CN1011970B - Method for using chinese alpine rush as raw material to make nitrocellulose - Google Patents
Method for using chinese alpine rush as raw material to make nitrocelluloseInfo
- Publication number
- CN1011970B CN1011970B CN 85106196 CN85106196A CN1011970B CN 1011970 B CN1011970 B CN 1011970B CN 85106196 CN85106196 CN 85106196 CN 85106196 A CN85106196 A CN 85106196A CN 1011970 B CN1011970 B CN 1011970B
- Authority
- CN
- China
- Prior art keywords
- cellulose
- alpine rush
- raw material
- saponification
- chinese alpine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Abstract
The present invention relates to a method for fabricating nitrocellulose by taking Chinese alpine rush as raw materials, which belongs to the fabrication technology of nitrocellulose and the refinement of cotton cellulose substitutes. The present invention takes Chinese alpine rush as raw materials, refines cellulose by a pre-hydrolysis saponification method and nitrifies the cellulose with the mixed acid of nitric acid and sulfuric acid. Because the present invention takes rosin as saponification agents, the hygroscopic level of the refined Chinese alpine rush cellulose can be enhanced by 2 to 3 times so that the present invention can greatly shorten the time of nitration reaction and enhance the production rate. Compared with the method taking cotton linter as raw materials, the present invention can lower the cost by 21%. The nitrified Chinese alpine rush cellulose can be made into nitrolacquer, xylonite, ping-pong balls or other military articles. The refined Chinese alpine rush cellulose can replace cotton cellulose, and has various functions of artificial cellulose.
Description
The present invention relates to the refining and nitrocellulosic manufacturing technology of gossypin surrogate.
At present, in order to replace gossypin to make nitrocellulosic have flaxen fiber element, bamboo cellulose and wood cellulose.Its production method is an example with the wood cellulose, and sulfite pulping is arranged; Soda processes and sodium sulfide method slurrying; Chlorination pulping process; Nitric acid-alkaline process.Wherein, nitric acid-alkaline process is that timber and 3% nitric acid were heated 1 hour, after washing a little with hot water, (caustic soda, Ke Xingjia or ammonia solution be warm 1 hour altogether, and less than 2.5 hours, its result can make the a-content of cellulose at 40～43% slurry during this operational cost with 2～3% alkali again, copy again and make cardboard, oven dry with mixed acid nitrification, can make soluble cotton after stability is handled.
Because bamboo, fiber crops and timber cost height, raw material is drawn materials restricted, and China's southwest cloud, expensive, Chuan San are economized the wild stem fiber plant Herba Poae Sphondylodis of abounding with, and its content of cellulose and bamboo are close, and is about about 55%, is one of raw material of paper industry at present.The present invention promptly utilizes wild stem fiber plant Herba Poae Sphondylodis to be the feed purification Mierocrystalline cellulose, replace gossypin to make soluble cotton, and then can replace nitro-cotton to make other purposes, as making pyroxylin(e)finish, zylonite, table tennis ... Deng, also can make other military products.The purified alpine rush cellulose also can be made the important source material of artificial silk.With the Herba Poae Sphondylodis is that raw material is made soluble cotton, draws materials conveniently, and abundant raw material and price are lower, can reduce cost.
Because the Herba Poae Sphondylodis stipe part is formed harder epidermis by pectin and albumen, in treating process, must be removed, so adopting, the present invention gives the refining alpine rush cellulose of hydrolysis saponification method, being about to the raw material Herba Poae Sphondylodis at first heats with 2～3.5% diluted acid (nitric acid) is common, make it give hydrolysis, under certain pressure, be incubated for some time, after washing, mixed alkali liquor with low levels heats jointly again, after the boiling two hours, add saponifying agent rosin and carry out the saponification processing, after chlorination, rinsing can obtain the a-content of cellulose at 94 ± 2% refining alpine rush cellulose, it is copied make the fiber thin paper, with mixed acid nitrification, can obtain soluble cotton through the stability processing.
Concrete production process is that the Herba Poae Sphondylodis that carries out mass analysis is cut into 50～70 millimeters long (no longer than 100 millimeters).After removing silt particle with iron wire sieve, heating jointly with rare nitric acid of about 0.3%, heat up after 60 minutes, is 130～140 ℃ in temperature, and pressure is 1 kilograms per centimeter
2About condition under, make it carry out prehydrolysis, mother liquor after hydrolysis control pH value is 2.5～3.Through the Herba Poae Sphondylodis of above-mentioned processing beat wash after, (addition amount of sodium hydroxide is about 4% of a slurry gross weight with the mixed alkali liquor of being made up of sodium hydroxide and sodium sulphite again, the sodium sulphite add-on be the slurry gross weight about 2%) common hot digestion, heat up after 60 minutes, in temperature is 150～160 ℃, and pressure is 2.3 kilograms per centimeter
2About condition under insulation after 60 minutes, add saponifying agent rosin (rosin add-on be slurry gross weight about 0.45%), be incubated 60～90 minutes again, make it to take place saponification reaction.Through boiling saponification and washed alpine rush cellulose, carry out chlorination, floating with sodium hypochlorite solution again.After two sections, three sections rinsings, go into the washing machine washing to there not being chlorion (pH7.2～7.5), neutralize with about 0.3% sulfuric acid or nitric acid then, washing (being washed till pH6.8～7.0) after deironing, the desanding, concentrates, and copy that to make thickness be 0.12～0.20 millimeter thin paper, be cut into 20 * 70 millimeters the scraps of paper, under 90～110 ℃ of temperature, give baking 5 minutes (make in the alpine rush cellulose water content less than below 3%), carry out nitrated with nitre, sulphur nitration mixture again.Nitrated equipment adopts U type continuous nitrification device.Nitrated finishing drives to go into the washing machine washing after the acid and wash with horizontal pusher centrifuge, carries out stability then and handles, and promptly boils at 112 ℃ with dilute sulphuric acid and washes (acid concentration is about 0.5%), carries out soda boiling with 0.078% sodium carbonate solution at 117 ℃ again.Nitrated alpine rush cellulose after stability is handled, preservation or transportation are all safe and reliable under the situation that contains 30% moisture content (neutrality).
That is adopted in above-mentioned production process gives hydrolysis saponification method refined cellulose, owing to added saponifying agent rosin, help the refining of alpine rush cellulose, can improve the quality of refined cellulose, the hydroscopicity ratio can not improve 2～3 times when not adding rosin, helping nitration reaction carries out, can shorten the nitration reaction time greatly, thereby improve the product yield, make soluble cotton with linters and compare, cost can reduce by 21%, can replace nitro-cotton to make pyroxylin(e)finish, zylonite, table tennis and other military products.Also can replace gossypin to make artificial cellulose's various uses.
When operating, can make as the refining alpine rush cellulose of the listed index of table 1 is nitrated and use paper and as the nitrated alpine rush cellulose of the listed quality index of table 2 by following process control condition.
One, process control condition
Stage project control index remarks
The ratio of 140 ℃ of Herba Poae Sphondylodiss of prehydrolysis top temperature and acid solution
Pressure 1.2 kilograms per centimeter
Solid-to-liquid ratio 1.7
Acid concentration 2.5～3.5%
The ratio of 160 ℃ of Herba Poae Sphondylodiss of boiling saponification top temperature and mixed alkali liquor
Pressure 2.2～2.5 kilograms per centimeter
Solid-to-liquid ratio 1.6～7
NaOH add-on 3.6～4.5%
Na
2S add-on 1～2.5%
Rosin add-on 0.4～0.5%
Chlorination rinsing slurry concentration 4～6%
Chlorine dosage (to slurry) 2～2.5%
Nitrated (mixed H
2SO
465.86%
The acid composition) HNO
324.99%
Nitrogen oxide 1.15%
Water 8.00%
Two, refining alpine rush cellulose and nitrocellulosic quality situation thereof:
Table 1: refining alpine rush cellulose is nitrated with paper quality index (%)
Project indicator remarks
A-Mierocrystalline cellulose＞94
Five-carbon sugar＜4.5
In the time of-5 ℃ 12%＞85
The NaOH insolubles
Viscosity 14～35 unit centipoises
5 minutes nitre＜6 not
Change thing
Xylogen＜0.5
Ash＜0.4
Resin＜0.3
Sulfuric acid insolubles＜0.3
Moisture content＜8
Weight＜50～60 gram/M
2
Tightness＞0.5～0.6 gram/cm
2
It is 120～130 that hydroscopicity was laterally creeped 90 centimetres/3 minutes
Gram water/gram paper
2 minutes
Vertically creeped 110 centimetres/3 minutes
0.12～0.20 millimeter of thickness
Indivedual briquetting things do not allow to exist
Table 2: the quality index of nitrated alpine rush cellulose
Project indicator remarks
Nitrogen content 13.394%
Alcohol ether solubleness 9.9%
Dissolve with ethanol degree 1.2%
Viscosity (E °) 3.0
Ash 0.353%
Quick-fried hot 837.5Kcal/kg
Specific volume 866.5L/kg
Yield 173.12%
Claims (7)
1, with the Herba Poae Sphondylodis is that raw material is made nitrated fine plain method, be that the diluted acid about raw material and 3% is warm altogether, heat jointly with the alkali lye of low levels again after the washing, through chlorination, can get refined cellulose after the rinsing, it is copied make cellulose paper, with mixed acid nitrification, handle through stability again and can make soluble cotton, feature of the present invention is: adopt the refining alpine rush cellulose of prehydrolysis saponification method, it is to carry out with diluted acid after prehydrolysis and washed raw material and low levels mixed alkali liquor heat certain hour at a certain temperature that its saponification is handled, add saponifying agent rosin again, make it within a certain period of time, saponification reaction takes place down in certain temperature and pressure condition, the Mierocrystalline cellulose that the refining alpine rush cellulose that makes like this makes when not adding rosin is compared, hydroscopicity can improve 2-3 doubly, helps nitration reaction and carries out, and can shorten the nitration reaction time greatly.
2, according to the described method of claim 1, it is characterized in that: raw material with low levels mixing alkali liquid boiling after 2 hours, just adds saponifying agent rosin after hydrolysis washing is given in acid.
3, according to the described method of claim 1, it is characterized in that: the rosin add-on is the 0.4-0.5% of slurry gross weight.
4, according to the described method of claim 1, it is characterized in that: the saponification reaction time was controlled at 60-90 minute.
5, according to the described method of claim 1, it is characterized in that: the temperature of saponification reaction is about 160 ℃, can be positive and negative 10 ℃.
6, method according to claim 1 is characterized in that: the pressure-controlling of saponification reaction is in the 2.2-2.5 kilograms per centimeter.
7, according to the described method of claim 1: it is characterized in that: addition amount of sodium hydroxide is the 3.6-4.5% of total amount of slurry in the mixed alkali liquor, and the sodium sulphite add-on is 1～2.5% of a slurry gross weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85106196 CN1011970B (en) | 1985-08-14 | 1985-08-14 | Method for using chinese alpine rush as raw material to make nitrocellulose |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85106196 CN1011970B (en) | 1985-08-14 | 1985-08-14 | Method for using chinese alpine rush as raw material to make nitrocellulose |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85106196A CN85106196A (en) | 1987-03-04 |
| CN1011970B true CN1011970B (en) | 1991-03-13 |
Family
ID=4794944
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85106196 Expired CN1011970B (en) | 1985-08-14 | 1985-08-14 | Method for using chinese alpine rush as raw material to make nitrocellulose |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1011970B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101838332B (en) * | 2010-07-09 | 2011-06-29 | 北京理工大学 | Method for preparing nanometer nitro celluloses |
| CN102219861B (en) * | 2011-05-30 | 2012-12-19 | 四川北方硝化棉股份有限公司 | Method for preparing cellulose nitrate for explosive from wood pulp |
| CN102219862B (en) * | 2011-05-30 | 2012-11-21 | 四川北方硝化棉股份有限公司 | Method for preparing superhigh-viscosity energy-containing cellulose nitrate |
| CN107075799B (en) * | 2014-11-05 | 2019-10-08 | 双子科技有限责任公司 | The preparation method of cellulose |
| CN109504487B (en) * | 2018-10-18 | 2022-02-22 | 梅万伦 | Method for preparing fuel by nitrating mixture of plant cellulose and lignin |
| CN111072785B (en) * | 2019-12-03 | 2020-12-01 | 北京理工大学 | Preparation method of high-nitrogen-content nitrified bamboo cellulose |
| CN111647090A (en) * | 2020-07-14 | 2020-09-11 | 北京理工大学 | Method for nitrifying bamboo cellulose by using waste acid |
-
1985
- 1985-08-14 CN CN 85106196 patent/CN1011970B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN85106196A (en) | 1987-03-04 |
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