CN104593528A - High pH value fast leather tanning method - Google Patents
High pH value fast leather tanning method Download PDFInfo
- Publication number
- CN104593528A CN104593528A CN201410840697.3A CN201410840697A CN104593528A CN 104593528 A CN104593528 A CN 104593528A CN 201410840697 A CN201410840697 A CN 201410840697A CN 104593528 A CN104593528 A CN 104593528A
- Authority
- CN
- China
- Prior art keywords
- leather
- agent
- pelt
- rotary drum
- value
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
- C14C1/06—Facilitating unhairing, e.g. by painting, by liming
-
- 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
- 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
-
- 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
-
- 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
- C14C3/08—Chemical tanning by organic agents
-
- 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
- C14C3/28—Multi-step processes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention discloses a high pH value fast leather tanning method. The high pH value fast leather tanning method mainly comprises the following steps: pre-treating bare leather, penetrating by using chrome tanning agent, extracting alkali and the like. Organic acids and salts of organic acid are used in the pre-treating step of the bare leather to reduce pH value of the bare leather around the isoelectric point so as to form effective masking, or organic acids and salts of organic acid are used to reduce pH value of the bare leather to 6+/-0.2 and 0.4-0.6wt% masking agent is added to the bare leather to form effective masking. In the chrome tanning step, positive chrome ions in the chrome tanning agent combine with peptide chain carboxyl ions R-COO- to form coordinate bonds to complete leather tanning. The high pH value fast leather tanning method provided in the invention has advantages such as short tanning time, is free of traditional acid etching process, and has small discharge of waste water with high chloride ion content, high use ratio of chrome tanning agent, high quality of finished leather and the like.
Description
Technical field
The present invention relates to a kind of leather tanning method, more specifically to the quick leather tanning method of a kind of high ph-values.
Background technology
Tradition leather production take water as medium, through chemistry, physics and mechanical effect, rawhide is processed as resultant Leather.The chemical treating process of tanning production carries out within the scope of very wide pH, as: immersion, liming, deliming, softening, pickling, tanning, neutralization etc., liming repeatedly, deliming, pickling, put forward the courses of processing such as alkali, the effect of acid repeatedly, alkali, salt makes the content of salt in leather-making waste water very high; Meanwhile, the damage that the effect of acid repeatedly, alkali, salt also makes cortex be subject in various degree.
In above-mentioned technique, pickling for the process that is absolutely necessary again leather tanning operation, the main purpose of traditional pickling procedure have following some:
(1) through the pelt pH of enzyme bating at alkaline range, generally about 8, and owse initial stage pH is generally about 3.0, if reduce its pH without pickling after enzyme bating just carry out tanning immediately, pelt will absorb acid and tannin molecule rapidly from owse; And the result of this rapid absorption, being the surperficial swelling that can cause pelt for pelt, is to cause chromium complex molecule in Chrome Tanning Liquor to be hydrolyzed rapidly for tanning solution; Finally cause tannin molecule to be combined rapidly with skin surface fiber and produce surface cross tan.
(2) can dispersion agent protofibril further, increase collagen reaction active group, be conducive to increasing tanning agent molecule and be combined with collagen.
(3) non-fibrous protein of intracutaneous can be removed further and collagen generating portion is dewatered, increasing the space between collegen filament, be conducive to infiltration and the combination of tanning agent molecule.
(4) carboxyl of collagen can be closed, strengthen the electropositivity of collagen, reduce the tanning agent molecule of positively charged chromic compound and the combination of collagen carboxyl; Be beneficial to tanning agent molecule endosmosis, prevent grain from crossing and tan, reaction formula is as Xia ﹕
As from the foregoing, can pickling process be well on for pelt, very crucial high-quality tanning, but, owing to employing the acid plumping (sour swelling) of the sodium chloride inhibition pickling of tare weight 5 ~ 8wt% in pickling process, the use of a large amount of salt, cause pelt dehydration on the one hand, make resultant Leather flat, not plentiful, the high-content chlorion that pickling causes on the other hand has also increased the weight of the intractability of leather-making waste water greatly; In addition, the acid-soluble protein in pickling process in pelt and salting-in protein enter water body also can make COD and the BOD pollution load in waste water rise.
In addition, in traditional leather tanning process, pickling and process for tanning need at least 20 hours usually, longevity of service and complex process.
Therefore, develop a kind of tanning time short, without traditional pickling procedure, very necessary without chlorine-contained wastewater discharge, leather tanning method that the utilization ratio quality that is high, resultant Leather of chrome tanning agent is high.
Summary of the invention
For the deficiencies in the prior art, the object of this invention is to provide a kind of tanning time short, without traditional pickling procedure, the high leather tanning method of utilization ratio quality that is high, resultant Leather without chlorine-contained wastewater discharge, chrome tanning agent.
The technical scheme that technical solution problem of the present invention adopts is: the quick leather tanning method of a kind of high ph-values, and described process for tanning comprises the following steps:
(1) pelt pre-treatment: the pelt obtained through immersion, liming, multiple ash, deashing and softening pre-treatment is put into rotary drum, with organic acid and organic acid salt, the pH value of described pelt is dropped to around iso-electric point, play masking effect;
(2) chrome tanning agent infiltration: appropriate sulfuric acid, formic acid and chromium powder are configured to chrome tanning agent, the main component of described chrome tanning agent is trivalent sun chromic compound, and the pH value of described chrome tanning agent is about 3; Joined by above-mentioned chrome tanning agent in the pelt processed through step 1, described chrome tanning agent penetrated into pelt completely through 80 ~ 100 minutes;
(3) chrome tanning: the chrome tanning agent of above-mentioned steps 2 penetrates in pelt, the trivalent sun chromium ion in described chrome tanning agent and the peptide chain carboxylic ions R – COO in collagen
–in conjunction with formation coordinate bond, the pH value of described pelt is reduced to 4.0 ~ 4.5;
(4) alkali is carried: the leather after above-mentioned steps 3 being processed continues rotary drum transfer 80 ~ 100 minutes, then 0.3 ~ 0.5wt% sodium bicarbonate is added, the pH value inside and outside leather is made evenly to remain on 3.5 ~ 3.8, add 100wt% water, temperature in rotary drum is risen to 37 ~ 39 DEG C, turn 3 hours again, pH value is 3.8 ~ 4.0, now surveys shrinkage temperature and can reach more than 95 DEG C.
In above-mentioned process for tanning, pelt adopts composite organic acid and organic acid salt pH value to be dropped to after around iso-electric point, the pH value of pelt can be made to reduce on the one hand, be conducive to the infiltration of chrome tanning agent molecule, prevent the peptide chain carboxylic ions R – COO in chrome tanning agent molecule and pelt
–rapid combination and produce surface cross tan; On the other hand, owing to not using the pickling procedure in traditional technology, the use of sodium-chlor in this process for tanning, is eliminated.
The quick leather tanning method of another kind of high ph-values, described process for tanning comprises the following steps:
(1) pelt pre-treatment: the pelt obtained through immersion, liming, multiple ash, deashing and softening pre-treatment is put into rotary drum, with organic acid and organic acid salt, the pH value of described pelt is down to 6 ± 0.2; The masking agent of 0.4 ~ 0.6wt% is added in above-mentioned pelt;
(2) chrome tanning agent infiltration: appropriate sulfuric acid, formic acid and chromium powder are configured to chrome tanning agent, the main component of described chrome tanning agent is trivalent sun chromic compound, and the pH value of described chrome tanning agent is about 3; Above-mentioned chrome tanning agent being joined the pH value processed through step 1 is in the pelt of 6 ± 0.2, forms complex compound between the trivalent sun chromium ion in described chrome tanning agent and the masking agent negatively charged ion in masking agent; The complex compound that described chrome tanning agent and masking agent are formed penetrated into pelt completely through 60 ~ 80 minutes;
(3) chrome tanning: described complex compound penetrates in pelt, when the pH value of described pelt is reduced to 4.2 ~ 4.5, the trivalent sun chromium ion in described chrome tanning agent and the peptide chain carboxylic ions R – COO in collagen
–in conjunction with formation coordinate bond; When the pH value of pelt continues to be down to 3.5 ~ 3.8, chrome tanning tentatively completes;
(4) alkali is carried: the leather after above-mentioned steps 3 being processed continues rotary drum transfer 60 ~ 80 minutes, then 0.1 ~ 0.2wt% sodium bicarbonate is added, the pH value inside and outside leather is made evenly to remain on 3.8 ~ 4.0, add 100wt% water, temperature in rotary drum is risen to 37 ~ 39 DEG C, turn 90 ~ 100 minutes again, now survey shrinkage temperature and can reach more than 95 DEG C.
In above-mentioned process for tanning, the Main Function of masking agent is the resistance to alkali ability that can improve chrome tanning agent, tannery can be carried out under higher pH and chrome tanning agent can not become the precipitation of oxyhydroxide, masking agent improves the stability of trivalent sun chromic compound in chrome tanning agent, produce the reason of this effect, instead of water molecules because masking agent negatively charged ion penetrates boundary in trivalent sun chromic compound, the structure of trivalent sun chromic compound and electric charge are changed, along with the minimizing of positive changes, the magnetism of collagen carboxyl anion in leather to positive chromium coordination ion also can correspondingly reduce, thus make the combination of chrome tanning agent and leather become mitigation, make chrome tanning agent can permeate in pelt and be uniformly distributed before being combined with collagen carboxyl anion.
When the trivalent sun chromic compound of suitable size penetrates into pelt and after being uniformly distributed, carboxylic ions R – COO electronegative on positive chromium coordination ion and collagen side chain
–between attract each other, when their distance reaches suitably near time, carboxylic ions R – COO
–just enter boundary and central ion coordination in chromic compound, generate firmly coordinate bond, thus complete leather tanning operation.
In above-mentioned process for tanning, described masking agent is wherein one or more the mixing in monocarboxylic acid and salt, di-carboxylic acid and salt thereof, hydroxycarboxylic acid and salt thereof.
To the further restriction of above-mentioned masking agent, described monocarboxylic acid is formic acid, acetic acid or propionic acid, and described di-carboxylic acid is oxalic acid or phthalic acid, and described hydroxycarboxylic acid is tartrate or citric acid; Described salt is the sodium salt of respective acids.
In above-mentioned process for tanning, in described step 1, be respectively formic acid and sodium formiate for the organic acid of adjust ph and organic acid salt.
Illustrate the pretreatment procedure of above-mentioned tannery, the immersion in described step 1 comprises pre-immersion and main immersion; Wet salted hide immerses in the solution containing 0.1 ~ 0.2wt% Soaking, 0.1 ~ 0.2wt% sterilant, 0.1 ~ 0.3wt% soda ash and 200wt% water under being specially normal temperature by described preimpregnation water, rotary drum for processing 90 ~ 100 minutes, carry out washing rear draining with 150wt% water, after pre-immersion, the pH value of body lotion is 7.0 ± 0.2; Fur through pre-immersion is carried out main immersion in containing the solution of 0.2 ~ 0.4wt% Soaking, 0.4 ~ 0.6wt% enzyme, 0.2 ~ 0.3wt% sterilant, 0.2 ~ 0.4wt% grease-removing agent and 150wt% water, in rotary drum for processing after 30 ~ 40 minutes, divide three times, all add 0.2 ~ 0.3wt% soda ash at every turn, the timed interval at every turn adding soda ash is 6 ~ 7 hours, and after main immersion, the pH value of body lotion is 9.3 ± 0.2.
The pretreatment procedure of above-mentioned tannery is illustrated, liming in described step 1 adopts micro-enzyme ash alkaline process to protect hair depilation, and detailed process is: by the fur after immersion process in the rotary drum for processing 2 hours containing 0.8 ~ 1.0wt% liming enzyme auxiliary agent, 0.3 ~ 0.5wt%NaHS, 0.1 ~ 0.2wt% soda ash and 250wt% water; Add 1.0 ~ 1.3wt% lime in above-mentioned rotary drum after, process 1 hour; 0.3 ~ 0.5wt%Na is added in above-mentioned rotary drum
2s and 0.7 ~ 0.9wt%NaHS, continues process 1 hour; Add 0.2 ~ 0.3wt% soda ash in above-mentioned rotary drum after, process 1 hour; Continue to add 1.5 ~ 2.5wt% lime and 0.1 ~ 0.2wt% poly-phosphate in above-mentioned rotary drum, process 1 hour; After finally adding 2.0 ~ 3.0wt% lime in above-mentioned rotary drum, continue process 22 hours; After liming process, the pH value of body lotion is 12.4 ± 0.1.
The pretreatment procedure of above-mentioned tannery is illustrated, multiple ash in described step 1 is specially: the leather after liming process is carried out drum, split, weigh after again drop in rotary drum, temperature in described rotary drum is 28 ~ 30 DEG C, 1.5 ~ 2.5wt% lime, 0.8 ~ 1.2wt% auxiliary liming agent and 250wt% water is added in described rotary drum, process after 18 hours, washing; The pH value of the body lotion after described multiple ash process is 9.6 ± 0.1.
The pretreatment procedure of above-mentioned tannery is illustrated, deashing and softening in described step 1 is specially: by the leather deashing and softening process 10 ~ 11 hours in rotary drum after multiple ash process, be placed with 1.2 ~ 1.6wt% without ammonia deliming agent, 1.2 ~ 1.5wt% macerating enzyme and 100wt% water in described rotary drum; Leather normal temperature after process washes 1 time, and then with water displacement wash 30 minutes, makes the pH value of body lotion be 7 ~ 8.
The invention has the beneficial effects as follows: compared with prior art, leather tanning method provided by the invention has the advantages such as tanning time is short, mineral acid pickling, Waste Water with High Chloride Ion Concentration quantity discharged utilization ratio that is few, chrome tanning agent are high without the need to using, the quality of resultant Leather is high.Adopt illiteracy to limit process, make chrome tanning agent just well can permeate at higher ph values and be uniformly distributed in pelt, make the combination of chrome tanning agent and leather become mitigation, prevent surperficial mistake to tan the generation of phenomenon; Meanwhile, in leather tanning method provided by the invention, whole tannery only needs 4 ~ 5 hours, is 1/4 ~ 1/3 (traditional technology at least needs 20 hours) of traditional technology.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
The quick leather tanning method of a kind of high ph-values, described process for tanning comprises the following steps:
(1) soak: comprise pre-immersion and main immersion, wet salted hide immerses in the solution containing 0.1wt% Soaking, 0.1wt% sterilant, 0.2wt% soda ash and 200wt% water under being specially normal temperature by described preimpregnation water, rotary drum for processing 90 minutes, carry out washing rear draining with 150wt% water, after pre-immersion, the pH value of body lotion is 7.0 ± 0.2; Fur through pre-immersion is carried out main immersion in the solution containing 0.3wt% Soaking, 0.5wt% enzyme, 0.2wt% sterilant, 0.3wt% grease-removing agent and 150wt% water, in rotary drum for processing after 30 minutes, divide three times, all add 0.2wt% soda ash at every turn, the timed interval at every turn adding soda ash is 6 ~ 7 hours, and after main immersion, the pH value of body lotion is 9.3 ± 0.2.
(2) liming: by the fur after above-mentioned immersion process the rotary drum for processing containing 0.9wt% liming enzyme auxiliary agent, 0.4wt%NaHS, 0.15wt% soda ash and 250wt% water 2 hours; Add 1.2wt% lime in above-mentioned rotary drum after, process 1 hour; 0.4wt%Na is added in above-mentioned rotary drum
2s and 0.8wt%NaHS, continues process 1 hour; Add 0.25wt% soda ash in above-mentioned rotary drum after, process 1 hour; Continue to add 2.0wt% lime and 0.15wt% poly-phosphate in above-mentioned rotary drum, process 1 hour; After finally adding 2.5wt% lime in above-mentioned rotary drum, continue process 22 hours; After liming process, the pH value of leather is 12.4 ± 0.1.
(3) multiple ash: the graywall after above-mentioned liming process is carried out drum, split, weighing, then again drop in rotary drum, temperature in described rotary drum is 28 ~ 30 DEG C, 2.0wt% lime, 1.0wt% auxiliary liming agent and 250wt% water is added in described rotary drum, process after 18 hours, washing; The pH value of the body lotion after described multiple ash process is 9.6 ± 0.1.
(4) deashing and softening: by the deashing and softening process 10 ~ 11 hours in rotary drum of the leather after above-mentioned multiple ash process, be placed with 1.4wt% in described rotary drum without ammonia deliming agent, 1.3wt% macerating enzyme and 100wt% water; Leather normal temperature after process washes 1 time, then uses water displacement wash 30 minutes, makes the pH value of body lotion be 7 ~ 8.
(5) pelt pre-treatment: the pelt obtained through immersion, liming, multiple ash, deashing and softening pre-treatment is put into rotary drum, with formic acid and sodium formiate, the pH value of described pelt is dropped to around iso-electric point;
(6) chrome tanning agent infiltration: appropriate sulfuric acid, formic acid and chromium powder are configured to chrome tanning agent, the main component of described chrome tanning agent is trivalent sun chromic compound, and the pH value of described chrome tanning agent is about 3; Joined by above-mentioned chrome tanning agent in the pelt processed through step 1, described chrome tanning agent penetrated into pelt completely through 90 minutes;
(7) chrome tanning: the chrome tanning agent of above-mentioned steps 2 penetrates in pelt, the trivalent sun chromium ion in described chrome tanning agent and the peptide chain carboxylic ions R – COO in collagen
–in conjunction with formation coordinate bond, the pH value of described pelt is reduced to 4.0 ~ 4.5;
(8) alkali is carried: the leather after above-mentioned steps 3 being processed continues rotary drum transfer 80 ~ 100 minutes, then 0.4wt% sodium bicarbonate is added, the pH value inside and outside leather is made evenly to remain on 3.5 ~ 3.8, add 100wt% water, temperature in rotary drum is risen to 37 ~ 39 DEG C, turn 3 hours again, pH value is 3.8 ~ 4.0, now surveys shrinkage temperature and can reach more than 95 DEG C.
In the above-described embodiment, pelt adopts composite organic acid and organic acid salt pH value to be dropped to after around iso-electric point, the pH value of pelt can be made to reduce on the one hand, be conducive to the infiltration of chrome tanning agent molecule, prevent the peptide chain carboxylic ions R – COO in chrome tanning agent molecule and pelt
–rapid combination and produce surface cross tan; On the other hand, owing to not using the pickling procedure in traditional technology, therefore, the discharge of high-content chlorion leather-making waste water is also greatly reduced.
Embodiment 2
The quick leather tanning method of a kind of high ph-values, described process for tanning comprises the following steps:
(1) soak: with embodiment 1.
(2) liming: with embodiment 1.
(3) multiple ash: with embodiment 1.
(4) deashing and softening: with embodiment 1.
(5) pelt pre-treatment: the pelt obtained through immersion, liming, multiple ash, deashing and softening pre-treatment is put into rotary drum, with formic acid and sodium formiate, the pH value of described pelt is down to 6 ± 0.2; In above-mentioned pelt, add the masking agent of 0.4wt%, described masking agent is oxalic acid and sodium salt thereof;
(6) chrome tanning agent infiltration: appropriate sulfuric acid, formic acid and chromium powder are configured to chrome tanning agent, the main component of described chrome tanning agent is trivalent sun chromic compound, and the pH value of described chrome tanning agent is about 3; Above-mentioned chrome tanning agent being joined the pH value processed through step 1 is in the pelt of 6 ± 0.2, forms complex compound between the trivalent sun chromium ion in described chrome tanning agent and the masking agent negatively charged ion in masking agent; The complex compound that described chrome tanning agent and masking agent are formed penetrated into pelt completely through 60 ~ 80 minutes;
(7) chrome tanning: described complex compound penetrates in pelt, when the pH value of described pelt is reduced to 4.2 ~ 4.5, the trivalent sun chromium ion in described chrome tanning agent and the peptide chain carboxylic ions R – COO in collagen
–in conjunction with formation coordinate bond; When the pH value of pelt continues to be down to 3.5 ~ 3.8, chrome tanning tentatively completes;
(8) alkali is carried: the leather after above-mentioned steps 3 being processed continues rotary drum transfer 60 ~ 80 minutes, then 0.1 ~ 0.2wt% sodium bicarbonate is added, the pH value inside and outside leather is made evenly to remain on 3.8 ~ 4.0, add 100wt% water, temperature in rotary drum is risen to 37 ~ 39 DEG C, turn 90 ~ 100 minutes again, now survey shrinkage temperature and can reach more than 95 DEG C.
Embodiment 3
The quick leather tanning method of a kind of high ph-values, described process for tanning comprises the following steps:
(1) soak: with embodiment 1.
(2) liming: with embodiment 1.
(3) multiple ash: with embodiment 1.
(4) deashing and softening: with embodiment 1.
(5) pelt pre-treatment: the pelt obtained through immersion, liming, multiple ash, deashing and softening pre-treatment is put into rotary drum, with formic acid and sodium formiate, the pH value of described pelt is down to 6 ± 0.2; In above-mentioned pelt, add the masking agent of 0.5wt%, described masking agent is acetic acid and sodium salt thereof.
(6) chrome tanning agent infiltration: with embodiment 2.
(7) chrome tanning: with embodiment 2.
(8) alkali is carried: with embodiment 2.
Embodiment 4
The quick leather tanning method of a kind of high ph-values, described process for tanning comprises the following steps:
(1) soak: with embodiment 1.
(2) liming: with embodiment 1.
(3) multiple ash: with embodiment 1.
(4) deashing and softening: with embodiment 1.
(5) pelt pre-treatment: the pelt obtained through immersion, liming, multiple ash, deashing and softening pre-treatment is put into rotary drum, with formic acid and sodium formiate, the pH value of described pelt is down to 6 ± 0.2; In above-mentioned pelt, add the masking agent of 0.6wt%, described masking agent is formic acid and sodium salt thereof.
(6) chrome tanning agent infiltration: with embodiment 2.
(7) chrome tanning: with embodiment 2.
(8) alkali is carried: with embodiment 2.
In above-described embodiment 2 ~ 4, the Main Function of masking agent is the resistance to alkali ability that can improve chrome tanning agent, tannery can be carried out under higher pH and chrome tanning agent can not become the precipitation of oxyhydroxide.Masking agent improves the stability of trivalent sun chromic compound in chrome tanning agent, produce the reason of this effect, instead of water molecules because masking agent negatively charged ion penetrates boundary in trivalent sun chromic compound, the structure of trivalent sun chromic compound and electric charge are changed, along with the minimizing of positive changes, the magnetism of collagen carboxyl anion in leather to positive chromium coordination ion also can correspondingly reduce, thus make the combination of chrome tanning agent and leather become mitigation, make chrome tanning agent can permeate in pelt and be uniformly distributed before being combined with collagen carboxyl anion.
Above embodiment is only for illustration of the present invention; and be not limitation of the present invention; the those of ordinary skill of relevant technical field; without departing from the spirit and scope of the present invention; can also make a variety of changes and modification; therefore all equivalent technical schemes also belong to category of the present invention, and scope of patent protection of the present invention should be defined by the claims.
Claims (9)
1. the quick leather tanning method of high ph-values, is characterized in that: described process for tanning comprises the following steps:
(1) pelt pre-treatment: the pelt obtained through immersion, liming, multiple ash, deashing and softening pre-treatment is put into rotary drum, with organic acid and organic acid salt, the pH value of described pelt is dropped to around iso-electric point, play masking effect;
(2) chrome tanning agent infiltration: appropriate sulfuric acid, formic acid and chromium powder are configured to chrome tanning agent, the main component of described chrome tanning agent is trivalent sun chromic compound, and the pH value of described chrome tanning agent is about 3; Joined by above-mentioned chrome tanning agent in the pelt processed through step 1, described chrome tanning agent penetrated into pelt completely through 80 ~ 100 minutes;
(3) chrome tanning: the chrome tanning agent of above-mentioned steps 2 penetrates in pelt, the peptide chain carboxylic ions R – COO – of trivalent sun chromium ion in collagen in described chrome tanning agent is combined and forms coordinate bond, and the pH value of described pelt is reduced to 4.0 ~ 4.5;
(4) alkali is carried: the leather after above-mentioned steps 3 being processed continues rotary drum transfer 80 ~ 100 minutes, then 0.3 ~ 0.5wt% sodium bicarbonate is added, the pH value inside and outside leather is made evenly to remain on 3.5 ~ 3.8, add 100wt% water, temperature in rotary drum is risen to 37 ~ 39 DEG C, turn 3 hours again, pH value is 3.8 ~ 4.0, now surveys shrinkage temperature and can reach more than 95 DEG C.
2. the quick leather tanning method of high ph-values, is characterized in that: described process for tanning comprises the following steps:
(1) pelt pre-treatment: the pelt obtained through immersion, liming, multiple ash, deashing and softening pre-treatment is put into rotary drum, with organic acid and organic acid salt, the pH value of described pelt is down to 6 ± 0.2; The masking agent of 0.4 ~ 0.6wt% is added in above-mentioned pelt;
(2) chrome tanning agent infiltration: appropriate sulfuric acid, formic acid and chromium powder are configured to chrome tanning agent, the main component of described chrome tanning agent is trivalent sun chromic compound, and the pH value of described chrome tanning agent is about 3; Above-mentioned chrome tanning agent being joined the pH value processed through step 1 is in the pelt of 6 ± 0.2, forms complex compound between the trivalent sun chromium ion in described chrome tanning agent and the masking agent negatively charged ion in masking agent; The complex compound that described chrome tanning agent and masking agent are formed penetrated into pelt completely through 60 ~ 80 minutes;
(3) chrome tanning: described complex compound penetrates in pelt, when the pH value of described pelt is reduced to 4.2 ~ 4.5, the peptide chain carboxylic ions R – COO – of trivalent sun chromium ion in collagen in described chrome tanning agent is combined and forms coordinate bond; When the pH value of pelt continues to be down to 3.5 ~ 3.8, chrome tanning tentatively completes;
(4) alkali is carried: the leather after above-mentioned steps 3 being processed continues rotary drum transfer 60 ~ 80 minutes, then 0.1 ~ 0.2wt% sodium bicarbonate is added, the pH value inside and outside leather is made evenly to remain on 3.8 ~ 4.0, add 100wt% water, temperature in rotary drum is risen to 37 ~ 39 DEG C, turn 90 ~ 100 minutes again, now survey shrinkage temperature and can reach more than 95 DEG C.
3. the quick leather tanning method of high ph-values according to claim 2, is characterized in that: described masking agent is wherein one or more the mixing in monocarboxylic acid and salt, di-carboxylic acid and salt thereof, hydroxycarboxylic acid and salt thereof.
4. the quick leather tanning method of high ph-values according to claim 3, is characterized in that: described monocarboxylic acid is formic acid, acetic acid or propionic acid, and described di-carboxylic acid is oxalic acid or phthalic acid, and described hydroxycarboxylic acid is tartrate or citric acid; Described salt is the sodium salt of above-mentioned respective acids.
5. the quick leather tanning method of high ph-values according to claim 1 and 2, is characterized in that: be respectively formic acid and sodium formiate for the organic acid of adjust ph and organic acid salt in described step 1.
6. the quick leather tanning method of high ph-values according to claim 1 and 2, is characterized in that: the immersion in described step 1 comprises pre-immersion and main immersion;
Wet salted hide immerses in the solution containing 0.1 ~ 0.2wt% Soaking, 0.1 ~ 0.2wt% sterilant, 0.1 ~ 0.3wt% soda ash and 200wt% water under being specially normal temperature by described preimpregnation water, rotary drum for processing 90 ~ 100 minutes, carry out washing rear draining with 150wt% water, after pre-immersion, the pH value of body lotion is 7.0 ± 0.2;
Fur through pre-immersion is carried out main immersion in containing the solution of 0.2 ~ 0.4wt% Soaking, 0.4 ~ 0.6wt% enzyme, 0.2 ~ 0.3wt% sterilant, 0.2 ~ 0.4wt% grease-removing agent and 150wt% water, in rotary drum for processing after 30 ~ 40 minutes, divide three times, all add 0.2 ~ 0.3wt% soda ash at every turn, the timed interval at every turn adding soda ash is 6 ~ 7 hours, and after main immersion, the pH value of body lotion is 9.3 ± 0.2.
7. the quick leather tanning method of high ph-values according to claim 1 and 2, is characterized in that: the liming in described step 1 adopts micro-enzyme ash alkaline process to protect hair depilation, and detailed process is:
By the fur after immersion process in the rotary drum for processing 2 hours containing 0.8 ~ 1.0wt% liming enzyme auxiliary agent, 0.3 ~ 0.5wt%NaHS, 0.1 ~ 0.2wt% soda ash and 250wt% water;
Add 1.0 ~ 1.3wt% lime in above-mentioned rotary drum after, process 1 hour;
In above-mentioned rotary drum, add 0.3 ~ 0.5wt%Na2S and 0.7 ~ 0.9wt%NaHS, continue process 1 hour;
Add 0.2 ~ 0.3wt% soda ash in above-mentioned rotary drum after, process 1 hour;
Continue to add 1.5 ~ 2.5wt% lime and 0.1 ~ 0.2wt% poly-phosphate in above-mentioned rotary drum, process 1 hour;
After finally adding 2.0 ~ 3.0wt% lime in above-mentioned rotary drum, continue process 22 hours; After liming process, the pH value of leather is 12.4 ± 0.1.
8. the quick leather tanning method of high ph-values according to claim 1 and 2, it is characterized in that: the multiple ash in described step 1 is specially: the graywall after liming process is carried out drum, split, weigh after again drop in rotary drum, temperature in described rotary drum is 28 ~ 30 DEG C, 1.5 ~ 2.5wt% lime, 0.8 ~ 1.2wt% auxiliary liming agent and 250wt% water is added in described rotary drum, process after 18 hours, washing; The pH value of the body lotion after described multiple ash process is 9.6 ± 0.1.
9. the quick leather tanning method of high ph-values according to claim 1, it is characterized in that: the deashing and softening in described step 1 is specially: by the leather deashing and softening process 10 ~ 11 hours in rotary drum after multiple ash process, be placed with 1.2 ~ 1.6wt% in described rotary drum without ammonia deliming agent, 1.2 ~ 1.5wt% macerating enzyme and 100wt% water; Leather normal temperature after process washes 1 time, and then with water displacement wash 30 minutes, makes the pH value of body lotion be 7 ~ 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410840697.3A CN104593528A (en) | 2014-12-30 | 2014-12-30 | High pH value fast leather tanning method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410840697.3A CN104593528A (en) | 2014-12-30 | 2014-12-30 | High pH value fast leather tanning method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104593528A true CN104593528A (en) | 2015-05-06 |
Family
ID=53119579
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410840697.3A Pending CN104593528A (en) | 2014-12-30 | 2014-12-30 | High pH value fast leather tanning method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104593528A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106319104A (en) * | 2016-08-18 | 2017-01-11 | 明新旭腾新材料股份有限公司 | Production technology of high-absorbability chrome tanned leather |
| CN109234477A (en) * | 2018-11-26 | 2019-01-18 | 四川大学 | A kind of preparation method of Chrome-free leather |
| CN109880943A (en) * | 2019-03-18 | 2019-06-14 | 四川大学 | A kind of salt-free not pickling Animal Skin chrome tanning method based on composite ligand synergistic effect |
| CN110184396A (en) * | 2019-05-20 | 2019-08-30 | 梁生 | A kind of leather tanning agent |
| CN113528717A (en) * | 2021-07-14 | 2021-10-22 | 台山市广一皮业有限公司 | Pickling and tanning integrated process for leather production and processing |
| CN114214471A (en) * | 2021-12-08 | 2022-03-22 | 兴业皮革科技股份有限公司 | Wet finishing method for improving uniformity of compact leather |
| CN114231672A (en) * | 2021-11-29 | 2022-03-25 | 无极县景森皮革制品有限公司 | Leather pickling-free, salt-free and high-absorption chrome tanning process method |
| CN116103451A (en) * | 2023-03-30 | 2023-05-12 | 精艺裘皮制品股份有限公司 | Multi-working-procedure effective synergistic beach sheepskin harmless tanning method |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1348994A (en) * | 2001-05-08 | 2002-05-15 | 四川大学 | Acid-free chromte tannage agent and its prepn |
| CN1740343A (en) * | 2005-09-13 | 2006-03-01 | 四川大学 | A method of clean high-absorption chrome tanning |
| US20090158530A1 (en) * | 2007-12-25 | 2009-06-25 | Soda Sanayi A.S. | Use of chromium complex in the leather industry |
| CN101974655A (en) * | 2010-10-15 | 2011-02-16 | 陕西科技大学 | Method for tanning non-pickling high-pH chrome leather by using chrome formate |
| CN103509888A (en) * | 2013-10-22 | 2014-01-15 | 陕西科技大学 | Salt-free pickling-free less-chrome combination tanning method for first layer cattle shoe upper leather |
| CN103773908A (en) * | 2014-01-21 | 2014-05-07 | 中国皮革和制鞋工业研究院 | Method for tanning leather without pickling |
-
2014
- 2014-12-30 CN CN201410840697.3A patent/CN104593528A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1348994A (en) * | 2001-05-08 | 2002-05-15 | 四川大学 | Acid-free chromte tannage agent and its prepn |
| CN1740343A (en) * | 2005-09-13 | 2006-03-01 | 四川大学 | A method of clean high-absorption chrome tanning |
| US20090158530A1 (en) * | 2007-12-25 | 2009-06-25 | Soda Sanayi A.S. | Use of chromium complex in the leather industry |
| CN101974655A (en) * | 2010-10-15 | 2011-02-16 | 陕西科技大学 | Method for tanning non-pickling high-pH chrome leather by using chrome formate |
| CN103509888A (en) * | 2013-10-22 | 2014-01-15 | 陕西科技大学 | Salt-free pickling-free less-chrome combination tanning method for first layer cattle shoe upper leather |
| CN103773908A (en) * | 2014-01-21 | 2014-05-07 | 中国皮革和制鞋工业研究院 | Method for tanning leather without pickling |
Non-Patent Citations (3)
| Title |
|---|
| 李国英等，: "高吸收铬鞣机理及其工艺技术（II）高pH值铬鞣工艺研究", 《中国皮革》 * |
| 李炳章: "黄牛沙发革水场工艺", 《中国皮革》 * |
| 王群智: "无盐浸酸与铬鞣", 《皮革科学与工程》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106319104A (en) * | 2016-08-18 | 2017-01-11 | 明新旭腾新材料股份有限公司 | Production technology of high-absorbability chrome tanned leather |
| CN106319104B (en) * | 2016-08-18 | 2019-12-13 | 明新旭腾新材料股份有限公司 | production process of high-absorption chrome tanned leather |
| CN109234477A (en) * | 2018-11-26 | 2019-01-18 | 四川大学 | A kind of preparation method of Chrome-free leather |
| CN109234477B (en) * | 2018-11-26 | 2021-06-29 | 四川大学 | Preparation method of chromium-free leather |
| CN109880943A (en) * | 2019-03-18 | 2019-06-14 | 四川大学 | A kind of salt-free not pickling Animal Skin chrome tanning method based on composite ligand synergistic effect |
| CN109880943B (en) * | 2019-03-18 | 2021-08-13 | 四川大学 | Salt-free pickling-free animal skin chrome tanning method based on synergistic effect of composite ligand |
| CN110184396A (en) * | 2019-05-20 | 2019-08-30 | 梁生 | A kind of leather tanning agent |
| CN113528717A (en) * | 2021-07-14 | 2021-10-22 | 台山市广一皮业有限公司 | Pickling and tanning integrated process for leather production and processing |
| CN114231672A (en) * | 2021-11-29 | 2022-03-25 | 无极县景森皮革制品有限公司 | Leather pickling-free, salt-free and high-absorption chrome tanning process method |
| CN114214471A (en) * | 2021-12-08 | 2022-03-22 | 兴业皮革科技股份有限公司 | Wet finishing method for improving uniformity of compact leather |
| CN114214471B (en) * | 2021-12-08 | 2024-04-02 | 兴业皮革科技股份有限公司 | Wet finishing method for improving uniformity of compact leather |
| CN116103451A (en) * | 2023-03-30 | 2023-05-12 | 精艺裘皮制品股份有限公司 | Multi-working-procedure effective synergistic beach sheepskin harmless tanning method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104593528A (en) | High pH value fast leather tanning method | |
| CN102839236B (en) | Dual-purpose modification process for native breed sheepskin leather | |
| CN102534056B (en) | Tanning production process capable of recycling waste water repeatedly from soaking to dyeing | |
| CN104789715B (en) | One kind is salt-free to exempt from pickling short route less chrome tannage method | |
| CN103773908B (en) | Ox-hide leather produces tanning without pickling method | |
| CN103773906B (en) | Integrated water saving method for leather-making | |
| CN102943139B (en) | Aldehyde vegetable-chrome tanning combined production method for waxed soft leather | |
| CN102010917A (en) | Ammonia nitrogen-free leather-making deliming agent and preparation method thereof | |
| CN101265505A (en) | Ashless and alkali sulfide free depilation liming treatment method for preparing leather from raw sheep skin | |
| CN105925735B (en) | One kind is salt-free to exempt from pickling short route bating method without chrome | |
| CN104673943A (en) | Method for manufacturing environment-friendly ecological tanned lamb skin | |
| CN102703619B (en) | A kind of energy saving and environment friendly standard mink skin process for tanning | |
| CN103805722B (en) | A kind of wet blue leather treatment process | |
| BRPI0805603A2 (en) | use of chromium complex in leather industry | |
| CN105316437A (en) | Production process of environment-friendly cattle hide mattress | |
| CN110144424B (en) | Processing technology for preparing retainable wet blue leather by using low-grade grey fur | |
| CN102443660B (en) | Fur tanning-piercing and printing process and tanning fur | |
| CN104694675A (en) | Novel process for manufacturing leather with simple procedures and equipment | |
| Cai et al. | Inverse chrome tanning technology based on wet white tanned by Al-Zr complex tanning agent | |
| CN103627827A (en) | Chrome-free tanning method of alligator skin | |
| CN102242228A (en) | Novel salt-free pickling leather additive | |
| CN106350619B (en) | The method of few chromium combination tanning after a kind of immersion of complex enzyme formulation | |
| CN111118234B (en) | Non-chrome leather tanning method | |
| CN104843807A (en) | Cycle engineering for realization of tanning waste water near-zero emission | |
| CN115838841B (en) | Method for preparing waterproof leather by using zeolite tanning agent and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20150506 |
|
| WD01 | Invention patent application deemed withdrawn after publication |