CN106435053B - It is a kind of to be used for complexing agent and its preparation method and application of the leather without chrome tanning tanning processes - Google Patents
It is a kind of to be used for complexing agent and its preparation method and application of the leather without chrome tanning tanning processes Download PDFInfo
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- CN106435053B CN106435053B CN201611140274.6A CN201611140274A CN106435053B CN 106435053 B CN106435053 B CN 106435053B CN 201611140274 A CN201611140274 A CN 201611140274A CN 106435053 B CN106435053 B CN 106435053B
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- 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
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Abstract
It being used for complexing agent and its preparation method and application of the leather without chrome tanning tanning processes the invention discloses a kind of, include the hydrophilic radical of resistance to strong acid, resistance to strong electrolyte and resisting high-concentration metallic solution, complexing agent is the sulfosuccinic acid monoester salt that total solids content is 35%, carboxyl degree of neutralization is 95%, sulfonation degree is 90%.The present invention can be prepared by conventional easy technological operation, which is applied in the technique of no chrome tanning, operating procedure is simple, environmentally friendly, and the shrinkage temperature of finished product skin reaches 90 DEG C or more, and the comprehensive performance of its tanning is close with chrome leather.
Description
Technical field
The present invention relates to leather tanning technical fields, and in particular to a kind of to be used for complexing agent of the leather without chrome tanning tanning processes
And its preparation method and application.
Background technology
Tanning is a most important procedure in leather making process.
Invention chrome tanning is studied from Knapp in 1858, especially since Dennis in 1893 has invented a bath chrome tanning,
It is easily controllable since it is easy to operate, it the advantages that finished leather hydrothermal stability is high, is used widely in leather industry quickly
And occupy leading position.By development in more than 100 years, modern leather industry formed based on chrome tanning a whole set of compared with
Perfect leather-making technology system.However, the chromium utilization rate of conventional chrome tanning is only 65%~75%, a large amount of unabsorbed chromium
It can be discharged.
It is known that.Chromium destroys the ecological balance, and there is the potential danger for generating hypertoxic Cr VI because it is difficult to degrade
Danger, is a kind of heavy metal that can bring environmental pollution.Exploitation, which can substitute chromium and meet the tanning agent of environmental protection requirement, just to be become
A kind of inexorable trend.
Existing non-chromium class tanning agent mainly has aldehyde tanning agent, organophosphor tanning agent, vegetable tanning agent and zirconium tanning agent, titanium tannage agent, aluminium
Tanning agent and rare earth metal salt etc., but a kind of any of the above described tanning agent all has larger difference in comprehensive performance compared with chrome tanning agent
Away from.
And strength of leather that wherein titanium tannage agent tanning comes out is high, consolidation, fillibility is good, the leather phase with other tanning agent tannings
Than closer to chrome leather in state.But titanium tannage leather shrinkage temperature is relatively low, at 78 DEG C or so, during subsequent arrangement
It is susceptible to leather quality accident, as titanium tannage leather may lead to leather " being cut coke " in shaving.The leather of zirconium tanning agent tanning is pure white,
Shrinkage temperature is higher (up to 97 DEG C), and elasticity is small, and pile is fine and closely woven, and has good wearability and keeping quality.But zirconates
Water-disintegrable strong, poor permeability, the tanning uniformity is low, and the leather plate of tanning is hard, and feel is poor, and finished leather is laid particular stress on, and water imbibition is strong.
Invention content
Have in the use of chrome-free tanning in view of the deficiencies of the prior art, the present invention intends to provide a kind of
Comprehensive performance is good, simple production process, environmental pollution are small is used for complexing agent and its system of the leather without chrome tanning tanning processes
Preparation Method and application.
To achieve the above object, the present invention provides following technical solutions：It is a kind of for leather without chrome tanning tanning processes
Complexing agent, includes the hydrophilic radical of resistance to strong acid, resistance to strong electrolyte and resisting high-concentration metallic solution, and complexing agent contains for total solid
Amount is 35%, the sulfosuccinic acid monoester salt that carboxyl degree of neutralization is 95%, sulfonation degree is 90%；
The preparation method for complexing agent of the leather without chrome tanning tanning processes, includes the following steps：
(1) 67~100 parts of glycerine is weighed respectively by mass fraction, 100 parts of maleic anhydride and 0.15 part are urged
Agent；
(2) glycerine is added in reactor, opens condensed water and blender, adjust 65-70 DEG C of temperature, maleic acid is added
Acid anhydride, charging process control temp are no more than 75 DEG C, disposably put into catalyst, and adition process controls temperature and is no more than 80 DEG C, adds
Material terminates, and starts to warm up, and temperature rises to 90-93 DEG C, it is 2.5 hours acylated after 45 DEG C of cooling hereinafter, discharging obtains working substance is
100% maleic acid glycerine mixing monoesters intermediate；
(3) weighed respectively by mass fraction 100 parts maleic acid glycerine mixing monoesters intermediate, 1267 parts of water, 95 parts
Ammonium hydroxide and 45~50 part 30% of sodium metabisulfite solution；
(4) reactor is added in water and maleic acid glycerine mixing monoesters intermediate, setting temperature is 50~55 DEG C, is beaten
Condensed water stirring is opened, intermediate is dispersed into white " milky "；Ammonium hydroxide is added dropwise and carries out neutralization reaction, time for adding is controlled 30~60
Minute, the control of process system temperature is added dropwise within 60 DEG C, neutralizing end system pH should be 5.5~6；After neutralization reaction
System is warming up to 60 DEG C, sodium pyrosulfite is added dropwise, sodium pyrosulfite control adds in 60~120 minutes, burnt sub- being added dropwise
System temperature control is within 65 DEG C during sodium sulphate, and at 80 DEG C, stirring carries out sulphur for system temperature control after completion of dropwise addition
Change reaction 210 minutes, system pH is about 6 after reaction, cooling discharge, and it is 35% to obtain solid content, and carboxyl degree of neutralization is
95%, the sulfosuccinic acid monoester salt that sulfonation degree is 90%.
The present invention is further arranged：The catalyst is to benzene methanesulfonic acid；
The present invention is further arranged：The ammonium hydroxide is 20% ammonia spirit.
Row addition again in 3 hours or so is reacted in tanning agent input system, dosage is the 50%-75% of tanning agent dosage.
Select maleic anhydride and glycerine, complexing agent need to be in strong acid, strong electrolyte, high concentration metal in starting material of the present invention
It is used in solution, because of its special reaction system, the complexing agent necessary resistance to strong acid, strong electrolyte, high concentration metallic solution, in turn
Determine the functional group that the complexing agent must be with resistance to strong acid, strong electrolyte, high concentration metallic solution in structure.Maleic anhydride
The five-membered cyclic cis-butenedioic anhydride containing unsaturated bond, the double bond in molecule and acid anhydrides Liang Zhong functional groups, can carry out addition reaction,
Diels --- Alder reactions, esterification, amidation process, polymerisation etc., and a functional group in maleic anhydride
After reaction, another luminous energy group can also continue to react.Maleic anhydride belongs to acylation reaction with the reaction of glycerine, and maleic anhydride is
A kind of acylating agent, the electropositive of carbonyl carbon is the reason of nucleopilic reagent is to the carbon atom attack in molecule.
Contain the functional groups such as carboxyl, hydroxyl, ester group, and two carboxyls in product obtained by reaction step (2) acylation reaction
The distance between farther out, determine that the unsaturation monoesters is cis-structure by the structure of maleic anhydride, cis-structure is in water
Solubility is much larger than trans-.Reaction step (4) i.e. maleic acid monoester obtains in aqueous phase system after sulphite sulfonation
Sulfosuccinate ester salt product, sodium pyrosulfite when maleic acid glycerine mixing monoesters sulfonation obtained by reaction step (2)
Sodium pyrosulfite is done, first maleic acid glycerine mixing monoesters is neutralized, then with sodium pyrosulfite sulfonation.Reaction step (2)
The maleic acid glycerine mixing monoesters of gained contains carboxyl, has certain hydrophily, can directly be scattered in water phase, therefore,
Disperse without solubilizer in subsequent sulfonating reaction, moreover, as the hydrophily of the progress product of sulfonating reaction can be further
Increase, product water-dispersed can be formed completely.In the sulfonating reaction that reaction step (4) is carried out, due to maleic anhydride
The C 〓 C double bonds of introducing are influenced by the highly polar ester group in both sides and carboxyl sucting electronic effect, and electron deficient (aobvious part is presented
Electropositive), it is highly prone to the attack of nucleopilic reagent and nucleophilic addition occurs, therefore, can occur under not exacting terms
Sulfonating reaction.When sulfonation, sulfonic group is always connected on α-C of monoesters.The sulfosuccinic acid monoester salt of hydroxyl can be obtained.
The relative molecular weight of the maleic acid glycerine mixing monoesters intermediate weighed in reaction step (3) is by reaction step
(1) what the number of the glycerine and maleic anhydride that are weighed in was determined, relative molecular weight is：(maleic anhydride relative molecular weight
Be multiplied by number+glycerine relative molecular weight and be multiplied by number) divided by maleic anhydride number.
For application of complexing agent of the leather without chrome tanning tanning processes in leather tanning, it is characterised in that：Including following
Step：
(1) sheep acid skin：Selection is used for the sheepskin of clothing leather by pickling；
(2) water squeezing：Normal process steps；
(3) it weighs：It increases weight to 300% calculating benchmark as the additive amount of subsequent handling additive after weighing；
(4) return water：The room temperature brine of 6%-8% is added in rotary drum, throws skin, rotates 30min, surveying bath foam pH value in drum is
2.5-2.8；
(5) tanning：3% is added without chrome tanning companion, rotates 15min；It is added 0.5% non-ionic oil, 6%-10% zirconium tanning agents,
Rotate 180min；The complexing agent of 3%-7.5% is added, rotates 120min；
(6) alkali is carried：Divide 3-4 addition to carry alkaline agent, often plus once rotate 30min, it is 3.8- to adjust bath foam pH value in rousing
4.0；100%60 DEG C of water is added, it is 38 DEG C to keep bath temperature in rotary drum, is slowly run, and the 2-3 per minute that turns turns, overnight；
(7) it washes, go out drum：Next day surveys shrinkage temperature, washes out drum, and standing is displayed 1 day or more；
(8) water squeezing, shaving：By tanning displayed without chrome tanning sheepskin water squeezing, shaving, bilayer thickness 0.9mm-
1.1mm weighs, the calculating benchmark of the additive amount as subsequent handling additive；
(9) it neutralizes：100% water is added in rotary drum for normal process steps, and it is 32 DEG C -35 DEG C that temperature in drum, which is arranged, is added 2%
Sodium formate rotates 30min, is added 0.5% and carries alkaline agent, rotates 60min, and survey pH value is 4.5-4.8, controls water；
(10) it washes：Normal process steps；
(11) stuffing, filling, dyeing：Normal process steps；
(12) it washes, go out drum：Normal process steps；
(13) dry to arrange：Normal process steps；
(14) whitening：Normal process steps, it is 0.4mm-0.8mm that shaving, which keeps bilayer thickness,；
(15) soft, flatiron is fallen：Normal process steps；
(16) ruler, storage are arranged：Normal process steps；
Wherein, raw materials used to count in parts by weight.
Compared with prior art, the device have the advantages that it is as follows：
(1) the present invention overcomes the deficiency of zirconium tanning agent and titanium tannage agent tanning properties, zirconium tanned leather and titanium can be improved by being one kind
Tanning comprehensive performance can make leather shrinking temperature without the small complexing agent of chromium, environmental pollution for leather without chrome tanning tanning
Reach 90 DEG C or more.
(2) present invention is using maleic anhydride and glycerine as initial reactant, and reaction temperature is low, and simple production process does not need
Special installation, and reaction process, without using organic solvent, environmental pollution is small, is environmentally friendly product.In chrome-free tanning
Use in have comprehensive performance good.
With reference to specification specific embodiment, the invention will be further described.
Specific implementation mode
Embodiment 1
It is disclosed by the invention a kind of for complexing agent of the leather without chrome tanning tanning processes, it is characterised in that：Include resistance to strong
The hydrophilic radical of sour, resistance to strong electrolyte and resisting high-concentration metallic solution, complexing agent be total solids content be 35%, carboxyl neutralize
The sulfosuccinic acid monoester salt that degree is 95%, sulfonation degree is 90%；
The preparation method for complexing agent of the leather without chrome tanning tanning processes, includes the following steps：
(1) 67~100 parts of glycerine is weighed respectively by mass fraction, 100 parts of maleic anhydride and 0.15 part are urged
Agent；
(2) glycerine is added in reactor, opens condensed water and blender, adjust 65-70 DEG C of temperature, maleic acid is added
Acid anhydride, charging process control temp are no more than 75 DEG C, disposably put into catalyst, and adition process controls temperature and is no more than 80 DEG C, adds
Material terminates, and starts to warm up, and temperature rises to 90-93 DEG C, it is 2.5 hours acylated after 45 DEG C of cooling hereinafter, discharging obtains working substance is
100% maleic acid glycerine mixing monoesters intermediate；
(3) weighed respectively by mass fraction 100 parts maleic acid glycerine mixing monoesters intermediate, 1267 parts of water, 95 parts
Ammonium hydroxide and 45~50 parts of sodium pyrosulfites；
(4) reactor is added in water and maleic acid glycerine mixing monoesters intermediate, setting temperature is 50~55 DEG C, is beaten
Condensed water stirring is opened, intermediate is dispersed into white " milky "；Ammonium hydroxide is added dropwise and carries out neutralization reaction, time for adding is controlled 30~60
Minute, the control of process system temperature is added dropwise within 60 DEG C, neutralizing end system pH should be 5.5~6；After neutralization reaction
System is warming up to 60 DEG C, sodium pyrosulfite is added dropwise, sodium pyrosulfite control adds in 60~120 minutes, burnt sub- being added dropwise
System temperature control is within 65 DEG C during sodium sulphate, and at 80 DEG C, stirring carries out sulphur for system temperature control after completion of dropwise addition
Change reaction 210 minutes, system pH is about 6 after reaction, cooling discharge, and it is 35% to obtain solid content, and carboxyl degree of neutralization is
95%, the sulfosuccinic acid monoester salt that sulfonation degree is 90%.
The present invention is further arranged：The catalyst is to benzene methanesulfonic acid；
The present invention is further arranged：The sodium pyrosulfite is 30% sodium metabisulfite solution；
The present invention is further arranged：The ammonium hydroxide is 20% ammonia spirit.
Row addition again in 3 hours or so is reacted in tanning agent input system, dosage is the 50%-75% of tanning agent dosage.
Select maleic anhydride and glycerine, complexing agent need to be in strong acid, strong electrolyte, high concentration metal in starting material of the present invention
It is used in solution, because of its special reaction system, the complexing agent necessary resistance to strong acid, strong electrolyte, high concentration metallic solution, in turn
Determine the functional group that the complexing agent must be with resistance to strong acid, strong electrolyte, high concentration metallic solution in structure.Maleic anhydride
The five-membered cyclic cis-butenedioic anhydride containing unsaturated bond, the double bond in molecule and acid anhydrides Liang Zhong functional groups, can carry out addition reaction,
Diels --- Alder reactions, esterification, amidation process, polymerisation etc., and a functional group in maleic anhydride
After reaction, another luminous energy group can also continue to react.Maleic anhydride belongs to acylation reaction with the reaction of glycerine, and maleic anhydride is
A kind of acylating agent, the electropositive of carbonyl carbon is the reason of nucleopilic reagent is to the carbon atom attack in molecule.
Contain the functional groups such as carboxyl, hydroxyl, ester group, and two carboxyls in product obtained by reaction step (2) acylation reaction
The distance between farther out, determine that the unsaturation monoesters is cis-structure by the structure of maleic anhydride, cis-structure is in water
Solubility is much larger than trans-.Reaction step (4) i.e. maleic acid monoester obtains in aqueous phase system after sulphite sulfonation
Sulfosuccinate ester salt product, sodium pyrosulfite when maleic acid glycerine mixing monoesters sulfonation obtained by reaction step (2)
Sodium pyrosulfite is done, first maleic acid glycerine mixing monoesters is neutralized, then with sodium pyrosulfite sulfonation.Reaction step (2)
The maleic acid glycerine mixing monoesters of gained contains carboxyl, has certain hydrophily, can directly be scattered in water phase, therefore,
Disperse without solubilizer in subsequent sulfonating reaction, moreover, as the hydrophily of the progress product of sulfonating reaction can be further
Increase, product water-dispersed can be formed completely.In the sulfonating reaction that reaction step (4) is carried out, due to maleic anhydride
The C 〓 C double bonds of introducing are influenced by the highly polar ester group in both sides and carboxyl sucting electronic effect, and electron deficient (aobvious part is presented
Electropositive), it is highly prone to the attack of nucleopilic reagent and nucleophilic addition occurs, therefore, can occur under not exacting terms
Sulfonating reaction.When sulfonation, sulfonic group is always connected on α-C of monoesters.The sulfosuccinic acid monoester salt of hydroxyl can be obtained.
The relative molecular weight of the maleic acid glycerine mixing monoesters intermediate weighed in reaction step (3) is by reaction step
(1) what the number of the glycerine and maleic anhydride that are weighed in was determined, relative molecular weight is：(maleic anhydride relative molecular weight
Be multiplied by number+glycerine relative molecular weight and be multiplied by number) divided by maleic anhydride number.
For application of complexing agent of the leather without chrome tanning tanning processes in leather tanning, it is characterised in that：Including following
Step：
(1) sheep acid skin：Selection is used for the sheepskin of clothing leather by pickling；
(2) water squeezing：Normal process steps；
(3) it weighs：It increases weight to 300% calculating benchmark as the additive amount of subsequent handling additive after weighing；
(4) return water：The room temperature brine of 6%-8% is added in rotary drum, throws skin, rotates 30min, surveying bath foam pH value in drum is
2.5-2.8；
(5) tanning：3% is added without chrome tanning companion, rotates 15min；It is added 0.5% non-ionic oil, 6%-10% zirconium tanning agents,
Rotate 180min；The complexing agent of 3%-7.5% is added, rotates 120min；
(6) alkali is carried：Divide 3-4 addition to carry alkaline agent, often plus once rotate 30min, it is 3.8- to adjust bath foam pH value in rousing
4.0；100%60 DEG C of water is added, it is 38 DEG C to keep bath temperature in rotary drum, is slowly run, and the 2-3 per minute that turns turns, overnight；
(7) it washes, go out drum：Next day surveys shrinkage temperature, washes out drum, and standing is displayed 1 day or more；
(8) water squeezing, shaving：By tanning displayed without chrome tanning sheepskin water squeezing, shaving, bilayer thickness 0.9mm-
1.1mm weighs, the calculating benchmark of the additive amount as subsequent handling additive；
(9) it neutralizes：100% water is added in rotary drum for normal process steps, and it is 32 DEG C -35 DEG C that temperature in drum, which is arranged, is added 2%
Sodium formate rotates 30min, is added 0.5% and carries alkaline agent, rotates 60min, and survey pH value is 4.5-4.8, controls water；
(10) it washes：Normal process steps；
(11) stuffing, filling, dyeing：Normal process steps；
(12) it washes, go out drum：Normal process steps；
(13) dry to arrange：Normal process steps；
(14) whitening：Normal process steps, it is 0.4mm-0.8mm that shaving, which keeps bilayer thickness,；
(15) soft, flatiron is fallen：Normal process steps；
(16) ruler, storage are arranged：Normal process steps；
Wherein, raw materials used to count in parts by weight.
The present embodiment has the advantage that as follows：
(1) the present invention overcomes the deficiency of zirconium tanning agent and titanium tannage agent tanning properties, zirconium tanned leather and titanium can be improved by being one kind
Tanning comprehensive performance can make leather shrinking temperature without the small complexing agent of chromium, environmental pollution for leather without chrome tanning tanning
Reach 90 DEG C or more.
(2) present invention is using maleic anhydride and glycerine as initial reactant, and reaction temperature is low, and simple production process does not need
Special installation, and reaction process, without using organic solvent, environmental pollution is small, is environmentally friendly product.In chrome-free tanning
Use in have comprehensive performance good.
Embodiment 2
The synthesis concrete operations of complexing agent：
(1) weigh 100 parts of glycerine respectively by mass fraction, 100 parts of maleic anhydride and 0.15 part to toluene sulphur
Acid.
(2) glycerine is added in four-hole bottle, adjusts 67 DEG C of the temperature of temperature control device for water bath, open condensed water and blender,
It is slowly added to maleic anhydride in whipping process, charging process control temp is no more than 75 DEG C.Disposable input catalyst, was added
Process control temperature is no more than 80 DEG C.Charging terminates, and starts to warm up, and temperature rises to 90-93 DEG C, is acylated 2.5 hours.Cool down 45 DEG C afterwards
Hereinafter, discharging obtains the maleic acid glycerine mixing monoesters intermediate that working substance is 100%.
(3) 100 parts of maleic acid glycerine mixing monoesters intermediates are weighed respectively by mass fraction, 1267 parts of water, 90 parts
20% ammonium hydroxide, 45 part 30% of sodium pyrosulfite.
(4) four-hole bottle is added in water and maleic acid glycerine mixing monoesters intermediate, adjusts the temperature of temperature control device for water bath
It is 52 DEG C, opens condensed water, intermediate is dispersed into white " milky " by stirring；The ammonium hydroxide for being added dropwise 20% carries out neutralization reaction, is added dropwise
At 30-60 minutes the control of process system temperature was added dropwise within 60 DEG C, neutralizing end system pH should be 5.9 in time control；In
System is warming up to 60 DEG C after reaction, 30% sodium pyrosulfite is added dropwise, sodium pyrosulfite was controlled at 60-120 minutes
It inside adds, system temperature control is within 65 DEG C during sodium pyrosulfite is added dropwise.System temperature controls after completion of dropwise addition
At 80 DEG C, stirring carries out sulfonating reaction 210 minutes.System pH is about 6 after reaction.Cooling discharge is to get to solid content
It is 35%, the sulfosuccinic acid monoester salt that carboxyl degree of neutralization is 95%, sulfonation degree is 89%.
The specific process of application of complexing agent is：
Conventional sheep acid skin → water squeezing → is weighed, and → return water → tanning → carries alkali → washes, goes out drum → water squeezing → neutralization → water
→ stuffing, filling, dyeing → is washed to wash, go out drum → dry arrangement → whitening → and fall soft, flatiron → row's ruler, storage.
(1) sheep acid skin：Selection is used for the sheepskin of clothing leather by pickling；
(2) water squeezing；
(3) it weighs：Weigh 600g, increases weight to 1800g, the calculating benchmark of the additive amount as subsequent handling additive is pressed
Mass percentage；
(4) return water：8% room temperature brine is added in rotary drum, throws skin, rotates 30min, it is 2.5 to survey bath foam pH value in drum；
(5) tanning：3% is added without chrome tanning companion, rotates 15min；0.5% non-ionic oil, 8% zirconium tanning agent, rotation is added
180min；6% complexing agent is added, rotates 120min；
(6) alkali is carried：It is added three times 2.1% and carries alkaline agent, often plus once rotate 30min, it is 3.8- to adjust bath foam pH value in drum
4.0；100%60 DEG C of water is added, it is 38 DEG C to keep bath temperature in rotary drum, is slowly run, and the 2-3 per minute that turns turns, overnight；
(7) it washes, go out drum：Next day, it is 94 DEG C to survey shrinkage temperature, adds 400% water, rotates 10min, goes out drum, and standing displays 1
It；
(8) water squeezing, shaving：By tanning displayed without chrome tanning sheepskin water squeezing, shaving, bilayer thickness 0.9mm-
1.1mm weighs, the calculating benchmark of the additive amount as subsequent handling additive；
(9) it neutralizes：100% water is added in rotary drum, it is 32 DEG C -35 DEG C that temperature in drum, which is arranged, and 2% sodium formate is added, and is turned
Dynamic 30min is added 0.5% and carries alkaline agent, rotates 60min, and it is 4.7 to survey pH value, controls water；
(10) it washes：400% water rotates 10min, controls water；
(11) stuffing, filling, dyeing：Normal process steps, it is 3.8 to survey pH value；
(12) it washes, go out drum：Normal process steps, it is 90.5 DEG C to survey shrinkage temperature；
(13) dry to arrange：Normal process steps；
(14) whitening：Normal process steps, it is 0.4mm-0.8mm that shaving, which keeps bilayer thickness,；
(15) soft, flatiron is fallen：Normal process steps；
(16) ruler, storage are arranged：Normal process steps.
Embodiment 3
The synthesis concrete operations of complexing agent：
(1) weigh 100 parts of glycerine respectively by mass fraction, 150 parts of maleic anhydride and 0.15 part to toluene sulphur
Acid.
(2) glycerine is added in four-hole bottle, adjusts 67 DEG C of the temperature of temperature control device for water bath, open condensed water and blender,
It is slowly added to maleic anhydride in whipping process, charging process control temp is no more than 75 DEG C.Disposable input catalyst, was added
Process control temperature is no more than 80 DEG C.Charging terminates, and starts to warm up, and temperature rises to 90-93 DEG C, is acylated 2.5 hours.Cool down 45 DEG C afterwards
Hereinafter, discharging obtains the maleic acid glycerine mixing monoesters intermediate that working substance is 100%.
(3) 100 parts of maleic acid glycerine mixing monoesters intermediates are weighed respectively by mass fraction, 1267 parts of water, 95 parts
20% ammonium hydroxide, 45 part 30% of sodium pyrosulfite.
(4) four-hole bottle is added in water and maleic acid glycerine mixing monoesters intermediate, adjusts the temperature of temperature control device for water bath
It is 52 DEG C, opens condensed water, intermediate is dispersed into white " milky " by stirring；The ammonium hydroxide for being added dropwise 20% carries out neutralization reaction, is added dropwise
At 30-60 minutes the control of process system temperature was added dropwise within 60 DEG C, neutralizing end system pH should be 6 in time control；It neutralizes
System is warming up to 60 DEG C after reaction, 30% sodium pyrosulfite is added dropwise, sodium pyrosulfite controlled in 60-120 minutes
It adds, system temperature control is within 65 DEG C during sodium pyrosulfite is added dropwise.System temperature control exists after completion of dropwise addition
80 DEG C, stirring carries out sulfonating reaction 210 minutes.System pH is about 6 after reaction.Cooling discharge is to get to solid content
35%, the sulfosuccinic acid monoester salt that carboxyl degree of neutralization is 95%, sulfonation degree is 90%.
The specific process of application of complexing agent is：
Conventional sheep acid skin → water squeezing → is weighed, and → return water → tanning → carries alkali → washes, goes out drum → water squeezing → neutralization → water
→ stuffing, filling, dyeing → is washed to wash, go out drum → dry arrangement → whitening → and fall soft, flatiron → row's ruler, storage.
(1) sheep acid skin：Selection is used for the sheepskin of clothing leather by pickling；
(2) water squeezing；
(3) it weighs：Weigh 470g, increases weight to 1410g, the calculating benchmark of the additive amount as subsequent handling additive is pressed
Mass percentage；
(4) return water：8% room temperature brine is added in rotary drum, throws skin, rotates 30min, it is 2.5 to survey bath foam pH value in drum；
(5) tanning：3% is added without chrome tanning companion, rotates 15min；0.5% non-ionic oil, 8% zirconium tanning agent, rotation is added
180min；6% complexing agent is added, rotates 120min；
(6) alkali is carried：It is added three times 2.1% and carries alkaline agent, often plus once rotate 30min, it is 3.8- to adjust bath foam pH value in drum
4.0；100%60 DEG C of water is added, it is 38 DEG C to keep bath temperature in rotary drum, is slowly run, and the 2-3 per minute that turns turns, overnight；
(7) it washes, go out drum：Next day, it is 93 DEG C to survey shrinkage temperature, adds 400% water, rotates 10min, goes out drum, and standing displays 1
It；
(8) water squeezing, shaving：By tanning displayed without chrome tanning sheepskin water squeezing, shaving, bilayer thickness 0.9mm-
1.1mm weighs, the calculating benchmark of the additive amount as subsequent handling additive；
(9) it neutralizes：100% water is added in rotary drum, it is 32 DEG C -35 DEG C that temperature in drum, which is arranged, and 2% sodium formate is added, and is turned
Dynamic 30min is added 0.5% and carries alkaline agent, rotates 60min, and it is 4.6 to survey pH value, controls water；
(10) it washes：400% water rotates 10min, controls water；
(11) stuffing, filling, dyeing：Normal process steps, it is 3.8 to survey pH value；
(12) it washes, go out drum：Normal process steps, it is 90 DEG C to survey shrinkage temperature；
(13) dry to arrange：Normal process steps；
(14) whitening：Normal process steps, it is 0.4mm-0.8mm that shaving, which keeps bilayer thickness,；
(15) soft, flatiron is fallen：Normal process steps；
(16) ruler, storage are arranged：Normal process steps.
Embodiment 4
The synthesis concrete operations of complexing agent：
(1) weigh 100 parts of glycerine respectively by mass fraction, 150 parts of maleic anhydride and 0.15 part to toluene sulphur
Acid.
(2) glycerine is added in four-hole bottle, adjusts 67 DEG C of the temperature of temperature control device for water bath, open condensed water and blender,
It is slowly added to maleic anhydride in whipping process, charging process control temp is no more than 75 DEG C.Disposable input catalyst, was added
Process control temperature is no more than 80 DEG C.Charging terminates, and starts to warm up, and temperature rises to 90-93 DEG C, is acylated 2.5 hours.Cool down 45 DEG C afterwards
Hereinafter, discharging obtains the maleic acid glycerine mixing monoesters intermediate that working substance is 100%.
(3) 100 parts of maleic acid glycerine mixing monoesters intermediates are weighed respectively by mass fraction, 1267 parts of water, 95 parts
20% ammonium hydroxide, 50 part 30% of sodium pyrosulfite.
(4) four-hole bottle is added in water and maleic acid glycerine mixing monoesters intermediate, adjusts the temperature of temperature control device for water bath
It is 52 DEG C, opens condensed water, intermediate is dispersed into white " milky " by stirring；The ammonium hydroxide for being added dropwise 20% carries out neutralization reaction, is added dropwise
At 30-60 minutes the control of process system temperature was added dropwise within 60 DEG C, neutralizing end system pH should be 6 in time control；It neutralizes
System is warming up to 60 DEG C after reaction, 30% sodium pyrosulfite is added dropwise, sodium pyrosulfite controlled in 60-120 minutes
It adds, system temperature control is within 65 DEG C during sodium pyrosulfite is added dropwise.System temperature control exists after completion of dropwise addition
80 DEG C, stirring carries out sulfonating reaction 210 minutes.System pH is about 6 after reaction.Cooling discharge is to get to solid content
35%, the sulfosuccinic acid monoester salt that carboxyl degree of neutralization is 95%, sulfonation degree is 90%.
The specific process of application of complexing agent is：
Conventional sheep acid skin → water squeezing → is weighed, and → return water → tanning → carries alkali → washes, goes out drum → water squeezing → neutralization → water
→ stuffing, filling, dyeing → is washed to wash, go out drum → dry arrangement → whitening → and fall soft, flatiron → row's ruler, storage.
(1) sheep acid skin：Selection is used for the sheepskin of clothing leather by pickling；
(2) water squeezing；
(3) it weighs：Weigh 530g, increases weight to 1590g, the calculating benchmark of the additive amount as subsequent handling additive is pressed
Mass percentage；
(4) return water：8% room temperature brine is added in rotary drum, throws skin, rotates 30min, it is 2.5 to survey bath foam pH value in drum；
(5) tanning：3% is added without chrome tanning companion, rotates 15min；0.5% non-ionic oil, 8% zirconium tanning agent, rotation is added
180min；6% complexing agent is added, rotates 120min；
(6) alkali is carried：It is added three times 2.1% and carries alkaline agent, often plus once rotate 30min, it is 3.8- to adjust bath foam pH value in drum
4.0；100%60 DEG C of water is added, it is 38 DEG C to keep bath temperature in rotary drum, is slowly run, and the 2-3 per minute that turns turns, overnight；
(7) it washes, go out drum：Next day, it is 96 DEG C to survey shrinkage temperature, adds 400% water, rotates 10min, goes out drum, and standing displays 1
It；
(8) water squeezing, shaving：By tanning displayed without chrome tanning sheepskin water squeezing, shaving, bilayer thickness 0.9mm-
1.1mm weighs, the calculating benchmark of the additive amount as subsequent handling additive；
(9) it neutralizes：100% water is added in rotary drum, it is 32 DEG C -35 DEG C that temperature in drum, which is arranged, and 2% sodium formate is added, and is turned
Dynamic 30min is added 0.5% and carries alkaline agent, rotates 60min, and it is 4.8 to survey pH value, controls water；
(10) it washes：400% water rotates 10min, controls water；
(11) stuffing, filling, dyeing：Normal process steps, it is 3.9 to survey pH value；
(12) it washes, go out drum：Normal process steps, it is 91 DEG C to survey shrinkage temperature；
(13) dry to arrange：Normal process steps；
(14) whitening：Normal process steps, it is 0.4mm-0.8mm that shaving, which keeps bilayer thickness,；
(15) soft, flatiron is fallen：Normal process steps；
(16) ruler, storage are arranged：Normal process steps.
Embodiment 5
The synthesis concrete operation step of complexing agent：
(1) weigh 100 parts of glycerine respectively by mass fraction, 130 parts of maleic anhydride and 0.15 part to toluene sulphur
Acid.
(2) glycerine is added in four-hole bottle, adjusts 67 DEG C of the temperature of temperature control device for water bath, open condensed water and blender,
It is slowly added to maleic anhydride in whipping process, charging process control temp is no more than 75 DEG C.Disposable input catalyst, was added
Process control temperature is no more than 80 DEG C.Charging terminates, and starts to warm up, and temperature rises to 90-93 DEG C, is acylated 2.5 hours.Cool down 45 DEG C afterwards
Hereinafter, discharging obtains the maleic acid glycerine mixing monoesters intermediate that working substance is 100%.
(3) 100 parts of maleic acid glycerine mixing monoesters intermediates are weighed respectively by mass fraction, 1267 parts of water, 95 parts
20% ammonium hydroxide, 50 part 30% of sodium pyrosulfite.
(4) four-hole bottle is added in water and maleic acid glycerine mixing monoesters intermediate, adjusts the temperature of temperature control device for water bath
It is 52 DEG C, opens condensed water, intermediate is dispersed into white " milky " by stirring；The ammonium hydroxide for being added dropwise 20% carries out neutralization reaction, is added dropwise
At 30-60 minutes the control of process system temperature was added dropwise within 60 DEG C, neutralizing end system pH should be 6 in time control；It neutralizes
System is warming up to 60 DEG C after reaction, 30% sodium pyrosulfite is added dropwise, sodium pyrosulfite controlled in 60-120 minutes
It adds, system temperature control is within 65 DEG C during sodium pyrosulfite is added dropwise.System temperature control exists after completion of dropwise addition
80 DEG C, stirring carries out sulfonating reaction 210 minutes.System pH is about 6 after reaction.Cooling discharge is to get to solid content
35%, the sulfosuccinic acid monoester salt that carboxyl degree of neutralization is 95%, sulfonation degree is 90%.
The specific process of application of complexing agent is：
Conventional sheep acid skin → water squeezing → is weighed, and → return water → tanning → carries alkali → washes, goes out drum → water squeezing → neutralization → water
→ stuffing, filling, dyeing → is washed to wash, go out drum → dry arrangement → whitening → and fall soft, flatiron → row's ruler, storage.
(1) sheep acid skin：Selection is used for the sheepskin of clothing leather by pickling；
(2) water squeezing；
(3) it weighs：Weigh 520g, increases weight to 1560g, the calculating benchmark of the additive amount as subsequent handling additive is pressed
Mass percentage；
(4) return water：8% room temperature brine is added in rotary drum, throws skin, rotates 30min, it is 2.5 to survey bath foam pH value in drum；
(5) tanning：3% is added without chrome tanning companion, rotates 15min；0.5% non-ionic oil, 8% zirconium tanning agent, rotation is added
180min；6% complexing agent is added, rotates 120min；
(6) alkali is carried：It is added three times 2.1% and carries alkaline agent, often plus once rotate 30min, it is 3.8- to adjust bath foam pH value in drum
4.0；100%60 DEG C of water is added, it is 38 DEG C to keep bath temperature in rotary drum, is slowly run, and the 2-3 per minute that turns turns, overnight；
(7) it washes, go out drum：Next day, it is 95.5 DEG C to survey shrinkage temperature, adds 400% water, rotates 10min, goes out drum, is stood old
It puts 1 day；
(8) water squeezing, shaving：By tanning displayed without chrome tanning sheepskin water squeezing, shaving, bilayer thickness 0.9mm-
1.1mm it weighs, the calculating benchmark of the additive amount as subsequent handling additive；
(9) it neutralizes：100% water is added in rotary drum, it is 32 DEG C -35 DEG C that temperature in drum, which is arranged, and 2% sodium formate is added, and is turned
Dynamic 30min is added 0.5% and carries alkaline agent, rotates 60min, and it is 4.8 to survey pH value, controls water；
(10) it washes：400% water rotates 10min, controls water；
(11) stuffing, filling, dyeing：Normal process steps, it is 3.9 to survey pH value
(12) it washes, go out drum：Normal process steps, it is 91 DEG C to survey shrinkage temperature；
(13) dry to arrange：Normal process steps；
(14) whitening：Normal process steps, it is 0.4mm-0.8mm that shaving, which keeps bilayer thickness,；
(15) soft, flatiron is fallen：Normal process steps；
(16) ruler, storage are arranged：Normal process steps.
Embodiment 6
The synthesis concrete operation step of complexing agent：
(1) weigh 100 parts of glycerine respectively by mass fraction, 120 parts of maleic anhydride and 0.15 part to toluene sulphur
Acid.
(2) glycerine is added in four-hole bottle, adjusts 67 DEG C of the temperature of temperature control device for water bath, open condensed water and blender,
It is slowly added to maleic anhydride in whipping process, charging process control temp is no more than 75 DEG C.Disposable input catalyst, was added
Process control temperature is no more than 80 DEG C.Charging terminates, and starts to warm up, and temperature rises to 90-93 DEG C, is acylated 2.5 hours.Cool down 45 DEG C afterwards
Hereinafter, discharging obtains the maleic acid glycerine mixing monoesters intermediate that working substance is 100%.
(3) 100 parts of maleic acid glycerine mixing monoesters intermediates are weighed respectively by mass fraction, 1267 parts of water, 95 parts
20% ammonium hydroxide, 50 part 30% of sodium pyrosulfite.
(4) four-hole bottle is added in water and maleic acid glycerine mixing monoesters intermediate, adjusts the temperature of temperature control device for water bath
It is 52 DEG C, opens condensed water, intermediate is dispersed into white " milky " by stirring；The ammonium hydroxide for being added dropwise 20% carries out neutralization reaction, is added dropwise
At 30-60 minutes the control of process system temperature was added dropwise within 60 DEG C, neutralizing end system pH should be 6 in time control；It neutralizes
System is warming up to 60 DEG C after reaction, 30% sodium pyrosulfite is added dropwise, sodium pyrosulfite controlled in 60-120 minutes
It adds, system temperature control is within 65 DEG C during sodium pyrosulfite is added dropwise.System temperature control exists after completion of dropwise addition
80 DEG C, stirring carries out sulfonating reaction 210 minutes.System pH is about 6 after reaction.Cooling discharge is to get to solid content
35%, the sulfosuccinic acid monoester salt that carboxyl degree of neutralization is 95%, sulfonation degree is 90%.
The specific process of application of complexing agent is：
Conventional sheep acid skin → water squeezing → is weighed, and → return water → tanning → carries alkali → washes, goes out drum → water squeezing → neutralization → water
→ stuffing, filling, dyeing → is washed to wash, go out drum → dry arrangement → whitening → and fall soft, flatiron → row's ruler, storage
(1) sheep acid skin：Selection is used for the sheepskin of clothing leather by pickling；
(2) water squeezing；
(3) it weighs：Weigh 550g, increases weight to 1650g, the calculating benchmark of the additive amount as subsequent handling additive is pressed
Mass percentage；
(4) return water：8% room temperature brine is added in rotary drum, throws skin, rotates 30min, it is 2.5 to survey bath foam pH value in drum；
(5) tanning：3% is added without chrome tanning companion, rotates 15min；0.5% non-ionic oil, 8% zirconium tanning agent, rotation is added
180min；6% complexing agent is added, rotates 120min；
(6) alkali is carried：It is added three times 2.1% and carries alkaline agent, often plus once rotate 30min, it is 3.8- to adjust bath foam pH value in drum
4.0；100%60 DEG C of water is added, it is 38 DEG C to keep bath temperature in rotary drum, is slowly run, and the 2-3 per minute that turns turns, overnight；
(7) it washes, go out drum：Next day, it is 94.5 DEG C to survey shrinkage temperature, adds 400% water, rotates 10min, goes out drum, is stood old
It puts 1 day；
(8) water squeezing, shaving：By tanning displayed without chrome tanning sheepskin water squeezing, shaving, bilayer thickness 0.9mm-
1.1mm weighs, the calculating benchmark of the additive amount as subsequent handling additive；
(9) it neutralizes：100% water is added in rotary drum, it is 32 DEG C -35 DEG C that temperature in drum, which is arranged, and 2% sodium formate is added, and is turned
Dynamic 30min is added 0.5% and carries alkaline agent, rotates 60min, and it is 4.8 to survey pH value, controls water；
(10) it washes：400% water rotates 10min, controls water；
(11) stuffing, filling, dyeing：Normal process steps, it is 3.8 to survey pH value；
(12) it washes, go out drum：Normal process steps, it is 91 DEG C to survey shrinkage temperature；
(13) dry to arrange：Normal process steps；
(14) whitening：Normal process steps, it is 0.4mm-0.8mm that shaving, which keeps bilayer thickness,；
(15) soft, flatiron is fallen：Normal process steps；
(16) ruler, storage are arranged：Normal process steps.
Embodiment 7
The synthesis concrete operation step of complexing agent：
(1) weigh 100 parts of glycerine respectively by mass fraction, 140 parts of maleic anhydride and 0.15 part to toluene sulphur
Acid.
(2) glycerine is added in four-hole bottle, adjusts 67 DEG C of the temperature of temperature control device for water bath, open condensed water and blender,
It is slowly added to maleic anhydride in whipping process, charging process control temp is no more than 75 DEG C.Disposable input catalyst, was added
Process control temperature is no more than 80 DEG C.Charging terminates, and starts to warm up, and temperature rises to 90-93 DEG C, is acylated 2.5 hours.Cool down 45 DEG C afterwards
Hereinafter, discharging obtains the maleic acid glycerine mixing monoesters intermediate that working substance is 100%.
(3) 100 parts of maleic acid glycerine mixing monoesters intermediates are weighed respectively by mass fraction, 1267 parts of water, 95 parts
20% ammonium hydroxide, 45 part 30% of sodium pyrosulfite.
(4) four-hole bottle is added in water and maleic acid glycerine mixing monoesters intermediate, adjusts the temperature of temperature control device for water bath
It is 52 DEG C, opens condensed water, intermediate is dispersed into white " milky " by stirring；The ammonium hydroxide for being added dropwise 20% carries out neutralization reaction, is added dropwise
At 30-60 minutes the control of process system temperature was added dropwise within 60 DEG C, neutralizing end system pH should be 6 in time control；It neutralizes
System is warming up to 60 DEG C after reaction, 30% sodium pyrosulfite is added dropwise, sodium pyrosulfite controlled in 60-120 minutes
It adds, system temperature control is within 65 DEG C during sodium pyrosulfite is added dropwise.System temperature control exists after completion of dropwise addition
80 DEG C, stirring carries out sulfonating reaction 210 minutes.System pH is about 6 after reaction.Cooling discharge is to get to solid content
35%, the sulfosuccinic acid monoester salt that carboxyl degree of neutralization is 95%, sulfonation degree is 89%.
The specific process of application of complexing agent is：
Conventional sheep acid skin → water squeezing → is weighed, and → return water → tanning → carries alkali → washes, goes out drum → water squeezing → neutralization → water
→ stuffing, filling, dyeing → is washed to wash, go out drum → dry arrangement → whitening → and fall soft, flatiron → row's ruler, storage
(1) sheep acid skin：Selection is used for the sheepskin of clothing leather by pickling；
(2) water squeezing；
(3) it weighs：Weigh 570g, increases weight to 1710g, the calculating benchmark of the additive amount as subsequent handling additive is pressed
Mass percentage；
(4) return water：8% room temperature brine is added in rotary drum, throws skin, rotates 30min, it is 2.5 to survey bath foam pH value in drum；
(5) tanning：3% is added without chrome tanning companion, rotates 15min；0.5% non-ionic oil, 8% zirconium tanning agent, rotation is added
180min；6% complexing agent is added, rotates 120min；
(6) alkali is carried：It is added three times 2.1% and carries alkaline agent, often plus once rotate 30min, it is 3.8- to adjust bath foam pH value in drum
4.0；100%60 DEG C of water is added, it is 38 DEG C to keep bath temperature in rotary drum, is slowly run, and the 2-3 per minute that turns turns, overnight；
(7) it washes, go out drum：Next day, it is 95 DEG C to survey shrinkage temperature, adds 400% water, rotates 10min, goes out drum, and standing displays 1
It；
(8) water squeezing, shaving：By tanning displayed without chrome tanning sheepskin water squeezing, shaving, bilayer thickness 0.9mm-
1.1mm weighs, the calculating benchmark of the additive amount as subsequent handling additive；
(9) it neutralizes：100% water is added in rotary drum, it is 32 DEG C -35 DEG C that temperature in drum, which is arranged, and 2% sodium formate is added, and is turned
Dynamic 30min is added 0.5% and carries alkaline agent, rotates 60min, and it is 4.8 to survey pH value, controls water；
(10) it washes：400% water rotates 10min, controls water；
(11) stuffing, filling, dyeing：Normal process steps, it is 3.9 to survey pH value；
(12) it washes, go out drum：Normal process steps, it is 90.5 DEG C to survey shrinkage temperature；
(13) dry to arrange：Normal process steps；
(14) whitening：Normal process steps, it is 0.4mm-0.8mm that shaving, which keeps bilayer thickness,；
(15) soft, flatiron is fallen：Normal process steps；
(16) ruler, storage are arranged：Normal process steps.
Above-described embodiment is served only for that invention is further explained to the specific descriptions of the present invention, should not be understood as
Limiting the scope of the present invention, it is non-that the technician of this field according to the content of foregoing invention makes some to the present invention
The modifications and adaptations of essence are each fallen within protection scope of the present invention.
Claims (2)
1. a kind of being used for application of complexing agent of the leather without chrome tanning tanning processes in leather tanning, including is used for leather without chrome tanning
The complexing agent of tanning processes, it is characterised in that：The complexing agent includes that resistance to strong acid, resistance to strong electrolyte and resisting high-concentration metal are molten
The hydrophilic radical of liquid, complexing agent are the sulfonation that total solids content is 35%, carboxyl degree of neutralization is 95%, sulfonation degree is 90%
Succinic monoester salt；
The preparation method of the complexing agent, includes the following steps：
(1) 67~100 parts of glycerine, 100 parts of maleic anhydride and 0.15 part of catalyst are weighed respectively by mass fraction；
(2) glycerine is added in reactor, opens condensed water and blender, adjust 65-70 DEG C of temperature, maleic anhydride is added, adds
Expect that process control temp is no more than 75 DEG C, disposably put into catalyst, adition process controls temperature and is no more than 80 DEG C, charging knot
Beam starts to warm up, and temperature rises to 90-93 DEG C, cools down 45 DEG C after 2.5 hours acylated hereinafter, it is 100% that discharging, which obtains working substance,
Maleic acid glycerine mixing monoesters intermediate；
(3) 100 parts of maleic acid glycerine mixing monoesters intermediate, 1267 parts of water, 95 parts of ammonium hydroxide are weighed respectively by mass fraction
With 45~50 part 30% of sodium metabisulfite solution；
(4) reactor is added in water and maleic acid glycerine mixing monoesters intermediate, setting temperature is 50~55 DEG C, is opened cold
Condensate stirs, and intermediate is dispersed into white " milky "；Ammonium hydroxide is added dropwise and carries out neutralization reaction, time for adding is controlled at 30~60 points
The control of process system temperature is added dropwise within 60 DEG C in clock, and neutralizing end system pH should be 5.5~6；It will after neutralization reaction
System is warming up to 60 DEG C, and sodium pyrosulfite is added dropwise, and sodium pyrosulfite control adds in 60~120 minutes, and burnt sulfurous is being added dropwise
System temperature control is within 65 DEG C during sour sodium, and at 80 DEG C, stirring carries out sulfonation for system temperature control after completion of dropwise addition
Reaction 210 minutes, after reaction system pH be 6, cooling discharge, obtain solid content be 35%, carboxyl degree of neutralization be 95%,
The sulfosuccinic acid monoester salt that sulfonation degree is 90%；
Application of the complexing agent in leather tanning includes the following steps：
(1) sheep acid skin：Selection is used for the sheepskin of clothing leather by pickling；
(2) water squeezing：Normal process steps；
(3) it weighs：It increases weight to 300% calculating benchmark as the additive amount of subsequent handling additive after weighing；
(4) return water：The room temperature brine of 6%-8% is added in rotary drum, throws skin, rotates 30min, it is 2.5- to survey bath foam pH value in drum
2.8；
(5) tanning：3% is added without chrome tanning companion, rotates 15min；0.5% non-ionic oil, 6%-10% zirconium tanning agents, rotation is added
180min；The complexing agent of 3%-7.5% is added, rotates 120min；
(6) alkali is carried：Divide 3-4 addition to carry alkaline agent, often plus once rotate 30min, it is 3.8-4.0 to adjust bath foam pH value in rousing；Add
Enter 100%60 DEG C of water, it is 38 DEG C to keep bath temperature in rotary drum, is slowly run, and the 2-3 per minute that turns turns, overnight；
(7) it washes, go out drum：Next day surveys shrinkage temperature, washes out drum, and standing is displayed 1 day or more；
(8) water squeezing, shaving：By tanning displayed without chrome tanning sheepskin water squeezing, shaving, bilayer thickness 0.9mm-1.1mm claims
Weight, the calculating benchmark of the additive amount as subsequent handling additive；
(9) it neutralizes：100% water is added in rotary drum for normal process steps, and it is 32 DEG C -35 DEG C that temperature in drum, which is arranged, and 2% formic acid is added
Sodium rotates 30min, is added 0.5% and carries alkaline agent, rotates 60min, and survey pH value is 4.5-4.8, controls water；
(10) it washes：Normal process steps；
(11) stuffing, filling, dyeing：Normal process steps；
(12) it washes, go out drum：Normal process steps；
(13) dry to arrange：Normal process steps；
(14) whitening：Normal process steps, it is 0.4mm-0.8mm that shaving, which keeps bilayer thickness,；
(15) soft, flatiron is fallen：Normal process steps；
(16) ruler, storage are arranged：Normal process steps；
Wherein, raw materials used to count in parts by weight.
2. according to claim 1 a kind of for complexing agent of the leather without chrome tanning tanning processes answering in leather tanning
With, it is characterised in that：The catalyst is benzene methanesulfonic acid；Ammonium hydroxide is ammonia spirit.
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| CN102776301B (en) * | 2012-06-21 | 2013-11-20 | 陕西科技大学 | Method for preparing leather fat liquoring agents |
| CN104357593B (en) * | 2014-11-25 | 2016-06-08 | 陕西科技大学 | Leather tanning water soluble sulfonated resorcinol calixarenes tanning agent and preparation method thereof |
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| 磺化琥珀酸酯盐类结合型加脂剂技术发展探讨;兰云军等;《中国皮革》;20130831;第36-39、42页 * |
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Application publication date: 20170222 Assignee: HAINING FUSHENG FURLEATHER Co.,Ltd. Assignor: Wenzhou University Contract record no.: X2020330000087 Denomination of invention: A complexing agent for chrome free leather tanning and its preparation method and Application Granted publication date: 20181019 License type: Common License Record date: 20201103 |
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