WO2015081624A1

WO2015081624A1 - Tanning process

Info

Publication number: WO2015081624A1
Application number: PCT/CN2014/070730
Authority: WO
Inventors: 张壮斗
Original assignee: 张壮斗
Priority date: 2013-12-04
Filing date: 2014-01-16
Publication date: 2015-06-11
Also published as: CN104694675A

Abstract

A tanning process is characterized in that waste liquid recycling is carried out in procedures of pre-soaking, main-soaking, liming, re-liming, deliming and softening, pickling and chrome tanning, retanning, neutralizing and dyeing step by step, and full-closed circulation recycling of waste liquid is implemented in all the procedures. In the process, circulation recycling of waste water is implemented from the pre-soaking to the dyeing, thereby reducing sewage discharging.

Description

说明书一种制革工艺 Description of the book

技术领域 Technical field

本发明涉及制革行业废水循环再利用领域。 The invention relates to the field of recycling and recycling of wastewater in the tanning industry.

背景技术 Background technique

在制革过程中，采用大量化工原料，如酸、碱、盐、硫化物、石灰、辂鞣剂、加脂剂、染料等，其中有相当一部分进入废水之中。制革废水主要来自于准备、鞣制和其他湿加工工段。从预浸水到染色的生产工序的排污量占整个制革过程中总排污量的 90%以上，其水质特点是含有大量成分复杂且有毒、有害物质。其中含有大量的石灰、盐类、油脂、氨氮化合物、蛋白质、硫化物、辂盐、染料、毛类、皮渣、泥沙等，且 COD、 BOD非常高。其污染物种类繁多，成分复杂，水质水量变化系数大且有恶臭现象，是较难治理的工业废水。 In the tanning process, a large number of chemical raw materials such as acids, alkalis, salts, sulfides, limes, strontiums, fatliquors, dyes, etc. are used, and a considerable part of them enter the waste water. Tannery wastewater is mainly from preparation, tanning and other wet processing sections. The amount of sewage discharged from the pre-soaked water to the dyeing production process accounts for more than 90% of the total sewage discharge during the whole tanning process. The water quality is characterized by a large amount of complex and toxic and harmful substances. It contains a large amount of lime, salt, oil, ammonia nitrogen compounds, proteins, sulfides, barium salts, dyes, hairs, pomace, sediment, etc., and COD and BOD are very high. It has a wide variety of pollutants, complex composition, large variation in water quality and quantity of water, and is stinky. It is an industrial wastewater that is difficult to treat.

随着环保技术设备的发展，目前制革废水已经形成比较成熟的处理工艺 (见下表）。但其运行过程往往花费高、效率低、效果差无法达到真正的治污目的。 With the development of environmentally-friendly technology equipment, the current tannery wastewater has formed a relatively mature treatment process (see table below). However, its operation process is often costly, inefficient, and poorly effective, and cannot achieve the true purpose of pollution control.

工艺名称技术优势技术缺陷 Process name Technical advantage Technical defect

传统活性污泥法该法对 BOD₅去除率在 90 对需处理污水水质要求高， The traditional activated sludge method has a high removal rate of BOD ₅ in 90 pairs, and requires high water quality.

%以上， COD在 60 %〜不适应冲击负荷，需要高的 80%间，色度在 50%〜90 动力和基建费用；占地面积 %间， S在 85 %〜98 %间。也大，一般的企业难以承受；同时对废水中的氨氮处理效果不佳。 More than %, COD is 60%~ not suitable for impact load, need high 80%, chroma 50%~90 power and infrastructure costs; between area %, S is between 85% and 98%. Also large, the average enterprise is unbearable; at the same time, the treatment of ammonia nitrogen in wastewater Not good.

生物接触氧化法对有机物去除率 BOD₅在容易产生堵塞，维护也比较 Biological contact oxidation method for organic matter removal rate BOD ₅ is prone to blockage, maintenance is also compared

95%左右， COD在 92% 困难。一旦出现问题， *** 左右， S在 98%左右。就得停止运行才能进行维护。 About 95%, COD is difficult at 92%. Once there is a problem, the system is around, and S is around 98%. You have to stop running to be able to maintain it.

氧化沟对 BOD₅去除率在 95%以处理效果不稳定，比较适宜上，于温度较高的南方，对于北The removal rate of BOD _{5 by} oxidation ditch is 95%, and the treatment effect is unstable. It is more suitable in the south of higher temperature, for the north.

S在 99%〜100%，方，冬季运行可能有问题。 S in 99%~100%, square, running in winter may have problems.

SS在 75%左右 SS is around 75%

双层生物滤池对 SS去除率在 95%，需要确定合适的回流比、选 The double-layer biofilter has a SS removal rate of 95%, and it is necessary to determine the appropriate reflux ratio.

BOD₅在 98 %， COD在择合适的滤料，运行费用比 90%, Cr (III)在 96%以较大。 BOD ₅ is 98%, COD is choosing the right filter material, the running cost is 90%, and Cr (III) is 96%.

上， S在 96%。 On, S is at 96%.

SBR法 SBR工艺对 COD、 S² 、运行费用比较大，规模较小 SBR method SBR process on COD, S ² , operating costs are relatively large, the scale is small

SS、 Cr的去除率分别为效率较低，维护也比较困难。 The removal rates of SS and Cr are respectively low efficiency and difficult to maintain.

93.3% > 99.0% > 90.3% > 93.3% > 99.0% > 90.3% >

99.4%。 99.4%.

在我们之前也有人对制革废水进行了循环再利用，但只是简单地对某一工序的废水进行了循环再利用，这样对污水排放量的减少、化料的节约、生产成本的降低等都非常有限。若想实现从预浸水到染色所有工序的废水一次性全部回收利用，却是一个极其复杂难解决的问题，并经常伴随以下问题的出现：灰皮增重率、蓝皮得革率均下降 1.5%-3.5%，收缩温度下降 1.5 °C-3.5°C, 还会使蓝皮粒面受损，粒面***，颜色变深，甚至产生 "毛面" 现象，致使成革某些性能指标达不到要求。 Before we used some people to recycle the tannery wastewater, but simply recycle the wastewater from a certain process, so that the reduction of sewage discharge, the saving of chemical materials, and the reduction of production costs are all Very limited. If you want to realize the complete recycling of waste water from pre-soaking to dyeing all the processes, it is an extremely complicated and difficult problem to solve, and often accompanied by the following problems: the gray weight gain rate and the blue leather leather rate are reduced by 1.5. %-3.5%, shrinkage temperature drops 1.5 °C-3.5 °C, it will also damage the blue grain surface, the grain surface becomes thicker, the color becomes darker, and even the "matte surface" is produced. Phenomenon, resulting in some performance indicators of the leather can not meet the requirements.

发明内容 Summary of the invention

本发明的目的：实现从预浸水到染色所有工序的废水循环再利用，特别是浸灰和辂鞣工段，废液可以反复循环再利用，除去自然状态下的正常挥发和不可避免的撒漏外，废水的回收率可达到 100%，彻底解决了制革污水排放的难题，而且此技术工艺和设备更加简化，适用于制革厂现有大生产工艺流程。由此生产的成品革各项性能指标均达要求，并有效降低了成革松面率，提高了成革的紧实度、丰满度，并可实现节约化料 15%-55%，如节约辂粉 35%-65%，部分化料可实现节约 90%以上，个别化料如食盐可实现节约 100%。 The object of the present invention is to realize the recycling of waste water from pre-soaking to dyeing all processes, especially the liming and finishing sections, and the waste liquid can be recycled and reused to remove normal volatilization and unavoidable leakage under natural conditions. The recovery rate of wastewater can reach 100%, which completely solves the problem of tannery wastewater discharge, and the technology and equipment are more simplified, and it is suitable for the existing large production process of the tannery. The performance indexes of the finished leather produced by the company all meet the requirements, and the rate of the finished leather is effectively reduced, the firmness and fullness of the finished leather are improved, and the saving of the material is 15%-55%, such as saving.辂 powder 35%-65%, part of the material can achieve more than 90% savings, individual chemicals such as salt can achieve 100% savings.

本发明的技术方案如下： The technical solution of the present invention is as follows:

一种工艺及设备更加简化的新型制革工艺，其特征在于在预浸水、主浸水、浸灰、复灰、脱灰软化、浸酸辂鞣、复鞣、中和、染色工序中分步进行废液循环再利用，各工序产生的废液可以不加特殊制剂处理，也可加入某种特殊制剂，加入量为 0%-0. 3% (以废液量为基数），上述工序全部实现全封闭循环，包括如下步骤： A novel tanning process with a more simplified process and equipment, characterized in that it is carried out step by step in pre-soaking, main immersion, liming, ash, deliming, pickling, retanning, neutralization, dyeing The waste liquid can be recycled and reused. The waste liquid produced in each process can be treated without special preparations, and a special preparation can be added. The addition amount is 0%-0.3% (based on the amount of waste liquid), and the above processes are all realized. A fully closed loop consisting of the following steps:

( 1 ) 预浸水工序的废液循环再利用：在预浸水转鼓旁设置预浸水废液储液池或储液罐，来自预浸水工序的废液滤去废液中固形物后排入预浸水废液储液池或储液罐，搅拌均匀，以备用于下批皮的预浸水；利用预浸水废液进行预浸水的工艺是：以原皮重量计， 5%-300%预浸水废液， 0%-0. 3%特殊制剂， 0. 2%-0. 4%杀菌剂，转 5-20分钟; 0. 1%-0. 8%浸水助剂， 0. 1%- 1. 0% 脱脂剂， 0. 05%-0. 5%纯碱，转 10-60分钟 /停 20-60分钟，转停结合进行 2-8 次；预浸水结束废液排入储液池或储液罐，应定期检测废液中的微生物数量，一般每循环二至三次检测一次； (1) Recycling of waste liquid in pre-soaking process: Pre-soaked water waste liquid storage tank or liquid storage tank is arranged next to the pre-dip water rotating drum, and the waste liquid from the pre-soaking water process filters out the solid matter in the waste liquid and then discharges into the pre-precipitated The immersion waste liquid storage tank or liquid storage tank is evenly mixed for pre-soaking of the next batch of skin; the pre-soaking process using pre-soaked water waste liquid is: 5%-300% pre-dip water waste liquid by weight of raw hide 0%-0. 3% special formulation, 0. 2%-0. 4% bactericide, 5-20 minutes; 0. 1%-0. 8% immersion aid, 0. 1%- 1. 0 % degreaser, 0. 05%-0. 5% soda ash, 10-60 minutes/stop 20-60 minutes, combined with 2-8 times of transfer; pre-soaked water to discharge waste liquid into storage tank or liquid storage tank , the number of microorganisms in the waste liquid should be regularly checked Quantity, usually detected two to three times per cycle;

( 2 ) 主浸水工序的废液循环再利用：在主浸水转鼓旁设置主浸水废液储液池或储液罐，来自主浸水工序的废液滤去废液中固形物后排入主浸水废液储液池或储液罐，搅拌均匀，以备用于下批皮的主浸水；利用主浸水废液进行主浸水的工艺是：以原皮重量计， 5%-300%主浸水废液， 0%-0. 3%特殊制剂， 0. 1%-1. 0%浸水助剂， 0. 1%-0. 8%脱脂剂， 0. 1%-1. 0%纯碱， 0. 05%- 0. 3% Na₂S，转 30-80分钟 /停 10-50分钟，转停结合进行 1-4次； 0. 1%-0. 4%杀菌剂，转 5-20分钟，然后每转 3-10分钟 /停 40-70分钟，过夜；次日连续转 10-50分钟；主浸水结束废液排入储液池或储液罐，应定期检测废液中的微生物数量，一般每循环二至三次检测一次； (2) Recycling of waste liquid in the main immersion process: The main immersion waste liquid storage tank or liquid storage tank is arranged beside the main immersion water drum, and the waste liquid from the main immersion water process filters out the solid matter in the waste liquid and then discharges into the main The immersion waste liquid storage tank or liquid storage tank is evenly mixed for the main immersion water of the next batch of leather; the main immersion water using the main immersion waste liquid is: 5%-300% main immersion water waste liquid by weight of the original skin 0%纯碱, 0. 05, 0%-0. 3% special preparation, 0. 1%-1. 0% immersion aid, 0. 1%-0. 8% degreaser, 0. 1%-1. 0% soda ash, 0. 05 %- 0. 3% Na ₂ S, 30-80 minutes/stop 10-50 minutes, transfer 1-4 times; 0. 1%-0. 4% fungicide, turn 5-20 minutes, then 3-10 minutes per turn / stop 40-70 minutes, overnight; continuous transfer for 10-50 minutes the next day; main immersion end of waste liquid discharged into the reservoir or liquid storage tank, the amount of microorganisms in the waste liquid should be regularly checked, generally Detected twice or three times per cycle;

( 3 ) 浸灰工序的废液循环再利用：在浸灰转鼓旁设置浸灰废液储液池或储液罐，来自浸灰工序的浸灰废液滤去废液中固形物后排入浸灰废液储液池或储液罐，搅拌均匀，以备用于下批皮的浸灰；利用浸灰废液进行浸灰的工艺是：以原皮重量计， 3%-200%废灰液， 0%-0. 3%特殊制剂， 0. 2%-2. 0% 浸灰助剂， 0. 05%- 1. 5% NaHS , 转 20-40分钟； 0. 3%_2. 5%石灰，转 20- 40 分钟 /停 20-40分钟； 0. 05%- 1. 5% NaHS, 转 10-30分钟 /停 10-30分钟；开始滤毛； 0. 05%- 1. 5%Na₂S, 0. 3%_2. 0%石灰， 0. 05%_0. 5%脱脂剂，转 10- 20 分钟 /停 20-30分钟，转停结合 2-4次； 3%-200%废灰液， 0%_0. 3%特殊制剂， 0. 5%Na₂S, 0. 2%-2. 0%浸灰助剂， 0. 3%_2. 0%石灰， 0%_0. 2%浸灰酶，转 10-30分钟 /停 10-30分钟，转停结合 1-3次，然后转 10-20分钟 /停 10-30 分钟，转停结合进行 5-7次； 3%-200%废灰液， 0%-0. 3%特殊制剂，转 10-30 分钟，然后每转 5-10分钟 /停 40-60分钟，过夜；浸灰结束废液排入储液池或储液罐，每次使用前均需化验废灰液中硫化碱、 Ca²⁺等含量，在浸灰过程中，视毛根脱落程度及时利用滤毛机滤毛； (3) Recycling of waste liquid in the liming process: a ash effluent liquid storage tank or a liquid storage tank is arranged beside the liming drum, and the ash ash waste liquid from the liming process is filtered to remove the solid matter in the waste liquid. Into the ash waste liquid storage tank or liquid storage tank, stir evenly to prepare for the ash ash of the next batch of leather; the liming process using ash ash waste liquid is: 3%-200% waste ash by weight of raw hide Liquid, 0%-0. 3% special preparation, 0. 2%-2. 0% liming aid, 0. 05%- 1. 5% NaHS, 20-40 minutes; 0. 3%_2. % lime, turn 20-40 minutes / stop 20-40 minutes; 0. 05%- 1. 5% NaHS, turn 10-30 minutes / stop 10-30 minutes; start filter; 0. 05%- 1. 5 %Na ₂ S, 0. 3%_2. 0% lime, 0. 05%_0. 5% degreaser, 10-20 minutes / stop 20-30 minutes, transfer combined 2-4 times; 3%-200 % 灰灰, 0%_0. 3% special preparation, 0. 5% Na ₂ S, 0. 2%-2. 0% ash auxiliaries, 0. 3%_2. 0% lime, 0%_0. 2% liming enzyme, 10-30 minutes / stop for 10-30 minutes, transfer 1-3 times, then 10-20 minutes / stop for 10-30 minutes, transfer combined for 5-7 times; 3% -200% waste ash, 0%-0. 3% special preparation, 10-30 minutes, Then every 5-10 minutes / stop for 40-60 minutes, overnight; ash ash waste liquid is discharged into the reservoir or liquid storage tank, the content of sulfide alkali, Ca ^2+, etc. in the waste ash liquid must be tested before each use. In liming In the process, depending on the degree of hair loss, the filter is used in time;

( 4 ) 复灰工序的废液循环再利用：在复灰转鼓旁设置复灰废液储液池或储液罐，来自复灰工序的废液滤去废液中固形物后排入复灰废液储液池或储液罐，搅拌均匀，以备用于下批皮的复灰；利用复灰废液进行复灰的工艺是：以原皮重量计， 3%-220%复灰废液， 0%-0. 3%特殊制剂， 0. 2%-1. 5% 石灰， 0. 05%- 1. 0% Na₂S或 NaHS, 0. 1%- 0. 7%浸灰助剂， 0. 05%- 0. 3%NaOH，转 20-40分钟 /停 30-60分钟，然后转 5-20分钟 /停 30-60分钟，转停结合进行 3-8次，过夜或直接出鼓；复灰结束废液排入储液池或储液罐； (4) Recycling of waste liquid in the ashing process: Set up a complex ash waste liquid storage tank or liquid storage tank next to the ash drum, and the waste liquid from the ash removing process removes the solid matter in the waste liquid and then discharges it into the complex The ash waste liquid storage tank or the liquid storage tank is evenly mixed to prepare the ash for the lower batch of leather; the process of using the ash waste liquid for ashing is: 3%-220% of the ash waste liquid by weight of the original skin , 7% 灰剂剂, 0%-0. 3% special preparation, 0. 2%-1. 5% lime, 0. 05%- 1. 0% Na ₂ S or NaHS, 0. 1%- 0. , 0. 05%- 0. 3% NaOH, turn 20-40 minutes / stop 30-60 minutes, then turn 5-20 minutes / stop 30-60 minutes, transfer together for 3-8 times, overnight or direct Drum; the end of the ash discharge into the reservoir or the reservoir;

( 5 ) 脱灰软化工序的废液循环再利用：在脱灰软化转鼓旁设置脱灰软化废液储液池或储液罐，来自脱灰软化工序的废液滤去废液中固形物后排入脱灰软化废液储液池或储液罐，搅拌均匀，以备用于下批皮的脱灰软化; 利用脱灰软化废液进行脱灰软化的工艺是：以灰皮重量计， 3%-220%脱灰软化废液， 0%-0. 3%特殊制剂， 0. 05%-0. 45%脱脂剂， 0. 2%-1. 5%脱灰剂， 0. 2%-1. 5%硫酸铵， 0. 05%- 0. 5%盐酸， 0. 1%- 0. 5%醋酸，转 15-60分钟； 0-0. 3% 软化酶，转 15-40分钟；脱灰软化结束废水排入储液池或储液罐，每循环一次都应检测废液中的蛋白酶及微生物数量，蛋白酶检测最好使用液质联用仪，亦可使用光电比色法，根据检测结果确定应加入的软化酶数量以及是否需要加入防腐剂； (5) Recycling of waste liquid in the deliming and softening process: a deliming and softening waste liquid storage tank or a liquid storage tank is arranged beside the deashing and softening drum, and the waste liquid from the deliming and softening process is filtered to remove the solid matter in the waste liquid. After the discharge into the deashing and softening waste liquid storage tank or the liquid storage tank, the mixture is evenly mixed, so as to be used for the deashing softening of the lower batch of leather; the process of deashing and softening by using the deliming and softening waste liquid is: 5%的脱灰剂, 0. 2% -1% 5% 脱灰剂, 0. 2% -1% 5% deashing agent, 0. 2% -1. 5% ammonium sulfate, 0. 05% - 0. 5% hydrochloric acid, 0.1% - 0. 5% acetic acid, for 15 - 60 minutes; 0-0. 3% softening enzyme, 15-40 minutes After deashing and softening, the waste water is discharged into the liquid storage tank or the liquid storage tank. The amount of protease and microorganisms in the waste liquid should be detected once every cycle. It is best to use the liquid chromatography-mass spectrometer for protease detection, or to use photoelectric colorimetry. Determine the amount of softening enzyme to be added and whether preservatives need to be added based on the test results;

( 6 ) 浸酸辂鞣工序的废液循环再利用：在浸酸辂鞣转鼓旁设置浸酸辂鞣废液储液池或储液罐，储液池最好深至地下 2-8米以利于控温，最好有备用池或罐，来自浸酸辂鞣工序的废液滤去废液中固形物后排入废液储液池或储液罐，搅拌均匀，以备用于下批皮的浸酸辂鞣，浸酸过程中盐的加入量为零，亦可加入少量（0%-5%) 食盐或其它有抑制酸肿作用的物质，利用辂鞣废液进行浸酸的工艺是：以灰皮重量计， 3%-100%废辂液，用酸调节废液的 pH值至 0. 3-5. 0， 0%-0.3%特殊制剂， 0%-5%盐， 0.05%-0.3%防霉剂，转 5-30分钟； 0%-2.0%甲酸或醋酸或其它有机酸，转 5-40分钟； 0%-3.5%硫酸或盐酸或其它无机酸，平分二至十次加入，每次间隔 5-15分钟，转 40-120分钟； 0%-1.0%加脂剂，转 30分钟左右,停 0.5-2小时；亦可调整工艺为： 0%-5%盐， 0.05%-0.3%防霉剂，转 5-30分钟; 0%-2.0%甲酸或醋酸或其它有机酸，转 5-20分钟； 0.5%-2.0%硫酸或盐酸或其它无机酸， 3%-100%废辂液， 0%-0.3%特殊制剂，转 70-120分钟；然后进行辂鞣，工艺是： 0·5%-2%辂粉，转 10-40分钟； 0.5%-3.5%辂粉，转 30-90分钟； 0.2%-1.2%甲酸钠或其它盐类，转 30分钟左右； 0.10%-0.55%提碱剂，转 2.0-4.5小时； 20%-80%废辂液， 0%-0.3%特殊制剂，鼓内升温至 28°C-42°C，将废辂液加温后再加入转鼓或先将废辂液加入转鼓中再整体升温均可，转 2-4小时；辂鞣结束废液排入储液池或储液罐，应每次化验废液中辂含量及 pH值，根据化验结果确定辂粉的加入量和调废液 pH值时加酸量，还应定期检测废液中的微生物数量，一般循环三至五次检测一次，主要检测霉菌数量，根据检测结果确定防霉剂的用量； (6) Recycling of waste liquid in the pickling process: Place a pickling liquid storage tank or a liquid storage tank next to the pickling drum. The liquid storage tank is preferably as deep as 2-8 meters underground. In order to facilitate temperature control, it is preferable to have a spare tank or tank. The waste liquid from the pickling process is filtered to remove the solid matter from the waste liquid, and then discharged into the waste liquid storage tank or the liquid storage tank, and stirred evenly for use in the next batch. The pickling of the skin, the amount of salt added during the pickling process is zero, and a small amount (0%-5%) of salt or other substance that inhibits the acid swelling may be added. The process of pickling with waste liquid is: 3%-100% waste sputum based on the weight of the gray ash, and the pH of the waste liquid is adjusted to 0. 3-5. 0, 0%-0.3% special Formulation, 0%-5% salt, 0.05%-0.3% anti-mold agent, 5-30 minutes; 0%-2.0% formic acid or acetic acid or other organic acid, 5-40 minutes; 0%-3.5% sulfuric acid or Hydrochloric acid or other inorganic acid, divided into two to ten times, each interval of 5-15 minutes, 40-120 minutes; 0%-1.0% fatliquor, about 30 minutes, 0.5-2 hours; can also be adjusted The process is: 0%-5% salt, 0.05%-0.3% anti-mold agent, 5-30 minutes; 0%-2.0% formic acid or acetic acid or other organic acid, 5-20 minutes; 0.5%-2.0% sulfuric acid Or hydrochloric acid or other inorganic acid, 3%-100% waste mash, 0%-0.3% special preparation, transfer 70-120 minutes; then carry out hydrazine, the process is: 0·5%-2% 辂 powder, turn 10 -40 minutes; 0.5%-3.5% glutinous powder, 30-90 minutes; 0.2%-1.2% sodium formate or other salts, about 30 minutes; 0.10%-0.55% alkali-raising agent, 2.0-4.5 hours; 20 %-80% waste sputum, 0%-0.3% special preparation, the temperature inside the drum is raised to 28 °C-42 °C, the waste mash is heated and then added to the drum Or first add the waste sputum to the drum and then heat up the whole temperature for 2-4 hours; 辂鞣 end the waste liquid into the liquid storage tank or the liquid storage tank, and test the strontium content and pH value in the waste liquid every time. According to the test results, determine the amount of strontium powder added and adjust the pH value of the waste liquid. The amount of microorganisms in the waste liquid should also be regularly checked. Generally, the test is repeated three to five times. The number of molds is mainly detected, and the number of molds is determined according to the test results. The amount of fungicide;

( 7 ) 复鞣工序的废液循环再利用：在复鞣转鼓旁设置复鞣废液储液池或储液罐，来自复鞣工序的废液滤去废液中固形物后排入复鞣废液储液池或储液罐，搅拌均匀，以备用于下批削匀革的复鞣；利用复鞣废液进行复鞣的工艺是：以削匀革重量计，用盐酸或硫酸或其它酸类物质将复鞣废液的 pH值调至 0. 7-3. 5， 3%-250%复鞣废液， 0%-0.3%特殊制剂，温度调至 32 V-42V , 0.1%-0.5%甲酸或醋酸，转 20-50分钟； 0.5%-2.5%丙烯酸复鞣剂或其它复鞣剂，转 10-40分钟； 0.5%-2.0%辂粉， 0.1%-0.6%加脂齐 ^，转 30-90 分钟； 0.5%-1.5%脂肪醛，转 20-50分钟； 0.3%-1.0%甲酸钠或醋酸钠， 0.1%-0.5%小苏打，转 30-90分钟，然后转 10分钟 /停 50分钟，转停结合进行 3-8次，或停鼓过夜， pH值要求 2.8-4.8; 复鞣结束废液排入储液池或储液罐，应定期化验废液中辂含量及 pH值，定期检测废液中的微生物数量，一般循环三至五次检测一次； (7) Recycling of waste liquid in the reclamation process: Set up a reclaimed waste liquid storage tank or liquid storage tank next to the re-twisting drum, and the waste liquid from the reclamation process filters out the solid matter in the waste liquid and discharges it into the complex The waste liquid storage tank or the liquid storage tank is evenly mixed for the retanning of the next batch of shaved leather; the retanning process by using the retanning waste liquid is: using the hydrochloric acid or sulfuric acid or Other acid substances adjust the pH of the retanning waste liquid to 0. 7-3. 5, 3%-250% retanning waste liquid, 0%-0.3% special preparation, the temperature is adjusted to 32 V-42V, 0.1% -0.5% formic acid or acetic acid, for 20-50 minutes; 0.5%-2.5% acrylic retanning agent or other retanning agent, for 10-40 minutes; 0.5%-2.0% strontium powder, 0.1%-0.6% fatliquoring ^, turn 30-90 Minutes; 0.5%-1.5% fatty aldehyde, 20-50 minutes; 0.3%-1.0% sodium formate or sodium acetate, 0.1%-0.5% baking soda, 30-90 minutes, then 10 minutes / stop for 50 minutes, turn Stop the combination for 3-8 times, or stop the drum overnight, the pH requirement is 2.8-4.8; After the reclamation ends, the waste liquid is discharged into the liquid storage tank or the liquid storage tank. The strontium content and pH value in the waste liquid should be periodically tested, and the waste should be periodically tested. The number of microorganisms in the liquid, usually three to five times of detection;

( 8 ) 中和工序的废液循环再利用：在中和转鼓旁设置中和废液储液池或储液罐，来自中和工序的废液滤去废液中固形物后排入中和废液储液池或储液罐，搅拌均匀，以备用于下批削匀革的中和；利用中和废液进行中和的工艺是：以削匀革重量计， 3%-250%中和废液， 0%-0.3%特殊制剂，温度调至 32°C-35°C， 1.0%-4.0%中和单宁， 0.5%-3.5%甲酸钠，转 20-40分钟； 0.2%-2.0%小苏打， 0.5%-5.0%加脂齐^转 30-60分钟，要求： pH值 4.0-6.5，切口透心；中和结束废液排入储液池或储液罐； (8) Recycling of waste liquid in the neutralization process: Set the neutralization waste liquid storage tank or liquid storage tank next to the neutralization drum, and the waste liquid from the neutralization process filters out the solid matter in the waste liquid and then discharges it into the middle And the waste liquid storage tank or liquid storage tank, stir evenly for neutralization of the next batch of shaved leather; the process of neutralization with neutralization waste liquid is: 3%-250% by weight of shaved leather Neutralize waste liquid, 0%-0.3% special preparation, adjust the temperature to 32°C-35°C, 1.0%-4.0% neutralize tannin, 0.5%-3.5% sodium formate, turn 20-40 minutes; 0.2%- 2.0% baking soda, 0.5%-5.0% fatliquoring ^ turn 30-60 minutes, requirements: pH 4.0-6.5, incision through the heart; neutralize the end of the waste liquid into the reservoir or reservoir;

(9 ) 染色工序废液循环再利用：在染色转鼓旁设置多个废液储液池或储液罐，不同色泽采用不同的储液池或储液罐，来自染色工序的废液滤去废液中固形物后排入相应色泽储液池或储液罐，搅拌均匀，以备用于下批削匀革的染色；利用染色废液进行染色的工艺是：以削匀革重量计， 3%-200% 染色废液， 0%-0. 3%特殊制剂，温度调至 30°C， 0. 5%-5. 0%丙烯酸复鞣剂，转 15 -40分钟； 0. 5%-6. 0%双聚氰胺复鞣剂， 0. 5%-5. 0%荆树皮栲胶， 0. 5%-4. 0%亚硫酸化植物油，转 30 -60分钟; 0. 5%-4. 0%染料， 0. 5%-5. 0% 复合型加脂剂，转 40 -80分钟，要求：切口透心；染色结束废液排入同一色泽储液池或储液罐。 (9) Dyeing process waste liquid recycling: A plurality of waste liquid storage tanks or liquid storage tanks are arranged beside the dyeing drum, different liquid pools or liquid storage tanks are used for different colors, and waste liquid from the dyeing process is filtered. After the solid matter in the waste liquid is discharged into the corresponding color liquid storage tank or liquid storage tank, it is evenly mixed for use in the dyeing of the next batch of shaved leather; the dyeing waste liquid is dyed by the weight of shaving leather, 3 %-200% dyeing waste liquid, 0%-0. 3% special preparation, the temperature is adjusted to 30 ° C, 0. 5% - 5. 0% acrylic retanning agent, 15 - 40 minutes; 0. 5% - 6. 0% lycopene retanning agent, 0. 5%-5. 0% wattle bark gum, 0. 5%-4. 0% sulfitized vegetable oil, 30-60 minutes; 0. 5 %-4. 0% dye, 0. 5%-5. 0% compound fatliquor, 40-80 minutes, required: incision through the heart; dyeing end waste liquid into the same color reservoir or liquid storage tank .

上述工艺中，每个储液池或储液罐都装有搅拌装置（个别池或罐亦可人工搅拌）；经预浸水及浸灰后的皮进行去肉及片皮，去肉和片皮过程中产生的废液分别收集入相应预浸水和浸灰废液储液池或储液罐以备循环再利用。经预浸水、主浸水、浸灰、复灰、脱灰软化、浸酸辂鞣、复鞣、中和及染色工序处理后的皮免去常规水洗步骤，亦可进行水洗，并将水洗废液进行循环再利用，当循环利用灰皮的水洗废液时应加入酸类物质将其 pH值调至 5-11. 5之间。 In the above process, each of the liquid storage tanks or the liquid storage tanks is equipped with a stirring device (the individual pools or tanks can also be manually stirred); the skin is pre-soaked and limed, and the meat and skin are removed, and the meat and skin are removed. Process in production The raw waste liquid is separately collected into the corresponding pre-soaked water and ash waste liquid storage tank or liquid storage tank for recycling. The skin treated by pre-soaking, main immersion, liming, ash, deliming, pickling, retanning, neutralization and dyeing processes is free of conventional washing steps, water washing, and washing waste 5之间之间。 The pH is adjusted to 5-11. 5 when the pH is adjusted to 5-11.

本发明所使用的初始废液分别来自于传统的预浸水、主浸水、浸灰、复灰、脱灰软化、浸酸辂鞣、复鞣、中和及染色工序，各种废液的构成情况是本领域技术人员已知的；一般来说，预浸水、主浸水废液中含有浸水齐 NaC Na₂C0₃、脱脂剂、油脂及其分解产物、毛、角蛋白质、粘蛋白、肉、血等，其中，一般情况下，废液中残留的脱脂剂含量通常为初始用量的 15%-30%，废液中残留的浸水剂含量通常为初始用量的 15%-25%，废液中残留的 ^₂( 0₃含量通常为初始用量的 30%-50%；浸灰、复灰废液中含有油脂及其分解产物、盐类、石灰、浸灰剂、 S²—、 0H―、 Na\ Ca²⁺、蛋白质及其分解产物、酶类及胺类物质等，其中，一般情况下，废液中残留的石灰通常为初始用量的 37%-55%，浸灰废液中残留的 Na₂S含量通常为 2. 4g/l_3. 2g/l ; 脱灰软化废液中含有蛋白质及其分解产物、脱灰剂、脱脂剂、油脂及其分解产物、酶类及铵盐、胺类物质等，其中废液中残留的酶含量通常为初始用量的 30%-50%，废液中残留的铵盐含量通常为初始用量的 30%-40%；辂鞣废液中含有 Cr³⁺、 Cl—、 SO/—、蛋白质及其分解产物、油脂及其分解产物等，其中废液中残留的 Cr³⁺通常为 2. 8g/l-3. 2g/l, CI—通常为 7g/l_15g/l, 废液中残留的酸根含量通常为初始用量的 30%-45%；复鞣废液中含有 Na⁺、 Cr³⁺ 及有机鞣剂等；中和废液中含有中性盐等；在染色工序中使用了加脂剂、染料及有机助染剂等化工材料，除一部分被吸收外，绝大部分进入废水中，这些污染物都属于大分子有机物，浓度高，但生物降解速度很慢。以上各种废液如果任意排放，不仅对环境造成极大的污染，而且会产生极大的资源浪费。 The initial waste liquid used in the present invention is derived from the traditional pre-immersion water, main immersion water, ash ash, ash ash, deliming softening, pickling sputum, retanning, neutralization and dyeing process, and the composition of various waste liquids. It is known to those skilled in the art; in general, pre-soaked water, main immersion waste liquid contains water soaked NaC Na ₂ C0 ₃ , degreaser, oil and its decomposition products, hair, keratin, mucin, meat, blood Etc., in which, in general, the residual degreasing agent content in the waste liquid is usually 15%-30% of the initial amount, and the residual water immersion agent content in the waste liquid is usually 15%-25% of the initial amount, and the residue in the waste liquid ^ ₂ (0 ₃ content is usually 30%-50% of the initial amount; ash, fly ash waste liquid contains oil and its decomposition products, salt, lime, liming agent, S ² -, 0H -, Na \ Ca ²⁺ , protein and its decomposition products, enzymes and amines, etc., in which, in general, the residual lime in the waste liquid is usually 37%-55% of the initial amount, and the residual Na in the ash waste liquid ₂的含含量为2. 4g / l_3. 2g / l ; There are proteins and their decomposition products, deliming agents, degreasing agents, oils and their decomposition products, enzymes and ammonium salts, amines, etc., wherein the residual enzyme content in the waste liquid is usually 30%-50% of the initial amount. The residual ammonium salt content in the waste liquid is usually 30%-40% of the initial amount; the waste liquid contains Cr ³⁺ , Cl-, SO/-, protein and its decomposition products, oil and its decomposition products, etc. The residual Cr ^{3+ in the} waste liquid is usually 2. 8g / l - 3. 2g / l, CI - usually 7g / l - 15g / l, the residual acid content in the waste liquid is usually 30% -45% of the initial amount; The retanning waste liquid contains Na ⁺ , Cr ³⁺ and organic bismuth agents; the neutralization waste liquid contains neutral salts; etc.; in the dyeing process, chemical materials such as fatliquors, dyes and organic dyeing agents are used, Part of it is absorbed, and most of it enters the wastewater. These contaminants are all macromolecular organics with high concentrations but very slow biodegradation. If any of the above waste liquids are discharged arbitrarily, it will not only cause great pollution to the environment, but also cause great waste of resources.

优选地，预浸水、主浸水和浸灰工序可以采用同一个转鼓，在转鼓旁分别设置预浸水、主浸水和浸灰废液储液池或储液罐，以阀门的方式控制转鼓向各储液池或储液罐进行废液排放；具体来说，当预浸水、主浸水和浸灰同用一个转鼓时，在转鼓上设置阀门 1，用于将预浸水废液排放到预浸水废液储液池或储液罐，同时，在转鼓上设置阀门 2，用于将主浸水废液排放到主浸水废液储液池或储液罐，同时，在转鼓上设置阀门 3，用于将浸灰废液排放到浸灰废液储液池或储液罐；排放预浸水废液时，阀门 1打开，阀门 2、 3关闭，废液经分流管道排放到预浸水废液储液池或储液罐；排放主浸水废液时，阀门 2打开，阀门 1、 3关闭，废液经分流管道排放到主浸水废液储液池或储液罐；排放浸灰废液时，阀门 1、 2关闭，阀门 3打开，废液经分流管道排放到浸灰废液储液池或储液罐。 Preferably, the pre-immersion water, the main immersion water and the liming process can adopt the same rotating drum, and a pre-immersion water, a main immersion water and a ash ash liquid storage tank or a liquid storage tank are respectively arranged beside the rotating drum, and the rotating drum is controlled by a valve. Discharging waste liquid into each liquid storage tank or liquid storage tank; specifically, when pre-immersion water, main water immersion water and immersion ash are used together with a rotating drum, a valve 1 is arranged on the rotating drum for discharging the pre-dip water waste liquid To the pre-soaked waste liquid storage tank or the liquid storage tank, and at the same time, a valve 2 is arranged on the rotating drum for discharging the main immersion water waste liquid into the main immersion liquid waste liquid storage tank or the liquid storage tank, and at the same time, on the rotating drum The valve 3 is arranged to discharge the ash waste liquid to the ash waste liquid storage tank or the liquid storage tank; when the pre-dip water waste liquid is discharged, the valve 1 is opened, the valves 2, 3 are closed, and the waste liquid is discharged to the pre-distribution pipeline Immersion waste liquid storage tank or liquid storage tank; When discharging the main immersion water waste liquid, the valve 2 is opened, the valves 1, 3 are closed, and the waste liquid is discharged to the main immersion waste liquid storage tank or the liquid storage tank through the branching pipe; When the waste liquid is used, the valves 1, 2 are closed, the valve 3 is opened, and the waste is Liming effluent is discharged to the sump or reservoir pipe via a shunt.

类似地，脱灰软化和浸酸辂鞣工序也可以采用同一个转鼓，在转鼓旁分别设置脱灰软化和浸酸辂鞣废液储液池或储液罐，以阀门的方式控制转鼓向各储液池或储液罐进行废液排放；具体来说，当脱灰软化和浸酸辂鞣同用一个转鼓时，在转鼓上设置阀门 4，用于将脱灰软化废液排放到脱灰软化废液储液池或储液罐，同时，在转鼓上设置阀门 5，用于将浸酸辂鞣废液排放到浸酸辂鞣废液储液池或储液罐。排放脱灰软化废液时，阀门 4打开，阀门 5关闭，废液经分流管道排放到脱灰软化废液储液池或储液罐；排放浸酸辂鞣废液时，阀门 4关闭，阀门 5打开，废液经分流管道排放到浸酸辂鞣废液储液池或储液罐。类似地，复鞣、中和及染色工序可以采用同一个转鼓，在转鼓旁分别设置复鞣、中和及染色废液储液池或储液罐，以阀门的方式控制转鼓向各储液池或储液罐进行废液排放。具体来说，当复鞣、中和及染色同用一个转鼓时，在转鼓上设置阀门 6，用于将复鞣废液排放到复鞣废液储液池或储液罐，同时，在转鼓上设置阀门 7，用于将中和废液排放到中和废液储液池或储液罐，同时，在转鼓上设置阀门 8，用于将染色废液排放到染色废液储液池或储液罐。排放复鞣废液时，阀门 6打开，阀门 7、 8关闭，废液经分流管道排放到复鞣废液储液池或储液罐；排放中和废液时，阀门 7打开，阀门 6、 8关闭，废液经分流管道排放到中和废液储液池或储液罐；排放染色废液时，阀门 6、 7关闭，阀门 8打开，废液经分流管道排放到染色废液储液池或储液罐。 Similarly, the same detonating drum can be used for the deliming softening and pickling process. The deashing softening and pickling waste liquid storage tank or liquid storage tank are respectively arranged beside the rotating drum, and the valve is controlled to rotate. The drum discharges waste liquid to each liquid storage tank or liquid storage tank; specifically, when the deashing softening and the pickling are used together with a rotating drum, a valve 4 is disposed on the rotating drum for softening and deashing The liquid is discharged to the deashing and softening waste liquid storage tank or the liquid storage tank, and at the same time, a valve 5 is arranged on the rotating drum for discharging the pickling waste liquid to the pickling waste liquid storage tank or the liquid storage tank . When the deashing and softening waste liquid is discharged, the valve 4 is opened, the valve 5 is closed, and the waste liquid is discharged to the deashing and softening waste liquid storage tank or the liquid storage tank through the branching pipe; when the acid pickling waste liquid is discharged, the valve 4 is closed, the valve is closed 5 Open, the waste liquid is discharged to the pickling waste liquid storage tank or liquid storage tank through the diverting pipe. Similarly, the same drum can be used for the retanning, neutralization and dyeing processes, and retanning, neutralization and dyeing waste liquid storage tanks or liquid storage tanks are respectively arranged beside the drum, and the drums are controlled by valves. The liquid storage tank or the liquid storage tank discharges waste liquid. Specifically, when a drum is used for retanning, neutralization, and dyeing, a valve 6 is disposed on the drum for discharging the retort waste liquid to the retort waste liquid storage tank or the liquid storage tank, and A valve 7 is disposed on the drum for discharging the neutralized waste liquid to the neutralizing waste liquid storage tank or the liquid storage tank, and at the same time, a valve 8 is disposed on the rotating drum for discharging the dyeing waste liquid to the dyeing waste liquid Reservoir or reservoir. When the retort waste liquid is discharged, the valve 6 is opened, the valves 7, 8 are closed, and the waste liquid is discharged to the retort waste liquid storage tank or the liquid storage tank through the branch pipe; when the waste liquid is discharged, the valve 7 is opened, the valve 6, 8 is closed, the waste liquid is discharged to the neutralizing waste liquid storage tank or the liquid storage tank through the diverting pipe; when the dyeing waste liquid is discharged, the valves 6, 7 are closed, the valve 8 is opened, and the waste liquid is discharged to the dyeing waste liquid storage through the diverting pipe. Pool or liquid storage tank.

在本发明的废液循环再利用过程中，对于预浸水、主浸水、浸灰、复灰、脱灰软化、浸酸辂鞣、复鞣、中和及染色这些全封闭废液循环的工序而言，可以根据各废液储液池或储液罐中废液的粘稠程度定期对废液进行清洁化处理，除去其中的固体物，并定期消毒，定期检测废液中的微生物、蛋白酶、 pH值、辂离子、钙离子、硫化物及其它相关成份，废液继续循环再利用。例如，用压滤的方式对废液进行清洁化处理，经压滤分离出的废固物用于填坑或制砖或其它用途，分离出的废液收集入各废液储液池或储液罐以备循环再利用。对废液清洁化处理的周期较传统处理方法长，且处理更简易。 In the recycling process of the waste liquid of the present invention, the process of circulating the fully enclosed waste liquid for pre-soaking, main immersion, ash, ash, deliming, pickling, retanning, neutralization and dyeing In other words, the waste liquid can be cleaned regularly according to the viscosity of the waste liquid in each waste liquid storage tank or liquid storage tank, the solid matter is removed, and it is periodically disinfected, and the microorganisms and proteases in the waste liquid are periodically detected. The pH, strontium ions, calcium ions, sulfides and other related components, the waste liquid continues to be recycled. For example, the waste liquid is cleaned by pressure filtration, and the waste solid separated by pressure filtration is used for filling or brick making or other purposes, and the separated waste liquid is collected into each waste liquid storage tank or stored. The tank is ready for recycling. The cycle of cleaning the waste liquid is longer than the conventional treatment method, and the treatment is easier.

本发明具有如下有益效果： The invention has the following beneficial effects:

本发明实现了制革中从预浸水到染色各工序的废液循环再利用，而且可以反复循环再利用，几乎不排放污水，彻底解决了制革污染难题，特别是利用废辂液，后期的补液升温比常规工艺少; c-i5°c，节省了能源。该废水循环工艺稍加变动后或不加变动均可适用于制革厂现有大生产工艺流程，由此生产的成品革各项性能指标均达要求，并有效降低了成革松面率，提高了成革的紧实度、丰满度。相对于传统工艺而言，工艺及设备更加简化，可实现节约化料 15%-55%，如节约辂粉 35%-65%，部分化料可实现节约 90%以上，个别化料如食盐可实现节约 100%。 The invention realizes the recycling and recycling of the waste liquid from the pre-immersion water to the dyeing process in the tanning, and can be repeatedly recycled and reused, and almost no sewage is discharged, completely solving the problem of tanning pollution, especially It is the use of waste sputum, the late rehydration temperature is less than the conventional process; c-i5 °c, saving energy. The waste water recycling process can be applied to the existing large-scale production process of the tannery with little or no change, and the performance indexes of the finished leather produced meet the requirements, and the rate of the finished leather is effectively reduced. Improve the firmness and fullness of the leather. Compared with the traditional process, the process and equipment are more simplified, and the material can be saved by 15%-55%, such as saving 35%-65% of the powder, and the partial material can achieve more than 90% savings. Individual chemicals such as salt can be used. Achieve 100% savings.

附图说明附图 1是根据本发明的一种工艺及设备更加简化的新型制革工艺的流程示意图。注：废液的处理可在储液池或储液罐内进行也可在转鼓内进行。具体实 ½^式 BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic flow diagram of a novel tanning process in which a process and apparatus are more simplified in accordance with the present invention. Note: The disposal of the waste liquid can be carried out in a liquid storage tank or a liquid storage tank or in a rotating drum. Specific actual 1⁄2^

下面结合附图 1和实施例对本发明进一步说明： The present invention is further described below in conjunction with FIG. 1 and the embodiment:

实施例 1 Example 1

如附图 1所示，在预浸水工序中，原皮进行预浸水后，废液滤去固形物后排放到预浸水废液储液池，搅拌均匀，然后由耐碱泵抽出排入到预浸水转鼓，利用预浸水废液进行预浸水的工艺是：以原皮重量计， 200%预浸水废液， 0. 15%特殊制剂， 0. 25%杀菌剂，转 15分钟； 0. 35%浸水助剂， 0. 2% 脱脂剂， 0. 2%纯碱，转 20分钟 /停 40分钟，转停结合进行 4次；预浸水结束废水排入储液池；将毛皮去肉，然后进行主浸水； As shown in Fig. 1, in the pre-soaking process, after the raw skin is pre-soaked, the waste liquid is filtered to remove the solid matter, discharged into the pre-dip water waste liquid storage tank, stirred uniformly, and then discharged by the alkali-resistant pump into the pre-soaked water. The drum, the pre-soaked water using the pre-soaked water waste liquid is: 200% pre-soaked water waste liquid, 0.15% special preparation, 0.25% fungicide, 15 minutes; 0. 35% water immersion Additive, 0. 2% degreaser, 0.2% soda ash, 20 minutes/stop for 40 minutes, transfer combined for 4 times; pre-soaked water to discharge waste water into the reservoir; remove the fur, then carry out the main immersion ;

在主浸水工序中，主浸水废液滤去固形物后排入主浸水废液储液池，搅拌均匀，然后由耐碱泵抽出排入到主浸水转鼓，利用主浸水废液进行主浸水的工艺是：以原皮重量计， 200%主浸水废液， 0. 15%特殊制剂， 0. 7% 浸水助剂， 0. 3%脱脂剂， 0. 5%纯碱， 0. l% Na₂S，转 40分钟 /停 40分钟，转停结合进行 3次； 0. 3%杀菌剂，转 20分钟，然后每转 3分钟 /停 57分钟，过夜；次日连续转 40分钟；主浸水结束废水排入储液池； In the main immersion process, the main immersion waste liquid is filtered to remove the solid matter, discharged into the main immersion waste liquid storage tank, stirred uniformly, and then discharged by the alkali-resistant pump to the main immersion drum, and the main immersion waste liquid is used for main immersion The process is: based on the weight of the original skin, 200% of the main immersion water effluent, 0. 15% special preparation, 0. 7% immersion aid, 0. 3% degreaser, 0. 5% soda ash, 0. l% Na ₂ S, turn 40 minutes / stop for 40 minutes, turn Stop the combination for 3 times; 0. 3% bactericide, transfer for 20 minutes, then every 3 minutes / stop for 57 minutes, overnight; the next day for 40 minutes; the main immersion water is discharged into the reservoir;

在浸灰工序中，浸灰废液滤去固形物后排入浸灰废液储液池，搅拌均匀，然后由耐碱泵抽出排入到浸灰转鼓，利用浸灰废液进行浸灰工艺是：以原皮重量计， 70%废灰液， 0. 15%特殊制剂， 1. 0%浸灰助剂， 0. 15% NaHS ，转 30分钟； 1. 2%石灰，转 30分钟 /停 30分钟； 0. 5%NaHS，转 20分钟 /停 20分钟; 开始滤毛； 0. 5%Na₂S, 0. 8%石灰， 0. 1%脱脂剂，转 20分钟 /停 30 分钟，转停结合 3次； 20%废灰液， 0. 15%特殊制剂， 0. 5%Na₂S, 0. 5%浸灰助剂， 1. 0%石灰，转 20分钟 /停 20分钟，转停结合 2次；然后转 10分钟 /停 20分钟，转停结合 6次； 80%废灰液， 0. 15%特殊制剂，转 10分钟；然后每转 5分钟 /停 55分钟，过夜；浸灰结束废水排入储液池；将灰皮进行去肉片皮，然后进行复灰； In the liming process, the ash ash waste liquid is filtered out and discharged into the ash effluent liquid storage tank, stirred uniformly, and then discharged by the alkali-resistant pump to the immersion drum, and the ash ash is immersed. The process is: based on the weight of the original skin, 70% waste ash, 0.15% special preparation, 1. 0% ash auxiliaries, 0. 15% NaHS, 30 minutes; 1. 2% lime, 30 minutes / Stop for 30 minutes; 0. 5% NaHS, turn 20 minutes / stop for 20 minutes; start filter; 0. 5% Na ₂ S, 0. 8% lime, 0.1% degreaser, turn 20 minutes / stop 30 minutes , transfer stop combined 3 times; 20% waste ash, 0. 15% special preparation, 0. 5% Na ₂ S, 0. 5% ash auxiliaries, 1. 0% lime, turn 20 minutes / stop 20 minutes , transfer and combine 2 times; then turn 10 minutes / stop 20 minutes, transfer combined 6 times; 80% waste ash, 0. 15% special preparation, turn 10 minutes; then every 5 minutes / stop 55 minutes, overnight After the ash is discharged, the waste water is discharged into the liquid storage tank; the gray skin is peeled off, and then the ash is removed;

在复灰工序中，复灰废液滤去固形物后排入复灰废液储液池，搅拌均匀，然后由耐碱泵抽出排入到浸灰转鼓，利用复灰废液进行复灰的工艺是: 以原皮重量计， 100%复灰废液， 0. 15%特殊制剂， 0. 8%石灰， 0. 2%硫化钠， 0. 4%浸灰助剂， 0. 10%NaOH，转 30分钟 /停 40分钟，然后每转 5分钟 / 停 55分钟，转停结合进行 6次，过夜；复灰结束废水排入储液池； In the ash-removing process, the ash waste liquid is filtered to remove the solid matter, discharged into the ash waste liquid storage tank, stirred uniformly, and then discharged by the alkali-resistant pump to the immersion drum, and the ash waste liquid is used for the ash. The process is: 100% complex ash waste, 0. 15% special preparation, 0. 8% lime, 0.2% sodium sulfide, 0.4% ash auxiliaries, 0. 10% NaOH , transfer for 30 minutes / stop for 40 minutes, then every 5 minutes / stop for 55 minutes, transfer and combine 6 times, overnight; waste ash to discharge wastewater into the reservoir;

在脱灰软化工序中，脱灰软化废液滤去固形物后排入脱灰软化废液储液池，然后由耐酸碱泵抽出排入到脱灰软化转鼓，利用废液进行脱灰软化的工艺是： 100%脱灰软化废液， 0. 15%特殊制剂， 0. 2%脱脂剂， 0. 6%脱灰剂， 1. 2%硫酸铵， 0. 2%盐酸， 0. 3%醋酸，转 40分钟; 0. 25%软化酶，转 30 分钟；脱灰软化结束废水排入储液池； In the deliming and softening process, the deashing and softening waste liquid is filtered to remove the solid matter, and then discharged into the deliming and softening waste liquid storage tank, and then discharged by the acid and alkali resistant pump to the deashing and softening rotating drum, and the waste liquid is used for deashing. The process of softening is: 100% deashing and softening waste liquid, 0. 15% special preparation, 0.2% degreasing agent, 0.6% deashing agent, 1. 2% ammonium sulfate, 0.2% hydrochloric acid, 0. 3% acetic acid, for 40 minutes; 0. 25% softening enzyme, for 30 minutes; deashing and softening, the waste water is discharged into the reservoir;

在浸酸辂鞣工序中，废辂液滤去固形物后排入到储液池，用硫酸调其 pH值为 0. 7，搅拌均匀，然后由耐酸泵抽出排入到辂鞣转鼓，利用辂鞣废液进行浸酸辂鞣，浸酸过程中盐的加入量为零，工艺是： 90%废辂液、 0.15% 特殊制剂， 0.25%防霉剂，转 10分钟； 0.5%甲酸，转 20分钟； 0.3%硫酸，平分三次加入，每次间隔 10分钟，然后转 90分钟； 0.2%加脂剂，转 30分钟，停 1.5小时； 1.8%辂粉，转 30分钟； 2.2%辂粉，转 1小时； 0.5%甲酸钠，转 30分钟； 0.25%提碱剂，转 4小时； 80%废辂液， 0.15%特殊制剂，升温至 35 V，转 3小时；辂鞣结束废水排入储液池； In the pickling process, the waste liquid is filtered to remove the solid matter, discharged into the liquid storage tank, and adjusted with sulfuric acid. The pH value is 0.7, and the mixture is evenly stirred. Then, it is pumped out by the acid-proof pump and discharged into the tamping drum. The leaching solution is used for pickling bismuth. The amount of salt added during the pickling process is zero. The process is: 90% Waste sputum, 0.15% special preparation, 0.25% anti-mold agent, 10 minutes; 0.5% formic acid, 20 minutes; 0.3% sulfuric acid, divided into three times, every 10 minutes, then 90 minutes; 0.2% fatliquoring Agent, transfer for 30 minutes, stop for 1.5 hours; 1.8% sputum powder, transfer for 30 minutes; 2.2% sputum powder, transfer for 1 hour; 0.5% sodium formate, for 30 minutes; 0.25% for alkali, for 4 hours; 80% for waste Liquid, 0.15% special preparation, heat up to 35 V, transfer for 3 hours; 辂鞣 end waste water discharged into the reservoir;

在复鞣工序中，复鞣废液滤去固形物后排入复鞣废液储液池，搅拌均匀，然后由耐酸泵抽出排入到复鞣转鼓，利用复鞣废液进行复鞣工艺是：以削匀革重量计，用硫酸将复鞣废液的 pH值调至 2.5， 150%复鞣废液， 0. 15% 特殊制剂，温度调至 36°C， 0.3%甲酸，转 30分钟； 1.5%丙烯酸复鞣剂，转 30分钟； 1.0%辂粉， 0.3%加脂齐转 60分钟； 1.0%脂肪醛，转 30分钟； 0.8%甲酸钠， 0.2%小苏打，转 60分钟，然后转 10分钟 /停 50分钟，转停结合进行 5次， pH值要求 2.8-4.8 ; 复鞣结束废水排入储液池； In the retanning process, the retort waste liquid is filtered to remove the solid matter, discharged into the retort waste liquid storage tank, stirred uniformly, and then discharged by the acid-proof pump to the retort drum, and the retanning process is performed by using the retanning waste liquid. YES: Adjust the pH of the retanning waste liquid to 2.5, 150% retanning waste liquid by using sulfuric acid, 0. 15% special preparation, adjust the temperature to 36 °C, 0.3% formic acid, turn 30 Minutes; 1.5% acrylic retanning agent, 30 minutes; 1.0% glutinous rice powder, 0.3% fatliquoring for 60 minutes; 1.0% fatty aldehyde, 30 minutes; 0.8% sodium formate, 0.2% baking soda, 60 minutes, then Transfer 10 minutes / stop for 50 minutes, transfer and combine 5 times, pH value 2.8-4.8; re-circulation waste water discharged into the reservoir;

在中和工序中，中和废液滤去固形物后排入中和废液储液池，搅拌均匀，然后由耐酸泵抽出排入到中和转鼓，利用中和废液进行中和工艺是： 200%中和废液， 0.15%特殊制剂，温度调至 35 °C， 2.0%中和单宁， 1.5%甲酸钠，转 20分钟； 1.2%小苏打， 3.0%加脂剂，转 60分钟，要求： pH 值 4.0-6.5，切口透心；中和结束废水排入储液池； In the neutralization process, the neutralized waste liquid is filtered to remove the solid matter, discharged into the neutralization waste liquid storage tank, stirred uniformly, and then discharged by the acid-proof pump to the neutralization drum, and neutralized by the neutralization waste liquid. Yes: 200% neutralized waste liquid, 0.15% special preparation, temperature adjusted to 35 °C, 2.0% neutralized tannin, 1.5% sodium formate, 20 minutes; 1.2% baking soda, 3.0% fatliquor, 60 minutes , Requirements: pH 4.0-6.5, incision through the heart; neutralization and discharge of wastewater into the reservoir;

在染色工序中，染色废液滤去固形物后排入同一色泽染色废液储液池，搅拌均匀，然后由耐酸泵抽出排入到染色转鼓，利用染色废液进行染色的工艺是： 80%染色废液， 0. 15%特殊制剂，温度调至 30 °C， 2. 5%丙烯酸复鞣剂，转 20分钟； 4. 0%双聚氰胺复鞣剂， 1. 5%荆树皮栲胶， 2. 0%亚硫酸化植物油，转 40分钟； 2. 0%染料， 1. 5%复合型加脂剂，转 60分钟，要求：切口透心；染色结束废水排入同一色泽储液池； In the dyeing process, the dyeing waste liquid is filtered to remove the solid matter, discharged into the same color dyeing waste liquid storage tank, stirred uniformly, and then discharged by the acid-proof pump to the dyeing drum, and the dyeing waste liquid is used for dyeing: 80 % dyeing waste liquid, 0. 15% special preparation, temperature adjusted to 30 °C, 2. 5% acrylic retanning agent, 20 minutes; 4. 0% melamine retanning agent, 1. 5% wattle Pipa gum, 2. 0% sulfite Oil, 40 minutes; 2. 0% dye, 1. 5% composite fatliquor, for 60 minutes, requirements: incision through the heart; dyeing end of the wastewater into the same color reservoir;

上述预浸水、主浸水、浸灰、复灰、脱灰软化、浸酸辂鞣、复鞣、中和及染色工序的循环废液视情况定期进行压滤处理，压滤得到的废液回收入相应的废液池继续循环再利用，压滤得到的废固物用于填坑或其他。 The above-mentioned pre-soaked water, main immersion water, liming ash, ash ash, deliming softening, pickling sputum, retanning, neutralization and dyeing process are periodically subjected to pressure filtration treatment, and the waste liquid obtained by pressure filtration is recycled. The corresponding waste liquid pool is continuously recycled, and the waste solid obtained by pressure filtration is used for filling pits or the like.

在不脱离本发明精神或实质特点的情况下，能以其它形式实施本发明，参照权利要求而非上述说明书，作为指示本发明的范围。 The invention may be embodied in other specific forms without departing from the spirit and scope of the invention.

Claims

权利要求书 claims

1、一种工艺及设备更加简化的新型制革工艺，其特征在于在预浸水、主浸水、浸灰、复灰、脱灰软化、浸酸辂鞣、复鞣、中和、染色工序中分步进行废液循环再利用，各工序产生的废液可以不加特殊制剂处理，也可加入某种特殊制剂，加入量为 0%-0. 3% (以废液量为基数），上述工序全部实现全封闭循环，包括如下步骤： 1. A new leather-making process with more simplified processes and equipment, which is characterized by dividing into pre-soaking, main water-soaking, liming, re-liming, deliming and softening, pickling tanning, re-tanning, neutralization and dyeing. Waste liquid is recycled step by step. The waste liquid generated in each process can be treated without adding special preparations, or some special preparation can be added. The addition amount is 0%-0.3% (based on the amount of waste liquid). The above processes All achieve a fully closed cycle, including the following steps:

( 1 ) 预浸水工序的废液循环再利用：在预浸水转鼓旁设置预浸水废液储液池或储液罐，来自预浸水工序的废液滤去废液中固形物后排入预浸水废液储液池或储液罐，搅拌均匀，以备用于下批皮的预浸水；利用预浸水废液进行预浸水的工艺是：以原皮重量计， 5%-300%预浸水废液， 0%-0. 3%特殊制剂， 0. 2%-0. 4% 杀菌剂，转 5-20分钟; 0. 1%-0. 8%浸水助剂， 0. 1%-1. 0%脱脂剂， 0. 05%- 0. 5% 纯碱，转 10-60分钟 /停 20-60分钟，转停结合进行 2-8次；预浸水结束废液排入储液池或储液罐，应定期检测废液中的微生物数量，一般每循环二至三次检 (1) Recycling of waste liquid from the pre-soaking process: Set up a pre-soaking water waste liquid storage pool or tank next to the pre-soaking water drum. The waste liquid from the pre-soaking water process is filtered to remove the solids in the waste liquid and then discharged into the pre-soaking water. Soaking waste liquid storage tank or tank, stir evenly to prepare pre-soaking water for the next batch of skins; The process of using pre-soaking water waste liquid for pre-soaking water is: based on the weight of the original hide, 5%-300% pre-soaking water waste liquid , 0%-0. 3% special preparation, 0. 2%-0. 4% fungicide, turn for 5-20 minutes; 0. 1%-0. 8% water immersion aid, 0. 1%-1. 0 % degreasing agent, 0. 05%- 0. 5% soda ash, turn for 10-60 minutes/stop for 20-60 minutes, a combination of turning and stopping for 2-8 times; after the pre-soaking, the waste liquid is discharged into the liquid storage pool or tank. , the number of microorganisms in the waste liquid should be tested regularly, usually two to three times per cycle.

( 2 ) 主浸水工序的废液循环再利用：在主浸水转鼓旁设置主浸水废液储液池或储液罐，来自主浸水工序的废液滤去废液中固形物后排入主浸水废液储液池或储液罐，搅拌均匀，以备用于下批皮的主浸水；利用主浸水废液进行主浸水的工艺是：以原皮重量计， 5%-300%主浸水废液， 0%-0. 3%特殊制剂， 0. 1%-1. 0% 浸水助剂， 0. 1%-0. 8%脱脂剂， 0. 1%-1. 0%纯碱， 0. 05%- 0. 3% Na₂S，转 30- 80分钟 /停 10-50分钟，转停结合进行 1-4次； 0. 1%-0. 4%杀菌剂，转 5-20分钟，然后每转 3-10分钟 /停 40-70分钟，过夜；次日连续转 10-50分钟；主浸水结束废液排入储液池或储液罐，应定期检测废液中的微生物数量，一般每循环二至三次检测一次； ( 3 ) 浸灰工序的废液循环再利用：在浸灰转鼓旁设置浸灰废液储液池或储液罐，来自浸灰工序的浸灰废液滤去废液中固形物后排入浸灰废液储液池或储液罐，搅拌均匀，以备用于下批皮的浸灰；利用浸灰废液进行浸灰的工艺是：以原皮重量计， 3%-200%废灰液， 0%-0. 3%特殊制剂， 0. 2%-2. 0%浸灰助剂， 0. 05%- 1. 5% NaHS, 转 20_40分钟； 0. 3%_2. 5%石灰，转 20_40分钟 /停 20_40分钟； 0. 05%- 1. 5% NaHS ,转 10_30分钟 /停 10_30分钟；开始滤毛； 0. 05%- 1. 5%Na₂S， 0. 3%-2. 0%石灰， 0. 05%-0. 5%脱脂剂，转 10-20分钟 /停 20-30分钟，转停结合 2- 4次; 3%_200%废灰液， 0%_0. 3%特殊制剂， 0. 5%Na₂S, 0. 2%_2. 0%浸灰助剂， 0. 3%-2. 0%石灰， 0%-0. 2%浸灰酶，转 10-30分钟 /停 10-30分钟，转停结合 1-3次，然后转 10-20分钟 /停 10-30分钟，转停结合进行 5-7次； 3%_200%废灰液， 0%-0. 3%特殊制剂，转 10-30分钟，然后每转 5-10分钟 /停 40-60分钟，过夜；浸灰结束废液排入储液池或储液罐，每次使用前均需化验废灰液中硫化碱、 Ca²⁺等含量，在浸灰过程中，视毛根脱落程度及时利用滤毛机滤毛； (2) Recycling of waste liquid from the main water immersion process: Set up a main water immersion waste liquid storage pool or tank next to the main water immersion drum. The waste liquid from the main water immersion process is filtered out of the solid matter in the waste liquid and then discharged into the main water immersion drum. Stir evenly in the soaking waste liquid storage pool or tank to prepare for the main soaking of the next batch of hides; the process of using the main soaking waste liquid for main soaking is: based on the weight of the original hide, 5%-300% of the main soaking waste liquid , 0%-0. 3% special preparation, 0. 1%-1. 0% water immersion aid, 0. 1%-0. 8% degreasing agent, 0. 1%-1. 0% soda ash, 0. 05 %- 0. 3% Na ₂ S, rotate for 30-80 minutes/stop for 10-50 minutes, combine rotation and stop for 1-4 times; 0. 1%-0. 4% fungicide, rotate for 5-20 minutes, then 3-10 minutes per rotation/stop 40-70 minutes, overnight; continuous rotation for 10-50 minutes the next day; After the main immersion, the waste liquid is discharged into the liquid storage tank or liquid storage tank. The number of microorganisms in the waste liquid should be regularly detected. Generally Test once every two to three cycles; (3) Recycling of waste liquid from the liming process: Set up a liming waste liquid storage pool or tank next to the liming drum. The liming waste liquid from the liming process will be filtered to remove the solids in the waste liquid before being discharged. Pour the liming waste liquid into the liming waste liquid storage pool or tank, and stir evenly to prepare for liming the next batch of skins; The liming process using liming waste liquid is: 3%-200% waste ash based on the weight of the original skins Liquid, 0%-0. 3% special preparation, 0. 2%-2. 0% liming aid, 0. 05%- 1. 5% NaHS, turn for 20-40 minutes; 0. 3%-2. 5% lime , turn for 20_40 minutes/stop for 20_40 minutes; 0. 05%- 1. 5% NaHS, turn for 10_30 minutes/stop for 10_30 minutes; start filtering; 0. 05%- 1. 5%Na ₂ S, 0. 3%- 2. 0% lime, 0.05%-0.5% degreasing agent, turn for 10-20 minutes/stop for 20-30 minutes, turn and stop 2-4 times; 3%_200% waste ash liquid, 0%_0. 3% special preparation, 0. 5% Na ₂ S, 0. 2%-2. 0% liming aid, 0. 3%-2. 0% lime, 0%-0. 2% liming enzyme, turn 10 -30 minutes/stop for 10-30 minutes, 1-3 times of turning and stopping, then 10-20 minutes/10-30 minutes of stopping, 5-7 times of turning and stopping; 3%_200% waste ash liquid, 0% -0. 3% special preparation, rotate for 10-30 minutes, then rotate for 5-10 minutes every time/stop for 40-60 minutes, overnight; after liming, the waste liquid is discharged into the liquid storage tank or liquid storage tank, and is cleaned before each use It is necessary to test the alkali sulfide, Ca ²⁺ and other contents in the waste ash liquid. During the liming process, use a hair filter to filter the hair in a timely manner depending on the degree of hair root shedding;

( 4 ) 复灰工序的废液循环再利用：在复灰转鼓旁设置复灰废液储液池或储液罐，来自复灰工序的废液滤去废液中固形物后排入复灰废液储液池或储液罐，搅拌均匀，以备用于下批皮的复灰；利用复灰废液进行复灰的工艺是：以原皮重量计， 3%-220%复灰废液， 0%-0. 3%特殊制剂， 0. 2%-1. 5%石灰， 0. 05%- 1. 0% Na₂S 或 NaHS, 0. 1%- 0. 7%浸灰助剂， 0. 05%- 0. 3%NaOH，转 20-40分钟 /停 30-60分钟，然后转 5-20分钟 /停 30-60分钟，转停结合进行 3-8次，过夜或直接出鼓；复灰结束废液排入储液池或储液罐； (4) Recycling and reuse of waste liquid from the reliming process: Set up a reliming waste liquid storage pool or tank next to the reliming drum. The waste liquid from the reliming process is filtered to remove the solids in the waste liquid and then discharged into the reliming drum. Ash waste liquid storage tank or liquid storage tank, stir evenly to prepare for re-liming of the next batch of skins; The process of using the re-liming waste liquid for re-liming is: based on the weight of the original hide, 3%-220% of the re-liming waste liquid , 0%-0. 3% special preparation, 0. 2%-1. 5% lime, 0. 05%- 1. 0% Na ₂ S or NaHS, 0. 1%- 0. 7% liming aid , 0.05%-0.3%NaOH, turn for 20-40 minutes/stop for 30-60 minutes, then turn for 5-20 minutes/stop for 30-60 minutes, perform a combination of turning and stopping 3-8 times, overnight or directly out. drum; the waste liquid after reashing is discharged into the liquid storage tank or liquid storage tank;

( 5 ) 脱灰软化工序的废液循环再利用：在脱灰软化转鼓旁设置脱灰软化废液储液池或储液罐，来自脱灰软化工序的废液滤去废液中固形物后排入脱灰软化废液储液池或储液罐，搅拌均匀，以备用于下批皮的脱灰软化；利用脱灰软化废液进行脱灰软化的工艺是：以灰皮重量计， 3%-220%脱灰软化废液， 0%-0. 3% 特殊制剂， 0. 05%-0. 45%脱脂剂， 0. 2%-1. 5%脱灰剂， 0. 2%-1. 5%硫酸铵， 0. 05%-0. 5%盐酸， 0. 1%-0. 5%醋酸，转 15-60分钟； 0_0. 3%软化酶，转 15- 40分钟；脱灰软化结束废水排入储液池或储液罐，每循环一次都应检测废液中的蛋白酶及微生物数量，蛋白酶检测最好使用液质联用仪，亦可使用光电比色法，根据检测结果确定应加入的软化酶数量以及是否需要加入防腐剂； (5) Recycling of waste liquid from the deliming and softening process: Set up a deliming and softening waste liquid storage pool or tank next to the deliming and softening drum, and filter the waste liquid from the deliming and softening process to remove the solids in the waste liquid. Then drain it into the deliming and softening waste liquid storage tank or liquid storage tank, and stir it evenly to prepare for the deliming and softening of the next batch of skins; use the deliming and softening liquid to The process of deliming and softening the waste liquid is: based on the weight of the ash skin, 3%-220% deliming and softening waste liquid, 0%-0.3% special preparation, 0.05%-0.45% degreasing agent, 0. 2%-1. 5% deliming agent, 0. 2%-1. 5% ammonium sulfate, 0. 05%-0. 5% hydrochloric acid, 0. 1%-0. 5% acetic acid, turn 15- 60 minutes; 0_0.3% softening enzyme, turn for 15-40 minutes; After deliming and softening, the wastewater is discharged into the liquid storage pool or liquid storage tank. The number of proteases and microorganisms in the waste liquid should be detected every cycle. Protease detection is the best. Use liquid mass spectrometry or photoelectric colorimetry to determine the amount of softening enzyme that should be added and whether preservatives need to be added based on the test results;

( 6 ) 浸酸辂鞣工序的废液循环再利用：在浸酸辂鞣转鼓旁设置浸酸辂鞣废液储液池或储液罐，储液池最好深至地下 2-8米以利于控温，最好有备用池或罐，来自浸酸辂鞣工序的废液滤去废液中固形物后排入废液储液池或储液罐，搅拌均匀，以备用于下批皮的浸酸辂鞣，浸酸过程中盐的加入量为零，亦可加入少量（0%-5%)食盐或其它有抑制酸肿作用的物质，利用辂鞣废液进行浸酸的工艺是：以灰皮重量计， 3%-100%废辂液，用酸调节废液的 pH值至 0. 3-5. 0， 0%-0.3%特殊制剂， 0%-5%盐， 0.05%-0.3%防霉剂，转 5-30分钟； 0%-2.0%甲酸或醋酸或其它有机酸，转 5-40分钟； 0%-3.5%硫酸或盐酸或其它无机酸，平分二至十次加入，每次间隔 5-15分钟，转 40-120分钟； 0%-1.0%加脂剂，转 30 分钟左右，停 0.5-2小时；亦可调整工艺为： 0%-5%盐， 0.05%-0.3%防霉剂，转 5-30分钟； 0%-2.0%甲酸或醋酸或其它有机酸，转 5-20分钟； 0.5%-2.0%硫酸或盐酸或其它无机酸， 3%-100%废辂液， 0%-0.3%特殊制剂，转 70-120分钟；然后进行辂鞣，工艺是： 0.5%-2%辂粉，转 10-40分钟； 0.5%-3.5%辂粉，转 30-90 分钟； 0.2%-1.2%甲酸钠或其它盐类，转 30分钟左右； 0.10%-0.55%提碱齐 ^，转 2.0-4.5小时; 20%-80%废辂液， 0%-0.3%特殊制剂，鼓内升温至 28°C-42°C (将废辂液加温后再加入转鼓或先将废辂液加入转鼓中再整体升温均可），转 2-4小时；辂鞣结束废液排入储液池或储液罐，应每次化验废液中辂含量及 pH值，根据化验结果确定辂粉的加入量和调废液 pH值时加酸量，还应定期检测废液中的微生物数量，一般循环三至五次检测一次，主要检测霉菌数量，根据检测结果确定防霉剂的用量； (6) Recycling of the waste liquid from the pickling and tanning process: Set up a pickling and tanning waste liquid storage pool or tank next to the pickling and tanning drum. The storage tank should preferably be 2-8 meters deep underground. In order to facilitate temperature control, it is best to have a backup pool or tank. The waste liquid from the pickling and tanning process is filtered to remove the solids in the waste liquid and then discharged into the waste liquid storage pool or tank. Stir evenly to prepare for the next batch. For pickling and tanning of skins, the amount of salt added during the pickling process is zero. A small amount (0%-5%) of salt or other substances that can inhibit acid swelling can also be added, and the tanning waste liquid is used for the pickling process. Yes: Based on the weight of the gray skin, 3%-100% waste liquid, use acid to adjust the pH value of the waste liquid to 0. 3-5. 0, 0%-0.3% special preparation, 0%-5% salt, 0.05 %-0.3% antifungal agent, turn for 5-30 minutes; 0%-2.0% formic acid or acetic acid or other organic acids, turn for 5-40 minutes; 0%-3.5% sulfuric acid or hydrochloric acid or other inorganic acids, divide equally into two to ten Add each time, with an interval of 5-15 minutes each time, and rotate for 40-120 minutes; 0%-1.0% fatliquor, rotate for about 30 minutes, and stop for 0.5-2 hours; the process can also be adjusted to: 0%-5% salt, 0.05%-0.3% antifungal agent, incubate for 5-30 minutes; 0%-2.0% formic acid or acetic acid or other organic acids, incubate for 5-20 minutes; 0.5%-2.0% sulfuric acid or hydrochloric acid or other inorganic acids, 3%- 100% waste liquor, 0%-0.3% special preparation, rotate for 70-120 minutes; then carry out tanning, the process is: 0.5%-2% powder, rotate for 10-40 minutes; 0.5%-3.5% powder, Turn for 30-90 minutes; 0.2%-1.2% sodium formate or other salts, turn for about 30 minutes; 0.10%-0.55% alkaline solution, turn for 2.0-4.5 hours; 20%-80% waste liquid, 0%- 0.3% special preparation, heat the drum to 28°C-42°C (heat the waste liquid and then add it to the drum, or add the waste liquid to the drum first and then raise the temperature as a whole), and rotate for 2-4 hours ; The waste liquid after tanning is discharged into the liquid storage pool or tank. The content and pH value of the waste liquid should be tested each time, based on Determine the amount of flour added and the amount of acid added when adjusting the pH value of the waste liquid based on the test results. The number of microorganisms in the waste liquid should also be tested regularly. Generally, the test is performed once every three to five times. The main purpose is to detect the number of molds and determine prevention based on the test results. The dosage of fungus;

( 7 ) 复鞣工序的废液循环再利用：在复鞣转鼓旁设置复鞣废液储液池或储液罐，来自复鞣工序的废液滤去废液中固形物后排入复鞣废液储液池或储液罐，搅拌均匀，以备用于下批削匀革的复鞣；利用复鞣废液进行复鞣的工艺是：以削匀革重量计，用盐酸或硫酸或其它酸类物质将复鞣废液的 pH值调至 0. 7-3. 5， 3%-250%复鞣废液， 0%-0.3%特殊制剂，温度调至 32°C-42°C， 0.1%-0.5%甲酸或醋酸，转 20-50分钟； 0.5%-2.5%丙烯酸复鞣剂或其它复鞣剂，转 10-40分钟； 0.5%-2.0%辂粉， 0.1%-0.6%加脂剂，转 30-90分钟； 0.5%-1.5%脂肪醛，转 20-50 分钟; 0.3%-1.0%甲酸钠或醋酸钠， 0.1%-0.5%小苏打，转 30-90分钟，然后转 10分钟 /停 50分钟，转停结合进行 3-8次，或停鼓过夜， pH值要求 2.8-4.8; 复鞣结束废液排入储液池或储液罐，应定期化验废液中辂含量及 pH值，定期检测废液中的微生物数量，一般循环三至五次检测一次； (7) Recycling of waste liquid from the retanning process: Set up a retanning waste liquid storage pool or tank next to the retanning drum. The waste liquid from the retanning process is filtered to remove the solids in the waste liquid and then discharged into the retanning drum. Tanning waste liquid storage pool or tank, stir evenly to prepare for retanning of the next batch of shaved leather; The process of using retanning waste liquid for retanning is: based on the weight of the shaved leather, use hydrochloric acid or sulfuric acid or Other acidic substances adjust the pH value of the retanning waste liquid to 0.7-3.5, 3%-250% retanning waste liquid, 0%-0.3% special preparation, and adjust the temperature to 32°C-42°C , 0.1%-0.5% formic acid or acetic acid, rotate for 20-50 minutes; 0.5%-2.5% acrylic retanning agent or other retanning agent, rotate for 10-40 minutes; 0.5%-2.0% flour, 0.1%-0.6% Fatliquor, turn for 30-90 minutes; 0.5%-1.5% fatty aldehyde, turn for 20-50 minutes; 0.3%-1.0% sodium formate or sodium acetate, 0.1%-0.5% baking soda, turn for 30-90 minutes, then turn 10 minutes/stop for 50 minutes, 3-8 times of turning and stopping, or stop the drum overnight, the pH value is required to be 2.8-4.8; the waste liquid after retanning is discharged into the liquid storage pool or tank, and the waste liquid should be tested regularly for content and pH value, regularly detect the number of microorganisms in the waste liquid, and generally test once every three to five cycles;

( 8 ) 中和工序的废液循环再利用：在中和转鼓旁设置中和废液储液池或储液罐，来自中和工序的废液滤去废液中固形物后排入中和废液储液池或储液罐，搅拌均匀，以备用于下批削匀革的中和；利用中和废液进行中和的工艺是：以削匀革重量计， 3%-250%中和废液， 0%-0.3%特殊制剂，温度调至 32°C-35 °C， 1.0%-4.0%中和单宁， 0.5%-3.5%甲酸钠，转 20-40分钟； 0.2%-2.0%小苏打， 0.5%-5.0%加脂剂，转 30-60分钟，要求： pH值 4.0-6.5，切口透心；中和结束废液排入储液池或储液罐； (8) Waste liquid recycling in the neutralization process: Set up a neutralization waste liquid storage pool or tank next to the neutralization drum. The waste liquid from the neutralization process is filtered out of the solid matter in the waste liquid and then discharged into the neutralization drum. And the waste liquid storage pool or liquid storage tank, stir evenly to prepare for the neutralization of the next batch of shaved leather; The process of using neutralization waste liquid for neutralization is: based on the weight of the shaved leather, 3%-250% Neutralized waste liquid, 0%-0.3% special preparation, adjust temperature to 32°C-35°C, 1.0%-4.0% neutralized tannin, 0.5%-3.5% sodium formate, rotate for 20-40 minutes; 0.2%- 2.0% baking soda, 0.5%-5.0% fatliquor, turn for 30-60 minutes, requirements: pH value 4.0-6.5, incision is transparent; after neutralization, the waste liquid is discharged into the liquid storage pool or liquid storage tank;

(9 ) 染色工序废液循环再利用：在染色转鼓旁设置多个废液储液池或储液罐，不同色泽采用不同的储液池或储液罐，来自染色工序的废液滤去废液中固形物后排入相应色泽储液池或储液罐，搅拌均匀，以备用于下批削匀革的染色; 利用染色废液进行染色的工艺是：以削匀革重量计， 3%-200%染色废液， 0%-0. 3% 特殊制剂，温度调至 30 °C， 0. 5%-5. 0%丙烯酸复鞣剂，转 15 -40分钟； 0. 5%- 6. 0% 双聚氰胺复鞣剂， 0. 5%-5. 0%荆树皮栲胶， 0. 5%-4. 0%亚硫酸化植物油，转 30 -60 分钟； 0. 5%-4. 0%染料， 0. 5%-5. 0%复合型加脂剂，转 40 -80分钟，要求：切口透心；染色结束废液排入同一色泽储液池或储液罐。 (9) Recycling of waste liquid from the dyeing process: Set up multiple waste liquid storage pools or tanks next to the dyeing drum. Different pools or tanks are used for different colors. The waste liquid from the dyeing process is filtered out. Solids in waste liquid After the shapes are formed, drain them into the corresponding color storage pool or tank, stir evenly, and prepare for the dyeing of the next batch of shaved leather; the dyeing process using dyeing waste liquid is: based on the weight of the shaved leather, 3%-200 % dyeing waste liquid, 0%-0. 3% special preparation, adjust the temperature to 30 °C, 0. 5%-5. 0% acrylic retanning agent, turn for 15-40 minutes; 0. 5%- 6. 0 % Dipolycyanamide retanning agent, 0. 5%-5. 0% wattle bark tannin, 0. 5%-4. 0% sulfite vegetable oil, turn for 30-60 minutes; 0. 5%-4 . 0% dye, 0. 5%-5. 0% compound fatliquor, turn for 40-80 minutes, requirements: The incision is transparent; the waste liquid after dyeing is discharged into the same color storage pool or liquid storage tank.

2、经过宝斯卡（商丘）化工有限公司制革车间的实际大生产使用证明，该废水循环工艺稍加变动后或不加变动均可适用于制革厂现有大生产工艺流程。 2. It has been proved by the actual large-scale production use in the tanning workshop of Baoska (Shangqiu) Chemical Co., Ltd. that the wastewater recycling process can be applied to the existing large-scale production process of the tannery with or without slight changes.

3、该废水循环工艺所生产的成品革松面率更低，丰满度更好，并可以根据皮革厂具体情况简化工艺和设备，如某些厂无场地或设备条件，可以不挖储液池，用储液罐，也可部分工序循环使用废水（仅需稍加调整工艺参数即可）。 3. The finished leather produced by this wastewater recycling process has a lower loose surface rate and better fullness. The process and equipment can be simplified according to the specific conditions of the tannery. If some factories do not have the space or equipment conditions, they do not need to dig a liquid storage tank. , using a liquid storage tank, wastewater can also be recycled in part of the process (just adjust the process parameters slightly).

4、在实际生产中，根据现场情况采用鼓外池内或罐内升降温也可在鼓内实现升降温过程，可用蒸汽加温亦可使用电加热，可用超载转鼓亦可用普通转鼓。 4. In actual production, according to the on-site conditions, the temperature can be raised or lowered in the pool outside the drum or in the tank, or the temperature raising and cooling process can be realized inside the drum. Steam heating or electric heating can be used, and overloaded drums or ordinary drums can be used.

5、该废水循环工艺用不锈钢转鼓进行浸酸辂鞣或储存废液时不增加废液中的金属（镍、辂）含量，若用新水则明显增加废液中及皮革中的金属含量，从而大大缩短不锈钢转鼓的寿命，当循环次数增加时，可在主浸水或浸灰时适当增减酶制剂或其它材料的用量以取得更好的效果。 5. This wastewater recycling process uses stainless steel drums for pickling tanning or storing waste liquid without increasing the metal (nickel, tanning) content in the waste liquid. If new water is used, the metal content in the waste liquid and leather will be significantly increased. , thus greatly shortening the life of the stainless steel drum. When the number of cycles increases, the amount of enzyme preparations or other materials can be appropriately increased or decreased during the main water immersion or liming to achieve better results.

6、如权利要求 1所述的一种工艺及设备更加简化的新型制革工艺，其特征在于在染色转鼓旁设置多个废液储液池或储液罐，不同色泽采用不同的储液池或储液罐。 6. A new leather-making process with more simplified processes and equipment as claimed in claim 1, characterized in that multiple waste liquid storage pools or storage tanks are provided next to the dyeing drum, and different liquid storage tanks are used for different colors. Pool or reservoir.

7、如权利要求 1所述的一种工艺及设备更加简化的新型制革工艺，其特征在于每个储液池或储液罐都安装有搅拌装置，亦可进行人工搅拌。 7. A new leather-making process with more simplified processes and equipment as claimed in claim 1, characterized in that each liquid storage pool or liquid storage tank is equipped with a stirring device, and manual stirring can also be performed.

8、如权利要求 1所述的一种工艺及设备更加简化的新型制革工艺，其特征在于经预浸水及浸灰后的皮进行去肉及片皮，去肉和片皮过程中产生的废液分别收集入相应预浸水和浸灰废液储液池或储液罐以备循环再利用。 8. A new leather-making process with more simplified processes and equipment as claimed in claim 1, characterized in that After pre-soaking and liming, the skin is removed and skinned. The waste liquid generated during the process of removing meat and skin is collected into the corresponding pre-soaked water and liming waste liquid storage tanks or tanks for recycling. .

9、如权利要求 1所述的一种工艺及设备更加简化的新型制革工艺，其特征在于预浸水、主浸水和浸灰工序可采用同一个转鼓，在转鼓旁分别设置预浸水、主浸水和浸灰废液储液池或储液罐，以阀门的方式或其它分流方式控制转鼓向各储液池或储液罐进行废液排放，类似的，脱灰软化和浸酸辂鞣工序可采用同一个转鼓，复鞣、中和及染色工序可采用同一个转鼓。 9. A new leather-making process with more simplified technology and equipment as claimed in claim 1, characterized in that the pre-soaking, main water-soaking and liming processes can use the same drum, and the pre-soaking water, main water immersing and liming processes are respectively provided next to the rotating drum. The main soaking and liming waste liquid storage pool or liquid storage tank controls the drum to discharge the waste liquid to each liquid storage pool or liquid storage tank through valves or other diverting methods. Similarly, the deliming, softening and pickling boilers The same drum can be used for the tanning process, and the same drum can be used for the retanning, neutralizing and dyeing processes.

10、如权利要求 1所述的一种工艺及设备更加简化的新型制革工艺，其特征在于根据各废液储液池或储液罐中废液的粘稠程度定期对废液进行清洁化处理，用压滤的方式对废液进行清洁化处理，经压滤分离出的废固物用于填坑或制砖或其它用途，分离出的废液收集入各废液储液池或储液罐以备循环再利用，对废液清洁化处理的周期较传统处理方法长，且处理更简易。 10. A new leather-making process with more simplified technology and equipment as claimed in claim 1, characterized in that the waste liquid is regularly cleaned according to the viscosity of the waste liquid in each waste liquid storage pool or liquid storage tank. Treatment, use filter press to clean the waste liquid. The waste solids separated by filter press are used for pit filling or brick making or other purposes. The separated waste liquid is collected into each waste liquid storage tank or storage tank. The liquid tank is ready for recycling. The cycle of cleaning and treatment of waste liquid is longer than that of traditional treatment methods, and the treatment is easier.

11、如权利要求 1所述的一种工艺及设备更加简化的新型制革工艺，其特征在于经预浸水、主浸水、浸灰、复灰、脱灰软化、浸酸辂鞣、复鞣、中和及染色工序处理后的皮免去常规水洗步骤，亦可进行水洗，并将水洗废液进行循环再利用，当循环利用灰皮的水洗废液时应加入酸类物质将其 pH值调至 5-11. 5之间。 11. A new leather-making process with more simplified technology and equipment as claimed in claim 1, characterized by pre-soaking, main water-soaking, liming, re-liming, deliming and softening, pickling, tanning, re-tanning, The leather after neutralization and dyeing processes can be exempted from conventional water washing steps. It can also be washed with water and the washing waste liquid can be recycled. When recycling the washing waste liquid of gray leather, acids should be added to adjust its pH value. to 5-11. 5.

12、如权利要求 1所述的一种工艺及设备更加简化的新型制革工艺，其特征在于在辂鞣废液储液池或储液罐旁再设置备用池或罐，其它工序如浸灰和脱灰软化工序等亦可设置备用池或罐。 12. A new tanning process with more simplified processes and equipment as claimed in claim 1, characterized in that a backup pool or tank is provided next to the tanning waste liquid storage pool or tank, and other processes such as liming Backup pools or tanks can also be set up for deliming and softening processes.

13、如权利要求 1所述的一种工艺及设备更加简化的新型制革工艺，其特征在于各种化学材料的用量及品种、废液用量、升降温幅度、操作时间、操作顺序、废液及化学材料的加入次数等均可根据使用者具体情况而做出大幅度调整，亦可根据使用者具体情况选择其它化学材料以替代上述材料。 13. A new leather-making process with more simplified processes and equipment as claimed in claim 1, characterized by the amount and type of various chemical materials, the amount of waste liquid, the temperature rise and fall range, operation time, operation sequence, waste liquid and the number of additions of chemical materials can be greatly adjusted according to the specific conditions of the user, and Other chemical materials can be selected to replace the above materials according to the user's specific conditions.

14、如权利要求 1所述的一种工艺及设备更加简化的新型制革工艺，其特征在于在浸灰过程中，视毛根脱落程度及时利用滤毛机滤毛，如所做原皮为山羊皮、绵羊皮和猪皮时，大部分毛的去除在鼓外进行，所剩部分毛亦可在浸灰过程中使用滤毛机滤出。 14. A new leather-making process with more simplified technology and equipment as claimed in claim 1, characterized in that during the liming process, a hair filtering machine is used to filter hair in a timely manner depending on the degree of hair root shedding. For example, the raw leather is goat skin. , sheepskin and pigskin, most of the wool is removed outside the drum, and the remaining hair can also be filtered out using a wool filter during the liming process.

15、如权利要求 1所述的一种工艺及设备更加简化的新型制革工艺，其特征在于浸酸辂鞣过程中，盐的加入量为 0，亦可加入少量（0%-5%) 的盐类或其它有抑制酸肿作用的物质。 15. A new tanning process with more simplified technology and equipment as claimed in claim 1, characterized in that during the pickling tanning process, the amount of salt added is 0, or a small amount (0%-5%) can be added. Salts or other substances that can inhibit acid swelling.

16、如权利要求 1所述的一种工艺及设备更加简化的新型制革工艺，其特征在于辂粉的总用量为 2. 0%-5. 5%。 16. A new leather-making process with more simplified technology and equipment as claimed in claim 1, characterized in that the total amount of leather powder is 2.0%-5.5%.

17、如权利要求 1所述的一种工艺及设备更加简化的新型制革工艺，其特征在于各工序产生的废液可以不加特殊制剂处理，也可加入某种特殊制剂，加入量为 0%-0. 3% (以废液量为基数）。 17. A new leather-making process with more simplified processes and equipment as claimed in claim 1, characterized in that the waste liquid produced in each process can be treated without adding special preparations, or some special preparations can be added, and the addition amount is 0 %-0. 3% (based on waste liquid volume).