CN104594041A - Biodegradable additive for improving property of PVA-substituted sizing agent - Google Patents
Biodegradable additive for improving property of PVA-substituted sizing agent Download PDFInfo
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Abstract
The invention relates to a biodegradable additive for improving the property of a PVA-substituted sizing agent. The biodegradable additive is prepared from the following steps: by adopting agricultural side products and wastes as materials, obtaining a biodegradable mixture by alkaline extraction, and preparing the additive based on the agricultural side products and the wastes; or adopting anhydride (acetic anhydride, butanedioic anhydride and the like), unsaturated polar monomers (crylic acid, acrylonitrile, styrene and derivative and the like) to modify the additive based on the agricultural side products and the wastes, and preparing the modified additive based on the agricultural side products and the wastes; or adopting biodegradable polyhydric alcohol or polyhydric alcohol amine as the materials and preparing a plasticizing additive based on the agricultural side products and the wastes together with the additive based on the agricultural side products and the wastes. The biodegradable additive has the advantages that the sizing property of the biodegradable textile sizing agent for cotton yarns, polyester, cotton-polyester blended yarns and other blended yarn threads can be improved, and simultaneously the degradability of the novel sizing agent is not weakened, so that the biodegradable additive is a green sizing-agent additive with low preparation cost and excellent biodegradability.
Description
Technical field
The present invention relates to a kind of biodegradable auxiliary agent substituting size performance for improving PVA, belonging to technical field of textile auxiliary agent.
Background technology
Warp sizing is step indispensable in textile weaving process.The existing all kinds of loom of China about 1,100,000, the annual slurry consumed has reached 550,000 tons.In addition, the number of units of high speed shuttleless loom, just to be greater than the speed of 10,000 every year in increase, more facilitates the demand to slurry.Polyvinyl alcohol (PVA) is due to its excellent film forming, adhesiveness and desizability, and be use the spinning sizing agent the widest, cost performance is the highest at present, be all the first-selection of terylene and polyester cotton blended yarn starching all the time.At present, the occupation rate of PVA slurry on global TEXTILE CHEMICALS market is 2.5%, and annual sales amount is about 5,000,000,000 dollars.But the chemical constitution of PVA is very stable, and in activated sludge, the degradation rate of 300 days is only 15%-25%, therefore can produce the waste water of a large amount of difficult degradation in desizing processes.Some European countries have prohibited the use of PVA slurry at present.In addition, as spinning sizing agent, PVA 23-28 unit/kilogram about, selling at exorbitant prices.
In order to substitution for PVA slurry, have some and research and propose use natural polymer base material for textile sizing, mainly comprise modified starch and protein two class material.Starch is the normal studied natural macromolecular for substitution for PVA.But even if use various chemical monomer and additive to carry out modification to starch, the sizing performance of gained slurry still cannot be equal to PVA.Protein is the novel slurry starting recently to receive publicity.When not using additive, protein size, comprises soybean protein, wheat gluten and chicken feather keratin, can obtain the starch finishing effect similar to PVA, but be far inferior to commercially available PVA in the test of laboratory on industrial weave effect.By effectively regulating and controlling the first order molecular structure of macromolecular chain and the secondary structure of protein or modified starch or recombinate, it is the key point improving protein, modified starch sizing performance.
Can to protein carry out secondary structure regulation and control efficient, at a low price, eco-friendly sizing aids and method of modifying be not yet in the news.Protein is carried out to the transformation of primary structure, such as chemical graft, have been reported.In patent US005208075A, adopt protein and the polymerization of vinyl monomer such as soybean protein, casein, gelatin, prepare grafted protein chylema material.But this patent protein size used is expensive.Wherein, soybean protein be 23-30 unit/kilogram, casein be 60-115 unit/kilogram, all higher than the price of PVA.This patent does not relate to the regulation and control to secondary protein structure.
Conventional agricultural byproducts and discarded object as shown in table 1.Agricultural by product and discarded object are rich in the compositions such as protein, starch, grease, alcohol and carbohydrate.Such as, protein containing 25%-30% in maize alcohol stillage, the carbohydrate of 35%-50%; Protein containing 75%-85% in glutelin, the starch of 15%-20%; Protein containing 45%-50% in soybean meal, the carbohydrate of 30%-35%, the starch of 5%, the grease of 0.5%-1%; Protein containing 85%-90% in bird filoplume and a small amount of grease.Wherein the fatty acid ester that generates of grease, alcohol, cellulose, hemicellulose, lignin, fat saponification and Bio-surfactant can improve the performance of spinning sizing agent, if serous coat mechanical performance, slurry are to adhesiveness, the ABRASION RESISTANCE of sizing yarn, the ability of coating filoplume of warp thread, also can not reduce the destarch performance of slurry and the degradability of desized wastewater simultaneously.
Table 1 part agricultural by product and discarded object
The spinning paste adjuvant cost deriving from agricultural by product and discarded object is low, biodegradability good, has good compatibility with bio-based slurry.Along with the extensive exploitation of bio-fuel, edible alcohol and edible oil, all kinds of low price byproduct, as the plant grain/dregs of rice/cake etc., produces thereupon in a large number.Such as, such as the annual production of spirit stillage of domestic alcohol by-product is 1,500 ten thousand tons, and price is 250-850 yuan/ton; Whole world starch byproduct such as the annual production of wheat bran is 2 to 3 hundred million tons, and price is 1400-1900 yuan/ton; The annual production of domestic oil plant byproduct soybean meal is about 4,000 ten thousand tons, and price is 3700-4100 yuan/ton; Bird filoplume is 2,000,000 tons as the global annual production of domestic fowl farming discarded object, and price is almost nil.Therefore the textile auxiliary cost extracted from agricultural by product or discarded object is lower.But, use this kind of material to have no precedent concrete report as spinning paste adjuvant.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of biodegradable auxiliary agent substituting size performance for improving PVA is provided, the sizing performance of Biodegradable spinning sizing agent to cotton yarn, terylene, polyester cotton blending and other blended yarn can be improved, originate extensively, preparation cost is low, degradable green.
According to technical scheme provided by the invention, the described biodegradable auxiliary agent substituting size performance for improving PVA, is characterized in that, adopts following processing step to prepare:
(1) select alcohol by-product, starch byproduct, oil plant byproduct or the waste and old fur of animal as raw material, raw material are mixed with the urea liquid of 1 ~ 8mol/L, and adds the reductant of raw material quality 0.1 ~ 20%, obtain mixed solution; Wherein, the mass percent that raw material are shared in mixed solution is 1% ~ 30%;
(2) adopt mass percentage concentration be 0.5% ~ 50% pH value to 6 ~ 12 of mixed solution that obtain of sodium hydroxide solution regulating step (1), 20 ~ 90 DEG C of insulations 1 ~ 24 hour;
(3) mixture step (2) obtained through centrifugal or solids removed by filtration residue, then regulates pH to 7 ~ 8 with the hydrochloric acid of concentration 37% or acetum, obtains the auxiliary agent of agricultural by product and discarded object base.
Further, further comprising the steps of: to obtain to step (3) polyalcohol or the polyhydric alcohol amine that add auxiliary agent quality 1% ~ 30% in the auxiliary agent of agricultural by product and discarded object base, with sodium hydroxide solution adjust ph to 6 ~ 12 that mass percentage concentration is 0.5% ~ 50%, then 20 ~ 90 DEG C of heating 0.5 ~ 2 hour; Filters solid residue, with hydrochloric acid or acetum adjustment pH to 7 ~ 8 of concentration 37%, obtains plasticizing adjuvant.
Further, further comprising the steps of: the modified monomer adding auxiliary agent quality 1% ~ 200% in the agricultural by product obtained to step (3) and the auxiliary agent of discarded object base, adopt sodium carbonate liquor adjust ph to 8 ~ 12 of mass percentage concentration 0.5% ~ 50%, 40 ~ 70 DEG C of agitating heating 0.5 ~ 4 hour, obtain modified agricultural by product and discarded object base auxiliary agent; Described modified monomer adopts acrylonitrile, acetic anhydride or succinic anhydride.
Further, further comprising the steps of: in the agricultural by product obtained to step (3) and the auxiliary agent of discarded object base, slowly to drip the potassium peroxydisulfate of auxiliary agent quality 0.005%, the sodium hydrogensulfite of 0.002% and the unsaturated polar monomer of 10%-30%, 50 ~ 90 DEG C of agitating heating 1 ~ 4 hour, obtain modified agricultural by product and discarded object base auxiliary agent; The dripping quantity of described potassium peroxydisulfate is 0.005 ~ 0.01% of auxiliary agent quality, and sodium hydrogensulfite dripping quantity is 0.002 ~ 0.004% of auxiliary agent quality, and the dripping quantity of acrylic monomer is 10% ~ 30% of auxiliary agent quality.
Further, described step (1) and step (2) replace by following steps: select alcohol by-product, starch byproduct, oil plant byproduct or the waste and old fur of animal as raw material, the sodium hydroxide solution being 0.5% ~ 50% by raw material and mass percentage concentration mixed, 20 ~ 90 DEG C of insulations 1 ~ 24 hour.
Further, described alcohol by-product is corn, Chinese sorghum or rice vinasse; Described starch byproduct is maize pulp, Gluten, wheat bran, rice rice bran, beans/coarse cereal vermicelli byproduct; Described oil plant byproduct is dregs of beans or cake, cotton dregs or cake, rapeseed dregs or cake, the mustard dregs of rice or cake, sesame seed meal or cake, peanut meal or cake, corn germ cake or cake, sunflower seed dregs or cake, prickly ash seed dregs or cake, leached tea oil slag or cake, castor seed meal or cake, flaxseed meal or cake, hemp seed meal or cake, palm kernel meal or cake or soya-bean oil; The waste and old fur of described animal is bird filoplume, Leather Waste, wool or pig hair.
Further, described reductant is vulcanized sodium, sodium pyrosulfite, sodium hydrogensulfite, sodium sulfite, cysteine, mercaptoethanol or dithiothreitol (DTT).
Further, described polyalcohol or polyhydric alcohol amine are glycerol, triethanolamine or diethanol amine.
Further, described acrylic monomer is acrylic acid, styrene or styrene derivative.
Auxiliary agent of the present invention can improve the sizing performance of biodegradable spinning sizing agent to cotton yarn, terylene, polyester cotton blended yarn and other blended yarns, do not weaken the degradability of novel slurry, be the green slurry auxiliary agent that a kind of preparation cost is low, biodegradability is excellent simultaneously.
Accompanying drawing explanation
Fig. 1 is that embodiment 1 Different Alkali is carried dregs of beans base auxiliary agent that condition obtains and affected schematic diagram to soybean protein serous coat tensile property; Wherein, abscissa is the mass percentage concentration of sodium hydroxide solution, and unit is %; Cylindricality 1-1 is tensile strength, and unit is MPa; Cylindricality 1-2 is ductility, and unit is %; Cylindricality 1-3 is work to break, and unit is a kilogram millimeter.
Fig. 2 is that the soybean soya-bean oil base auxiliary agent that obtains of embodiment 2 affects schematic diagram to soybean protein serous coat tensile property; Wherein, abscissa is the addition of soybean soya-bean oil base auxiliary agent, and unit is %; Cylindricality 2-1 is tensile strength, and unit is MPa; Cylindricality 2-2 is ductility, and unit is %; Cylindricality 2-3 is work to break, and unit is a kilogram millimeter.
Fig. 3 be the soybean protein slurry that adds variable concentrations dregs of beans plasticizing adjuvant in embodiment 4 on terylene, polyester-cotton blend fuzzy yarn rate affect schematic diagram; Wherein, ordinate is the filoplume number that length is greater than 2mm; Cylindricality 3-1 is the filoplume number of soybean protein slurry to terylene starching not adding plasticizing adjuvant; Cylindricality 3-2 is the filoplume number of soybean protein slurry to terylene starching of the plasticizing adjuvant of interpolation 10%; Cylindricality 3-3 is the filoplume number of soybean protein slurry to terylene starching of the plasticizing adjuvant of interpolation 20%; Cylindricality 3-4 is the filoplume number of soybean protein slurry to terylene starching of the plasticizing adjuvant of interpolation 30%; Cylindricality 3-5 is the filoplume number of soybean protein slurry to polyester-cotton blend starching of the plasticizing adjuvant of interpolation 10%; Cylindricality 3-6 is the filoplume number of soybean protein slurry to polyester-cotton blend starching of the plasticizing adjuvant of interpolation 10%; Cylindricality 3-7 is the filoplume number of soybean protein slurry to polyester-cotton blend starching of the plasticizing adjuvant of interpolation 20%; Cylindricality 3-8 is the filoplume number of soybean protein slurry to polyester-cotton blend starching of the plasticizing adjuvant of interpolation 30%; Cylindricality 3-9 is the filoplume number of PVA slurry to terylene starching; Cylindricality 3-10 is the filoplume number of PVA slurry to polyester-cotton blend starching.
Fig. 4 is that in embodiment 4, different soybean protein is starched under the different rate of sizing the impact of spun polyester thread intensity; Wherein, abscissa is the terylene rate of sizing, and unit is %; Ordinate is fracture strength, and unit is MPa; Curve 4-1 is not for adding plasticizing adjuvant soybean protein slurry, and curve 4-2 is the soybean protein slurry of interpolation 20% plasticizing adjuvant, and curve 4-3 is PVA slurry.
Fig. 5 is that in embodiment 4, different soybean protein is starched under the different rate of sizing the impact of polyester line strength; Wherein, abscissa is the terylene rate of sizing, and unit is %; Ordinate is fracture strength, and unit is MPa; Curve 5-1 is not for adding plasticizing adjuvant soybean protein slurry, and curve 5-2 is the soybean protein slurry of interpolation 20% plasticizing adjuvant, and curve 5-3 is PVA slurry.
Fig. 6 is that the modified bean pulp auxiliary agent of different degree of substitution in embodiment 6 affects schematic diagram to soybean protein serous coat tensile property; Wherein, abscissa is substitution value, and unit is %; Left side ordinate is intensity, and unit is MPa; Right side ordinate is percentage elongation, and unit is %; Curve 6-1 is intensity, and curve 6-2 is percentage elongation.
Fig. 7 a is the change schematic diagram of chemical oxygen consumption (COC) in biodegradation process in embodiment 8; Wherein, abscissa is activated sludge process number of days; Ordinate is chemical oxygen consumption (COC), and unit is mg/L; Cylindricality 7-1a is the soybean protein slurry of interpolation 20% plasticizing adjuvant, and cylindricality 7-2a is modified starch, and cylindricality 7-3a is PVA slurry.
Fig. 7 b is the change schematic diagram of biological oxygen demand (BOD) on the five in biodegradation process in embodiment 8; Wherein, abscissa is activated sludge process number of days; Ordinate is biological oxygen demand (BOD) on the five, and unit is mg/L; Cylindricality 7-1b is the soybean protein slurry of interpolation 20% plasticizing adjuvant, and cylindricality 7-2b is modified starch, and cylindricality 7-3b is PVA slurry.
Fig. 8 is the variation diagram of soybean protein slurry total nitrogen and the ammonia-nitrogen content in biodegradation process adding 20% plasticizing adjuvant in embodiment 8; Wherein, abscissa is activated sludge process number of days; Left side ordinate is total nitrogen content, and unit is mg/L; Right side ordinate is ammonia-nitrogen content, and unit is mg/L; Curve 8-1 is total nitrogen content, and curve 8-2 is ammonia-nitrogen content.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1: a kind of biodegradable auxiliary agent substituting size performance for improving PVA, adopts following processing step to prepare:
By soybean meal with mass percentage concentration be respectively 0.5%, 1% and 2% sodium hydroxide solution mix with the mass ratio of 1:7.5,90 DEG C heating 1 hour after, by undissolved solid matter elimination; Use 37% salt acid for adjusting pH to 8, obtain dregs of beans base auxiliary agent.
10 grams of soybean proteins are mixed with 90 gram of 0.01% sodium hydroxide solution, 90 DEG C of heating, to stir 30 minutes, use 37% salt acid for adjusting pH to 7, obtain soy bean proteinous soln.Now, dregs of beans auxiliary agent variable concentrations naoh treatment obtained joins in soy bean proteinous soln, and the dregs of beans auxiliary agent that Different Alkali puies forward condition accounts for 5% of soybean protein quality, and uniform stirring 5 minutes, obtains mixed solution.Mixed solution is poured in the mould of polytetrafluorethylecoatings coatings, at room temperature place and dry for 48 hours, form serous coat.As shown in Figure 1, the tensile property of the soybean protein serous coat of the dregs of beans auxiliary agent that 1% naoh treatment obtains is added higher than the serous coat adding the dregs of beans auxiliary agent that other two treatment conditions obtain.
Embodiment 2: a kind of biodegradable auxiliary agent substituting size performance for improving PVA, adopts following processing step to prepare:
(1) by soybean soya-bean oil and mass percentage concentration be 50% sodium hydroxide solution in mass ratio 1:1 mix, 100 DEG C of Heat preservations 3 hours.Use 37% salt acid for adjusting pH to 8, obtain soybean soya-bean oil base auxiliary agent.
The sodium hydroxide solution being 0.01% by 10 grams of soybean proteins and 90 gram mass percentage concentrations mixes, and 90 DEG C add thermal agitation 30 minutes, use 37% salt acid for adjusting pH to 7, obtain soy bean proteinous soln.Now, respectively to adding the soybean soya-bean oil base auxiliary agent being equivalent to soy bean proteinous soln quality 10%, 20% and 40% in soy bean proteinous soln, being warming up to 90 DEG C and uniform stirring 5 minutes, obtaining mixed solution.Mixed solution is poured in the mould of polytetrafluorethylecoatings coatings, at room temperature place 48 hours, form serous coat.Although soybean protein slurry film forming is better, the serous coat formed lacks extensibility, crisp and easily split, and cannot carry out tensile property test.As shown in Figure 2, the tensile property adding the soybean protein serous coat of 20% soybean soya-bean oil base auxiliary agent relative to 10% and 40% addition all higher.
Embodiment 3: a kind of biodegradable auxiliary agent substituting size performance for improving PVA, adopts following processing step to prepare:
For avoiding the ethanolic solution used costly, aqueous slkali can be used to dissolve glutelin and maize alcohol stillage.Glutelin, maize alcohol stillage are mixed with 1:7.5 mass ratio with the alkali lye of mass percentage concentration 0.5% respectively, 90 DEG C of heating after 1 hour, filtration obtains glutelin, maize alcohol stillage lysate, through 37% salt acid for adjusting pH to 8, obtains alkali karst valley protein, maize alcohol stillage base auxiliary agent.
Embodiment 4: a kind of biodegradable auxiliary agent substituting size performance for improving PVA, adopts following processing step to prepare:
The sodium hydroxide solution being 0.5% by soybean meal and mass percentage concentration mixes with the mass ratio of 1:7.5, after 1 hour, by undissolved solid matter elimination, obtains soybean meal extract 90 DEG C of heating.Add the triethanolamine of soybean meal extract quality 30%, stir after 30 minutes, use 37% salt acid for adjusting pH to 8, obtain plasticising dregs of beans auxiliary agent.
The sodium hydroxide solution being 0.01% by 10 grams of soybean proteins and 90 gram mass percentage concentrations mixes, and 90 DEG C add thermal agitation 30 minutes, use 37% salt acid for adjusting pH to 7, obtain soy bean proteinous soln.Now, in soy bean proteinous soln, the plasticising dregs of beans auxiliary agent being equivalent to soy bean proteinous soln quality 0%, 10%, 20%, 30% is added, uniform stirring 5 minutes.Treat that slurry temperature rises to 90 DEG C, starching can be carried out to polyester-cotton blend, terylene spun yarn.Add the soybean protein slurry of triethanolamine plasticising dregs of beans auxiliary agent to the coating effect (Yarn filoplume index variation) of the filoplume of polyester-cotton blend, terylene spun yarn as shown in Figure 3.Add the spun yarn of filoplume amount higher than commercially available PVA slurry sizing of the terylene spun yarn of the soybean protein slurry sizing of 20% plasticizing adjuvant, but well below not adding the spun yarn of original slurry material starching of auxiliary agent; And the filoplume amount adding the polyester-cotton blend spun yarn after the soybean protein slurry sizing of 20% plasticizing adjuvant is starkly lower than the spun yarn of commercially available PVA slurry sizing, also well below the spun yarn of original slurry material starching not adding auxiliary agent.As shown in Figure 4 and Figure 5, along with the raising of the rate of sizing, add the terylene of the soybean protein slurry sizing of 20% auxiliary agent, polyester-cotton blend yarn strength all higher than the similar yarn of unplasticised soybean meal slurry sizing.Further, when the rate of sizing is less than 10%, adds the terylene of the soybean protein slurry sizing of 20% plasticizing adjuvant, the brute force of polyester-cotton blend yarn is all better than commercially available PVA slurry.
Embodiment 5:
After the soybean protein slurry of the interpolation plasticizing adjuvant adopting embodiment 4 to prepare, commercially available PVA slurry, commercially available modified starch 130 slurry carry out starching to terylene, polyester-cotton blend, cotton, high-speed weaving machine PICANOL (plus OMNI 800) weaves with the speed of a motor vehicle of 750r/min.As shown in table 2, compared with PVA and modified starch, add the soybean protein slurry of plasticizing adjuvant at the low 21%-35% of the rate of sizing of terylene, polyester-cotton blend and cotton, but obtain higher weaving efficiency.Compared with PVA and modified starch, the weaving efficiency of soybean protein slurry on cotton yarn adding plasticizing adjuvant exceeds 10% and 62% respectively, and polyester exceeds 5% and 13% respectively.The rate of sizing of soybean protein slurry on spun polyester thread of adding plasticising dregs of beans auxiliary agent is lower than PVA by 47%, and weaving efficiency is low by 27%; Meanwhile, its rate of sizing is lower than modified starch by 58%, and weaving efficiency is high by 52%.
Table 2
Embodiment 6:
The sodium hydroxide solution being 0.5% by soybean meal and mass percentage concentration mixes with the mass ratio of 1:7.5, after 1 hour, by undissolved solid matter elimination, obtains soybean meal extract 90 DEG C of heating.Add acrylonitrile (accounting for 50%, 65%, 75%, 85%, 100% of soybean meal extract quality respectively), stir 2 hours at 70 DEG C.Remove unreacted acrylonitrile monemer by decompression distillation, obtain modified bean pulp auxiliary agent.
Mixed by the sodium hydroxide solution of 10 grams of soybean proteins with 90 gram mass percentage concentrations 0.01%, 90 DEG C add thermal agitation 30 minutes, use 37% salt acid for adjusting pH to 7.Now, join in soy bean proteinous soln by the modified bean pulp auxiliary agent of different degree of substitution, the modified bean pulp auxiliary agent of different degree of substitution accounts for 20% of soybean protein quality, uniform stirring 5 minutes.And pour film forming in Teflon mould into.Serous coat is placed in constant-temperature constant-humidity environment after within 24 hours, drying, test its tensile property.In modified bean pulp auxiliary agent, acrylonitrile substitution value on the impact of soybean protein serous coat tensile strength, percentage elongation as shown in Figure 6.When in modified bean pulp auxiliary agent, acrylonitrile substitution value rises to 11.4 from 4.6, the percentage elongation adding the soybean protein serous coat serous coat of modified bean pulp auxiliary agent is increased to 221% ± 9.8% from 58% ± 0.1%, and serous coat brute force is basically stable at 4.56 ± 0.25 MPas.The tensile strength of commercially available PVA serous coat is 24.3 ± 3.9 MPas, and percentage elongation is 271% ± 14%.In sum, the tensile property adding the soybean protein slurry film of modified bean pulp auxiliary agent is similar to commercially available PVA slurry.
Embodiment 7:
The complexity of destarch is one of standard passing judgment on slurry quality.Table 3 enumerates soybean protein slurry and the PVA slurry destarch effect at different conditions of the interpolation plasticising dregs of beans auxiliary agent on terylene, polyester-cotton fabric.Terylene, the destarch rate of polyester-cotton fabric under the conditions such as different wash temperature, time, bath raio, rinsing bath raio and washing times of the known rate of sizing are different.Under low temperature rinsing condition (20 DEG C), the destarch rate of the soybean protein slurry on terylene, polyester-cotton fabric is far above PVA slurry.The destarch rate of the soybean protein slurry on polyester-mixed cotton cloth reaches 98%, and the PVA destarch rate under same destarch condition is only 82%.Under the rinsing condition of high temperature low wash water (90 DEG C, washing, rinsing bath raio 5:1, rinsing times 1 time), the destarch rate of the soybean protein slurry of the interpolation plasticising dregs of beans auxiliary agent on terylene, polyester-cotton fabric is also far above PVA slurry.On terylene and polyester-cotton fabric, the destarch rate of adding the soybean protein slurry of plasticising dregs of beans auxiliary agent is respectively 94% and 96%, and the destarch rate of PVA under the same terms is 77%.Under the destarch condition of the high temperature high water yield (90 DEG C, washing, rinsing bath raio 5:1 or 10:1, rinsing times 1 or 2 times), the destarch effect of two kinds of slurries is similar, can obtain the destarch rate of more than 95%.As can be seen here, the soybean protein slurry adding plasticising dregs of beans auxiliary agent can obtain high destarch rate under low temperature, low water conditions, can accomplish energy-saving and water-saving.
Table 3
Embodiment 8:
The biodegradability of embodiment 7 agricultural by product and discarded object based sizing auxiliary agent
Biodegradability is one of major advantage of agricultural by product and discarded object base auxiliary agent.Select the soybean protein slurry that with the addition of plasticizing adjuvant of 300ppm, test its unprocessed with through the COD of activated sludge process after 3 days (COD) value and BOD
5(five-day BOD) value, and compare with commercially available PVA slurry.As shown in Fig. 7 a, Fig. 7 b, the soybean protein slurry that with the addition of plasticizing adjuvant before treatment is substantially suitable with the COD value of PVA slurry, and its BOD
5(five-day BOD) value is far away higher than PVA slurry; And the COD value that with the addition of the soybean protein slurry of plasticizing adjuvant after process in 2 days is far below PVA slurry, and BOD5 is still higher than PVA slurry.Have good degradability because soybean protein slurry has been proved to be, the agricultural by product therefore added here and discarded object based sizing auxiliary agent have excellent biological degradability equally.
Nitrogen content is also used to the important indicator judging contaminated wastewater.Show total nitrogen and the ammonia nitrogen amount of plasticising dregs of beans auxiliary agent in this embodiment.As shown in Figure 8, owing to containing protein in plasticising dregs of beans auxiliary agent, its initial nitrogen pool is higher than PVA slurry.But its nitrogen pool just starts when activated sludge is degraded the 1st day to decline, 5 days or 5 days afterwards total values of nitrogen might no longer change.Visible, plasticising dregs of beans auxiliary agent, after biodegradation process, can significantly reduce its nitrogen content, can not cause body eutrophication.
Claims (9)
1. substituting a biodegradable auxiliary agent for size performance for improving PVA, it is characterized in that, adopt following processing step to prepare:
(1) select alcohol by-product, starch byproduct, oil plant byproduct or the waste and old fur of animal as raw material, the urea liquid of raw material with 1 ~ 8 mol/L is mixed, and adds the reductant of raw material quality 0.1 ~ 20%, obtain mixed solution; Wherein, the mass percent that raw material are shared in mixed solution is 1% ~ 30%;
(2) adopt mass percentage concentration be 0.5% ~ 50% pH value to 6 ~ 12 of mixed solution that obtain of sodium hydroxide solution regulating step (1), 20 ~ 90 DEG C of insulations 1 ~ 24 hour;
(3) mixture step (2) obtained through centrifugal or solids removed by filtration residue, then regulates pH to 7 ~ 8 with the hydrochloric acid of concentration 37% or acetum, obtains the auxiliary agent of agricultural by product and discarded object base.
2. the biodegradable auxiliary agent substituting size performance for improving PVA as claimed in claim 1, it is characterized in that: further comprising the steps of: the polyalcohol from auxiliary agent quality 1% ~ 30% to step (3) or the polyhydric alcohol amine that obtain adding in the auxiliary agent of agricultural by product and discarded object base, with sodium hydroxide solution adjust ph to 6 ~ 12 that mass percentage concentration is 0.5% ~ 50%, then 20 ~ 90 DEG C of heating 0.5 ~ 2 hour; Filters solid residue, with hydrochloric acid or acetum adjustment pH to 7 ~ 8 of concentration 37%, obtains plasticizing adjuvant.
3. the biodegradable auxiliary agent substituting size performance for improving PVA as claimed in claim 1, it is characterized in that: further comprising the steps of: the modified monomer adding auxiliary agent quality 1% ~ 200% in the agricultural by product obtained to step (3) and the auxiliary agent of discarded object base, adopt sodium carbonate liquor adjust ph to 8 ~ 12 of mass percentage concentration 0.5% ~ 50%, 40 ~ 70 DEG C of agitating heating 0.5 ~ 4 hour, obtain modified agricultural by product and discarded object base auxiliary agent; Described modified monomer adopts acrylonitrile, acetic anhydride or succinic anhydride.
4. the biodegradable auxiliary agent substituting size performance for improving PVA as claimed in claim 1, it is characterized in that: further comprising the steps of: in the agricultural by product obtained to step (3) and the auxiliary agent of discarded object base, slowly drip the potassium peroxydisulfate of auxiliary agent quality 0.005%, the sodium hydrogensulfite of 0.002% and the unsaturated polar monomer of 10%-30%, 50 ~ 90 DEG C of agitating heating 1 ~ 4 hour, obtain modified agricultural by product and discarded object base auxiliary agent; The dripping quantity of described potassium peroxydisulfate is 0.005 ~ 0.01% of auxiliary agent quality, and sodium hydrogensulfite dripping quantity is 0.002 ~ 0.004% of auxiliary agent quality, and the dripping quantity of unsaturated polar monomer is 10% ~ 30% of auxiliary agent quality.
5. the biodegradable auxiliary agent substituting size performance for improving PVA as claimed in claim 1, it is characterized in that: described step (1) and step (2) replace by following steps: select alcohol by-product, starch byproduct, oil plant byproduct or the waste and old fur of animal as raw material, the sodium hydroxide solution being 0.5% ~ 50% by raw material and mass percentage concentration mixed, 20 ~ 90 DEG C of insulations 1 ~ 24 hour.
6. the biodegradable auxiliary agent substituting size performance for improving PVA as claimed in claim 1, is characterized in that: described alcohol by-product is corn, Chinese sorghum or rice vinasse; Described starch byproduct is maize pulp, Gluten, wheat bran, rice rice bran, beans/coarse cereal vermicelli byproduct; Described oil plant byproduct is dregs of beans or cake, cotton dregs or cake, rapeseed dregs or cake, the mustard dregs of rice or cake, sesame seed meal or cake, peanut meal or cake, corn germ cake or cake, sunflower seed dregs or cake, prickly ash seed dregs or cake, leached tea oil slag or cake, castor seed meal or cake, flaxseed meal or cake, hemp seed meal or cake, palm kernel meal or cake or soya-bean oil; The waste and old fur of described animal is bird filoplume, Leather Waste, wool or pig hair.
7. the biodegradable auxiliary agent substituting size performance for improving PVA as claimed in claim 1, is characterized in that: described reductant is vulcanized sodium, sodium pyrosulfite, sodium hydrogensulfite, sodium sulfite, cysteine, mercaptoethanol or dithiothreitol (DTT).
8. the biodegradable auxiliary agent substituting size performance for improving PVA as claimed in claim 2, is characterized in that: described polyalcohol or polyhydric alcohol amine are glycerol, triethanolamine or diethanol amine.
9. the biodegradable auxiliary agent substituting size performance for improving PVA as claimed in claim 4, is characterized in that: described unsaturated polar monomer is acrylic acid, styrene or styrene derivative.
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| CN201510010518.8A Withdrawn CN104594041A (en) | 2015-01-08 | 2015-01-08 | Biodegradable additive for improving property of PVA-substituted sizing agent |
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| CN (1) | CN104594041A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105088424A (en) * | 2015-07-08 | 2015-11-25 | 立天集团有限公司 | Method for extracting regenerated cotton from waste cloth corner |
| CN105088583A (en) * | 2015-07-08 | 2015-11-25 | 立天集团有限公司 | Ecological sizing method for linen viscose blended yarn |
| CN110028699A (en) * | 2019-04-15 | 2019-07-19 | 青岛科技大学 | A kind of biodegradation method of cross-linked polyester |
-
2015
- 2015-01-08 CN CN201510010518.8A patent/CN104594041A/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105088424A (en) * | 2015-07-08 | 2015-11-25 | 立天集团有限公司 | Method for extracting regenerated cotton from waste cloth corner |
| CN105088583A (en) * | 2015-07-08 | 2015-11-25 | 立天集团有限公司 | Ecological sizing method for linen viscose blended yarn |
| CN105088583B (en) * | 2015-07-08 | 2017-01-18 | 立天集团有限公司 | Ecological sizing method for linen viscose blended yarn |
| CN105088424B (en) * | 2015-07-08 | 2017-08-25 | 立天集团有限公司 | A kind of method that regeneration cotton is extracted in useless cloth angle |
| CN110028699A (en) * | 2019-04-15 | 2019-07-19 | 青岛科技大学 | A kind of biodegradation method of cross-linked polyester |
| CN110028699B (en) * | 2019-04-15 | 2022-09-23 | 青岛科技大学 | Biodegradation method of crosslinked polyester |
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Application publication date: 20150506 |