CN103525954A - Immobilized composite unhairing enzyme with leather-making secondary waste as carrier and preparation method thereof - Google Patents
Immobilized composite unhairing enzyme with leather-making secondary waste as carrier and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of an immobilized composite unhairing enzyme with leather-making secondary waste as a carrier. The method is characterized by: firstly soaking the leather-making secondary waste in deionized water at room temperature, then reacting the leather-making secondary waste with glutaraldehyde, conducting filtration and washing off the residual glutaraldehyde on the leather-making secondary waste by deionized water; reacting the glutaraldehyde treated carrier with the composite unhairing enzyme, performing filtration and washing off the residual composite enzyme on the carrier, thus obtaining the immobilized composite unhairing enzyme with leather-making secondary waste as the carrier. Specifically, every 100 parts of the composite unhairing enzyme comprise 55-80 parts of neutral protease, 10-25 parts of alpha amylase and 5-15 parts of pancreatin. The immobilized composite unhairing enzyme prepared by the method involved in the invention has a high immobilized enzyme amount and high enzyme activity yield, and has good stability and reusability. The immobilized composite unhairing enzyme can be used for raw hide unhairing and collagen fiber dispersion, the production conditions are mild, high controllability can be achieved on a hide collagen hydrolysis process and the separation and loose degree of collagen fibers, and also the product quality fluctuation can be avoided in production.
Description
Technical field
The present invention is specifically related to a kind of preparation method of take the compound depilation enzyme of immobilization that the secondary refuse of process hides is carrier, belongs to technical field prepared by process hides dedicated immobilized enzyme.
Background technology
Liming depilation, as a kind of ancient method, plays an important role in leather-making technology process.Conventional grey alkaline process depilation adopts sulfide and lime, and is hydrolyzed hair, is removed the effect that the effects such as interfibrillar substance reach depilation and disperse materials with hide glue fibril by sulfide and lime.Because the method has raw material, be easy to get, cost is low, simple to operate, control easily, the advantage such as resultant leather quality is stable, use range wide (pig, ox, sheepskin are all applicable), tanning production still be take grey alkaline process depilation as main both at home and abroad at present.Yet there are some fatal shortcomings in the depilation of grey alkaline process, the problems such as Organic pollutants that when polluting and lose hair or feathers because of liming as sulphide staining, lime, a large amount of maos and epidermis are degraded and are caused.Therefore, process hides worker is just making great efforts to seek the dispersing of other more clean depilation and collegen filament, to reduce the pollution of even eliminating liming depilation operation.
In the century in the past, people developed several do not use sulfide and lime clean depilation and collegen filament dispersion technology.Ecological depilation technical elements, mainly comprises oxidative unhairing method, biological enzyme epilation, organic sulfide epilation etc.Yet, by ecological viewpoint, weigh, only have enzyme unhairing method to be only guarantor's hair epilation truly, be also the most clean depilating method.Proteolytic enzyme is topmost depilation enzyme, and its hair removal effect is good.But in the time of proteolytic enzyme depilation, unavoidably can damage the structure of corium, affect the use properties of leather goods, this has just seriously limited the application of enzyme unhairing technology.In the last few years, along with process hides cleaner production is put on agenda, the research of enzyme unhairing became again study hotspot once again.Conventional grey alkaline process liming depilation, collegen filament are in obtaining separated loose process, removed especially proteoglycan of most interfibrillar substances, and fiber and the fibrillose system of collagen of the effect by lime and the osmotic pressure generation rule set up in rawhide matrix.In recent years, increasingly serious along with process hides ecological problem, for the grey alkaline process of routine, produce the shortcoming of large quantities of lime mud in liming process, investigator has done a large amount of work both at home and abroad, to look for the separated loose materials with hide glue fibril of new green leather chemical replace lime.Based on above-mentioned principle, at present also someone by adopting liquid caustic soda, silicate and biological enzyme etc. to disperse the method for materials with hide glue fibril.In traditional process hides process, enzyme is just used as and disperses one of hide fiber to supplement to lime, is mainly reflected in softening process, as adopted pancreatin to act on the softening processing of deliming pelt.In recent years, Thanikaivelan. the people such as P successful development go out to use α-amylase without lime fiber opening method (Thanikaivelan. P, Chandrasekara. B. Bharath. C. K, et al. Single step hair removal and fiber opening process:simultaneous and successive addition of protease and α-amylase[J]. J. Amer. Leather Chem, Ass., 2006,101:388-398.).The method has been applied to the pelt that loses hair or feathers and process with commercial protease and sodium sulphite, is a method that two steps are processed.Yet the present invention mainly provides a kind of method of immobilization prozyme depilation, is combined with by proteolytic enzyme, pancreatin, α-amylase, is only processed and just can be guaranteed except unhairing and opening fiber by a step simultaneously.
Mainly there is following shortcoming in the method for enzymatically treating adopting in leather industry at present: the poor stability of (1) zymin, easily inactivation; (2) zymin conventionally and other material in same system, use, some material using in operation easily causes the inactivation of enzyme; (3) catalytic activity of enzyme is too high, and process controllability is poor.Therefore, be necessary to study the application of immobilized enzyme in process hides field, to form the effect of protection and slowly-releasing, strengthen the wearing quality of process hides special enzyme preparation and extend time of enzymatic reacting.But in enzyme immobilization technology, the selection of carrier has vital effect to the activity of immobilized enzyme and service performance.In order to obtain the immobilized enzyme that has good catalytic, carrying capacity is high, cost is low, prior art has been utilized cheap, the natural polymer being easy to get, as: gac, diatomite, alum, chitosan and alginate calcium etc. are as fixation support.Wherein, chitosan, alginate calcium are more extensive as the research of fixation support.But while using these natural polymers as fixed enzyme vector, because consistency and the affinity of they and enzyme are limited, supported quantity and the vigor of the enzyme in the immobilized enzyme obtaining are lower.In tanning production, by raw material skin, be processed into the solid waste output without process hides utility value that leather produces very high, be mainly divided into the secondary refuse of solid of not tanning and tanning.Increasingly serious along with global ecological problems such as environment, high-value-use solid leather wastes how fully, the secondary refuse of solid that particularly passes through tanning, alleviates environmental pollution to greatest extent, becomes the focus and emphasis content in the high value Study on Transformation of the secondary refuse of process hides solid.Solid leather wastes belongs to natural high molecular substance, contains a large amount of amino and carboxyl, has both been easy to and enzyme covalent attachment, again can bind metal ion, and enzyme is strengthened to the resistibility of metal ion.Meanwhile, easily graft modification, is the good carrier of immobilized enzyme again.
The present invention has studied that to take the secondary refuse of the solid of processing through tanning producing in process hides process be immobilized enzyme carrier.The effect such as covalently bound that utilizes the specificity avidity existing between the secondary refuse of process hides and enzyme molecule, immobilized metal ion to secondary refuse to have avidity to a certain degree and a linking agent to enzyme molecule realizes the immobilization of enzyme.In view of the new situations of current environment protection, the recycling of the secondary refuse of a large amount of solids that this also produces for leather industry has found new approach.
Therefore, when submitting the application to, the present invention is not apparent to those skilled in the art, therefore can not expect carrying out rawhide enzyme unhairing simultaneously and disperseing materials with hide glue fibril with neutral protease, α-amylase and pancreatin, more can not expect adopting solid leather wastes through tanning as carrier, the load of being fixed of enzyme is processed.Creativeness of the present invention is to use take carries out rawhide enzyme unhairing and dispersion agent protofibril through the secondary refuse of process hides solid of tanning as the immobilization prozyme that carrier prepares simultaneously.
Novelty of the present invention and unobviousness are take that the secondary refuse of process hides solid is carrier immobilized prozyme, make immobilization prozyme in a step treating processes, realize depilation and opening fiber simultaneously, thereby provide a kind of ecological property the novel depilation based on cellulase treatment and hide fiber dispersion technology system good, safety.
Summary of the invention
The object of the invention is the deficiency for existing biological enzyme, compound depilation enzyme of immobilization of a kind of improvement and preparation method thereof is provided, easily causes the difficult problems such as resultant leather quality problem (accidents such as rotten skin, rotten, loose side and intensity difference easily occur), technology controlling and process be poor when solving current enzyme unhairing and loose hide fiber.
Immobilization prozyme provided by the invention and preparation method thereof is as follows:
1) first will 100 parts be soaked in 1-4h in deionized water under the secondary refuse room temperatures of process hides solids, then add 10-30 part glutaraldehyde, and in 15-35 ℃ of water-bath oscillatory reaction 1-3h, filter also and wash away glutaraldehyde residual on carrier with deionized water;
2) accurately take a certain amount of prozyme and be dissolved in pH value in damping fluid 6.0-8.5, that ionic strength is 0.01-0.5mol/L, be mixed with composite enzyme solution, then centrifugal 10min under 5 ℃, 8000r/min, collects supernatant liquid;
3) the secondary refuse of the process hides solid preparing is joined in composite enzyme solution, making the secondary refuse ratio of enzyme and process hides solid is 0.2-0.4, oscillatory reaction 0.5-2h in 5-25 ℃ of water-bath, filter and wash away prozyme residual on carrier with deionized water, being able to the compound depilation enzyme of immobilization that the secondary refuse of process hides solid is carrier;
4) umber of above each material is weight part.
5) in above method, the secondary refuse of process hides solid used is for adopting arbitrary metal-salts such as zirconium, aluminium, titanium, iron, zinc, rare earth, silicon or any two or two or more metal-salt mixing pretan or masters to tan, and the median size that gained crust leather obtains through shaving, deburring, pulverization process is the saccharoid of 5-50 μ m.
6) compound depilation enzyme used in above method, its feature is neutral protease, the α-amylase of 10-25 part and the pancreatin of 5-15 part that every 100 parts of compound depilation enzymes comprise 55-80 part.
Tool of the present invention has the following advantages:
1) adopt the synchronous depilation of proteolytic enzyme, pancreatin and α-amylase and disperse materials with hide glue fibril, thering is synergy.Can reduce the effect degree of proteolytic enzyme, alleviate or avoid the damage of skin.Meanwhile, utilizing α-amylase, the hydrolysis of pancreatin to protein-polysaccharide, spandex fiber etc., play the effect of loose fiber, softening hide, is a kind of comprehensive depilatory enzyme that integrates depilation, loosen collagen fibre, softening hide.
2) the secondary refuse of process hides solid adopting due to the present invention not only can by and enzyme molecule between the specificity avidity that exists prepare immobilized enzyme, and the avidity that immobilized metal tanning agents to the secondary refuse of process hides solid has to a certain degree enzyme molecule causes immobilization, moreover prepare all higher immobilized enzyme of enzyme carrying capacity and vigor through the crosslinked action of glutaraldehyde., for immobilized enzyme has searched out the good carrier of a kind of new character, be not only also that the high value conversion of the secondary refuse of process hides solid opens up a new way simultaneously.
3) by the immobilized supported processing to compound depilation enzyme, enzyme is formed to the effect of protection and slowly-releasing, strengthen the wearing quality of the special-purpose depilation of process hides enzyme and extend time of enzymatic reacting.Can be in actual production, the position catalytic activity poor, enzyme that the difference of skin base, raw material skin exist is crossed the generation of the enzyme processing accident that the problems such as height may cause, guarantee that enzyme in use slowly releases its vigor, evenly, act on longer skin tissue, greatly improve the use properties of enzyme, thereby improve the controllability to process hides enzyme treating processes.
4) carrier that the present invention adopts is from the secondary refuse of process hides solid, and it not only originates abundant, and its cheap market price, stable chemical nature.
5) the inventive method technique is simple, easy to implement, is convenient to promote.
Accompanying drawing explanation
Fig. 1 is the compound depilation enzyme of immobilization prepared of the present invention and relative activity and the environment pH variation relation correlation curve of free enzyme
Fig. 2 is that the compound depilation enzyme of immobilization prepared of the present invention and relative activity and the variation of ambient temperature of free enzyme are related to correlation curve
Fig. 3 is the hair removal effect of the compound depilation enzyme of immobilization provided by the invention
Fig. 4 is the cattle hide upper grain SEM observation figure that the compound depilation enzyme processing of immobilization provided by the invention obtains
Fig. 5 is the cattle hide upper leather section SEM observation figure that the compound depilation enzyme processing of immobilization provided by the invention obtains.
Embodiment
Below by embodiment, the present invention is specifically described; be necessary to be pointed out that at this present embodiment is only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
In addition, what deserves to be explained is, in following embodiment, the umber of material is weight part.
Embodiment 1
100 parts, the secondary refuse of titaniferous is soaked in to 2h in deionized water under room temperature, then adds 24 parts of glutaraldehyde, oscillatory reaction 2h in 25 ℃ of water-baths, filters and washes away glutaraldehyde residual on carrier with deionized water; (wherein neutral protease is 21 parts to take the prozyme of 30 parts, 6 parts of α-amylases, 3 parts of pancreatin) being dissolved in pH value is in damping fluid 6.5, that ionic strength is 0.1mol/L, is mixed with concentration and is 6% composite enzyme solution, then centrifugal 10min under 5 ℃, 8000r/min, collects the upper strata stillness of night; The secondary refuse of the titaniferous preparing is joined in composite enzyme solution, making the secondary refuse ratio of enzyme and titaniferous is 0.3, oscillatory reaction 1h in 5 ℃ of water-baths, filters and washes away prozyme residual on carrier with deionized water, is able to the compound depilation enzyme of immobilization that the secondary refuse of titaniferous is carrier.
Embodiment 2
To under room temperature, be soaked in 2h in deionized water containing 100 parts, the secondary refuse of zirconium-aluminium, and then add 20 parts of glutaraldehyde, oscillatory reaction 3h in 35 ℃ of water-baths, filters and washes away glutaraldehyde residual on carrier with deionized water; Take prozyme (wherein, 30 parts of neutral proteases, 6 parts of the α-amylases of 40 parts, 4 parts of pancreatin) being dissolved in pH value is in damping fluid 7.0, that ionic strength is 0.05mol/L, be mixed with concentration and be 6% composite enzyme solution, then centrifugal 10min under 5 ℃, 8000r/min, collects the upper strata stillness of night; By joining in composite enzyme solution containing the secondary refuse of zirconium-aluminium of preparing, making enzyme is 0.4 with containing the secondary refuse ratio of zirconium-aluminium, oscillatory reaction 0.5h in 15 ℃ of water-baths, filter and wash away prozyme residual on carrier with deionized water, being contained the compound depilation enzyme of immobilization that the secondary refuse of zirconium-aluminium is carrier.
Embodiment 3
To under room temperature, be soaked in 4h in deionized water containing 100 parts, the secondary refuse of Zirconium-aluminum-titanium, and then add 15 parts of glutaraldehyde, oscillatory reaction 3h in 15 ℃ of water-baths, filters and washes away glutaraldehyde residual on carrier with deionized water; Take prozyme (wherein, 16 parts of neutral proteases, 2 parts of the α-amylases of 20 parts, 2 parts of pancreatin) being dissolved in pH value is 6.5, in the damping fluid that ionic strength is 0.05mol/L, is mixed with concentration and is 6% composite enzyme solution, then centrifugal 10min under 5 ℃, 8000r/min, collects the upper strata stillness of night; By joining in enzyme solution containing the secondary refuse of Zirconium-aluminum-titanium of preparing, making enzyme is 0.2 with containing the secondary refuse ratio of Zirconium-aluminum-titanium, oscillatory reaction 0.5h in 25 ℃ of water-baths, filter and wash away prozyme residual on carrier with deionized water, being contained the compound depilation enzyme of immobilization that the secondary refuse of Zirconium-aluminum-titanium is carrier.
Application Example 1
Get according to a conventional method the cattle hide 100kg after immersion, fleshing, in rotary drum, add water 100kg, adjust the temperature to about 18-22 ℃, regulate pH to approximately 7.5, add the compound depilation enzyme of the immobilization preparing by embodiment 1 (enzyme dosage is 150-200u/g skin), rotate 60min, stop 30min, later intermittent rotary, rotate 10min, stop 20min, total time 2-4 hour, comes off with mechanical effect after hair is loosening.
Application Example 2
The pigskin 100kg getting after immersion according to a conventional method, degreasing, fleshing adds rotary drum, add water 60kg, adjust the temperature to about 25-28 ℃, regulate pH to approximately 8.0, add the compound depilation enzyme of the immobilization preparing by embodiment 2 (enzyme dosage is 150-200u/g skin), rotate 60min, intermittent rotary, rotates 15min later, stops 30min, total time 4-6 hour, goes out drum, epilation after hair is loosening.
Application Example 3
Get according to a conventional method the goatskin 100kg after immersion, fleshing, in rotary drum, add water 80kg, adjust the temperature to about 28-30 ℃, regulate pH to approximately 8.5, add the compound depilation enzyme of the immobilization preparing by embodiment 3 (enzyme dosage is 150-200u/g skin), rotate 60min, stop 30min, later intermittent rotary, rotate 10min, stop 20min, total time 3-5 hour, comes off with mechanical effect after hair is loosening.
In order to investigate the enzyme supported quantity of the compound depilation enzyme of immobilization and the situation of vigor maintenance of preparation, the present invention chooses the compound depilation enzyme of immobilization prepared by above embodiment at random, and respectively according to Xylene Brilliant Cyanine G method (Bradford. M. M. A rapid and sensitive method for the quantitation of microgram quantities of protein utilizing the principle of protein dye binding[J]. Anal Biochem, 1976, 72 (1/2): 248-254.), measuring method (the Ku Hansheng of immobilized enzyme, Yao Xiaoling, Zhang Ting, Deng. the measuring method of immobilizing trypsinase vigor is inquired into [J]. amino acid and Biological resources, 2007, 29(2): 33-35. the People's Republic of China light industry standard. QB/T 1803-1993[S]. industrial enzyme preparation universal test method, 1993.) carried out the mensuration that enzyme supported quantity and vigor keep, measurement result is in Table 1.
Secondly, the present invention has also investigated pH, the influence degree of envrionment temperature to the compound depilation enzyme activity of immobilization of preparation.Under 40 ℃ of conditions, immobilized enzyme and free enzyme are placed in respectively after damping fluid that pH value is 6.0-9.0 is incubated 10min and measure its enzyme activity, then obtained the impact of pH value on the compound depilation enzyme of immobilization and free enzyme activity, the results are shown in Figure 1.As seen from Figure 1, the compound depilation enzyme of immobilization freer enzyme within the scope of investigation pH value has all shown higher relative activity.In pH value, be 6.0 o'clock, the relative activity of immobilized enzyme is in 90% left and right, and free enzyme is in 60% left and right.As can be seen here, compound depilation enzyme is the Reduced susceptibility to pH after the inventive method is fixing, can within the scope of wider pH, bring into play higher catalysis activity.When investigating envrionment temperature on the affecting of the compound depilation enzyme activity of immobilization, immobilized enzyme and free enzyme are placed at 5-75 ℃, pH value is to measure its enzyme activity after being incubated 10min in 8.0 phosphate buffered saline buffer, then obtain the impact of temperature on the compound depilation enzyme of immobilization and free enzyme activity, the results are shown in Figure 2.As seen from Figure 2, the compound depilation enzyme of immobilization freer enzyme in investigated temperature range all shows higher relative activity, and when temperature reaches 75 ℃, it is former great-hearted 80% that immobilized enzyme still can keep, and free enzyme is only 35%.As can be seen here, compound depilation enzyme is the Reduced susceptibility to temperature after this method is fixing, and can in temperature range, bring into play higher catalysis activity widely.
Finally, the present invention has also investigated the effect of the compound depilation enzyme of immobilization of preparation.The pelt obtaining by Application Example 1 processing is supplemented after depilation, loosen collagen fibre through 1.0% sodium sulphite and 0.7% liquid caustic soda (sodium hydroxide solution that massfraction is 30%), without multiple ash, softening operation, directly routinely technique carry out pickling, tanning, tan after wet processing and do the rear arrangement such as soft and process.In this process, adopt digital camera to using the pelt after the compound depilation enzyme unhairing of immobilization to take pictures, the results are shown in Figure 3.Meanwhile, adopt cattle hide upper leather sample that the method for JEOL JSM-5900LV type sem observation obtains processing to carry out grain and section situation is observed, the results are shown in Figure 4, Fig. 5.As seen from Figure 3, adopt the cattle hide after the compound depilation enzyme unhairing of immobilization almost only to have a small amount of short and small fine hair and newborn little Mao.From grain form, can see, adopt the pelt after the compound depilation enzyme unhairing of immobilization, surface is pure white, and grain pore is clear, and flexibility is good, and the visible compound depilation enzyme of immobilization has desirable depilation comprehensive action result.As seen from Figure 4, the cattle hide upper leather that adopts the compound depilation enzyme processing of immobilization to obtain, grain is smooth, smooth, and pore is more complete.Show, the compound depilation enzyme of immobilization is different from conventional biological enzyme, and the leather quality that it does not obtain processing brings very significant negative impact, has tight security, and technique and resultant leather quality stability are high, the ability that has gentle depilation and disperse materials with hide glue fibril.As seen from Figure 5, the cattle hide upper leather that adopts the compound depilation enzyme processing of immobilization to obtain, separated loosening degree and the homogeneity of its collegen filament are better, and larger fibrous bundle longitudinal splitting becomes compared with O-fiber, can clearly see indivedual loose tiny collagenous fiber bundles.In addition, can also see, collegen filament interfascicular presents certain space.This space is mainly because of the formation of removing of interfibrillar substance in sample processing treatment process.Visible, to compare with conventional biological enzyme, the compound depilation endonuclease capable of immobilization is removed interfibrillar substance, dispersion agent protofibril better.
Table 1
。
Claims (3)
1. the preparation method that the secondary refuse of the process hides of take is carrier immobilized compound depilation enzyme, processing step and the condition of the method are as follows:
(1) first will 100 parts be soaked in 1-4h in deionized water under the secondary refuse room temperatures of process hides solids, then add 10-30 part glutaraldehyde, and in 15-35 ℃ of water-bath oscillatory reaction 1-3h, filter also and wash away glutaraldehyde residual on carrier with deionized water;
(2) accurately take a certain amount of prozyme and be dissolved in pH value in damping fluid 6.0-8.5, that ionic strength is 0.01-0.5mol/L, be mixed with composite enzyme solution, then centrifugal 10min under 5 ℃, 8000r/min, collects supernatant liquid;
(3) the secondary refuse of the process hides solid preparing is joined in composite enzyme solution, making the secondary refuse ratio of enzyme and process hides solid is 0.2-0.4, oscillatory reaction 0.5-2h in 5-25 ℃ of water-bath, filter and wash away prozyme residual on carrier with deionized water, being able to the compound depilation enzyme of immobilization that the secondary refuse of process hides solid is carrier;
The umber of each material is weight part above.
2. in above method, the secondary refuse of process hides solid used is for adopting arbitrary metal-salts such as zirconium, aluminium, titanium, iron, zinc, rare earth, silicon or any two or two or more metal-salt mixings pretan or leading and tan, and the median size of gained crust leather after shaving, deburring, pulverization process is the saccharoid of 5-50 μ m.
3. compound depilation enzyme used in above method, its feature is neutral protease, the α-amylase of 10-25 part and the pancreatin of 5-15 part that every 100 parts of compound depilation enzymes comprise 55-80 part.
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| CN105053144A (en) * | 2015-07-24 | 2015-11-18 | 淄博黄河龙生物工程有限公司 | Leather pickling technology |
| CN105400768A (en) * | 2015-06-23 | 2016-03-16 | 兴业皮革科技股份有限公司 | Immobilized composite hair removing enzyme adopting porous carboxymethyl cellulose-polyvinyl alcohol microspheres as carrier, and preparation method thereof |
| CN105441602A (en) * | 2015-12-23 | 2016-03-30 | 天津科技大学 | Method for tanning by jointly using compound protease soaked with water, titanium salt and zinc salt |
| CN105734183A (en) * | 2016-04-08 | 2016-07-06 | 吴全永 | Parchment for writing and painting |
| CN109490274A (en) * | 2019-01-04 | 2019-03-19 | 齐鲁工业大学 | A kind of experimental provision and application method for studying enzyme unidirectional mass transfer in the leather |
| CN113502355A (en) * | 2021-07-21 | 2021-10-15 | 四川大学 | Ultrathin multifunctional microfiltration membrane based on animal hides and preparation method and application |
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| CN104293763A (en) * | 2014-08-28 | 2015-01-21 | 四川大学 | Lipase immobilization carrier and method for immobilizing lipase |
| CN105400768A (en) * | 2015-06-23 | 2016-03-16 | 兴业皮革科技股份有限公司 | Immobilized composite hair removing enzyme adopting porous carboxymethyl cellulose-polyvinyl alcohol microspheres as carrier, and preparation method thereof |
| CN105400768B (en) * | 2015-06-23 | 2018-11-02 | 兴业皮革科技股份有限公司 | Using porous carboxymethyl cellulose-polyvinyl alcohol microparticles as compound depilation enzyme of the immobilization of carrier and preparation method thereof |
| CN105053144A (en) * | 2015-07-24 | 2015-11-18 | 淄博黄河龙生物工程有限公司 | Leather pickling technology |
| CN105441602A (en) * | 2015-12-23 | 2016-03-30 | 天津科技大学 | Method for tanning by jointly using compound protease soaked with water, titanium salt and zinc salt |
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| CN105734183A (en) * | 2016-04-08 | 2016-07-06 | 吴全永 | Parchment for writing and painting |
| CN109490274A (en) * | 2019-01-04 | 2019-03-19 | 齐鲁工业大学 | A kind of experimental provision and application method for studying enzyme unidirectional mass transfer in the leather |
| CN113502355A (en) * | 2021-07-21 | 2021-10-15 | 四川大学 | Ultrathin multifunctional microfiltration membrane based on animal hides and preparation method and application |
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