CN111593147A - Hexavalent chromium scavenger, preparation method and application thereof - Google Patents
Hexavalent chromium scavenger, preparation method and application thereof Download PDFInfo
- Publication number
- CN111593147A CN111593147A CN202010487687.1A CN202010487687A CN111593147A CN 111593147 A CN111593147 A CN 111593147A CN 202010487687 A CN202010487687 A CN 202010487687A CN 111593147 A CN111593147 A CN 111593147A
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- hexavalent chromium
- portions
- scavenger
- reducing agent
- leather
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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
- C14C15/00—Apparatus for chemical treatment or washing of hides, skins, or leather
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention provides a hexavalent chromium scavenging agent, a preparation method and application thereof, and relates to the technical field of leather treatment agents. The hexavalent chromium scavenger comprises the following components in parts by weight: 400 portions of reducing agent and 600 portions; 200 portions of gallic acid 100-; 50-100 parts of carotenoid; and 100 portions of antioxidant and 200 portions. The hexavalent chromium scavenger can rapidly eliminate hexavalent chromium generated in leather after being applied to leather fatting agent treatment, thoroughly eliminate hexavalent chromium generated in the leather fatting agent treatment process, and simultaneously inhibit oxidation reaction from proceeding, so as to achieve the purpose of inhibiting the generation of hexavalent chromium for a long time along with the prolonging of time.
Description
Technical Field
The invention relates to the technical field of leather treatment agents, in particular to a hexavalent chromium scavenging agent, a preparation method and application thereof.
Background
Trivalent chromium plays an important role in tanning leather, can make leather soft and elastic, and is an essential tanning agent. The tanned leather is treated by a fatting agent, and the leather can absorb a proper amount of grease, so that the mutual mobility among leather fibers can be increased, and the leather has excellent physical and mechanical properties of softness, folding resistance, fullness, water resistance, high tensile strength, high elongation and the like. The leather fatting agent generally consists of grease or grease derivatives, an emulsifier, an emulsification aid, water and other additives, so the fatting agent usually contains unsaturated double bonds, the unsaturated double bonds are easily oxidized into peroxide by air, and the peroxide converts trivalent chromium in the leather into hexavalent chromium. However, if the leather contains hexavalent chromium, the contact with the skin may cause allergy, may cause genetic defects, cause carcinogenesis by inhalation, and cause persistent danger to the environment, so that the hexavalent chromium is required to be removed in the leather fatliquoring treatment.
The applicant has found that at least the following technical problems exist in the prior art: the hexavalent chromium scavenger on the current market cannot completely remove hexavalent chromium, the content of the hexavalent chromium in the product exceeds 3ppm, the standard of European Union cannot be met, and the content of the hexavalent chromium in the product rises along with the prolonging of the placing time of the product. Therefore, there is a need for a scavenger capable of completely removing hexavalent chromium generated during leather treatment and capable of inhibiting the generation of hexavalent chromium for a long period of time.
Disclosure of Invention
The invention aims to provide a hexavalent chromium scavenging agent, a preparation method and application thereof. The technical effects that can be produced by the preferred technical scheme in the technical schemes provided by the invention are described in detail in the following.
In order to achieve the purpose, the invention provides the following technical scheme:
the invention provides a hexavalent chromium scavenging agent which comprises the following components in parts by weight:
400 portions of reducing agent and 600 portions;
200 portions of gallic acid 100-;
50-100 parts of carotenoid; and
100 portions of antioxidant and 200 portions of antioxidant.
According to a preferred embodiment, the reducing agent is a sulfite reducing agent.
According to a preferred embodiment, the sulfite reducing agent is selected from one or more of sodium sulfite, sodium bisulfite and sodium metabisulfite.
According to a preferred embodiment, the sulfite reducing agent is selected from sodium metabisulfite.
According to a preferred embodiment, the carotenoid is selected from beta carotene.
According to a preferred embodiment, the antioxidant is a hindered phenolic antioxidant.
According to a preferred embodiment, the hindered phenolic antioxidant is selected from basf antioxidants 245.
According to a preferred embodiment, the hexavalent chromium scavenger is in the form of a solid powder.
The invention also provides a preparation method of the hexavalent chromium scavenging agent, which comprises the following steps:
grinding 400 portions of reducing agent, 100 portions of gallic acid, 50 portions to 100 portions of carotenoid and 200 portions of antioxidant into powder at normal temperature;
and mixing and stirring the powder in the step uniformly.
The invention also provides an application of the hexavalent chromium scavenger, which comprises the step of applying the hexavalent chromium scavenger to the fatliquor treatment of leather.
Based on the technical scheme, the hexavalent chromium scavenger, the preparation method and the application thereof at least have the following technical effects:
the hexavalent chromium scavenger comprises the following components in parts by weight: 400 portions of reducing agent and 600 portions; 200 portions of gallic acid 100-; 50-100 parts of carotenoid; and 100 portions of antioxidant and 200 portions. The reducing agent in the hexavalent chromium scavenging agent can convert generated hexavalent chromium into trivalent chromium, and simultaneously reduce oxides or peroxides generated in a fatliquoring environment, so that the trivalent chromium is prevented from being further oxidized. Gallic acid has a phenolic hydroxyl structure substance, and is a trapping agent of free radicals, which can inhibit the unsaturated bonds of the grease from being oxidized, thereby essentially eliminating the factor of trivalent chromium oxide. The carotenoid contains many double bonds, is a good singlet oxygen quencher, and has the functions of filtering light and quenching1O2The functions of inactivating the photosensitizer and eliminating free radicals; the mechanism of action is that excited singlet oxygen transfers energy to carotenoid to change carotenoid from ground state carotenoid to excited state carotenoid, and the latter can be directly restored to ground state, thus being capable of repeatedly using and eliminating generated oxygenThe functional singlet oxygen plays a role in inhibiting oxidation of trivalent chromium for a long time. Antioxidants can donate hydrogen atoms to free radicals and convert them to more stable non-free radical products, preventing oxidation reactions from proceeding. Therefore, the hexavalent chromium scavenger can rapidly eliminate the hexavalent chromium generated in the leather during the leather fatliquoring treatment process, and can inhibit the generation of the hexavalent chromium for a long time.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
The invention provides a hexavalent chromium scavenging agent, which comprises the following components in parts by weight:
400 portions of reducing agent and 600 portions; preferably, the reducing agent is a sulfite reducing agent. Preferably, the sulfite reducing agent selected for use in the present invention is a sulfite reducing agent well known to those skilled in the art and commercially available. Preferably, the sulfite reducing agent is selected from one or more of sodium sulfite, sodium bisulfite and sodium metabisulfite. Preferably, the sulfite reducing agent of the present invention is selected from sodium metabisulfite. The sodium metabisulfite selected by the invention is sodium metabisulfite provided by Chengdouding chemical products Co. The sulfite reducing agent has the function of converting the generated hexavalent chromium into trivalent chromium, and reducing oxides or peroxides generated in a fatliquoring environment, so that the trivalent chromium is prevented from being further oxidized. Therefore, the action of the reducing agent after the addition enables the hexavalent chromium produced in the leather to be eliminated rapidly.
200 portions of gallic acid 100-; preferably, the gallic acid used in the present invention is one known to those skilled in the art and can be obtained commercially. Preferably, the gallic acid of the present invention is selected from gallic acid provided by Shizuo Chenguang Biotech company. The gallic acid has phenolic hydroxyl structure substance, is a scavenger of free radicals, and can inhibit unsaturated bonds in the grease from being oxidized, and essentially eliminate the factor of trivalent chromium oxidation. Therefore, the addition of the gallic acid can eliminate free radicals with oxidation effect, so that unsaturated bonds in the grease are not oxidized into peroxide, and trivalent chromium in the leather is inhibited from being oxidized into hexavalent chromium. Radically eliminates free radical oxidizing elements.
Preferably, the carotenoid selected by the invention is carotenoid which is well known to those skilled in the art and can be purchased from the market, preferably, the carotenoid is selected from β carotene, preferably, the β carotene is selected from β carotene provided by Zhengzhou Wanbo chemical products Limited company, the carotenoid has the functions of filtering light and quenching singlet oxygen, and the carotenoid has the advantages of filtering light and quenching singlet oxygen1O2The functions of inactivating photosensitizer and eliminating free radical. The mechanism of action is that excited singlet oxygen transfers energy to the carotenoid, which changes the carotenoid from a ground state (carotenoid) to an excited state (carotenoid), and the excited carotenoid can be directly restored to the ground state. Therefore, singlet oxygen and generated free radicals can be removed repeatedly through the carotenoid, unsaturated bonds in the grease are fundamentally inhibited from being oxidized, and trivalent chromium in the leather is further inhibited from being oxidized into hexavalent chromium.
100 portions of antioxidant and 200 portions of antioxidant. Preferably, the antioxidant is a hindered phenolic antioxidant. Preferably, the hindered phenolic antioxidant is selected from the group consisting of basf 245 high potency hindered phenolic antioxidants. The hindered phenolic antioxidants function to donate hydrogen atoms to free radicals and convert them to more stable non-free radical products, preventing oxidation reactions from proceeding. The use of hindered phenol antioxidants can further eliminate free radicals and prevent the progress of oxidation reactions.
Preferably, the hexavalent chromium scavenger of the present invention is in the form of a solid powder.
The invention also provides a preparation method of the hexavalent chromium scavenging agent, which comprises the following steps:
grinding 400 portions of reducing agent, 100 portions of gallic acid, 50 portions to 100 portions of carotenoid and 200 portions of antioxidant into powder at normal temperature;
and mixing and stirring the powder in the step uniformly. Thus obtaining the hexavalent chromium scavenger of the invention.
The invention also provides an application of the hexavalent chromium scavenger, which comprises the step of applying the hexavalent chromium scavenger to the fatliquor treatment of leather.
In order to further illustrate the technical solution of the present invention, the following embodiments are specifically described.
Example 1
The process for preparing the hexavalent chromium scavenger of example 1 is as follows:
450 parts of sodium metabisulfite reducing agent, 100 parts of gallic acid, 50 parts of beta carotene and 150 parts of high-efficiency hindered phenol antioxidant 245 are ground and stirred uniformly at normal temperature.
Example 2
The hexavalent chromium scavenger of example 2 is prepared by the following process:
500 parts of sodium metabisulfite reducing agent, 150 parts of gallic acid, 75 parts of beta carotene and 150 parts of high-efficiency hindered phenol antioxidant 245 are ground and stirred uniformly at normal temperature.
Example 3
The hexavalent chromium scavenger of example 3 is prepared by the following process:
grinding and uniformly stirring 600 parts of sodium metabisulfite reducing agent, 100 parts of gallic acid, 100 parts of beta carotene and 100 parts of high-efficiency hindered phenol antioxidant 245 of Pasteur antioxidant at normal temperature.
Example 4
The hexavalent chromium scavenger of example 4 is prepared by the following process:
500 parts of sodium metabisulfite reducing agent, 150 parts of gallic acid, 100 parts of beta carotene and 100 parts of high-efficiency hindered phenol antioxidant 245 are ground and stirred uniformly at normal temperature.
The hexavalent chromium scavengers prepared in the examples 1 to 4 are compared with the hexavalent chromium scavengers on the market, and are applied to leather fatliquor treatment experiments, wherein the use amount of each component is the percentage of the weight of leather, and the application process is shown in table 1.
TABLE 1
After applying the hexavalent chromium scavengers prepared in examples 1 to 4 to a commercially available hexavalent chromium scavenger, the treated skin blank was dried and aged to determine the hexavalent chromium content, and the results are shown in table 2.
TABLE 2
As can be seen from Table 2, the hexavalent chromium scavenger prepared by the present invention can rapidly eliminate the produced hexavalent chromium, and the hexavalent chromium is detected after use. Compared with the market products, the product has obvious inhibition effect on hexavalent chromium along with the prolonging of time.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (10)
1. A hexavalent chromium scavenger is characterized by comprising the following components in parts by weight:
400 portions of reducing agent and 600 portions;
200 portions of gallic acid 100-;
50-100 parts of carotenoid; and
100 portions of antioxidant and 200 portions of antioxidant.
2. The hexavalent chromium scavenger of claim 1, wherein the reducing agent is a sulfite reducing agent.
3. The hexavalent chromium scavenger of claim 2, wherein the sulfite reducing agent is selected from one or more of sodium sulfite, sodium bisulfite, and sodium metabisulfite.
4. The hexavalent chromium scavenger of claim 3, wherein the sulfite reducing agent is selected from the group consisting of sodium metabisulfite.
5. The hexavalent chromium scavenger of claim 1, wherein the carotenoid is selected from the group consisting of beta carotene.
6. The hexavalent chromium scavenger of claim 1, wherein the antioxidant is a hindered phenolic antioxidant.
7. The hexavalent chromium scavenger of claim 6, wherein the hindered phenolic antioxidant is selected from the group consisting of basf antioxidants 245.
8. The hexavalent chromium scavenger of claim 1, wherein the hexavalent chromium scavenger is in the form of a solid powder.
9. A process for the preparation of a hexavalent chromium scavenger according to any one of claims 1 to 8, characterized in that it comprises the following steps:
grinding 400 portions of reducing agent, 100 portions of gallic acid, 50 portions to 100 portions of carotenoid and 200 portions of antioxidant into powder at normal temperature;
and mixing and stirring the powder in the step uniformly.
10. Use of the hexavalent chromium scavenger prepared according to claim 9, comprising the use of the hexavalent chromium scavenger in the fatliquor treatment of leather.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010487687.1A CN111593147A (en) | 2020-06-02 | 2020-06-02 | Hexavalent chromium scavenger, preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010487687.1A CN111593147A (en) | 2020-06-02 | 2020-06-02 | Hexavalent chromium scavenger, preparation method and application thereof |
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| CN111593147A true CN111593147A (en) | 2020-08-28 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101525674A (en) * | 2009-04-02 | 2009-09-09 | 西藏自治区拉萨皮革厂 | Method for stabilizing content of trivalent chromium and minimum hexavalent chrome in leather |
| CN103374634A (en) * | 2012-04-19 | 2013-10-30 | 咸阳银河无机材料有限公司 | Accessory ingredient capable of removing and avoiding generating hexavalent chromium in leather and preparation method of accessory ingredient |
| CN104419015A (en) * | 2013-09-03 | 2015-03-18 | 中国科学院化学研究所 | Composition with capability of providing thermal stability for polymer and application of composition |
-
2020
- 2020-06-02 CN CN202010487687.1A patent/CN111593147A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101525674A (en) * | 2009-04-02 | 2009-09-09 | 西藏自治区拉萨皮革厂 | Method for stabilizing content of trivalent chromium and minimum hexavalent chrome in leather |
| CN103374634A (en) * | 2012-04-19 | 2013-10-30 | 咸阳银河无机材料有限公司 | Accessory ingredient capable of removing and avoiding generating hexavalent chromium in leather and preparation method of accessory ingredient |
| CN104419015A (en) * | 2013-09-03 | 2015-03-18 | 中国科学院化学研究所 | Composition with capability of providing thermal stability for polymer and application of composition |
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Application publication date: 20200828 |