CN101314796A - Method for preparing multiple metallic ion leather tanning agents - Google Patents
Method for preparing multiple metallic ion leather tanning agents Download PDFInfo
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- CN101314796A CN101314796A CNA2008100383766A CN200810038376A CN101314796A CN 101314796 A CN101314796 A CN 101314796A CN A2008100383766 A CNA2008100383766 A CN A2008100383766A CN 200810038376 A CN200810038376 A CN 200810038376A CN 101314796 A CN101314796 A CN 101314796A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
Abstract
The invention discloses a method for preparing a plurality of metal ion leather tanning agents by utilizing chromium-containing and collagen solid wastes. Materials belonging to leather originally such as leather meal, leather bits and pieces, waste leather are used as raw materials for preparing chemical material which can be processed into leather; the chemical material is used in leather tanning and then is applied back to the leather; the chemical material has the best compatibility with the leather and can effectively form the self-closed recycle of materials. Namely, the chromium-containing and collagen solid wastes are used as a reducing agent instead of glucose, sulfur dioxide, etc., and ferrous sulfate is used as a supplementary reducing agent, so as to deoxidize sodium bichromate to prepare the leather tanning agents; chromium compounds in the solid wastes again become part of the metal ions which are used for preparing the tanning agents; collagen hydrolysate or oxidation products become filling materials in the tanning agents; the supplementary reducing agent becomes another metal ion in the tanning agents after being oxidized; the leather tanning agents containing a plurality of metal ions are prepared through the bridge link between sodium citrate and sodium tartrate.
Description
Technical field
The present invention relates to a kind of preparation method of leather retanning agent, the solid waste preparation that contains chromium and collagen more specifically to a kind of utilization has the preparation method of the leather retanning agent of multiple metal ion.
Background technology
China is leather production and consumption big country, because most manufacturers are at present still based on chrome tanning, therefore can produce a large amount of chromium solid waste that contain, as chrome leather scrap, make leatherware sideline judge clout, waste and old leatherware etc.The above-mentioned matrix thing that contains the chromium solid waste is an animal skin collagen, and contains a large amount of chromium cpds, wherein contains collagen more than 90%, contains chromium cpd folding sodium dichromate about 7%.The annual chrome leather scrap that only produces of China just has 300,000 tons approximately, if these are contained the chromium waste abandons it, causes waste first, second serious environment pollution.The problem of environmental pollution of solution curriery has become the emphasis problem in the environmental protection work of countries in the world, also is the key issue of leather Sustainable development.Chinese patent CN200410025967.1 discloses a kind of method of utilizing chrome leather scrap to prepare chrome tanning agent, with originally belong on the leather material---chrome leather scrap is as raw material, the material that is prepared into the energy processing leather is used for leather processing, turn in the leather again and go, form the self-enclosed recycle of material, promptly replace glucose, sulfurous gas etc. to make reductive agent with chrome leather scrap, the reduction sodium dichromate is prepared into the leather chrome tanning agent, makes the chromium cpd in the leather bits become a part for preparing chrome tanning agent again.
But, prevent to pollute, protect the work of environment more and more to cause people's attention along with the enhancing of people's environmental consciousness.Therefore tanning industry also develops towards less contamination, free of contamination direction.Chrome tanning is occupied an leading position in leather processing always for a long time.But because chromium to the pollution of environment and the poorness of chromium resource, lacks the inexorable trend that chromium and chrome-free tanning just become the leather technology development.Through the effort of nearly half a century, though,, do not find the material of substitute chromium tanning agent fully so far yet from the over-all properties of leather having carried out big quantity research aspect the chrome-free tanning material and technology method.Can be used as in the inorganic metal salt of tanning agent in minority, molysite is unique metal tanning agent that does not have pollution.On tanning industry history, molysite also is to be used for one of inorganic salt of process hides the earliest, but because there is obvious defects in iron tanned leather, as water-fastly wash, loss of properties on aging, so independent iron tannage is difficult to obtain industrialization promotion; The pollution of aluminium salt is also less, but adopts not water-fast the washing of leather of aluminum tanning separately.Employing has the tanning agent tanning of multiple metal ion, has synergistic effect between the different metal ions, than much better, therefore use leather retanning agent for realizing that the few chrome tanning of leather is significant with multiple metal ion with the tanning agent tanning effect that contains a metal ion species.
Summary of the invention
The object of the present invention is to provide a kind of preparation method simple, make reductive agent with the collagen that contains in chromium and the collagen solid waste, ferrous sulfate makes to replenish reductive agent reduction sodium dichromate, and as bridging agent, preparation contains the method for the leather retanning agent of multiple metal ion with Trisodium Citrate, sodium tartrate.This method makes the chromium cpd that contains in chromium and the collagen solid waste become a part of metal ion starting material of freshly prepd multiple metallic ion leather tanning agents again, collagen hydrolysate and oxidation products become the weighting agent of the multiple metallic ion leather tanning agents of new preparation, having ferric iron compound that the ferrous sulfate of strong reducing property generated by the sodium dichromate oxidation then becomes another kind of metal ion raw material in the tanning agent, utilizes the bridge linking effect of Trisodium Citrate and sodium tartrate to make it to generate the leather retanning agent of the multiple metal ion with masking effect.
For achieving the above object, the preparation method that the present invention adopts is:
To contain collecting solid castoff, the removal of impurities dedusting of chromium and collagen, organic content is surveyed in classification, pulverizing.100 parts of sodium dichromates are added reactor, add water of 150-200 part and the sulfuric acid of 95-100 part, stir and make the sodium dichromate dissolving, make bichromate solutions.Add the solid waste that contains chromium and collagen that crushes in bichromate solutions, it is 45-50 part that its amount is amounted to into organism, is incubated 90-95 ℃ and stirs 120-150 minute.Take by weighing 25-20 part sulfuric acid again, with 100 parts of water dilutions, and with it with the dissolving of ferrous sulfate of 125-100 part, splash into then in 90-95 ℃ the reaction system, stirred 10-20 minute, and after sampling detects no Cr (VI), added 10-15 part sodium tartrate and 13-16 part Trisodium Citrate solid, 90-95 ℃ was stirred 20-60 minute down, and still aging then liquid contains the leather retanning agent of multiple metal ion.Above-mentioned " part " all refers to " weight part "
Of the present inventionly contain chromium and the collagen solid waste will be carried out the removal of impurities dedusting earlier before adding, classification and pulverizing is surveyed organic content, and is measured with rolling over synthetic organism amount; Sulfuric acid adds at twice.Replenish reduction will adding the strong reductant ferrous sulfate, and ferrous sulfate to dissolve it before adding with the sulphuric acid soln of the adding second time with the later stage that contains chromium and collagen solid waste reduction sodium dichromate.With 10-15 part sodium tartrate and 13-16 part Trisodium Citrate as bridging agent.
Because the present invention will originally belong to material (leather bits) on the leather or waste and old leather, leather sideline judge clout---contain chromium and collagen waste as raw material, be prepared into the chemical materials of energy processing leather, be used for leather tanning, turn in the leather again and go, itself and leather have best consistency, can effectively form the self-enclosed recycle of material.Promptly make reductive agent with replacement glucose, the sulfurous gas etc. such as solid waste leather bits that contain chromium and collagen, make to replenish reductive agent with ferrous sulfate, the reduction sodium dichromate is prepared into leather retanning agent, make the chromium cpd in the solid waste become a part of metal ion for preparing tanning agent again, collagen hydrolysate or oxidation products become the packing material in the tanning agent, become the another kind of metal ion in the tanning agent after additional reductive agent is oxidized, by the bridge linking effect of sodium tartrate and Trisodium Citrate, thereby prepare a kind of leather retanning agent that contains multiple metal ion.
Embodiment
The present invention will be further elaborated below by specific embodiment, but embodiment does not limit protection scope of the present invention.
Embodiment 1:
100 parts sodium dichromates are added in the reactor, and water and 95 parts of sulfuric acid of adding 150 parts make the sodium dichromate dissolving, make bichromate solutions; That add to pulverize in bichromate solutions contains chromium and collagen solid waste, and it is 45 parts that its amount is amounted to into organism, is heated to 90 ℃ with water-bath, stirs 120 minutes.Take by weighing 25 parts of sulfuric acid again, with 100 parts of water dilutions, and with it with the dissolving of ferrous sulfate of 125 parts, splash into then in 90 ℃ the reaction system, stirred 10 minutes, sampling adds 10 parts of sodium tartrates and 13 parts of Trisodium Citrate solids after detecting no Cr (VI), 90 ℃ were stirred 20 minutes down, and still aging then liquid contains the leather retanning agent of multiple metal ion.
Embodiment 2:
100 parts of sodium dichromates are added in the reactor, add 160 parts water and 96 parts sulfuric acid, stir and make the sodium dichromate dissolving, make bichromate solutions.Add the solid waste that contains chromium and collagen that crushes in bichromate solutions, it is 46 parts that its amount is converted into organism, is incubated 92 ℃ and stirs 130 minutes.Take by weighing 24 parts of sulfuric acid again, with 100 parts of water dilutions, and with it with the dissolving of ferrous sulfate of 120 parts, splash into then in 92 ℃ the reaction system, stirred 15 minutes, sampling adds 11 parts of sodium tartrates and 14 parts of Trisodium Citrate solids after detecting no Cr (VI), 92 ℃ were stirred 30 minutes down, and still aging then liquid contains the leather retanning agent of multiple metal ion.
Embodiment 3:
100 parts of sodium dichromates are added reactor, add 170 parts water and 97 parts sulfuric acid, stir and make the sodium dichromate dissolving, make bichromate solutions.Add the solid waste that contains chromium and collagen that crushes in bichromate solutions, it is 47 parts that its amount is converted into organism, is incubated 94 ℃ and stirs 140 minutes.Take by weighing 23 parts of sulfuric acid again, with 100 parts of water dilutions, and with it with the dissolving of ferrous sulfate of 115 parts, splash into then in 94 ℃ the reaction system, stirred 15 minutes, and after sampling detects no Cr (VI), added 12-part sodium tartrate and 15 parts of Trisodium Citrate solids, 94 ℃ were stirred 40 minutes down, and still aging then liquid contains the leather retanning agent of multiple metal ion.
Embodiment 4:
100 parts of sodium dichromates are added reactor, add 180 parts water and 98 parts sulfuric acid, stir and make the arsenic dissolving, make bichromate solutions.Add the solid waste that contains chromium and collagen that crushes in bichromate solutions, it is 48 parts that its amount is amounted to into organism, is incubated 95 ℃ and stirs 140 minutes.Take by weighing 22 parts of sulfuric acid again, with 100 parts of water dilutions, and with it with the dissolving of ferrous sulfate of 110 parts, splash into then in 95 ℃ the reaction system, stirred 18 minutes, sampling adds 13 parts of sodium tartrates and 15 parts of Trisodium Citrate solids after detecting no Cr (VI), 95 ℃ were stirred 50 minutes down, and still aging then liquid contains the leather retanning agent of multiple metal ion.
Embodiment 5:
100 parts of sodium dichromates are added reactor, add 190 parts water and 99 parts sulfuric acid, stir and make the arsenic dissolving, make bichromate solutions.The back adds the solid waste that contains chromium and collagen that crushes in bichromate solutions, and it is 49 parts that its amount is amounted to into organism, is incubated 95 ℃ and stirs 140 minutes.Take by weighing 21 parts of sulfuric acid again, with 100 parts of water dilutions, and with it with the dissolving of ferrous sulfate of 105 parts, splash into then in 95 ℃ the reaction system, stirred 20 minutes, sampling adds 14 parts of sodium tartrates and 16 parts of Trisodium Citrate solids after detecting no Cr (VI), 95 ℃ were stirred 60 minutes down, and still aging then liquid contains the leather retanning agent of multiple metal ion.
Embodiment 6:
100 parts of sodium dichromates are added reactor, add 200 parts water and 100 parts sulfuric acid, stir and make the arsenic dissolving, make bichromate solutions.The back adds the solid waste that contains chromium and collagen that crushes in bichromate solutions, and it is 50 parts that its amount is amounted to into organism, is incubated 95 ℃ and stirs 150 minutes.Take by weighing 20 parts of sulfuric acid again, with 100 parts of water dilutions, and with it with the dissolving of ferrous sulfate of 100 parts, splash into then in 95 ℃ the reaction system, stirred 20 minutes, sampling adds 15 parts of sodium tartrates and 16 parts of Trisodium Citrate solids after detecting no Cr (VI), 95 ℃ were stirred 60 minutes down, and still aging then liquid contains the leather retanning agent of multiple metal ion.
The present invention measures moisture content and the ash oontent contain in chromium and the collagen waste with conventional method of analysis, according to formula: and organism (%)=100%-moisture (%)-ash content (%), calculate organic content in the waste;
The mensuration of moisture and volatile matter content
Crucible dries to constant weight in 130 ℃ ± 2 baking oven.Accurately take by weighing to crush and contain chromium and collagen waste 1.5-2.0g in crucible, put into the baking oven baking 45min of temperature adjustment to 130 ℃ ± 2, add a cover taking-up, put into moisture eliminator, be cooled to room temperature and weigh.Down dry by the fire 15min again in synthermal again, weigh after the cooling, be not more than 0.001g to twice quality change.
Quality before moisture level volatile content (%)=100% * (quality before the oven dry-oven dry back quality)/oven dry
The mensuration of ash
In advance with crucible calcination in 800 ℃ of High Temperature Furnaces Heating Apparatuss, cool off, weigh, calcination is to constant weight again.
Accurately take by weighing to crush and contain chromium and collagen waste 2-3g in the crucible of constant weight, to cover crack, make slowly charing of sample with little fire heating earlier, avoid taking place the charcoal ball or with the phenomenon of crucible fusion bonding, when waiting not have the charcoal cigarette, it is thoroughly wetting to drip 1mol/L sulfuric acid, and low-temperature heat disappears to the SO3 cigarette, intense heating.It is complete to ashing to be put in 800 ℃ of High Temperature Furnaces Heating Apparatuss calcination then.In moisture eliminator, be cooled to room temperature, weigh.Repeat to add acid, heating, cool off, weigh, be not more than 0.001g to twice quality change.
Quality before ash content (%)=100% * (quality after the preceding quality-calcination of calcination)/calcination
The present invention checks the method that has or not Cr (VI) in the tanning agent: get owse and drip in phosphoric acid acidifying water, shake up the back and add several 1% Starch Indicators and 10% liquor kalii iodide, if the constant indigo plant of solution colour shows no Cr (VI) residue; If solution turned blue shows that Cr (VI) does not reduce fully, need add ferrous sulfate to can not detecting Cr (VI).
The present invention adopts improvement sodium peroxide method to measure chromium, iron level and the total oxide content of the tanning agent of prepared multiple metal ion, adopts oxalate method to survey the basicity of tanning agent.
Chromium-iron tannage agent oxide content and basicity are measured concrete grammar
In the 200mL volumetric flask, constant volume shakes up the back and is used for following mensuration as liquid to be measured with pipette, extract 10mL owse.
(1) ferrochrome assay---sodium peroxide method
Measuring method: draw 2mL liquid to be measured in the 250mL iodine flask, add 1: 1 sulfuric acid of 5mL nitric acid, 2mL and 10mL distilled water, careful heating is cleared up, to a large amount of dense smokes of emerging, till the solution transparent clear.Cooling back adds in the 10%NaOH solution and excessive acid, becomes pale brown look to solution colour, adds 2g sodium peroxide and 15-20mL distilled water then, slowly boils 5min.For promoting remaining Na
2O
2Decompose, add 5% nickel sulfate solution 5mL, boil again to no small bubbles and emit, can carry out total flow measurement of ferrochrome or chrome determination after the cooling.
1. the total flow measurement of ferrochrome adds 1: 1 hydrochloric acid to resolution of precipitate, adds 15mL again, cooling.Add the 15mL10% liquor kalii iodide, the rearmounted dark place 5min of lid bottle stopper and water seal, flushing bottle stopper and bottle wall.Be bale of straw with 0.01mol/L sodium thiosulfate standard solution titration to solution colour, add the 1mL Starch Indicator, continue titration and disappear to blue, solution is the emerald green terminal point that is.The volume of the sodium thiosulfate standard solution that consumes is designated as V
1
2. chromium, iron level are measured and are added 1: 1 phosphoric acid-hydrochloric acid mixed solution (phosphoric acid is with after hydrochloric acid mixes with volume ratio at 1: 2, and nitration mixture mixes with the water equal-volume again), add 15mL again to resolution of precipitate, use iodometric determination after cooling off, and method together 1..The volume of the sodium thiosulfate standard solution that consumes is designated as V
2Calculation formula Fe
2O
3(g/L)=159.7 * 5 * N * (V
1-V
2)
Cr
2O
3(g/L)＝152.0×5×N×V
2/3
In the formula: N---the concentration (mol/L) of sodium thiosulfate standard solution;
V
1---consume the volume (mL) of sodium thiosulfate standard solution in the total flow measurement of ferrochrome;
V
2---consume the volume (mL) of sodium thiosulfate standard solution in the chrome determination;
152.0---Cr
2O
3Relative molecular mass;
159.7---Fe
2O
3Relative molecular mass.
(2) basicity is measured---the sodium oxalate method
Measuring method: pipette 5mL liquid to be measured in 250mL ground triangular flask, add 20mL0.25mol/L sulphuric acid soln and 50mL2.5% sodium oxalate solution with transfer pipet again, load onto reflux condensing tube reflux 1h, cooling is with distilled water flushing prolong inwall.Use the titration of 0.4mol/L standard solution of sodium hydroxide then, make indicator with thymolphthalein.When appearring in solution, little yellow is terminal point.By same operation, do not add owse and do blank test.
Calculation formula basicity (%)=(V
0-V) * N * 200/[(M
1/ 152.0+M
2/ 159.7) * 3]
In the formula: V
0---blank test consumes standard solution of sodium hydroxide volume (mL);
V---analytic sample consumes standard solution of sodium hydroxide volume (mL);
The concentration of N---standard solution of sodium hydroxide (mol/L);
M
1---the Cr before the tanning agent dilution
2O
3Content (g/L);
M
2---the Fe before the tanning agent dilution
2O
3Content (g/L).
The technical indicator of the multiple metallic ion leather tanning agents of the present invention's preparation:
Basicity 15%-20%; Total oxide content about 10%;
Ferrochrome is than 1.5: 1-2: 1; Outward appearance palm fibre blue liquid.
Claims (7)
1. a utilization contains the method that chromium and collagen solid waste prepare multiple metallic ion leather tanning agents, and it comprises the steps:
A) will contain chromium and collagen collecting solid castoff, removal of impurities dedusting, organic content is surveyed in classification, pulverizing, carries out the waste metering with organic content;
B) 100 parts of sodium dichromates are added reactor, add 150～200 parts water and 95～100 parts sulfuric acid, stir and make the sodium dichromate dissolving, make bichromate solutions;
C) add the solid waste that contains chromium and collagen that crushes in bichromate solutions, it is 45～50 parts that its amount is amounted to into organism, is incubated 90～95 ℃, stirs 120～150 minutes;
D) water is 25～20 parts of Dilution of sulphuric acid, and with its ferrous sulfate dissolving with 125～100 parts, splashes into temperature then and is in 90～95 ℃ the reaction system, stirs 10～20 minutes;
E) after sampling detects no sexavalence Cr, add 10～15 parts of sodium tartrates and 13～16 parts of Trisodium Citrate solids, stirred 20～60 minutes down for 90～95 ℃ in temperature, still aging, get the leather retanning agent that liquid contains multiple metal ion;
The above-mentioned unit of feeding intake all refers to " weight part ".
2. utilization as claimed in claim 1 contains the method that chromium and collagen solid waste prepare multiple metallic ion leather tanning agents, it is characterized in that, 100 parts sodium dichromates are added in the reactor, and water and 95 parts of sulfuric acid of adding 150 parts make the sodium dichromate dissolving, make bichromate solutions; That add to pulverize in bichromate solutions contains chromium and collagen solid waste, and it is 45 parts that its amount is amounted to into organism, is heated to 90 ℃ with water-bath, stirs 120 minutes.Take by weighing 25 parts of sulfuric acid again, with 100 parts of water dilutions, and with it with the dissolving of ferrous sulfate of 125 parts, splash into then in 90 ℃ the reaction system, stirred 10 minutes, sampling adds 10 parts of sodium tartrates and 13 parts of Trisodium Citrate solids after detecting no Cr (VI), 90 ℃ were stirred 20 minutes down, and still aging then liquid contains the leather retanning agent of multiple metal ion.
3. utilization as claimed in claim 1 contains the method that chromium and collagen solid waste prepare multiple metallic ion leather tanning agents, it is characterized in that, 100 parts of sodium dichromates are added in the reactor, add 160 parts water and 96 parts sulfuric acid, stirring makes the sodium dichromate dissolving, makes bichromate solutions.Add the solid waste that contains chromium and collagen that crushes in bichromate solutions, it is 46 parts that its amount is amounted to into organism, is incubated 92 ℃ and stirs 130 minutes.Take by weighing 24 parts of sulfuric acid again, with 100 parts of water dilutions, and with it with the dissolving of ferrous sulfate of 120 parts, splash into then in 92 ℃ the reaction system, stirred 15 minutes, sampling adds 11 parts of sodium tartrates and 14 parts of Trisodium Citrate solids after detecting no Cr (VI), 92 ℃ were stirred 30 minutes down, and still aging then liquid contains the leather retanning agent of multiple metal ion.
4. utilization as claimed in claim 1 contains the method that chromium and collagen solid waste prepare multiple metallic ion leather tanning agents, it is characterized in that, 100 parts of sodium dichromates are added reactor, add 170 parts water and 97 parts sulfuric acid, stirring makes the sodium dichromate dissolving, makes bichromate solutions.Add the solid waste that contains chromium and collagen that crushes in bichromate solutions, it is 47 parts that its amount is amounted to into organism, is incubated 94 ℃ and stirs 140 minutes.Take by weighing 23 parts of sulfuric acid again, with 100 parts of water dilutions, and with it with the dissolving of ferrous sulfate of 115 parts, splash into then in 94 ℃ the reaction system, stirred 15 minutes, sampling adds 12 parts of sodium tartrates and 15 parts of Trisodium Citrate solids after detecting no Cr (VI), 94 ℃ were stirred 40 minutes down, and still aging then liquid contains the leather retanning agent of multiple metal ion.
5. utilization as claimed in claim 1 contains the method that chromium and collagen solid waste prepare multiple metallic ion leather tanning agents, it is characterized in that, 100 parts of sodium dichromates are added reactor, add 180 parts water and 98 parts sulfuric acid, stirring makes the arsenic dissolving, makes bichromate solutions.Add the solid waste that contains chromium and collagen that crushes in bichromate solutions, it is 48 parts that its amount is amounted to into organism, is incubated 95 ℃ and stirs 140 minutes.Take by weighing 22 parts of sulfuric acid again, with 100 parts of water dilutions, and with it with the dissolving of ferrous sulfate of 110 parts, splash into then in 95 ℃ the reaction system, stirred 18 minutes, sampling adds 13 parts of sodium tartrates and 15 parts of Trisodium Citrate solids after detecting no Cr (VI), 95 ℃ were stirred 50 minutes down, and still aging then liquid contains the leather retanning agent of multiple metal ion.
6. utilization as claimed in claim 1 contains the method that chromium and collagen solid waste prepare multiple metallic ion leather tanning agents, it is characterized in that, 100 parts of sodium dichromates are added reactor, add 190 parts water and 99 parts sulfuric acid, stirring makes the arsenic dissolving, makes bichromate solutions.The back adds the solid waste that contains chromium and collagen that crushes in bichromate solutions, and it is 49 parts that its amount is amounted to into organism, is incubated 95 ℃ and stirs 140 minutes.Take by weighing 21 parts of sulfuric acid again, with 100 parts of water dilutions, and with it with the dissolving of ferrous sulfate of 105 parts, splash into then in 95 ℃ the reaction system, stirred 20 minutes, sampling adds 14 parts of sodium tartrates and 16 parts of Trisodium Citrate solids after detecting no Cr (VI), 95 ℃ were stirred 60 minutes down, and still aging then liquid contains the leather retanning agent of multiple metal ion.
7. utilization according to claim 1 contains the method that chromium and collagen solid waste prepare multiple metallic ion leather tanning agents, it is characterized in that 100 parts of sodium dichromates are added reactor, add 200 parts water and 100 parts sulfuric acid, stir and make the arsenic dissolving, make bichromate solutions.The back adds the solid waste that contains chromium and collagen that crushes in bichromate solutions, and it is 50 parts that its amount is amounted to into organism, is incubated 95 ℃ and stirs 150 minutes.Take by weighing 20 parts of sulfuric acid again, with 100 parts of water dilutions, and with it with the dissolving of ferrous sulfate of 100 parts, splash into then in 95 ℃ the reaction system, stirred 20 minutes, sampling adds 15 parts of sodium tartrates and 16 parts of Trisodium Citrate solids after detecting no Cr (VI), 95 ℃ were stirred 60 minutes down, and still aging then liquid contains the leather retanning agent of multiple metal ion.
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|---|---|---|---|
| CN2008100383766A CN101314796B (en) | 2008-05-30 | 2008-05-30 | Method for preparing multiple metallic ion leather tanning agents |
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|---|---|---|---|
| CN2008100383766A CN101314796B (en) | 2008-05-30 | 2008-05-30 | Method for preparing multiple metallic ion leather tanning agents |
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| CN101314796B CN101314796B (en) | 2011-03-09 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921881A (en) * | 2010-04-22 | 2010-12-22 | 张壮斗 | Novel process for recycling waste leather-making liquid step by step |
| CN102746128A (en) * | 2011-04-22 | 2012-10-24 | 汤普勒化工染料(嘉兴)有限公司 | Method for preparing organic tanning agent by using starch as raw material |
| CN107893134A (en) * | 2017-12-15 | 2018-04-10 | 湖北微控生物科技有限公司 | A kind of preparation method of environment-friendly type aldehydic acid leather retanning agent |
| CN109852741A (en) * | 2019-04-03 | 2019-06-07 | 四川大学 | A kind of preparation method of acid-free chromte tannage agent |
-
2008
- 2008-05-30 CN CN2008100383766A patent/CN101314796B/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921881A (en) * | 2010-04-22 | 2010-12-22 | 张壮斗 | Novel process for recycling waste leather-making liquid step by step |
| CN101921881B (en) * | 2010-04-22 | 2014-05-21 | 张壮斗 | Novel process for recycling waste leather-making liquid step by step |
| CN102746128A (en) * | 2011-04-22 | 2012-10-24 | 汤普勒化工染料(嘉兴)有限公司 | Method for preparing organic tanning agent by using starch as raw material |
| CN107893134A (en) * | 2017-12-15 | 2018-04-10 | 湖北微控生物科技有限公司 | A kind of preparation method of environment-friendly type aldehydic acid leather retanning agent |
| CN107893134B (en) * | 2017-12-15 | 2020-05-12 | 湖北微控生物科技有限公司 | Preparation method of environment-friendly aldehyde acid leather tanning agent |
| CN109852741A (en) * | 2019-04-03 | 2019-06-07 | 四川大学 | A kind of preparation method of acid-free chromte tannage agent |
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| Publication number | Publication date |
|---|---|
| CN101314796B (en) | 2011-03-09 |
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