Background technology
Fibrous raw material shortage, the higher three big problems with environmental pollution being seriously China's paper industry and facing of energy resource consumption,And within considerable time from now on, govern optimum, the sound development of paper industry to a certain extent.Over nearly 20 years, China's paperWith 79,800,000 tons that paper pulp gross annual output amount has risen to 2008 from 5,400,000 tons of 1985, production occupies the second in the world, butYear per capita paper and Board consumption figure be only 1/10th of developed country.Along with the fast development of Chinese society Yu national economy,Still can quickly increase the demand of paper, China's paper industry also has huge development space.How papermaking is solved in developmentThe raw material of industry and pollution problem, be China's paper industry road of walking sustainable development, be economy and society development mustAsk.Promoting overall technology and the equipment of paper industry, the utilization rate improving raw material is polluted from the source of production process abatementThe discharge capacity of thing, meanwhile, actively taking effective end treatment measure is that there is lack of raw materials and pollution problem for solution paper industryEffective way.
Fibrous raw material used by papermaking includes timber, wheat straw, Caulis et Folium Oryzae, cotton stalk, phragmites communis, bamboo, bamboo grass, bagasse etc.The process that slurrying is made by chemistry, the method for physics makes frotation come.According to the combination that this two classes method is different, createThe various paper pulp such as chemical pulp, mechanical pulp, chemi-mechanical pulp, semi-chemical pulp.
The production of current domestic paper pulp, whether chemical method or Physical still with sodium hydroxide be main matching surface activityThe auxiliary agents such as agent carry out steaming and decocting to fibrous raw material, by the effect of auxiliary agent, accelerate the diffusion of sodium hydroxide, osmosis, make fiberRaw material deliquescing, it is simple to the process of later operation, and shorten mixing time.
Summary of the invention
The technical problem that present invention mainly solves: in current pulp making process, conventional paper pulp auxiliary agent is often adoptedWith anion surfactant, although make fibrous raw material deliquescing, shorten mixing time, but be typically weak to highly basic, have impact onIts dispersion, chemosmotic present situation, it is provided that one extracts to obtain drake feather protein powder from drake feather, more molten with sodium hydroxide solutionSolving and filter, after filtrate being regulated with hydrochloric acid, stir and filter to solid, filtering residue dries to obtain protein modified dose, and with triethanolamine, ringOxygen chloropropane, sodium bicarbonate and deionized water mixing, add glutaraldehyde cross-linking agent, and insulation reaction obtains reactant, is eventually addingThe surfactant prepared, magnesium sulfate, sodium carbonate and laccase, i.e. can get the preparation method of clean type pulping agents.The partyMethod raw material is simple and easy to get, and reaction condition is gentle, the surfactant prepared and protein modified dose compound can be notable in highly basicReduce interfacial tension, the infiltration to fiber, diffusion, the resistance to highly basic of prepared pulping agents can be strengthened, cut down in paper-making processThe discharge capacity of pollutant, green cleaning, improve work efficiency,.
In order to solve above-mentioned technical problem, the technical solution adopted in the present invention is:
(1) 200～250g Radix Platycodoniss, 50～80g bean cake, 60～100g Saponaria officinalis and 80～120g soapbarks are weighed respectively, choppingRear mixing, is mixed mixture with mass fraction 90% ethanol by solid-to-liquid ratio 1:5, and is heated to reflux state, carries out backflow extraction50～70min, extraction filters to get filtrate after terminating, and filtrate is put in vacuum concentration pot and subtracts under 0.08～0.09MPaPressure concentrates, until being concentrated into the 15～20% of original volume, obtaining concentrated solution, being surfactant, standby；
(2) weigh 50～80g drake feathers, first drake feather be immersed in mass fraction 15% hydrochloric acid solution by solid-to-liquid ratio 1:5, soak 1～Filtering residue is filtered to obtain, by filtering residue again by solid-to-liquid ratio 1:8 and the mixing of mass fraction 20% sodium sulfite solution, and by mixture after 2hIn 180～200W microwave treatment 20～25min, filter after process and remove filtrate, filtering residue is put in baking oven, at 50～70 DEG CIt is dried 8～10h, grinds after drying, sieve to obtain 80～100 mesh drake feather protein powders；
(3) it is that 10g/L sodium hydroxide solution mixes by the protein powder of above-mentioned preparation by solid-to-liquid ratio 1:10 and concentration, fills after mixingEnter in beaker, and move in water-bath stirring and dissolving at 60～80 DEG C, filter, remove insoluble matter, by filtrate with mass fraction 15%Salt acid for adjusting pH is 3.5～4.0, and stirring filters to obtain filtering residue after separating out completely to solid, puts in baking oven dry at 50～60 DEG CDry 5～6h, obtain protein modified dose；
(4) above-mentioned protein modified dose and triethanolamine, epoxychloropropane, sodium hydroxide 3:2:2:1 in mass ratio is mixed, put intoIn flask, adding deionized water by solid-to-liquid ratio 1:2 in flask, mechanical agitation is completely dissolved to solid, moves in water-bath, heats upTo 70～90 DEG C, adding gross mass 2～5% glutaraldehyde in flask, insulated and stirred reaction 3～5h, reaction is cooled to room after terminatingTemperature, obtains reactant；
(5) agent by weight, chooses 5～8 parts of standby surfactants of step (1) respectively, 15～25 parts of above-mentioned reactants,30～40 parts of magnesium sulfate, 10～15 parts of sodium carbonate and 6～8 parts of laccases, mechanical agitation 30～40min after mixing, i.e. available clearClean type pulping agents.
The application process of the present invention is: in pulp making process, and the clean type pulping agents present invention prepared addsIn fibrous raw material (by phragmites communis pulverization process), the most every 1～2t fibrous raw material in add 8～15kg pulping agents, be sufficiently stirred forUniformly, make paper by paper flow process processed, after testing, owing to the addition of the pulping agents that the present invention prepares so that black after preparationLiquid generation amount reduces more than 80% than traditional pulp-making method, can be in large-scale application.
The invention has the beneficial effects as follows:
(1) raw material of the present invention is simple and easy to get, and reaction condition is gentle, without special process equipment during operation, simplifiesPreparation technology；
(2) present invention prepares surfactant and protein modified dose compound can significantly reduce interfacial tension in highly basic, canTo strengthen the infiltration to fiber, diffusion, the resistance to highly basic of prepared pulping agents, cut down the discharge capacity of pollutant in paper-making process,Green cleaning.
Detailed description of the invention
Weigh 200～250g Radix Platycodoniss, 50～80g bean cake, 60～100g Saponaria officinalis and 80～120g soapbarks the most respectively,Mix after chopping, mixture is mixed with mass fraction 90% ethanol by solid-to-liquid ratio 1:5, and is heated to reflux state, refluxExtraction 50～70min, extraction filters to get filtrate after terminating, puts into filtrate in vacuum concentration pot to enter under 0.08～0.09MPaRow concentrating under reduced pressure, until being concentrated into the 15～20% of original volume, obtaining concentrated solution, being surfactant, standby；Then 50 are weighed～80g drake feather, first drake feather is immersed in mass fraction 15% hydrochloric acid solution by solid-to-liquid ratio 1:5, after soaking 1～2h, filters to obtain filterSlag, by solid-to-liquid ratio 1:8 and the mixing of mass fraction 20% sodium sulfite solution and mixture is micro-180～200W again by filtering residueRipple processes 20～25min, filters and removes filtrate, put into by filtering residue in baking oven after process, is dried 8～10h, does at 50～70 DEG CGrind after dry, sieve to obtain 80～100 mesh drake feather protein powders；Next by the protein powder of above-mentioned preparation by solid-to-liquid ratio 1:10 withConcentration is the mixing of 10g/L sodium hydroxide solution, loads in beaker after mixing, and move into water-bath is stirred at 60～80 DEG C moltenSolving, filter, remove insoluble matter, be 3.5～4.0 by filtrate mass fraction 15% salt acid for adjusting pH, stirring to solid separates out completelyAfter filter to obtain filtering residue, put in baking oven at 50～60 DEG C, to be dried 5～6h, obtain protein modified dose；Subsequently by above-mentioned protein modifiedAgent and triethanolamine, epoxychloropropane, sodium hydroxide 3:2:2:1 in mass ratio mixing, put in flask, add and press in flaskSolid-to-liquid ratio 1:2 adds deionized water, and mechanical agitation is completely dissolved to solid, moves in water-bath, is warming up to 70～90 DEG C, to flaskMiddle addition gross mass 2～5% glutaraldehyde, insulated and stirred reaction 3～5h, reaction is cooled to room temperature after terminating, and obtains reactant；FinallyAgent by weight, chooses 5～8 parts of above-mentioned standby surfactants, 15～25 parts of above-mentioned reactants, 30～40 parts of sulfur respectivelyAcid magnesium, 10～15 parts of sodium carbonate and 6～8 parts of laccases, mechanical agitation 30～40min after mixing, i.e. can get clean type slurrying and helpAgent.
Example 1
Weigh 200g Radix Platycodonis, 50g bean cake, 60g Saponaria officinalis and 80g soapbark the most respectively, mix after chopping, by mixture by solidLiquor ratio 1:5 mixes with mass fraction 90% ethanol, and is heated to reflux state, carries out backflow extraction 50min, extracts mistake after terminatingFilter to obtain filtrate, filtrate is put into vacuum concentration pot carries out under 0.08MPa concentrating under reduced pressure, until being concentrated into the 15% of original volume,Obtain concentrated solution, be surfactant, standby；Then weigh 50g drake feather, first drake feather is immersed in quality by solid-to-liquid ratio 1:5 and dividesIn several 15% hydrochloric acid solutions, after soaking 1h, filter to obtain filtering residue, by filtering residue again by solid-to-liquid ratio 1:8 and mass fraction 20% sodium sulfiteSolution mixes, and by mixture in 180W microwave treatment 20min, filters and remove filtrate, put into by filtering residue in baking oven after process,It is dried 8h at 50 DEG C, grinds after drying, sieve to obtain 80 mesh drake feather protein powders；Next by the protein powder of above-mentioned preparation by solidLiquor ratio 1:10 is that 10g/L sodium hydroxide solution mixes with concentration, loads in beaker after mixing, and moves in water-bath and stir at 60 DEG CMixing dissolving, filter, remove insoluble matter, be 3.5 by filtrate mass fraction 15% salt acid for adjusting pH, stirring to solid separates out completelyAfter filter to obtain filtering residue, put in baking oven at 50 DEG C, to be dried 5h, obtain protein modified dose；Subsequently by above-mentioned protein modified dose and three secondHydramine, epoxychloropropane, sodium hydroxide 3:2:2:1 in mass ratio mixes, and puts in flask, adds by solid-to-liquid ratio 1 in flask:2 add deionized water, and mechanical agitation is completely dissolved to solid, move in water-bath, are warming up to 70 DEG C, add gross mass in flask2% glutaraldehyde, insulated and stirred reaction 3h, reaction is cooled to room temperature after terminating, obtains reactant；Last agent by weight, selects respectivelyTake 5 parts of above-mentioned standby surfactants, 15 parts of above-mentioned reactants, 30 parts of magnesium sulfate, 10 parts of sodium carbonate and 6 parts of laccases, mixingRear mechanical agitation 30min, i.e. can get clean type pulping agents.
This example operation is easy, and in pulp making process, the clean type pulping agents present invention prepared adds fiberIn raw material (by phragmites communis pulverization process), wherein every 1t fibrous raw material adds 8kg pulping agents, stir, by systemPaper flow process makes paper, after testing, owing to the addition of the pulping agents that the present invention prepares so that after preparation, black liquor generation amount is than passingControlling slurry processes reduces 85%, can be in large-scale application.
Example 2
Weigh 230g Radix Platycodonis, 65g bean cake, 80g Saponaria officinalis and 100g soapbark the most respectively, mix after chopping, mixture is pressedSolid-to-liquid ratio 1:5 mixes with mass fraction 90% ethanol, and is heated to reflux state, carries out backflow extraction 60min, after extraction terminatesFilter to get filtrate, filtrate is put into vacuum concentration pot carries out under 0.085MPa concentrating under reduced pressure, until being concentrated into original volume18%, obtain concentrated solution, be surfactant, standby；Then weigh 65g drake feather, first drake feather is immersed in matter by solid-to-liquid ratio 1:5In amount mark 15% hydrochloric acid solution, after soaking 1.5h, filter to obtain filtering residue, by filtering residue again by solid-to-liquid ratio 1:8 and mass fraction 20% sulfurousAcid hydrogen sodium solution mixing, and by mixture in 190W microwave treatment 23min, filter after process and remove filtrate, filtering residue is put into bakingIn case, at 60 DEG C, it is dried 9h, grinds after drying, sieve to obtain 90 mesh drake feather protein powders；Next by the albumen of above-mentioned preparationPowder is that 10g/L sodium hydroxide solution mixes by solid-to-liquid ratio 1:10 and concentration, loads in beaker after mixing, and move in water-bathStirring and dissolving at 70 DEG C, filters, and removes insoluble matter, is 3.8 by filtrate mass fraction 15% salt acid for adjusting pH, and stirring is to solidFilter to obtain filtering residue after separating out completely, put into and baking oven is dried at 55 DEG C 5.5h, obtain protein modified dose；Subsequently above-mentioned albumen is changedProperty agent and triethanolamine, epoxychloropropane, sodium hydroxide 3:2:2:1 in mass ratio mixing, put in flask, in flask addAdding deionized water by solid-to-liquid ratio 1:2, mechanical agitation is completely dissolved to solid, moves in water-bath, is warming up to 80 DEG C, in flaskAdding gross mass 4% glutaraldehyde, insulated and stirred reaction 4h, reaction is cooled to room temperature after terminating, obtains reactant；The most by weightSeveral doses, choose 6 parts of above-mentioned standby surfactants, 20 parts of above-mentioned reactants, 35 parts of magnesium sulfate, 13 parts of sodium carbonate and 7 respectivelyPart laccase, mechanical agitation 35min after mixing, i.e. can get clean type pulping agents.
This example operation is easy, and in pulp making process, the clean type pulping agents present invention prepared adds fiberIn raw material (by phragmites communis pulverization process), wherein every 1.5t fibrous raw material adds 10kg pulping agents, stir, pass throughPaper flow process processed makes paper, and after testing, owing to the addition of the pulping agents that the present invention prepares, after preparation, black liquor generation amount is than traditionPulp-making method reduces 88%, can be in large-scale application.
Example 3
Weigh 250g Radix Platycodonis, 80g bean cake, 100g Saponaria officinalis and 120g soapbark the most respectively, mix after chopping, mixture is pressedSolid-to-liquid ratio 1:5 mixes with mass fraction 90% ethanol, and is heated to reflux state, carries out backflow extraction 70min, after extraction terminatesFilter to get filtrate, filtrate is put into vacuum concentration pot carries out under 0.09MPa concentrating under reduced pressure, until being concentrated into original volume20%, obtain concentrated solution, be surfactant, standby；Then weigh 80g drake feather, first drake feather is immersed in matter by solid-to-liquid ratio 1:5In amount mark 15% hydrochloric acid solution, after soaking 2h, filter to obtain filtering residue, by filtering residue again by solid-to-liquid ratio 1:8 and mass fraction 20% sulfurous acidHydrogen sodium solution mixes, and by mixture in 200W microwave treatment 25min, filters and remove filtrate, filtering residue is put into baking oven after processIn, at 70 DEG C, it is dried 10h, grinds after drying, sieve to obtain 100 mesh drake feather protein powders；Next by the albumen of above-mentioned preparationPowder is that 10g/L sodium hydroxide solution mixes by solid-to-liquid ratio 1:10 and concentration, loads in beaker after mixing, and move in water-bathStirring and dissolving at 80 DEG C, filters, and removes insoluble matter, is 4.0 by filtrate mass fraction 15% salt acid for adjusting pH, and stirring is to solidFilter to obtain filtering residue after separating out completely, put into and baking oven is dried at 60 DEG C 6h, obtain protein modified dose；Subsequently by above-mentioned protein modifiedAgent and triethanolamine, epoxychloropropane, sodium hydroxide 3:2:2:1 in mass ratio mixing, put in flask, add and press in flaskSolid-to-liquid ratio 1:2 adds deionized water, and mechanical agitation is completely dissolved to solid, moves in water-bath, is warming up to 90 DEG C, adds in flaskEntering gross mass 5% glutaraldehyde, insulated and stirred reaction 5h, reaction is cooled to room temperature after terminating, obtains reactant；The most by weightAgent, chooses 8 parts of above-mentioned standby surfactants, 25 parts of above-mentioned reactants, 40 parts of magnesium sulfate, 15 parts of sodium carbonate and 8 parts respectivelyLaccase, mechanical agitation 40min after mixing, i.e. can get clean type pulping agents.
This example operation is easy, and in pulp making process, the clean type pulping agents present invention prepared adds fiberIn raw material (by phragmites communis pulverization process), wherein every 2t fibrous raw material adds 15kg pulping agents, stir, by systemPaper flow process makes paper, and after testing, owing to the addition of the pulping agents that the present invention prepares, after preparation, black liquor generation amount is than tradition systemSlurry processes reduces 90%, can be in large-scale application.