CN104387477B - The preparation method of food stage high substituted degree ultralow-viscosity sodium carboxymethyl cellulose - Google Patents
The preparation method of food stage high substituted degree ultralow-viscosity sodium carboxymethyl cellulose Download PDFInfo
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- CN104387477B CN104387477B CN201410737944.7A CN201410737944A CN104387477B CN 104387477 B CN104387477 B CN 104387477B CN 201410737944 A CN201410737944 A CN 201410737944A CN 104387477 B CN104387477 B CN 104387477B
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- viscosity
- carboxymethyl cellulose
- sodium carboxymethyl
- cellulosic material
- food stage
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- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 title claims abstract description 37
- 239000001768 carboxy methyl cellulose Substances 0.000 title claims abstract description 36
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 title claims abstract description 36
- 235000013305 food Nutrition 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 109
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 56
- 239000000463 material Substances 0.000 claims abstract description 35
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 238000006266 etherification reaction Methods 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 45
- 239000007864 aqueous solution Substances 0.000 claims description 29
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- 229920001131 Pulp (paper) Polymers 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 229920002678 cellulose Polymers 0.000 claims description 16
- 239000001913 cellulose Substances 0.000 claims description 16
- SJRXVLUZMMDCNG-UHFFFAOYSA-N Gossypin Natural products OC1C(O)C(O)C(CO)OC1OC1=C(O)C=C(O)C2=C1OC(C=1C=C(O)C(O)=CC=1)=C(O)C2=O SJRXVLUZMMDCNG-UHFFFAOYSA-N 0.000 claims description 14
- SJRXVLUZMMDCNG-KKPQBLLMSA-N gossypin Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=C(O)C=C(O)C2=C1OC(C=1C=C(O)C(O)=CC=1)=C(O)C2=O SJRXVLUZMMDCNG-KKPQBLLMSA-N 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 238000010790 dilution Methods 0.000 claims description 9
- 239000012895 dilution Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 238000011946 reduction process Methods 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 abstract description 36
- 235000010948 carboxy methyl cellulose Nutrition 0.000 abstract description 36
- 238000006467 substitution reaction Methods 0.000 abstract description 22
- 235000013361 beverage Nutrition 0.000 abstract description 10
- 229920000297 Rayon Polymers 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000006641 stabilisation Effects 0.000 abstract description 3
- 238000011105 stabilization Methods 0.000 abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 10
- 229920000742 Cotton Polymers 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 235000013336 milk Nutrition 0.000 description 6
- 239000008267 milk Substances 0.000 description 6
- 210000004080 milk Anatomy 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000000796 flavoring agent Substances 0.000 description 4
- 235000013373 food additive Nutrition 0.000 description 4
- 239000002778 food additive Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 3
- 210000000481 breast Anatomy 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 235000019634 flavors Nutrition 0.000 description 3
- 235000020124 milk-based beverage Nutrition 0.000 description 3
- 108090000623 proteins and genes Proteins 0.000 description 3
- 102000004169 proteins and genes Human genes 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- KUBWXQUHENSKGC-UHFFFAOYSA-N 2-chloroacetic acid;ethanol Chemical compound CCO.OC(=O)CCl KUBWXQUHENSKGC-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- YENBJQJVQRQIKV-UHFFFAOYSA-N OO.CCO Chemical compound OO.CCO YENBJQJVQRQIKV-UHFFFAOYSA-N 0.000 description 2
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 2
- 244000046052 Phaseolus vulgaris Species 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 description 2
- 229940063834 carboxymethylcellulose sodium Drugs 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- -1 drying Substances 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 235000015203 fruit juice Nutrition 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000005956 quaternization reaction Methods 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- 235000013618 yogurt Nutrition 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- AQLLBJAXUCIJSR-UHFFFAOYSA-N OC(=O)C[Na] Chemical compound OC(=O)C[Na] AQLLBJAXUCIJSR-UHFFFAOYSA-N 0.000 description 1
- 235000009392 Vitis Nutrition 0.000 description 1
- 241000219095 Vitis Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 229920006321 anionic cellulose Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000037406 food intake Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 235000013882 gravy Nutrition 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 235000015243 ice cream Nutrition 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000013324 preserved food Nutrition 0.000 description 1
- 239000012460 protein solution Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000001835 salubrious effect Effects 0.000 description 1
- 210000000582 semen Anatomy 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- VILMUCRZVVVJCA-UHFFFAOYSA-M sodium glycolate Chemical compound [Na+].OCC([O-])=O VILMUCRZVVVJCA-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000013555 soy sauce Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000009955 starching Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 235000015192 vegetable juice Nutrition 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Jellies, Jams, And Syrups (AREA)
Abstract
The present invention relates to the preparation method of a kind of food stage high substituted degree ultralow-viscosity sodium carboxymethyl cellulose (SG30), belong to sodium carboxymethyl cellulose production technical field.The present invention comprises the following steps: that the liquid caustic soda of high concentration adds in cellulosic material, is simultaneously introduced thinner ethanol, by a viscosity reduction, first to cellulosic material viscosity reduction, alkalizes cellulosic material simultaneously.It is subsequently adding etherifying agent to be etherified.After etherification reaction terminates, neutralized, with the ethanol solution of certain concentration, wash according to certain bath raio (cellulosic material/ethanol solution), through de-liquid, be dried, pulverize and obtain food stage extra low viscose degree CMC.The product of the present invention has relatively high substituted degree, the lowest viscosity, and Brookfield viscometer (Brookfield) 2% is 10 30CPS, and substitution value is more than 1.20, purity more than 98%.CMC solution is limpid, viscosity stabilization.It is particularly well-suited to be added in the light beverage of delicate mouthfeel.
Description
Technical field
The invention mainly relates to a kind of food stage high substituted degree spy being applicable to the light beverage of delicate mouthfeel low
The preparation method of viscosity carboxymethyl cellulose sodium, belongs to sodium carboxymethyl cellulose production technical field.
Background technology
Sodium carboxymethyl cellulose is the sodium salt of carboxymethyl cellulose ether, belongs to anionic cellulose ether, for white
Slightly yellow fibrous powder or granule, density 0.5-0.7 gram/cc, odorless, tasteless, have hygroscopicity.
It is readily dispersed in water one-tenth clear gum solution, insoluble in the organic solvents such as ethanol.1% aqueous solution pH
It is 6.5～8.5, as pH>10 or<when 5, cement viscosity significantly reduces, and when pH=7, performance is optimal.
To thermally-stabilised, below 20 DEG C, viscosity rises rapidly, and when 45 DEG C, change is relatively slow, and more than 80 DEG C add for a long time
Heat can make its colloid degeneration and viscosity and performance are decreased obviously.Soluble in water, solution is transparent；Molten in alkalescence
In liquid more stable, meet acid then facile hydrolysis, have certain acid-resisting, pH value is to there will be precipitation during 2-3,
Meet multivalent metal salt and also can react appearance precipitation.Different according to specifications of raw materials, reaction condition is different,
To the product that different degree of substitution is different with different molecular weight and replacement uniformity.
Pure CMC is used for food by FAO and WHO approved at present, and it is through the strictest biology
Just getting the Green Light after, toxicologic study and test, the amount safe for ingestion (ADI) of international standard is
25mg/ (kg d), the most about everyone 1.5g/d.Once it was reported that, someone tests intake and reaches 10kg
The most toxic reaction.CMC is not only good emulsion stabilizer, thickening agent in food applications, and
And there is the freezing of excellence, melt stability, and the local flavor of product can be improved, prolongation storage time.?
Consumption in bean milk, ice cream, popsicle, fruit jelly, beverage, canned food is about 1%～1.5%.CMC is also
The emulsified dispersed liquid of stable performance can be formed with vinegar, soy sauce, vegetable oil, fruit juice, gravy, vegetable juice etc.,
Its consumption is 0.2%～0.5%.The particularly emulsifiability to animal and vegetable oil, protein and aqueous solution
Extremely excellent, the homogeneous emulsion of stable performance can be formed it into.Because it is safe and reliable, therefore, it is used
Amount is not limited by national food hygienic standard ADI.CMC is continuously developed at field of food, at Fructus Vitis viniferae
Wine applies the research of sodium carboxymethyl cellulose the most to carry out in producing.
Along with the development of biotechnology and the appearance of new material and consumer spending idea reach its maturity and
Rationality, functional drinks and milk beverage are towards more healthy, and closer to natural, safer direction is developed.
Past is that by a large amount of thick, Luzhou-flavors adding chemosynthesis additive and produce, mouthfeel thickness
Yoghourt, milk beverage all will be unfeelingly by market, the substitute is clean taste, light outward appearance power
Seek the asymptotic natural Yoghourt close to former breast, and milk beverage (functionalization such as Liu Peng, Li little Lin, light
The developing direction of China's beverage, milk and the mankind, the 2nd phase in 2008).Under this market background,
CMC as thickening agent and stabilizer is just had higher requirement.Current domestic CMC food stage
Low viscous product be substitution value about 1.0 mostly, viscosity 100CPS (2%B type viscometer) left and right, because of
Of a relatively high for viscosity, mouthfeel more thickness, it is impossible to meet people's beverage light to delicate mouthfeel and want
Ask.And the viscosity of SG30 only has 10-30CPS (2%B type viscometer), substitution value is more than 1.20, because of it
Viscosity is extremely low, will not cover the local flavor of former breast, can meet clean taste, light requirement.Meanwhile, because of
Its substitution value is high, and strong with the complexing power of protein, stabilizing power is strong, improves the stability of beverage.
Application No. 200810035606.3, the Chinese patent application of Publication No. CN101455286A is a kind of
The preparation method of sodium carboxymethyl cellulose for foodstuff discloses the preparation of a kind of sodium carboxymethyl cellulose for foodstuff
Method.It is (0.25-1.5) that 100 parts of wood pulps and purified cotton are mainly pressed mixing ratio by the method: the composite fibre of 1
Element raw material, adds in kneader with three kinds of materials of alcohol solvent and sodium hydrate aqueous solution, at 20-40 DEG C
After quaternization under stirring condition 50-100 minute, be then respectively added slowly to chloroacetic acid ethanol solution,
Sodium hydrate aqueous solution, carries out etherification reaction under 75-80 DEG C of stirring condition and lowers the temperature after 40-100 minute
Material；Gained material acetic acid neutralizes, and washs at twice with ethanol water simultaneously, divides while washing
Add the steps such as aqueous hydrogen peroxide solution once or twice and prepare sodium carboxymethyl cellulose.
Viscosity reduction technique in this patent is to carry out in the washing process after CMC reaction generates, and viscosity reduction is imitated
The most poor, and owing to there is no the residual of thinner, the appearance color of CMC can be affected, and the present invention drops
Adhering process is carried out in alkalization and etherification procedure, and viscosity reducing effect is good, and the CMC generated is through ethanol
After washing, do not have thinner residual, do not interfere with the appearance color of CMC.
Additionally, the CMC viscosity that this patent produces is high, for 70-240CPS, substitution value is about 1.0, takes
Dai Du is the highest.
Application No. 201110315222.9, the Chinese patent application spy of Publication No. CN 102367279A is low
The preparation method of viscosity carboxymethyl cellulose sodium discloses a kind of employing kneader commercial production and is applicable to high
The preparation method of the ultralow-viscosity sodium carboxymethyl cellulose of yarn starching.The present invention comprises the following steps: handle
The liquid caustic soda of ethanol and high concentration adds in cotton fiber, adds thinner with the time-division several times, the most first will
Cotton fiber viscosity reduction, alkalizes to cotton fiber simultaneously.It is subsequently adding etherifying agent, is etherified, after etherification reaction,
Add thinner, again viscosity reduction, add sodium sulfite reduction and fall in reaction medium ethanol and reactant
The thinner of middle remnants.The most neutralized washing, centrifugal, be dried, pulverize and obtain textile sizing extra low viscose
Degree CMC.
Although the CMC viscosity that the program produces is the lowest, 8-17CPS (4%B type viscometer), but substitution value
The highest, only about 0.8, and also purity is relatively low, and only 97%, do not meet country's mark of edible CMC
Purity requirement (more than 98%) in quasi-GB1904-2005, is only used for industrial circle, in weaving
Slurry CMC.
Summary of the invention
It is an object of the invention to provide the preparation of food stage high substituted degree ultralow-viscosity sodium carboxymethyl cellulose
Method, easy and simple to handle, the ultralow-viscosity sodium carboxymethyl cellulose of production has relatively high substituted degree, extra low viscose
Degree, Brookfield viscometer (Brookfield) 2% is 10-30CPS, purity more than 98%.Food-grade high-purity
Ultralow-viscosity sodium carboxymethyl cellulose aqueous solution is limpid, and viscosity stabilization is particularly well-suited to delicate mouthfeel salubrious
In type beverage.
The technical solution adopted for the present invention to solve the technical problems is:
The preparation method of food stage high substituted degree ultralow-viscosity sodium carboxymethyl cellulose, described preparation method bag
Include following steps:
A. alkalize
By cellulosic material, mass concentration 40-50% sodium hydrate aqueous solution and mass concentration 85-95% ethanol
Solution is simultaneously introduced stirring (cellulosic material: sodium hydrate aqueous solution: ethanol solution in alkalization kneader
Mass ratio be 1:(1.9-5.1): (1.5-4.0), sodium hydrate aqueous solution and ethanol solution are pre-mixed uniformly)；
B. viscosity reduction
The thinner adding cellulosic material 0.3-1.5% (mass fraction) in alkalization kneader again drops
Viscous, viscosity reduction process temperature controls at 20-50 DEG C, and the time is 40-80 minute, the thinner choosing used by viscosity reduction
With hydrogen peroxide solution, it is 1:(5-10 in the ratio (mass ratio) of hydrogen peroxide solution and 95% ethanol solution)
After dilution, it is slowly added to.
C. it is etherified
From alkalization kneader, material is entered etherificate kneader, and etherifying agent sprayed in 20-40 minute equably
On material, etherifying agent is monoxone ethanol solution (cellulosic material and the etherificate of mass concentration 60-80%
The mass ratio of agent is 1:(1.8-3.0)), the temperature of etherification reaction is stepped up, and controls at 50-80 DEG C, instead
It is 60-120 minute between Ying Shi, is then cooled to 40-60 DEG C.
D. washing and drying
Cooling discharge, through neutralizing, repeatedly washs (fiber with 70-80% (percent by volume) ethanol solution
Element raw material and alcoholic solution mass ratio are 1:(10-20), de-liquid, then obtain high-purity after dried, crushed
The low viscous sodium carboxymethyl cellulose finished product of food stage.
Wherein cellulosic material described in step A is the mixture of wood pulp cellulose and gossypin, and wood pulp is fine
Dimension element is (0.1-0.3) with the mass ratio of gossypin: 1, and the gossypin degree of polymerization used is 500-600, wood pulp
Cellulose 1000-1500.
Wherein in step A, it is also preferred that the left cellulosic material: sodium hydrate aqueous solution: the quality of ethanol solution
Ratio is 1:(2.3-2.5): (1.75-2.0).
Wherein in step C, it is also preferred that the left the mass ratio of cellulosic material and etherifying agent is 1:(1.9-2.3).
Described alkalization and etherificate kneader are plain edition CMC biaxial kneader.
As preferably, in step B, hydrogen peroxide selected by the thinner used by a viscosity reduction, should be equal at material stirring
Add after even.
As preferably, in step B, the addition of thinner is all to add with the ethanol solutions of hydrogen peroxide,
Hydrogen peroxide solution concentration used is 30% (mass fraction).The hydrogen peroxide of mass fraction 30% 95% second
Alcoholic solution is in 1:(5-10) ratio (mass ratio) dilution after, be slowly added to, thinner is molten with ethanol dilution
Liquid form adds, and is to dilute thinner so that the uniformity that thinner adds is good, and safety is high,
It is unlikely to locally to occur vigorous reaction to affect product quality at material, even produces security incident.
As preferably, the etherifying agent described in step C is the monoxone ethanol solution of mass concentration 60-80%.
Add fashionable reaction temperature should control below 50 DEG C as far as possible (when i.e. etherifying agent sprays on material equably,
Temperature controls below 50 DEG C).
As preferably, in step D, ethanol solution concentration used is 70-80%, should be according to the CMC produced
Viscosity and substitution value regulate concentration.
Wherein, step D takes off concretely comprising the following steps of liquid: by the way of extruding or be centrifugal, allow CMC and wash
The ethanol solution washed separates.
Wherein, in step C, etherification temperature is stepped up beneficially improving substitution value.
The high substituted degree CMC of indication of the present invention refers to CMC substitution value >=1.20；High-purity refers to CMC
Purity >=98%；Extra low viscose degree refers to CMC Brookfield viscometer (Brookfield) 2%≤30cps.
The invention has the beneficial effects as follows:
1, preparation method is simple, and product meets FAO and WHO approved and is used for eating by pure CMC
The requirement of product；
2, the high substituted degree ultralow-viscosity sodium carboxymethyl cellulose (SG30) produced has relatively high substituted degree,
Extra low viscose degree, Brookfield viscometer (Brookfield) 2% is 10-30CPS, the feature of purity more than 98%；
3, high substituted degree ultralow-viscosity sodium carboxymethyl cellulose (SG30) good water solubility produced, solution is clear
Bright, viscosity stabilization, it is particularly well-suited in the light beverage of delicate mouthfeel；
4, the high substituted degree ultralow-viscosity sodium carboxymethyl cellulose (SG30) produced have good acid resistance,
Emulsibility and heat stability, aqueous solution transparency is high, liquid milk, bean milk, fruit juice milk, Semen arachidis hypogaeae milk and
The acidic beverages such as lactic acid, fruit acid uses, can make solution-stabilized, clean taste, and adapt to superhigh temperature and go out
The sterilization process that bacterium (UHT) and pasteurize (pasteurized) etc. are conventional.
The viscosity of SG30 only has 10-30CPS (2%B type viscometer), and substitution value is more than 1.20, because it glues
Spend extremely low, the local flavor of former breast will not be covered, clean taste, light requirement can be met.Meanwhile, because of it
Substitution value is high, and strong with the complexing power of protein, stabilizing power is strong, improves the stability of beverage.
Detailed description of the invention
Below by specific embodiment, technical scheme is described in further detail.
In following example, alkalization kneader, etherificate kneader are CMC plain edition biaxial kneader, type
Number being: NH-100, manufacturer is that machinery plant is mediated in Nantong banburying.
Embodiment 1
By 1kg cellulosic material, (wood pulp cellulose and gossypin mass ratio are 0.2:1, wherein gossypin
The degree of polymerization is 600, and the wood pulp cellulose degree of polymerization is 1000) and 2.35kg mass concentration 48% sodium hydroxide
The ethanol of aqueous solution and 1.75kg mass concentration 95% be simultaneously introduced in kneader (sodium hydrate aqueous solution with
Ethanol shifts to an earlier date mix homogeneously), then by after the hydrogen peroxide solution 0.009kg ethanol dilution of mass concentration 30%
Add, under stirring, be warmed up to 35-45 DEG C, stir 60 minutes.By chloroacetic for 1.9kg ethanol solution (chlorine
The mass concentration 70% of acetic acid) it is sprayed to equably in kneader, stir 20 minutes.The most progressively heat up,
Carry out etherification reaction, react 60 minutes at 76-80 DEG C, cooling discharge, neutralize, wash, de-liquid, baking
Dry, pulverizing obtains food stage high substituted degree extra low viscose sodium carboxymethyl cellulose.Substitution value 1.24, Type B
(Brookfield) 2% viscosity 19cps, purity 98.5%, CMC solution is bright.
Embodiment 2
By 1kg cellulosic material, (wood pulp cellulose and gossypin mass ratio are 0.15:1, wherein cotton fiber
The element degree of polymerization is 500, and the wood pulp cellulose degree of polymerization is 1000) and 2.5kg mass concentration 48% hydroxide
Sodium water solution and the ethanol of 1.85kg mass concentration 95% are simultaneously introduced the interior (sodium hydrate aqueous solution of kneader
Shift to an earlier date with ethanol and mix homogeneously), then by the hydrogen peroxide solution 0.013kg ethanol dilution of mass concentration 30%
Rear addition, under stirring, is warmed up to 35-45 DEG C, stirs 70 minutes.By chloroacetic for 2.0kg ethanol solution
(chloroacetic mass concentration 70%) is sprayed in kneader equably, after stirring 20 minutes.Then by
Step heats up, and carries out etherification reaction, reacts 60 minutes at 76-80 DEG C, cooling discharge, neutralize, wash,
De-liquid, dry, pulverize and obtain food stage high substituted degree extra low viscose sodium carboxymethyl cellulose.Substitution value 1.26,
Type B (Brookfield) 2% viscosity 16cps, purity 99.0%, CMC solution is bright.
Embodiment 3
By 1kg cellulosic material, (wood pulp cellulose and gossypin mass ratio are 0.25:1, wherein cotton fiber
The element degree of polymerization is 500, and the wood pulp cellulose degree of polymerization is 1000) and 2.3kg mass concentration 50% sodium hydroxide
Aqueous solution and the ethanol of 2kg mass concentration 85% are simultaneously introduced kneader interior (sodium hydrate aqueous solution and second
Alcohol shifts to an earlier date mix homogeneously), then add after the hydrogen peroxide solution 0.01kg ethanol dilution of mass concentration 30%
Enter, under stirring, be warmed up to 35-45 DEG C, stir 70 minutes.By chloroacetic for 1.95kg ethanol solution (chlorine
The mass concentration 70% of acetic acid) it is sprayed to equably in kneader, stir 20 minutes.The most progressively heat up,
Carry out etherification reaction, react 65 minutes at 76-80 DEG C, cooling discharge, neutralize, wash, de-liquid, baking
Dry, pulverizing obtains food stage high substituted degree extra low viscose sodium carboxymethyl cellulose.Substitution value 1.25, Type B
(Brookfield) 2% viscosity 18cps, purity 98.8%, CMC solution is bright.
Embodiment 4
By 1kg cellulosic material, (wood pulp cellulose and gossypin mass ratio are 0.3:1, wherein gossypin
The degree of polymerization is 500, wood pulp cellulose 1500) with 1.9kg mass concentration 50% sodium hydrate aqueous solution with
The ethanol of 1.5kg mass concentration 95% is simultaneously introduced in kneader that (sodium hydrate aqueous solution mixes in advance with ethanol
Close uniformly), then will add after the hydrogen peroxide solution 0.003kg ethanol dilution of mass concentration 30%, stirring
Under, it is warmed up to 35-50 DEG C, stirs 80 minutes.By chloroacetic for 1.8kg ethanol solution (chloroacetic matter
Amount concentration 60%) it is sprayed to equably in kneader, stir 20 minutes, then carry out etherification reaction, by
Step heats up, and reacts 60 minutes at 76-80 DEG C, cooling discharge, neutralize, wash, de-liquid, drying, powder
Broken obtain the high-purity grade of low viscous sodium carboxymethyl cellulose of food stage.Substitution value 1.20, Type B (Brookfield) 2%
Viscosity 30cps, purity 99.2%, CMC solution is bright.
Wherein the hydrogen peroxide of mass fraction 30% is diluted in the ratio (mass ratio) of 1:5 with 95% ethanol solution
After, it is slowly added to.
Embodiment 5
By 1kg cellulosic material, (wood pulp cellulose and gossypin mass ratio are 0.1:1, wherein gossypin
The degree of polymerization is 1500, wood pulp cellulose 500) with 5.1kg mass concentration 40% sodium hydrate aqueous solution with
The ethanol of 4.0kg mass concentration 95% is simultaneously introduced in kneader that (sodium hydrate aqueous solution mixes in advance with ethanol
Close uniformly), then will add after the hydrogen peroxide solution 0.015kg ethanol dilution of mass concentration 30%, stirring
Under, it is warmed up to 30-45 DEG C, stirs 40 minutes.By chloroacetic for 3.0kg ethanol solution (chloroacetic matter
Amount concentration 80%) it is sprayed to equably in kneader, stir 40 minutes, then carry out etherification reaction, by
Step heats up, and reacts 120 minutes at 50-76 DEG C, cooling discharge, neutralize, wash, de-liquid, drying, powder
Broken obtain the high-purity grade of low viscous sodium carboxymethyl cellulose of food stage.Substitution value 1.35, Type B (Brookfield) 2%
Viscosity 10cps, purity 98.1%, CMC solution is bright.
Wherein the hydrogen peroxide of mass fraction 30% is dilute in the ratio (mass ratio) of 1:10 with 95% ethanol solution
After releasing, it is slowly added to.
Comparative example 1
With reference to Application No. 200810035606.3 in background technology, in Publication No. CN 101455286A
Embodiment 1:
When 30 DEG C of temperature of kneader, by cotton for 30 parts of wood pulps and the 70 parts of exquisitenesses that average degree of polymerization is 300
The sodium hydrate aqueous solution of 136 part 47% and 250 part of 96% (volume) second it is even added at 20 minutes
In the mixed solution of alcohol, and under agitation quaternization 80 minutes；140 parts it are slowly added in 40 minutes
The chloroacetic acid ethanol solution of 65%, then 34 part of 47% sodium hydrate aqueous solution it was uniformly added at 10 minutes,
Slowly it is warmed up to 78 DEG C, etherification reaction 40 minutes, cooling discharge under stirring condition；The acetic acid of dropping 20%
Remaining sodium hydroxide in 11 parts of neutralization systems, washs with the ethanol water of 2000 part 76% (volume)
40 minutes, being simultaneously introduced 27.5% aqueous hydrogen peroxide solution, centrifugation goes out ethanol water, after being centrifuged
Material washs 45 minutes with the ethanol water of 3000 part 70% (volume) again, and centrifugation goes out
Ethanol water recovered process Posterior circle uses.Reaction mass drying again, the process such as pulverizing obtains carboxylic
Sodium carboxymethylcellulose pyce product.Above-described embodiment is prepared product by mass fraction 2% aqueous solution, with NDJ-79
Type viscometer viscosimetric.Remaining project presses " food additive sodium carboxymethyl cellulose " GB-1904-2005
Standard test, result is as shown in the table；
| Viscosity mpa.s | Substitution value | Purity % | PH | Moisture % | The viscous ratio of acid | |
| Comparative example 1 | 160 | 1.02 | 98.7 | 7.0 | 9 | 0.85 |
Comparative example 2
With reference to Application No. 201110315222.9 in background technology, in Publication No. CN 102367279A
Embodiment 3:
By the 1KG cotton fiber of shredding and 1.25KG 47% sodium hydrate aqueous solution and 1.5KG 90%
Ethanol be added simultaneously in kneader, add 50% hydrogen peroxide ethanol solution 0.16KG (ethanol accounts for
50%), point 3 additions, stirring is warmed up to 60 DEG C, viscosity reduction 40 minutes.0.65KG is chloroacetic
Ethanol solution (chloroacetic concentration 60%), carries out carboxymethylation reaction in spraying kneader equably,
React 60 minutes at 78 DEG C, then cool to 60 DEG C, be further continued for adding 68% hydrogen peroxide ethanol solution
0.8KG, viscosity reduction 60 minutes, add 0.6KG sodium sulfite powder (based on cotton quality), reaction
10 minutes, then neutralize according to a conventional method, wash, be centrifuged, dry, pulverize that to obtain pure low viscous carboxymethyl fine
Dimension element sodium substitution value 0.68.
Type B (Brookfield) 4% viscosity 17cps, purity 97.6%, cmc solution is bright.
Test example
Viscosity: 2% aqueous solution, Brookfield type viscosity apparatus, detects under the conditions of 25 DEG C.
Substitution value (DS): according in GB 1904-2005 " food additive sodium carboxymethyl cellulose " 5.5
Method detects.
Purity: according to ASTM D1439-03 standard or GB 1904-2005 " food additive carboxymethyl
Sodium cellulosate " in 5.8 methods detection sodium chloride and sodium glycollate content, then obtain with minusing.
Product standard: according to GB 1904-2005 " food additive sodium carboxymethyl cellulose ".
The test data contrast of embodiment of the present invention CMC, existing food stage CMC and comparative example CMC is shown in
Table 1 below:
Table 1 embodiment CMC, existing food stage CMC and the test data of comparative example CMC
From list, can be seen that the purity in standard GB/T 1904-2005 meeting edible CMC is wanted
Asking in the product of (more than 98%), our product is either gone back on substitution value the most excellent in viscosity
In other existing product.Although and CMC product viscosity in comparative example 2 is relatively low, but substitution value is the highest,
And purity is the most useless reaches food stage requirement.
Embodiment described above is the one preferably scheme of the present invention, and the present invention not makees any shape
Restriction in formula, also has other variant on the premise of without departing from the technical scheme described in claim
And remodeling.
Claims (6)
1. the preparation method of food stage high substituted degree ultralow-viscosity sodium carboxymethyl cellulose, prepares by the following method:
A. alkalize
By cellulosic material, mass concentration 40-50% sodium hydrate aqueous solution and mass concentration 85-95% ethanol
Solution is simultaneously introduced stirring in alkalization kneader, cellulosic material: sodium hydrate aqueous solution: ethanol solution
Mass ratio be 1:(1.9-5.1): (1.5-4.0), sodium hydrate aqueous solution and ethanol solution are pre-mixed uniformly；
B. viscosity reduction
The thinner adding cellulosic material mass fraction 0.3-1.5% again in alkalization kneader carries out viscosity reduction,
Viscosity reduction process temperature controls at 20-50 DEG C, and the time is 40-80 minute, and the thinner used by viscosity reduction is selected double
Oxygen aqueous solution, after being 1:5-10 dilution by the mass ratio of hydrogen peroxide solution and 95% ethanol solution, slowly
Adding, the mass concentration of described hydrogen peroxide solution is 30%；
C. it is etherified
From alkalization kneader, material is entered etherificate kneader, and etherifying agent sprayed in 20-40 minute equably
On material, etherifying agent is the monoxone ethanol solution of mass concentration 60-80%, wherein cellulosic material with
The mass ratio of etherifying agent is 1:1.8-3.0, and the temperature of etherification reaction is stepped up, and controls at 50-80 DEG C, instead
It is 60-120 minute between Ying Shi, is then cooled to 40-60 DEG C；
D. washing and drying
Cooling discharge, through neutralizing, washs more than 2 times with the ethanol solution of percent by volume 70-80%,
De-liquid, then obtain food stage high substituted degree ultralow-viscosity sodium carboxymethyl cellulose finished product after dried, crushed.
The preparation of food stage high substituted degree ultralow-viscosity sodium carboxymethyl cellulose the most according to claim 1
Method, it is characterised in that: in described step A cellulosic material be wood pulp cellulose with gossypin mixed
Compound, wood pulp cellulose is 0.1-0.3:1 with the mass ratio of gossypin, and the gossypin degree of polymerization used is
500-600, wood pulp cellulose 1000-1500.
The preparation of food stage high substituted degree ultralow-viscosity sodium carboxymethyl cellulose the most according to claim 1
Method, it is characterised in that: wherein in step A, cellulosic material: sodium hydrate aqueous solution: ethanol is molten
The mass ratio of liquid is 1:2.3-2.5:1.75-2.0.
The preparation of food stage high substituted degree ultralow-viscosity sodium carboxymethyl cellulose the most according to claim 1
Method, it is characterised in that: wherein in step C, cellulosic material is 1:1.9-2.3 with the mass ratio of etherifying agent.
The preparation of food stage high substituted degree ultralow-viscosity sodium carboxymethyl cellulose the most according to claim 1
Method, it is characterised in that: in step D, concentration used is that the consumption of 70-80% ethanol solution is: cellulose
Raw material and 70-80% ethanol solution mass ratio are 1:10-20.
The preparation of food stage high substituted degree ultralow-viscosity sodium carboxymethyl cellulose the most according to claim 1
Method, it is characterised in that: in step D de-liquid concretely comprise the following steps by extruding or centrifugal by the way of allow carboxylic
Sodium carboxymethylcellulose pyce separates with the ethanol solution of washing.
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| CN105906724A (en) * | 2016-06-07 | 2016-08-31 | 常熟威怡科技有限公司 | Preparation method of low-turbidity high-performance sodium carboxymethylcellulose |
| CN109021119A (en) * | 2018-06-14 | 2018-12-18 | 恒达亲水胶体泰州有限公司 | A kind of preparation method of the sodium carboxymethylcellulose for thermal dye sublimation transfer printing paper |
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