CN101880735B - Preparation method of high-performance carbon nanotube modified chrome tanning agent - Google Patents
Preparation method of high-performance carbon nanotube modified chrome tanning agent Download PDFInfo
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- CN101880735B CN101880735B CN 201010210028 CN201010210028A CN101880735B CN 101880735 B CN101880735 B CN 101880735B CN 201010210028 CN201010210028 CN 201010210028 CN 201010210028 A CN201010210028 A CN 201010210028A CN 101880735 B CN101880735 B CN 101880735B
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Abstract
The invention provides a preparation method of high-performance carbon nanotube modified chrome tanning agent, which comprises the following steps of: after mixing a carbon nanotube with an acid solution, and ultrasonically processing the mixture to prepare a suspension; then, heating, condensing, refluxing, repeatedly washing and centrifugally separating until the pH value becomes neutral; subsequently, after dissolving dichromate in water, slowly adding sulfuric acid and the treated carbon nanotube; ultrasonically processing to prepare a stable suspension; taking glucose and adding water to dissolve the glucose; dropwise adding the water solution of glucose into the suspension containing dichromate while stirring so as to produce a carbon nanotube modified chrome tanning liquid in-situ; and finally, settling and placing for long time. The chrome tanning agent enhances the bonding force of chrome, increases the quality and the properties of leather, is friendly to environment, reduces pollution and decreases resource waste.
Description
[technical field]
The invention belongs to the preparation method in leather field, particularly a kind of high-performance carbon nanotube modified chrome tanning agent.
[background technology]
The qualitative change process that rawhide is converted into leather is called tanning, be called tanning agent and be used for the chemical material that tanning can change skin into leather, spendable tanning agent kind is a lot of in leather production, in various inorganic tanning agents, chrome tanning agent has very strong hydrothermal stability, anti-storage, soft plentiful, the performance such as dyeing behavior is good with the leather of its tanning, still has so far the effect that can't substitute fully in numerous tanning agents.
The common valence state of chromium has :+0 ,+3 ,+6 three kinds, wherein only have the chromium of trivalent that flexibility is just arranged, and occurring in nature chromium mainly exists with chromic form in potassium bichromate or sodium dichromate 99, the Chrome Tanning Liquor (or chromium powder) that uses during leather is produced, it is formulated normally to add reductive agent by dichromate under acidic conditions, makes the triatomic base formula chromic salts that does not have the sexavalence of flexibility chromic salts to be reduced to have flexibility.
But, produce chrome tanning agent raw material-not only reserves are limited on earth for red vanadium (potassium bichromate, sodium dichromate 99).And the trivalent chromium in the useless chrome liquor that is not absorbed fully by skin is easy to change into the very strong sexavalent chrome of toxicity under certain condition, and environment is brought disadvantageous effect.Therefore, further improve the consumption of chrome-tanned performance, minimizing chrome tanning agent, increase leather to the absorption of chrome tanning agent, the utilization ratio of raising chrome tanning agent, reduce the discharging of waste liquid, not only can save limited resources but also can alleviate pollution to environment, have significant economic benefit and social benefit, significant.
[summary of the invention]
Technical problem to be solved by this invention provides a kind of preparation method of high-performance carbon nanotube modified chrome tanning agent, use modified chrome tanning agent of the present invention, not only can reduce chromium consumption, reduce waste and environmental pollution to resource, can also increase quality and the performance of leather.
For achieving the above object, the present invention also provides a kind of preparation method of high-performance carbon nanotube modified chrome tanning agent, comprises the steps:
Step 1: get carbon nanotube and with it with after acidic solution mixes, supersound process is mixed with suspension, then, heating-condensing refluxes, at last repeatedly washing and centrifugation until PH be neutrality;
Step 2: to be 100 parts of mass concentrations be dissolved in quality according to 100% dichromate with quality is that 350 parts, temperature are in 75 ℃ the water, obtain dichromate solution, then, in dichromate solution, slowly add quality and be carbon nanotube that 0.01 part of step 1 obtains and mass concentration according to 100% sulfuric acid, subsequently, supersound process is mixed with stable suspension;
Step 3: get quality and be 25 parts glucose and add water and make it dissolving, then, drip while stirring D/W in the suspension that obtains to step 2, make its original position generate the Chrome Tanning Liquor of carbon nano-tube modification, last, leave standstill to display and get final product.
As the preferred embodiments of the present invention, in the step 1, the addition of described carbon nanotube is: 0.025 times of the acidic solution quality relatively;
As the preferred embodiments of the present invention, the acidic solution in the described step 1 is the nitration mixture that sulfuric acid and nitric acid form with 1:1;
As the preferred embodiments of the present invention, described dichromate is selected from potassium bichromate or sodium dichromate 99.
The preparation method of high-performance carbon nanotube modified chrome tanning agent of the present invention has the following advantages at least:
1. the carbon nanotube after the modification like this, is conducive to the coordination of carbon nanotube and chromic compound on the one hand with more carboxyl isoreactivity group, and the binding capacity of chromium and materials with hide glue fibril when increasing chrome tanning so, can make the trivalent chromium that is converted to of sexavalent chrome maximum; Can be combined with forms such as covalent linkage, ionic linkage or hydrogen bonds such as amino, hydroxyl etc. by the active group on collegen filament on the other hand.Therefore, chrome tanning agent of the present invention not only can improve chrome-tanned shrinkage temperature, thicken the content of chromium sesquioxide in rate and the chrome tanned leather, and environmentally friendly, reduces the wasting of resources.
2. the carboxyl on the carbon nanotube after the modification has certain masking effect to chrome tanning agent, therefore, can improve the effect of tanning; In addition, because carbon nanotube has the enhancing toughening effect, therefore, chrome tanning agent of the present invention can improve chrome-tanned tensile strength and elongation at break.
[embodiment]
Embodiment one:
Step 1: the purifying of carbon nanotube and modification: at first, with mass concentration be 95% sulfuric acid and mass concentration be 68% nitric acid by volume for 1:1 mixes, be made into mixed acid solution; Then, the carbon nanotube of getting 0.025 times of relative nitration mixture quality joins in the mixed acid solution, the ultrasonic stable suspension of its formation that makes; Soaked 24 hours again, and then, refluxed 1 hour at 120 ℃ of heating-condensings, washing and centrifugation removing the impurity in the carbon nanotube, and make active reactive group on its surface band until pH value is 7 repeatedly again;
Step 2: take by weighing quality and be 100 parts of mass concentrations according to 100% potassium bichromate, making it be dissolved in quality is that 350 parts of temperature are in 75 ℃ the water, and then slowly add the carbon nanotube that step 1 that quality is 0.01 part for (133.3-B) part mass concentration according to 100% sulfuric acid and quality obtains, subsequently, be passed in the ultrasonic cell disrupte machine, make it form stable suspension;
Step 3: take by weighing quality and be 25 parts glucose, and add water and make its dissolving, then, in churned mechanically situation, drip slowly glucose solution in the suspension that obtains to step 2 and carry out redox reaction, make its original position generate the Chrome Tanning Liquor of carbon nano-tube modification;
Step 4: the basicity of measuring and regulating the Chrome Tanning Liquor of carbon nano-tube modification;
Step 5: leave standstill and display, namely get high-performance carbon nanotube modified chrome tanning agent;
Step 6: spraying drying namely gets the chromium powder of carbon nano-tube modification.
Embodiment two:
Step 1: the purifying of carbon nanotube and modification: at first, with mass concentration be 96% sulfuric acid and mass concentration be 67% nitric acid by volume for 1:1 mixes, be made into mixed acid solution; Then, the carbon nanotube of getting 0.025 times of relative nitration mixture quality joins in the mixed acid solution, the ultrasonic stable suspension of its formation that makes; Soaked 24 hours again, and then, refluxed 1 hour at 120 ℃ of heating-condensings, washing and centrifugation removing the impurity in the carbon nanotube, and make active reactive group on its surface band until pH value is 6 repeatedly again;
Step 2: take by weighing quality and be 100 parts of mass concentrations according to 100% sodium dichromate 99, making it be dissolved in quality is that 350 parts of temperature are in 75 ℃ the water, and then slowly add the carbon nanotube that step 1 that quality is 0.01 part for (132-B) part mass concentration according to 100% sulfuric acid and quality obtains, subsequently, be passed in the ultrasonic cell disrupte machine, make it form stable suspension;
Step 3: take by weighing quality and be 25 parts glucose, and add water and make its dissolving, then, in churned mechanically situation, drip slowly glucose solution in the suspension that obtains to step 2 and carry out redox reaction, make its original position generate the Chrome Tanning Liquor of carbon nano-tube modification;
Step 4: the basicity of measuring and regulating the Chrome Tanning Liquor of carbon nano-tube modification;
Step 5: leave standstill and display, namely get high-performance carbon nanotube modified chrome tanning agent;
Step 6: spraying drying namely gets the chromium powder of carbon nano-tube modification.
Embodiment three:
Step 1: the purifying of carbon nanotube and modification: at first, with mass concentration be 98% sulfuric acid and mass concentration be 65% nitric acid by volume for 1:1 mixes, be made into mixed acid solution; Then, the carbon nanotube of getting 0.025 times of relative nitration mixture quality joins in the mixed acid solution, the ultrasonic stable suspension of its formation that makes; Soaked 24 hours again, and then, refluxed 1 hour at 120 ℃ of heating-condensings, washing and centrifugation removing the impurity in the carbon nanotube, and make active reactive group on its surface band until pH value is 8 repeatedly again;
Step 2: take by weighing quality and be 100 parts of mass concentrations according to 100% potassium bichromate, making it be dissolved in quality is that 350 parts of temperature are in 75 ℃ the water, and then slowly add the carbon nanotube that step 1 that quality is 0.01 part for (133.3-B) part mass concentration according to 100% sulfuric acid and quality obtains, subsequently, be passed in the ultrasonic cell disrupte machine, make it form stable suspension;
Step 3: take by weighing quality and be 25 parts glucose, and add water and make its dissolving, then, in churned mechanically situation, drip slowly glucose solution in the suspension that obtains to step 2 and carry out redox reaction, make its original position generate the Chrome Tanning Liquor of carbon nano-tube modification;
Step 4: the basicity of measuring and regulating the Chrome Tanning Liquor of carbon nano-tube modification;
Step 5: leave standstill and display, namely get high-performance carbon nanotube modified chrome tanning agent;
Step 6: spraying drying namely gets the chromium powder of carbon nano-tube modification.
In the above-described embodiments, described mass concentration is according to 100% potassium bichromate or sodium dichromate 99, pure potassium bichromate or the sodium dichromate 99 of any impurity refer to undope, general potassium bichromate or the sodium dichromate 99 that obtains from occurring in nature is not very pure, therefore, adding fashionablely, it should be converted into absolutely pure potassium bichromate or sodium dichromate 99;
Described mass concentration refers to pure sulfuric acid, for example according to 100% sulfuric acid, be 98% from the mass concentration of the sulfuric acid bought on the market, then, in the present embodiment, if add this sulfuric acid, then the addition of this sulfuric acid is: (133.3-B)/98% or (132-B) 98%;
The add-on of described bright sulfur acid (133.3-B) or (132-B) in B refer to the basicity of target chrome tanning agent;
In addition, repeatedly washing and centrifugation described in the step 1 refers at first wash, then centrifugation, get rid of clear liquid and keep solids, then, in solids, add again water and wash, then, again centrifugation, remove clear liquid and keep solids, so repeatedly carry out, until PH reaches the requirement of regulation.
The above only is one embodiment of the present invention, it or not whole or unique embodiment, the conversion of any equivalence that those of ordinary skills take technical solution of the present invention by reading specification sheets of the present invention is claim of the present invention and contains.
Claims (6)
1. the preparation method of high-performance carbon nanotube modified chrome tanning agent is characterized in that: may further comprise the steps:
Step 1: get carbon nanotube and with it with after acidic solution mixes, supersound process is mixed with suspension, then, heating-condensing refluxes, at last repeatedly washing and centrifugation until pH be neutrality;
Step 2: to be 100 parts of mass concentrations be dissolved in quality according to 100% dichromate with quality is that 350 parts, temperature are in 75 ℃ the water, obtain dichromate solution, then, in dichromate solution, slowly add quality and be carbon nanotube that 0.01 part of step 1 obtains and mass concentration according to 100% sulfuric acid, subsequently, supersound process is mixed with stable suspension;
Step 3: get quality and be 25 parts glucose and add water and make it dissolving, then, drip while stirring D/W in the suspension that obtains to step 2, make its original position generate the Chrome Tanning Liquor of carbon nano-tube modification, last, leave standstill to display and get final product.
2. the preparation method of high-performance carbon nanotube modified chrome tanning agent as claimed in claim 1, it is characterized in that: in step 1, the addition of described carbon nanotube is: 0.025 times of the acidic solution quality relatively.
3. the preparation method of high-performance carbon nanotube modified chrome tanning agent as claimed in claim 1 or 2 is characterized in that: the acidic solution in the described step 1 refers to that sulfuric acid and nitric acid are the nitration mixture that 1:1 forms according to volume ratio.
4. the preparation method of high-performance carbon nanotube modified chrome tanning agent as claimed in claim 1, it is characterized in that: described dichromate is selected from potassium bichromate or sodium dichromate 99.
5. the preparation method of high-performance carbon nanotube modified chrome tanning agent is characterized in that: may further comprise the steps:
Step 1: be 0.025:1 with carbon nanotube with after acidic solution mixes according to mass ratio, supersound process is mixed with suspension, then, refluxes 1 hour at 120 ℃ of heating-condensings, repeatedly wash at last and separate until pH for neutral;
Step 2: to be 100 parts of mass concentrations be dissolved in quality according to 100% potassium bichromate with quality is that 350 parts, temperature are in 75 ℃ the water, obtain potassium bichromate solution, then, slowly adding quality in potassium bichromate solution is 0.01 part of carbon nanotube that step 1 obtains for (133.3-B) part mass concentration according to 100% sulfuric acid and quality, subsequently, supersound process is mixed with stable suspension, and wherein, B is the basicity of target chrome tanning agent;
Step 3: get quality and be 25 parts glucose and add water and make it dissolving, then, drip while stirring D/W in the suspension that obtains to step 2, make its original position generate the Chrome Tanning Liquor of carbon nano-tube modification, last, leave standstill to display and get final product.
6. the preparation method of high-performance carbon nanotube modified chrome tanning agent is characterized in that: may further comprise the steps:
Step 1: be 1:1 according to volume ratio, be after the sulfuric acid of 95-98% and nitric acid that mass concentration is 65-68% are mixed into nitration mixture with mass concentration, add the carbon nanotube of 0.025 times of relative nitration mixture quality to it, supersound process is mixed with suspension, then, refluxed 1 hour at 120 ℃ of heating-condensings, at last repeatedly washing and centrifugation until pH be neutrality;
Step 2: to be 100 parts of mass concentrations be dissolved in quality according to 100% sodium dichromate 99 with quality is that 350 parts, temperature are in 75 ℃ the water, obtain sodium dichromate solution, then, slowly adding quality in sodium dichromate solution is 0.01 part of carbon nanotube that step 1 obtains for (132-B) part mass concentration according to 100% sulfuric acid and quality, subsequently, supersound process is mixed with stable suspension, and wherein, B is the basicity of target chrome tanning agent;
Step 3: get quality and be 25 parts glucose and add water and make it dissolving, then, drip while stirring D/W in the suspension that obtains to step 2, make its original position generate the Chrome Tanning Liquor of carbon nano-tube modification, last, leave standstill to display and get final product.
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| CN 201010210028 CN101880735B (en) | 2010-06-27 | 2010-06-27 | Preparation method of high-performance carbon nanotube modified chrome tanning agent |
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| CN 201010210028 CN101880735B (en) | 2010-06-27 | 2010-06-27 | Preparation method of high-performance carbon nanotube modified chrome tanning agent |
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| CN101880735B true CN101880735B (en) | 2013-04-10 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103320552B (en) * | 2013-07-15 | 2014-11-05 | 四川大学 | Ultrasonic-assisted through-type four-bath chromium tanning method with separated penetration and fixation |
| CN104232808B (en) * | 2014-09-23 | 2016-06-29 | 陕西科技大学 | graphene oxide and trivalent chromium complex tanning agent and preparation method thereof |
| CN109852740B (en) * | 2019-01-21 | 2021-05-04 | 齐鲁工业大学 | Preparation method for preparing chrome tanning agent by using carboxymethyl cellulose |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001031067A1 (en) * | 1999-10-29 | 2001-05-03 | Commissariat A L'energie Atomique | Method for tanning skins or materials containing collagen, with a dense fluid under pressure |
| CN1584058A (en) * | 2004-04-14 | 2005-02-23 | 陕西科技大学 | Preparing method for aldehyde acid tanning agent |
| CN101086026A (en) * | 2007-06-08 | 2007-12-12 | 陕西科技大学 | End carboxyl super branched polymer as high absorption chrome tanning adjuvant and its synthesis method |
| CN101440208A (en) * | 2008-12-09 | 2009-05-27 | 东华大学 | Preparation of functionalized carbon nano-tube modification polyurethane elastomer |
| CN101664676A (en) * | 2009-09-15 | 2010-03-10 | 北京化工大学 | Preparation method of composite metal oxide/carbon nanotube type visible light catalyst |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001031067A1 (en) * | 1999-10-29 | 2001-05-03 | Commissariat A L'energie Atomique | Method for tanning skins or materials containing collagen, with a dense fluid under pressure |
| CN1584058A (en) * | 2004-04-14 | 2005-02-23 | 陕西科技大学 | Preparing method for aldehyde acid tanning agent |
| CN101086026A (en) * | 2007-06-08 | 2007-12-12 | 陕西科技大学 | End carboxyl super branched polymer as high absorption chrome tanning adjuvant and its synthesis method |
| CN101440208A (en) * | 2008-12-09 | 2009-05-27 | 东华大学 | Preparation of functionalized carbon nano-tube modification polyurethane elastomer |
| CN101664676A (en) * | 2009-09-15 | 2010-03-10 | 北京化工大学 | Preparation method of composite metal oxide/carbon nanotube type visible light catalyst |
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