CN106755627B - A kind of few salt auxiliary pickling agent and preparation method thereof - Google Patents
A kind of few salt auxiliary pickling agent and preparation method thereof Download PDFInfo
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- CN106755627B CN106755627B CN201710015103.9A CN201710015103A CN106755627B CN 106755627 B CN106755627 B CN 106755627B CN 201710015103 A CN201710015103 A CN 201710015103A CN 106755627 B CN106755627 B CN 106755627B
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- pickling agent
- pickling
- auxiliary pickling
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- few salt
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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
- C14C1/00—Chemical treatment prior to tanning
- C14C1/08—Deliming; Bating; Pickling; Degreasing
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention belongs to leather technology fields, and in particular to a kind of few salt auxiliary pickling agent and preparation method thereof, the primary structure of the auxiliary pickling agent is：Wherein：M represents Na+ or H+；X represent H orY is representedAuxiliary pickling agent prepared by the present invention is added in process hides pickling procedure, and can inhibiting sour skin, the few salt pickling chrome tanning process method of implementation can fundamentally greatly reduce the salt pollution during process hides pickling in the swelling of few salt；H can be ionized out due to containing in the auxiliary pickling agent molecular structure of synthesis+Sulfonic group and phenolic hydroxyl group, it is possible to reduce the dosage of inorganic acid during pickling；Traditional process hides pickling technique need not be changed, operating procedure is simple and easy to do.
Description
Technical field
The invention belongs to leather technology fields, and in particular to a kind of few salt auxiliary pickling agent and preparation method thereof.
Background technology
Pickling is a process important in process hides process, pickling can not only suitably loose collagenous fibres, and
Bath foam system pH can be adjusted and be ready for subsequent chrome tanning.During conventional pickling, based on grey tare weight 6~8%
Industrial table salt be used to sour skin be inhibited to expand, a large amount of Cl-It is discharged, the production and living of the mankind is seriously affected, to soil environment
It influences very big.One type of new leather chemicals that few salt auxiliary pickling agent is specific to reduction pickling salt and opens.
The visible research to few salt auxiliary pickling agent in the patent having disclosed.Strong west bosom et al. utilizes bisphenol-A/bisphenol S
And p-aminobenzene sulfonic acid/taurine has synthesized a kind of phenolic hydroxy group and the leaching of sulfonic small molecule under the conditions of existing for formaldehyde
Acid assistant, using its can effectively reduce the use of salt in pickling (a kind of auxiliary pickling agent and preparation method thereof,
CN103361447).But bisphenol S and bisphenol-A water solubility are poor, prepare the less efficient of synthetic reaction, it is more difficult to prepare synthetic
Valency is than good auxiliary pickling agent.In addition to this, Yi Jie et al. uses phenol, and naphthols is raw material, is used to soak after sulfonation through being condensed
Acid realizes few salt pickling, but the phenolic compound flexibility after polycondensation is excessive, and grain convergence is stronger, and chromium powder can be permeated and made
Into certain influence (Yi Jie, Chen Hui, Dan Zhihua.Application [J] Chinese leathers of auxiliary pickling agent, 2011,15:24-27).
Invention content
In order to overcome above-mentioned shortcoming of the existing technology, the present invention is original with sulfonated phenol, aniline -2,5- disulfonic acid
Material, by simple technique, is prepared into new auxiliary pickling agent；Auxiliary pickling agent prepared by the present invention is added in process hides pickling procedure
In, can inhibiting sour skin, salt pickling chrome tanning process method is lacked in implementation in the swelling of few salt, can be fundamentally big
The big salt pollution reduced during process hides pickling；H can be ionized out due to containing in the auxiliary pickling agent molecular structure of synthesis+Sulphur
Acidic group and phenolic hydroxyl group, it is possible to reduce the dosage of inorganic acid during pickling；Traditional process hides pickling technique, operating procedure need not be changed
It is simple and easy to do.
What the present invention was achieved through the following technical solutions.
A kind of primary structure of few salt auxiliary pickling agent of the present invention is：
Wherein:M represents Na+OrX represent H orY tables
Show
In order to achieve the above object, the technical solution taken of the present invention is：
Step (1) is calculated with mass fraction, the sulfonated phenol of 16.0~18.5 parts of addition, 25.3~50.6 parts of aniline -2,
5- disulfonic acids and 20~30 parts of deionized waters with mass fraction are that 25-35% sodium hydrate aqueous solutions will after stirring at normal temperature 0.5h
System pH is adjusted to 3.5~4.5；
The formaldehyde that the mass fraction that the speed of 18~20 drops/min is added dropwise 8.1~16.2 parts after step (2) is 35-40%
Solution；
Raising system temperature after being stirred to react 6~7h, is cooled to room temperature to 90~100 DEG C after step (3) is added dropwise,
Deionized water is added, regulation system solid content is 48~52%, obtains the rufous that pH value is 3.0~4.0 and lacks salt auxiliary pickling agent.
Wherein preferably：System pH is adjusted to 3.5 for 30% sodium hydrate aqueous solution with mass fraction after stirring at normal temperature 0.5h~
4.5。
Wherein preferably：The formaldehyde that the mass fraction that the speed of 18~20 drops/min is added dropwise 8.1~16.2 parts later is 37%
Solution.
Wherein preferably：Add deionized water, regulation system solid content is 50.2%, obtain pH value be 3.0~4.0 it is reddish brown
Color lacks salt auxiliary pickling agent.
In order to achieve the above object, the technical solution taken of the present invention is：Few salt auxiliary pickling agent, the auxiliary pickling agent it is main
Structure is：
Wherein：M represents Na+Or H+；X represent H orY is representedThe preparation method of few salt auxiliary pickling agent, includes the following steps：
It is calculated with mass fraction, sulfonated phenol, 25.3~50.6 parts of aniline -2, the 5- disulfonic acids of 16.0~18.5 parts of addition
With mass fraction it is 25-35% sodium hydrate aqueous solutions by system pH after stirring at normal temperature 0.5h with 20~30 parts of deionized waters
3.5~4.5 are adjusted to, the formaldehyde that the mass fraction that the speed of 18~20 drops/min is added dropwise 8.1~16.2 parts later is 35-40%
Solution increases system temperature to 90~100 DEG C, after being stirred to react 6~7h, is cooled to room temperature, adds deionization after being added dropwise
Water, regulation system solid content are 48~52%, obtain the rufous that pH value is 3.0~4.0 and lack salt auxiliary pickling agent.
Wherein preferably：System pH is adjusted to for 30% sodium hydrate aqueous solution with mass fraction after stirring at normal temperature 0.5h
3.5~4.5.
Wherein preferably：The formaldehyde that the mass fraction that the speed of 18~20 drops/min is added dropwise 8.1~16.2 parts later is 37%
Solution.
Wherein preferably：Add deionized water, regulation system solid content is 50.2%, obtain pH value be 3.0~4.0 it is reddish brown
Color lacks salt auxiliary pickling agent.
The invention has the advantages that：
(1) auxiliary pickling agent prepared by the present invention is added in process hides pickling procedure, can inhibit sour skin in few salt
Swelling, implement few salt pickling chrome tanning process method, the salt that can fundamentally greatly reduce during process hides pickling is dirty
Dye.
(2) H can be ionized out due to containing in the auxiliary pickling agent molecular structure of synthesis+Sulfonic group and phenolic hydroxyl group, can be with
The dosage of inorganic acid during reduction pickling.
(3) traditional process hides pickling technique need not be changed, operating procedure is simple and easy to do.
Specific embodiment
The preparation method of the present invention is described in detail below by embodiment.
Embodiment 1
A kind of preparation method of few salt auxiliary pickling agent, includes the following steps：
Take 17.4g sulfonated phenols, 25.3g aniline -2,5- disulfonic acid, 20g deionized waters, stirring at normal temperature and with 30% mass
The sodium hydroxide solution regulation system pH to 4.2 of score, after system stirs evenly, it is 37% to start that 8.1g mass fractions are added dropwise
Formalin, control rate of addition be 18 drops/min, after being added dropwise increase system temperature to 90 DEG C, react 7h, be cooled to
Deionized water is added in after room temperature, regulation system solid content is 48.5%, obtains the rufous that pH is 3.8 and lacks salt auxiliary pickling agent.
Embodiment 2
A kind of preparation method of few salt auxiliary pickling agent, includes the following steps：
Take 18.2g sulfonated phenols, 38.0g aniline -2,5- disulfonic acid, 25g deionized waters, stirring at normal temperature and with 30% mass
The sodium hydroxide solution regulation system pH to 3.6 of score, after system stirs evenly, starting 12.2 parts of mass fractions of dropwise addition is
37% formalin, control rate of addition are 20 drops/min, and system temperature is increased after being added dropwise to 95 DEG C, reacts 6.5h,
It is cooled to after room temperature and adds in deionized water, regulation system solid content is 50.2%, obtains the rufous that pH is 3.2 and lack salt pickling helping
Agent.
Embodiment 3
A kind of preparation method of few salt auxiliary pickling agent, includes the following steps：
Take 18.2g sulfonated phenols, 50.6g aniline -2,5- disulfonic acid, 30g deionized waters, stirring at normal temperature and with 30% mass
The sodium hydroxide solution regulation system pH to 4.0 of score, after system stirs evenly, starting 16.2 parts of mass fractions of dropwise addition is
37% formalin, control rate of addition are 20 drops/min, and system temperature is increased after being added dropwise to 92 DEG C, reacts 6.5h,
It is cooled to after room temperature and adds in deionized water, regulation system solid content is 49.2%, obtains the rufous that pH is 3.4 and lack salt pickling helping
Agent.
In above-described embodiment：Sulfonated phenol is purchased from Bang Hua group companies of Zhejiang Province, product batch number 20150909；
Aniline -2,5- disulfonic acid is purchased from Bang Hua group companies of Zhejiang Province, product batch number 20150901；
Test example
The application of few salt auxiliary pickling agent：Cattle hide by conventional pre- immersion, main immersion, fleshing, liming, depilation, fleshing,
For few salt pickling experiment after deliming and softening.Skin thickness is 2.3~2.5cm, and material dosage is with graywall restatement.It is specific few
Salt pickling technique is shown in Table 1.
1 salt-free pickling chrome tanning process of table
2 waste tanning liquor qualification result of table
Test brief summary：As shown in Table 2, the compound rich in multi-sulfonic based on phenol of invention,
The use of salt can be reduced during pickling, few salt pickling can be implemented completely, so as to ensure that chlorion is in waste tanning liquor
0, Cr2O3Content is less than 1.0, so as to avoid the pollution to environment, further reduces environmentally friendly cost.
The wet blue leather Ts and physical property of 3 finished leather of table
Conclusion (of pressure testing)：It is above-mentioned experiments have shown that, auxiliary agent using the present invention is using less sodium chloride, organic acid etc.
On the basis of, ensure that acid soaking step is completed very well, be further able to ensure the quality of finished leather, absolutely prove auxiliary pickling agent tool of the present invention
It is significant.
Claims (5)
1. a kind of few salt auxiliary pickling agent, it is characterised in that：The structure of the auxiliary pickling agent is：
Wherein：M represents Na+Or H+；X represent H orY is represented
2. a kind of few salt auxiliary pickling agent according to claim 1, it is characterised in that：A kind of preparation side of few salt auxiliary pickling agent
Method includes the following steps：
It is calculated with mass fraction, adds in 16.0~18.5 parts of sulfonated phenol, 25.3~50.6 parts of aniline -2,5- disulfonic acids and 20
~30 parts of deionized waters with mass fraction are that 25-35% sodium hydrate aqueous solutions adjust system pH after stirring at normal temperature 0.5h
It is 3.5~4.5, the formaldehyde that the mass fraction that the speed of 18~20 drops/min is added dropwise 8.1~16.2 parts later is 35-40% is molten
Liquid increases system temperature to 90~100 DEG C, after being stirred to react 6~7h, is cooled to room temperature, adds deionized water after being added dropwise,
Regulation system solid content is 48~52%, obtains the rufous that pH value is 3.0~4.0 and lacks salt auxiliary pickling agent.
3. a kind of few salt auxiliary pickling agent according to claim 2, wherein：It is 30% that mass fraction is used after stirring at normal temperature 0.5h
System pH is adjusted to 3.5~4.5 by sodium hydrate aqueous solution.
4. a kind of few salt auxiliary pickling agent according to claim 2, wherein：The speed of 18~20 drops/min is added dropwise 8.1 later
~16.2 parts of mass fraction is 37% formalin.
5. a kind of few salt auxiliary pickling agent according to claim 2, wherein：Deionized water is added, regulation system solid content is
50.2%, it obtains the rufous that pH value is 3.0~4.0 and lacks salt auxiliary pickling agent.
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| CN106755627B true CN106755627B (en) | 2018-06-26 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5427594A (en) * | 1992-01-28 | 1995-06-27 | Ciba-Geigy Corporation | Process for pickling raw hides |
| CN103361447A (en) * | 2013-06-26 | 2013-10-23 | 陕西科技大学 | Pickling aid and preparation method thereof |
| CN106065422A (en) * | 2016-06-06 | 2016-11-02 | 陕西科技大学 | A kind of synthetic method of little molecule pickling auxiliary tanning agent |
-
2017
- 2017-01-09 CN CN201710015103.9A patent/CN106755627B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5427594A (en) * | 1992-01-28 | 1995-06-27 | Ciba-Geigy Corporation | Process for pickling raw hides |
| CN103361447A (en) * | 2013-06-26 | 2013-10-23 | 陕西科技大学 | Pickling aid and preparation method thereof |
| CN106065422A (en) * | 2016-06-06 | 2016-11-02 | 陕西科技大学 | A kind of synthetic method of little molecule pickling auxiliary tanning agent |
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| CN106755627A (en) | 2017-05-31 |
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Address after: 512400 Pearl Industrial Park, Nanxiong, Shaoguan, Guangdong Patentee after: Guang Dong Dongdun New Material Technology Co., Ltd. Address before: No. 1 West, Ping'an 3rd Road, Zhuji Industrial Park, Nanxiong City, Shaoguan City, Guangdong Province, 512400 Patentee before: NANXIONG SEATON CHEMICALS LTD. |