CN1128229C - Process for preparing chrome tanning agent from organic waste containing cellulose - Google Patents
Process for preparing chrome tanning agent from organic waste containing cellulose Download PDFInfo
- Publication number
- CN1128229C CN1128229C CN 00129406 CN00129406A CN1128229C CN 1128229 C CN1128229 C CN 1128229C CN 00129406 CN00129406 CN 00129406 CN 00129406 A CN00129406 A CN 00129406A CN 1128229 C CN1128229 C CN 1128229C
- Authority
- CN
- China
- Prior art keywords
- tanning agent
- organic waste
- chrome tanning
- parts
- chrome
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- Treatment And Processing Of Natural Fur Or Leather (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The present invention relates to a preparation method of a chrome-containing tanning agent. A compound containing hexavalent chrome is used as an oxidizing agent source; an organic waste containing plant cellulose is used as a reducing agent source; an oxidizing agent and a reducing agent are added into a reactor; sulphuric acid or hydrochloric acid is added under the temperature condition which is no greater than 65DEG C, and after an agitating reaction under the temperature from 85 to 100 DEG C, a green chrome-containing tanning agent of trivalent chromium is obtained by complete reduction. The method has the advantages of simple performance, saved working procedures and reduced cost and environmental pollution. The chrome tanning agent prepared by the method of the present invention has the advantages of high permeability, strong selection filling properties and obvious thickening ratio.
Description
(1) technical field
The present invention relates to a kind of preparation method who contains chrome tanning agent, belong to the leather chemical industry technical field.
(2) background technology
In the leather chrome tanning agent was produced, the reductive agent that uses had inorganic reducing agent and organic reducing agent at present, resembles SO
2, Na
2S
2O
3, Na
2SO
3, glucose, sucrose etc., using more organic reducing agent is glucose.The production of sugar needs that starting material decompose, acid evaporation, sugar from etc. many operations.In chrome tanning agent production, need to add acid and dissolving sugar etc. again, so not only bothered but also uneconomical, and in sugared production process separated the removing of many useful byproducts.
(3) summary of the invention
The present invention is directed to the shortcoming of prior art, provide a kind of organic waste that utilize cellulose directly to prepare the method for chrome tanning liquid.
Technical scheme of the present invention is as follows.
Method of the present invention comprises: with chromyl compound is oxidizer source, as: chromium alum or dichromate; With the organic waste that contain plant cellulose is the reductive agent source; Oxidizing and Reducing Agents is added reactor, oxygenant needs complete water dissolution, stirs then and heats up, and adds sulfuric acid or hydrochloric acid not being higher than under 65 ℃ the temperature condition, 85～100 ℃ of stirring reactions 1～15 hour, be reduced into chromic green chrome tanning agent fully.
The consumption of above-mentioned each raw material is as follows, is weight part:
Chromium alum M
2SO
4Cr
2(SO
4)
324H
2O or dichromate M
2Cr
2O
7, M=K
+, Na
+
100～150 parts
12～90 parts of organic waste that contain plant cellulose
50～300 parts of industrial sulphuric acid or technical hydrochloric acids
700～2500 parts in water.
The basicity of also can be again adjusting above-mentioned chrome tanning agent with alkaline reagents is 2～4.5 green chrome tanning agent to PH.Used alkaline reagents is ammoniacal liquor, yellow soda ash, sodium hydroxide etc.
The above-mentioned organic waste that contain plant cellulose are various waste paper, waste wood, waste molasses (sugaring tankage), careless class etc.
Principle of the present invention is:
Utilize in the refuse Mierocrystalline cellulose under acidic conditions, the water soluble mixt that is generated with dichromate generation chemical reaction is with Cr
6+Be reduced into Cr
3+, and make chrome liquor have special reactivity, fillibility, perviousness.
Have reductibility and tart SURGICEL concurrently because of comprising in the cellulose hydrolysis product, most of carboxyls are alditol acid types, also have a series of terminal carboxylic acid or non-terminal carboxylic acid, resemble arabonic acid, glucuronic acid, dicarboxylic acid etc.And the water soluble component that obtains of cellulosic acid hydrolysis mainly is sugar, as wood sugar, glucose, cellobiose, and alditol class (furfural, hydroxymethylfurfural) and organic acid components such as (levulinic acid, formic acid, acetate).
As from the foregoing, hexavalent chrome reduction being become trivalent chromium, mainly is glucose, and because of its reductibility is the strongest, this is with single identical with glucose reduction chrome liquor.Different is other component except glucose, formic acid, oxalic acid in the fiber water hydrolysis products, be that glucose reduction preparation chrome liquor is not available, the also existence of these components just, can give the chrome liquor special performances, as the existence of the aldehyde radical in these components, the flexibility of chrome liquor is strengthened, because of aldehyde radical can with collagen generation covalent attachment, make chrome liquor except with the coordinate bond of collagen combines, increased covalent linkage again.Terminal or the non-terminal acid of long-chain except small molecular organic acid in addition both can play masking effect in chrome liquor, can react with collagen again, can also with chromium (III) complex coordination, make the reactive enhancing of complex compound and collagen.The existence of cellobiose etc. except that the filling effect that can make chrome liquor strengthens, also can combine with H key, covalent linkage etc. with collagen between collagen, and the performance of leather is taken on a new look greatly.
Compare with the existing simple method of making reductive agent with sugar, method of the present invention is easier, can utilize sugar and organic acid in the organic waste hydrolysate directly to prepare chrome tanning agent, saves operation and reduces cost, and has reduced environmental pollution.Chrome tanning agent good penetrability, the selection fillibility of the inventive method preparation are strong, and it is obvious to thicken rate, and the leather performance is good.Especially can also under high pH value, be used for leather tanning, make the leather asperities and be unlikely.
(4) embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1.
Proportioning raw materials is weight part or weight percent, down together:
100 parts of chromium alum
12 parts of waste cotton cloth
(88%) 85 part in sulfuric acid
1500 parts in water
Concrete steps are as follows:
(1) chromium alum dissolving back is added reactor;
(2) will give up cloth weigh washing clean after, the reactor of packing into was supplied the water yield, stirs to heat up, and in the time of 65 ℃, slowly adds sulfuric acid, 96 ℃ of following insulation reaction 8 hours.
Transfer PH=3 with yellow soda ash at last.
Embodiment 2:
Proportioning raw materials:
100 parts of potassium bichromate
85 parts of waste woods
(90%) 300 part in sulfuric acid
2000 parts in water
Step is as follows:
(1) potassium bichromate is added in the reactor, add 500 parts of water dissolution;
(2) 1500 parts of water are joined in the wood chip, add sulfuric acid reaction then about 30 hours, 80 ℃ of temperature of reaction;
(3) with the reaction solution cooled and filtered, it is stand-by to get filtrate;
(4) under 60 ℃ of temperature, filtrate is joined in the potassium bichromate solution while stirring at leisure, and 95 ℃ of following insulation reaction 5 hours.
Embodiment 3:
Proportioning raw materials:
100 parts of sodium dichromate 99s
(40%) 100 part of waste molasses
(35%) 286 part of hydrochloric acid
700 parts in water
Step is as follows:
(1) earlier water and sodium dichromate 99 are added in the reactor stirring and dissolving;
(2) waste molasses is added reactor, behind the question response thing uniform mixing, be warmed up to 50 ℃;
(3) then under agitation, required hydrochloric acid is slowly joined in the reactor, 92 ℃ of following insulation reaction to 6 times.
Embodiment 4:
Proportioning raw materials:
100 parts of potassium bichromate
83 parts of wheat straws
(95%) 265 part in sulfuric acid
2300 parts in water
Step is as follows:
(1) at first wheat straw is pulverized, the reactor of packing into adds entry;
(2) with the dissolved potassium dichromate solution, under agitation add in the above-mentioned reactor, heat temperature raising when solution temperature is raised to 63 ℃, adds sulfuric acid at leisure, and 96 ℃ of following insulation reaction 8 hours.
Embodiment 5:
Proportioning raw materials:
100 parts of chromium alum
Write 30 parts in waste paper
(95%) 76 part in sulfuric acid
1500 parts in water
Step is as follows:
(1) waste paper and water are joined in the reactor, after under agitation add dissolved chromium alum, be warmed up to 65 ℃;
(2) join sulfuric acid in the reactor at leisure;
(3) be incubated 5 hours down at 90 ℃.
Claims (4)
1. organic waste that utilize cellulose prepare the method for chrome tanning agent, it is characterized in that, comprise that with chromyl compound be oxidizer source; With the organic waste that contain plant cellulose is the reductive agent source; Oxidizing and Reducing Agents is added reactor, oxygenant needs complete water dissolution, stirs then and heats up, and adds sulfuric acid or hydrochloric acid not being higher than under 65 ℃ the temperature condition, 85～100 ℃ of stirring reactions 1～15 hour, be reduced into chromic green chrome tanning agent fully;
The consumption of above-mentioned each raw material is as follows, is weight part:
100～150 parts of chromyl compounds
12～90 parts of organic waste that contain plant cellulose
50～300 parts of industrial sulphuric acid or technical hydrochloric acids
700～2500 parts in water.
2. the organic waste that utilize cellulose as claimed in claim 1 prepare the method for chrome tanning agent, it is characterized in that described chromyl compound is chromium alum M
2SO
4Cr
2(SO
4)
324H
2O or dichromate chromium M
2Cr
2O
7, M=K
+, Na
+
3. the organic waste that utilize cellulose as claimed in claim 1 prepare the method for chrome tanning agent, it is characterized in that the basicity of adjusting described chrome tanning agent with alkaline reagents is 2～4.5 green chrome tanning agent to PH.
4. the organic waste that utilize cellulose as claimed in claim 1 prepare the method for chrome tanning agent, it is characterized in that the described organic waste that contain plant cellulose are various waste paper, waste wood, waste molasses, careless class.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00129406 CN1128229C (en) | 2000-12-15 | 2000-12-15 | Process for preparing chrome tanning agent from organic waste containing cellulose |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00129406 CN1128229C (en) | 2000-12-15 | 2000-12-15 | Process for preparing chrome tanning agent from organic waste containing cellulose |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1298955A CN1298955A (en) | 2001-06-13 |
| CN1128229C true CN1128229C (en) | 2003-11-19 |
Family
ID=4593478
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00129406 Expired - Lifetime CN1128229C (en) | 2000-12-15 | 2000-12-15 | Process for preparing chrome tanning agent from organic waste containing cellulose |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1128229C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105710106B (en) * | 2016-01-20 | 2018-05-04 | 安徽浩悦环境科技有限责任公司 | The method for the treatment of of wastes produced containing chromium |
-
2000
- 2000-12-15 CN CN 00129406 patent/CN1128229C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1298955A (en) | 2001-06-13 |
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