CN109628665B - Vitamin K3Chrome tanning liquid using waste liquid as raw material and preparation method thereof - Google Patents
Vitamin K3Chrome tanning liquid using waste liquid as raw material and preparation method thereof Download PDFInfo
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- CN109628665B CN109628665B CN201910097819.7A CN201910097819A CN109628665B CN 109628665 B CN109628665 B CN 109628665B CN 201910097819 A CN201910097819 A CN 201910097819A CN 109628665 B CN109628665 B CN 109628665B
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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
- C14C3/04—Mineral tanning
- C14C3/06—Mineral tanning using chromium compounds
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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
- C14C3/10—Vegetable tanning
- C14C3/12—Vegetable tanning using purified or modified vegetable tanning agents
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- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention discloses a vitamin K3Chrome tanning liquid with waste liquid as raw material, the raw material includes vitamin K3Waste liquid, chromate, and reducing agent. Comprises the following steps: dissolving at normal temperature: firstly, vitamin K is added3Adding the waste liquid into a normal-temperature dissolver, then sequentially adding chromate and a reducing agent into the normal-temperature dissolver, stirring to completely dissolve the chromate and the reducing agent to obtain a mixed solution, wherein the addition amount of the chromate is vitamin K32-10% of the mass of the waste liquid, wherein the addition amount of the reducing agent is vitamin K31-3% of the mass of the waste liquid; high-pressure reaction: and (3) placing the mixed solution prepared in the step one in a high-pressure reaction kettle, and reacting for 4-10 hours at the temperature of 140-180 ℃ and under the pressure of 1.4-2.0 MPa to prepare the chrome tanning liquid. The invention effectively treats vitamin K3The waste liquid in the production process can not cause waste and secondary pollution, the preparation process is simple, the cost is lower, the organic content of the prepared chrome tanning liquid is less, the performance of the product is stable, and the large-scale popularization is easy.
Description
Technical Field
The invention belongs to the technical field of waste resource utilization, and particularly relates to vitamin K3The waste liquor is the chrome tanning liquor of the raw material.
Background
Vitamin K3The chemical name of the derivative is 2-methyl-1, 4-naphthoquinone, also called beta-menadione, and the derivative has extremely wide application in the aspects of medicine and biology. In biological terms, vitamin K3Referred to as anti-bleeding factors; in medicine, vitamin K3Are widely used as blood clotting agents; in addition, vitamin K3Or preparing other vitamins such as vitamin K1(chlorophyll), vitamin K2(menadione), vitamin K4The important intermediate of (acetyl menadione) is also used as feed additive in a large amount, and also can be used as herbicide and coating of warships, ships and the like, so that the wide application and the excellent performance in various fields enable vitamin K3The compound plays a very important role in our productive life and has become an indispensable chemical compound in our modern life.
Domestic current synthesisVitamin K3The main process of the method is a beta-methylnaphthalene oxidation method, the process flow is that 2-methylnaphthalene is dissolved in solvent acetic acid by stirring, the temperature is controlled to be about 45 ℃, chromic anhydride is dissolved in water to prepare solution, then the solution is slowly added into the mixed solution of the 2-methylnaphthalene and the acetic acid, the temperature is continuously kept at 45 ℃, the stirring is carried out for 30 minutes, the temperature is raised to 75 ℃, then the stirring is carried out for 30 minutes, finally the temperature is raised to 85 ℃, and the temperature is kept for 15 minutes. Pouring the mixture into distilled water after the time is up, and continuously stirring to make vitamin K3Precipitating in the form of crystal, filtering the reaction solution, washing the obtained filter cake until the pH is 3-4, and filtering to obtain vitamin K3. The obtained vitamin K3Accounting for ninety percent of the overall yield. (Huiwen. vitamin K3 Synthesis Process Studies and structural characterization [ D ]]2016 research on preparation of 2-methyl-1, 4-naphthoquinone by clean oxidation of Yangtfeng 2-methylnaphthalene [ D ] from Shanxi science and technology university]Southeast university 2012.)
The beta-methylnaphthalene oxidation method has simple synthesis process and difficult operation, but the process also has the obvious defect that the generated waste liquid contains a large amount of trivalent chromium ions, hexavalent chromium ions and residual 2-methylnaphthalene and 2-methyl-1, 4-naphthoquinone. These substances are harmful to the environment and cannot be discharged directly into the natural environment, and must be disposed of accordingly. Of these contaminants, the most difficult to treat and most harmful is the hexavalent chromium ion. At present, the main treatment method for hexavalent chromium ions is to introduce a reducing agent to generate trivalent chromium ions through oxidation-reduction reaction of the hexavalent chromium ions, and then the trivalent chromium ions are precipitated and removed through reaction. Other methods for treating hexavalent chromium ions, such as adsorption, ion exchange resin, electrolysis, membrane separation, photocatalytic methods, are still under investigation and are not suitable for large-scale treatment of waste solutions containing hexavalent chromium ions for various reasons such as technology, cost, etc.,so the hexavalent chromium-containing waste liquid is still pollution which is difficult to treat at present. And besides hexavalent chromium ions, vitamin K3The waste liquid also contains residual organic matters such as 2-methylnaphthalene, 2-methyl-1, 4 naphthoquinone, etc., which have certain influence on the environment after being discharged into the environment, and the organic matters are naphthalene and naphthalene derivatives, which have stable structures and are not easy to be oxidized, so that the waste liquid is difficult to treat. (composition analysis of waste liquid from preparation of 2-methyl-1, 4-naphthoquinone by Shirui, Wanglang Jing, Chengwong, Chronic acid salt Oxidation method [ J)]China leather 2015, (05) 4-7, delicate, plum, grand, Huaxin, buyiyao, Zweiming chromium-containing waste liquid treatment technology and research progress [ J]Environmental science and technology, 2013, (S2): 150-
In the environment of environmental protection, the production of a chemical composition must meet the environmental requirements, in order to be widely applied, and not only have wide application and good performance. At present, because of the trivalent chromium ions and the hexavalent chromium ions contained in the waste liquid and the residual pollutants of 2-methylnaphthalene, 2-methyl-1, 4-naphthoquinone and the like, the vitamin K3The production of (b) may cause certain environmental hazards. According to the previous treatment experience, the treatment of the pollutants is complex, time-consuming and labor-consuming, the treatment cost is high, and vitamin K is increased3Production cost of not good for vitamin K3Is widely used. Therefore, the vitamin K3 has to play more roles at present, and the problem of waste liquid treatment needs to be solved.
Because of vitamin K3The waste liquid contains a certain amount of trivalent chromium ions and hexavalent chromium ions, and the waste liquid is acidic, so that some domestic leather chemicals for producing chrome tanning agent also begin to react with vitamin K3The waste liquid is recycled, and the method mainly comprises the steps of reducing hexavalent chromium ions in the waste liquid into trivalent chromium ions in an acid environment by using glucose, then adjusting alkalinity, directly preparing chromium powder by spray drying, and directly using the chromium powder as a chromium tanning agent to be applied to a tanning working section. However, the blue wet leather tanned by the chrome tanning agent prepared by the method has grey color, which greatly influences the appearance and simultaneously can also cause the blue wet leather to have grey colorThe subsequent processing of wet blue leather is influenced to a certain extent, so that the chrome tanning agent prepared by the method can be applied only in a few cases and cannot be popularized on a large scale3The problem of grey blue wet leather color obtained by tanning the chrome tanning agent prepared from the waste liquid is solved, so the solution has extremely high feasibility and generalization, and can be applied to factories to solve the problem of vitamin K on a large scale3The problem of waste liquid. Therefore, the vitamin K is developed and used with scientific and reasonable materials, simple method and low cost, which can not only utilize the waste as resources, but also realize the industrial production3The chrome tanning liquid which takes waste liquid as raw material is objectively needed.
Disclosure of Invention
In order to solve the problems in the background art, the invention aims to provide the vitamin K which has scientific and reasonable materials, simple method and low cost, can recycle wastes and can be industrially produced3Chrome tanning liquid with waste liquid as raw material and its preparation process. It is characterized by that it utilizes wet oxidation process to treat vitamin K3Organic matters such as 2-methylnaphthalene and 2-methyl-1, 4-naphthoquinone in the waste liquid are reduced, hexavalent chromium in the chromium liquid is reduced, the vitamin K3 waste liquid is prepared into chromium tanning liquid, and the vitamin K is treated3The waste liquor is used for obtaining the chrome tanning liquor with lower cost.
The vitamin K is3Chrome tanning liquid with waste liquid as raw material, the raw material includes vitamin K3Waste liquid, chromate, and reducing agent.
The preparation method of the chrome tanning liquid comprises the following steps:
dissolving at normal temperature: firstly, vitamin K is added3Adding the waste liquid into a normal-temperature dissolver, then sequentially adding chromate and a reducing agent into the normal-temperature dissolver, stirring to completely dissolve the chromate and the reducing agent to obtain a mixed solution, wherein the addition amount of the chromate is vitamin K32-10% of the mass of the waste liquid, wherein the addition amount of the reducing agent is vitamin K31-3% of the mass of the waste liquid;
high-pressure reaction: and (3) placing the mixed solution prepared in the step one in a high-pressure reaction kettle, and reacting for 4-10 hours at the temperature of 140-180 ℃ and under the pressure of 1.4-2.0 MPa to prepare the chrome tanning liquid.
The invention has the following beneficial effects:
the invention effectively treats vitamin K3The waste liquid in the production process can not cause waste and secondary pollution, protects the environment, realizes the complete and effective utilization of the waste liquid, and can be used for vitamin K3Has promoting effect, and is favorable for better exerting vitamin K3Has effects in medicine, feed additive, plant growth regulator and promoter.
Secondly, the invention uses oxygen in the air and hexavalent chromium in the waste liquid as the oxidant, avoids adding the oxidant additionally, can obtain the chromium tanning liquid with lower cost, is beneficial to reducing the tanning cost and promoting the development of the tanning industry, and simultaneously, the preparation process of the method is simple, has lower cost and is beneficial to being promoted in a factory on a large scale.
The chrome tanning liquid prepared by the invention has low organic content and stable product performance, and the color, the mechanical property and the shrinkage temperature of the wet blue leather tanned by the chrome tanning liquid are all equivalent to those of wet blue leather prepared by commercial chrome tanning agents.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to be limiting in any way, and any modifications or alterations based on the teachings of the present invention are intended to fall within the scope of the present invention.
Example 1:
vitamin K as described in example 13The chrome tanning liquid with waste liquid as raw material is characterized in that the chrome tanning liquid comprises 100g of vitamin K3Waste liquid, 5g of chromate and 1.8g of reducing agent, wherein the chromate is sodium dichromate, the reducing agent is glucose, and the vitamin K3The waste liquid is from Luliang and Hi-Tech Co.
The vitamin K is used as the vitamin3The preparation method of the chrome tanning liquid with the waste liquid as the raw material comprises the following steps:
alwaysWarm dissolution: firstly 100g vitamin K3Adding the waste liquid into a normal-temperature dissolver, then sequentially adding 5g of sodium dichromate and 1.8g of glucose into the normal-temperature dissolver, and stirring to completely dissolve the sodium dichromate and the glucose to obtain a mixed solution;
high-pressure reaction: putting the mixed solution prepared in the step I into a high-pressure reaction kettle, and reacting for 8 hours at the temperature of 160 ℃ and the pressure of 1.8MPa to prepare the chrome tanning liquid.
The preparation process of the embodiment 1 is simple, the cost is low, the content of organic matters in the prepared chrome tanning liquid is low, the content of the organic matters in the prepared chrome tanning liquid is reduced from initial 6.5682g/L to 1.9066g/L, the performance of the prepared product is stable, and the color, the mechanical property and the shrinkage temperature of the wet blue leather tanned by the chrome tanning liquid are equivalent to those of the wet blue leather prepared by a commercial chrome tanning agent.
Example 2
Vitamin K as described in example 23Chrome tanning liquid with waste liquid as raw material, comprising 100g vitamin K3Waste liquid, 6g of chromate and 1.9g of reducing agent, wherein the chromate is potassium dichromate, the reducing agent is glucose, and the vitamin K3The waste liquid is from Luliang and Hi-Tech Co.
The vitamin K is used as the vitamin3The preparation method of the chrome tanning liquid with the waste liquid as the raw material comprises the following steps:
dissolving at normal temperature: firstly 100g vitamin K3Adding the waste liquid into a normal-temperature dissolver, then sequentially adding 6g of potassium dichromate and 1.9g of glucose into the normal-temperature dissolver, and stirring to completely dissolve the potassium dichromate and the glucose to obtain a mixed solution;
high-pressure reaction: putting the mixed solution prepared in the step I into a high-pressure reaction kettle, and reacting for 4 hours at the temperature of 150 ℃ and the pressure of 1.8MPa to prepare the chrome tanning liquid.
The preparation process of the embodiment 2 is simple, the cost is low, the content of organic matters in the prepared chrome tanning liquid is low, the content of the organic matters in the prepared chrome tanning liquid is reduced from initial 6.5682g/L to 2.3022g/L, the performance of the prepared product is stable, and the color, the mechanical property and the shrinkage temperature of the wet blue leather tanned by the chrome tanning liquid are equivalent to those of the wet blue leather prepared by a commercial chrome tanning agent.
Example 3
Vitamin K as described in example 33The chrome tanning liquid with waste liquid as raw material is characterized in that the chrome tanning liquid comprises 100g of vitamin K3Waste liquid, 8g of chromate and 3g of reducing agent, wherein the chromate is sodium dichromate, the reducing agent is glucose, and the vitamin K3The waste liquid is from Luliang and Hi-Tech Co.
The vitamin K is used as the vitamin3The preparation method of the chrome tanning liquid with the waste liquid as the raw material comprises the following steps:
dissolving at normal temperature: firstly 100g vitamin K3Adding the waste liquid into a normal-temperature dissolver, then sequentially adding 8g of sodium dichromate and 3g of glucose into the normal-temperature dissolver, and stirring to completely dissolve the sodium dichromate and the glucose to obtain a mixed solution;
high-pressure reaction: putting the mixed solution prepared in the step I into a high-pressure reaction kettle, and reacting for 6 hours at the temperature of 180 ℃ and the pressure of 1.6MPa to prepare the chrome tanning liquid.
The preparation process of the embodiment 3 is simple, the cost is low, the content of organic matters in the prepared chrome tanning liquid is low, the content of the organic matters is reduced from initial 6.5682g/L to 1.8034g/L, the performance of the prepared product is stable, and the color, the mechanical property and the shrinkage temperature of the wet blue leather tanned by the chrome tanning liquid are equivalent to those of the wet blue leather prepared by a commercial chrome tanning agent.
Example 4
Vitamin K as described in example 43Chrome tanning liquid with waste liquid as raw material, comprising 100g vitamin K3Waste liquid, 2g of chromate and 1g of reducing agent, wherein the chromate is potassium dichromate, the reducing agent is glucose, and the vitamin K3The waste liquid is from Luliang and Hi-Tech Co.
The vitamin K is used as the vitamin3The preparation method of the chrome tanning liquid with the waste liquid as the raw material comprises the following steps:
dissolving at normal temperature: firstly 100g of vitaminK3Adding the waste liquid into a normal-temperature dissolver, then sequentially adding 2g of potassium dichromate and 1g of glucose into the normal-temperature dissolver, and stirring to completely dissolve the potassium dichromate and the glucose to obtain a mixed solution;
high-pressure reaction: putting the mixed solution prepared in the step I into a high-pressure reaction kettle, and reacting for 10 hours at the temperature of 170 ℃ and the pressure of 1.4MPa to prepare the chrome tanning liquid.
The preparation process of the embodiment 4 is simple, the cost is low, the content of organic matters in the prepared chrome tanning liquid is low, the content of the organic matters is reduced from initial 6.5682g/L to 2.4156g/L, the performance of the prepared product is stable, and the color, the mechanical property and the shrinkage temperature of the wet blue leather tanned by the chrome tanning liquid are equivalent to those of the wet blue leather prepared by a commercial chrome tanning agent.
Example 5
Vitamin K as described in example 53Chrome tanning liquid with waste liquid as raw material, comprising 100g vitamin K3Waste liquid, 10g of chromate and 3g of reducing agent, wherein the chromate is sodium dichromate, the reducing agent is sulfur dioxide, and the vitamin K3The waste liquid is from Luliang and Hi-Tech Co Ltd of Yunnan province
The vitamin K is used as the vitamin3The preparation method of the chrome tanning liquid with the waste liquid as the raw material comprises the following steps:
dissolving at normal temperature: firstly, 100g of vitamin K3 waste liquid is added into a normal-temperature dissolver, then 10g of sodium dichromate and enough sulfur dioxide gas are sequentially added into the normal-temperature dissolver, and a mixed solution is obtained after the sodium dichromate and the sufficient sulfur dioxide gas are completely dissolved by stirring;
high-pressure reaction: putting the mixed solution prepared in the step I into a high-pressure reaction kettle, and reacting for 5 hours at the temperature of 140 ℃ and the pressure of 2.0MPa to prepare the chrome tanning liquid.
The preparation process of the embodiment 5 is simple, the cost is low, the content of organic matters in the prepared chrome tanning liquid is low, the content of the organic matters is reduced from initial 6.5682g/L to 1.9588g/L, the performance of the prepared product is stable, and the color, the mechanical property and the shrinkage temperature of the wet blue leather tanned by the chrome tanning liquid are equivalent to those of the wet blue leather prepared by a commercial chrome tanning agent.
Example 6
Vitamin K as described in example 63Chrome tanning liquid with waste liquid as raw material, comprising 100g vitamin K3Waste liquid, 7g of chromate and 2.4g of reducing agent, wherein the chromate is a mixture of sodium dichromate and potassium dichromate, the reducing agent is a mixture of glucose and sulfur dioxide, and the vitamin K3The waste liquid is from Luliang and Hi-Tech Co.
The vitamin K is used as the vitamin3The preparation method of the chrome tanning liquid with the waste liquid as the raw material comprises the following steps:
dissolving at normal temperature: firstly 100g vitamin K3Adding the waste liquid into a normal-temperature dissolver, then sequentially adding a mixture of 7g of sodium dichromate and potassium dichromate and a mixture of 2.4g of glucose and sulfur dioxide into the normal-temperature dissolver, and stirring to completely dissolve the mixture to obtain a mixed solution;
high-pressure reaction: putting the mixed solution prepared in the step I into a high-pressure reaction kettle, and reacting for 7 hours at the temperature of 150 ℃ and the pressure of 1.6MPa to prepare the chrome tanning liquid.
The preparation process of the embodiment 6 is simple, the cost is low, the content of organic matters in the prepared chrome tanning liquid is low, the content of the organic matters is reduced from initial 6.5682g/L to 2.2095g/L, the performance of the prepared product is stable, and the color, the mechanical property and the shrinkage temperature of the wet blue leather tanned by the chrome tanning liquid are equivalent to those of the wet blue leather prepared by a commercial chrome tanning agent.
Claims (1)
1. Vitamin K3The preparation method of the chrome tanning liquid with the waste liquid as the raw material is characterized by comprising the following steps:
dissolving at normal temperature: firstly, vitamin K is added3Adding the waste liquid into a normal-temperature dissolver, then sequentially adding chromate and a reducing agent into the normal-temperature dissolver, stirring to completely dissolve the chromate and the reducing agent to obtain a mixed solution, wherein the addition amount of the chromate is vitamin K38% of the mass of the waste liquid, and the reducing agentThe additive amount of vitamin K33% of the mass of the waste liquid; the chromate is sodium dichromate; the reducing agent is glucose;
high-pressure reaction: and (3) placing the mixed solution prepared in the step I into a high-pressure reaction kettle, and reacting for 6 hours at the temperature of 180 ℃ and the pressure of 1.6MPa to prepare the chrome tanning liquid, wherein the content of organic matters in the chrome tanning liquid is 1.8034 g/L.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101041500A (en) * | 2007-03-28 | 2007-09-26 | 中国皮革和制鞋工业研究院 | Highly effective reusing method for leather producing chrome tanning exhausted liquid |
| CN103352092A (en) * | 2012-12-24 | 2013-10-16 | 山东华升化工科技有限公司 | Method for preparation of chrome tanning agent and combined production of vitamin K3 through using chromium-rich sludge |
| CN107099623A (en) * | 2017-03-08 | 2017-08-29 | 四川大学 | The method that a kind of utilization Vitamin K3 production waste liquid of microwave radiation technology prepares chrome tanning agent |
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|---|---|---|---|---|
| CN104386752B (en) * | 2014-11-14 | 2016-05-18 | 四川省银河化学股份有限公司 | A kind of method that menadione gained raffinate is prepared chromium sulfate basic of producing of utilizing |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101041500A (en) * | 2007-03-28 | 2007-09-26 | 中国皮革和制鞋工业研究院 | Highly effective reusing method for leather producing chrome tanning exhausted liquid |
| CN103352092A (en) * | 2012-12-24 | 2013-10-16 | 山东华升化工科技有限公司 | Method for preparation of chrome tanning agent and combined production of vitamin K3 through using chromium-rich sludge |
| CN107099623A (en) * | 2017-03-08 | 2017-08-29 | 四川大学 | The method that a kind of utilization Vitamin K3 production waste liquid of microwave radiation technology prepares chrome tanning agent |
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