CN106367544B - A kind of amino resins is modified process hides and gives up the method that ox hair keratin prepares compound protein filler - Google Patents
A kind of amino resins is modified process hides and gives up the method that ox hair keratin prepares compound protein filler Download PDFInfo
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- CN106367544B CN106367544B CN201610758153.1A CN201610758153A CN106367544B CN 106367544 B CN106367544 B CN 106367544B CN 201610758153 A CN201610758153 A CN 201610758153A CN 106367544 B CN106367544 B CN 106367544B
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/08—Chemical tanning by organic agents
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K14/00—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof
- C07K14/435—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans
- C07K14/46—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans from vertebrates
- C07K14/47—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans from vertebrates from mammals
- C07K14/4701—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans from vertebrates from mammals not used
- C07K14/4741—Keratin; Cytokeratin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H1/00—Macromolecular products derived from proteins
- C08H1/06—Macromolecular products derived from proteins derived from horn, hoofs, hair, skin or leather
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C11/00—Surface finishing of leather
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Abstract
The present invention relates to tanning waste technical field of resource utilization, it a kind of amino resins is provided is modified process hides and give up the method that ox hair keratin prepares compound protein filler, hydrolysis ox hair is combined with alkaline process by oxidizing process, shorten the hydrolysis time of ox hair, improve ox hair dissolution rate, the keratin solution obtained simultaneously using amino resins to hydrolysis is modified, increase its relative molecular mass, and introducing more can be with leather fiber and the functional group of chromium ion stable bond, enhance keratin with removing from office the binding ability of fiber, so that as the amino resins be modified process hides give up ox hair keratin prepare the method for compound protein filler made from protein filling be applied to process hides when, the better organoleptic properties of finished leather and physical mechanical property can be assigned；And when hydrolysis ox hair is combined with alkaline process by the oxidizing process, can also blanching effect be played to ox hair, so as to obtain the shallower protein filling of color, can be applied to the filling of light-colored leather and brightly painted leather.
Description
Technical field
The present invention relates to tanning waste technical field of resource utilization, more particularly to a kind of amino resins is modified process hides and gives up ox
The method that feather keratin prepares compound protein filler.
Background technology
With the development of cleanning tan leater technology, hair saving process is increasingly becoming one of mainstream depilating method of process hides, protects hair
Epilation can effectively reduce the content of organics in leather-making waste water, if but useless ox hair cannot be effective caused by hair saving process
Recycling, will also result in environmental pollution.Domestic process hides is given up at present, and ox hair recycling example is less, and majority is to pass through
It burns or landfill disposal, waste of resource pollutes environment.
The main component of ox hair is keratin, and keratin is a kind of important available resources, and ox hair is hydrolyzed angulation egg
White or polypeptide is conducive to the recycling of ox hair.Since the useless ox hair that process hides hair saving process generates is by protecting hair processing, production
The effect of shield hair is given birth to, cystine is more in the keratin of ox hair that gives up, and cystine linkage content is also more so that the chemistry of keratin
Property is more stable, and hydrolysis is more difficult, is difficult to obtain more satisfactory effect using single method for hydrolysis.
The patent on ox hair hydrolysis mainly has two classes at present, and one kind is to be used in combination using metal salt with other methods pair
Hair is hydrolyzed, and reagent dosage is big needed for this method, of high cost, and hydrolysis rate is slow, and percent hydrolysis is low；One kind be directly with alkali into
Row hydrolysis, keratin color obtained by this method is deep, molecular weight is small, and light-colored leather and bright-colored is cannot be used for as protein filling
Leather filling, and the fullness of select operator and finished leather is poor.
The content of the invention
Therefore, in view of the problems of the existing technology, the present invention proposes that a kind of amino resins is modified process hides and gives up ox hair angle egg
The white method for preparing compound protein filler, the amino resins are modified the process hides ox hair keratin that gives up and prepare the side of compound protein filler
Method is combined hydrolysis ox hair by oxidizing process with alkaline process, is shortened the hydrolysis time of ox hair, is improved ox hair dissolution rate, utilize simultaneously
The keratin solution that amino resins obtains hydrolysis is modified, and increases its relative molecular mass, and introducing more can be with leather
The functional group of fiber and chromium ion stable bond, enhancing keratin and the binding ability for removing from office fiber so that by the amino resins
Modified process hides gives up ox hair keratin when preparing protein filling made from the method for compound protein filler applied to process hides, can assign
The better organoleptic properties of finished leather and physical mechanical property；And when hydrolysis ox hair is combined with alkaline process by the oxidizing process, also can
It is enough that blanching effect is played to ox hair, so as to obtain the shallower protein filling of color, light-colored leather and color can be applied to
The filling of bright-coloured leather.
To realize above-mentioned technical problem, the solution that the present invention takes is：A kind of amino resins is modified process hides and gives up ox hair
The method that keratin prepares compound protein filler, includes the following steps：
Step 1, useless ox hair cleaning：Useless ox hair quality is weighed, the parts by weight of agents useful for same in the step are determined with the quality,
Useless ox hair is put into retort, adds in the surfactant of 0.01 parts by weight and the water of 20 parts by weight, 20min is stirred, then adds
Entering the water of 10-20 parts by weight, wash twice, draining, the mass fraction for then adding in 10-15 parts by weight is 0.5% dilute hydrochloric acid,
Soaking and stirring 2-3h, is then filtered, dry；
Step 2, useless ox hair hydrolysis：The dried ox hair quality of step 1 is weighed, examination used in the step is determined with the quality
The parts by weight of agent, the useless ox hair obtained after step 1 is dried are added in retort, add in the water of 10 parts by weight and 0.2-0.3 weights
The oxidant of part is measured, is stirred to react 3-4h, the alkali of 0.2-0.4 parts by weight is then added in, is warming up to 60 DEG C, is stirred to react 2h, so
After be cooled to room temperature, in hydrochloric acid and adjust pH=7-8, keratin solution be obtained by filtration, with keratin quality be equal to ox hair quality into
Row calculates, and calculates the concentration of keratin solution, concentration c=m of keratin solutionKeratin/V=mOx hair/ V, wherein, mKeratinFor keratin
Quality, mOx hairFor the quality of ox hair, V is the volume of keratin solution；
Step 3, keratin solution are modified：The keratin solution obtained by the step 2 of certain volume is measured, is calculated under the volume
Keratin solution in contained keratin quality, the weight of amino-compound monomer used is determined with the keratin quality
Part；The amino-compound monomer of 0.4-1 parts by weight is added in reaction kettle, adds in the formalin of 0.5-3 parts by weight, control temperature
Degree reacts 1-1.5h at 60-80 DEG C, pH=7-8, adds the keratin solution that has measured the reaction was continued 1-1.5h, addition
The sodium hydrogensulfite of 0.02-0.1 parts by weight reacts 1-1.5h, cooling, and pH is adjusted to 7-8, obtains protein filling solution；
Step 4, the filtering of protein filling solution：The protein filling solution obtained by Treatment with Ultrafiltration step 3, except deproteinized is filled out
Expect the salts substances in solution, the protein filling solution concentrated；
Step 5, the drying of protein filling solution：With spray dryer in step 4 gained concentration protein filling solution into
Row spray drying, obtains compound protein filler powder.
It is further that the surfactant described in step 1 is dodecyl sodium sulfate or lauryl sodium sulfate.
It is further that the oxidant described in step 2 is H2O2Or sodium hypochlorite.
It is further that the alkali described in step 2 is sodium hydroxide or potassium hydroxide.
It is further that the amino-compound monomer described in step 3 is melamine monomer, keratin quality in step 3
Mass ratio with melamine monomer quality is keratin quality：Melamine monomer quality=1：（0.4-0.8）；Melamine
Amount ratio with the substance of formaldehyde is melamine：Formaldehyde=1：（2.5-3.5）.
It is further that the amino-compound monomer described in step 3 is urea, keratin quality and urea matter in step 3
The mass ratio of amount is keratin quality：Urea quality=1：（0.5-1）；The amount ratio of the substance of urea and formaldehyde is urea：Formaldehyde=
1：（1.5-2）.
Further that the amino-compound monomer described in step 3 is dicyandiamide monomer, in step 3 keratin quality with
The mass ratio of dicyandiamide monomer mass is keratin quality：Dicyandiamide monomer mass=1：（0.5-1）；Dicyandiamide monomer and formaldehyde
Substance amount ratio be dicyandiamide monomer：Formaldehyde=1：（2-3）.
It is further that ultrafiltration membrane molecule interception used in ultrafiltration is 1-2kD in step 4, operating pressure is
0.2-0.3MPa。
It is further that the inlet air temperature of spray dryer is 120-160 DEG C in step 5, leaving air temp is 70-80 DEG C,
Feed rate is 20-40mL/min.
By using preceding solution, the beneficial effects of the invention are as follows：The amino resins designed as described above is modified system
The method that the useless ox hair keratin of leather prepares compound protein filler, is combined hydrolysis ox hair with alkaline process by oxidizing process, shortens ox hair
Hydrolysis time, improve ox hair dissolution rate, while be modified using the keratin solution that amino resins obtains hydrolysis, increase
Its big relative molecular mass, and introduce more can with leather fiber and the functional group of chromium ion stable bond, enhancing keratin with
Remove from office the binding ability of fiber so that process hides is modified by the amino resins and is given up the method that ox hair keratin prepares compound protein filler
When protein filling obtained is applied to process hides, the more preferably soft and full property of finished leather and the flat fineness of grain and Physical Mechanical can be assigned
Energy；And when hydrolysis ox hair is combined with alkaline process by the oxidizing process, can also blanching effect be played to ox hair, so as to obtain face
The shallower protein filling of color can be applied to the filling of light-colored leather and brightly painted leather；Therefore, by the amino
Resin modified process hides give up ox hair keratin prepare compound protein filler method obtain protein filling select operator it is good, be suitble to
It is highly practical for the leather that position difference is larger.
Specific embodiment
Carry out the embodiment that the present invention will be described in detail below with reference to specific embodiment, how skill is applied to the present invention whereby
Art means solve technical problem, and the realization process for reaching technique effect can fully understand and implement according to this.If it does not refer in particular to
Conventional means bright, that the technological means employed in embodiment is well known to those skilled in the art, used reagent and production
Product are also available commercial.The various processes and method not being described in detail are conventional methods as known in the art, this hair
Useless ox hair used in bright is the ox hair that gives up caused by XingYe Leather Science Co., Ltd's process hides depilation, and agents useful for same is equal
For the common agents being commercially available by commercial sources.
A kind of amino resins is modified process hides and gives up the method that ox hair keratin prepares compound protein filler, includes the following steps：
Step 1, useless ox hair cleaning：Useless ox hair weight is weighed, the parts by weight of agents useful for same in the step are determined with the weight,
Useless ox hair is put into retort, adds in the dodecyl sodium sulfate of 0.01 parts by weight and the water of 20 parts by weight, stirs 20min,
The water of 15 parts by weight is added, is washed twice, draining, the mass fraction for then adding in 13 parts by weight is 0.5% dilute hydrochloric acid, is soaked
Bubble stirring 2.5h, is then filtered, dry；
Step 2, useless ox hair hydrolysis：The dried ox hair weight of step 1 is weighed, examination used in the step is determined with the weight
The parts by weight of agent.The useless ox hair obtained after step 1 is dried is added in retort, adds in the water and 0.25 parts by weight of 10 parts by weight
H2O2, 3-4h is stirred to react, then adds in the sodium hydroxide of 0.25 parts by weight, is warming up to 60 DEG C, 2h is stirred to react, then drops
Temperature in hydrochloric acid and adjusts pH=7-8, keratin solution is obtained by filtration to room temperature, carried out equal to ox hair quality by keratin quality in terms of
It calculates, calculates the concentration of keratin solution, concentration c=m of keratin solutionKeratin/V=mOx hair/ V, wherein, mKeratinFor the matter of keratin
Amount, mOx hairFor the quality of ox hair, V is the volume of keratin solution；
Step 3, keratin solution are modified：The keratin solution obtained by the step 2 of certain volume is measured, is calculated under the volume
Keratin quality, on the basis of keratin quality determine melamine monomer quality；By 0.5 parts by weight melamine monomer
It adds in reaction kettle, adds in 0.9 parts by weight of formaldehyde solution（Mass fraction is 37%-40%）, temperature is controlled at 80 DEG C, pH=7-8,
1.5h is reacted, keratin solution is added the reaction was continued 1h, add in 0.04 parts by weight sodium hydrogensulfite, react 1h, cooling, pH tune
7-8 is saved, obtains protein filling solution；
Step 4, the filtering of protein filling solution：The protein filling solution obtained by Treatment with Ultrafiltration step 3, except deproteinized is filled out
Expect solution in salts substances, the protein filling solution concentrated, wherein ultrafiltration membrane molecule interception be 1kD, operating pressure
For 0.25MPa；
Step 5, the drying of protein filling solution：With spray dryer in step 4 gained concentration protein filling solution into
Row spray drying obtains compound protein filler powder, and the wherein inlet air temperature of spray dryer is 140 DEG C, leaving air temp 70
DEG C, feed rate 25mL/min.
As above-mentioned amino resins be modified process hides give up ox hair keratin prepare the method for compound protein filler made from albumen fill out
When feed powder end is used for process hides, select operator is good, is suitable for the larger leather of position difference, and it is more preferable soft rich can to assign finished leather
Full property and the flat fineness of grain and physical mechanical property, it is highly practical.
The foregoing descriptions are merely the embodiment using this origination techniques content, any those skilled in the art use this wound
Make done modifications and changes, all belong to the scope of the claims of this creation opinion, and be not limited to those disclosed embodiments.
Claims (9)
- A kind of method that ox hair keratin prepares compound protein filler 1. amino resins modification process hides is given up, which is characterized in that including Following steps：Step 1, useless ox hair cleaning：Useless ox hair quality is weighed, the parts by weight of agents useful for same in the step are determined with the quality, it will be useless In ox hair input retort, the surfactant of 0.01 parts by weight and the water of 20 parts by weight are added in, 20min is stirred, adds 10- The water of 20 parts by weight is washed twice, draining, and the mass fraction for then adding in 10-15 parts by weight is 0.5% dilute hydrochloric acid, and immersion is stirred 2-3h is mixed, is then filtered, it is dry；Step 2, useless ox hair hydrolysis：The dried ox hair quality of step 1 is weighed, agents useful for same in the step is determined with the quality Parts by weight, the useless ox hair obtained after step 1 is dried are added in retort, add in the water of 10 parts by weight and 0.2-0.3 parts by weight Oxidant, be stirred to react 3-4h, then add in 0.2-0.4 parts by weight alkali, be warming up to 60 DEG C, be stirred to react 2h, then drop Temperature in hydrochloric acid and adjusts pH=7-8, keratin solution is obtained by filtration to room temperature, carried out equal to ox hair quality by keratin quality in terms of It calculates, calculates the concentration of keratin solution, concentration c=m of keratin solutionKeratin/V=mOx hair/ V, wherein, mKeratinFor the matter of keratin Amount, mOx hairFor the quality of ox hair, V is the volume of keratin solution；Step 3, keratin solution are modified：The keratin solution obtained by the step 2 of certain volume is measured, calculates the angle under the volume Contained keratin quality in protein solution determines the parts by weight of amino-compound monomer used with the keratin quality；It will The amino-compound monomer of 0.4-1 parts by weight is added in reaction kettle, adds in the formalin of 0.5-3 parts by weight, and control temperature exists 60-80 DEG C, pH=7-8,1-1.5h is reacted, adds the keratin solution that has measured the reaction was continued 1-1.5h, addition 0.02-0.1 The sodium hydrogensulfite of parts by weight reacts 1-1.5h, cooling, and pH is adjusted to 7-8, obtains protein filling solution；Step 4, the filtering of protein filling solution：With gained protein filling solution in Treatment with Ultrafiltration step 3, it is molten to remove protein filling Salts substances in liquid, the protein filling solution concentrated；Step 5, the drying of protein filling solution：The protein filling solution of gained concentration in step 4 is sprayed with spray dryer Mist is dried, and obtains compound protein filler powder.
- The method that ox hair keratin prepares compound protein filler 2. amino resins modification process hides according to claim 1 is given up, It is characterized in that：Surfactant described in step 1 is dodecyl sodium sulfate or lauryl sodium sulfate.
- The method that ox hair keratin prepares compound protein filler 3. amino resins modification process hides according to claim 1 is given up, It is characterized in that：Oxidant described in step 2 is H2O2Or sodium hypochlorite.
- The method that ox hair keratin prepares compound protein filler 4. amino resins modification process hides according to claim 1 is given up, It is characterized in that：Alkali described in step 2 is sodium hydroxide or potassium hydroxide.
- The method that ox hair keratin prepares compound protein filler 5. amino resins modification process hides according to claim 1 is given up, It is characterized in that：Amino-compound monomer described in step 3 is melamine monomer, keratin quality and melamine in step 3 The mass ratio of amine monomers quality is keratin quality：Melamine monomer quality=1：（0.4-0.8）；Melamine monomer and first The amount ratio of the substance of aldehyde is melamine：Formaldehyde=1：（2.5-3.5）.
- The method that ox hair keratin prepares compound protein filler 6. amino resins modification process hides according to claim 1 is given up, It is characterized in that：Amino-compound monomer described in step 3 is urea, keratin quality and the quality of urea quality in step 3 Than for keratin quality：Urea quality=1：（0.5-1）；The amount ratio of the substance of urea and formaldehyde is urea：Formaldehyde=1：（1.5- 2）.
- The method that ox hair keratin prepares compound protein filler 7. amino resins modification process hides according to claim 1 is given up, It is characterized in that：Amino-compound monomer described in step 3 is dicyandiamide monomer, keratin quality and dicyandiamide list in step 3 The mass ratio of weight is keratin quality：Dicyandiamide monomer mass=1：（0.5-1）；The substance of dicyandiamide monomer and formaldehyde Amount is than being dicyandiamide monomer：Formaldehyde=1：（2-3）.
- The method that ox hair keratin prepares compound protein filler 8. amino resins modification process hides according to claim 1 is given up, It is characterized in that：Ultrafiltration membrane molecule interception used in ultrafiltration is 1-2kD, operating pressure 0.2-0.3MPa in step 4.
- The method that ox hair keratin prepares compound protein filler 9. amino resins modification process hides according to claim 1 is given up, It is characterized in that：The inlet air temperature of spray dryer is 120-160 DEG C in step 5, and leaving air temp is 70-80 DEG C, feed rate For 20-40mL/min.
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Effective date of registration: 20190701 Address after: 221200 Guangming Road, Suining Economic Development Zone, Xuzhou City, Jiangsu Province Patentee after: Xuzhou Xingning Leather Co. Ltd. Address before: 362261 Anhai Second Industrial Zone, Jinjiang City, Quanzhou City, Fujian Province Patentee before: Xingye Leather Technology Co., Ltd. |