CN107502686A - A kind of preparation method of aromatic sulphonic acid amphoteric retanning agent - Google Patents
A kind of preparation method of aromatic sulphonic acid amphoteric retanning agent Download PDFInfo
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- CN107502686A CN107502686A CN201710736692.XA CN201710736692A CN107502686A CN 107502686 A CN107502686 A CN 107502686A CN 201710736692 A CN201710736692 A CN 201710736692A CN 107502686 A CN107502686 A CN 107502686A
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- preparation
- retanning agent
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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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention discloses a kind of preparation method of aromatic sulphonic acid amphoteric retanning agent, by sulfonation, for the first time condensation, resinon synthesis, second of condensation and drying steps, completes the preparation of amphoteric retanning agent.It the advantage is that：The present invention adds excessive ammonium sulfite during secondary condensation, is reacted with the free formaldehyde in material, and the content of formaldehyde for making to dissociate in product is reduced, more environmentally friendly；The amphoteric retanning agent of preparation and can have peptizaiton with conventional cation retanning agent, chrome tanning agent and compatible containing chrome tanning agent to vegetable tanning agent；For the amphoteric retanning agent of preparation compared with traditional syntans, blanching effect is smaller, and finished leather easily dyes dark color, and finished leather can be made, which to obtain solid, fine and smooth grain and moderate richness and flexibility, finished leather, has preferable light resistance and heat resistance.
Description
Technical field
The invention belongs to leather chemicals synthesis technical field, and in particular to a kind of system of aromatic sulphonic acid amphoteric retanning agent
Preparation Method.
Background technology
Retanning is occupied an important position in light leather production, " Golden Touch " being described as by leather circle in process hides, and retanning is imitated
The quality of fruit directly depends on the quality of retanning agent performance.Therefore, excellent performance is developed, retanning agent with conspicuous characteristics is always skin
Remove from office one of target of chemical materials research.
Anion retanning agent has excellent filling, improves the performances such as feel, but easily retan is produced phenomenon of losing colour.
Cation retanning agent is difficult to permeate between anionic property leather fiber, does not use typically, is mainly used as separately as retanning agent
The solid oil assistant of the fixation in dyeing and stuffing later stage.Both sexes leather composite tanning agent can take into account anionic and cationic retanning agent
Advantage, existing anionic retanning agent fillibility is good, improves the characteristics of leather feel, the performance for also having the solid oil of excellent fixation.
Aromatic sulphonic acid amphoteric retanning agent is also known as amphoteric retanning agent AN, and preparation technology is simple, can be with a variety of retanning agent phases
Hold, but non-PARA FORMALDEHYDE PRILLS(91,95) is handled through row in traditional preparation process so that the content of formaldehyde wandered about as a refugee in product is more, does not meet environmental protection
Requirement.
The content of the invention
The purpose of the present invention is overcome the deficiencies in the prior art, now provides that a kind of technique is simple, content of formaldehyde is few, environmentally friendly
The preparation method of aromatic sulphonic acid amphoteric retanning agent.
In order to solve the above technical problems, the technical solution adopted by the present invention is：A kind of aromatic sulphonic acid amphoteric retanning agent
Preparation method, its innovative point are：It is complete by sulfonation, for the first time condensation, resinon synthesis, second of condensation and drying steps
Into the preparation of amphoteric retanning agent；It is described to comprise the following steps that：
（1）Sulfonation：Added after first 95-100Kg phenol is dissolved in sulfonating reaction kettle, open stirring, then add 110-120kg
Concentration is 98% concentrated sulfuric acid, in 100 DEG C of anti-1.5-2.5h of insulation；
（2）It is condensed for the first time：Material after sulfonating reaction is all transferred to condensation kettle, adds 50-70Kg urea, temperature control
At 70 DEG C, 90-100Kg formaldehyde is added, after formaldehyde adds, cooling, adds 95Kg liquid caustic soda；
（3）Resinon synthesizes：170-190Kg water is added in synthesis reactor, is then turned on stirring, adds 95-100Kg pyrosulfurous acids
Sodium, after sodium pyrosulfite is completely dissolved, 70-80Kg formaldehyde is added, temperature in the kettle is risen to 80 DEG C, then sequentially added：18-
19Kg aniline, 7-8Kg melamines, 12-13Kg urea, 22-23Kg formaldehyde, continue to react 1.5-2.5h at 80 DEG C；
（4）Second of condensation：The material that above-mentioned synthetic resinon is all transferred into condensation kettle and has been condensed for the first time mixes,
15-25kg formaldehyde is added, continues to react 1.5-2.5h at 80 DEG C, then addition 25-35Kg liquid caustic soda, 5-15Kg sodium hydrogensulfites,
Cool to 50-60 DEG C to continue to react 1h, then add 10-20Kg formic acid, it is 4 to adjust material pH value in kettle, is removed by filtration miscellaneous
Matter, filtrate are transferred to semi-finished product tank；
（5）Dry：Material in semi-finished product tank is delivered to press spray drying tower through pump, is spray-dried, product is through two
Secondary cyclonic separation enters feed bin, and water vapour is vented through secondary water film dedusting in drying tower, completes the preparation of amphoteric retanning agent.
Further, the step（2）And step（4）Middle liquid caustic soda is sodium hydroxide solution, and the mass concentration of liquid caustic soda is
32%。
Further, the step（5）Middle drying tower EAT is 250-270 DEG C, leaving air temp is 110-130 DEG C.
Beneficial effects of the present invention are as follows：
（1）The present invention adds excessive ammonium sulfite during secondary condensation, occurs with the free formaldehyde in material anti-
Should, the content of formaldehyde for making to dissociate in product is reduced, more environmentally friendly；
（2）Amphoteric retanning agent prepared by the present invention can be with conventional cation retanning agent, chrome tanning agent and compatible containing chrome tanning agent and right
Vegetable tanning agent has peptizaiton；
（3）For amphoteric retanning agent prepared by the present invention compared with traditional syntans, blanching effect is smaller, and finished leather easily dyes depth
Color, finished leather can be made to obtain solid, fine and smooth grain and moderate richness and flexibility, finished leather has preferable light resistance and resistance to
It is hot.
Brief description of the drawings
The present invention is described in further details with reference to the accompanying drawings and detailed description.
Fig. 1 is the process chart of the present invention.
Embodiment
Embodiments of the present invention are illustrated by particular specific embodiment below, those skilled in the art can be by this explanation
Content disclosed by book understands other advantages and effect of the present invention easily.
Embodiment 1
A kind of preparation method of aromatic sulphonic acid amphoteric retanning agent, synthesized, for the second time by sulfonation, for the first time condensation, resinon
Condensation and drying steps, complete the preparation of amphoteric retanning agent；Comprise the following steps that：
（1）Sulfonation：Added after first 95Kg phenol is dissolved in sulfonating reaction kettle, open stirring, then adding 110kg concentration is
98% concentrated sulfuric acid, in 100 DEG C of anti-1.5h of insulation；
（2）It is condensed for the first time：Material after sulfonating reaction is all transferred to condensation kettle, adds 50Kg urea, temperature control exists
70 DEG C, 90Kg formaldehyde is added, after formaldehyde adds, cooling, adds the sodium hydroxide solution that 95Kg mass concentrations are 32%；
（3）Resinon synthesizes：170Kg water is added in synthesis reactor, is then turned on stirring, 95Kg sodium pyrosulfites is added, treats Jiao
After sodium sulfite is completely dissolved, 70Kg formaldehyde is added, temperature in the kettle is risen to 80 DEG C, then sequentially added：18Kg aniline, 7Kg
Melamine, 12Kg urea, 22Kg formaldehyde, continue to react 1.5h at 80 DEG C；
（4）Second of condensation：The material that above-mentioned synthetic resinon is all transferred into condensation kettle and has been condensed for the first time mixes,
15kg formaldehyde is added, continues to react 1.5h at 80 DEG C, then adds the sodium hydroxide solution that 25Kg mass concentrations are 32%, 5Kg is sub-
Niter cake, cool to 50 DEG C and continue to react 1h, then add 10Kg formic acid, it is 4 to adjust material pH value in kettle, is removed by filtration
Impurity, filtrate are transferred to semi-finished product tank；
（5）Dry：Material in semi-finished product tank is delivered to press spray drying tower through pump, is spray-dried, drying tower enters
Air temperature is 250 DEG C, leaving air temp is 110 DEG C, and product is segregated into feed bin through secondary cyclone, and water vapour is through secondary in drying tower
Water film dedusting is vented, and completes the preparation of amphoteric retanning agent.
Embodiment 2
A kind of preparation method of aromatic sulphonic acid amphoteric retanning agent, synthesized, for the second time by sulfonation, for the first time condensation, resinon
Condensation and drying steps, complete the preparation of amphoteric retanning agent；Comprise the following steps that：
（1）Sulfonation：Added after first 100Kg phenol is dissolved in sulfonating reaction kettle, open stirring, then adding 120kg concentration is
98% concentrated sulfuric acid, in 100 DEG C of anti-2.5h of insulation；
（2）It is condensed for the first time：Material after sulfonating reaction is all transferred to condensation kettle, adds 70Kg urea, temperature control exists
70 DEG C, 100Kg formaldehyde is added, after formaldehyde adds, cooling, adds the sodium hydroxide solution that 95Kg mass concentrations are 32%；
（3）Resinon synthesizes：190Kg water is added in synthesis reactor, is then turned on stirring, 100Kg sodium pyrosulfites is added, treats Jiao
After sodium sulfite is completely dissolved, 80Kg formaldehyde is added, temperature in the kettle is risen to 80 DEG C, then sequentially added：19Kg aniline, 8Kg
Melamine, 13Kg urea, 23Kg formaldehyde, continue to react 2.5h at 80 DEG C；
（4）Second of condensation：The material that above-mentioned synthetic resinon is all transferred into condensation kettle and has been condensed for the first time mixes,
25kg formaldehyde is added, continues to react 2.5h at 80 DEG C, then adds the sodium hydroxide solution that 35Kg mass concentrations are 32%, 15Kg
Sodium hydrogensulfite, cool to 60 DEG C and continue to react 1h, then add 20Kg formic acid, it is 4 to adjust material pH value in kettle, filtered to remove
Decontamination, filtrate are transferred to semi-finished product tank；
（5）Dry：Material in semi-finished product tank is delivered to press spray drying tower through pump, is spray-dried, drying tower enters
Air temperature is 270 DEG C, leaving air temp is 130 DEG C, and product is segregated into feed bin through secondary cyclone, and water vapour is through secondary in drying tower
Water film dedusting is vented, and completes the preparation of amphoteric retanning agent.
Embodiment 3
A kind of preparation method of aromatic sulphonic acid amphoteric retanning agent, synthesized, for the second time by sulfonation, for the first time condensation, resinon
Condensation and drying steps, complete the preparation of amphoteric retanning agent；Comprise the following steps that：
（1）Sulfonation：Added after first 97Kg phenol is dissolved in sulfonating reaction kettle, open stirring, then adding 114kg concentration is
98% concentrated sulfuric acid, in 100 DEG C of anti-2h of insulation；
（2）It is condensed for the first time：Material after sulfonating reaction is all transferred to condensation kettle, adds 60Kg urea, temperature control exists
70 DEG C, 94Kg formaldehyde is added, after formaldehyde adds, cooling, adds the sodium hydroxide solution that 95Kg mass concentrations are 32%；
（3）Resinon synthesizes：180Kg water is added in synthesis reactor, is then turned on stirring, 97Kg sodium pyrosulfites is added, treats Jiao
After sodium sulfite is completely dissolved, 74Kg formaldehyde is added, temperature in the kettle is risen to 80 DEG C, then sequentially added：18.5Kg aniline,
7.5Kg melamines, 12.5Kg urea, 22.5Kg formaldehyde, continue to react 2h at 80 DEG C；
（4）Second of condensation：The material that above-mentioned synthetic resinon is all transferred into condensation kettle and has been condensed for the first time mixes,
20kg formaldehyde is added, continues to react 2h at 80 DEG C, then adds the sodium hydroxide solution that 30Kg mass concentrations are 32%, 10Kg is sub-
Niter cake, cool to 55 DEG C and continue to react 1h, then add 15Kg formic acid, it is 4 to adjust material pH value in kettle, is removed by filtration
Impurity, filtrate are transferred to semi-finished product tank；
（5）Dry：Material in semi-finished product tank is delivered to press spray drying tower through pump, is spray-dried, drying tower enters
Air temperature is 260 DEG C, leaving air temp is 120 DEG C, and product is segregated into feed bin through secondary cyclone, and water vapour is through secondary in drying tower
Water film dedusting is vented, and completes the preparation of amphoteric retanning agent.
Physical and chemical index by the embodiment 1-3 aromatic sulphonic acid amphoteric retanning agents prepared is as shown in table 1.
It is as shown in table 2 to the application index of crust leather retanning by aromatic sulphonic acid amphoteric retanning agent prepared by embodiment 1-3.
The physical and chemical index of aromatic sulphonic acid amphoteric retanning agent prepared by the embodiment 1-3 of table 1
Note：Outward appearance is tested with eyesight；Solid content presses GB/T2793-1995 standards；10% aromatic sulphonic acid amphoteric retanning agent is water-soluble
Liquid pH value presses GB/T6368-2008 standards；Free formaldehyde content presses HJ601-2011 standards.
The application index of aromatic sulphonic acid amphoteric retanning agent prepared by the embodiment 1-3 of table 2 to crust leather retanning
Note：Rate is thickened by QB/T2709-2005 standards, is calculated according to formula（Wherein d1 is the thickness of rawhide, and d2 is tanning finished leather
Thickness after drying）；Shrinkage temperature presses QB/T2713-2005 standards；Richness, flexibility, grain particulate degree are according to sense organ
Evaluation, wherein full marks are 10 points.
From Tables 1 and 2, aromatic sulphonic acid amphoteric retanning agent made from embodiment 1-3 can with cation retanning agent,
Chromium retanning agent is compatible with containing chrome syntans, and the content of formaldehyde concentration dissociated in product is relatively low；Have by finished leather after tanning
Preferable richness and moderate flexibility, finished leather have fine and smooth grain.
Described above is the preferred embodiment of the present invention, it is impossible to the interest field of the present invention is limited with this.It should refer to
Go out, for those skilled in the art, technical scheme is modified or equivalent substitution, all
Protection scope of the present invention is not departed from.
Claims (3)
- A kind of 1. preparation method of aromatic sulphonic acid amphoteric retanning agent, it is characterised in that：By sulfonation, for the first time condensation, resin Oil synthesis, second of condensation and drying steps, complete the preparation of amphoteric retanning agent；It is described to comprise the following steps that：（1）Sulfonation：Added after first 95-100Kg phenol is dissolved in sulfonating reaction kettle, open stirring, then add 110-120kg Concentration is 98% concentrated sulfuric acid, in 100 DEG C of anti-1.5-2.5h of insulation；（2）It is condensed for the first time：Material after sulfonating reaction is all transferred to condensation kettle, adds 50-70Kg urea, temperature control At 70 DEG C, 90-100Kg formaldehyde is added, after formaldehyde adds, cooling, adds 95Kg liquid caustic soda；（3）Resinon synthesizes：170-190Kg water is added in synthesis reactor, is then turned on stirring, adds 95-100Kg pyrosulfurous acids Sodium, after sodium pyrosulfite is completely dissolved, 70-80Kg formaldehyde is added, temperature in the kettle is risen to 80 DEG C, then sequentially added：18- 19Kg aniline, 7-8Kg melamines, 12-13Kg urea, 22-23Kg formaldehyde, continue to react 1.5-2.5h at 80 DEG C；（4）Second of condensation：The material that above-mentioned synthetic resinon is all transferred into condensation kettle and has been condensed for the first time mixes, 15-25kg formaldehyde is added, continues to react 1.5-2.5h at 80 DEG C, then addition 25-35Kg liquid caustic soda, 5-15Kg sodium hydrogensulfites, Cool to 50-60 DEG C to continue to react 1h, then add 10-20Kg formic acid, it is 4 to adjust material pH value in kettle, is removed by filtration miscellaneous Matter, filtrate are transferred to semi-finished product tank；（5）Dry：Material in semi-finished product tank is delivered to press spray drying tower through pump, is spray-dried, product is through two Secondary cyclonic separation enters feed bin, and water vapour is vented through secondary water film dedusting in drying tower, completes the preparation of amphoteric retanning agent.
- A kind of 2. preparation method of aromatic sulphonic acid amphoteric retanning agent according to claim 1, it is characterised in that：The step Suddenly（2）And step（4）Middle liquid caustic soda is sodium hydroxide solution, and the mass concentration of liquid caustic soda is 32%.
- A kind of 3. preparation method of aromatic sulphonic acid amphoteric retanning agent according to claim 1, it is characterised in that：The step Suddenly（5）Middle drying tower EAT is 250-270 DEG C, leaving air temp is 110-130 DEG C.
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| CN201710736692.XA CN107502686B (en) | 2017-08-24 | 2017-08-24 | Preparation method of aromatic sulfonic acid amphoteric retanning agent |
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| CN201710736692.XA CN107502686B (en) | 2017-08-24 | 2017-08-24 | Preparation method of aromatic sulfonic acid amphoteric retanning agent |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103665290A (en) * | 2013-12-06 | 2014-03-26 | 上海金狮化工有限公司 | Preparation method for low-formaldehyde melamine resin retanning agent |
| CN104017920A (en) * | 2014-06-11 | 2014-09-03 | 四川德赛尔化工实业有限公司 | Formaldehyde-free amino resin retanning agent |
| CN105586444A (en) * | 2016-01-06 | 2016-05-18 | 四川大学 | Leather retaining-filling agent prepared by means of phenolsulfonic acid hydrolysis leather-making waste |
-
2017
- 2017-08-24 CN CN201710736692.XA patent/CN107502686B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103665290A (en) * | 2013-12-06 | 2014-03-26 | 上海金狮化工有限公司 | Preparation method for low-formaldehyde melamine resin retanning agent |
| CN104017920A (en) * | 2014-06-11 | 2014-09-03 | 四川德赛尔化工实业有限公司 | Formaldehyde-free amino resin retanning agent |
| CN105586444A (en) * | 2016-01-06 | 2016-05-18 | 四川大学 | Leather retaining-filling agent prepared by means of phenolsulfonic acid hydrolysis leather-making waste |
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| CN107502686B (en) | 2020-05-15 |
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Effective date of registration: 20200422 Address after: No.169, Lifa Avenue, Chengdong Town, Haian Development Zone, Nantong City, Jiangsu Province Applicant after: HAIAN JIDE ELECTROMECHANICAL TECHNOLOGY DEVELOPMENT Co.,Ltd. Address before: 226400 south side of the Yellow Sea three road, Nantong Coastal Economic Development Zone, Rudong County, Jiangsu Applicant before: NANTONG SHUANGSHI CHEMICAL Co.,Ltd. |
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