CN102206695A - Method for preparing silk short peptides and silk amino acids by using waste silks - Google Patents
Method for preparing silk short peptides and silk amino acids by using waste silks Download PDFInfo
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Abstract
The invention relates to a method for preparing silk short peptides and silk amino acids by using waste silks, comprising the following steps of: pretreating by taking the waste silks as raw materials and adopting a steam explosion method; then hydrolyzing under certain pressure by using dilute sulphuric acids; carrying out appropriate deacidification treatment, and then adding an acid protease for hydrolysis; then decoloring, neutralizing and refining; and finally carrying out vacuum concentration and blending to obtain the products. The invention has the advantages of moderate hydrolysis condition, high hydrolysis rate, easiness in operation, lower cost, safety in cleaning, and the like; with the method, waste calcium sulfate generated in the production process can be used for the production of cement and gypsum boards, and a spent acid solution generated by regenerated strong-acid cation exchange resins is neutralized to reach the standard and then discharged without poisonous and harmful wastes, and therefore clean production is basically realized; in addition, the silk short peptides and the silk amino acids which are prepared by adopting the method disclosed by the invention have good solubility and high purity and can be widely used for the fields of cosmetics, medicines, foods, and the like.
Description
One, technical field
The invention belongs to silk and utilize technical field, be specifically related to the method that the useless silk of a kind of usefulness prepares silk small peptide and silk amino acid.
Two, background technology
Silk small peptide and silk amino acid is water-soluble, seepage force is strong, but skin nutrition, ultraviolet blocking-up; suppressing melanochrome generates; some small peptides or silk amino acid also have pharmaceutical use, and as L-Ala protection liver, glycine and Serine are prevented and treated diseases such as hypertension, cerebral thrombosis and Intracerebral hemorrhage.Therefore, silk small peptide and silk amino acid can be widely used in fields such as medicine, food, daily use chemicals, as the raw material of nutrition agent, medicine, daily use chemicals and tensio-active agent etc.
At present, the method that is the feedstock production silk amino acid with useless silk has acid system, alkaline process or enzyme process.For example in " silkworm industry science " " adopting optimization of orthogonal test tussah silk peptide working condition " literary composition in the fourth phase in 2006, disclosed method is: be raw material with the tussah silk, after coming unstuck, hydrolysis under sulfuric acid high temperature, neutralization, decolouring obtain product.The main drawback of this method is: used sulfuric acid concentration is higher, and hydrolysis time is long, and hydrolysising by-product is many, hydrolyzate molecular weight heterogeneity, in and waste residue many, raw material utilizes fully, is unfavorable for Sustainable development.And for example the publication number of announcing on March 11st, 2009 is " being extracted the method for silk peptide by silk " patent of CN101381758A, disclosed method is to be raw material with the silk after the sodium carbonate solution refining, join in the calcium chloride solution and dissolve, with the proteolytic enzyme reaction that is hydrolyzed, hydrolyzed solution after ultrafiltration and nanofiltration separation, the spray-dried silk peptide powder that obtains of the feed liquid that obtains.The main drawback of this method is: fibroin solubleness in calcium chloride is low, enzyme volatility, hydrolysis efficiency under the condition of high salt concentration is low, salts contg height in the product, brine waste amount are big, has " three wastes " to produce, and is unfavorable for Sustainable development.
Three, summary of the invention
The objective of the invention is weak point, provide the useless silk of a kind of usefulness to prepare the method for silk small peptide and silk amino acid at existing preparation silk small peptide and silk amino acid method.This method has the hydrolysising condition gentleness, the percent hydrolysis height, and simple to operate, cost is lower, characteristics such as clean and safe.Silk small peptide and the silk amino acid that employing a process for preparing has that solvability is good, purity is high, can be widely used in fields such as makeup, medicine, food.
Cardinal principle of the present invention is: steam explosion is that raw material is placed high temperature, highly compressed environment, raw material is full of steam by the superheated liquid swollen in the hole, when moment is removed high pressure, superheated liquid in the raw material hole is vaporized rapidly, and volume sharply expands and makes cell " explosion ".Crystalline texture through this method pretreating raw material is broken, and the accessibility of enzyme is significantly increased, thereby improves hydrolysis efficiency.The natural polymer that silk-protein is made up of by molecular interaction (hydrogen bond and hydrophobic interaction etc.) several peptide chains is positioned over it in environment of suitable high temperature and pressure and carries out steam " explosion ", can make its intermolecular connection portion or complete rupture.The a large amount of peptide bond of the silk-protein of " explosion " comes out, and for diluted acid and proteolytic enzyme adheres to and hydrolysis, generates silk small peptide and silk amino acid.The silk small peptide is made up of several amino acid, molecular weight is significantly greater than silk amino acid, through membrane sepn, the silk small peptide that molecular weight is bigger separates with the less silk amino acid of molecular weight, obtain silk small peptide and processing such as silk amino acid, vacuum concentration through decolouring, separation, can prepare wire vent small peptide and silk amino acid concentrated solution.
The technical scheme that realizes the object of the invention is: the useless silk of a kind of usefulness prepares the method for silk small peptide and silk amino acid, be raw material with useless silk earlier, adopt steam explosion to carry out pre-treatment, under certain pressure, use the dilute sulphuric acid hydrolysis again, after carrying out suitable depickling processing, then add acid protease hydrolysis, decolour then, neutralize, make with extra care, carry out vacuum concentration and allotment at last and obtain product.Its concrete method steps is as follows:
(1) pre-treatment
With useless silk is raw material, cuts up with a hay cutter into the short silk section that length is 1～3cm with the chopper silk that will give up earlier, is positioned in the stainless steel autoclave again, and then is connected with high pressure steam generator, forms homemade steam blasting device.Then again according to cutting up with a hay cutter into the quality (g) that length is the short silk section of 1～3cm: the volume of stainless steel autoclave (mL) is than the ratio that is 1: 10～30, to lack the silk section earlier adds in the stainless steel autoclave, feed high pressure steam again, till when the still internal pressure reaches 3.0～6.0MPa, press butterfly valve in keeping opening after 30～60 minutes, carry out quick-fried gas disposal, collect the quick-fried silk section of breathing hard.The quick-fried silk section of breathing hard for collecting is used for next step dilute sulphuric acid hydrolysis.
(2) dilute sulphuric acid hydrolysis
(1) step finish after, quick-fried quality (g) of section of breathing hard according to the collection of (1) step: volumetric concentration is that 1～3% vitriolic volume (mL) is than the ratio that is 1: 10～20, earlier the quick-fried silk section of breathing hard is positioned in the glassed steel reaction vessels, in glassed steel reaction vessels, add dilute sulphuric acid and closed reactor again, and then be warming up to 130～150 ℃, at pressure is under the condition of 0.3～0.45MPa, is hydrolyzed 2～4 hours.After hydrolysis is finished, feed water coolant in the reactor interlayer, the question response still is opened baiting valve after being cooled to 40～60 ℃, and hydrolyzed solution is pumped in the suction filtration machine, carries out suction filtration.Abandon filter residue, collect filtrate.For the filtrate of collecting, promptly the dilute sulphuric acid hydrolyzed solution is used for next step depickling.
(3) depickling
(2) step finish after, go on foot the filtrate of collecting with (2) earlier, by molecular weight cut-off is the ultra-fine filter of 3000～5000Da, at pressure is under 0.08～0.2MPa, carry out the ultrafiltration depickling first time, till ultrafiltration trapped fluid volume is reduced to original volume 20～30% o'clock, collect filtered solution of ultrafiltration for the first time and the trapped fluid of ultrafiltration for the first time respectively.For the ultrafiltration first time trapped fluid of collecting, replenish pure water to original volume, under equal conditions, carry out the ultrafiltration depickling second time, collect filtered solution of ultrafiltration for the second time and the trapped fluid of ultrafiltration for the second time respectively.For the first time of collecting, the filtered solution of ultrafiltration for the second time, behind the vacuum concentration, be used for the pre-treatment in (1) step once more; Ultrafiltration second time trapped fluid for collecting is diluted to original volume with pure water, is the depickling hydrolyzed solution, and its pH is 2～3.5, is used for next step processing.
(4) preparation enzyme hydrolyzate
(3) step finish after, the depickling hydrolyzed solution that (3) step was prepared pumps in the glassed steel reaction vessels, earlier under agitation be warming up to 50～60 ℃, again according to the quality (g) of aspartic protease: the volume of depickling hydrolyzed solution (mL) is than the ratio that is 1: 50～200, in glassed steel reaction vessels, add aspartic protease, carried out the constant temperature enzymic hydrolysis 1～2 hour.After hydrolysis is finished, continue to be warming up to 80～100 ℃, and be incubated 5～15 minutes, the activity that is used to go out and dezymotizes, collecting goes out dezymotizes active liquid.Dezymotize active liquid for going out of collection, just the enzyme hydrolyzate for preparing is used for next step decolouring and handles.
(5) decolouring
After (4) step finished, going out of collecting of (4) step dezymotized active liquid pumps in the activated carbon decolorizing post, decolour, when effusive destainer is colourless till, collect destainer and decolouring waste active carbon post respectively.Destainer for collecting is used for next step neutralizing treatment; Decolouring waste active carbon post for collecting send regeneration of activated carbon company, can utilize after the regeneration again.
(6) neutralization
After (5) step finished, during the destainer that (5) step was collected pumps into and in the still, under agitation add calcium carbonate powders, be used for and the residual sulfuric acid root, till the pH of system value reaches at 5.0～5.5 o'clock.After neutralization is finished, the neutralization reaction liquid pump is gone in the suction filtration machine, carry out the suction filtration first time, collect filtered solution and filter residue for the first time for the first time respectively.For the filter residue of the collecting first time, the pure water with 6～10 times of its volumes washs earlier, removes the useless silk hydrolyzate that is mingled with, and then under equal conditions, carries out the suction filtration second time, collects filtered solution and filter residue for the second time for the second time respectively.For the filtered solution of the collecting second time, merge with the filtered solution of the collecting first time, just prepared neutralizer, be used for next step desalting treatment; The filter residue second time for collecting is calcium sulfate, send cement manufacturing company or plasterboard manufacturing company, as cement additire or manufacturing plasterboard.
(7) desalination
(6) step finish after, according to storng-acid cation exchange resin (i.e. 001 * 7 resin or HZ-016 resin etc.): the volume ratio of the neutralizer that (6) step prepared is 1: 25～50 ratio, earlier neutralizer is pumped in the strong acid cation exchange resin column, at flow velocity is under 2～6 times/hour the condition of resin column volume, carry out desalting treatment, collect demineralised liquid and desalination strong acid cation exchange resin column respectively.Demineralised liquid for collecting is used for next step nanofiltration classification; For the desalination strong acid cation exchange resin column of collecting, pumping into earlier with the isopyknic hydrochloric acid volumetric concentration of desalination strong acid cation exchange resin column is 4～7% hydrochloric acid soln, left standstill 30～60 minutes, pump into the hydrochloric acid volumetric concentration again and be 4～7% hydrochloric acid soln, flow velocity be 2～4 times of strong acid cation exchange resin column volumes/hour condition under, washed 30～60 minutes, at last with pure water wash to pH be till 5.0～5.5 o'clock, collect the hydrochloric acid volumetric concentration respectively and be 4～7% regeneration of hydrochloric acid liquid and pure water washings and through the strong acid cation exchange resin column of manipulation of regeneration.For collect 4～7% dilute hydrochloric acid regenerated liquid and pure water washings, pump into treating pond and carry out neutralizing treatment, back up to standard discharging; Strong acid cation exchange resin column for the process manipulation of regeneration of collecting is the regeneration strong acid cation exchange resin column, can be used for the desalting treatment in (7) step once more.
(8) nanofiltration classification
(7) step finish after, the demineralised liquid that (7) step was collected pumps in the nanofiltration device that molecular weight cut-off is 500～1000Da, is under 0.3～0.6MPa at pressure, carries out the nanofiltration classification, till no nanofiltration filtered solution flows out, collect nanofiltration filtered solution and nanofiltration trapped fluid respectively.Nanofiltration filtered solution for collecting is silk amino acid classification liquid, mainly contains the free amine group acid molecule, is used for vacuum concentration and handles; Nanofiltration trapped fluid to collecting mainly contains a small peptide, is a small peptide classification liquid, is used for vacuum concentration and handles.
(9) vacuum concentration
After (8) step finished, silk amino acid classification liquid and silk small peptide classification liquid that (8) step was collected pumped into respectively in the vacuum decker, were that 0.6～0.9MPa, temperature are under 75～90 ℃ the condition in vacuum tightness respectively, carried out vacuum concentration respectively.Wherein silk amino acid classification liquid is concentrated into amino-acid nitrogen and reaches at 2.0～3.0% o'clock and end, and silk small peptide classification liquid is concentrated into amino-acid nitrogen and reaches at 1.0～1.5% o'clock and end, and collects a silk amino acid concentrated solution and a silk small peptide concentrated solution respectively.For silk amino acid concentrated solution of collecting respectively and silk small peptide concentrated solution, be respectively applied for preparation silk amino acid and silk small peptide concentrated solution goods.
(10) preparation silk amino acid and silk small peptide concentrated solution goods
(9) step finish after, silk amino acid concentrated solution and silk small peptide concentrated solution that (9) step was collected respectively pump into respectively in the blend tank, and respectively according to the silk amino acid concentrated solution: glycerine: hundred mould volume ratios of killing sanitas are 1: 0.1～0.2: 0.003～0.005 ratio; Silk small peptide concentrated solution: glycerine: hundred mould volume ratios of killing sanitas are 1: 0.05～0.1: 0.003～0.005 ratio, under gnotobasis, in silk amino acid concentrated solution and silk small peptide concentrated solution, add glycerine and the hundred mould sanitass that kill respectively, stir respectively, just preparing silk amino acid concentrated solution and the molecular-weight average that molecular-weight average is 150～250Da respectively is 650～1050Da silk small peptide concentrated solution.
After the present invention adopts technique scheme, mainly contain following effect:
(1) the present invention is a raw material with useless silk, and preparation silk small peptide and silk amino acid concentrated solution product can be widely used in fields such as makeup.
(2) adopt steam explosion pre-treatment silk to shorten the operating time, significantly reduce the sulfuric acid consumption, reduced the byproduct calcium sulfate growing amount, help environment protection.
(3) press the technology of diluted acid and aspartic protease associating hydrolysis during production technique adopts, significantly reduce the sulfuric acid consumption, shortened hydrolysis time, the hydrolyzate molecular weight is more even.
(4) realize in the production reuse once more of most of vitriolic is obtained a silk small peptide, two kinds of products of silk amino acid concentrated solution simultaneously, production cost is low, realizes suitability for industrialized production easily, the economic benefit height.
(5) the waste calcium sulfate that produces of the present invention can be used for cement and gypsum board manufacture, and the spent acid solution that the regeneration storng-acid cation exchange resin produces discharges through the back up to standard that neutralizes, and no poisonous and harmful trash discharge is realized cleaner production substantially.
It is feedstock production silk peptide and silk amino acid that technology of the present invention can be applicable to the tussah silk.The product that adopts the inventive method to prepare can be widely used in fields such as food, makeup, medicine, healthcare products and chemical industry through suitable allotment.
Four, embodiment
Below in conjunction with embodiment, further specify the present invention.
Embodiment 1
(1) pre-treatment
With useless silk is raw material, cuts up with a hay cutter into the short silk section that length is 1cm with the chopper silk that will give up earlier, is positioned in the stainless steel autoclave again, and then is connected with high pressure steam generator, forms homemade steam blasting device.Then again according to cutting up with a hay cutter into the quality (g) that length is the short silk section of 1cm: the volume of stainless steel autoclave (mL) is than the ratio that is 1: 10, to lack the silk section earlier adds in the stainless steel autoclave, feed high pressure steam again, till when the still internal pressure reaches 3.0MPa, press butterfly valve in keeping opening after 30 minutes, carry out quick-fried gas disposal, collect the quick-fried silk section of breathing hard.The quick-fried silk section of breathing hard for collecting is used for next step dilute sulphuric acid hydrolysis.
(2) dilute sulphuric acid hydrolysis
(1) step finish after, quick-fried quality (g) of section of breathing hard according to the collection of (1) step: volumetric concentration is that 1% vitriolic volume (mL) is than the ratio that is 1: 10, earlier the quick-fried silk section of breathing hard is positioned in the glassed steel reaction vessels, in glassed steel reaction vessels, add dilute sulphuric acid and closed reactor again, and then be warming up to 130 ℃, at pressure is under the condition of 0.3MPa, is hydrolyzed 2 hours.After hydrolysis is finished, feed water coolant in the reactor interlayer, the question response still is opened baiting valve after being cooled to 40 ℃, and hydrolyzed solution is pumped in the suction filtration machine, carries out suction filtration.Abandon filter residue, collect filtrate.For the filtrate of collecting, promptly the dilute sulphuric acid hydrolyzed solution is used for next step depickling.
(3) depickling
(2) step finish after, go on foot the filtrate of collecting with (2) earlier, by molecular weight cut-off is the ultra-fine filter of 3000Da, at pressure is under the 0.08MPa, carry out the ultrafiltration depickling first time, till when ultrafiltration trapped fluid volume is reduced to original volume 20%, collect filtered solution of ultrafiltration for the first time and the trapped fluid of ultrafiltration for the first time respectively.For the ultrafiltration first time trapped fluid of collecting, replenish pure water to original volume, under equal conditions, carry out the ultrafiltration depickling second time, collect filtered solution of ultrafiltration for the second time and the trapped fluid of ultrafiltration for the second time respectively.For the first time of collecting, the filtered solution of ultrafiltration for the second time, behind the vacuum concentration, be used for the pre-treatment in (1) step once more; Ultrafiltration second time trapped fluid for collecting is diluted to original volume with pure water, is the depickling hydrolyzed solution, and its pH is 2, is used for next step processing.
(4) preparation enzyme hydrolyzate
(3) step finish after, the depickling hydrolyzed solution that (3) step was prepared pumps in the glassed steel reaction vessels, earlier under agitation be warming up to 50 ℃, again according to the quality (g) of aspartic protease: the volume of depickling hydrolyzed solution (mL) is than the ratio that is 1: 50, in glassed steel reaction vessels, add aspartic protease, carried out the constant temperature enzymic hydrolysis 1 hour.After hydrolysis is finished, continue to be warming up to 80 ℃, and be incubated 5 minutes, the activity that is used to go out and dezymotizes, collecting goes out dezymotizes active liquid.Dezymotize active liquid for going out of collection, just the enzyme hydrolyzate for preparing is used for next step decolouring and handles.
(5) decolouring
After (4) step finished, going out of collecting of (4) step dezymotized active liquid pumps in the activated carbon decolorizing post, decolour, when effusive destainer is colourless till, collect destainer and decolouring waste active carbon post respectively.Destainer for collecting is used for next step neutralizing treatment; Decolouring waste active carbon post for collecting send regeneration of activated carbon company, can utilize after the regeneration again.
(6) neutralization
After (5) step finished, during the destainer that (5) step was collected pumps into and in the still, under agitation add calcium carbonate powders, be used for and the residual sulfuric acid root, till the pH of system value reaches at 5.0 o'clock.After neutralization is finished, the neutralization reaction liquid pump is gone in the suction filtration machine, carry out the suction filtration first time, collect filtered solution and filter residue for the first time for the first time respectively.For the filter residue of the collecting first time, the pure water with 6 times of its volumes washs earlier, removes the useless silk hydrolyzate that is mingled with, and then under equal conditions, carries out the suction filtration second time, collects filtered solution and filter residue for the second time for the second time respectively.For the filtered solution of the collecting second time, merge with the filtered solution of the collecting first time, just prepared neutralizer, be used for next step desalting treatment; The filter residue second time for collecting is calcium sulfate, send cement manufacturing company or plasterboard manufacturing company, as cement additire or manufacturing plasterboard.
(7) desalination
(6) step finish after, according to storng-acid cation exchange resin (i.e. 001 * 7 resin or HZ-016 resin etc.): the volume ratio of the neutralizer that (6) step prepared is 1: 25 a ratio, earlier neutralizer is pumped in the strong acid cation exchange resin column, at flow velocity is under 2 times/hour the condition of resin column volume, carry out desalting treatment, collect demineralised liquid and desalination strong acid cation exchange resin column respectively.Demineralised liquid for collecting is used for next step nanofiltration classification; For the desalination strong acid cation exchange resin column of collecting, pumping into earlier with the isopyknic hydrochloric acid volumetric concentration of desalination strong acid cation exchange resin column is 4% hydrochloric acid soln, left standstill 30 minutes, pump into the hydrochloric acid volumetric concentration again and be 4% hydrochloric acid soln, flow velocity be 2 times of strong acid cation exchange resin column volumes/hour condition under, washed 30 minutes, at last with pure water wash to pH be till 5.0 o'clock, collect the hydrochloric acid volumetric concentration respectively and be 4% regeneration of hydrochloric acid liquid, pure water washings and through the strong acid cation exchange resin column of manipulation of regeneration.For collect 4% dilute hydrochloric acid regenerated liquid and pure water washings, pump into treating pond and carry out neutralizing treatment, back up to standard discharging; Strong acid cation exchange resin column for the process manipulation of regeneration of collecting is the regeneration strong acid cation exchange resin column, can be used for the desalting treatment in (7) step once more.
(8) nanofiltration classification
(7) step went on foot the demineralised liquid of collecting with (7) and pumps in the nanofiltration device that molecular weight cut-off is 500Da after finishing, and was under the 0.3MPa at pressure, carried out the nanofiltration classification, till no nanofiltration filtered solution flows out, collected nanofiltration filtered solution and nanofiltration trapped fluid respectively.Nanofiltration filtered solution for collecting is silk amino acid classification liquid, mainly contains the free amine group acid molecule, is used for vacuum concentration and handles; Nanofiltration trapped fluid to collecting mainly contains a small peptide, is a small peptide classification liquid, is used for vacuum concentration and handles.
(9) vacuum concentration
After (8) step finished, silk amino acid classification liquid and silk small peptide classification liquid that (8) step was collected pumped into respectively in the vacuum decker, were that 0.6MPa, temperature are under 75 ℃ the condition in vacuum tightness respectively, carried out vacuum concentration respectively.Wherein silk amino acid classification liquid is concentrated into amino-acid nitrogen and reaches at 2.0% o'clock and end, and silk small peptide classification liquid is concentrated into amino-acid nitrogen and reaches at 1.0% o'clock and end, and collects a silk amino acid concentrated solution and a silk small peptide concentrated solution respectively.For silk amino acid concentrated solution of collecting respectively and silk small peptide concentrated solution, be respectively applied for preparation silk amino acid and silk small peptide concentrated solution goods.
(10) preparation silk amino acid and silk small peptide concentrated solution goods
(9) step went on foot a silk amino acid concentrated solution and the silk small peptide concentrated solution collected respectively with (9) and pumps into respectively in the blend tank after finishing, and respectively according to the silk amino acid concentrated solution: glycerine: hundred mould volume ratios of killing sanitas are 1: 0.1: 0.003 ratio; Silk small peptide concentrated solution: glycerine: hundred mould volume ratios of killing sanitas are 1: 0.05: 0.003 ratio, under gnotobasis, in silk amino acid concentrated solution and silk small peptide concentrated solution, add glycerine and the hundred mould sanitass that kill respectively, stir respectively, just preparing silk amino acid concentrated solution and the molecular-weight average that molecular-weight average is 150Da respectively is 650Da silk small peptide concentrated solution.
Embodiment 2
A kind of useless silk prepares the method for silk small peptide and silk amino acid, with embodiment 1, wherein:
In (1) step, useless silk is cut up with a hay cutter into the short silk section that length is 2cm, cut up with a hay cutter into length and be the quality of the short silk section of 2cm: the volume ratio of stainless steel autoclave is 1g: 20mL, when the still internal pressure reaches 4.5MPa till, keeps pressing butterfly valve in the unlatching after 45 minutes;
In (2) step, the quality of the quick-fried silk section of breathing hard that (1) step collected: volumetric concentration is that 2% vitriolic volume ratio is 1g: 15mL, is warming up to 140 ℃, is under the condition of 0.37MPa at pressure, be hydrolyzed 3 hours, the question response still is opened baiting valve after being cooled to 50 ℃;
In (3) step, be 4000Da at the molecular weight cut-off of ultra-fine filter, pressure is under the 0.14MPa, when ultrafiltration trapped fluid volume is reduced to original volume 25% till;
In (4) step, under agitation be warming up to 55 ℃, the quality of aspartic protease: the volume ratio of depickling hydrolyzed solution is 1g: 130mL, carries out the constant temperature enzymic hydrolysis 1.5 hours, continues to be warming up to 90 ℃, and is incubated 10 minutes;
In (6) step, till the pH of system value reaches at 5.2 o'clock, with the pure water washing of 8 times of its volumes;
In (7) step, storng-acid cation exchange resin, be that the volume ratio that HZ-016 portions of resin (6) goes on foot the neutralizer of preparing is 1: 37, at flow velocity is under 4 times/hour the condition of resin column volume, pumping into earlier with the isopyknic hydrochloric acid volumetric concentration of desalination strong acid cation exchange resin column is 5.5% hydrochloric acid soln, left standstill 45 minutes, pump into the hydrochloric acid volumetric concentration again and be 5.5% hydrochloric acid soln, flow velocity be 3 times of strong acid cation exchange resin column volumes/hour condition under, washed 45 minutes, at last with pure water wash to pH be till 5.2 o'clock;
In (8) step, the molecular weight cut-off of nanofiltration device is 750Da, and pressure is under the 0.45MPa;
In (9) step, the vacuum tightness of carrying out vacuum concentration is that 0.75MPa, temperature are under 82 ℃ the condition, and wherein silk amino acid classification liquid is concentrated into amino-acid nitrogen and reaches at 2.5% o'clock and end, and silk small peptide classification liquid is concentrated into amino-acid nitrogen and reaches at 1.25% o'clock and end;
In (10) step, silk amino acid concentrated solution: glycerine: hundred mould volume ratios of killing sanitas are 1: 0.15: 0.004 ratio; Silk small peptide concentrated solution: glycerine: hundred mould volume ratios of killing sanitas are 1: 0.08: 0.004 ratio, and just preparing silk amino acid concentrated solution and the molecular-weight average that molecular-weight average is 200Da respectively is 850Da silk small peptide concentrated solution.
Embodiment 3
A kind of useless silk prepares the method for silk small peptide and silk amino acid, with embodiment 1, wherein:
In (1) step, useless silk is cut up with a hay cutter into the short silk section that length is 3cm, cut up with a hay cutter into length and be the quality of the short silk section of 3cm: the volume ratio of stainless steel autoclave is 1g: 30mL, when the still internal pressure reaches 6.0MPa till, keeps pressing butterfly valve in the unlatching after 60 minutes;
In (2) step, the quality of the quick-fried silk section of breathing hard that (1) step collected: volumetric concentration is that 3% vitriolic volume ratio is 1g: 20mL, is warming up to 150 ℃, is under the condition of 0.45MPa at pressure, be hydrolyzed 4 hours, the question response still is opened baiting valve after being cooled to 60 ℃;
In (3) step, be 5000Da at the molecular weight cut-off of ultra-fine filter, pressure is under the 0.2MPa, when ultrafiltration trapped fluid volume is reduced to original volume 30% till;
In (4) step, under agitation be warming up to 60 ℃, the quality of aspartic protease: the volume ratio of depickling hydrolyzed solution is 1g: 200mL, carries out the constant temperature enzymic hydrolysis 2 hours, continues to be warming up to 100 ℃, and is incubated 15 minutes;
In (6) step, till the pH of system value reaches at 5.5 o'clock, with the pure water washing of 10 times of its volumes;
In (7) step, storng-acid cation exchange resin, promptly the volume ratio of the neutralizer prepared of 001 * 7 portions of resin (6) step is 1: 50, at flow velocity is under 6 times/hour the condition of resin column volume, pumping into earlier with the isopyknic hydrochloric acid volumetric concentration of desalination strong acid cation exchange resin column is 7% hydrochloric acid soln, left standstill 60 minutes, pump into the hydrochloric acid volumetric concentration again and be 7% hydrochloric acid soln, flow velocity be 4 times of strong acid cation exchange resin column volumes/hour condition under, washed 60 minutes, at last with pure water wash to pH be till 5.5 o'clock;
In (8) step, the molecular weight cut-off of nanofiltration device is 1000Da, and pressure is under the 0.6MPa;
In (9) step, the vacuum tightness of carrying out vacuum concentration is that 0.9MPa, temperature are under 90 ℃ the condition, and wherein silk amino acid classification liquid is concentrated into amino-acid nitrogen and reaches at 3.0% o'clock and end, and silk small peptide classification liquid is concentrated into amino-acid nitrogen and reaches at 1.5% o'clock and end; In (10) step, silk amino acid concentrated solution: glycerine: hundred mould volume ratios of killing sanitas are 1: 0.2: 0.005 ratio; Silk small peptide concentrated solution: glycerine: hundred mould volume ratios of killing sanitas are 1: 0.1: 0.005 ratio, and just preparing silk amino acid concentrated solution and the molecular-weight average that molecular-weight average is 250Da respectively is 1050Da silk small peptide concentrated solution.
Claims (4)
1. a useless silk prepares the method for silk small peptide and silk amino acid, and concrete steps are as follows:
(1) pre-treatment
With useless silk is raw material, earlier cut up with a hay cutter into the short silk section that length is 1～3cm with the chopper silk that will give up, be positioned over again in the stainless steel autoclave, and then be connected with high pressure steam generator, then again according to cutting up with a hay cutter into the quality that length is the short silk section of 1～3cm: the volume ratio of stainless steel autoclave is the ratio of 1g: 10～30mL, to lack the silk section earlier adds in the stainless steel autoclave, feed high pressure steam again, till when the still internal pressure reaches 3.0～6.0MPa, press butterfly valve in keeping opening after 30～60 minutes, carry out quick-fried gas disposal, collect the quick-fried silk section of breathing hard;
(2) dilute sulphuric acid hydrolysis
(1) step finish after, quick-fried quality of section of breathing hard according to the collection of (1) step: volumetric concentration is that 1～3% vitriolic volume ratio is the ratio of 1g: 10～20mL, earlier the quick-fried silk section of breathing hard is positioned in the glassed steel reaction vessels, in glassed steel reaction vessels, add dilute sulphuric acid and closed reactor again, and then be warming up to 130～150 ℃, at pressure is under the condition of 0.3～0.45MPa, be hydrolyzed 2～4 hours, in the reactor interlayer, feed water coolant, the question response still is opened baiting valve after being cooled to 40～60 ℃, and hydrolyzed solution is pumped in the suction filtration machine, carries out suction filtration, abandon filter residue, collect filtrate;
(3) depickling
(2) step finish after, go on foot the filtrate of collecting with (2) earlier, by molecular weight cut-off is the ultra-fine filter of 3000～5000Da, at pressure is under 0.08～0.2MPa, carry out the ultrafiltration depickling first time, till ultrafiltration trapped fluid volume is reduced to original volume 20～30% o'clock, collect filtered solution of ultrafiltration for the first time and the trapped fluid of ultrafiltration for the first time respectively, for the ultrafiltration first time trapped fluid of collecting, replenish pure water to original volume, under equal conditions, carry out the ultrafiltration depickling second time, collect filtered solution of ultrafiltration for the second time and the trapped fluid of ultrafiltration for the second time respectively;
(4) preparation enzyme hydrolyzate
(3) step finish after, the depickling hydrolyzed solution that (3) step was prepared pumps in the glassed steel reaction vessels, earlier under agitation be warming up to 50～60 ℃, again according to the quality of aspartic protease: the volume ratio of depickling hydrolyzed solution is the ratio of 1g: 50～200mL, in glassed steel reaction vessels, add aspartic protease, carried out the constant temperature enzymic hydrolysis 1～2 hour, continue to be warming up to 80～100 ℃, and be incubated 5～15 minutes, collecting goes out dezymotizes active liquid;
(5) decolouring
After (4) step finished, going out of collecting of (4) step dezymotized active liquid pumps in the activated carbon decolorizing post, decolour, when effusive destainer is colourless till, collect destainer and decolouring waste active carbon post respectively;
(6) neutralization
(5) step finish after, during the destainer that (5) step was collected pumps into and in the still, under agitation add calcium carbonate powders, till the pH of system value reaches at 5.0～5.5 o'clock, the neutralization reaction liquid pump is gone in the suction filtration machine, carry out the suction filtration first time, collect filtered solution and filter residue for the first time for the first time respectively, for the filter residue of the collecting first time, pure water with 6～10 times of its volumes washs earlier, then under equal conditions, carry out the suction filtration second time, collect filtered solution and filter residue for the second time for the second time respectively;
(7) desalination
(6) step finish after, according to storng-acid cation exchange resin, promptly the volume ratio of the neutralizer prepared of (6) step of 001 * 7 resin or HZ-016 portions of resin is 1: 25～50 ratio, earlier neutralizer is pumped in the strong acid cation exchange resin column, at flow velocity is under 2～6 times/hour the condition of resin column volume, carry out desalting treatment, collect demineralised liquid and desalination strong acid cation exchange resin column respectively, for the desalination strong acid cation exchange resin column of collecting, pumping into earlier with the isopyknic hydrochloric acid volumetric concentration of desalination strong acid cation exchange resin column is 4～7% hydrochloric acid soln, left standstill 30～60 minutes, pump into the hydrochloric acid volumetric concentration again and be 4～7% hydrochloric acid soln, flow velocity be 2～4 times of strong acid cation exchange resin column volumes/hour condition under, washed 30～60 minutes, at last with pure water wash to pH be till 5.0～5.5 o'clock, collect the hydrochloric acid volumetric concentration respectively and be 4～7% regeneration of hydrochloric acid liquid, the strong acid cation exchange resin column of pure water washings and process manipulation of regeneration;
(8) nanofiltration classification
(7) step finish after, the demineralised liquid that (7) step was collected pumps in the nanofiltration device that molecular weight cut-off is 500～1000Da, is under 0.3～0.6MPa at pressure, carries out the nanofiltration classification, till no nanofiltration filtered solution flows out, collect nanofiltration filtered solution and nanofiltration trapped fluid respectively;
(9) vacuum concentration
(8) step finish after, silk amino acid classification liquid and silk small peptide classification liquid that (8) step was collected pump in the vacuum decker respectively, be that 0.6～0.9MPa, temperature are under 75～90 ℃ the condition in vacuum tightness respectively, carry out vacuum concentration respectively, wherein silk amino acid classification liquid is concentrated into amino-acid nitrogen and reaches at 2.0～3.0% o'clock and end, silk small peptide classification liquid is concentrated into amino-acid nitrogen and reaches at 1.0～1.5% o'clock only, collects a silk amino acid concentrated solution and a silk small peptide concentrated solution respectively;
(10) preparation silk amino acid and silk small peptide concentrated solution goods
(9) step finish after, silk amino acid concentrated solution and silk small peptide concentrated solution that (9) step was collected respectively pump into respectively in the blend tank, and respectively according to the silk amino acid concentrated solution: glycerine: hundred mould volume ratios of killing sanitas are 1: 0.1～0.2: 0.003～0.005 ratio; Silk small peptide concentrated solution: glycerine: hundred mould volume ratios of killing sanitas are 1: 0.05～0.1: 0.003～0.005 ratio, under gnotobasis, in silk amino acid concentrated solution and silk small peptide concentrated solution, add glycerine and the hundred mould sanitass that kill respectively, stir respectively, just preparing silk amino acid concentrated solution and the molecular-weight average that molecular-weight average is 150～250Da respectively is 650～1050Da silk small peptide concentrated solution.
2. prepare the method for silk small peptide and silk amino acid according to the described a kind of useless silk of claim 1, it is characterized in that:
In (1) step, useless silk is cut up with a hay cutter into the short silk section that length is 1cm, cut up with a hay cutter into length and be the quality of the short silk section of 1cm: the volume ratio of stainless steel autoclave is 1g: 10mL, when the still internal pressure reaches 3.0MPa till, keeps pressing butterfly valve in the unlatching after 30 minutes;
In (2) step, the quality of the quick-fried silk section of breathing hard that (1) step collected: volumetric concentration is that 1% vitriolic volume ratio is 1g: 10mL, is warming up to 130 ℃, is under the condition of 0.3MPa at pressure, be hydrolyzed 2 hours, the question response still is opened baiting valve after being cooled to 40 ℃;
In (3) step, be 3000Da at the molecular weight cut-off of ultra-fine filter, pressure is under the 0.08MPa, when ultrafiltration trapped fluid volume is reduced to original volume 20% till;
In (4) step, under agitation be warming up to 50 ℃, the quality of aspartic protease: the volume ratio of depickling hydrolyzed solution is 1g: 50mL, carries out the constant temperature enzymic hydrolysis 1 hour, continues to be warming up to 80 ℃, and is incubated 5 minutes;
In (6) step, till the pH of system value reaches at 5.0 o'clock, with the pure water washing of 6 times of its volumes;
In (7) step, storng-acid cation exchange resin, promptly the volume ratio of the neutralizer prepared of 001 * 7 portions of resin (6) step is 1: 25, at flow velocity is under 2 times/hour the condition of resin column volume, pumping into earlier with the isopyknic hydrochloric acid volumetric concentration of desalination strong acid cation exchange resin column is 4% hydrochloric acid soln, left standstill 30 minutes, pump into the hydrochloric acid volumetric concentration again and be 4% hydrochloric acid soln, flow velocity be 2 times of strong acid cation exchange resin column volumes/hour condition under, washed 30 minutes, at last with pure water wash to pH be till 5.0 o'clock;
In (8) step, the molecular weight cut-off of nanofiltration device is 500Da, and pressure is under the 0.3MPa;
In (9) step, the vacuum tightness of carrying out vacuum concentration is that 0.6MPa, temperature are under 75 ℃ the condition, and wherein silk amino acid classification liquid is concentrated into amino-acid nitrogen and reaches at 2.0% o'clock and end, and silk small peptide classification liquid is concentrated into amino-acid nitrogen and reaches at 1.0% o'clock and end;
In (10) step, silk amino acid concentrated solution: glycerine: hundred mould volume ratios of killing sanitas are 1: 0.1: 0.003 ratio; Silk small peptide concentrated solution: glycerine: hundred mould volume ratios of killing sanitas are 1: 0.05: 0.003 ratio, and just preparing silk amino acid concentrated solution and the molecular-weight average that molecular-weight average is 150Da respectively is 650Da silk small peptide concentrated solution.
3. prepare the method for silk small peptide and silk amino acid according to the described a kind of useless silk of claim 1, it is characterized in that:
In (1) step, useless silk is cut up with a hay cutter into the short silk section that length is 2cm, cut up with a hay cutter into length and be the quality of the short silk section of 2cm: the volume ratio of stainless steel autoclave is 1g: 20mL, when the still internal pressure reaches 4.5MPa till, keeps pressing butterfly valve in the unlatching after 45 minutes;
In (2) step, the quality of the quick-fried silk section of breathing hard that (1) step collected: volumetric concentration is that 2% vitriolic volume ratio is 1g: 15mL, is warming up to 140 ℃, is under the condition of 0.37MPa at pressure, be hydrolyzed 3 hours, the question response still is opened baiting valve after being cooled to 50 ℃;
In (3) step, be 4000Da at the molecular weight cut-off of ultra-fine filter, pressure is under the 0.14MPa, when ultrafiltration trapped fluid volume is reduced to original volume 25% till;
In (4) step, under agitation be warming up to 55 ℃, the quality of aspartic protease: the volume ratio of depickling hydrolyzed solution is 1g: 130mL, carries out the constant temperature enzymic hydrolysis 1.5 hours, continues to be warming up to 90 ℃, and is incubated 10 minutes;
In (6) step, till the pH of system value reaches at 5.2 o'clock, with the pure water washing of 8 times of its volumes;
In (7) step, storng-acid cation exchange resin, be that the volume ratio that HZ-016 portions of resin (6) goes on foot the neutralizer of preparing is 1: 37, at flow velocity is under 4 times/hour the condition of resin column volume, pumping into earlier with the isopyknic hydrochloric acid volumetric concentration of desalination strong acid cation exchange resin column is 5.5% hydrochloric acid soln, left standstill 45 minutes, pump into the hydrochloric acid volumetric concentration again and be 5.5% hydrochloric acid soln, flow velocity be 3 times of strong acid cation exchange resin column volumes/hour condition under, washed 45 minutes, at last with pure water wash to pH be till 5.2 o'clock;
In (8) step, the molecular weight cut-off of nanofiltration device is 750Da, and pressure is under the 0.45MPa;
In (9) step, the vacuum tightness of carrying out vacuum concentration is that 0.75MPa, temperature are under 82 ℃ the condition, and wherein silk amino acid classification liquid is concentrated into amino-acid nitrogen and reaches at 2.5% o'clock and end, and silk small peptide classification liquid is concentrated into amino-acid nitrogen and reaches at 1.25% o'clock and end;
In (10) step, silk amino acid concentrated solution: glycerine: hundred mould volume ratios of killing sanitas are 1: 0.15: 0.004 ratio; Silk small peptide concentrated solution: glycerine: hundred mould volume ratios of killing sanitas are 1: 0.08: 0.004 ratio, and just preparing silk amino acid concentrated solution and the molecular-weight average that molecular-weight average is 200Da respectively is 850Da silk small peptide concentrated solution.
4. prepare the method for silk small peptide and silk amino acid according to the described a kind of useless silk of claim 1, it is characterized in that:
In (1) step, useless silk is cut up with a hay cutter into the short silk section that length is 3cm, cut up with a hay cutter into length and be the quality of the short silk section of 3cm: the volume ratio of stainless steel autoclave is 1g: 30mL, when the still internal pressure reaches 6.0MPa till, keeps pressing butterfly valve in the unlatching after 60 minutes;
In (2) step, the quality of the quick-fried silk section of breathing hard that (1) step collected: volumetric concentration is that 3% vitriolic volume ratio is 1g: 20mL, is warming up to 150 ℃, is under the condition of 0.45MPa at pressure, be hydrolyzed 4 hours, the question response still is opened baiting valve after being cooled to 60 ℃;
In (3) step, be 5000Da at the molecular weight cut-off of ultra-fine filter, pressure is under the 0.2MPa, when ultrafiltration trapped fluid volume is reduced to original volume 30% till;
In (4) step, under agitation be warming up to 60 ℃, the quality of aspartic protease: the volume ratio of depickling hydrolyzed solution is 1g: 200mL, carries out the constant temperature enzymic hydrolysis 2 hours, continues to be warming up to 100 ℃, and is incubated 15 minutes;
In (6) step, till the pH of system value reaches at 5.5 o'clock, with the pure water washing of 10 times of its volumes;
In (7) step, storng-acid cation exchange resin, promptly the volume ratio of the neutralizer prepared of 001 * 7 portions of resin (6) step is 1: 50, at flow velocity is under 6 times/hour the condition of resin column volume, pumping into earlier with the isopyknic hydrochloric acid volumetric concentration of desalination strong acid cation exchange resin column is 7% hydrochloric acid soln, left standstill 60 minutes, pump into the hydrochloric acid volumetric concentration again and be 7% hydrochloric acid soln, flow velocity be 4 times of strong acid cation exchange resin column volumes/hour condition under, washed 60 minutes, at last with pure water wash to pH be till 5.5 o'clock;
In (8) step, the molecular weight cut-off of nanofiltration device is 1000Da, and pressure is under the 0.6MPa;
In (9) step, the vacuum tightness of carrying out vacuum concentration is that 0.9MPa, temperature are under 90 ℃ the condition, and wherein silk amino acid classification liquid is concentrated into amino-acid nitrogen and reaches at 3.0% o'clock and end, and silk small peptide classification liquid is concentrated into amino-acid nitrogen and reaches at 1.5% o'clock and end;
In (10) step, silk amino acid concentrated solution: glycerine: hundred mould volume ratios of killing sanitas are 1: 0.2: 0.005 ratio; Silk small peptide concentrated solution: glycerine: hundred mould volume ratios of killing sanitas are 1: 0.1: 0.005 ratio, and just preparing silk amino acid concentrated solution and the molecular-weight average that molecular-weight average is 250Da respectively is 1050Da silk small peptide concentrated solution.
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| CN105155254A (en) * | 2015-10-19 | 2015-12-16 | 耿云花 | Decoloration method for yak hairs |
| CN105648008A (en) * | 2016-01-04 | 2016-06-08 | 山东润牧生物科技有限公司 | Feeding silk antibacterial peptide preparation and preparation method thereof |
| CN106048766A (en) * | 2016-05-27 | 2016-10-26 | 东莞市联洲知识产权运营管理有限公司 | Anti-corrosive granulation-promoting fabric containing silk protein and preparation method thereof |
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