CN105178102B - The method for preparing paper surface-sizing agent as raw material with the fermentation residues of cellulosic ethanol - Google Patents
The method for preparing paper surface-sizing agent as raw material with the fermentation residues of cellulosic ethanol Download PDFInfo
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- CN105178102B CN105178102B CN201510486389.XA CN201510486389A CN105178102B CN 105178102 B CN105178102 B CN 105178102B CN 201510486389 A CN201510486389 A CN 201510486389A CN 105178102 B CN105178102 B CN 105178102B
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- alcoholic fermentation
- cellulose
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000000855 fermentation Methods 0.000 title claims abstract description 47
- 230000004151 fermentation Effects 0.000 title claims abstract description 47
- 238000004513 sizing Methods 0.000 title claims abstract description 39
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 14
- 239000002994 raw material Substances 0.000 title claims abstract description 11
- 239000001913 cellulose Substances 0.000 claims abstract description 38
- 229920002678 cellulose Polymers 0.000 claims abstract description 38
- 229920002472 Starch Polymers 0.000 claims abstract description 29
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 29
- 239000008107 starch Substances 0.000 claims abstract description 29
- 235000019698 starch Nutrition 0.000 claims abstract description 29
- 239000012978 lignocellulosic material Substances 0.000 claims abstract description 7
- 102000004190 Enzymes Human genes 0.000 claims abstract description 5
- 108090000790 Enzymes Proteins 0.000 claims abstract description 5
- 230000007062 hydrolysis Effects 0.000 claims abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 238000002203 pretreatment Methods 0.000 claims abstract description 4
- 239000000123 paper Substances 0.000 claims description 23
- 244000085692 Cordia alliodora Species 0.000 claims description 17
- 235000004258 Cordia alliodora Nutrition 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000003292 glue Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 7
- 229920005610 lignin Polymers 0.000 claims description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 4
- 108090000623 proteins and genes Proteins 0.000 claims description 4
- 102000004169 proteins and genes Human genes 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 239000011087 paperboard Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 241000274582 Pycnanthus angolensis Species 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 239000000839 emulsion Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 5
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000010902 straw Substances 0.000 description 4
- 229920002488 Hemicellulose Polymers 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 240000008042 Zea mays Species 0.000 description 2
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 230000009172 bursting Effects 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 235000009973 maize Nutrition 0.000 description 2
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 229920002261 Corn starch Polymers 0.000 description 1
- 108010058643 Fungal Proteins Proteins 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- -1 alkyl ketene dimer Chemical compound 0.000 description 1
- 239000011111 cardboard Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 229940099112 cornstarch Drugs 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000012262 fermentative production Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- MHWRYTCHHJGQFQ-UHFFFAOYSA-N prop-2-enoic acid hydrate Chemical compound O.OC(=O)C=C MHWRYTCHHJGQFQ-UHFFFAOYSA-N 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Abstract
The present invention relates to a kind of method that fermentation residues with cellulosic ethanol prepare paper surface-sizing agent as raw material, including：1) acquisition of cellulose alcoholic fermentation residue：By lignocellulosic material by pretreatment, enzyme hydrolysis, fermentation, separation of ethanol operation, cellulose alcoholic fermentation residue is obtained；2) cellulose alcoholic fermentation residue pre-treatment:The residue of acquisition is carried out into miniaturization treatment, reduces residue particles particle diameter, reach paper surface-sizing agent requirement；3) prepared by paper surface-sizing agent：The cellulose alcoholic fermentation residue that will be obtained mixes with starch, and paper surface-sizing agent is prepared as raw material.The present invention is applied to the top sizing of paper industry using the fermentation residues part substituted starch of cellulosic ethanol, the benign development of strong promotion cellulosic ethanol industry, not only reducing environmental pollution can also create economic worth, with economic benefit and social benefit higher.
Description
Technical field
The present invention relates to pulp technology for making paper, and in particular to a kind of fermentation residues with cellulosic ethanol are raw material preparation
The method of paper surface-sizing agent.
Background technology
At present, with the increasingly rising of global energy total amount consumed, petroleum resources day are becoming tight, and finding a kind of cleaning can be again
Raw alternative energy source turns into the task of top priority, is that raw material production ethanol turns into the important of solution energy crisis instantly with lignocellulosic
And effective way.
Stalk quantum of output is more than 700,000,000 tons in the annual agricultural production of China, extensive using providing for biomass resource
Raw material ensures.Therefore, according to the situation of the current biomass resource of China, using conversion technology, agricultural stalk is converted into
The fuel such as alcohol fuel.
Lignocellulosic material main component is cellulose, hemicellulose and lignin.Cellulose therein and hemicellulose
Utilization technology it is more ripe；In whole conversion process, lignin is difficult to be utilized effectively.In cellulosic ethanol production
During, hemicellulose and cellulose can be with fermentative production of ethanol, and remaining residue is that part does not convert completely after fermentation
The material, referred to as cellulose alcoholic fermentation residue such as cellulose, the lignin that is difficult by and Yeast protein.
In view of the reason for current technology level and material composition, cellulosic ethanol is produced using lignocellulosic material
During inevitably generate abundant residues thing.If, if not being subject to trans-utilization, bulk deposition will be as ring for residue
The major source of pollutant in border.
Cypres are a class important chemicals in paper industry, by improving the interfibrous adhesion of page, are reached
Strengthen the purpose of paper physical intensity.At present, the conventional Cypres of paper industry mainly have starch, cellulose derivative,
Animal glue, polyvinyl alcohol, polyacrylamide and synthetic latex etc., wherein, using it is most be starch surface sizing agent, examine
Consider the world till now and be faced with serious crisis in food, if it is possible to which finding a kind of suitable raw material can completely or partially take
Will be significant for starch.
The content of the invention
The problem that above-mentioned prior art is present is aimed to solve the problem that, inventor has found by studying, because Ethanol Production Process with Straw is residual
The main component of excess is the compositions such as lignin, cellulose and protein, it can be considered to use residual fraction substituted starch
The top sizing of paper industry is applied to, the benign development of strong promotion straw ethanol industry is not only reduced environment dirty by this
Dye can also create economic worth, with economic benefit and social benefit higher.
Therefore, the present invention provides following technical scheme：
The present invention provides a kind of the answering as paper surface-sizing agent of the fermentation residues after Production of Alcohol from Lignocellulose
With；Routine as those skilled in the art understands that the fermentation residues of cellulosic ethanol are pre- for lignocellulosic material passes through
The cellulose alcoholic fermentation residue obtained after the operations such as treatment, enzyme hydrolysis, fermentation, separation of ethanol；The main component of the material
Including lignin (30%~60%), cellulose (30%~60%), protein (5~15%) etc., outward appearance is in muddy, be water not
Soluble substance.
The present invention provides a kind of method for preparing paper surface-sizing agent and its application, including：
1st, the acquisition of cellulose alcoholic fermentation residue：By lignocellulosic material by pretreatment, enzyme hydrolysis, fermentation,
The operations such as separation of ethanol, obtain cellulose alcoholic fermentation residue, can be used as the raw material for preparing glue used in paper-making.
2nd, cellulose alcoholic fermentation residue pre-treatment：According to application scenario, cellulosic ethanol residue can be in hygrometric state
Or applied under dry state, and be required to carry out miniaturization treatment, reduce residue particles particle diameter, reach paper surface-sizing agent
It is required that.
Under hygrometric state, cellulose alcoholic fermentation residue can use high pressure homogenizer, dispersion emulsifying machine or high speed point
Machine treatment is dissipated, reduces its average grain diameter to less than 30 μm, for preparing Cypres.
If being used under dry state, cellulose alcoholic fermentation residue is dried first, then using mechanical means by its powder
It is broken, screened with the screen cloth of 60~200 mesh, took screen portion standby.
Repeatedly put into practice through inventor, it is found that when hygrometric state is processed, when residue average grain diameter is below 30 μm, effect is optimal,
Particle is excessive, both influences Process of Applying Glue, again tensile strength, ring crush intensity, bursting strength of page etc. after influence applying glue；And at dry state
During reason, sieve number is excessive, and Cypres prepared by the cellulose alcoholic fermentation residue for being obtained are sometimes up to less than this Shen
Expected Results please.
3rd, prepared by paper surface-sizing agent：The cellulose alcoholic fermentation residue that will be previously obtained is matched somebody with somebody with starch mixing and water adding
It is made the suspension of concentration 2~18%, the ratio of cellulose alcoholic fermentation residue and starch is 2~100:98~0, starch can be with
It is cornstarch, tapioca, farina etc.；It is preferred that 2~80:98~20；Ammonium persulfate is subsequently adding, consumption is 0.01
~5%, after being well mixed, heat under constant agitation, 80~95 DEG C are warming up to, and 10~60min is incubated, it is eventually adding
Aluminum sulfate, consumption 0.5~5% is well mixed, and by the screen cloth of 60 mesh, pumps into dilution trap, and adds warm water to be diluted,
By the concentration of starch glue regulation to process stipulation.The starch glue that will have been diluted, pumps into storagetank, and keeps certain temperature
Degree, you can for top sizing.
Studied through inventor and found, by controlling the proportioning of cellulose alcoholic fermentation residue and starch, carried out surface and apply
After glue, different page physical strengths can be obtained, be 2~80 in the ratio of cellulose alcoholic fermentation residue and starch:98
In the range of~20, relatively good effect can be reached, its top sizing effect is close with starch surface sizing agent or higher；
Additionally, inventor has found, by the Cypres (cellulose alcoholic fermentation residue and the shallow lake that are prepared in the present invention
Powder is raw material) in further add aluminum sulfate, can further improve page physical strength, achieve more prominent effect.
4th, the top sizing of page：The application mode of the Cypres prepared by the present invention and common starch surface are applied
Jelly is the same.
Additionally, the present invention also provides the application process of the above-mentioned Cypres for preparing；Table prepared by the invention
Surface sizing agent, can be used for the true qualities Paper or cardboard such as fluting medium, boxboard or cop tube paper, to improve tensile strength, the ring of page
Compressive Strength, bursting strength etc..If the water repelling property of page need to be improved further, alkyl ketene dimer (AKD), styrene can be added
Esters of acrylic acid water repellent agent etc..
The present invention achieves following technique effect relative to prior art：
1) solve cellulosic ethanol in the prior art fermentation residues it is more difficult be subject to trans-utilization, bulk deposition is asked
Topic, for the utilization of the fermentation residues of cellulosic ethanol provides a kind of new way；
2) problem that paper surface-sizing agent in the prior art excessively depends on starch is overcome；
3) for relatively inherently more cheap starch surface sizing agent, the Cypres of the application further drop
Low production cost；
4) Cypres of the invention reach the conventional effect using Cypres in the prior art；And make outside product
See the tough U.S. for producing similar " brown paper ".
5) optimize (addition aluminum sulfate) by the preliminary Cypres for obtaining, further increase Cypres
Treatment effect.
Specific embodiment
Embodiment 1：
Take maize straw produce cellulose alcoholic fermentation residue 90g (over dry, similarly hereinafter) add water be configured to concentration 10% hang
Supernatant liquid, 10min is processed using high-shearing dispersion emulsifying machine, and rotating speed is controlled to 13000r/min.Take 30g starch and add water and be configured to
10% concentration suspensions, both are mixed, cellulosic ethanol residue：Starch=75:25, it is subsequently adding the persulfuric acid of consumption 3%
Ammonium, is heated to 90 DEG C of temperature, insulation 30min.During top sizing, it is 10g/m to control resin added2Left and right, and with 100% starch table
Surface sizing agent is contrasted.Page physical strength data such as table 1.
Table 1
Embodiment 2：
Take maize straw produce cellulose alcoholic fermentation residue 30g (over dry, similarly hereinafter) add water be configured to concentration 10% hang
Supernatant liquid, 10min is processed using high-shearing dispersion emulsifying machine, and rotating speed is controlled to 10000r/min.Take 90g starch and add water and be configured to
10% concentration suspensions, both are mixed, cellulosic ethanol residue：Starch=25:75, it is subsequently adding the persulfuric acid of consumption 3%
Ammonium, is heated to 90 DEG C of temperature, insulation 30min.During top sizing, it is 10g/m to control resin added2Left and right, and with 100% starch table
Surface sizing agent is contrasted.Page physical strength data such as table 2.
Table 2
Embodiment 3：
Dry corncob production cellulose alcoholic fermentation residue 30g is taken, using multifunctional crusher micronization processes, mistake
100 mesh sieves, then mix with 30g starch, add water and are configured to the suspension of concentration 8%, add 0.3% ammonium persulfate.It is heated to temperature
95 DEG C of degree, soaking time are 10min, and it is 10g/m that resin added is controlled during top sizing2Left and right, and with 100% starch surface sizing
Agent is contrasted.Page physical strength data such as table 3.
Table 3
Embodiment 4：
The Cypres that will be prepared in embodiment 3 add 2% aluminum sulfate, and it is 10g/ that resin added is controlled during top sizing
m2Left and right.Page physical strength data such as table 4.
Table 4
Embodiment 5：
The Cypres that will be prepared in embodiment 3 add 2% aluminum sulfate, top sizing to use one side and two-sided applying glue
Mode, page physical strength data such as table 5.
Table 5
Although above-mentioned be described to specific embodiment of the invention, not to the limit of the scope of the present invention
System, one of ordinary skill in the art should be understood that on the basis of technical scheme those skilled in the art need not pay
The various modifications or deformation made by going out creative work are still within protection scope of the present invention.
Claims (9)
1. the fermentation residues after Production of Alcohol from Lignocellulose as paper surface-sizing agent application, it is characterised in that it is fine
The plain alcohol fermentation residue of dimension is that lignocellulosic material is obtained by operations such as pretreatment, enzyme hydrolysis, fermentation, separation of ethanol,
Described cellulose alcoholic fermentation residue be main component include 30%~60% lignin, 30%~60% cellulose, 5~
The water insoluble muddy material of 15% protein.
2. apply according to claim 1, it is characterised in that the residue mixes with starch and makes as Cypres
With.
3. application according to claim 1 or claim 2, it is characterised in that the Cypres further add aluminum sulfate, then
For top sizing.
4. a kind of preparation method of paper surface-sizing agent, it is characterised in that remaining with the fermentation after Production of Alcohol from Lignocellulose
Thing is prepared as raw material, including：
1) acquisition of cellulose alcoholic fermentation residue：By lignocellulosic material by pretreatment, enzyme hydrolysis, fermentation, ethanol
Separation circuit, obtains cellulose alcoholic fermentation residue；The cellulose alcoholic fermentation residue main component include 30%~
60% lignin, 30%~60% cellulose, 5~15% protein, outward appearance are in muddy, water insoluble；
2) cellulose alcoholic fermentation residue pre-treatment：By step 1) obtain residue carry out miniaturization treatment, make residue
Grain diameter reduces, and reaches paper surface-sizing agent requirement；
3) prepared by paper surface-sizing agent：By step 2) the cellulose alcoholic fermentation residue that obtains mixes with starch, as original
Material prepares paper surface-sizing agent.
5. method according to claim 4, it is characterised in that step 3) in the Cypres that prepare further add sulfuric acid
Aluminium, is used for top sizing after cooling.
6. according to the methods described of claim 4 or 5, it is characterised in that step 2) it is middle according to residue state, the pre-treatment is
Hygrometric state treatment or dry state treatment, the hygrometric state are processed as：Cellulose alcoholic fermentation residue uses high pressure homogenizer, dispersion and emulsion
Machine or high speed dispersor are processed, and reduce its average grain diameter to less than 30 μm；The dry state is processed as：Cellulosic ethanol is sent out
Ferment residue is dried, and is then crushed using mechanical means, is screened with the screen cloth of 60~200 mesh, takes screen portion standby.
7. the methods described of claim 4 or 5, it is characterised in that step 3) in, by step 2) cellulose alcoholic fermentation that obtains is residual
Excess and starch mixing and water adding are configured to suspension, and cellulose alcoholic fermentation residue is 2~80 with the ratio of starch:98~
20, ammonium persulfate is subsequently adding, consumption is 0.01~5%, after being well mixed, is heated under constant agitation, is warming up to 80
~95 DEG C, and 10~60min is incubated, aluminum sulfate is eventually adding, consumption 0.5~5% is well mixed, and is subsequently used for top sizing.
8. the paper surface-sizing agent that prepared by the preparation method according to claim 4-5.
9. paper surface-sizing agent described in claim 8 is used for the application of page surface applying glue, it is characterised in that the page is
Fluting medium, boxboard, cop tube paper or other types paper.
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| CN109826048B (en) * | 2017-11-23 | 2021-11-19 | 瑞辰星生物技术（广州）有限公司 | Surface sizing agent for papermaking and papermaking method for improving paper strength |
| CN108330738A (en) * | 2018-02-12 | 2018-07-27 | 广东轻工职业技术学院 | Complex fiber material and the preparation method and application thereof for top sizing |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3386879A (en) * | 1965-03-09 | 1968-06-04 | Abitibi Power & Paper Co | Process for forming board containing cellulosic fibers, thermosetting binder and pinewood resin |
| CN101712805A (en) * | 2009-11-06 | 2010-05-26 | 北京化工大学 | Method for preparing degradable mulch by reusing organic waste residues of biomass |
| CN102076505A (en) * | 2008-06-27 | 2011-05-25 | 惠普开发有限公司 | Surface treatment composition, inkjet printable article and method of making the same |
| CN103835185A (en) * | 2014-03-26 | 2014-06-04 | 云南省轻工业科学研究院 | Lacquer wax sizing agent and preparation method thereof |
| CN104005249A (en) * | 2014-05-22 | 2014-08-27 | 云南省轻工业科学研究院 | Preparation method of mixed additive for papermaking |
| CN104593448A (en) * | 2014-12-25 | 2015-05-06 | 山东龙力生物科技股份有限公司 | Method for producing ethanol from lignocellulosic biomass |
-
2015
- 2015-08-07 CN CN201510486389.XA patent/CN105178102B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3386879A (en) * | 1965-03-09 | 1968-06-04 | Abitibi Power & Paper Co | Process for forming board containing cellulosic fibers, thermosetting binder and pinewood resin |
| CN102076505A (en) * | 2008-06-27 | 2011-05-25 | 惠普开发有限公司 | Surface treatment composition, inkjet printable article and method of making the same |
| CN101712805A (en) * | 2009-11-06 | 2010-05-26 | 北京化工大学 | Method for preparing degradable mulch by reusing organic waste residues of biomass |
| CN103835185A (en) * | 2014-03-26 | 2014-06-04 | 云南省轻工业科学研究院 | Lacquer wax sizing agent and preparation method thereof |
| CN104005249A (en) * | 2014-05-22 | 2014-08-27 | 云南省轻工业科学研究院 | Preparation method of mixed additive for papermaking |
| CN104593448A (en) * | 2014-12-25 | 2015-05-06 | 山东龙力生物科技股份有限公司 | Method for producing ethanol from lignocellulosic biomass |
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