CN109369811A - A kind of optimization process preparing carboxymethyl cellulose nitrate - Google Patents
A kind of optimization process preparing carboxymethyl cellulose nitrate Download PDFInfo
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- CN109369811A CN109369811A CN201811094450.6A CN201811094450A CN109369811A CN 109369811 A CN109369811 A CN 109369811A CN 201811094450 A CN201811094450 A CN 201811094450A CN 109369811 A CN109369811 A CN 109369811A
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- kettle
- carboxymethyl cellulose
- cellulose nitrate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B13/00—Preparation of cellulose ether-esters
Abstract
The invention discloses a kind of optimization processes for preparing carboxymethyl cellulose nitrate for preparing carboxymethyl cellulose nitrate technical field, the process need to prepare the following raw material: A. prepares CMC raw material: the purified cotton that the degree of polymerization is 2024, the sodium hydroxide of content 99%, the isopropanol of content 98%, the monoxone of content 98%, water, the acetic acid that content is 99%, B. carboxymethyl cellulose nitrate raw material: the CMC that degree of substitution is 12% is prepared, the concentrated sulfuric acid of content 98%, the nitric acid of content 98%, C. equipment needed for carboxymethyl cellulose nitrate: pulverizer is prepared, cyclone separator, weighing hopper, alkalize kettle, etherification kettle, washing kettle, centrifuge, vibrated fluidized bed, D. preparation method: a. matches liquid: taking mass ratio is the sodium hydroxide and water of 1.3:40, configuration NaOH aqueous solution；When the present invention is used for water paint, the usage amount of organic solvent, reduces toxicity and the pollution to environment when can reduce coating spraying, can be improved production capacity by mechanization, increases production efficiency.
Description
Technical field
It is specially a kind of to prepare carboxymethyl cellulose nitre the present invention relates to carboxymethyl cellulose nitrate technical field is prepared
The optimization process of acid esters.
Background technique
Carboxymethyl cellulose nitrate abbreviation CMCN is most wide one of the cellulose esters of purposes, carboxymethyl cellulose nitre
Soluble, excellent film forming of the acid esters in common solvent and at CMC be the intermediate for preparing CMCN, the height of product
Mechanical performance etc., so that this esters can be used in the manufacture of coating, plastics etc., with the progress of science, carboxylic first in the market
The demand of base cellulose nitrate is also improving, and traditional method is will be by beaker human configuration, and efficiency is slow, in order to subtract
The pressure of small carboxymethyl cellulose nitrate demand improves production efficiency, for this purpose, it is proposed that a kind of prepare carboxymethyl cellulose
The optimization process of plain nitrate.
Summary of the invention
The purpose of the present invention is to provide a kind of optimization processes for preparing carboxymethyl cellulose nitrate, on solving
State the problem of proposing in background technique.
To achieve the above object, the invention provides the following technical scheme: a kind of prepare the excellent of carboxymethyl cellulose nitrate
Chemical industry process, the process need to prepare the following raw material:
A. CMC raw material is prepared: the isopropyl of the sodium hydroxide of purified cotton, content 99% that the degree of polymerization is 2024, content 98%
Alcohol, the monoxone of content 98%, water, the acetic acid that content is 99%.
B. carboxymethyl cellulose nitrate raw material: CMC, the concentrated sulfuric acid of content 98%, content of the degree of substitution for 12% is prepared
98% nitric acid；
C. equipment needed for carboxymethyl cellulose nitrate: pulverizer, cyclone separator, weighing hopper, alkalization kettle, etherificate is prepared
Kettle, washing kettle, centrifuge, vibrated fluidized bed；
Preparation method:
A. match liquid: taking mass ratio is the sodium hydroxide and water of 1.3:40, configures NaOH aqueous solution；
B. it stocks up: purified cotton essence being ground into exquisite cotton powder through pulverizer, is accurately measured through weighing hopper；
C. it alkalizes: pouring into isopropanol and NaOH aqueous solution in alkalization kettle, alkalizing solution is made, by the purification in weighing hopper
Cotton powder pours into alkalizing solution, alkalizes；
D. it is etherified: after alkalizing in step c, solution being poured into etherification kettle, when system is cooled to 18 DEG C, slowly drip
Chlorination acetic acid-aqueous isopropanol is etherified 140min；
E. it neutralizes: the solution in etherification kettle being pumped into washing kettle by centrifuge, ethyl alcohol is diluted to 75% with water
Concentration distinguishes 3 ethyl alcohol of middle addition into washing kettle in three times, adds 15L every time；
F. it dries: the solution in washing kettle is evacuated in vibrated fluidized bed, be heated to 75 DEG C, heating 20min is dried, with
Dry CMC solid enters in pulverizer and crushes as CMC powder afterwards；
G. complex acid: the water of 40 times of concentrated sulfuric acid mass ratioes being poured into reaction kettle, the concentrated sulfuric acid is slowly poured into water along kettle wall,
Edge to edge is stirred with acid proof slab, after pouring into the concentrated sulfuric acid, then is poured slowly into concentrated nitric acid, stands cooling；
H.CMC reaction: CMC powder is slowly uniformly added in reaction kettle, reaction kettle opens rotation, is stirred to react
60min is linked into the dry bucket of the acidproof plastics of 25L, with strainer filtering object under stirring from reactor bottom by material
Material, and spent acid is collected in waste liquid barrel；
I. it washs: filter material is poured into 15L soft water, wash 10min, then go to be centrifuged, prevent from running and expect.
Preferably, it in washing, with 200 mesh net filtrations, washes repeatedly 4 times, until cleaning solution pH > 6, washing terminate,
Last time is separated again after crossing 200 mesh.
Preferably, it in etherification reaction, pours into alkalizing solution and takes around 20min, it is cold to stir 10min, it is warming up to 50 DEG C of ethers
Change 80min, be warming up to 75 DEG C, is etherified 30min.
Preferably, in CMC reaction, used filter screen is stainless steel filter screen, and density is 200 mesh.
Preferably, it when quaternization, needs in 20 degrees Celsius of alkalization 1.5h.
Preferably, in CMC reaction, used filter screen is stainless steel filter screen, and density is 200 mesh.
Preferably, purified cotton, sodium hydroxide, monoxone, CMC powder, sulfuric acid, nitric acid feed intake mass ratio be 1:0.2:
0.23:0.5:13:4.9.
Compared with prior art, the beneficial effects of the present invention are:
1, the technological operation is simple, high-efficient, and technical process meteyage is for CMC and prepares carboxymethyl cellulose nitrate two
Step, turns to alkali cellulose for cellulose alkali first when preparing CMC, monoxone is converted into sodium chloroacetate, then neutralizes washing again
Carboxyl methyl cellulose is made, when preparing carboxymethyl cellulose nitrate, the carboxyl methyl cellulose as made from by before
It is acidified again to be transformed into carboxymethyl cellulose nitrate, carboxymethyl cellulose nitrate obtained both had good film forming and
Excellent mechanical performance, and can disperse in water, when being used for water paint, the use of organic solvent when can reduce coating spraying
Amount reduces toxicity and the pollution to environment；
2, the present invention is separated by that will refine silk floss by cyclone separator, then is accurately weighed by weighing hopper, then
It is reacted in each reaction kettle, pumps in each reaction kettle through centrifuge, most dried afterwards through vibrated fluidized bed, whole process is certainly
Dynamicization can be accurately controlled the precision of reaction, accelerate production efficiency.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
Belong to the scope of protection of the invention.
The present invention provides a kind of technical solution: a kind of optimization process preparing carboxymethyl cellulose nitrate, the work
Process need to prepare the following raw material and equipment:
A. prepare CMC raw material (CMC is the intermediate for preparing CMCN): the degree of polymerization be 2024 purified cotton, content 99%
Sodium hydroxide, the isopropanol of content 98%, the monoxone of content 98%, water, content be 99% acetic acid；
B. carboxymethyl cellulose nitrate raw material: CMC, the concentrated sulfuric acid of content 98%, content of the degree of substitution for 12% is prepared
98% nitric acid；
C. equipment needed for carboxymethyl cellulose nitrate: pulverizer, cyclone separator, weighing hopper, alkalization kettle, etherificate is prepared
Kettle, washing kettle, centrifuge, vibrated fluidized bed；
Preparation method:
A. match liquid: taking mass ratio is the sodium hydroxide and water of 1.3:40, configures NaOH aqueous solution, is used for purified cotton alkali
Change；
B. it stocks up: purified cotton essence being ground into exquisite cotton powder through pulverizer, is accurately measured through weighing hopper；
C. it alkalizes: pouring into isopropanol and NaOH aqueous solution in alkalization kettle, alkalizing solution is made, by the purification in weighing hopper
Cotton powder pours into alkalizing solution, alkalizes, and the reaction equation of alkalization is Cell- (OH) 3+xNaOH → Cell- (OH) 3-x (O-
Na+)x+xH2O；
D. it is etherified: after alkalizing in step c, solution being poured into etherification kettle, when system is cooled to 18 DEG C, slowly drip
Chlorination acetic acid-aqueous isopropanol is etherified 140min, ClCH2COOH+NaOH → ClCH2COONa+H2O；
E. it neutralizes: the solution in etherification kettle being pumped into washing kettle by centrifuge, ethyl alcohol is diluted to 75% with water
Concentration distinguishes 3 ethyl alcohol of middle addition into washing kettle in three times, adds 15L every time, guarantee pure and fresh clean noresidue；
F. it dries: the solution in washing kettle is evacuated in vibrated fluidized bed, be heated to 75 DEG C, heating 20min is dried, with
Dry CMC solid, which enters in pulverizer, afterwards crushes as CMC powder, Cell- (OH) 3-x (ONa) x-n (OCH2COO-Na+) n+
(x-n)CH3COOH→Cell-(OH)3 -n(OCH2COO-Na+)n+(x-n)CH3COONa；
G. complex acid: the water of 40 times of concentrated sulfuric acid mass ratioes being poured into reaction kettle, the concentrated sulfuric acid is slowly poured into water along kettle wall,
Edge to edge is stirred with acid proof slab, after pouring into the concentrated sulfuric acid, then is poured slowly into concentrated nitric acid, is stood and is cooled down, the cooling requirement time,
Generally mention the previous day progress complex acid；
H.CMC reaction: CMC powder is slowly uniformly added in reaction kettle, reaction kettle opens rotation, is stirred to react
60min is linked into the dry bucket of the acidproof plastics of 25L, with strainer filtering object under stirring from reactor bottom by material
Material, and spent acid is collected in waste liquid barrel；
I. it washs: filter material is poured into 15L soft water, wash 10min, then go to be centrifuged, prevent from running and expect.
Wherein, it in washing, with 200 mesh net filtrations, washes repeatedly 4 times, until cleaning solution pH > 6, washing terminate, most
It is separated again after primary 200 mesh of mistake afterwards, guarantees the precision of filtering；
In etherification reaction, pours into alkalizing solution and take around 20min, it is cold to stir 10min, 50 DEG C of etherificate 80min are warming up to,
75 DEG C are warming up to, 30min is etherified；
When quaternization, need in 20 degrees Celsius of alkalization 1.5h, sufficiently alkalization when, it is to replace that x, which levels off to 3, n,
The number of carboxymethyl in each cellulose glucose ring group；
In CMC reaction, used filter screen is stainless steel filter screen, prevents acid and alkali corrosion, and density is 200 mesh；
Purified cotton, sodium hydroxide, monoxone, CMC powder, sulfuric acid, nitric acid feed intake mass ratio be 1:0.2:0.23:0.5:
13:4.9, as long as the compound ratio, can be mass-produced.
Working principle: technical process meteyage is for CMC and prepares two step of carboxymethyl cellulose nitrate, when preparing CMC
Cellulose alkali is turned into alkali cellulose first: Cell- (OH) 3+xNaOH → Cell- (OH) 3-x (O-Na+) x+xH2O, chloroethene
Acid is converted into sodium chloroacetate: ClCH2COOH+NaOH → ClCH2COONa+H2O, then neutralizes washing again and carboxymethyl cellulose is made
3-n of plain CMC:Cell- (OH) 3-x (ONa) x-n (OCH2COO-Na+) n+ (x-n) CH3COOH → Cell- (OH)
(OCH2COO-Na+) n+ (x-n) CH3COONa, when preparing carboxymethyl cellulose nitrate, the carboxymethyl as made from by before
Cellulose CMC is acidified again to be transformed into carboxymethyl cellulose nitrate:
Cell-(OH)3-x(OCH2COO-Na+)x+yHNO3→Cell-(OH)3-x-y(OCH2COO-Na +)x(ONO2)
Y+yH2O, in above-mentioned reaction, x is less than the number equal to 3, when using suitable stirring, dicyandiamide solution and suitable temperature, fills
Point alkalization when, x level off to 3, n be the carboxymethyl being substituted in each cellulose glucose ring group number,
Become after ell- (ONa) 3-n (OCH2COO-na+) n is washed
Cell- (OH) 3-n (OCH2COO-na+) n, using being obtained after nitrification
Cell- (OH) 3-x-y (OCH2COO-Na+) x (ONO2) y, this is final product carboxymethyl cellulose nitrate.
The eight major indicators comparison of carboxymethyl cellulose nitrate produced by the present invention and original product D grades of nitrocotton NC is as follows
Table:
| Product | D grades of nitrocotton NC | CMCN |
| Nitrogen content/% | 11.75-12.1 | 11.0-12.0 |
| Viscosity/cp | 1.9-2.6 | 25.5 |
| Carefully disconnected degree/ml | On demand | 68 |
| Basicity/% | < 0.2 | 0.02 |
| Permanence/mlg-1 | < 2.5 | 2.25 |
| Ethyl alcohol solubility/% | < 12 | 10.3 |
| Alcohol ether solubility/% | >98 | 19.9 |
| Ash content/% | < 0.5 | 0.08 |
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (6)
1. a kind of optimization process for preparing carboxymethyl cellulose nitrate, it is characterised in that: the process need to prepare such as
Lower raw material and equipment:
A. prepare CMC raw material: the sodium hydroxide of purified cotton, content 99% that the degree of polymerization is 2024, content 98% isopropanol, contain
The monoxone of amount 98%, water, the acetic acid that content is 99%；
B. carboxymethyl cellulose nitrate raw material: CMC, the concentrated sulfuric acid of content 98%, content 98% of the degree of substitution for 12% is prepared
Nitric acid；
C. prepare equipment needed for carboxymethyl cellulose nitrate: pulverizer, cyclone separator, weighing hopper, alkalization kettle, etherification kettle,
Washing kettle, centrifuge, vibrated fluidized bed；
The step of process, is as follows:
A. match liquid: taking mass ratio is the sodium hydroxide and water of 1.3:40, configures NaOH aqueous solution；
B. it stocks up: purified cotton essence being ground into exquisite cotton powder through pulverizer, is accurately measured through weighing hopper；
C. it alkalizes: pouring into isopropanol and NaOH aqueous solution in alkalization kettle, alkalizing solution is made, by the purified cotton powder in weighing hopper
It pours into alkalizing solution, alkalizes；
D. it is etherified: after alkalizing in step c, solution being poured into etherification kettle, when system is cooled to 18 DEG C, chlorine is slowly added dropwise
Acetic acid-aqueous isopropanol is etherified 140min；
E, it neutralizes: the solution in etherification kettle being pumped into washing kettle by centrifuge, ethyl alcohol is diluted to 75% concentration with water,
Distinguish 3 ethyl alcohol of middle addition into washing kettle in three times, adds 15L every time；
F. it dries: the solution in washing kettle is evacuated in vibrated fluidized bed, be heated to 75 DEG C, heating 20min drying is then dry
Dry CMC solid, which enters in pulverizer, to be crushed as CMC powder；
G. complex acid: the water of 40 times of concentrated sulfuric acid mass ratioes is poured into reaction kettle, the concentrated sulfuric acid is slowly poured into water along kettle wall, while arriving
While being stirred with acid proof slab, after pouring into the concentrated sulfuric acid, then it is poured slowly into concentrated nitric acid, stands cooling；
H.CMC reaction: CMC powder is slowly uniformly added in reaction kettle, and reaction kettle opens rotation, is stirred to react 60min,
Under stirring, material is linked into from reactor bottom in the dry bucket of the acidproof plastics of 25L, with strainer filtering material, and collected
Spent acid is in waste liquid barrel；
I. it washs: filter material is poured into 15L soft water, wash 10min, then go to be centrifuged, prevent from running and expect.
2. a kind of optimization process for preparing carboxymethyl cellulose nitrate according to claim 1, it is characterised in that: washing
When washing, 200 mesh screens are being crossed for the last time until cleaning solution pH > 6, washing terminate with 200 mesh net filtrations, repeated washing 4 times
It is separated again afterwards.
3. a kind of optimization process for preparing carboxymethyl cellulose nitrate according to claim 1, it is characterised in that: in ether
When changing reaction, pours into alkalizing solution and take around 20min, it is cold to stir 10min, 50 DEG C of etherificate 80min are warming up to, are warming up to 75 DEG C,
It is etherified 30min.
4. a kind of optimization process for preparing carboxymethyl cellulose nitrate according to claim 1, it is characterised in that: in alkali
When changing reaction, need in 20 degrees Celsius of alkalization 1.5h.
5. a kind of optimization process for preparing carboxymethyl cellulose nitrate according to claim 1, it is characterised in that:
In CMC reaction, used filter screen is stainless steel filter screen, and density is 200 mesh.
6. a kind of optimization process for preparing carboxymethyl cellulose nitrate according to claim 1, it is characterised in that: purification
Cotton, sodium hydroxide, monoxone, CMC powder, sulfuric acid, nitric acid feed intake mass ratio be 1:0.2:0.23:0.5:13:4.9.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0925445A (en) * | 1995-07-10 | 1997-01-28 | Asahi Chem Ind Co Ltd | Aqueous ink composition |
| CN101081872A (en) * | 2007-06-07 | 2007-12-05 | 北京北方世纪纤维素技术开发有限公司 | Low bath ratio kneading method production of polyanion cellulose |
| CN101343329A (en) * | 2008-08-04 | 2009-01-14 | 北京理工大学 | Multi-hydroxyalkyl cellulose ether nitrate and preparation thereof |
| CN101735324A (en) * | 2010-01-13 | 2010-06-16 | 北京理工大学 | Carboxymethyl cellulose nitrate and preparation method thereof |
| CN105801710A (en) * | 2016-05-24 | 2016-07-27 | 江苏泰利达新材料股份有限公司 | Production process of ultralow-viscosity sodium carboxymethylcellulose |
-
2018
- 2018-09-19 CN CN201811094450.6A patent/CN109369811A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0925445A (en) * | 1995-07-10 | 1997-01-28 | Asahi Chem Ind Co Ltd | Aqueous ink composition |
| CN101081872A (en) * | 2007-06-07 | 2007-12-05 | 北京北方世纪纤维素技术开发有限公司 | Low bath ratio kneading method production of polyanion cellulose |
| CN101343329A (en) * | 2008-08-04 | 2009-01-14 | 北京理工大学 | Multi-hydroxyalkyl cellulose ether nitrate and preparation thereof |
| CN101735324A (en) * | 2010-01-13 | 2010-06-16 | 北京理工大学 | Carboxymethyl cellulose nitrate and preparation method thereof |
| CN105801710A (en) * | 2016-05-24 | 2016-07-27 | 江苏泰利达新材料股份有限公司 | Production process of ultralow-viscosity sodium carboxymethylcellulose |
Non-Patent Citations (1)
| Title |
|---|
| 段洪涛: "羧甲基纤维素化学改性及水性分散体的制备与性能", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
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