body lotion of adjusting tanning agent and pH, add stablizer and the buffer reagent that 0-1/2 mentions in steps A; The raffinate of adjusting tanning agent, pH, stablizer and buffer reagent fully just can continue to use, and guarantees the leather tanning mass conservation; Repeat the purpose that this step can reach the unlimited use of body lotion.
2, described polyhydroxy alkyl phosphine of claim 1 and derivative thereof recycle utilization in leather tanning is used is characterized in that tensio-active agent is dodecyl alcohol polyoxyethylene 9 ethers.
3, described polyhydroxy alkyl phosphine of claim 1 and derivative thereof recycle utilization in leather tanning is used is characterized in that polyol is white sugar, polyvinyl alcohol, poly-ethanol.
4, described polyhydroxy alkyl phosphine of claim 1 and derivative thereof recycle utilization in leather tanning is used is characterized in that microcosmic salt can be positive microcosmic salt, pyrophosphate salt, metaphosphate, hydrophosphate and derivative thereof.
5, described polyhydroxy alkyl phosphine of claim 1 and derivative thereof recycle utilization in leather tanning is used is characterized in that buffer reagent is the mixture of formic acid, acetate and highly basic salt thereof.
6, described polyhydroxy alkyl phosphine of claim 1 and derivative thereof recycle utilization in leather tanning is used is characterized in that buffer reagent is the mixture of formic acid and sodium formiate.
7, described polyhydroxy alkyl phosphine of claim 1 and derivative thereof recycle utilization in leather tanning is used, it is characterized in that polyhydroxy alkyl phosphine and derivative thereof be Tetrakis hydroxymethyl phosphonium chloride and with the polymkeric substance of urea, four hydroxyethyl phosphorus chloride and with the polymkeric substance of urea, four hydroxypropyl phosphorus chloride and with the polymkeric substance of urea, four hydroxyl normal-butyl chlorination phosphorus and with the polymkeric substance of urea, four hydroxyl n-pentyl chlorination phosphorus and with the polymkeric substance of urea, tetra methylol sulfuric acid phosphorus and with the polymkeric substance of urea and/or four ethylene hydroxy sulfuric acid phosphorus and with the polymkeric substance of urea.
8, described polyhydroxy alkyl phosphine of claim 1 and derivative thereof recycle utilization in leather tanning is used is characterized in that acid is one or more in sulfate of ammoniac, formic acid, acetic acid, lactic acid, hydrochloric acid, sulfuric acid, nitric acid, the phosphoric acid.
CN200810007506A 2008-02-26 2008-02-26 Recycling technology of polyhydroxyalkylphosphine and derivants thereof in leather tanning application Pending CN101519701A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CN200810007506A CN101519701A (en) 2008-02-26 2008-02-26 Recycling technology of polyhydroxyalkylphosphine and derivants thereof in leather tanning application
NZ587313A NZ587313A (en) 2008-02-26 2009-02-24 Leather tanning process based on the recycling of poly hydroxyl alkyl phosphine and its derivatives
PCT/CN2009/000192 WO2009105962A1 (en) 2008-02-26 2009-02-24 Leather tanning process based on the recycling of poly hydroxyl alkyl phosphine and its derivatives
CN200980107007.0A CN101965411B (en) 2008-02-26 2009-02-24 Leather tanning process based on the recycling of poly hydroxyl alkyl phosphine and its derivatives
AU2009218971A AU2009218971B2 (en) 2008-02-26 2009-02-24 Leather tanning process based on the recycling of poly hydroxyl alkyl phosphine and its derivatives

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Application Number Priority Date Filing Date Title
CN200810007506A CN101519701A (en) 2008-02-26 2008-02-26 Recycling technology of polyhydroxyalkylphosphine and derivants thereof in leather tanning application

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CN200980107007.0A Expired - Fee Related CN101965411B (en) 2008-02-26 2009-02-24 Leather tanning process based on the recycling of poly hydroxyl alkyl phosphine and its derivatives

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AU (1) AU2009218971B2 (en)
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WO (1) WO2009105962A1 (en)

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CN104988251A (en) * 2015-07-03 2015-10-21 西藏自治区拉萨皮革有限责任公司 Method for directly recycling vegetable tanning waste liquor

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US10280474B2 (en) 2015-07-13 2019-05-07 Council Of Scientific & Industrial Research Dispersing agent composition for tanning of hides/skins and process for the preparation thereof
CN105567887B (en) * 2016-01-28 2017-08-04 四川大学 A kind of few chromium combination tannage of nano silicate
CN112522455B (en) * 2020-11-26 2022-02-11 无极县景森皮革制品有限公司 Non-pickling tanning method for leather

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GB9120652D0 (en) * 1991-09-27 1991-11-06 Albright & Wilson Use of phosphonium compounds in the preparation of leather
KR100529797B1 (en) * 1997-10-30 2005-11-22 로우디아 컨수머 스페셜티즈 리미티드 Tanning leather
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Publication number Priority date Publication date Assignee Title
CN104988251A (en) * 2015-07-03 2015-10-21 西藏自治区拉萨皮革有限责任公司 Method for directly recycling vegetable tanning waste liquor
CN104988251B (en) * 2015-07-03 2018-01-09 西藏自治区拉萨皮革有限责任公司 A kind of method that vegetable tanning waste liquid direct circulation utilizes

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WO2009105962A1 (en) 2009-09-03
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CN101965411A (en) 2011-02-02
NZ587313A (en) 2012-01-12

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Application publication date: 20090902