CN1924187A - Paper making method for straw fiber pulping by 'enzymatic conversion and puffing' - Google Patents
Paper making method for straw fiber pulping by 'enzymatic conversion and puffing' Download PDFInfo
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Abstract
This invention relates to one enzyme and puffing weed fiber pastry paper processing method, which combines biological science, life science and mechanic process to realize paper process without dirty water discharge. The method is characterized by the following: through grinding for clutter and mixture removing and cutting into short weed fiber materials into press machine; adding H2O2 solution and fiber enzyme B and induce agent C for pressing then for enzyme transmission and sending into puffing machine to get rough pastry.
Description
Technical field
The present invention relates to pulp and paper technology, be specifically related to the pulp and paper technology of grass fiber, the pulp and paper making method that particularly a kind of bioscience, life science and machine-building combine.
Background technology
Traditional papermaking straw pulp production method adopts the alkaline process chemical pulping, the straw pulp black liquor that this method produces, its improvement is the emphasis of efforts at environmental protection, treatment technology to straw pulp black liquor has become a universally acknowledged difficult problem, the optimal path of the improvement wheat straw black liquor of generally acknowledging is that alkali reclaims, but, be that a slurry of alkali recovery technology difficulty maximum is planted because there are unfavorable factors such as water filtering performance is poor, black liquor viscosity is big, silicon content height in Straw Pulp.Particularly for small-sized, even medium-sized, enterprise, investment is big, operating cost is high owing to curb environmental pollution, and is raw material papermaking with the wheat straw, produce profit and avoids polluting and hardly may.Have the little paper mill of 6000-7000 family to close because of not solving the pulp-making waste-water pollution in recent years, available resources such as a large amount of wheat straws go out of use; Because economic interests drive, still also have many wastewater treatments not up to standard in, small paper mill do not close; Some cost a huge sum of money pollution treatment engineerings of building are because the operating cost height, still sewage effluent stealthily.The national at present straw pulp black liquor that the alkaline process chemical pulp generation more than 30% is arranged approximately directly effluxes basically without any processing, accounts for the 80-90% of gross contamination thing generating capacity.The black waste liquid of discharging contains a large amount of pollutants, and is the most serious to water pollution.For the pollution prevention technique of Chinese alkaline process chemical pulping, expert Mr. Lin Qiaoyuan has comprehensive introduction and deep analysis in " Chinese papermaking " article " evaluation and the prospects of the prevention and cure of pollution of Chinese paper industry non-wood pulping " literary composition of 2006 the 25th the 5th phases of volume.
At the pollution control of straw pulp black liquor, domesticly carried out a large amount of tackling of key scientific and technical problems work, also built the engineering project of the traditional black liquor treatment method of many improvement, mainly contain three major types:
1, changes and improvements boiling method:
2, change the black liquid comprehensive utilization approach:
3, black liquor and middle section water mixed processing:
The economic benefit of the various new technologies of preventing and remedying pollution and environmental benefit all are far from producing a desired effect.Cause the total amount of pollutants discharged that accounts for national industrial COD total emission volumn paper industry more than half not to be effectively controlled, country is tens billion of for having spent for improvement paper-making pollution accumulative total, but ecocatastrophe and colony's cancer that paper-making pollution forms are died at present still constantly by media report.
The drawback of traditional papermaking process for a change, many for many years inventors have declared the papermaking patented technology, but form also not having of commercial production scale.As:
Patent application 1 (pulping technology with gas mixing and explosion, applying date 1999.12.24)
Material 0.3 → 1.2MPa saturated vapour depress handle 10-40 minute → be pressurized to 1.6-2.4MPa pressure → quick-fried spray at the explosion pulping device
Patent application 2 (physical explosion pulping process, applying date 2001.06.14)
Raw material → 2-4% lime slurry mix → put into cavity charge containers → temperature 180-230 ℃, pressure 1.5-2MPa → heat-insulation pressure keeping 3-18 branch → quick-fried spray
Application 1,2 weak point: raw material is handled simple, and lignin and cellulose separating effect are bad, jar or the explosion pulping body amass the restriction that is subjected to secure context, single jar of production capacity is low, produces discontinuously, is difficult to satisfy the large-scale production requirement.
Patent application 3 (Chinese alpine rush under a kind of batch production condition/kenaf bast bio-pulping process, applying date 2003.01.17)
Dried → boiling shelling → whitewashing screening the pulp → sediment bleaching → defibrination making sheet etc. is rolled in former bacterial classification dosing → raw material inoculation → wet fermentation → washing
Patent application 4 (a kind of papermaking bio-pulping process, applying date 2004.04.12)
Add in bioactivator cultivation → spray raw material → rotary spherical digester the active culture agent mix 30 minutes → add 3 hours → mill → rinsing of 1.5-2% ammoniacal liquor → boiling → usefulness MF micropore filter for molten recovery activating agent.
Patent 5 (a kind of process for pulping by biochemical solvent, applying date 2005.02.07)
Soak 2-2.5 hour → extruding in the biochemical solvent of raw material → pulverizing removal of impurities → normal temperature and pressure and reclaim solvent → mill → rinsing → finished product slurry
Application 3,4,5 all is that raw material carries out mechanical jordaning after biochemical technology is handled.Patent application 5 is the simplest technologies, but owing to invade bubble raw material time weak point at normal temperatures and pressures, biochemical reaction is insufficient, will influence the straw pulp quality; Patent 4 also is that biochemical reaction is insufficient, though increased boiling, influences the straw pulp quality equally.The 3 biochemical reaction times of patent are abundant relatively, carried out pilot scale, and weak point is that the pollution of solution straw pulp is not thorough, and used enzyme bacterium is in inoculated and cultured, need for a long time, large space, with high investment, cause enzyme bacterium cost height, because bacterial classification price height is given to apply and brought difficulty.This patented method still will add NaOH and carry out boiling and handle this part pollution behind biochemistry.
In a word, these patented technologies satisfy pulp quality, pollution control and industrial-scale production aspect etc. at the same time and are short of to some extent.
Summary of the invention
Purpose of the present invention is that with the biotechnology by " enzyme conversion " manufacturing technique of " machinery is expanded " combines in addition, and the grass fiber pulp and paper making method of a kind of " enzyme conversion+expanded " is provided.
Technical scheme of the present invention is as follows.
The grass fiber pulp and paper making method of a kind of " enzyme conversion+expanded ", what comprise straw fiber raw material rolls that fragmentation, removal of impurities, shearing, kneading are soaked into, fermentation transforms, expanded, the step of pulling an oar, manufacture paper with pulp.With grass fiber raw material and the H that gets ready
2O
2Water solution A, A also can be organic solvent such as oxalic acid, acetone or methyl alcohol, cellulase B induces fusogen C to mediate in kneader and soaked into 30-40 minute, wherein the raw material oven-dry weight and the H of grass fiber
2O
2The weight ratio of the aqueous solution is 100: 19 ± 1, H
2O
2The concentration of the aqueous solution is 15 ± 3%, and raw material is 100: 0.4 ± 0.1 with the ratio of the oven-dry weight of cellulase B, and raw material is 100: 0.7 ± 0.3 with the ratio of the oven-dry weight of inducing fusogen C; Raw material after the infiltration was sent in the storage tank sealed fermenting 24 hours, and fermentation temperature is controlled at 45-55 ℃; Raw material after the fermentation obtains thick slurry product after bulking machine is expanded.
Described cellulase B can be restriction endonuclease or excision enzyme.
The described fusogen C that induces can be macrogol or polyethylene glycol.
In manufacture process, destroy the raw material external skins through rolling, form crack and numerous micro-crack, enlarging the contact-making surface of string and biochemical preparation, and after removal of impurities, cut into 2-3 centimetre pipe nipple or fragment.
Raw material after the fermentation obtains slightly to starch product after bulking machine is expanded, be 120-200 ℃ in the inner material temperature scope of bulking machine outlet, and pressure limit is 1.2-2.6MPa.Change inner cross-sectional area of bulking machine outlet and the inner passage length of outlet, or utilize the heating or the refrigerating function of bulking machine self, can regulate inner feed pressure and the temperature of bulking machine outlet.
Rely on existing conventional making beating, discongest equipment and conventional paper making equipment, the thick slurry product after expanded can be produced toilet paper, paperboard and corrugated paper, but also processing becomes other paper product.
Advantage that the present invention compared with prior art has and good effect:
The grass fiber pulp and paper making method of " enzyme conversion+expanded " of the present invention is compared with existing alkaline process chemical pulping technology, has the following advantages:
1, H2O2 that adds in the pulping process and biological products are after bulking machine is expanded, be converted into carbohydrate and water, slightly starch without boiling, production process is sewage effluent not fully, simplified pulping process flow, reduce production equipment and auxiliary equipment, save slurrying and environmental protection water in a large number, energy efficient, the consumption that saves material, the operation workman reduces, save operating cost, save a large amount of environmental protection investments and social environment control expense, significantly net income increase;
2, adopt unique " enzyme conversion+expanded " pulping process, make the plant fiber cells broken wall abundant, lignin, hemicellulose are decomposed by complex enzyme easily and degrade, conversion formation staple fibre remains and is utilized, new method wheat straw unscreened yield reaches about 90%, improve 20%40% than the pulp yield that adopts the chemical pulping method, improve 10%_25% than the pulp yield that adopts the semichemical pulping method.
3, specific China's actual conditions determine vast rural area must use aboundresources, grass fiber with low cost, and pulping and paper-making becomes most realistic even also is unique selection.Vast rural area small paper mill, be among the encirclement on straw fiber raw material ground closely, peasant's Work in Place, there is raw material to disperse advantages such as storage, transportation and the price of labour power are cheap, not papermaking of small paper mill slurrying, sell big factory after producing thick slurry, sewage effluent neither, profit reciprocation steady in a long-term are arranged again, be particularly suitable for the rural area and disperse to do factory, be suitable for local countryside and peasantry employment and shake off poverty and set out on the road to prosperity, the small paper mill that can allow several thousand families close is come back to life, also become the local profits tax rich and influential family and the employment main force easily, can promote rural economic development.
4, solve the high problem of big paper plant production cost.Big paper plant is far away relatively apart from straw pulp raw material ground, and remote transportation, the storage of raw materials is uneconomical in a large number, the cost of sewage disposal height.China's paper pulp breach is very big, the expense height.Import grass fiber in 2004 is starched 1,100 ten thousand tons and is accounted for 24.7% of national paper pulp consumption, and new method can reduce pulp inlet.Big paper plant no matter own production still buys the thick slurry of little factory, can significantly save cost, increases profit.Can concentrate more person property's power to handle other sewage of paper.Realize making full use of of efficient resource, crucial overall economic efficiency, social benefit are arranged.
5, new method is applicable to large, medium and small various production-scale paper mill, can be used for the large and medium-sized paper plant of existing grass fiber slurrying is undergone technological transformation, because new method is saved paper making water and is administered water, reducing water pollutes, particularly, important ecological benefits are arranged in northwest, North China, the East China of lack of water.
Description of drawings
Accompanying drawing is a process flow diagram of the present invention.
The specific embodiment
With reference to accompanying drawing, preparation method of the present invention realizes with following concrete steps:
1, roll brokenly skin:
The employing forage that paves in the stock ground, remove some tangible bulk foreign material, with rolling apparatus as equipment such as light-duty road roller, tractors, forage is rolled, stirs, rolls, by the epidermal structure of extruding and tearing destruction forage, form more crackle or microcrack on the string surface, enlarge the contact-making surface of string and biochemical preparation, so that H2O2 water solution A, cellulase B and induce fusogen C fully to soak into to penetrate into plant epidermis inside carry out biochemical reaction and transform lignin.
2, removal of impurities: screen out foreign material such as silt by the flat board concussion.
3, shear: the pipe nipple fragment that forage is cut into 2-3 centimetre with chaffcutter.
4, mediate infiltration: the forage of getting ready is delivered in the kneader, the running kneader, spray the H2O2 water solution A earlier, also can be aqueous solutions of organic solvent such as oxalic acid, acetone or methyl alcohol, stirring, the back disperses to be sprinkled into cellulase B, the back that stirs disperses to be sprinkled into to induce fusogen C again, mediate infiltration 30-40 minute altogether up to forage in kneader, wherein the weight ratio of the forage oven-dry weight and the H2O2 aqueous solution is 100: 19 ± 1, and the concentration of the H2O2 aqueous solution is 15 ± 3%; Forage is 100: 0.4 ± 0.1 with the oven-dry weight ratio of cellulase B; Forage is 100: 0.7 ± 0.3 with the oven-dry weight ratio of inducing fusogen C; Kneader forces extruding H2O2 water solution A, cellulase goods B, induce that each pipe nipple fragment of fusogen C and forage is full and uniform to contact infiltration, and infiltration epidermis inside reacts from the surface crack of each pipe nipple fragment and micro-crack.At H2O2 water solution A, cellulase with induce under the fusogen C acting in conjunction, make forage obtain softening and swollen, help fibrous inside fibrillating and part degraded when expanded.
5, fermentation transforms:
Forage after mediate soaking into was put in the storage tank sealed fermenting 24 hours, and the temperature of fermentation is controlled at 45 ℃ to 55 ℃.The factor of unwinding under the catalytic action of the various enzymes that generate in foreign aid's condition of cellulase and the forage plant cell and accumulate in the plant is activated, complicated lignin chain hydrogen bond interior or interchain is opened, remove from the phenylpropyl structure of lignin connecting heteroproteose cells such as forming the macromolecular methoxyl group of lignin, hydroxyl, cloves base, allowing it be changed gene transforms, melt under the induction of the factor short, will take off heteroproteose cells such as becoming micromolecular hydroxyl and transform, merge the utilizable staple fibre of formation.
6, expanded: the forage after the fermentation enters bulking machine, under high shear force, high pressure, action of high temperature, the physical characteristic of forage changes, each layer asked some lignin fusing and pyrohydrolysises in the forage cell membrane, hydrogen bond rupture and absorbing water, cellulose is partly degraded, refinement, and high temperature can make various injurious factors and enzyme deactivation.Select or adjust bulking machine for use, forming the inner forage temperature range of outlet when making bulking machine work can be at 120-200 ℃, and pressure limit can be at 1.2-2.6MPa.The desirable running parameter of different plant fiber materials is difference to some extent, needs to optimize and determines.Under the screw rod extruding of forage, export the moment of extruding from bulking machine at bulking machine, enter the normal temperature and pressure state from High Temperature High Pressure, pressure and temperature reduces suddenly causes forage energy stored under High Temperature High Pressure to discharge suddenly, the moisture evaporation of sharply vaporizing in the material, under the effect of crunch difference, moment, steam diffused out from material, producing tension force expands the volume of material rapidly, originally interconnected the destroyed separation of fibre structure closely, plant fiber cells marshalling before expanded, eucaryotic cell structure is complete; Expanded back cell is destroyed free, becomes the amorphous cellulose element, and iuntercellular is apart from widening, and stalk shape thing reduces, and improves fiber softening, and cell membrane is torn and become wadding fibrously, and total surface area increases.After expanded, obtain slightly slurry.
Change the inner cross-sectional area size of bulking machine outlet and the length of exit passageway, or utilize the heating or the refrigerating function of bulking machine self, can regulate the pressure and temperature that bulking machine exports inner raw material, make different forages obtain comparatively ideal bulking pressure and swelling temperature.
8, making beating: rely on existing conventional making beating and discongest equipment, thick slurry changes qualified production paper pulp into.If the condition that small paper mill does not possess making beating and manufactures paper with pulp can or be extracted oven dry and be sold to big paper plant the thick slurry direct distribution after expanded.
9, manufacture paper with pulp: rely on existing conventional paper making equipment, can produce toilet paper, careless paperboard and corrugated paper, but also processing becomes other paper product.
Further specify the specific embodiment of pulp and paper making method of the present invention by the following examples.It should be understood that this example only provides as a kind of embodiment of string, is not limited to scope of the present invention.
Embodiment 1
Forage is wheat straw, wheat straw is spread out in the threshing ground, wheat straw thickness is roughly even, after rolling, stir, roll again with tractor, screen out foreign material such as dust removal soil with the flat board concussion, with chaffcutter wheat straw is cut into the pipe nipple of 2-3 centimeter length, the content of sampling and testing wheat straw moisture content, cellulose, hemicellulose and lignin again.And 100 kilograms of the forages of weighing, the volume of packing into is in 1000 liters the kneader, start kneader, spray the H2O2 water solution A earlier, also can be oxalic acid, aqueous solutions of organic solvent such as acetone or methyl alcohol, after stirring, after the plain enzyme B of loosen collagen fibre stirs again, disperse to be sprinkled into again to induce fusogen C, mediate infiltration 30-40 minute altogether up to forage in kneader, wherein the weight ratio of the forage oven-dry weight and the H2O2 aqueous solution is 100: 19 ± 1, and the concentration of the H2O2 aqueous solution is 15 ± 3%, the oven-dry weight weight ratio of forage and cellulase is 100: 0.4 ± 0.1, forage and the oven-dry weight weight ratio 100: 0.7 ± 0.3 of inducing fusogen.Pack into and ferment in the storage tank soaking into good forage, airtight insulation, temperature was controlled at 45 ℃ of-55 ℃ of following static reactions after 12 hours, forage is stirred one time continue airtight insulation, end after 45 ℃-55 ℃ continuation is reacted 12 hours down, and this moment, forage was finished the process of enzyme conversion.The forage after the enzyme conversion is sent into again and carried out expandedly in the bulking machine, requiring the inner forage pressure limit of control bulking machine outlet is that 1.3-1.5Mpa, temperature range are 130-150 ℃.
Confirm through tens of result of the test tests, " enzyme conversion+expanded " not only makes lignin separate with cellulose, and makes lignin be subjected to a certain degree degraded and conversion, makes three big constituent contents of thick slurry that bigger variation be arranged, lignin and hemicellulose reduce, and cellulose increases.Three big constituent contents meet the semi-chemical pulp standard.
Test result sees Table 1:
[table 1] is as follows:
| Composition | |||
| Content | Cellulose | Lignin | Hemicellulose |
| Expanded back increase and decrease before expanded | 44.61％ 57.15％ +28.11％ | 22.23％ 15.04％ -32.34％ | 23.5％ 12.52％ -46.72％ |
Thick slurry after expanded is put into conventional beater pulls an oar, and will meet straw pulp that the technology beating degree requires through defibrination, copy sheet.Physical performance of paper sees Table 2 after tested:
Table 2
| Project | Fracture length | Tear index | Burst index | Ring crush index |
| Index | 5.13Km | 7.83mN.m 2/g | 3.18kPa.m 2/g | 7.67N.m/g |
Straw Pulp unscreened yield 〉=90% of the present invention's preparation meets boxboard and highly intensified corrugated paper standard.
Method of the present invention need not boiling in process of production, sewage effluent not, and the paper pulp of being produced can be produced toilet paper, paperboard and corrugated paper on the spot.The final purpose of invention is to realize that the grass fiber natural resources makes full use of, low investment, low-cost, few water, free from environmental pollution, high benefit, the nearly ten thousand tame small paper mills that are closed bankruptcy are come back to life, increase hundreds thousand of rural migrant workers' job opportunity, bring considerable ecological benefits to society, economic benefit and social benefit.Solve the short supply of Chinese paper industry fibrous raw material from a side simultaneously, environmental protection is ineffective and crucial production technology progress three big problems slowly, for paper industry provides huge development space; In the China of water scarcity, keep the water demand of development from local solution of industry angle, for Constructing Water-saved Society contributes by sacrificing ecology and water-use for environment.
Claims (7)
1, the grass fiber pulp and paper making method of a kind of " enzyme conversion+expanded ", what comprise straw fiber raw material rolls that fragmentation, removal of impurities, shearing, kneading are soaked into, fermentation transforms, expanded, the step of pulling an oar, manufacture paper with pulp, and it is characterized in that: with grass fiber raw material and the H that gets ready
2O
2Water solution A, A also can be organic solvent such as oxalic acid, acetone or methyl alcohol, cellulase B induces fusogen C to mediate in kneader and soaked into 30-40 minute, wherein the raw material oven-dry weight and the H of grass fiber
2O
2The weight ratio of the aqueous solution is 100: 19 ± 1, H
2O
2The concentration of the aqueous solution is 15 ± 3%, and raw material is 100: 0.4 ± 0.1 with the ratio of the oven-dry weight of cellulase B, and raw material is 100: 0.7 ± 0.3 with the ratio of the oven-dry weight of inducing fusogen C; Raw material after the infiltration was sent in the storage tank sealed fermenting 24 hours, and fermentation temperature is controlled at 45-55 ℃; Raw material after the fermentation obtains thick slurry product after bulking machine is expanded.
2, require the grass fiber pulp and paper making method of described " enzyme conversion+expanded " as right 1, it is characterized in that: described cellulase B can be restriction endonuclease or excision enzyme.
3, require the grass fiber pulp and paper making method of described " enzyme conversion+expanded " as right 1, it is characterized in that: the described fusogen C that induces can be macrogol or polyethylene glycol.
4, require the grass fiber pulp and paper making method of described " enzyme conversion+expanded " as right 1, it is characterized in that: in the manufacture process, destroy the raw material external skins through rolling, form crack and numerous micro-crack, enlarging the contact-making surface of string and biochemical preparation, and after removal of impurities, cut into 2-3 centimetre pipe nipple or fragment.
5, require the grass fiber pulp and paper making method of described a kind of " enzyme conversion+expanded " as right 1, it is characterized in that: the raw material after the fermentation obtains slightly to starch product after bulking machine is expanded, in the inner material temperature scope of bulking machine outlet is 120-200 ℃, and pressure limit is 1.2-2.6MPa.
6, require the grass fiber pulp and paper making method of described a kind of " enzyme conversion+expanded " as right 1, it is characterized in that: change inner cross-sectional area of bulking machine outlet and the inner passage length of outlet, or utilize the heating or the refrigerating function of bulking machine self, can regulate inner feed pressure and the temperature of bulking machine outlet.
7, require the grass fiber pulp and paper making method of described a kind of " enzyme conversion+expanded " as right 1, it is characterized in that: rely on existing conventional making beating, discongest equipment and conventional paper making equipment, thick slurry product after expanded can be produced toilet paper, paperboard and corrugated paper, but also processing becomes other paper product.
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| CN 200610152767 CN1924187A (en) | 2006-09-28 | 2006-09-28 | Paper making method for straw fiber pulping by 'enzymatic conversion and puffing' |
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| CN 200610152767 CN1924187A (en) | 2006-09-28 | 2006-09-28 | Paper making method for straw fiber pulping by 'enzymatic conversion and puffing' |
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| CN101806005A (en) * | 2010-04-03 | 2010-08-18 | 才景志 | Paper pulp making method capable of reducing large amount of waste liquid and lowering consumption of materials |
| CN102677511A (en) * | 2012-05-28 | 2012-09-19 | 黄润燕 | Method for preparing virgin pulp for papermaking by utilizing organic enzyme to carry out enzyme treatment on herbaceous plants |
| CN107419588A (en) * | 2017-05-23 | 2017-12-01 | 东莞市白天鹅纸业有限公司 | A kind of preparation method of paper for daily use paper pulp |
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| CN101806005A (en) * | 2010-04-03 | 2010-08-18 | 才景志 | Paper pulp making method capable of reducing large amount of waste liquid and lowering consumption of materials |
| CN102677511A (en) * | 2012-05-28 | 2012-09-19 | 黄润燕 | Method for preparing virgin pulp for papermaking by utilizing organic enzyme to carry out enzyme treatment on herbaceous plants |
| CN102677511B (en) * | 2012-05-28 | 2014-07-09 | 黄润燕 | Method for preparing virgin pulp for papermaking by utilizing organic enzyme to carry out enzyme treatment on herbaceous plants |
| CN107419588A (en) * | 2017-05-23 | 2017-12-01 | 东莞市白天鹅纸业有限公司 | A kind of preparation method of paper for daily use paper pulp |
| CN107419588B (en) * | 2017-05-23 | 2019-06-25 | 东莞市白天鹅纸业有限公司 | A kind of preparation method of paper for daily use paper pulp |
| CN109893010A (en) * | 2017-12-12 | 2019-06-18 | 株洲千金药业股份有限公司 | A kind of tender sensitivity skin paper of children and its method of the preparation of prescriptions worth thousand gold dregs of a decoction resource regeneration |
| CN109914145A (en) * | 2017-12-12 | 2019-06-21 | 株洲千金药业股份有限公司 | A kind of paper for kitchen and its method of the preparation of dreg fibers material |
| CN109914154A (en) * | 2017-12-12 | 2019-06-21 | 株洲千金药业股份有限公司 | A kind of face tissue and its method of the preparation of dreg fibers material |
| CN109914144A (en) * | 2017-12-12 | 2019-06-21 | 株洲千金药业股份有限公司 | A kind of face tissue and its method of the preparation of prescriptions worth thousand gold dregs of a decoction resource regeneration |
| CN109914153A (en) * | 2017-12-12 | 2019-06-21 | 株洲千金药业股份有限公司 | A kind of paper for kitchen and its method of the preparation of prescriptions worth thousand gold dregs of a decoction resource regeneration |
| CN109914155A (en) * | 2017-12-12 | 2019-06-21 | 株洲千金药业股份有限公司 | A kind of paper for kitchen and preparation method thereof |
| CN109137591A (en) * | 2018-09-20 | 2019-01-04 | 上海同化新材料科技有限公司 | It is used to prepare the device of powdered cellulose |
| CN109695170A (en) * | 2019-03-11 | 2019-04-30 | 樊士英 | A kind of technique of activity legal system pulping |
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