CN113528717A - Pickling and tanning integrated process for leather production and processing - Google Patents
Pickling and tanning integrated process for leather production and processing Download PDFInfo
- Publication number
- CN113528717A CN113528717A CN202110795090.8A CN202110795090A CN113528717A CN 113528717 A CN113528717 A CN 113528717A CN 202110795090 A CN202110795090 A CN 202110795090A CN 113528717 A CN113528717 A CN 113528717A
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- leather
- tanning
- pickling
- weight
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- 239000010985 leather Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000005554 pickling Methods 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 34
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 33
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 102000004190 Enzymes Human genes 0.000 claims description 13
- 108090000790 Enzymes Proteins 0.000 claims description 13
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 7
- 235000019253 formic acid Nutrition 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 235000015217 chromium(III) sulphate Nutrition 0.000 claims description 4
- 239000011696 chromium(III) sulphate Substances 0.000 claims description 4
- 230000003449 preventive effect Effects 0.000 claims description 4
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- DSHWASKZZBZKOE-UHFFFAOYSA-K chromium(3+);hydroxide;sulfate Chemical compound [OH-].[Cr+3].[O-]S([O-])(=O)=O DSHWASKZZBZKOE-UHFFFAOYSA-K 0.000 claims description 3
- 229910000356 chromium(III) sulfate Inorganic materials 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 238000006722 reduction reaction Methods 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 102000004142 Trypsin Human genes 0.000 claims 1
- 108090000631 Trypsin Proteins 0.000 claims 1
- 239000012588 trypsin Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 7
- 230000001360 synchronised effect Effects 0.000 abstract description 7
- 239000002351 wastewater Substances 0.000 abstract description 6
- 230000005611 electricity Effects 0.000 abstract description 4
- 239000012466 permeate Substances 0.000 abstract description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 230000001810 trypsinlike Effects 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
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
- C14C1/00—Chemical treatment prior to tanning
- C14C1/08—Deliming; Bating; Pickling; Degreasing
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14B—MECHANICAL TREATMENT OR PROCESSING OF SKINS, HIDES OR LEATHER IN GENERAL; PELT-SHEARING MACHINES; INTESTINE-SPLITTING MACHINES
- C14B1/00—Manufacture of leather; Machines or devices therefor
- C14B1/44—Mechanical treatment of leather surfaces
- C14B1/56—Ornamenting, producing designs, embossing
-
- 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
- C14C11/00—Surface finishing of leather
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/04—Mineral tanning
- C14C3/06—Mineral tanning using chromium compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention discloses a pickling and tanning integrated process for leather production and processing, belongs to the technical field of clean leather manufacturing, and particularly comprises deliming, softening and pickling and tanning. The invention mainly carries out the pickling and tanning steps in the leather production synchronously, improves the production efficiency, greatly reduces the salt dosage of the pickling process, reduces the discharge of chloride ions in wastewater, improves the absorption efficiency of a chrome tanning agent, improves the fullness and compactness of tanned leather, and can reduce the discharge of chloride ions by 50 percent; the absorption rate of the chrome tanning agent is improved, the chrome emission concentration is reduced by 40-50%, and the electricity is saved by 20%. The characteristic that the chrome tanning agent contains salt and slightly slowly permeates when being synchronized with sulfuric acid is effectively utilized in the technology, the chrome absorption rate is creatively improved, the action time of acid on leather damage is shortened, and the fullness and compactness of the processed leather are improved.
Description
Technical Field
The invention belongs to the technical field of clean leather manufacturing, and particularly relates to a pickling and tanning integrated process for leather production and processing.
Background
The traditional tanning process uses water as medium to process the hide into leather through chemical, physical and mechanical action. Tanning and pretreatment processes in leather making are carried out in a wide pH range, such as: soaking, unhairing, liming, deliming, softening, pickling, tanning and the like, and liming and deliming for many times; the repeated actions of acid, alkali and salt in the processing processes of pickling, alkali extraction and the like cause the salt content in the tannery wastewater to be very high. Meanwhile, the cortex is damaged to different degrees by repeated actions of acid, alkali and salt.
The existing tanning pickling and tanning process has some non-negligible environmental problems, and mainly (1) in the pickling process, sodium chloride with the tare weight of 5-8% (w/w) is used for inhibiting acid swelling (acid swelling) of pickling. The use of a large amount of salt can cause the bare leather to be dehydrated, so that the finished leather is flat and not full; on the other hand, the salt in the wastewater is polluted; (2) acid soluble protein and salt soluble protein in the pelts enter the water body in the pickling process, so that the pollution load of COD and BOD in the wastewater is increased; (3) the utilization rate of the chrome tanning agent in the tanning process is low, and the like. The application of the process method makes the subsequent sewage treatment difficult.
The emission standard of water pollutants for the leather and fur processing industry (GB 30486-2013) issued by the national environmental protection ministry in 2013 has strict limit values on chloride ions in wastewater directly and indirectly discharged by leather and fur enterprises.
Disclosure of Invention
Compared with the traditional steps, the technical problem to be solved by the invention is that the synchronous method can reduce the emission of chloride ions by 50 percent; the absorptivity of the chrome tanning agent is improved, and the chromium emission concentration is reduced by 40-50%; the electricity is saved by 20%, the characteristic that the chrome tanning agent contains salt and permeates slightly slowly when being synchronized with sulfuric acid is effectively utilized technically, the chrome absorption rate is creatively improved, the action time of acid on leather damage is shortened, and the fullness and compactness of the processed leather are improved.
The invention adopts the following technical scheme for solving the technical problems:
a pickling and tanning integrated process for leather production and processing specifically comprises the following steps:
step 1, deashing: deliming the naked leather after being cut with the gray leather under the action of an ammonium-free deliming agent, wherein the dosage of the ammonium-free deliming agent is 1.5 +/-relative to the weight of the naked leather;
step 2, softening: softening under the action of softening enzyme, wherein the dosage of the softening enzyme is 0.3-1% of the tare weight;
step 3, pickling and tanning: the pickled tanning treatment is carried out on the softened pelts under the action of pickling chrome tanning by an integrated method, which comprises the following steps:
adding normal temperature water into the tanning drum at the temperature of 20-22 ℃, wherein the normal temperature water accounts for 30% of the weight of the leather;
adding 3-4% of industrial salt by weight, and rotating for 10 minutes;
adding formic acid which is 0.5 percent of the tare weight, and rotating for 10 minutes;
adding sulfuric acid which accounts for 0.4-0.6% of the weight of the leather, simultaneously adding a chrome tanning agent which accounts for 2% of the weight of the leather, and rotating for 90 minutes;
adding a chrome tanning agent which accounts for 3-4% of the weight of the leather, and rotating for 90 minutes;
adding an alkali extracting agent which is 0.3 plus or minus percent of the tare weight, and rotating for 60 minutes;
adding mildew preventive which is 0.1-0.2% of the tare weight, and rotating for 60 minutes;
adding hot water which is 50 +/-50 percent of the tare weight, and rotating for 180 minutes;
step 4, finishing: and (4) carrying out post finishing on the tanned wet blue leather to obtain finished leather.
As a further preferable scheme of the pickling and tanning integrated process for leather production and processing, in the step 1, the ammonium-free deliming agent is a macromolecular organic acid or/and a polysuccinamide deliming agent;
as a further preferable scheme of the pickling and tanning integrated process for leather production and processing, in the step 2, the softening enzyme is low-temperature trypsin-like softening enzyme, and the unit of the activity of the softening enzyme is 1000-1500 u/g;
as a further preferable scheme of the pickling and tanning integrated process for leather production and processing, the chrome tanning agent adopts basic chromium sulfate [ cr (oh) SO4] and is generated by sodium dichromate, proper amount of sulfuric acid and sufficient reducing agent through full reduction reaction.
Compared with the prior art, the invention adopting the technical scheme has the following technical effects:
1. the invention mainly carries out the two steps of pickling and tanning synchronously in the leather production, thereby improving the production efficiency, greatly reducing the salt dosage of the pickling process, reducing the discharge of chloride ions in waste water, improving the absorption efficiency of a chrome tanning agent and improving the fullness and compactness of tanned leather;
2. compared with the traditional steps, the synchronous method can reduce the emission of chloride ions by 50 percent; the absorptivity of the chrome tanning agent is improved, and the chromium emission concentration is reduced by 40-50%; the electricity is saved by 20 percent. The characteristic that the chrome tanning agent contains salt and slightly slowly permeates when being synchronized with sulfuric acid is effectively utilized in the technology, the chrome absorption rate is creatively improved, the action time of acid on leather damage is shortened, and the fullness and compactness of the processed leather are improved.
Detailed Description
The technical scheme of the invention is further explained in detail as follows:
a pickling and tanning integrated process for leather production and processing specifically comprises the following steps:
deliming and softening: according to the characteristics of the product, low-temperature softening enzyme is adopted for softening treatment, the dosage of the softening enzyme is 0.3-1% of the tare weight, and the softening time (rotation of a rotary drum) is 30-60 minutes (equivalent to the softening strength of the conventional low-temperature softening enzyme). The temperature is preferably 30-32 ℃, the deashing needs to be thorough, and the pH value of the bath liquid is 8.0-8.5. The rotating speed of the rotary drum is the same as the requirement of the prior art;
pickling and tanning:
the traditional pickling-tanning process:
pickling: adding water at normal temperature into a tanning drum: 30-50%, temperature: 20-22 ℃;
addition of technical salt (NaCl): rotating for 10 minutes at the speed of 5-8%;
addition of formic acid (HCOOH): 0.5% rotation for 10 minutes;
addition of sulfuric acid (H2SO 4): rotating for 120 minutes at 0.4-0.8%;
tanning: adding a chrome tanning agent: rotating for 120 minutes by 5-7 percent;
adding an alkali extracting agent: rotating for 120 minutes at 0.3-0.5%;
adding a mildew preventive: rotating for 60 minutes at 0.1-0.2%;
adding hot water: rotating for 180 minutes at 50% +/-;
the pickled tanning treatment is carried out on the softened pelts under the action of pickling chrome tanning by an integrated method, which comprises the following steps:
adding normal temperature water into the tanning drum at the temperature of 20-22 ℃, wherein the normal temperature water accounts for 30% of the weight of the leather;
adding 3-4% of industrial salt by weight, and rotating for 10 minutes;
adding formic acid which is 0.5 percent of the tare weight, and rotating for 10 minutes;
adding sulfuric acid which accounts for 0.4-0.6% of the weight of the leather, simultaneously adding a chrome tanning agent which accounts for 2% of the weight of the leather, and rotating for 90 minutes;
adding a chrome tanning agent which accounts for 3-4% of the weight of the leather, and rotating for 90 minutes;
adding an alkali extracting agent which is 0.3 plus or minus percent of the tare weight, and rotating for 60 minutes;
adding mildew preventive which is 0.1-0.2% of the tare weight, and rotating for 60 minutes;
adding hot water to 50% +/-the tare weight, and rotating for 180 minutes;
step 4, finishing: and (4) carrying out post finishing on the tanned wet blue leather to obtain finished leather.
Compared with the traditional steps, the synchronous method can reduce the emission of chloride ions by 50 percent; the absorptivity of the chrome tanning agent is improved, and the chromium emission concentration is reduced by 40-50%; the electricity is saved by 20 percent. The characteristic that the chrome tanning agent contains salt and slightly slowly permeates when being synchronized with sulfuric acid is effectively utilized in the technology, the chrome absorption rate is creatively improved, the action time of acid on leather damage is shortened, and the fullness and compactness of the processed leather are improved.
Chrome tanning agents are known by the chemical name basic chromium sulphate [ cr (oh) SO4] and are typically produced by the intensive reduction of sodium dichromate, a suitable amount of sulphuric acid and a sufficient amount of reducing agent (e.g. SO 2). 55 percent of powdery chrome tanning agent basic chromium sulfate for commodities, 25 percent of sodium sulfate, and 10 percent of crystal water and free water respectively.
The present invention may be embodied in other forms without departing from the spirit or essential characteristics thereof, and reference is made to the appended claims, rather than to the foregoing specification, as indicating the scope of the invention.
Claims (4)
1. A pickling and tanning integrated process for leather production and processing is characterized in that: the method specifically comprises the following steps:
step 1, deashing: deliming the naked leather after being cut with the gray leather under the action of an ammonium-free deliming agent, wherein the dosage of the ammonium-free deliming agent is 1.5 +/-relative to the weight of the naked leather;
step 2, softening: softening under the action of softening enzyme, wherein the dosage of the softening enzyme is 0.3-1% of the tare weight;
step 3, pickling and tanning: the pickled tanning treatment is carried out on the softened pelts under the action of pickling chrome tanning by an integrated method, which comprises the following steps:
adding normal temperature water into the tanning drum at the temperature of 20-22 ℃, wherein the normal temperature water accounts for 30% of the weight of the leather;
adding 3-4% of industrial salt by weight, and rotating for 10 minutes;
adding formic acid which is 0.5 percent of the tare weight, and rotating for 10 minutes;
adding sulfuric acid which accounts for 0.4-0.6% of the weight of the leather, simultaneously adding a chrome tanning agent which accounts for 2% of the weight of the leather, and rotating for 90 minutes;
adding a chrome tanning agent which accounts for 3-4% of the weight of the leather, and rotating for 90 minutes;
adding an alkali extracting agent which is 0.3 plus or minus percent of the tare weight, and rotating for 60 minutes;
adding mildew preventive which is 0.1-0.2% of the tare weight, and rotating for 60 minutes;
adding hot water which is 50 +/-50 percent of the tare weight, and rotating for 180 minutes;
step 4, finishing: and (4) carrying out post finishing on the tanned wet blue leather to obtain finished leather.
2. The integrated pickling and tanning process for leather production and processing according to claim 1, characterized in that: in the step 1, the ammonium-free deliming agent is a macromolecular organic acid or/and a polysuccinamide deliming agent.
3. The integrated pickling and tanning process for leather production and processing according to claim 1, characterized in that: in the step 2, the softening enzyme is low-temperature trypsin softening enzyme, and the unit of the activity of the softening enzyme is 1000-1500 u/g.
4. The integrated pickling and tanning process for leather production and processing according to claim 1, characterized in that: the chrome tanning agent is prepared by adopting basic chromium sulfate [ Cr (OH) SO4] and through full reduction reaction of sodium dichromate, a proper amount of sulfuric acid and a sufficient amount of reducing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110795090.8A CN113528717A (en) | 2021-07-14 | 2021-07-14 | Pickling and tanning integrated process for leather production and processing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110795090.8A CN113528717A (en) | 2021-07-14 | 2021-07-14 | Pickling and tanning integrated process for leather production and processing |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113528717A true CN113528717A (en) | 2021-10-22 |
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ID=78099068
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110795090.8A Pending CN113528717A (en) | 2021-07-14 | 2021-07-14 | Pickling and tanning integrated process for leather production and processing |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113528717A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103773906A (en) * | 2014-01-21 | 2014-05-07 | 徐州南海皮厂有限公司 | Integrated waterproof leather preparation method |
| CN104593528A (en) * | 2014-12-30 | 2015-05-06 | 海宁瑞星皮革有限公司 | High pH value fast leather tanning method |
| CN105063253A (en) * | 2015-08-10 | 2015-11-18 | 四川大学 | Salt-free high-chrome-absorption chrome tanning method for animal skin and application of salt-free high-chrome-absorption chrome tanning method |
-
2021
- 2021-07-14 CN CN202110795090.8A patent/CN113528717A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103773906A (en) * | 2014-01-21 | 2014-05-07 | 徐州南海皮厂有限公司 | Integrated waterproof leather preparation method |
| CN104593528A (en) * | 2014-12-30 | 2015-05-06 | 海宁瑞星皮革有限公司 | High pH value fast leather tanning method |
| CN105063253A (en) * | 2015-08-10 | 2015-11-18 | 四川大学 | Salt-free high-chrome-absorption chrome tanning method for animal skin and application of salt-free high-chrome-absorption chrome tanning method |
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Application publication date: 20211022 |
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