WO2013107293A1 - Method for treating leather by using leather production wastewater and method for producing leather - Google Patents

Method for treating leather by using leather production wastewater and method for producing leather Download PDF

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Publication number
WO2013107293A1
WO2013107293A1 PCT/CN2013/070038 CN2013070038W WO2013107293A1 WO 2013107293 A1 WO2013107293 A1 WO 2013107293A1 CN 2013070038 W CN2013070038 W CN 2013070038W WO 2013107293 A1 WO2013107293 A1 WO 2013107293A1
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Prior art keywords
leather
wastewater
concentration
acid
tanning
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PCT/CN2013/070038
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French (fr)
Chinese (zh)
Inventor
李靖
赵婧
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朗盛（常州）有限公司
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Publication of WO2013107293A1 publication Critical patent/WO2013107293A1/en

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Classifications

    • 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
    • C14C3/32—Recovering tanning agents from leather
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N21/3577—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing liquids, e.g. polluted water
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/22—Nature of the water, waste water, sewage or sludge to be treated from the processing of animals, e.g. poultry, fish, or parts thereof
    • C02F2103/24—Nature of the water, waste water, sewage or sludge to be treated from the processing of animals, e.g. poultry, fish, or parts thereof from tanneries
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N21/359—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using near infrared light
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies

Definitions

  • the present invention relates to a method of treating leather using tannery wastewater and a method of producing leather.
  • BACKGROUND OF THE INVENTION With the rapid development of the economy, people's understanding of health and environmental protection has become more and more in-depth. At present, the waste water produced in the tanning contains a large amount of organic matter, and if it is directly discharged into the river, it will cause irreversible damage to the water environment. Therefore, the treatment and discharge of wastewater has become an increasingly strict curse in the tanning industry. How to treat wastewater, reduce wastewater, and reduce emissions is a topic that research institutions and tanneries are currently exploring.
  • reducing wastewater discharge can be considered in three ways:
  • the first idea is to control from the source. Avoid the use of toxic and hazardous substances from the choice of chemical species, but due to material limitations and limited knowledge of leather, some materials have to be used because they are harmful because there are no substitutes. In this case, we must consider how to improve their reaction efficiency from the tanning process, and increase their bonding rate with leather as much as possible, so that the same effect can be achieved with the least amount of use, and they can also be reduced in water.
  • the residual amount and the grounding function play a role in reducing the waste water. This is a permanent issue for leather chemists.
  • the second is to treat the wastewater efficiently. Remove heavy metals, organic matter, inorganic salts, etc., and discharge them after reaching emission standards.
  • Waste water is prone to bacteria. Since the wastewater contains a lot of organic matter, when the pH and temperature are appropriate, the bacteria and molds multiply very quickly, and the next day, an unpleasant smell is produced. If this wastewater is recycled, it is necessary to find a suitable preservative.
  • the present invention is directed to a method of treating leather using tannery wastewater, comprising: (a) obtaining a near infrared spectrum of the tannery wastewater produced by the tanning process using a near infrared spectroscopy sensor;
  • the near-infrared spectral data model includes a correspondence between the near-infrared spectrum and the component concentration.
  • the near infrared spectral data model is obtained by the following method:
  • each aqueous solution sample contains at least an active ingredient.
  • each aqueous sample also contains other components that may be present in the wastewater, wherein the other components are components that interfere with the near infrared spectral data model of the active component.
  • the active ingredient is selected from one or more of an aromatic compound, a sulfone, a polyacrylic compound, a dicyandiamide compound, a melamine compound, a polyurethane compound, a surfactant, an organic acid, and a salt thereof.
  • the aromatic compound is selected from the group consisting of phenols, aryl sulfonates, and naphthalenes.
  • the organic acid and its salt are selected from one or more of the group consisting of citric acid, glutaric acid, succinic acid, succinic acid, adipic acid, fumaric acid, and salts thereof.
  • the near infrared spectral data model includes a correspondence between the concentration of the active ingredient and the near infrared spectrum.
  • each aqueous sample contains:
  • each aqueous sample contains:
  • each aqueous solution sample contains: a phenolic compound, an acrylic compound, and a dicyandiamide compound.
  • each aqueous solution sample contains: an aryl sulfonate, an acrylic compound, and a dicyandiamide compound.
  • each aqueous sample contains: an aryl sulfonate methylene condensate, a polyacrylate, and a methylene condensate of an aromatic sulfamic acid.
  • the active ingredient is selected from the group consisting of retanning agents, chrome tanning agents, neutralizing agents, degreasers or fatliquors used in the tanning process.
  • the tanning process is a leather chrome tanning process, a neutralization process, a retanning process, a degreasing process or a fatliquoring process.
  • the neutralization process is a blue wet skin neutralization process.
  • the retanning process is a simple retanning process or a standard retanning process.
  • the retanning process is a blue wet skin simple retanning process or a blue wet skin standard retanning process.
  • the method further comprises:
  • step (e) On-line monitoring of the concentration of the active ingredient in the same manner as in steps (a) and (b) during the treatment of the leather.
  • step (c) a preservative is also added to the tanning wastewater.
  • the tannery wastewater is recycled at least twice.
  • the invention also relates to a method of producing leather, comprising:
  • FIG. 1 shows the relationship between the theoretical value of the TANIGANPAK-NC standard solution and the model prediction value in Example 1.
  • FIG. 2 is a graph showing the relationship between the theoretical value of the TANIGAN LT-C standard solution and the model prediction value in Example 2.
  • Fig. 3 (a) shows the relationship between the theoretical value of the TANIGAN LT-C standard solution and the model prediction value in the third embodiment.
  • Fig. 3(b) shows the relationship between the theoretical value of the LELEVOTAN 1084 standard solution and the model prediction value in the third embodiment.
  • Fig. 3(c) shows the relationship between the theoretical value of the RETINGAN R7 standard solution and the model prediction value in the third embodiment.
  • DETAILED DESCRIPTION OF THE INVENTION Due to the variety of chemical materials in wastewater, it is necessary to find a suitable method to detect and control the concentration of chemical materials.
  • concentration monitoring means wastewater recycling can be realized and the quality of each batch of recycled water can be maintained. Guarantee the quality of the finished leather.
  • the inventor finally selected near-infrared spectroscopy technology, and after a large number of experiments, invented a relatively simple and easy way to create a data model, and established an effective concentration control method to achieve a quantitative recycling and utilization method of wastewater.
  • the inventors have surprisingly found that the quality of the leather produced by the directly recovered tanning waste water is substantially the same as that of the treatment agent prepared with fresh water.
  • the "active ingredient” generally means a component which functions in a tanning process, such as a retanning agent, a chrome tanning agent, a neutralizing agent, a degreasing agent, and a fatliquor.
  • a retanning agent such as a retanning agent, a chrome tanning agent, a neutralizing agent, a degreasing agent, and a fatliquor.
  • equipment, devices, components, and the like are either commercially available or can be made in accordance with the teachings of the present invention.
  • some conventional operations and equipment, devices, components are omitted or simply described.
  • One aspect of the invention relates to a method for monitoring the concentration of a tanning process water or a tanning wastewater, comprising:
  • One aspect of the invention relates to a method for recycling tannery wastewater, comprising: (a) obtaining a near-infrared spectrum of the tannery wastewater produced by the tanning process using a near-infrared spectroscopy induction probe;
  • the raw materials are added to the tannery wastewater to the concentration required for the tanning process, and the prepared tannery wastewater is obtained to realize the recycling of the tannery wastewater; wherein, the near-infrared spectrum data
  • the model includes the correspondence between the near-infrared spectrum and the concentration of the components.
  • the method for recycling tannery wastewater is a method for quantitative recycling of tannery wastewater.
  • Another aspect of the invention relates to a method of treating leather using tannery wastewater, comprising:
  • steps (a) to (d) are repeated.
  • steps (a) through (d) are repeated until the tannery wastewater is no longer usable.
  • steps (a) through (d) are repeated until the recovered tanning wastewater does not meet the requirements of the tanning process.
  • the tannery wastewater is recycled (recycled) at least once, preferably at least 2 times, more preferably at least 3 times, and most preferably at least 4 times.
  • the tannery wastewater is recycled (recycled) at least once, preferably at least 3 times, more preferably at least 5 times, still more preferably at least 8 times.
  • the tannery wastewater is recycled (recycled) up to 20 times, preferably up to 18 times, more preferably up to 15 times, further preferably up to 12 times.
  • the tanning waste water is reused (recycled) 1 to 20 times, preferably 2 to 18 times, more preferably 5 to 15 times, further preferably 5 to 12 times, and most preferably 8 to 12 times, for example, 10 times.
  • steps (a), (c) and (d) are carried out in situ, preferably in a rotating drum.
  • a preservative is also added to the tanning wastewater.
  • the amount of the preservative added is from 0.01% to 0.5%, preferably from 0.05% to 0.3%.
  • the tanning wastewater is filtered and used.
  • the leather processing method of the present invention further comprises:
  • the concentration of the active ingredient in the tannery wastewater is obtained.
  • the tanning process is a leather chrome tanning process, a neutralization process, a retanning process, a degreasing process or a fatliquoring process.
  • the neutralization process is a blue wet skin neutralization process.
  • the retanning process is a simple retanning process or a standard retanning process, preferably a blue wet skin simple retanning process or a blue wet skin standard retanning process.
  • the near infrared spectral data model is obtained by the following method:
  • a near-infrared spectral data model is established based on the concentration of the components of each aqueous sample and the near-infrared spectrum, and the near-infrared spectral data model includes the relationship between the concentration of the component and the near-infrared spectrum.
  • the near infrared spectral data model is a near infrared spectral computer data model.
  • the establishment of a near-infrared spectral data model can be performed by TQ Analyst computer software.
  • the near infrared spectral data model includes a concentration of the active component and a near infrared spectral correspondence.
  • each aqueous solution sample contains a plurality of ingredients.
  • each aqueous solution sample contains at least an active ingredient.
  • each of the aqueous solution samples further contains other components (hereinafter referred to as "other components") which may be present in the wastewater.
  • the other component is a component that interferes with the near-infrared spectral data model of the active ingredient.
  • each aqueous solution sample contains the active ingredient and other ingredients.
  • the active ingredient and other ingredients in each aqueous sample are varied. It is also possible to change one of the ingredients while the other ingredients are unchanged. It may be a change in the concentration of the active ingredient while the other ingredients are unchanged. It is also possible to simultaneously change the concentration of the active ingredient and other ingredients.
  • the concentration range of the aqueous solution sample encompasses the range of concentration variations during the tanning process.
  • the concentration of the aqueous sample comprises the maximum and minimum concentrations that will occur for each component (especially the active ingredient) and the intermediate concentration therebetween.
  • the concentration of the aqueous sample includes the maximum concentration of each component (especially the active ingredient) before use, a concentration close to 0 (eg, 0.01%, 0.1%, 0.5%), and the concentration therebetween.
  • the active ingredient is selected from aromatic hydrocarbon compounds such as phenols, arylsulfonates, naphthalenes, sulfones, polyacrylic compounds, dicyandiamides, melamines, polyurethanes, surfactants
  • aromatic hydrocarbon compounds such as phenols, arylsulfonates, naphthalenes, sulfones, polyacrylic compounds, dicyandiamides, melamines, polyurethanes, surfactants
  • an organic acid such as citric acid / glutaric acid / succinic acid / succinic acid / adipic acid / fumaric acid / etc.
  • each aqueous sample contains:
  • an aromatic hydrocarbon compound such as a phenol, an arylsulfonate or a naphthalene, a sulfone, a polyacrylic compound, a dicyandiamide compound, a melamine compound, a polyurethane compound or a surfactant or Multiple;
  • each aqueous solution sample contains a phenolic compound, a salt of an organic acid, or a salt of an inorganic acid.
  • each aqueous solution sample contains an aryl sulfonate, a salt of an organic acid, or a salt of a mineral acid.
  • each aqueous sample contains an aryl sulfonate (such as TANIGANPAK-NC (aqueous formulation of aryl sulfonate)), a salt of an organic acid, a salt of an inorganic acid.
  • each aqueous sample contains a phenolic compound such as TANIGANPAK-NC (an aqueous formulation of an aryl sulfonate), sodium formate and sodium hydrogencarbonate NaHC0 3 .
  • each aqueous solution sample contains a phenolic compound, an organic acid.
  • each aqueous sample contains an aryl sulfonate, an organic acid.
  • each aqueous solution sample contains TANIGAN LT-C (an aqueous solution of an arylsulfonic acid methylene condensate) and formic acid.
  • each aqueous solution sample contains a phenol compound, an acrylic compound, and a dicyandiamide compound.
  • each aqueous solution sample contains an aryl sulfonate, an acrylic compound, a dicyandiamide compound.
  • each aqueous solution sample contains TANIGAN LT-C (aqueous solution of arylsulfonic acid methylene condensate), LEVOTAN 1084 (polyacrylate aqueous emulsion), RATINGAN R7 (methylene condensate of arylsulfamic acid) .
  • the more the number of aqueous samples the more accurate the model data.
  • the amount of aqueous sample is at least 15, preferably at least 20, more preferably at least 30, and most preferably at least 40.
  • the number of aqueous samples is 30 100, preferably 40 100, and most preferably 50 100.
  • the residual effective content of each batch of wastewater is monitored by NIR technology.
  • the method of the present invention is to introduce chemical materials (which can be obtained through the tanning formula and process) in the wastewater, simulate the possible concentration ranges of the wastewater, and respectively configure 40-50 sets of samples with different predetermined concentrations to obtain data of the individual components.
  • the invention also relates to a method of producing leather, comprising:
  • the retort leather is subjected to a fatliquoring process; wherein at least one of the process steps (1), (II) and (III) is carried out by the method of treating leather of the present invention.
  • the process steps (1), (II) and (III) are carried out by the method of the present invention for treating leather.
  • respective near infrared spectral data models are constructed for process steps (1), (II) and (III), respectively.
  • the leather material is a wet blue skin.
  • Example Example 1 Blue wet leather (cowhide upper leather) neutralization process
  • the material TANIGAN PAK-N-C is added in 4% of the tare weight.
  • TANIGAN PAK-NC With fresh water, the material TANIGAN PAK-NC is added in an amount of 8% tare, 150 parts water (40 ° C), P 8.0 parts TANIGAN PAK-NC (manufactured by LANXESS) 1.5 parts sodium formate and 0.5 parts baking soda at Treat at 40 ° C for 60 minutes.
  • TANIGAN PAK-N-C is added to 4%.
  • concentration of the components in the tannery wastewater was read from the obtained near-infrared spectrum, 150 parts of recovered wastewater (40 ° C), supplemented with TANIGAN PAK-NC (manufactured by LANXESS) to 4 parts, supplemented Sodium formate to 1.5 parts, supplemented with baking soda to 0.5 parts, and treated at 40 ° C for 60 minutes.
  • the wastewater is discharged, filtered and supplemented with the required materials, and then recycled to the next batch, with 0.1% preservative added.
  • the leather in the drum is made according to the uniform retanning and fatliquoring process, and is judged after drying.
  • Fig. 1 shows the relationship between the theoretical value of the TANIGANPAK-NC standard solution and the model prediction value in Example 1.
  • the properties of the final leather obtained from the recycling of fresh water and wastewater were tested. There is no significant difference in performance between the freshly produced water and the recycled leather.
  • Example 2 Blue wet skin simple retanning process:
  • TANIGAN LT-C a product of LANXESS.
  • Process (the amount added here is the weight of the processed skin, and the weight is 100 parts) Process: (blue skin) Shaved ⁇ Weighing - Washing ⁇ Neutralizing (to pH 5.0) ⁇ Recovering ⁇ Washing ⁇ Adding fat ⁇ Adjusting value 11 ⁇ Washing ⁇ Drumming. After the blue skin is shaved, weighed, washed, neutralized, the retanning begins, and the four groups A, B, C, and D are as follows: A. It is a blank sample, no TANIGAN LT-C is added, and 100 parts of water is added. After treatment at 40 ° C for 60 minutes, 0.5 parts of 85% formic acid was added for 20 minutes. B.
  • the material TANIGAN LT-C is added in 6% of the tare weight, and 100 parts of water (40 °C) and P 6.0 parts of TANIGAN LT-C (manufactured by LANXESS) are added for 60 minutes, plus 0.5. A portion of 85% formic acid was treated for 20 minutes. C.
  • the material TA GAN LT-C is added in a tare weight of 12%, added with 100 parts of water (40 ° C) and 12.0 parts of TANIGAN LT-C (manufactured by LANXESS) for 60 minutes, plus 0.5 parts. 85% formic acid was treated for 20 minutes.
  • TANIGAN LT-C 0-18.0%; Formic acid: 0-2.0%.
  • Table 2-1 Modeling data
  • the spectrum was acquired by a NIR transmission-sensing probe every 10 minutes, and the concentration of the TANIGAN LT-C solution was quickly read by a pre-built TANIGAN LT-C near-infrared spectral data model.
  • Fig. 2 is a graph showing the relationship between the theoretical value of the TANIGAN LT-C standard solution and the model prediction value in Example 2. The performance of the leather obtained by recycling fresh water and waste water was tested, and the final obtained leather fresh water was not significantly different from the wastewater.
  • TANIGAN LT-C phenolic
  • LEVOTAN 1084 (Acrylic), a product of LANXESS.
  • RATINGAN R7 (dicyandiamide), a product of LANXESS.
  • Process (the amount added here is the weight of the processed skin, and the weight is 100 parts) Process: (blue skin) Shaved ⁇ Weighing - Washing ⁇ Neutralizing (to pH 5.0) ⁇ Recovering ⁇ Washing ⁇ Adding fat ⁇ Adjusting value 11 ⁇ Washing ⁇ Drumming. After the blue skin is shaved, weighed, washed, neutralized, the retanning begins, and the two groups are divided into A and B, as follows:
  • RETINGAN R7 was treated at 40 ° C for 60 minutes and 0.5 parts of 85% formic acid was added for 20 minutes.
  • the concentration of the components in the tannery wastewater is read from the obtained near-infrared spectrum, and 100 parts of wastewater is added first, and then added to 6 parts of TANIGAN.
  • LT-C, 4 parts of LEVOTAN 1084, 6 parts of RETINGAN R7 were treated at 40 ° C for 60 minutes, and 0.5 parts of 85% formic acid was added for 20 minutes.
  • the wastewater will be discharged. After filtering and replenishing the required materials, the next batch will be recycled. It is recommended to add 0.1% preservative.
  • the leather in the drum is made according to the uniform retanning and fatliquoring process, and is judged after drying.
  • the content of LT-C, 1084, and R7 in the wastewater was measured every 10 minutes (NIR method), and the retanning was completed in 60 minutes.
  • the process also tracks the content of the mixture after three kinds of retanning agents are separately modeled by NIR.
  • Fig. 3 (a) shows the relationship between the theoretical value of the TANIGAN LT-C standard solution and the model prediction value in the third embodiment.
  • Fig. 3(b) shows the relationship between the theoretical value of the LELEVOTAN 1084 standard solution and the model prediction value in the third embodiment.
  • Fig. 3(c) shows the relationship between the theoretical value of the RETINGAN R7 standard solution and the model prediction value in the third embodiment.
  • the theoretical value is close to the measured value, and the speed of the concentration reduction in the process is consistent with the actual value.
  • the performance of the leather obtained by recycling fresh water and waste water was tested. Finally, there was no significant difference in the performance of the leather obtained by recycling the wastewater (as shown in Table 3-3).
  • Table 3-3 shows the relationship between the theoretical value of the TANIGAN LT-C standard solution and the model prediction value in the third embodiment.
  • Fig. 3(b) shows the relationship between the theoretical value of the LELEVOTAN 1084 standard solution and the model prediction value in the third embodiment.
  • the medium-sized tannery produces 1 million cowhide per year, which will produce 560,000 tons of waste water.
  • the wastewater from the reclamation process will be recycled after 10 times, and the total amount of wastewater that can be discharged is about 500,000 tons.
  • the present invention may be embodied in other specific forms, and the above is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention; those skilled in the art, regardless of the spirit of the present invention, SUMMARY OF THE INVENTION Various changes and modifications may be made without departing from the scope of the invention.

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Abstract

A method for treating leather by using leather production wastewater and a method for producing leather. The method for treating leather by using leather production wastewater comprises: (a) obtaining the near infrared spectrum of leather production wastewater generated from leather production processes with a near infrared spectrum sensing probe; (b) determining or reading the concentration of components in the leather production wastewater through the obtained near infrared spectrum by means of a pre-established near infrared spectrum data model; (c) adding, according to the concentration of components in the leather production wastewater, raw materials into the leather production wastewater until being up to the concentration required for the leather production processes to obtain prepared leather production wastewater; (d) treating leather by using the prepared leather production wastewater to perform the leather production processes, the near infrared spectrum data model comprising the mapping between the near infrared spectrum and the concentration of components. The method for treating leather by using leather production wastewater implements the cyclic use of leather production wastewater and is environmentally friendly.

Description

利用制革废水处理皮革的方法及生产皮革的方法 技术领域 本发明涉及利用制革废水处理皮革的方法及生产皮革的方法。 背景技术 随着经济的迅速发展， 人们对健康环保的认识越来越深入。 目前制革中产生的废 水含大量的有机物质， 如果直接排放入河， 对水环境会造成不可逆转的破坏。 因此， 废水的处理及排放成了制革行业一道越来越严的紧箍咒， 如何处理废水， 减少废水， 降低排放， 是目前研究机构以及制革厂都在探索的课题。 通常， 降低废水的排放可从三方面来考虑： 第一种思路是从源头控制。 从化学品种类的选择上避免使用有毒有害的物质， 但 是由于材料的局限， 以及对皮革的认识有限， 有些材料虽然有害还不得不使用因为没 有代用品。 这种情况下就要从制革工艺上考虑怎样提高他们的反应效率， 尽可能的提 高他们与皮革的结合率， 这样就可以以最少的使用量达到同样的效果， 也可以降低它 们在水中的残余量， 间接地起到降低废水的作用。 这是皮革化学家们永远的课题。 第二种是将废水进行有效的处理。 去除其中的重金属、 有机物、 无机盐等等， 达 到排放标准后排放。 如何高效又低成本的处理废水， 这也是现在一些设备工程师、 化 学工作者努力的方向。 第三种是废水的回收利用。 经市场调研， 发现废水的回收利用在某些工厂， 某些 特殊的工艺中已经存在， 但是量很少。 据调查， 阻碍废水回收利用的关键有两点：  BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of treating leather using tannery wastewater and a method of producing leather. BACKGROUND OF THE INVENTION With the rapid development of the economy, people's understanding of health and environmental protection has become more and more in-depth. At present, the waste water produced in the tanning contains a large amount of organic matter, and if it is directly discharged into the river, it will cause irreversible damage to the water environment. Therefore, the treatment and discharge of wastewater has become an increasingly strict curse in the tanning industry. How to treat wastewater, reduce wastewater, and reduce emissions is a topic that research institutions and tanneries are currently exploring. In general, reducing wastewater discharge can be considered in three ways: The first idea is to control from the source. Avoid the use of toxic and hazardous substances from the choice of chemical species, but due to material limitations and limited knowledge of leather, some materials have to be used because they are harmful because there are no substitutes. In this case, we must consider how to improve their reaction efficiency from the tanning process, and increase their bonding rate with leather as much as possible, so that the same effect can be achieved with the least amount of use, and they can also be reduced in water. The residual amount and the grounding function play a role in reducing the waste water. This is a permanent issue for leather chemists. The second is to treat the wastewater efficiently. Remove heavy metals, organic matter, inorganic salts, etc., and discharge them after reaching emission standards. How to treat wastewater efficiently and at low cost is the direction of some equipment engineers and chemical workers. The third type is the recycling of wastewater. According to market research, it is found that the recycling of wastewater has existed in some factories, but in some special processes, but the amount is small. According to the survey, there are two key points that hinder the recycling of wastewater:
( 1 ) 废水容易长菌。 由于废水中含有大量有机物， 当 pH、 温度合适， 细菌和霉 菌的繁殖是非常快的， 第二天就会产生难闻的气味。 这种废水如果回收利用， 需要找 到比较合适的防腐剂。 (1) Waste water is prone to bacteria. Since the wastewater contains a lot of organic matter, when the pH and temperature are appropriate, the bacteria and molds multiply very quickly, and the next day, an unpleasant smell is produced. If this wastewater is recycled, it is necessary to find a suitable preservative.
(2)废水中的成分难以测定。 即使解决了防菌的问题， 废水中含有大量未结合的 化学原料。虽然可以回收利用但是废水成分太复杂， 回收利用时是否要补充化学原料， 补多少， 都是未知数， 这样做出来的皮质量就很难保证。 工厂的技师们只能根据经验 来大致判断， 经验好的估的准一点， 人为因素太强， 这也是废水回收利用不能大范围 推广的主要原因。 目前能用于化学品成分检测的方法很多，但针对制革废水中成分复杂的化学材料， 相互之间交叉干扰， 要逐个加以区分并定量检测难度非常大。 同样成分复杂的中药成 分控制目前在试验一种新技术一指纹图谱技术， 但需要花费大量的人力物力去建立 图谱库， 目前实际应用还有很多问题。 而且废水和中药还不一样， 因为废水的成分根 据制革处理配方和工艺会经常变换， 所以该技术不适合废水的定量分析。 长期以来， 人们一直在寻找能够简单、 快速在线监测皮革处理水 （制革废水） 成 分的方法， 以便实现制革废水的循环利用。 但据发明人所知， 在本发明之前， 尚未找 到这样的简单有效的方法， 也没有实现制革废水的完全循环利用。 制革废水的循环利 用成为本领域内长期未解决的技术难题。 因此， 需要一种实现制革废水的循环利用、 环境友好处理皮革的方法。 发明内容 本发明涉及利用制革废水处理皮革的方法， 包括： ( a) 用近红外光谱感应探头获得制革工艺所产生的制革废水的近红外光谱； (2) The components in the wastewater are difficult to measure. Even if the problem of antibacterial is solved, the wastewater contains a large amount of unbound chemical raw materials. Although it can be recycled, but the wastewater composition is too complicated, whether to replenish chemical raw materials when recycling, and how much to make up is unknown, the quality of the skin is difficult to guarantee. Factory technicians can only rely on experience To judge roughly, the experience is good, and the human factor is too strong. This is the main reason why wastewater recycling cannot be widely promoted. At present, there are many methods for detecting chemical components. However, for the complex chemical materials in tannery wastewater, cross-interference between them is difficult to distinguish one by one and quantitative detection is very difficult. The control of traditional Chinese medicine components with the same complex composition is currently testing a new technology-fingerprint technology, but it takes a lot of manpower and material resources to build the map library. At present, there are still many problems in practical application. Moreover, wastewater and traditional Chinese medicine are different, because the composition of wastewater is often changed according to the tanning treatment formula and process, so this technology is not suitable for quantitative analysis of wastewater. For a long time, people have been looking for ways to monitor the composition of leather treated water (tannery wastewater) simply and quickly, in order to recycle the tannery wastewater. However, to the knowledge of the inventors, prior to the present invention, such a simple and effective method has not been found, and complete recycling of the tannery wastewater has not been achieved. The recycling of tannery wastewater has become a long-standing unsolved technical problem in the field. Therefore, there is a need for a method for achieving recycling of tannery wastewater and environmentally friendly treatment of leather. SUMMARY OF THE INVENTION The present invention is directed to a method of treating leather using tannery wastewater, comprising: (a) obtaining a near infrared spectrum of the tannery wastewater produced by the tanning process using a near infrared spectroscopy sensor;
(b)通过预先建好的近红外光谱数据模型， 由获得的近红外光谱确定或读取制革 废水中成分的浓度； (b) determining or reading the concentration of the constituents in the tannery wastewater from the obtained near-infrared spectroscopy by a pre-built near-infrared spectral data model;
( c)根据制革废水中成分的浓度， 向制革废水中补充原料至该制革工艺所需的浓 度， 获得配制的制革废水； ( d) 用配制的制革废水对皮革进行处理， 进行该制革工艺； 其中， 近红外光谱数据模型包括近红外光谱与成分浓度的对应关系。 优选地， 近红外光谱数据模型通过以下方法获得： (c) obtaining the tannery wastewater according to the concentration of the components in the tannery wastewater by adding the raw materials to the tannery wastewater to the concentration required for the tanning process; (d) treating the leather with the prepared tanning waste water, The tannery process is performed; wherein the near-infrared spectral data model includes a correspondence between the near-infrared spectrum and the component concentration. Preferably, the near infrared spectral data model is obtained by the following method:
(bl ) 根据制革工艺所产生的制革废水中的成分， 配制一系列具有预定浓度的水 溶液样品， 各个水溶液样品含有制革废水中的成分； (b2) 获得各个水溶液样品的近红外光谱； (b3 ) 根据各个水溶液样品的成分的浓度和近红外光谱， 建立近红外光谱数据模 型， 近红外光谱数据模型包括成分的浓度和近红外光谱对应关系。 优选地， 各个水溶液样品至少包含有效物成分。 优选地， 各个水溶液样品还包含会出现在废水中的其他成分， 其中其他成分是对 有效物成分的近红外光谱数据模型有干扰的成分。 优选地， 有效物成分选自芳香族化合物、 砜类、 聚丙烯酸类化合物、 双氰胺类化 合物、 三聚氰胺类化合物、 聚氨酯类化合物、 表面活性剂、 有机酸及其盐中的一种或 多种。 优选地， 芳香族化合物选自酚类、 芳基磺酸盐、 萘类化合物。 优选地， 有机酸及其盐选自柠檬酸、 戊二酸、 琥珀酸、 丁二酸、 己二酸、 富马酸 及其盐中的一种或多种。 优选地， 近红外光谱数据模型包括有效物成分的浓度和近红外光谱的对应关系。 优选地， 各个水溶液样品含有： (b) preparing a series of aqueous solution samples having a predetermined concentration according to the components in the tanning waste water produced by the tanning process, each aqueous solution sample containing components in the tanning waste water; (b2) obtaining a near-infrared spectrum of each aqueous solution sample; (b3) A near-infrared spectral data model is established based on the concentration of the components of each aqueous sample and the near-infrared spectrum. The near-infrared spectral data model includes the relationship between the concentration of the component and the near-infrared spectrum. Preferably, each aqueous solution sample contains at least an active ingredient. Preferably, each aqueous sample also contains other components that may be present in the wastewater, wherein the other components are components that interfere with the near infrared spectral data model of the active component. Preferably, the active ingredient is selected from one or more of an aromatic compound, a sulfone, a polyacrylic compound, a dicyandiamide compound, a melamine compound, a polyurethane compound, a surfactant, an organic acid, and a salt thereof. . Preferably, the aromatic compound is selected from the group consisting of phenols, aryl sulfonates, and naphthalenes. Preferably, the organic acid and its salt are selected from one or more of the group consisting of citric acid, glutaric acid, succinic acid, succinic acid, adipic acid, fumaric acid, and salts thereof. Preferably, the near infrared spectral data model includes a correspondence between the concentration of the active ingredient and the near infrared spectrum. Preferably, each aqueous sample contains:
( i) 酚类化合物； ( ii) 有机酸、 有机酸的盐、 无机酸、 无机酸的盐中的至少一种。 优选地， 各个水溶液样品含有： (i) a phenolic compound; (ii) at least one of an organic acid, a salt of an organic acid, a mineral acid, and a salt of an inorganic acid. Preferably, each aqueous sample contains:
( i) 芳基磺酸盐； (i) an aryl sulfonate;
( ii) 有机酸、 有机酸的盐、 无机酸、 无机酸的盐中的至少一种。 优选地， 各个水溶液样品含有： 酚类化合物、 丙烯酸类化合物以及双氰胺类化合 物。 优选地， 各个水溶液样品含有： 芳基磺酸盐、 丙烯酸类化合物以及双氰胺类化合 物。 优选地， 各个水溶液样品含有： 芳基磺酸亚甲基缩合物、 聚丙烯酸酯以及芳代氨 基磺酸的亚甲基缩合物。 优选地， 有效物成分选自制革工艺中所使用的复鞣剂、 铬鞣剂、 中和剂、 脱脂剂 或加脂剂。 优选地， 制革工艺是皮革铬鞣工艺、 中和工艺、 复鞣工艺、 脱脂工艺或加脂工艺。 优选地， 中和工艺是蓝湿皮中和工艺。 优选地， 复鞣工艺是简单复鞣工艺或标准复鞣工艺。 优选地， 复鞣工艺是蓝湿皮简单复鞣工艺或蓝湿皮标准复鞣工艺。 优选地， 该方法进一步包括： (ii) at least one of an organic acid, a salt of an organic acid, a mineral acid, and a salt of an inorganic acid. Preferably, each aqueous solution sample contains: a phenolic compound, an acrylic compound, and a dicyandiamide compound. Preferably, each aqueous solution sample contains: an aryl sulfonate, an acrylic compound, and a dicyandiamide compound. Preferably, each aqueous sample contains: an aryl sulfonate methylene condensate, a polyacrylate, and a methylene condensate of an aromatic sulfamic acid. Preferably, the active ingredient is selected from the group consisting of retanning agents, chrome tanning agents, neutralizing agents, degreasers or fatliquors used in the tanning process. Preferably, the tanning process is a leather chrome tanning process, a neutralization process, a retanning process, a degreasing process or a fatliquoring process. Preferably, the neutralization process is a blue wet skin neutralization process. Preferably, the retanning process is a simple retanning process or a standard retanning process. Preferably, the retanning process is a blue wet skin simple retanning process or a blue wet skin standard retanning process. Preferably, the method further comprises:
(e)在对皮革进行处理过程中， 使用步骤 （a)和 （b)相同的方式对有效物成分 的浓度进行在线监测。 优选地， 在步骤 （c) 中， 还向制革废水中加入防腐剂。 优选地， 制革废水循环使用至少 2次。 本发明还涉及生产皮革的方法， 包括： (e) On-line monitoring of the concentration of the active ingredient in the same manner as in steps (a) and (b) during the treatment of the leather. Preferably, in step (c), a preservative is also added to the tanning wastewater. Preferably, the tannery wastewater is recycled at least twice. The invention also relates to a method of producing leather, comprising:
(I) 对皮革原料进行中和工艺， 得到中和处理后的皮革； (I) Neutralizing the leather material to obtain a neutralized leather;
(II) 对中和处理后的皮革进行复鞣工艺， 得到复鞣后的皮革； (III) 对复鞣后的皮革进行加脂工艺； 其中， 工艺步骤 （1)、 (II) 和 （III) 中的至少一个通过本发明处理皮革的方法进 行。 优选地， 工艺步骤 （1)、 (II) 和 （III) 均通过本发明处理皮革的方法进行。 优选地， 皮革原料是蓝湿皮。 本发明的方法实现制革废水的循环利用， 是环境友好处理皮革的方法。 附图说明 图 1示出了实施例 1中 TANIGANPAK-N-C标准液理论值和模型预测值的关系。 图 2示出了实施例 2中 TANIGAN LT-C标准液理论值和模型预测值的关系。 图 3 (a) 示出了实施例 3中 TANIGAN LT-C标准液理论值和模型预测值的关系。 图 3 (b) 示出了实施例 3中 LELEVOTAN 1084标准液理论值和模型预测值的关 系。 图 3 (c) 示出了实施例 3中 RETINGAN R7标准液理论值和模型预测值的关系。 具体实施方式 由于废水中化料品种多， 需要寻找一种合适的方法来检测和控制化料的浓度， 有 了浓度监控手段， 才可以实现废水回收利用并保持每批回收利用水的质量， 从而保证 制成革的质量。 发明人最后选择近红外光谱技术， 经过大量的实验， 发明一种相对简单易行的创 建数据模型的方法， 并建立有效的浓度控制手段， 由此实现废水的定量回收利用方法。 发明人出人意料地发现， 与采用新鲜水配制的处理剂相比， 采用直接回收的制革 废水所生产的皮革质量基本相同。 在本发明中， "有效物成分 "通常是指在制革工艺中起作用的成分， 例如复鞣剂、 铬鞣剂、 中和剂、 脱脂剂、 加脂剂。 在本发明中， 在不矛盾或冲突的情况下， 本发明的所有实施例、 实施方式以及特 征可以相互组合。 在本发明中， 设备、 装置、 部件等， 既可以商购， 也可以根据本发明公开的内容 自制。 在本发明中， 为了突出本发明的重点， 对一些常规的操作和设备、 装置、 部件进 行的省略， 或仅作简单描述。 本发明一方面涉及制革工艺水或制革废水成分浓度的监测方法， 包括： (II) retanning the neutralized leather to obtain retanning leather; (III) fatliquoring the retapped leather; wherein, process steps (1), (II) and (III) At least one of the processes is carried out by the method of the present invention for treating leather. Preferably, process steps (1), (II) and (III) are carried out by the method of the present invention for treating leather. Preferably, the leather material is a wet blue skin. The method of the present invention realizes the recycling of tannery wastewater and is a method for environmentally friendly treatment of leather. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows the relationship between the theoretical value of the TANIGANPAK-NC standard solution and the model prediction value in Example 1. Fig. 2 is a graph showing the relationship between the theoretical value of the TANIGAN LT-C standard solution and the model prediction value in Example 2. Fig. 3 (a) shows the relationship between the theoretical value of the TANIGAN LT-C standard solution and the model prediction value in the third embodiment. Fig. 3(b) shows the relationship between the theoretical value of the LELEVOTAN 1084 standard solution and the model prediction value in the third embodiment. Fig. 3(c) shows the relationship between the theoretical value of the RETINGAN R7 standard solution and the model prediction value in the third embodiment. DETAILED DESCRIPTION OF THE INVENTION Due to the variety of chemical materials in wastewater, it is necessary to find a suitable method to detect and control the concentration of chemical materials. With concentration monitoring means, wastewater recycling can be realized and the quality of each batch of recycled water can be maintained. Guarantee the quality of the finished leather. The inventor finally selected near-infrared spectroscopy technology, and after a large number of experiments, invented a relatively simple and easy way to create a data model, and established an effective concentration control method to achieve a quantitative recycling and utilization method of wastewater. The inventors have surprisingly found that the quality of the leather produced by the directly recovered tanning waste water is substantially the same as that of the treatment agent prepared with fresh water. In the present invention, the "active ingredient" generally means a component which functions in a tanning process, such as a retanning agent, a chrome tanning agent, a neutralizing agent, a degreasing agent, and a fatliquor. In the present invention, all of the embodiments, embodiments, and features of the present invention can be combined with each other without contradiction or conflict. In the present invention, equipment, devices, components, and the like, are either commercially available or can be made in accordance with the teachings of the present invention. In the present invention, in order to highlight the gist of the present invention, some conventional operations and equipment, devices, components are omitted or simply described. One aspect of the invention relates to a method for monitoring the concentration of a tanning process water or a tanning wastewater, comprising:
(a)用近红外光谱感应探头获得制革工艺所产生的制革工艺水或制革废水的近红 外光谱； (a) obtaining a near-infrared spectrum of the tanning process water or the tanning waste water produced by the tanning process using a near-infrared spectroscopy induction probe;
(b)通过预先建好的近红外光谱数据模型， 由获得的近红外光谱确定或读取制革 工艺水或制革废水中成分的浓度。 本发明一方面涉及制革废水的回收利用方法， 包括： ( a) 用近红外光谱感应探头获得制革工艺所产生的制革废水的近红外光谱； (b) Determine or read the concentration of the components in the tanning process water or tannery wastewater from the obtained near-infrared spectroscopy by a pre-built near-infrared spectral data model. One aspect of the invention relates to a method for recycling tannery wastewater, comprising: (a) obtaining a near-infrared spectrum of the tannery wastewater produced by the tanning process using a near-infrared spectroscopy induction probe;
(b)通过预先建好的近红外光谱数据模型， 由获得的近红外光谱确定或读取制革 废水中成分的浓度； (b) determining or reading the concentration of the constituents in the tannery wastewater from the obtained near-infrared spectroscopy by a pre-built near-infrared spectral data model;
( c)根据制革废水中成分的浓度， 向制革废水中补充原料至该制革工艺所需的浓 度， 获得配制的制革废水， 实现制革废水的回收利用； 其中， 近红外光谱数据模型包括近红外光谱与成分浓度的对应关系。 优选地， 制革废水的回收利用方法是制革废水的定量回收利用方法。 本发明另一方面涉及利用制革废水处理皮革的方法， 包括： (c) According to the concentration of the components in the tannery wastewater, the raw materials are added to the tannery wastewater to the concentration required for the tanning process, and the prepared tannery wastewater is obtained to realize the recycling of the tannery wastewater; wherein, the near-infrared spectrum data The model includes the correspondence between the near-infrared spectrum and the concentration of the components. Preferably, the method for recycling tannery wastewater is a method for quantitative recycling of tannery wastewater. Another aspect of the invention relates to a method of treating leather using tannery wastewater, comprising:
( a) 用近红外光谱感应探头获得制革工艺所产生的制革废水的近红外光谱； (b)通过预先建好的近红外光谱数据模型， 由获得的近红外光谱确定或读取制革 废水中成分的浓度； (a) obtaining near-infrared spectra of tannery wastewater produced by the tanning process using a near-infrared spectroscopy probe; (b) determining or reading tanning from the obtained near-infrared spectroscopy through a pre-built near-infrared spectral data model The concentration of the components in the wastewater;
( c)根据制革废水中成分的浓度， 向制革废水中补充原料至该制革工艺所需的浓 度， 获得配制的制革废水； (c) according to the concentration of the components in the tannery wastewater, adding the raw materials to the tanning waste water to the concentration required for the tanning process, and obtaining the prepared tanning waste water;
( d) 用配制的制革废水对皮革进行处理， 进行该制革工艺； 其中， 近红外光谱数据模型包括近红外光谱与成分浓度的对应关系。 优选地， 步骤 （a) 至 （d) 重复进行。 优选地， 重复步骤 （a) 至 （d)， 直到制革 废水无法再用。 优选地， 重复步骤 （a) 至 （d) 直到回收的制革废水无法达到该制革 工艺的要求。 优选地， 制革废水回用 （循环使用）至少 1次， 优选至少 2次， 更优选至少 3次， 最优选至少 4次。 优选地， 制革废水回用 （循环使用）至少 1次， 优选至少 3次， 更优选至少 5次， 进一步优选至少 8次。 优选地， 制革废水回用 （循环使用） 至多 20次， 优选至多 18次， 更优选至多 15 次， 进一步优选至多 12次。 优选地， 制革废水回用 （循环使用） 1~20次， 优选 2~18次， 更优选 5~15次， 进 一步优选 5~12次， 最优选 8~12次， 例如 10次。 优选地， 步骤 （a)、 (c) 和 （d) 均原位进行， 优选在转鼓中进行。 优选地， 在步骤（c) 中， 还向制革废水中加入防腐剂。 例如， 防腐剂的加入量为 0.01%~0.5%, 优选 0.05%~0.3%。 优选地， 将制革废水过滤后使用。 优选地， 本发明的皮革处理方法进一步包括： (d) The leather is treated with the prepared tanning waste water to carry out the tanning process; wherein the near-infrared spectral data model includes the correspondence between the near-infrared spectrum and the component concentration. Preferably, steps (a) to (d) are repeated. Preferably, steps (a) through (d) are repeated until the tannery wastewater is no longer usable. Preferably, steps (a) through (d) are repeated until the recovered tanning wastewater does not meet the requirements of the tanning process. Preferably, the tannery wastewater is recycled (recycled) at least once, preferably at least 2 times, more preferably at least 3 times, and most preferably at least 4 times. Preferably, the tannery wastewater is recycled (recycled) at least once, preferably at least 3 times, more preferably at least 5 times, still more preferably at least 8 times. Preferably, the tannery wastewater is recycled (recycled) up to 20 times, preferably up to 18 times, more preferably up to 15 times, further preferably up to 12 times. Preferably, the tanning waste water is reused (recycled) 1 to 20 times, preferably 2 to 18 times, more preferably 5 to 15 times, further preferably 5 to 12 times, and most preferably 8 to 12 times, for example, 10 times. Preferably, steps (a), (c) and (d) are carried out in situ, preferably in a rotating drum. Preferably, in step (c), a preservative is also added to the tanning wastewater. For example, the amount of the preservative added is from 0.01% to 0.5%, preferably from 0.05% to 0.3%. Preferably, the tanning wastewater is filtered and used. Preferably, the leather processing method of the present invention further comprises:
(e)在该制革工艺过程中， 用本发明的监测方法对有效物成分的浓度进行在线监 (e) Online monitoring of the concentration of the active ingredient by the monitoring method of the present invention during the tanning process
优选地， 在步骤 （b) 中， 获得制革废水中有效物成分的浓度。 优选地， 制革工艺是皮革铬鞣工艺、 中和工艺、 复鞣工艺、 脱脂工艺或加脂工艺。 优选地， 中和工艺是蓝湿皮中和工艺。 优选地， 复鞣工艺是简单复鞣工艺或标准复鞣工艺， 优选蓝湿皮简单复鞣工艺或 蓝湿皮标准复鞣工艺。 优选地， 近红外光谱数据模型通过以下方法获得： Preferably, in step (b), the concentration of the active ingredient in the tannery wastewater is obtained. Preferably, the tanning process is a leather chrome tanning process, a neutralization process, a retanning process, a degreasing process or a fatliquoring process. Preferably, the neutralization process is a blue wet skin neutralization process. Preferably, the retanning process is a simple retanning process or a standard retanning process, preferably a blue wet skin simple retanning process or a blue wet skin standard retanning process. Preferably, the near infrared spectral data model is obtained by the following method:
(bl ) 根据制革工艺所产生的制革废水中的成分， 配制一系列具有预定浓度的水 溶液样品， 各个水溶液样品含有制革废水中的成分； (bl) preparing a series of samples of the aqueous solution having a predetermined concentration according to the components in the tanning waste water produced by the tanning process, each of the aqueous solution samples containing the components in the tanning waste water;
(b2) 获得各个水溶液样品的近红外光谱； (b2) obtaining a near-infrared spectrum of each aqueous solution sample;
(b3 ) 根据各个水溶液样品的成分的浓度和近红外光谱， 建立近红外光谱数据模 型， 该近红外光谱数据模型包括成分的浓度和近红外光谱对应关系。 优选地， 近红外光谱数据模型是近红外光谱电脑数据模型。 例如建立近红外光谱 数据模型可以通过 TQ Analyst电脑软件进行。 优选地， 近红外光谱数据模型包括有效物成分的浓度和近红外光谱对应关系。 优选地， 各个水溶液样品包含多种成分。 优选地， 各个水溶液样品至少包含有效物成分。 进一步优选地， 各个水溶液样品 还包含会出现在废水中的其他成分（下文简称"其他成分"）。 优选地， 其他成分是对有 效物成分近红外光谱数据模型有干扰的成分。 优选地， 各个水溶液样品包含有效物成 分和其他成分。 优选地， 各个水溶液样品中有效物成分和其他成分均是变化的。 也可以其中一种 成分变化， 而另外的成分不变。 可以是有效物成分的浓度变化， 而其他成分不变。 也 可以是有效物成分和其他成分不变的浓度同时变化。 优选地， 水溶液样品的浓度范围涵盖制革工艺过程中浓度变化范围。 在优选的实 施方式中， 水溶液样品的浓度包括各个成分 （尤其有效物成分） 的会出现的最大浓度 和最低浓度以及二者之间的中间浓度。 例如， 水溶液样品的浓度包括各个成分 （尤其 有效物成分） 的在使用前的最大浓度、 接近 0的浓度 （例如 0.01%、 0.1%、 0.5%) 以 及二者之间的浓度。 优选地， 有效物成分选自如酚类、 芳基磺酸盐、 萘类等芳香烃类化合物、 砜类、 聚丙烯酸类化合物、 双氰胺类化合物、 三聚氰胺类化合物、 聚氨酯类化合物、 表面活 性剂、 有机酸 （如柠檬酸 /戊二酸 /琥珀酸 /丁二酸 /己二酸 /富马酸 /等） 及其盐中的一种 或多种。 优选地， 各个水溶液样品含有： (b3) A near-infrared spectral data model is established based on the concentration of the components of each aqueous sample and the near-infrared spectrum, and the near-infrared spectral data model includes the relationship between the concentration of the component and the near-infrared spectrum. Preferably, the near infrared spectral data model is a near infrared spectral computer data model. For example, the establishment of a near-infrared spectral data model can be performed by TQ Analyst computer software. Preferably, the near infrared spectral data model includes a concentration of the active component and a near infrared spectral correspondence. Preferably, each aqueous solution sample contains a plurality of ingredients. Preferably, each aqueous solution sample contains at least an active ingredient. Further preferably, each of the aqueous solution samples further contains other components (hereinafter referred to as "other components") which may be present in the wastewater. Preferably, the other component is a component that interferes with the near-infrared spectral data model of the active ingredient. Preferably, each aqueous solution sample contains the active ingredient and other ingredients. Preferably, the active ingredient and other ingredients in each aqueous sample are varied. It is also possible to change one of the ingredients while the other ingredients are unchanged. It may be a change in the concentration of the active ingredient while the other ingredients are unchanged. It is also possible to simultaneously change the concentration of the active ingredient and other ingredients. Preferably, the concentration range of the aqueous solution sample encompasses the range of concentration variations during the tanning process. In a preferred embodiment, the concentration of the aqueous sample comprises the maximum and minimum concentrations that will occur for each component (especially the active ingredient) and the intermediate concentration therebetween. For example, the concentration of the aqueous sample includes the maximum concentration of each component (especially the active ingredient) before use, a concentration close to 0 (eg, 0.01%, 0.1%, 0.5%), and the concentration therebetween. Preferably, the active ingredient is selected from aromatic hydrocarbon compounds such as phenols, arylsulfonates, naphthalenes, sulfones, polyacrylic compounds, dicyandiamides, melamines, polyurethanes, surfactants One or more of an organic acid (such as citric acid / glutaric acid / succinic acid / succinic acid / adipic acid / fumaric acid / etc.) and a salt thereof. Preferably, each aqueous sample contains:
(i)酚类、 芳基磺酸盐、 萘类等芳香烃类化合物、 砜类、 聚丙烯酸类化合物、 双 氰胺类化合物、 三聚氰胺类化合物、 聚氨酯类化合物、 表面活性剂中的一种或多种； 以及 (i) one of an aromatic hydrocarbon compound such as a phenol, an arylsulfonate or a naphthalene, a sulfone, a polyacrylic compound, a dicyandiamide compound, a melamine compound, a polyurethane compound or a surfactant or Multiple;
(ii)有机酸 （如柠檬酸 /戊二酸 /琥珀酸 /丁二酸 /己二酸 /富马酸 /等）及其盐、 无机 酸及其盐中的一种或多种。 优选地， 废水中的其他成分选自机酸 （如柠檬酸 /戊二酸 /琥珀酸 /丁二酸 /己二酸 / 富马酸 /等） 及其盐、 无机酸及其盐中的一种或多种。 优选地， 各个水溶液样品含有酚类化合物、 有机酸的盐、 无机酸的盐。 优选地， 各个水溶液样品含有芳基磺酸盐、 有机酸的盐、 无机酸的盐。 优选地， 各个水溶液样品含有芳基磺酸盐 （如 TANIGANPAK-N-C (芳基磺酸盐 的水性配制品））、 有机酸的盐、 无机酸的盐。 优选地， 各个水溶液样品含有酚类化合物 （如 TANIGANPAK-N-C (芳基磺酸盐 的水性配制品））、 甲酸钠和碳酸氢钠 NaHC03。 优选地， 各个水溶液样品含有酚类化合物、 有机酸。 优选地， 各个水溶液样品含有芳基磺酸盐、 有机酸。 优选地，各个水溶液样品含有 TANIGAN LT-C (芳基磺酸亚甲基缩合物的水溶液） 和甲酸。 优选地， 各个水溶液样品含有酚类化合物、 丙烯酸类化合物、 双氰胺类化合物。 优选地， 各个水溶液样品含有芳基磺酸盐、 丙烯酸类化合物、 双氰胺类化合物。 优选地，各个水溶液样品含有 TANIGAN LT-C (芳基磺酸亚甲基缩合物的水溶液）、 LEVOTAN 1084 (聚丙烯酸酯水性乳液）、 RATINGAN R7 (芳代氨基磺酸的亚甲基缩 合物）。 水溶液样品数量越多模型数据越精确。优选地， 水溶液样品数量为至少 15个， 优 选至少 20个， 更优选至少 30个， 最优选至少 40个。例如， 水溶液样品数量为 30 100 个， 优选 40 100个， 最优选 50 100个。 ( 1 ) 通过 NIR技术监控每批废水的残余有效物含量。 如果按照常规的建模 （数据模型） 的方法， 需要取 30-40组废水样品扫描光谱信 息， 然后通过常规的化学分析和色谱分析得到其实时的成分数据。 但制革废水成分复 杂， 很难通过常规的化学分析和色谱分析得到其实时的成分数据， 也就无法建立光谱 信息和含量数据的对应关系。 所以本发明的方法是将废水中会出现的化学材料 （通过 制革配方和工艺可以得到）， 模拟废水可能出现的浓度范围， 分别配置不同预定浓度 40-50组样品， 得到各单一成分的数据模型， 然后再实验其他材料的加入是否有干扰， 如果没有干扰即可认为该材料的数据模型成功。 如果有干扰， 必须用造成干扰的材料 按理论浓度混合配置 40-50组样品对原来的数据进行校正， 样品数量越多模型数据越 精确。该方法在建模时需要花费一定人力， 但简单易行， 操作人员稍加培训即可操作。 (2)基于废水回收利用的中和， 复鞣工艺， 使用近红外光谱技术对转鼓液体中各 种化学材料的含量进行跟踪， 不仅可以了解各种材料在皮革中的吸收情况， 便于工艺 的优化， 而且对废水中的材料含量进行定量监控， 下一次回收利用时将各种材料补充 至所需的浓度即可。 近红外光谱建模的方法： 目前没有合适的建模方法， 本发明方法原理简单， 操作 也容易。 利用近红外光谱技术监控废水中有效物含量实现废水的定量回收利用工艺， 包括 但不仅限于中和以及复鞣工艺， 同样的原理适合前道的铬鞣工艺、 脱脂工艺及后道的 加脂工艺。 本发明还涉及生产皮革的方法， 包括： (ii) one or more of an organic acid (such as citric acid / glutaric acid / succinic acid / succinic acid / adipic acid / fumaric acid / etc.) and salts thereof, inorganic acids and salts thereof. Preferably, the other components in the wastewater are selected from the group consisting of organic acids (such as citric acid / glutaric acid / succinic acid / succinic acid / adipic acid / fumaric acid / etc.) and salts thereof, inorganic acids and salts thereof Kind or more. Preferably, each aqueous solution sample contains a phenolic compound, a salt of an organic acid, or a salt of an inorganic acid. Preferably, each aqueous solution sample contains an aryl sulfonate, a salt of an organic acid, or a salt of a mineral acid. Preferably, each aqueous sample contains an aryl sulfonate (such as TANIGANPAK-NC (aqueous formulation of aryl sulfonate)), a salt of an organic acid, a salt of an inorganic acid. Preferably, each aqueous sample contains a phenolic compound such as TANIGANPAK-NC (an aqueous formulation of an aryl sulfonate), sodium formate and sodium hydrogencarbonate NaHC0 3 . Preferably, each aqueous solution sample contains a phenolic compound, an organic acid. Preferably, each aqueous sample contains an aryl sulfonate, an organic acid. Preferably, each aqueous solution sample contains TANIGAN LT-C (an aqueous solution of an arylsulfonic acid methylene condensate) and formic acid. Preferably, each aqueous solution sample contains a phenol compound, an acrylic compound, and a dicyandiamide compound. Preferably, each aqueous solution sample contains an aryl sulfonate, an acrylic compound, a dicyandiamide compound. Preferably, each aqueous solution sample contains TANIGAN LT-C (aqueous solution of arylsulfonic acid methylene condensate), LEVOTAN 1084 (polyacrylate aqueous emulsion), RATINGAN R7 (methylene condensate of arylsulfamic acid) . The more the number of aqueous samples, the more accurate the model data. Preferably, the amount of aqueous sample is at least 15, preferably at least 20, more preferably at least 30, and most preferably at least 40. For example, the number of aqueous samples is 30 100, preferably 40 100, and most preferably 50 100. (1) The residual effective content of each batch of wastewater is monitored by NIR technology. If the conventional modeling (data model) method is used, it is necessary to take 30-40 sets of wastewater samples to scan the spectral information, and then obtain the real-time component data by conventional chemical analysis and chromatographic analysis. However, the composition of tannery wastewater is complex, and it is difficult to obtain real-time component data by conventional chemical analysis and chromatographic analysis, and the correspondence between spectral information and content data cannot be established. Therefore, the method of the present invention is to introduce chemical materials (which can be obtained through the tanning formula and process) in the wastewater, simulate the possible concentration ranges of the wastewater, and respectively configure 40-50 sets of samples with different predetermined concentrations to obtain data of the individual components. Model, and then experiment with the addition of other materials to see if there is interference, if there is no interference, the data model of the material is considered successful. If there is interference, the original data should be corrected by mixing 40-50 samples with the theoretical concentration of the material causing the interference. The more the number of samples, the more accurate the model data. This method requires a certain amount of manpower in modeling, but it is simple and easy, and the operator can operate with a little training. (2) Based on the neutralization and recycling process of wastewater recycling, using near-infrared spectroscopy technology to track the content of various chemical materials in the drum liquid, not only can understand the absorption of various materials in leather, but also facilitate the process. Optimized, and quantitatively monitor the amount of material in the wastewater, and replenish the various materials to the required concentration in the next recycling. Method for modeling near-infrared spectroscopy: There is currently no suitable modeling method, and the method of the invention is simple in principle and easy to operate. The near-infrared spectroscopy technology is used to monitor the effective content of wastewater to realize the quantitative recycling process of wastewater, including but not limited to neutralization and reclamation processes. The same principle is suitable for the former chrome tanning process, degreasing process and subsequent fatliquoring process. . The invention also relates to a method of producing leather, comprising:
(I) 对皮革原料进行中和工艺， 得到中和处理后的皮革； (I) Neutralizing the leather material to obtain a neutralized leather;
(II) 对中和处理后的皮革进行复鞣工艺， 得到复鞣后的皮革； (II) performing a retanning process on the neutralized leather to obtain retanning leather;
(III) 对复鞣后的皮革进行加脂工艺； 其中， 工艺步骤 （1)、 (II) 和 （III) 中的至少一个通过本发明处理皮革的方法进 行。 优选地， 工艺步骤 （1)、 (II) 和 （III) 均通过本发明处理皮革的方法进行。 优选 地， 针对工艺步骤 （1)、 (II) 和 （III) 分别构建各自的近红外光谱数据模型。 优选地， 皮革原料是蓝湿皮。 在本发明的方法中， 将皮革处理完取出后， 无需将制革废水从转鼓排出， 可以直 接补充原料后进行下一次皮革处理。 也可以将废水排出， 进行过滤和补充原料后进行 下一次皮革处理。 这两种方式均可实行制革废水的原位回用， 无需废水的复杂后处理 或净化工序。 由于本发明的方法可以将废水原位回用或直接回用， 而不需要对废水进行复杂的 净化和处理， 可以大大节省生产费用， 减少废水处理设备和成本。 除另外声明外， 本发明所有的浓度、 含量、 配比、 比例均是以重量计。 在本文中尤其实施例中， 各成分的加入量是对所加工的皮的重量而言的， 以皮重(III) The retort leather is subjected to a fatliquoring process; wherein at least one of the process steps (1), (II) and (III) is carried out by the method of treating leather of the present invention. Preferably, the process steps (1), (II) and (III) are carried out by the method of the present invention for treating leather. Preferably, respective near infrared spectral data models are constructed for process steps (1), (II) and (III), respectively. Preferably, the leather material is a wet blue skin. In the method of the present invention, after the leather is processed and taken out, it is not necessary to discharge the tanning waste water from the rotating drum, and the raw material can be directly replenished and then subjected to the next leather treatment. It is also possible to drain the wastewater, filter and replenish the raw materials for the next leather treatment. Both methods can be used for in-situ reuse of tannery wastewater without the need for complicated post-treatment or purification of wastewater. Since the method of the present invention can reuse the wastewater in situ or directly reuse, without complicated purification and treatment of the wastewater, the production cost can be greatly reduced, and the wastewater treatment equipment and cost can be reduced. All concentrations, amounts, ratios, and ratios of the present invention are by weight unless otherwise stated. In particular embodiments herein, the amount of each component added is the weight of the processed skin, and the tare weight
100份计。例如， 材料 TANIGAN PAK-N-C加入量为皮重的 4%， 是指每 100重量份的 皮革， 加入 4重量份的 TANIGAN PAK-N-C, 简称 4%。 换句话说， 各成分的加入量是 基于 100重量份皮革。 实施例 实施例 1 : 蓝湿皮 （牛皮鞋面革） 中和工艺 100 parts. For example, the material TANIGAN PAK-NC is added in an amount of 4% of the tare weight, which means that 4 parts by weight of TANIGAN PAK-NC, abbreviated as 4%, is added per 100 parts by weight of the leather. In other words, the amount of each component added is based on 100 parts by weight of leather. Example Example 1: Blue wet leather (cowhide upper leather) neutralization process
(I) 主要化学材料： TANIGAN PAK-N-C (酚类）， LAXESS公司产品。 蓝湿皮 （牛皮鞋面革）； (II) 工艺 （此处加量是对所加工的皮的重量而言的， 以皮重 100份计） 工艺过程： （蓝皮） 削匀 → 称重— 水洗 → 中和 （至 pH5.0) →复鞣 → 水洗 → 加脂 → 调 11值 → 水洗 → 出鼓。 蓝皮经过削匀、 称重、 水洗后， 开始中和， 分 A、 B、 C、 D四组， 具体如下： (I) Main chemical materials: TANIGAN PAK-N-C (phenolic), LAXESS products. Blue wet leather (leather upper leather); (II) Process (the amount here is the weight of the processed leather, in 100 parts by weight) Process: (blue skin) Shaved → Weighing — Washing → Neutralizing (to pH 5.0) → Recovering → Washing → Adding fat → Adjusting the value of 11 → Washing → Drumming. After the blue skin is shaved, weighed, and washed, it begins to neutralize and is divided into four groups: A, B, C, and D. The details are as follows:
A. 为空白样， 未加入 TANIGAN PAK-N-C, 150份水 （40°C ) 和 1.5份甲酸钠和 0.5份小苏打在 40°C左右处理 60分钟。 A. As a blank, no TANIGAN PAK-N-C, 150 parts of water (40 ° C) and 1.5 parts of sodium formate and 0.5 parts of baking soda were treated at 40 ° C for 60 minutes.
B . 用新鲜水， 材料 TANIGAN PAK-N-C加入量为皮重的 4%， B. With fresh water, the material TANIGAN PAK-N-C is added in 4% of the tare weight.
150份水（40°C ) 禾 P 4.0份 TANIGAN PAK-N-C (朗盛公司生产） 1.5份甲酸钠和 0.5 份小苏打在 40°C左右处理 60分钟。 150 parts of water (40 ° C) Wo P 4.0 parts TANIGAN PAK-N-C (manufactured by LANXESS) 1.5 parts of sodium formate and 0.5 parts of baking soda were treated at 40 ° C for 60 minutes.
C. 用新鲜水， 材料 TANIGAN PAK-N-C加入量为皮重 8%， 150份水（40°C ) 禾 P 8.0份 TANIGAN PAK-N-C (朗盛公司生产） 1.5份甲酸钠和 0.5 份小苏打在 40°C左右处理 60分钟。 C. With fresh water, the material TANIGAN PAK-NC is added in an amount of 8% tare, 150 parts water (40 ° C), P 8.0 parts TANIGAN PAK-NC (manufactured by LANXESS) 1.5 parts sodium formate and 0.5 parts baking soda at Treat at 40 ° C for 60 minutes.
D. 为回收利用废水经补加材料 TANIGAN PAK-N-C至 4%。 根据下文近红外光谱数据模型，由获得的近红外光谱读取制革废水中成分的浓度， 150份回收废水 （40°C )， 补充 TANIGAN PAK-N-C (朗盛公司生产)到 4份， 补充甲酸 钠到 1.5份， 补充小苏打到 0.5份， 在 40°C左右处理 60分钟。 中和结束将废水排出， 经过滤及补充所需材料后至下一批回收利用， 加 0.1%防腐 剂。 鼓内的皮革按照统一的复鞣加脂工艺制作完成， 干燥后统一评判。 D. To replenish wastewater, TANIGAN PAK-N-C is added to 4%. According to the near-infrared spectroscopy data model below, the concentration of the components in the tannery wastewater was read from the obtained near-infrared spectrum, 150 parts of recovered wastewater (40 ° C), supplemented with TANIGAN PAK-NC (manufactured by LANXESS) to 4 parts, supplemented Sodium formate to 1.5 parts, supplemented with baking soda to 0.5 parts, and treated at 40 ° C for 60 minutes. At the end of the neutralization process, the wastewater is discharged, filtered and supplemented with the required materials, and then recycled to the next batch, with 0.1% preservative added. The leather in the drum is made according to the uniform retanning and fatliquoring process, and is judged after drying.
(III) 建模 本工艺共三种化学物质， 按照各自的含量范围； TANIGAN PAK-N-C: 0-8.0%； 甲酸钠： 0-5%； 小苏打： 0-2%。 每组随机按三种成分不同比例配置 27个样品 （如表 1-1所示）。 样品个数越多并 且比例分配合理， 则所建数据模型精确度越高。 表 1-1 建模数据 (III) Modeling The process consists of three chemical substances, according to their respective content ranges; TANIGAN PAK-NC: 0-8.0%; sodium formate: 0-5%; baking soda: 0-2%. Each group was randomly assigned 27 samples in different proportions of the three components (as shown in Table 1-1). The more the number of samples and the reasonable proportion distribution, the higher the accuracy of the built data model. Table 1-1 Modeling data
Figure imgf000014_0001
Figure imgf000014_0001
每 10分钟通过 NIR透射感应探头获取光谱，通过预先建好的 TANIGAN PAK-N-C 近红外光谱数据模型， 通过电脑数据模型， 很快可以读取 TANIGAN PAK-N-C溶液的 浓度。 60分钟结束实验， 取出皮样。 (IV) 验证及效果 测得废水中 TANIGAN PAK-N-C含量如下。 表 1-2数据验证 The spectrum was acquired by a NIR transmission-sensing probe every 10 minutes, and the concentration of the TANIGAN PAK-NC solution was quickly read by a computer data model through a pre-built TANIGAN PAK-NC near-infrared spectral data model. The experiment was terminated in 60 minutes, and the skin samples were taken out. (IV) Verification and effect The TANIGAN PAK-NC content in the wastewater was determined as follows. Table 1-2 Data verification
Figure imgf000015_0001
Figure imgf000015_0001
理论值与实测值接近， 过程中浓度降低速度与实际相符。 图 1示出了实施例 1中 TANIGANPAK-N-C标准液理论值和模型预测值的关系。 对新鲜水与废水回收利用所得最终制得的皮革性能进行测试。 新鲜水与废水回收 利用所得最终制得的皮革在性能上没有明显区别。 The theoretical value is close to the measured value, and the speed of the concentration reduction in the process is consistent with the actual value. Fig. 1 shows the relationship between the theoretical value of the TANIGANPAK-NC standard solution and the model prediction value in Example 1. The properties of the final leather obtained from the recycling of fresh water and wastewater were tested. There is no significant difference in performance between the freshly produced water and the recycled leather.
表 1-3 Table 1-3
Figure imgf000016_0001
实施例 2: 蓝湿皮简单复鞣工艺：
Figure imgf000016_0001
Example 2: Blue wet skin simple retanning process:
(I) 主要材料  (I) Main materials
TANIGAN LT-C, 朗盛公司产品。  TANIGAN LT-C, a product of LANXESS.
待处理的皮革： 中和后的蓝湿皮 （牛皮鞋面革）。  Leather to be treated: Blue wet leather (leather upper leather) after neutralization.
(II) 工艺  (II) Process
工艺过程 （此处加量是对所加工的皮的重量而言的， 以皮重 100份计) 工艺过程： （蓝皮） 削匀 → 称重— 水洗 → 中和 （至 pH5.0) →复鞣 → 水洗 → 加脂 → 调 11值 → 水洗 → 出鼓。 蓝皮经过削匀、 称重、 水洗、 中和后， 开始复鞣， 分 A 、 B、 C、 D 四组， 具 体如下： A. 为空白样， 未加入 TANIGAN LT-C, 加入 100份水， 在 40°C下处理 60分钟， 再加 0.5份 85%的甲酸处理 20分钟。 B . 用新鲜水， 材料 TANIGAN LT-C加入量为皮重的 6%， 加入 100份水（40 °C ) 禾 P 6.0份 TANIGAN LT-C (朗盛公司生产)处理 60分钟， 再 加 0.5份 85%的甲酸处理 20分钟。 C. 用新鲜水， 材料 TA GAN LT-C加入量为皮重 12%， 加入 100份水 （40 °C ) 和 12.0份 TANIGAN LT-C (朗盛公司生产)处理 60分钟， 再加 0.5份 85%的甲酸处理 20分钟。 Process (the amount added here is the weight of the processed skin, and the weight is 100 parts) Process: (blue skin) Shaved → Weighing - Washing → Neutralizing (to pH 5.0) → Recovering → Washing → Adding fat → Adjusting value 11 → Washing → Drumming. After the blue skin is shaved, weighed, washed, neutralized, the retanning begins, and the four groups A, B, C, and D are as follows: A. It is a blank sample, no TANIGAN LT-C is added, and 100 parts of water is added. After treatment at 40 ° C for 60 minutes, 0.5 parts of 85% formic acid was added for 20 minutes. B. With fresh water, the material TANIGAN LT-C is added in 6% of the tare weight, and 100 parts of water (40 °C) and P 6.0 parts of TANIGAN LT-C (manufactured by LANXESS) are added for 60 minutes, plus 0.5. A portion of 85% formic acid was treated for 20 minutes. C. With fresh water, the material TA GAN LT-C is added in a tare weight of 12%, added with 100 parts of water (40 ° C) and 12.0 parts of TANIGAN LT-C (manufactured by LANXESS) for 60 minutes, plus 0.5 parts. 85% formic acid was treated for 20 minutes.
D. 为回收利用废水经补加材料 TANIGAN LT-C至 6%。 根据下文近红外光谱数据模型，由获得的近红外光谱读取制革废水中成分的浓度， 将 100份回收废水 （40°C )， 补充 TANIGAN LT-C (朗盛公司生产)到 6份， 处理 60分 钟， 再加 0.5份 85%的甲酸处理 20分钟。 复鞣结束将废水排出， 经过滤及补充所需材料后至下一批回收利用， 建议加 0.1% 防腐剂。 鼓内的皮革按照统一的复鞣加脂工艺制作完成， 干燥后统一评判。 (III) 建模： D. TANIGAN LT-C to 6% for recycled wastewater. According to the near-infrared spectroscopy data model below, the concentration of the components in the tannery wastewater is read from the obtained near-infrared spectrum, and 100 parts of the recovered wastewater (40 ° C) is supplemented with TANIGAN LT-C (manufactured by LANXESS) to 6 parts. After 60 minutes of treatment, 0.5 parts of 85% formic acid was added for 20 minutes. At the end of the reclamation, the wastewater will be discharged. After filtering and replenishing the required materials, the next batch will be recycled. It is recommended to add 0.1% preservative. The leather in the drum is made according to the uniform retanning and fatliquoring process, and is judged after drying. (III) Modeling:
TANIGAN LT-C: 0-18.0%； 甲酸： 0-2.0%。 每组随机按两种成分不同比例配置 29个样品 （如表 2-1所示）。 样品个数越多并 且比例分配合理， 则所建数据模型精确度越高。 表 2-1 建模数据 TANIGAN LT-C: 0-18.0%; Formic acid: 0-2.0%. Each group was randomly assigned 29 samples in different proportions of the two components (as shown in Table 2-1). The more the number of samples and the reasonable proportion distribution, the higher the accuracy of the built data model. Table 2-1 Modeling data
Figure imgf000018_0001
Figure imgf000018_0001
每 10分钟通过 NIR透射感应探头获取光谱， 通过预先建好的 TANIGAN LT-C近 红外光谱数据模型， 很快读取 TANIGAN LT-C溶液的浓度。  The spectrum was acquired by a NIR transmission-sensing probe every 10 minutes, and the concentration of the TANIGAN LT-C solution was quickly read by a pre-built TANIGAN LT-C near-infrared spectral data model.
60分钟结束实验， 取出皮样。 The experiment was terminated in 60 minutes, and the skin samples were taken out.
(IV) 验证及效果 测得水中 LT-C含量： 表 2-2数据验证 (IV) Verification and effect measurement of LT-C content in water: Table 2-2 Data Verification
Figure imgf000019_0001
Figure imgf000019_0001
理论值与实测值接近， 过程中浓度降低速度与实际相符。 图 2示出了实施例 2中 TANIGAN LT-C标准液理论值和模型预测值的关系。 对新鲜水与废水回收利用制得的皮革性能进行测试， 最终制得的皮革新鲜水与废 水回收利用所得在性能上没有明显区别。 The theoretical value is close to the measured value, and the speed of the concentration reduction in the process is consistent with the actual value. Fig. 2 is a graph showing the relationship between the theoretical value of the TANIGAN LT-C standard solution and the model prediction value in Example 2. The performance of the leather obtained by recycling fresh water and waste water was tested, and the final obtained leather fresh water was not significantly different from the wastewater.
表 2-3 Table 2-3
Figure imgf000020_0001
Figure imgf000020_0001
实施例 3 : 标准复鞣工艺  Example 3: Standard retanning process
(I) 主要材料  (I) Main materials
TANIGAN LT-C (酚类）， 朗盛公司产品。  TANIGAN LT-C (phenolic), a product of LANXESS.
LEVOTAN 1084 (丙烯酸类）， 朗盛公司产品。  LEVOTAN 1084 (Acrylic), a product of LANXESS.
RATINGAN R7 (双氰胺类） ， 朗盛公司产品。  RATINGAN R7 (dicyandiamide), a product of LANXESS.
待处理的皮革： 蓝湿皮 （牛皮鞋面革）。  Leather to be treated: Blue wet leather (cowhide upper leather).
(II) 工艺  (II) Process
工艺过程 （此处加量是对所加工的皮的重量而言的， 以皮重 100份计) 工艺过程： （蓝皮） 削匀 → 称重— 水洗 → 中和 （至 pH5.0) →复鞣 → 水洗 → 加脂 → 调 11值 → 水洗 → 出鼓。 蓝皮经过削匀、 称重、 水洗、 中和后， 开始复鞣， 分 A 、 B两组， 具体如下： Process (the amount added here is the weight of the processed skin, and the weight is 100 parts) Process: (blue skin) Shaved → Weighing - Washing → Neutralizing (to pH 5.0) → Recovering → Washing → Adding fat → Adjusting value 11 → Washing → Drumming. After the blue skin is shaved, weighed, washed, neutralized, the retanning begins, and the two groups are divided into A and B, as follows:
A. 为新鲜水中加鞣制材料处理， 先加入 100份水， 后加入 6份 TANIGAN LT-C 、 4份 LEVOTAN 1084、 6份A. For the treatment of fresh water, add 100 parts of water, then add 6 parts of TANIGAN LT-C, 4 parts of LEVOTAN 1084, 6 parts.
RETINGAN R7在 40°C下处理 60分钟， 再加 0.5份 85%的甲酸处理 20分钟。 RETINGAN R7 was treated at 40 ° C for 60 minutes and 0.5 parts of 85% formic acid was added for 20 minutes.
B. 为回收利用废水补加鞣制材料处理皮革， 根据下文近红外光谱数据模型，由获得的近红外光谱读取制革废水中成分的浓度， 先加入 100份废水， 后补加到 6份 TANIGAN LT-C 、 4份 LEVOTAN 1084、 6份 RETINGAN R7在 40°C下处理 60分钟， 再加 0.5份 85%的甲酸处理 20分钟。 复鞣结束将废水排出， 经过滤及补充所需材料后至下一批回收利用， 建议加 0.1% 防腐剂。 鼓内的皮革按照统一的复鞣加脂工艺制作完成， 干燥后统一评判。 B. To process the leather by adding waste material to the recycled wastewater, according to the near-infrared spectral data model below, the concentration of the components in the tannery wastewater is read from the obtained near-infrared spectrum, and 100 parts of wastewater is added first, and then added to 6 parts of TANIGAN. LT-C, 4 parts of LEVOTAN 1084, 6 parts of RETINGAN R7 were treated at 40 ° C for 60 minutes, and 0.5 parts of 85% formic acid was added for 20 minutes. At the end of the reclamation, the wastewater will be discharged. After filtering and replenishing the required materials, the next batch will be recycled. It is recommended to add 0.1% preservative. The leather in the drum is made according to the uniform retanning and fatliquoring process, and is judged after drying.
(III) 建模 TANIGAN LT-C: 0-18.0%； (III) Modeling TANIGAN LT-C: 0-18.0%;
LEVOTAN 1084: 0-11%； RETIGAN R7:0-18%; 甲酸： 0-2% 每组随机按四种成分不同比例配置 28个样品 （如表 3-1所示）。 样品个数越多并 且比例分配合理， 则所建数据模型精确度越高。 表 3-1 建模数据 LEVOTAN 1084: 0-11%; RETIGAN R7: 0-18%; Formic acid: 0-2% Each group was randomly assigned 28 samples in different proportions of the four components (as shown in Table 3-1). The more the number of samples and the reasonable proportion distribution, the higher the accuracy of the built data model. Table 3-1 Modeling data
TANIGAN LT-C LEVOTAN 1084 RETIGAN R7 甲酸 TANIGAN LT-C LEVOTAN 1084 RETIGAN R7 Formic acid
(%) (%) (%) (%)(%) (%) (%) (%)
1. 9.52 6.02 9.46 1.241. 9.52 6.02 9.46 1.24
2. 0.58 11.43 0.21 1.752. 0.58 11.43 0.21 1.75
3. 18.93 0.90 17.96 0.633. 18.93 0.90 17.96 0.63
4. 0.11 11.27 18.40 0.774. 0.11 11.27 18.40 0.77
5. 17.98 0.11 0.08 1.47 18.66 11.36 1.33 0.775. 17.98 0.11 0.08 1.47 18.66 11.36 1.33 0.77
0.74 0.29 18.02 0.060.74 0.29 18.02 0.06
18.39 11.96 18.17 1.1318.39 11.96 18.17 1.13
0.58 0.53 0.67 1.340.58 0.53 0.67 1.34
8.92 0.12 18.11 2.408.92 0.12 18.11 2.40
9.78 10.97 0.05 0.649.78 10.97 0.05 0.64
0.35 9.52 8.85 2.040.35 9.52 8.85 2.04
8.78 0.86 2.29 2.018.78 0.86 2.29 2.01
10.03 11.36 18.15 2.3510.03 11.36 18.15 2.35
18.62 6.79 10.33 0.7418.62 6.79 10.33 0.74
0.02 7.86 9.14 1.120.02 7.86 9.14 1.12
9.35 2.10 0.91 0.049.35 2.10 0.91 0.04
0.08 0.15 8.74 0.160.08 0.15 8.74 0.16
18.95 0.12 7.44 2.0918.95 0.12 7.44 2.09
5.59 6.90 16.94 0.475.59 6.90 16.94 0.47
13.32 4.58 15.24 0.6013.32 4.58 15.24 0.60
16.32 0.18 7.33 0.6716.32 0.18 7.33 0.67
13.92 11.45 12.11 0.7113.92 11.45 12.11 0.71
5.06 11.42 13.41 2.415.06 11.42 13.41 2.41
0.75 5.99 15.11 0.010.75 5.99 15.11 0.01
14.75 5.46 0.99 1.5014.75 5.46 0.99 1.50
6.06 7.06 18.66 2.376.06 7.06 18.66 2.37
15.41 10.56 6.30 0.44 15.41 10.56 6.30 0.44
(IV) 验证及效果 (IV) Verification and effect
每 10分钟测废水中 LT-C、 1084、 R7的含量 （NIR法）， 60分钟结束复鞣。 The content of LT-C, 1084, and R7 in the wastewater was measured every 10 minutes (NIR method), and the retanning was completed in 60 minutes.
本工艺同时跟踪了三种复鞣剂用 NIR分别建模后测定混合物的含量。 The process also tracks the content of the mixture after three kinds of retanning agents are separately modeled by NIR.
表 3-2数据验证 （B组） Table 3-2 Data Verification (Group B)
Figure imgf000022_0001
Figure imgf000022_0001
图 3 ( a) 示出了实施例 3中 TANIGAN LT-C标准液理论值和模型预测值的关系。 图 3 (b) 示出了实施例 3中 LELEVOTAN 1084标准液理论值和模型预测值的关 系。 图 3 (c) 示出了实施例 3中 RETINGAN R7标准液理论值和模型预测值的关系。 理论值与实测值接近， 过程中浓度降低速度与实际相符。 对新鲜水与废水回收利用制得的皮革性能进行测试， 最终用废水回收利用所得皮 革在性能上没有明显区别 （如表 3-3所示）。 表 3-3 Fig. 3 (a) shows the relationship between the theoretical value of the TANIGAN LT-C standard solution and the model prediction value in the third embodiment. Fig. 3(b) shows the relationship between the theoretical value of the LELEVOTAN 1084 standard solution and the model prediction value in the third embodiment. Fig. 3(c) shows the relationship between the theoretical value of the RETINGAN R7 standard solution and the model prediction value in the third embodiment. The theoretical value is close to the measured value, and the speed of the concentration reduction in the process is consistent with the actual value. The performance of the leather obtained by recycling fresh water and waste water was tested. Finally, there was no significant difference in the performance of the leather obtained by recycling the wastewater (as shown in Table 3-3). Table 3-3
Figure imgf000023_0001
Figure imgf000023_0001
中等大小的制革厂年产量 100万张牛皮，会产生鞣制废水 56万吨，将复鞣过程中 的废水回收利用 10次后排放， 可少排放废水的总量约为 50万吨。 当然， 本发明还可有其他具体实施方式， 以上仅为本发明的优选实施方式， 并非 用来限定本发明的保护范围； 在不背离本发明精神的情况下， 本领域普通技术人员凡 是依本发明内容所做出各种相应的变化与修改，都属于本发明的权利要求的保护范围。  The medium-sized tannery produces 1 million cowhide per year, which will produce 560,000 tons of waste water. The wastewater from the reclamation process will be recycled after 10 times, and the total amount of wastewater that can be discharged is about 500,000 tons. Of course, the present invention may be embodied in other specific forms, and the above is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention; those skilled in the art, regardless of the spirit of the present invention, SUMMARY OF THE INVENTION Various changes and modifications may be made without departing from the scope of the invention.

Claims

权 利 要 求 书 Claim
1. 利用制革废水处理皮革的方法， 包括： 1. A method of treating leather using tannery wastewater, comprising:
( a) 用近红外光谱感应探头获得制革工艺所产生的制革废水的近红外光 谱；  (a) obtaining a near-infrared spectrum of tannery wastewater produced by the tanning process using a near-infrared spectroscopy induction probe;
(b)通过预先建好的近红外光谱数据模型， 由获得的近红外光谱确定或读 取所述制革废水中成分的浓度；  (b) determining or reading the concentration of the components in the tannery wastewater from the obtained near-infrared spectroscopy by a pre-built near-infrared spectral data model;
( c)根据所述制革废水中成分的浓度， 向所述制革废水中补充原料至该制 革工艺所需的浓度， 获得配制的制革废水；  (c) adding the raw material to the tannery wastewater according to the concentration of the components in the tannery wastewater to a concentration required for the leather making process to obtain a prepared tannery wastewater;
( d) 用所述配制的制革废水对皮革进行处理， 进行该制革工艺； 其中， 所述近红外光谱数据模型包括近红外光谱与所述成分浓度的对应关 系。  (d) treating the leather with the formulated tanning waste water to perform the tanning process; wherein the near infrared spectral data model includes a correlation between the near infrared spectrum and the concentration of the component.
2. 根据权利要求 1所述的方法， 其中， 所述近红外光谱数据模型通过以下方法获 得： 2. The method according to claim 1, wherein the near infrared spectral data model is obtained by the following method:
(bl ) 根据所述制革工艺所产生的制革废水中的成分， 配制一系列具有预 定浓度的水溶液样品， 各个水溶液样品含有制革废水中的成分；  (bl) preparing a series of aqueous solution samples having a predetermined concentration according to the components in the tanning waste water produced by the tanning process, each aqueous solution sample containing components in the tanning waste water;
(b2) 获得各个水溶液样品的近红外光谱；  (b2) obtaining a near-infrared spectrum of each aqueous solution sample;
(b3 ) 根据各个水溶液样品的成分的浓度和近红外光谱， 建立所述近红外 光谱数据模型， 所述近红外光谱数据模型包括成分的浓度和近红外光谱对应关 系。  (b3) The near-infrared spectral data model is established based on the concentration of the components of each aqueous sample and the near-infrared spectrum, the near-infrared spectral data model including the concentration of the component and the near-infrared spectral correspondence.
3. 根据权利要求 2所述的方法， 其中， 各个水溶液样品至少包含有效物成分。 3. The method according to claim 2, wherein each of the aqueous solution samples contains at least an active ingredient.
4. 根据权利要求 3所述的方法， 其中， 各个水溶液样品还包含会出现在废水中的 其他成分， 其中所述其他成分是对所述有效物成分的近红外光谱数据模型有干 扰的成分。 4. The method of claim 3, wherein each aqueous sample further comprises other components that may be present in the wastewater, wherein the other components are components that interfere with the near infrared spectral data model of the active component.
5. 根据权利要求 3所述的方法， 其中， 所述有效物成分选自芳香族化合物、砜类、 聚丙烯酸类化合物、 双氰胺类化合物、 三聚氰胺类化合物、 聚氨酯类化合物、 表面活性剂、 有机酸及其盐中的一种或多种。 The method according to claim 3, wherein the active ingredient is selected from the group consisting of an aromatic compound, a sulfone, a polyacrylic compound, a dicyandiamide compound, a melamine compound, a polyurethane compound, a surfactant, One or more of an organic acid and a salt thereof.
6. 根据权利要求 5所述的方法， 其中， 所述芳香族化合物选自酚类、芳基磺酸盐、 萘类化合物。 The method according to claim 5, wherein the aromatic compound is selected from the group consisting of a phenol, an aryl sulfonate, and a naphthalene compound.
7. 根据权利要求 5所述的方法， 其中， 所述有机酸及其盐选自柠檬酸、 戊二酸、 琥珀酸、 丁二酸、 己二酸、 富马酸及其盐中的一种或多种。 The method according to claim 5, wherein the organic acid and a salt thereof are selected from the group consisting of citric acid, glutaric acid, succinic acid, succinic acid, adipic acid, fumaric acid, and a salt thereof Or a variety.
8. 根据权利要求 2所述的方法， 其中， 所述近红外光谱数据模型包括有效物成分 的浓度和近红外光谱的对应关系。 The method according to claim 2, wherein the near-infrared spectral data model includes a correspondence between a concentration of an active substance component and a near-infrared spectrum.
9. 根据权利要求 2所述的方法， 其中， 各个水溶液样品含有： 9. The method of claim 2, wherein each aqueous sample contains:
(i) 酚类化合物；  (i) phenolic compounds;
(ii) 有机酸、 有机酸的盐、 无机酸、 无机酸的盐中的至少一种。  (ii) at least one of an organic acid, a salt of an organic acid, a mineral acid, and a salt of an inorganic acid.
10. 根据权利要求 2所述的方法， 其中， 各个水溶液样品含有： 10. The method of claim 2, wherein each aqueous sample contains:
(i) 芳基磺酸盐；  (i) an aryl sulfonate;
(ii) 有机酸、 有机酸的盐、 无机酸、 无机酸的盐中的至少一种。  (ii) at least one of an organic acid, a salt of an organic acid, a mineral acid, and a salt of an inorganic acid.
11. 根据权利要求 2所述的方法， 其中， 各个水溶液样品含有： 芳基磺酸盐、 丙烯 酸类化合物以及双氰胺类化合物。 The method according to claim 2, wherein each of the aqueous solution samples contains: an arylsulfonate, an acrylic compound, and a dicyandiamide compound.
12. 根据权利要求 2所述的方法， 其中， 各个水溶液样品含有： 芳基磺酸亚甲基缩 合物、 聚丙烯酸酯以及芳代氨基磺酸的亚甲基缩合物。 12. The method according to claim 2, wherein each of the aqueous solution samples contains: a methylene condensate of an arylsulfonate, a polyacrylate, and a methylene condensate of an arylsulfamic acid.
13. 根据权利要求 3所述的方法， 其中， 所述有效物成分选自制革工艺中所使用的 复鞣剂、 铬鞣剂、 中和剂、 脱脂剂或加脂剂。 13. The method according to claim 3, wherein the active ingredient is selected from the group consisting of a retanning agent, a chrome tanning agent, a neutralizing agent, a degreasing agent or a fatliquor used in a tanning process.
14. 根据权利要求 1至 13任一项所述的方法，其中，所述制革工艺是皮革铬鞣工艺、 中和工艺、 复鞣工艺、 脱脂工艺或加脂工艺。 The method according to any one of claims 1 to 13, wherein the tanning process is a leather chrome tanning process, a neutralization process, a retanning process, a degreasing process or a fatliquoring process.
15. 根据权利要求 14所述的方法， 其中， 所述中和工艺是蓝湿皮中和工艺。 15. The method according to claim 14, wherein the neutralization process is a blue wet skin neutralization process.
16. 根据权利要求 14所述的方法，其中，所述复鞣工艺是简单复鞣工艺或标准复鞣 工艺。 16. The method of claim 14, wherein the retanning process is a simple retanning process or a standard retanning process.
17. 根据权利要求 14所述的方法，其中，所述复鞣工艺是蓝湿皮简单复鞣工艺或蓝 湿皮标准复鞣工艺。 17. The method according to claim 14, wherein the retanning process is a blue wet skin simple retanning process or a blue wet skin standard retanning process.
18. 根据权利要求 1至 17任一项所述的方法， 其中， 进一步包括： (e)在对皮革进行处理过程中， 使用步骤（a)和 （b)相同的方式对有效 物成分的浓度进行在线监测。 The method according to any one of claims 1 to 17, further comprising: (e) On-line monitoring of the concentration of the active ingredient in the same manner as in steps (a) and (b) during the treatment of the leather.
19. 根据权利要求 1至 17任一项所述的方法， 其中， 在步骤 （c) 中， 还向所述制 革废水中加入防腐剂。 The method according to any one of claims 1 to 17, wherein, in the step (c), a preservative is further added to the tannery wastewater.
20. 根据权利要求 1至 17任一项所述的方法， 其中， 所述制革废水循环使用至少 2 次。 The method according to any one of claims 1 to 17, wherein the tanning waste water is recycled at least twice.
21. 生产皮革的方法， 包括： 21. Methods of producing leather, including:
(I) 对皮革原料进行中和工艺， 得到中和处理后的皮革；  (I) Neutralizing the leather material to obtain a neutralized leather;
(II) 对中和处理后的皮革进行复鞣工艺， 得到复鞣后的皮革； (II) performing a retanning process on the neutralized leather to obtain retanning leather;
(III) 对复鞣后的皮革进行加脂工艺； (III) fatliquoring process of the leather after retanning;
其中， 工艺步骤 （1)、 (II) 和 （III) 中的至少一个通过根据权利要求 1至 Wherein at least one of the process steps (1), (II) and (III) is passed according to claim 1
20任一项所述的方法进行。 The method of any of 20 is carried out.
22. 根据权利要求 21所述的方法， 其中， 工艺步骤（1)、 (II)和 （III)均通过根据 权利要求 1至 20任一项所述的方法进行。 22. The method according to claim 21, wherein the process steps (1), (II) and (III) are all carried out by the method according to any one of claims 1 to 20.
23. 根据权利要求 21所述的方法， 其中， 所述皮革原料是蓝湿皮。 23. The method of claim 21, wherein the leather material is a wet blue skin.
Corr. Coeff.： 0.99930 Bias: (0.122e-4) 均方差： 0.104 Corr. Coeff.: 0.99930 Bias: (0.122e-4) Mean Square: 0.104
实测值 图 1 o + Δ□ Measured value Figure 1 o + Δ□
校骑交修 正证叉正 修 正  School riding, repairing, correcting the fork, correcting
Coir. Coeff.: 099396 均方差： D.G499 Coir. Coeff.: 099396 Mean variance: D.G499
Figure imgf000027_0001
Figure imgf000027_0001
o校 ιΕ + ife证 o school ιΕ + ife certificate
Δ修 itΔ修 it
□夂叉修 iH 实测值 图 2 □ 夂 修 repair iH measured value Figure 2
1/3 1/3
Figure imgf000028_0001
Figure imgf000028_0001
图 3(a)
Figure imgf000028_0002
Figure 3 (a)
Figure imgf000028_0002
图 3(b) Figure 3(b)
2/3 2/3
Figure imgf000029_0001
Figure imgf000029_0001
3/3 3/3
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