CN100390302C - Cleaning depilation method - Google Patents
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- CN100390302C CN100390302C CNB2004100093981A CN200410009398A CN100390302C CN 100390302 C CN100390302 C CN 100390302C CN B2004100093981 A CNB2004100093981 A CN B2004100093981A CN 200410009398 A CN200410009398 A CN 200410009398A CN 100390302 C CN100390302 C CN 100390302C
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Abstract
The present invention provides a clean depilation method which comprises the steps that the depilation is carried out by an ordinary sulfide depilation method; then 0.001 to 1 tare weight% of catalyst and 0.2 to 10.0 tare weight% of oxidizing agent are added to act for 5 to 120 minutes after the depilation is completely carried out; gray hide and sulfide in waste liquid structure are discharged out of the hide after being completely oxidized; the waste liquid is collected, the pH value of the waste liquid is regulated to 2 to 6 by acid, and thereby, proteins are deposited; then the waste liquid is settled or centrifugally separated to remove proteins in the waste liquid, and thereby, the pollution of organic substances in the waste liquid is reduced. The clean depilation method fundamentally does not change the existing sulfide depilation method, has no influence on the quality of products and can completely eliminate the pollution of sulfide in the depilation waste liquid and the pollution of suspended substances, chrominance and organic substances in the waste liquid.
Description
The method field
The invention belongs to the depilating method of leather production technical field, specially refer to a kind of depilating method that cleans.
Background method
Leather industry is one of traditional industrial sector of China, has long history in several thousand, after founding the state and reforming and opening up to the outside world swift and violent development has been arranged.In late nineteen eighties the early 1990s, owing to polluting and labour-intensive reason, world's leather industry begins by developed country gradually to developing country's transfer, and China has become the machining center and the trade center of world's leather industry at present.More than China's year processing leather 1.6 hundred million standards are opened, account for 1/5 of world's leather output, more than 20 hundred million pairs of leather shoes account for 1/2 of world's leather shoes output, development of China leather industry foreign exchange earning in 2003 reaches 23,200,000,000 dollars, and leather industry is still keeping the development trend of rapid growth at present.
Development of China leather industry create brilliant in, also be to pollute one of maximum industrial sector, the pollution of environment is only second to paper industry in light industry, mind-set China shifts and says it also is the transfer of pollution to a certain extent in world's leather industry.Tanning sewage has the sewage complicated component, administers difficult, big to environmental hazard characteristics, traditional elder generation's pollution, the method existence that the back is administered are invested greatly, cost is high, the shortcoming of weak effect, the development need of incompatible modern leather industry, and method for cleaning is with abatement of pollution in process of production, meets the requirement of Sustainable development.
The pollution of leather industry mainly comes from prepares workshop section, and the pollution of preparing workshop section mainly comes from the depilation operation, in the pollution that leather production produces except sulphide staining fully from the sulfide depilation operation, also has the pervaporation residue more than 65%, organism more than 61%, total nitrogen more than 40% and 70% above chemical oxygen demand (COD
Cr) also from the depilation operation.
In occupation of absolute dominant position, reason is that the sulfide depilation method has the unrivaled advantage of other epilation to the sulfide depilation method in the depilating method that current leather is produced: 1. depilation is clean and speed is fast; 2. the material that loses hair or feathers obtains easily and is with low cost; 3. easy, the easy control of epilation operation can realize protecting the hair depilation or ruin the hair depilation; 4. good product quality and more stable, the leather kind that is suitable for is wide.
But also there is heavy-polluted fatal shortcoming in the sulfide depilation method simultaneously, and it pollutes and mainly shows as three aspects: the pollution of the pollution of sulfide, organic pollution and lime.
(1) pollution of sulfide
Employed environmental pollution of sulfide is very big in the depilation operation, the waste water of sulfur compound enters can make the smelly blackening of water quality in the rivers, many fresh-water fishes sulfide content be in the water of 1.0-25mg/L 1-3 days will be dead, containing a large amount of sulfide in the soil can make the old root blackout of plant rot, new root is long bad, cause farm crop withered, thereby sulfide content must not be higher than 1mg/L in the trade effluent of national regulation discharging.Processing to sulfur compound sewage is expensive very big in addition, and the energy of its consumption is three times of no sulphur sewage except that equipment, and if sulfide content surpasses 50mg/L in the sewage, sludge bacteria can be died, and has reduced water treatment effect.
Another the most serious harm of sulfide is exactly that it can be converted into the stronger hydrogen sulfide of toxicity.Hydrogen sulfide has the intense stimulus effect to eyes and respiratory tract, be subjected to low concentration hydrogen sulphide effect meeting to make people's dizziness, general weakness, easily tired, hidrosis for a long time, pleasantly sweet in mouthful, feel sick, concentration of hydrogen sulfide Gao Shihui make people's dim eyesight, dizzy until lose consciousness, death.When airborne concentration of hydrogen sulfide reaches 0.015mg/L, will cause toxicity symptom, concentration then can cause death when surpassing 1mg/L, so hygienic standard regulation Air Hydrogen Sulfide maximum acceptable concentration is 0.01mg/L.
(2) organic pollution
Hair of degrading from the raw material skin during depilation and organism such as epidermis can increase chemical oxygen demand and the biological oxygen demand the water greatly.General chemical oxygen demand can make the microorganism in the water when 500-3000mg/l, comprise that disease carrying germ obtains enough nutrition and breeding rapidly, causes pollution of waterhead, is detrimental to health.When containing large amount of organic in the water in addition, the dissolved oxygen in the water is consumed in a large number, when oxygen in water less than 4 the time, hydrocoles such as the fish expiratory dyspnea that can become gradually, so be choked to death and die.Thereby national Specification, chemical oxygen demand should be less than 300mg/l when discharging for leather-making waste water, and biological oxygen demand (BOD) should be less than 60mg/l.
(3) pollution of lime
Used a large amount of lime in the sulfide depilation, major part all is in not dissolved state, does not obtain utilizing, and can increase the basicity and the suspension content of waste liquid after the discharging, and lime and hair slag can form duricrust, obstruction sewer line in pipe.
In order to improve the with serious pollution shortcoming of sulfide depilation method, carried out number of research projects to cleaning dehairing process both at home and abroad, some dehairing process that clean have been developed, but owing to complicated operation, clean that degree is not high, cost is too high, or quality product had a strong impact on and can not be applied producing, mainly contain following several method:
Protect the hair epilation: by the condition of control alkali and reductive agent, make the depilation material only act on hair root and stay complete hair, reduced suspended solid and organism, reduced the value of BOD and COD, also reduced the consumption of sulfide.Protect the hair epilation and can be divided into two classes: first sulfide is handled the method for alkaline purification again and the method that first alkaline purification postcure thing is handled, the former typical case's representative is that the HS of the successful Sirolime guarantor hair depilation system of Australian Union's science and industrial research institute (CSIRO) research and Romo Co.,Ltd's exploitation protects the hair depilation system, and the latter typically representative is Blair's epilation of rom Haars Co., Ltd exploitation.The shortcoming of protecting the hair epilation is complex process, control difficulty, protects mao phenomenon easily and hair can not taken off, or fleece excessive dissolution and can't reclaim hair, and the hair that reclaims is owing to the effect of having passed through alkali and sulfide no longer has use value.Also need in addition to replenish depilation with hair-destroying process, it is limited to reduce sulfide and organic pollution level.
Depilatory solution circulation method: can be divided into two kinds of the abnormal circulation methods of direct circulation method of depilatory solution and sulfide, the former directly reclaims depilation waste liquor, is used further to depilation and not only can reduces pollution, can also save material, the shortcoming of this method is that the process stabilizing performance is poor, the quality product susceptible to; The latter is with the abnormal recovery of the sulfide in the depilation waste liquor, produces sodium sulphite, is used further to the operation of losing hair or feathers after the analysis, and the shortcoming of this method is to need special corrosion resistant reactor and absorption tower, and complicated operation, cost are than higher.
Organosulfur epilation: use organosulfur compound to replace sulfide to lose hair or feathers with strong reducing property, as: Thiovanic acid, mercaptoethanol etc., thereby eliminate the pollution of sulfide, the shortcoming of this method is that organosulfur compound price height, consumption are big, the depilation cost is too high, can't be applied in the actual production.
The oxidation style depilation: the oxidation style depilation is meant the cystine linkage that uses in the oxygenant destruction keratin protein, and makes a mao dissolved depilating method, can avoid using and discharging of sulfide fully.The maximum shortcoming of oxidation style depilation is exactly that oxygenant has corrosive nature to wooden rotary drum, use the stainless steel rotary drum instead and also have the big problem of facility investment, and the oxygenant of high density can produce certain destruction to leather fiber, influences the quality of product.The cost of this method is also than general sulfide depilation method cost height in addition.
Enzyme unhairing: the principle of enzyme unhairing is to destroy the mucoid that plays ligation between hair and corium with protease preparation, relends to help mechanical effect that hair is come off.Enzyme unhairing has the shortcoming of two aspects, and the one, the easy loose side of finished leather, this is because enzyme also can destroy collegen filament except mucoid is hydrolyzed in epilation process, thereby has a strong impact on the quality of product; The 2nd, little Mao takes off endless, and this replenishes depilation with regard to the additional sulfide depilation method of needs, thereby has influenced the effect that cleans of this method to a great extent.
In sum, the existing various depilating method that cleans can't be applied major cause shortcoming aspect following five is arranged in leather production: 1. complicated operation, be difficult to control; 2. lose hair or feathers cost than higher; 3. it is more limited to clean effect; 4. equipment there is particular requirement; 5. influential to quality product.Table 1 is the existing various comparisons that clean depilating method.
Table 1 has the various comparisons that clean depilating method now
| Complicated operation, be difficult to control | The depilation cost is than higher | It is more limited to clean effect | Equipment there is particular requirement | Influential to quality product | |
| Protect the hair epilation | √ | √ | √ | ||
| The depilatory solution circulation method | √ | √ | |||
| The hydrogen peroxide epilation | √ | √ | √ | ||
| The enzyme unhairing method | √ | √ | √ | √ | |
| The organosulfur epilation | √ |
Summary of the invention
The objective of the invention is to pollute big and existingly variously clean that depilating method control is complicated, cost is high and clean shortcoming such as weak effect, a kind of depilating method that cleans of practicality is provided at traditional sulfide depilation method.
The depilating method that cleans of the present invention loses hair or feathers with general sulfide depilation method earlier, add catalyzer and oxygenant again after the depilation fully, with residual sulfide oxidation in rawhide after the depilation and the waste liquid is free of contamination sulphur compound, as: thiosulphate, sulphite and vitriol etc., used catalyzer is a mantoquita, ferrous salt, molysite, chromic salts, nickel salt, manganese salt, in the cobalt salt one or more, go out skin after eliminating the pollution of sulfide fully, adjust the pH value of waste liquid near isoelectric point of protein with acid again, protein precipitation in the waste liquid is come out, leave standstill then or centrifugation reclaiming the protein in the waste liquid, thereby reduce the organic content (COD) in the depilation waste liquor significantly.
The existing depilating method that cleans is revised traditional sulfide depilation method or operation, though brought certain effect that cleans, but also lost the advantage of traditional sulfide depilation method, thereby brought complicated operation, cost high and shortcomings such as quality product are influential.The advantage that cleans depilating method of the present invention is not change traditional sulfide depilation method and operation, thus make of the present inventionly clean that depilating method has that depilation speed is fast, the advantage of control easily, with low cost and good product quality.
Remaining sulfide in the rawhide of the effect that utilizes catalyzer and oxygenant after depilation finishes after with waste liquid and depilation directly all is converted into other free of contamination sulphur compound in rotary drum, eliminate the pollution of sulfide, this treatment process is simply efficient, its advantage is to lose hair or feathers when finishing in the rotary drum residual sulfide concentration than higher, if regather depilation waste liquor complicated operation on the one hand after going out the drum washing, the sulfide concentration in the waste liquid descends significantly after sneaking into washing water on the other hand.And when carrying out oxide treatment, speed of response is fast and relatively more thorough under the high density, and the oxidant content of consumption is fewer.Thereby the oxide treatment of directly carrying out sulfide in rotary drum helps reducing the consumption of oxygenant, the saving cost.
Another advantage of carrying out the oxide treatment of sulfide in rotary drum is a residual sulfide in the rawhide that can remove simultaneously after the depilation, the rawhide after the depilation of sulfur compound can not produce the sulfide of pollution in subsequent washing, and does not have the potential hazard that generates hypertoxic hydrogen sulfide in follow-up deliming operation.
Of the present invention cleaning behind the sulfide of depilating method in removing waste liquid with the isoelectric precipitation method reclaimed most of protein in the depilation waste liquor, thereby can reduce the Organic pollutants in the waste liquid significantly, the protein that reclaims can also be used as feed or fertilizer, increases enterprise's income.The method of this reduction Organic pollutants is simple, efficient, can not cause disadvantageous effect to the quality of product.
The depilating method that cleans of the present invention can be briefly described as follows: add in the rotary drum behind the immersion of raw material skin process, the fleshing, add entry and auxiliary liming agent, add sodium sulphite more in batches, or sodium bisulfide and sodium sulphite, add lime and water more in batches, total time, up to depilation fully, operation so far was with traditional sulfide depilation method unanimity more than 15 hours.Then, in rotary drum, add catalyzer and oxygenant, wherein can after adding and rotate evenly, catalyzer add oxygenant more in batches, with remaining sulfide oxidation in the rawhide after waste liquid and the depilation is the sulphur compound of free of contamination higher valence state, as sulphur, thiosulphate, sulphite and vitriol etc.After going out drum, the subsequent operations of the rawhide after the depilation of sulfur compound is not with traditional method.Reclaim waste liquid, the pH value of regulating waste liquid is to isoelectric point of protein, and the protein in the waste liquid is precipitated out because of dehydration, and isolated protein can be used as fodder additives or fertilizer after the drying.Waste liquid behind the recovery protein is limpid, and COD content descends significantly.
The operation that cleans depilating method of the present invention is consistent with traditional sulfide depilation method, just after depilation fully, add catalyzer and oxygenant, residual sulfide is oxidized to the sulphur compound of free of contamination higher valence state in the rawhide after making waste liquid and losing hair or feathers, and eliminates the pollution of sulfide.Because epilation operation is to carry out simultaneously with the liming operation, reach 15～20 hours total time, depilation is just finished substantially at preceding several hrs, most of the time is to be used for the structure of liming with loose collegen filament, thereby with oxygenant residual sulfide oxidation is had the competent time for other sulphur compound in rotary drum.
Depilation is to carry out under strong alkaline condition, because sulfide has very strong reductibility under strong alkaline condition, is easy to carry out oxidation with oxygenant.The used oxygenant of the present invention is commonly used in this area, as long as it can play oxygenizement.Can use some cheap oxygenants in order to reduce cost, as oxygen, oxygenous gas (as mixed gas of air, oxygen and other gas etc.), hydrogen peroxide, hypochlorite and ozone etc.For usage quantity and the production cost that reduces oxygenant, can use catalyzer to make the sulphur compound of sulfide oxidation generation during oxidation than lower valency, as elemental sulfur and thiosulphate, used catalyzer is one or more in mantoquita, ferrous salt, molysite, chromic salts, nickel salt, manganese salt, the cobalt salt.
Is example with hydrogen peroxide as oxygenant:
If generate elemental sulfur: Na
2S+H
2O
2The 2NaOH+S of===↓
The reaction mol ratio is 1: 1
If generate Na
2S
2O
3: 2Na
2S+4H
2O
2The 2NaOH+Na of===
2S
2O
3+ 3H
2O
The reaction mol ratio is 1: 2
If generate Na
2SO
3: Na
2S+3H
2O
2The Na of===
2SO
3+ 3H
2O
The reaction mol ratio is 1: 3
If generate Na
2SO4:Na
2S+4H
2O
2The Na of===
2SO
4+ 4H
2O
The reaction mol ratio is 1: 4
The consumption of hydrogen peroxide is only when generating sodium sulfate 1/4 of the hydrogen peroxide consumption in the time of can finding to generate elemental sulfur, thereby the consumption of oxygenant significantly reduces production costs.
The depilation waste liquor of sulfide has been removed in recovery, add diluted acid behind the filtering solid lime particle and adjust the pH value of waste liquid to isoelectric point of protein, protein has lost water soluble characteristic and has been precipitated out under iso-electric point, the protein that precipitation separation comes out can be used as fodder additives or fertilizer after this protein drying.Depilation waste liquor among the present invention is adjusted to the hydrogen sulfide that can not produce severe toxicity under the acidic conditions owing to there has not been sulfide, and contains a large amount of sulfide in the waste liquid of general sulfide depilation method, is adjusted to the hydrogen sulfide that can produce severe toxicity under the acidic conditions.The Keratin sulfate that the dissolving of hair and epidermis was produced when the Organic pollutants in the depilation waste liquor mainly were depilation, and the interfibrillar substance that is dissolved out (Saliva Orthana and mucoid) and a small amount of collagen protein, the grease and the glucide that also have some rawhides after the depilation to be dissolved out.Use the iso-electric point settling process can reclaim 85%～90% protein, thereby 80%～90% organism (COD) pollute in the minimizing depilation waste liquor.
A purpose that cleans depilating method of the present invention is the sulfide of removing in the depilation waste liquor, and another purpose is the protein that reclaims in the depilation waste liquor.
The depilating method that cleans of the present invention is in epilation process depilation waste liquor to be handled, thereby is applicable to the depilating method that contains sulfide in any depilation waste liquor, comprises the method that generates sulfide in method that sulfide loses hair or feathers and the epilation process of using.The sulfide that contains in the depilation waste liquor comprises one or more in sodium sulphite, Sodium sulfhydrate, potassium sulphide, potassium bisulfide, sulfurated lime, calcium sulfhydrate, the red arsenic.In some depilating methods, do not use sulfide although the sulfide that generates is meant, in epilation process, can generate sulfide, thereby residual in depilation waste liquor there is sulfide, the sulfide of this generation also is suitable for handling with method of the present invention.Being suitable for the sulfide depilation method that the present invention cleans the depilating method scheme comprises: little liquor ratio epilation, big liquor ratio epilation, earlier epilation, the ash alkali unhairing method of big liquor ratio after the little liquor ratio, be coated with ash alkali unhairing method, saline and alkaline epilation, protect hair epilation and the depilation of alkali alkaline process etc.
The depilating method that cleans of the present invention is made up of following four steps:
(1) rawhide loses hair or feathers with the sulfide depilation method earlier;
(2) depilation adds catalyzer and oxygenant in the back fully, with residual sulfide oxidation in rawhide after the depilation and the waste liquid;
(3) rawhide after the depilation and the sulfide in the waste liquid are oxidized goes out skin after fully, comes out to protein precipitation with the pH value of acid adjustment waste liquid;
(4) by standing separation or centrifugation throw out, to reclaim the protein in the waste liquid;
Used catalyzer is a mantoquita, ferrous salt, molysite, chromic salts, nickel salt, manganese salt, in the cobalt salt one or more, as copper sulfate, ferrous sulfate, ferric sulfate, chromium sulphate, single nickel salt, manganous sulfate, rose vitriol, cupric chloride, iron protochloride, iron(ic) chloride, chromium chloride, nickelous chloride, Manganous chloride tetrahydrate, cobalt chloride, cupric nitrate, Iron nitrate, iron nitrate, chromium nitrate, nickelous nitrate, manganous nitrate, Xiao Suangu, cupric oxide, iron protoxide, ferric oxide, Z 250, chromic oxide, nickel oxide, manganese oxide, cobalt oxide etc., catalyst consumption is 0.001%～1% of a tare weight, be preferably 0.01～0.7%, more preferably 0.02～0.5%.
Used oxygenant is one or more in hydrogen peroxide, hypochlorite, oxygen, oxygenous gas (as mixed gas of air, oxygen and other gas etc.), the ozone, and the consumption of oxygenant is 0.2～10.0% of a tare weight, is preferably 0.5～5.0%.
The rawhide after the depilation and the oxidization time of the sulfide in the waste liquid are 5～120 minutes.
The sulfide depilation method is meant uses sulfide as the residual depilating method that sulfide is arranged in depilation material, the waste liquid, though perhaps in epilation process, do not use sulfide as the depilation material, can generation sulfide in epilation process and remain in depilating method in the depilation waste liquor.The used equipment that loses hair or feathers can be that rotary drum, paddle-tumble or other can be used for carrying out the equipment of epilation operation.
In aforesaid operations, adjust pH value to 2～6 of depilation waste liquor, be preferably 3～5, protein precipitation is come out with acid.The subsequent operations of the rawhide after the depilation after the depilation is produced with general.
Before the above-mentioned pH value of adjusting waste liquid with acid, can be earlier some impurity of filtering roughly, as undissolved lime particle with do not dissolve completely broken wool etc.The filtering lime particle can reduce the usage quantity of acid, in the fewer epilation operation of lime consumption, does not contain undissolved lime substantially, can not carry out filter operation.The filtering broken wool is in order to improve the follow-up proteinic quality that reclaims, and when the proteinic specification of quality of reclaim is not high, can not need the filtering broken wool.
The present invention cleans depilating method and has the following advantages:
(1) do not change existing sulfide depilation method of factory and operation substantially, do not need the production technique of factory is carried out bigger adjustment, thereby applied widely, simple to operate, and do not influence the quality of product;
(2) it is very obvious to clean effect: eliminate rawhide after the depilation and the sulphide staining in the depilation waste liquor fully, reclaim protein in the waste liquid as feed or fertilizer, with the organic content (COD of waste liquid
Cr) reduce more than 80～90%, the colourity of waste liquid reduces more than 95%, and the suspension content of waste liquid reduces more than 85%～90%;
(3) clean the used material of depilating method and all be this area common used material, with low cost, accepted by vast leather-making enterprises easily.
Specific implementation method
The present invention is further illustrated below in conjunction with embodiment.
Embodiment 1
With weigh, pigskin after the immersion, degreasing, epilation, hip bag enzyme drops in the rotary drum, adds the normal-temperature water of tare weight 50% and the auxiliary liming agent MB (product of De Rui company) of tare weight 1.0%, rotated 15 minutes;
Add the Sodium sulfhydrate of tare weight 1.0%, rotated 15 minutes;
Add the sodium sulphite (60%) of tare weight 1.5%, rotated 30 minutes;
Add the dry hydrate of tare weight 1.5%, rotated 45 minutes;
Add the water of tare weight 100% and 1.5% dry hydrate, rotated 15 minutes, stopped 30 minutes;
Add the water of tare weight 100% and 1.5% dry hydrate, rotated 15 minutes, stopped 30 minutes;
Per hour changeed totally 15 hours later on 5 minutes.Get the depilation waste liquor sample to be used for the analysis of the every contamination index of waste liquid.
Add the ferrous sulfate (be dissolved in earlier before the adding ten times water in) of tare weight 0.5%, rotated 60 minutes;
Add the hydrogen peroxide of tare weight 1%, rotated 60 minutes.Remove the depilation waste liquor sample that removes behind the sulfide to be used for the analysis of the every contamination index of waste liquid.
Go out skin, collect waste liquid, the pH value to 3.5 that the hydrochloric acid that adds 10 times of dilutions is adjusted waste liquid makes the protein precipitation in the waste liquid, and standing separation protein is got waste liquid sample behind the isolated protein to be used for the analysis of the every contamination index of waste liquid.
Measure sodium sulfide content in three kinds of waste liquid samples, measure suspension content in three kinds of waste liquid samples, measure colourity in three kinds of waste liquid samples, measure nitrogen content (expression Protein content) in three kinds of waste liquid samples, measure COD content in three kinds of waste liquid samples with potassium dichromate process with Kjeldahl determination with the extension rate method with filtration method with the high-potassium ferricyanide method, the results are shown in Table 2.
Table 2 pigskin cleans the waste liquid analytical results of dehairing process
| Na 2S content (g/L) | Suspended substance (mg/L) | Colourity (multiple) | Nitrogen content (gN/L) | COD Cr (mg/L) | |
| Depilation waste liquor | 3.43 | 12120 | 1000 | 1.49 | 5040 |
| Waste liquid behind the removal sulfide | 0 | 11810 | 300 | 1.39 | 4496 |
| Waste liquid behind the recovery protein | 0 | 1250 | 10 | 0.14 | 686.4 |
| Clearance (%) | 100％ | 89.7％ | 99％ | 90.6％ | 86.4％ |
Of the present inventionly as can be seen from Table 2 clean suspended substance, colourity, protein and the COD that depilating method can be eliminated sulphide staining in the depilation waste liquor fully, can eliminate the overwhelming majority in the waste liquid
CrPollute.
Embodiment 2
Ox wet salted hide after weighing, soaking is dropped in the rotary drum, add the normal-temperature water of tare weight 50% and the auxiliary liming agent MB (product of De Rui company) of tare weight 1.0%, rotated 15 minutes;
Add the Sodium sulfhydrate of tare weight 0.8%, rotated 15 minutes;
Add the sodium sulphite (60%) of tare weight 0.8%, rotated 15 minutes;
Add the sodium sulphite (60%) of tare weight 0.9%, rotated 15 minutes;
Add the dry hydrate of tare weight 1%, rotated 45 minutes;
Add the water of tare weight 100% and 1% dry hydrate, rotated 15 minutes, stopped 30 minutes;
Add the water of tare weight 100% and 1% dry hydrate, rotated 15 minutes, stopped 30 minutes;
Per hour changeed totally 15 hours later on 5 minutes.Get the depilation waste liquor sample to be used for the analysis of the every contamination index of waste liquid.
Add the cupric nitrate (be dissolved in earlier before the adding ten times water in) of tare weight 0.4%, rotated 10 minutes;
Add the Losantin of tare weight 4%, rotated 20 minutes.Remove the depilation waste liquor sample that removes behind the sulfide to be used for the analysis of the every contamination index of waste liquid.
Go out skin, collect waste liquid, the pH value to 4 that the hydrochloric acid that adds 10 times of dilutions is adjusted waste liquid makes the protein precipitation in the waste liquid, and standing separation protein is got waste liquid sample behind the isolated protein to be used for the analysis of the every contamination index of waste liquid.
Measure sodium sulfide content in three kinds of waste liquid samples, measure suspension content in three kinds of waste liquid samples, measure colourity in three kinds of waste liquid samples, measure nitrogen content (expression Protein content) in three kinds of waste liquid samples, measure COD content in three kinds of waste liquid samples with potassium dichromate process with Kjeldahl determination with the extension rate method with filtration method with the high-potassium ferricyanide method, the results are shown in Table 3.
Table 3 ox-hide cleans the waste liquid analytical results of dehairing process
| Na 2S content (g/L) | Suspended substance (mg/L) | Colourity (multiple) | Nitrogen content (gN/L) | COD Cr (mg/L) | |
| Depilation waste liquor | 4.15 | 9680 | 700 | 1.24 | 4364 |
| Waste liquid behind the removal sulfide | 0 | 6980 | 300 | 0.999 | 3360 |
| Waste liquid behind the recovery protein | 0 | 1240 | 30 | 0.215 | 769.8 |
| Clearance (%) | 100％ | 87.2％ | 96％ | 82.7％ | 82.4％ |
Of the present inventionly as can be seen from Table 3 clean suspended substance, colourity, protein and the COD that depilating method can be eliminated sulphide staining in the depilation waste liquor fully, can eliminate the overwhelming majority in the waste liquid
CrPollute.
Embodiment 3
Immersion, lamb skin flesh noodles behind the fleshing are coated with grey alkali lye, the consisting of of grey alkali lye:
Ridge portion limit belly
Sodium sulphite (60%): 10 parts of sodium sulphite (60%): 4 parts
Water: 50 parts of water: 50 parts
JFC:0.4 part JFC:0.4 part
Dry hydrate: 20～30 parts of dry hydrates: 20～30 parts
The furnishing pasty state is applied to flesh noodles during use in advance, and doubling was left standstill 2.5～4 hours, pushed away hair, weighed.
The lamb skin that pushes away behind the hair is dropped in the rotary drum, add the normal-temperature water of tare weight 50% and the auxiliary liming agent MB (product of De Rui company) of tare weight 0.8%, rotated 15 minutes;
Add the sodium sulphite (60%) of tare weight 0.8%, rotated 15 minutes;
Add the sodium sulphite (60%) of tare weight 0.7%, rotated 30 minutes;
Add the dry hydrate of tare weight 1%, rotated 45 minutes;
Add the water of tare weight 100% and 0.5% dry hydrate, rotated 15 minutes, stopped 30 minutes;
Add the water of tare weight 100% and 0.5% dry hydrate, rotated 15 minutes, stopped 30 minutes;
Per hour changeed totally 15 hours later on 5 minutes.Get the depilation waste liquor sample to be used for the analysis of the every contamination index of waste liquid.
Add the Manganous chloride tetrahydrate (be dissolved in earlier before the adding ten times water in) of tare weight 0.05%, rotated 10 minutes;
Feed the oxygen of tare weight 5%, rotated 30 minutes.Remove the depilation waste liquor sample that removes behind the sulfide to be used for the analysis of the every contamination index of waste liquid.
Go out skin, collect waste liquid, the pH value to 4.5 that the hydrochloric acid that adds 10 times of dilutions is adjusted waste liquid makes the protein precipitation in the waste liquid, and standing separation protein is got waste liquid sample behind the isolated protein to be used for the analysis of the every contamination index of waste liquid.
Measure sodium sulfide content in three kinds of waste liquid samples, measure suspension content in three kinds of waste liquid samples, measure colourity in three kinds of waste liquid samples, measure nitrogen content (expression Protein content) in three kinds of waste liquid samples, measure COD content in three kinds of waste liquid samples with potassium dichromate process with Kjeldahl determination with the extension rate method with filtration method with the high-potassium ferricyanide method, the results are shown in Table 4.
Table 4 lamb skin cleans the waste liquid analytical results of dehairing process
| Na 2S content (g/L) | Suspended substance (mg/L) | Colourity (multiple) | Nitrogen content (gN/L) | COD Cr (mg/L) | |
| Depilation waste liquor | 3.45 | 5570 | 500 | 1.20 | 3792 |
| Waste liquid behind the removal sulfide | 0 | 4380 | 300 | 0.807 | 3272 |
| Waste liquid behind the recovery protein | 0 | 760 | 10 | 0.207 | 750.8 |
| Clearance (%) | 100％ | 86.4％ | 98％ | 82.8％ | 80.2％ |
Of the present inventionly as can be seen from Table 4 clean suspended substance, colourity, protein and the COD that depilating method can be eliminated sulphide staining in the depilation waste liquor fully, can eliminate the overwhelming majority in the waste liquid
CrPollute.
Claims (10)
1. one kind cleans depilating method, it is characterized in that being made up of following four steps:
(1) rawhide loses hair or feathers with the sulfide depilation method earlier;
(2) depilation adds catalyzer and oxygenant in the back fully, with residual sulfide oxidation in rawhide after the depilation and the waste liquid;
(3) rawhide after the depilation and the sulfide in the waste liquid are oxidized goes out skin after fully, comes out to protein precipitation with the pH value of acid adjustment waste liquid;
(4) by standing separation or centrifugation throw out, to reclaim the protein in the waste liquid;
Used catalyzer is one or more in mantoquita, ferrous salt, molysite, chromic salts, nickel salt, manganese salt, the cobalt salt.
2. the depilating method that cleans according to claim 1, it is characterized in that the sulfide depilation method that this method is used is meant that use sulfide is as the residual depilating method that sulfide is arranged in depilation material, the waste liquid, though perhaps in epilation process, do not use sulfide as the depilation material, can generation sulfide in epilation process and remain in depilating method in the depilation waste liquor.
3. the depilating method that cleans according to claim 1 is characterized in that used catalyst consumption is 0.001%～1% of a tare weight.
4. the depilating method that cleans according to claim 3 is characterized in that used catalyst consumption is 0.02～0.5%.
5. the depilating method that cleans according to claim 1 is characterized in that used oxygenant is hydrogen peroxide, hypochlorite, oxygen, oxygenous gas, in the ozone one or more.
6. the depilating method that cleans according to claim 1 is characterized in that used oxygenant consumption is 0.2～10.0% of a tare weight.
7. the depilating method that cleans according to claim 6 is characterized in that used oxygenant consumption is 0.5～5.0% of a tare weight.
8. the depilating method that cleans according to claim 1 is characterized in that adjusting the pH value of waste liquid to pH2～6 with acid.
9. the depilating method that cleans according to claim 1, the rawhide after it is characterized in that losing hair or feathers and the oxidization time of the sulfide in the waste liquid are 5～120 minutes.
10. the depilating method that cleans according to claim 1 is characterized in that filtering some impurity of removing in the depilation waste liquor earlier before the pH value with acid adjustment depilation waste liquor.
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| CNB2004100093981A CN100390302C (en) | 2004-08-04 | 2004-08-04 | Cleaning depilation method |
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| CNB2004100093981A CN100390302C (en) | 2004-08-04 | 2004-08-04 | Cleaning depilation method |
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| CN100390302C true CN100390302C (en) | 2008-05-28 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101497929B (en) * | 2009-02-26 | 2012-07-25 | 温州大学 | Hair protecting, dehairing and liming method for cattle hide tanning |
| CN102010917A (en) * | 2010-11-22 | 2011-04-13 | 陕西科技大学 | Ammonia nitrogen-free leather-making deliming agent and preparation method thereof |
| CN102505056B (en) * | 2011-10-21 | 2013-10-16 | 中国皮革和制鞋工业研究院 | Hair-protection unhairing and liming waste liquor recycling method |
| CN102505057B (en) * | 2011-10-21 | 2013-10-16 | 中国皮革和制鞋工业研究院 | Cyclic utilization method of chrome tanning waste liquid |
| CN103243182B (en) * | 2013-04-26 | 2014-11-26 | 四川大学 | Tanning method free of lime, sulfide, chloride ion and heavy metal chromium pollution |
| CN105010737A (en) * | 2015-07-27 | 2015-11-04 | 徐州鸿丰高分子材料有限公司 | Method for preparing meat powder based on removed meat and waste residues of alkali tanning skins |
| CN107736266B (en) * | 2017-09-06 | 2020-11-13 | 佩蒂动物营养科技股份有限公司 | Pet chew and preparation method thereof |
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| US5328677A (en) * | 1992-06-17 | 1994-07-12 | Pvl Limited Partnership I | Recovery of sulfides from tannery waste liquor |
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Assignee: Quanzhou Jinye Leather Industry Co., Ltd. Assignor: China Leather and Shoe-making Industry Inst. Contract fulfillment period: 2009.4.25 to 2015.4.24 contract change Contract record no.: 2009350000142 Denomination of invention: Cleaning depilation method Granted publication date: 20080528 License type: Exclusive license Record date: 2009.7.16 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2009.4.25 TO 2015.4.24; CHANGE OF CONTRACT Name of requester: QUANZHOU JINXING LEATHER INDUSTRY CO., LTD. Effective date: 20090716 |
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