CN102558366B - Preparation method of ammonium carboxymethylcellulose - Google Patents
Preparation method of ammonium carboxymethylcellulose Download PDFInfo
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- CN102558366B CN102558366B CN201110457650.5A CN201110457650A CN102558366B CN 102558366 B CN102558366 B CN 102558366B CN 201110457650 A CN201110457650 A CN 201110457650A CN 102558366 B CN102558366 B CN 102558366B
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Abstract
The invention provides a preparation method of ammonium carboxymethylcellulose, which includes first evenly mixing sodium carboxymethylcellulose powder and dilute sulphuric acid solution in stirring mode, placing the mixture statically for a time, conducting acidification reaction, conducting washing and centrifuging, adding hartshorn to conduct ammonium compounding, finally conducting washing, centrifuging, drying and crushing to obtain a ammonium carboxymethylcellulose product. The whole production process is simple in process, short in reaction period, less in equipment investment and low in raw material consumption.
Description
Technical field
The present invention relates to a kind of carboxymethyl cellulose ammonium (CMC-NH
4) preparation method, belong to natural macromolecular material chemical modification field.
Background technology
Coal in China consumption is large, and the environmental pollution causing is thus particularly serious, wherein flue dust, SO
2and NO
xfor principal pollutant.NOx is the main pollutent of thermal power generation discharge, is one of main source of acid rain, or the precursor substance of photo-chemical smog.To HUMAN HEALTH and ecotope, will form larger harm simultaneously.In current various denitration technologies, selective-catalytic-reduction denitrified (SCR) applies maximum, most effective, and its nitric efficiency is 80～90%, even can be up to 95%, and be one of proven technique, its processing unit compactness, reliable.The key of SCR is high performance catalyzer, generally take SCR catalyst powder as matrix, with shaping assistant etc. by mixing, the process such as kneading, extrusion molding, dry, roasting obtains.In order to obtain character homogeneous, there is the plasticity lotion of better physical strength and pore structure, need to add tackiness agent, extrusion aid, pore-forming material, glass fibre and lubricant etc.Wherein, carboxymethyl cellulose ammonium (CMC-NH
4) be a kind of conventional tackiness agent, there is cohesiveness good, residual few feature after roasting, the at present domestic CMC-NH for denitration industry
4main dependence on import, generally adopts ion exchange column method to produce, and cost is higher, and domestic rarely seen production report.The present invention, take CMC-Na as raw material, successfully prepares and meets the CMC-NH that denitrating catalyst is used after acidified reaction and ammoniumization reaction
4product, and technique is simple, and reaction time is short, and facility investment is few, and raw material consumption is low.
Summary of the invention
It is good that object of the present invention adopts lower-cost chemical synthesis to prepare a kind of solvability, has good viscosity performance, and the ash content residual volume after calcining is few, meets the CMC-NH that denitrating catalyst is used
4.
Technical scheme of the present invention is as follows:
A kind of CMC-NH
4preparation method, it is characterized in that comprising the following steps:
A, Xylo-Mucine (CMC-Na) is mixed with a certain amount of sulphuric acid soln, carry out acidification reaction;
After b, acidification reaction finish, a certain amount of water is added in product to agitator treating, centrifugation.
C, the product obtaining in step b is mixed with a certain amount of ammoniacal liquor ethanolic soln, carry out ammonium reaction;
D, by the material centrifugation after ammonium;
E, the product that obtains in steps d is dried, pulverized.
The mass percent concentration of described sulphuric acid soln is 10～40%, and in step c, take aqueous ethanolic solution as reaction medium, the mass percentage concentration of aqueous ethanolic solution is 70～95%, and the mass percentage concentration of ammoniacal liquor is 10～25%.
Mass ratio 6.5～9.0:1 of sulphuric acid soln and CMC;
Mass ratio 2.0～4.0:1 of ethanolic soln and CMC;
Mass ratio 0.5～3.0:1 of ammoniacal liquor and CMC.
Wherein, in step a, the acidification reaction time is 100～200min, and temperature of reaction is normal temperature.
In step c, the ammonium reaction times is 150～250min, and temperature of reaction is normal temperature.
In step e, bake out temperature is 60～80 ℃, prevents that excess Temperature from causing the volatilization of ammonia.
The inventive method production process technology is simple, and reaction time is short, and facility investment is few, and raw material consumption is low, and the carboxymethyl cellulose ammonium that adopts the method to produce, has good viscosity performance, and the ash content residual volume after calcining is little simultaneously.
Accompanying drawing explanation
Fig. 1 is Production Flow Chart block diagram of the present invention.
Embodiment
Below in conjunction with Fig. 1 and embodiment, the present invention is further illustrated.
Embodiment 1:
By a certain amount of Xylo-Mucine powder (2%NDJ-79 viscosity 850, substitution value 0.62), concentration 10% aqueous sulfuric acid of 6.5 times of quality, stirs after 60min, more standing acidifying 40min; Then a certain amount of water is added in product to agitator treating, centrifugation; The ammonia soln that the concentration that adds 0.5 times of quality after centrifugal is 10%, the ethanolic soln that the concentration that simultaneously adds 2.0 times of quality is 70%, standing and reacting 150min after stirring and evenly mixing, and then centrifugation, and in baking oven, dry 120min, bake out temperature is 60～80 ℃, obtains refining CMC-NH after pulverizing
4finished product, 1% solution viscosity that Brookfield type viscometer is measured is 92, ash oontent 0.20%.
Embodiment 2:
By a certain amount of Xylo-Mucine powder (2%NDJ-79 viscosity 850, substitution value 0.62), concentration 20% aqueous sulfuric acid of 7.5 times of quality, stirs after 60min, more standing acidifying 90min; A certain amount of water is added in product to agitator treating, centrifugation; The ammonia soln that the concentration that adds 1.0 times of quality after centrifugal is 15%, the ethanolic soln that the concentration that simultaneously adds 4.0 times of quality is 80%, standing and reacting 180min after stirring and evenly mixing, and then centrifugation, and in baking oven, dry 120min, bake out temperature is 60～80 ℃, obtains refining CMC-NH after pulverizing
4finished product, 1% solution viscosity that Brookfield type viscometer is measured is 97, ash oontent 0.15%.
Embodiment 3:
By a certain amount of Xylo-Mucine powder (2%NDJ-79 viscosity 850, substitution value 0.62), concentration 20% aqueous sulfuric acid of 8.0 times of quality, stirs after 60min, more standing acidifying 120min; Then remove supernatant liquid, a certain amount of water is added in product, agitator treating, centrifugation; The ammonia soln that the concentration that adds 1.5 times of quality after centrifugal is 20%, the ethanolic soln that the concentration that simultaneously adds 3.0 times of quality is 90%, standing and reacting 210min after stirring and evenly mixing, and then centrifugation, and in baking oven, dry 120min, bake out temperature is 60～80 ℃, obtains refining CMC-NH after pulverizing
4finished product, 1% solution viscosity that Brookfield type viscometer is measured is 105, ash oontent 0.08%.
Embodiment 4:
By a certain amount of Xylo-Mucine powder (2%NDJ-79 viscosity 510, substitution value 0.85), concentration 30% aqueous sulfuric acid of 9.0 times of quality, stirs after 60min, more standing acidifying 120min; A certain amount of water is added in product to agitator treating, centrifugation; The ammonia soln that the concentration that adds 2.5 times of quality after centrifugal is 25%, the ethanolic soln that the concentration that simultaneously adds 3.0 times of quality is 90%, standing and reacting 240min after stirring and evenly mixing, and then centrifugation, and in baking oven, dry 120min, bake out temperature is 60～80 ℃, obtains refining CMC-NH after pulverizing
4finished product, 1% solution viscosity that Brookfield type viscometer is measured is 50, ash oontent 0.08%.
Embodiment 5:
By a certain amount of Xylo-Mucine powder (2%NDJ-79 viscosity 1350, substitution value 0.72), concentration 40% aqueous sulfuric acid of 8.0 times of quality, stirs after 60min, more standing acidifying 140min; A certain amount of water is added in product to agitator treating, centrifugation; The ammonia soln that the concentration that adds 3.0 times of quality after centrifugal is 25%, the ethanolic soln that the concentration that simultaneously adds 3.0 times of quality is 95%, standing and reacting 250min after stirring and evenly mixing, and then centrifugation, and in baking oven, dry 120min, bake out temperature is 60～80 ℃, obtains refining CMC-NH after pulverizing
4finished product, 1% solution viscosity that Brookfield type viscometer is measured is 95, ash oontent 0.07%.
term:
viscosity: 1% aqueous solution, 1% aqueous solution Type B viscosity, detects under 25 ℃ of conditions.
ash content: ash oontent.
Claims (4)
1. a preparation method for carboxymethyl cellulose ammonium, is characterized in that comprising the following steps:
A, Xylo-Mucine is mixed with sulphuric acid soln, carry out acidification reaction;
After b, acidification reaction finish, water is added in product to agitator treating, centrifugation;
C, the product obtaining in step b is mixed with ammoniacal liquor ethanolic soln, carry out ammonium reaction;
D, by the material centrifugation after ammonium;
E, the product that obtains in steps d is dried, pulverized;
The mass percent concentration of described sulphuric acid soln is 10～40%, and in step c, take aqueous ethanolic solution as reaction medium, the mass percentage concentration of aqueous ethanolic solution is 70～95%, and the mass percentage concentration of ammoniacal liquor is 10～25%;
Mass ratio 6.5～the 9.0:1 of sulphuric acid soln and Xylo-Mucine;
Mass ratio 2.0～the 4.0:1 of ethanolic soln and Xylo-Mucine;
Mass ratio 0.5～the 3.0:1 of ammoniacal liquor and Xylo-Mucine.
2. the method for preparing carboxymethyl cellulose ammonium according to claim 1, is characterized in that: in step a, the acidification reaction time is 100～200min, and temperature of reaction is normal temperature.
3. the method for preparing carboxymethyl cellulose ammonium according to claim 1, is characterized in that: in step c, the reaction times is 150～250min, and temperature of reaction is normal temperature.
4. the method for preparing carboxymethyl cellulose ammonium according to claim 1, is characterized in that: in step e, bake out temperature is 60～80 ℃, prevents that excess Temperature from causing the volatilization of ammonia.
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103242454A (en) * | 2013-05-13 | 2013-08-14 | 宜兴市通达化学有限公司 | Method for preparing high-substitution degree ammonium carboxymethyl cellulose by means of mixed strong acid |
| CN106336462A (en) * | 2016-10-13 | 2017-01-18 | 重庆力宏精细化工有限公司 | Method for preparing carboxymethyl cellulose |
| CN106496336A (en) * | 2016-11-25 | 2017-03-15 | 泸州北方化学工业有限公司 | The method that nitrate method prepares carboxymethyl cellulose ammonium |
| CN108715617A (en) * | 2018-04-25 | 2018-10-30 | 山东滕新材料股份有限公司 | Native cellulose prepares carboxymethyl cellulose ammonium |
| CN109627349A (en) * | 2018-11-30 | 2019-04-16 | 泸州北方纤维素有限公司 | The ammonium chemical industry skill of carboxymethyl cellulose ammonium |
| CN109609036A (en) * | 2018-12-06 | 2019-04-12 | 武汉科丝力纤维制造有限公司 | A kind of environment-friendly modified foamed ceramics adhesive and its preparation process |
| CN110467682B (en) * | 2019-09-24 | 2020-11-10 | 北京理工大学 | Cellulose derivative and preparation method and application thereof |
| CN112321730A (en) * | 2020-11-10 | 2021-02-05 | 重庆纤磊新材料科技有限公司 | Preparation method of high-viscosity carboxymethyl cellulose ammonium |
| CN114335541A (en) * | 2021-12-29 | 2022-04-12 | 蜂巢能源科技股份有限公司 | Positive electrode slurry and preparation method and application thereof |
| CN115260943A (en) * | 2022-07-14 | 2022-11-01 | 向能新型材料科技(河北)有限公司 | Preparation method of carboxymethyl cellulose ammonium aqueous adhesive |
| CN116462775A (en) * | 2023-05-06 | 2023-07-21 | 绿能纤材(重庆)科技有限公司 | Preparation method of high-purity battery-grade ammonium carboxymethyl cellulose |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1265922A (en) * | 2000-01-27 | 2000-09-13 | 华南理工大学 | Process for preparing calcium carboxymethyl cellulose |
| CN102206286A (en) * | 2011-05-16 | 2011-10-05 | 北京理工大学 | Preparation method of lithium carboxymethyl cellulose for lithium battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1265922A (en) * | 2000-01-27 | 2000-09-13 | 华南理工大学 | Process for preparing calcium carboxymethyl cellulose |
| CN102206286A (en) * | 2011-05-16 | 2011-10-05 | 北京理工大学 | Preparation method of lithium carboxymethyl cellulose for lithium battery |
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