CN104387477A - Preparation method of food-grade sodium carboxymethyl cellulose (CMC) with high substitution degree and ultra-low viscosity - Google Patents
Preparation method of food-grade sodium carboxymethyl cellulose (CMC) with high substitution degree and ultra-low viscosity Download PDFInfo
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- CN104387477A CN104387477A CN201410737944.7A CN201410737944A CN104387477A CN 104387477 A CN104387477 A CN 104387477A CN 201410737944 A CN201410737944 A CN 201410737944A CN 104387477 A CN104387477 A CN 104387477A
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- carboxymethyl cellulose
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- 238000006467 substitution reaction Methods 0.000 title claims abstract description 46
- 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 30
- 239000001768 carboxy methyl cellulose Substances 0.000 title claims abstract description 25
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 title claims abstract description 23
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229920002134 Carboxymethyl cellulose Polymers 0.000 title abstract description 37
- 235000010948 carboxy methyl cellulose Nutrition 0.000 title abstract description 37
- 239000008112 carboxymethyl-cellulose Substances 0.000 title abstract 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 78
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- 229920002678 cellulose Polymers 0.000 claims abstract description 22
- 239000001913 cellulose Substances 0.000 claims abstract description 22
- 238000006266 etherification reaction Methods 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 34
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 27
- 235000013305 food Nutrition 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 19
- 229920001131 Pulp (paper) Polymers 0.000 claims description 18
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 17
- 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 16
- 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 16
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000006386 neutralization reaction Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000011946 reduction process Methods 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 51
- 235000011121 sodium hydroxide Nutrition 0.000 abstract description 22
- 235000013361 beverage Nutrition 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000001603 reducing effect Effects 0.000 abstract description 3
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 39
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000010790 dilution Methods 0.000 description 9
- 239000012895 dilution Substances 0.000 description 9
- 229920000742 Cotton Polymers 0.000 description 8
- 229920000297 Rayon Polymers 0.000 description 7
- 238000010298 pulverizing process Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 239000000796 flavoring agent Substances 0.000 description 4
- 235000013336 milk Nutrition 0.000 description 4
- 210000004080 milk Anatomy 0.000 description 4
- 239000008267 milk Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 210000000481 breast Anatomy 0.000 description 3
- 230000001804 emulsifying effect Effects 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
- 108090000623 proteins and genes Proteins 0.000 description 3
- 102000004169 proteins and genes Human genes 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 235000015203 fruit juice Nutrition 0.000 description 2
- 235000015243 ice cream 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
- 238000004513 sizing Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 235000013322 soy milk Nutrition 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- 235000013618 yogurt Nutrition 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
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- 230000007062 hydrolysis Effects 0.000 description 1
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- 235000015110 jellies Nutrition 0.000 description 1
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- 230000001404 mediated effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
- 210000000582 semen Anatomy 0.000 description 1
- 229940023144 sodium glycolate Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000013555 soy sauce Nutrition 0.000 description 1
- 238000009955 starching Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 230000009967 tasteless effect Effects 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
- JEJAMASKDTUEBZ-UHFFFAOYSA-N tris(1,1,3-tribromo-2,2-dimethylpropyl) phosphate Chemical compound BrCC(C)(C)C(Br)(Br)OP(=O)(OC(Br)(Br)C(C)(C)CBr)OC(Br)(Br)C(C)(C)CBr JEJAMASKDTUEBZ-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
Landscapes
- Jellies, Jams, And Syrups (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention relates to a preparation method of food-grade sodium carboxymethyl cellulose (CMC) (SG30) with high substitution degree and ultra-low viscosity, belonging to the technical field of sodium CMC production. The preparation method comprises the following steps of adding ethanol and liquid caustic soda with high concentration into a cellulose raw material, meanwhile, adding a viscosity reducer, reducing the viscosity of the cellulose raw material through primary viscosity reduction, and meanwhile alkalifying the cellulose raw material; then, adding an etherifying agent to etherify; and after the etherification reaction is ended, neutralizing, washing by using an ethanol solution with specific concentration according to a certain bath ratio (the cellulose raw material/the ethanol solution), removing the solution, drying and crushing to obtain the food-grade sodium CMC with ultra-low viscosity. The food-grade sodium CMC disclosed by the invention is relatively-high in substitution degree and ultra-low in viscosity and has the 2% Brookfield viscosity of 10-30CPS (measured by using a type-B viscometer), the substitution degree of larger than 1.20 and the purity of higher than 98%. The CMC is clear in solution and stable in viscosity. The food-grade sodium CMC is particularly suitable for being added into a refreshing beverage which is fine and smooth in taste.
Description
Technical field
The present invention relates generally to a kind of preparation method being applicable to the food grade high substitution value ultralow-viscosity sodium carboxymethyl cellulose of the light beverage of delicate mouthfeel, belongs to Xylo-Mucine production technical field.
Background technology
Xylo-Mucine is the sodium salt of carboxymethyl cellulose ether, and belonging to anionic ether of cellulose, is the micro-yellow fibers sprills of white or particle, density 0.5-0.7 gram/cc, odorless, tasteless, tool water absorbability.Be easy to be dispersed in water into clear gum solution, insoluble in the organic solvents such as ethanol.1% aqueous solution pH is 6.5 ~ 8.5, and as pH>10 or <5, cement viscosity significantly reduces, and when pH=7, performance is best.To thermally-stabilised, below 20 DEG C, viscosity rises rapidly, and when 45 DEG C, change is comparatively slow, and more than 80 DEG C long-time heating can make its colloid sex change and viscosity and performance obviously decline.Soluble in water, solution is transparent; More stable in basic solution, meet acid then facile hydrolysis, have certain resistance to acid, when pH value is 2-3, there will be precipitation, meet polyvalent metal salt and also can react appearance precipitation.Different according to specifications of raw materials, reaction conditions is different, obtains the product that different degree of substitution is different with different molecular weight and replacement homogeneity.
Pure CMC is used for food by current FAO and WHO approved, it just gets the Green Light after being through very strict biology, toxicologic study and test, the safe intake (ADI) of international standard is 25mg/ (kgd), i.e. everyone 1.5g/d about.Once it was reported that, someone tests intake and reaches 10kg also not toxic reaction.CMC is not only good emulsifying stablizer, thickening material in food applications, and has and excellent to freeze, melt stability, and can improve the local flavor of product, prolongation storage time.Consumption in soymilk, ice-creams, ice cream, jelly, beverage, can is about 1% ~ 1.5%.CMC also can be stable with forming property such as vinegar, soy sauce, vegetables oil, fruit juice, gravy, vegetables juice emulsified dispersed liquid, its consumption is 0.2% ~ 0.5%.Particularly very excellent to the emulsifying property of animal and vegetable oil, protein and the aqueous solution, the homogeneous milk sap that its forming property is stable can be made.Because it is safe and reliable, therefore, its consumption does not limit by national food hygienic standard ADI.CMC is constantly developed at field of food, and the research of applying Xylo-Mucine in Production of Wine is also carried out.
Along with reaching its maturity and rationality of the development of biotechnology and the appearance of novel material and consumer spending idea, functional drinks and milky-drinks towards more healthy, closer to natural, safer future development.Past that dense thick, the Luzhou-flavor produced by a large amount of interpolation chemosynthesis additive, Yoghourt, the milky-drinks of mouthfeel thickness all will unfeelingly by market, the substitute is clean taste, light outward appearance makes every effort to the asymptotic natural Yoghourt close to former breast, milky-drinks (functionalization such as Liu Peng, Li little Lin, light---the developing direction of Chinese beverage, dairy products and the mankind, the 2nd phase in 2008).Under this market background, the CMC as thickening material and stablizer is just had higher requirement.The low sticky product of current domestic CMC food grade is substitution value about 1.0 mostly, and viscosity is in 100CPS (2%B type viscometer) left and right, because viscosity is relatively high, mouthfeel is thickness comparatively, cannot meet the requirement of people to the light beverage of delicate mouthfeel.And the viscosity of SG30 only has 10-30CPS (2%B type viscometer), substitution value is greater than 1.20, because its viscosity pole is low, can not cover the local flavor of former breast, can meet clean taste, light requirement.Meanwhile, because its substitution value is high, strong with the complex ability of protein, stabilizing power is strong, improves the stability of beverage.
Application number is 200810035606.3, and publication number is the preparation method that the preparation method of a kind of sodium carboxymethyl cellulose for foodstuff of Chinese patent application of CN101455286A discloses a kind of sodium carboxymethyl cellulose for foodstuff.It is (0.25-1.5) that 100 parts of wood pulps and purified cotton are mainly pressed ratio of mixture by the method: the cellulose mixture raw material of 1, add in kneader with three kinds of materials of alcohol solvent and aqueous sodium hydroxide solution, under 20-40 DEG C and agitation condition after quaternization 50-100 minute, then slowly add Monochloro Acetic Acid ethanolic soln, aqueous sodium hydroxide solution respectively, under 75-80 DEG C of agitation condition, carry out cooling discharge after etherification reaction 40-100 minute; Gained material acetic acid neutralizes, and washs at twice with aqueous ethanolic solution simultaneously, adds the steps such as aqueous hydrogen peroxide solution once or twice obtain Xylo-Mucine in the same time-division of washing.
Viscosity reduction technique in this patent is carried out in the washing process after CMC reaction generates, viscosity reducing effect is poor, and owing to there is no the residual of viscosity-depression agent, the appearance color of CMC can be affected, and viscosity reduction technique of the present invention is carried out in alkalization and etherification procedure, viscosity reducing effect is good, and the CMC generated is after ethanol wash, do not have viscosity-depression agent to remain, the appearance color of CMC can not be affected.
In addition, the CMC viscosity that this patent is produced is high, and be 70-240CPS, substitution value is about 1.0, and substitution value is not high.
Application number is 201110315222.9, and publication number is that the preparation method of the Chinese patent application ultralow-viscosity sodium carboxymethyl cellulose of CN 102367279A discloses a kind of preparation method adopting kneader industrial production to be applicable to the ultralow-viscosity sodium carboxymethyl cellulose of high grade cotton yarn starching.The present invention includes the following step: the liquid caustic soda of ethanol and high density is added in cotton fibre, adds viscosity-depression agent several times with the time-division, at high temperature first by cotton fibre viscosity reduction, cotton fibre is alkalized simultaneously.Then add etherifying agent, carry out etherificate, after etherification reaction, then add viscosity-depression agent, again viscosity reduction, then add S-WAT reduction and to fall in reaction medium ethanol and viscosity-depression agent remaining in reactant.Again through neutralization washing, centrifugal, dry, pulverizing obtain textile sizing extra low viscose degree CMC.
Although the CMC viscosity that the program is produced is very low, 8-17CPS (4%B type viscometer), but substitution value is not high, only have about 0.8, and purity is lower, only have 97%, do not meet the purity requirement (being greater than 98%) in the standard GB/T 1904-2005 of edible CMC, can only be used for industrial circle, be textile sizing CMC.
Summary of the invention
The object of the present invention is to provide the preparation method of food grade high substitution value ultralow-viscosity sodium carboxymethyl cellulose, easy and simple to handle, the ultralow-viscosity sodium carboxymethyl cellulose produced has comparatively high substitution value, extra low viscose degree, Brookfield viscometer (Brookfield) 2% is 10-30CPS, purity more than 98%.The food-grade high-purity ultralow-viscosity sodium carboxymethyl cellulose aqueous solution is limpid, stable viscosity, is specially adapted in the light beverage of delicate mouthfeel.
The technical solution adopted for the present invention to solve the technical problems is:
The preparation method of food grade high substitution value ultralow-viscosity sodium carboxymethyl cellulose, described preparation method comprises the steps:
A. alkalize
By cellulosic material, mass concentration 40-50% aqueous sodium hydroxide solution and mass concentration 85-95% ethanolic soln add stirring (cellulosic material: aqueous sodium hydroxide solution: the mass ratio of ethanolic soln is 1:(1.9-5.1) in alkalization kneader simultaneously: (1.5-4.0), and aqueous sodium hydroxide solution and ethanolic soln are pre-mixed evenly);
B. viscosity reduction
The viscosity-depression agent adding cellulosic material 0.3-1.5% (massfraction) again in alkalization kneader carries out viscosity reduction, viscosity reduction process temperature controls at 20-50 DEG C, time is 40-80 minute, hydrogen peroxide solution selected by viscosity reduction viscosity-depression agent used, be 1:(5-10 in the ratio (mass ratio) of hydrogen peroxide solution and 95% ethanolic soln) dilute after, slowly add.
C. etherificate
Material is entered etherificate kneader from alkalization kneader, etherifying agent sprayed equably on material in 20-40 minute, etherifying agent is the Mono Chloro Acetic Acid ethanolic soln (mass ratio of cellulosic material and etherifying agent is 1:(1.8-3.0) of mass concentration 60-80%), the temperature of etherification reaction progressively raises, control at 50-80 DEG C, reaction times is 60-120 minute, is then cooled to 40-60 DEG C.
D. washing and drying
Cooling discharge, through neutralization, repeatedly use 70-80% (volume percent) ethanolic soln to wash (cellulosic material and spirituous solution mass ratio are 1:(10-20), de-liquid, then obtain the low sticky Xylo-Mucine finished product of food-class high-purity after dried, crushed.
Wherein cellulosic material described in steps A is the mixture of wood pulp cellulose and gossypin, and the mass ratio of wood pulp cellulose and gossypin is (0.1-0.3): 1, and the gossypin polymerization degree used is 500-600, wood pulp cellulose 1000-1500.
Wherein in steps A, preferably, cellulosic material: aqueous sodium hydroxide solution: the mass ratio of ethanolic soln is 1:(2.3-2.5): (1.75-2.0).
Wherein in step C, preferably, the mass ratio of cellulosic material and etherifying agent is 1:(1.9-2.3).
Described alkalization and etherificate kneader are coventional type CMC biaxial kneader.
As preferably, hydrogen peroxide selected by the viscosity-depression agent that in step B, viscosity reduction is used, should material stirring evenly after add.
As preferably, in step B, adding of viscosity-depression agent is all add with the ethanol solutions of hydrogen peroxide, and hydrogen peroxide solution concentration used is 30% (massfraction).The hydrogen peroxide of massfraction 30% with 95% ethanolic soln in 1:(5-10) ratio (mass ratio) dilution after, slowly add, viscosity-depression agent adds with alcohol dilution solution form, to dilute viscosity-depression agent, make the good uniformity that viscosity-depression agent adds, and security is high, being unlikely to, at material, vigorous reaction locally occurs affects quality product, even produces security incident.
As preferably, the etherifying agent described in step C is the Mono Chloro Acetic Acid ethanolic soln of mass concentration 60-80%.Add fashionable temperature of reaction and should control below 50 DEG C (when namely etherifying agent sprays on material equably, temperature controls below 50 DEG C) as far as possible.
As preferably, in step D, ethanol solution concentration used is 70-80%, should regulate concentration according to produced CMC viscosity and substitution value.
Wherein, in step D, the concrete steps of de-liquid are: allow CMC be separated with the ethanolic soln of washing by extruding or centrifugal mode.
Wherein, in step C etherification temperature progressively raise be conducive to improve substitution value.
The high substitution value 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 the requirement that pure CMC is used for food by FAO and WHO approved;
2, the high substitution value ultralow-viscosity sodium carboxymethyl cellulose (SG30) produced has comparatively high substitution value, extra low viscose degree, and Brookfield viscometer (Brookfield) 2% is the feature of 10-30CPS, purity more than 98%;
High substitution value ultralow-viscosity sodium carboxymethyl cellulose (SG30) good water solubility of 3, producing, solution is limpid, stable viscosity, is specially adapted in the light beverage of delicate mouthfeel;
4, the high substitution value ultralow-viscosity sodium carboxymethyl cellulose (SG30) produced has good acid resistance, emulsifying property and thermostability, aqueous solution transparency is high, use in liquid state milk, soymilk, fruit juice milk, Semen arachidis hypogaeae milk and the acidic drinks such as lactic acid, tartaric acid, solution-stabilized, clean taste can be made, and adapt to the conventional sterilization process such as ultra high temperature sterilization (UHTS) (UHT) and pasteurize (pasteurized).
The viscosity of SG30 only has 10-30CPS (2%B type viscometer), and substitution value is greater than 1.20, because its viscosity pole is low, can not cover the local flavor of former breast, can meet clean taste, light requirement.Meanwhile, because its substitution value is high, strong with the complex ability of protein, stabilizing power is strong, improves the stability of beverage.
Embodiment
Below by specific embodiment, technical scheme of the present invention is described in further detail.
Alkalize in following examples kneader, etherificate kneader is CMC coventional type biaxial kneader, and model is: NH-100, and manufacturer is that machine works is mediated in Nantong banburying.
Embodiment 1
By 1kg cellulosic material, (wood pulp cellulose and gossypin mass ratio are 0.2:1, wherein the gossypin polymerization degree is 600, the wood pulp cellulose polymerization degree is 1000) add in kneader (aqueous sodium hydroxide solution mixes in advance with ethanol) with 2.35kg mass concentration 48% aqueous sodium hydroxide solution and the ethanol of 1.75kg mass concentration 95% simultaneously, add after the hydrogen peroxide solution 0.009kg alcohol dilution of mass concentration 30% again, under stirring, be warmed up to 35-45 DEG C, stir 60 minutes.Chloroacetic for 1.9kg ethanolic soln (chloroacetic mass concentration 70%) is sprayed in kneader equably, stirs 20 minutes.Then progressively heat up, carry out etherification reaction, 76-80 DEG C of reaction 60 minutes, cooling discharge, neutralization, washing, de-liquid, oven dry, pulverizing obtained food grade high substitution value extra low viscose Xylo-Mucine.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 the gossypin polymerization degree is 500, the wood pulp cellulose polymerization degree is 1000) add in kneader (aqueous sodium hydroxide solution mixes in advance with ethanol) with 2.5kg mass concentration 48% aqueous sodium hydroxide solution and the ethanol of 1.85kg mass concentration 95% simultaneously, add after the hydrogen peroxide solution 0.013kg alcohol dilution of mass concentration 30% again, under stirring, be warmed up to 35-45 DEG C, stir 70 minutes.Chloroacetic for 2.0kg ethanolic soln (chloroacetic mass concentration 70%) is sprayed in kneader equably, stirs after 20 minutes.Then progressively heat up, carry out etherification reaction, 76-80 DEG C of reaction 60 minutes, cooling discharge, neutralization, washing, de-liquid, oven dry, pulverizing obtained food grade high substitution value extra low viscose Xylo-Mucine.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 the gossypin polymerization degree is 500, the wood pulp cellulose polymerization degree is 1000) add in kneader (aqueous sodium hydroxide solution mixes in advance with ethanol) with 2.3kg mass concentration 50% aqueous sodium hydroxide solution and the ethanol of 2kg mass concentration 85% simultaneously, add after the hydrogen peroxide solution 0.01kg alcohol dilution of mass concentration 30% again, under stirring, be warmed up to 35-45 DEG C, stir 70 minutes.Chloroacetic for 1.95kg ethanolic soln (chloroacetic mass concentration 70%) is sprayed in kneader equably, stirs 20 minutes.Then progressively heat up, carry out etherification reaction, 76-80 DEG C of reaction 65 minutes, cooling discharge, neutralization, washing, de-liquid, oven dry, pulverizing obtained food grade high substitution value extra low viscose Xylo-Mucine.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 the gossypin polymerization degree is 500, wood pulp cellulose 1500) add in kneader (aqueous sodium hydroxide solution mixes in advance with ethanol) with 1.9kg mass concentration 50% aqueous sodium hydroxide solution and the ethanol of 1.5kg mass concentration 95% simultaneously, add after the hydrogen peroxide solution 0.003kg alcohol dilution of mass concentration 30% again, under stirring, be warmed up to 35-50 DEG C, stir 80 minutes.Chloroacetic for 1.8kg ethanolic soln (chloroacetic mass concentration 60%) is sprayed in kneader equably, stir 20 minutes, then etherification reaction is carried out, progressively heat up, 76-80 DEG C of reaction 60 minutes, cooling discharge, neutralization, washing, de-liquid, oven dry, pulverizing obtained the high-purity grade of low sticky Xylo-Mucine of food grade.Substitution value 1.20, Type B (Brookfield) 2% viscosity 30cps, purity 99.2%, CMC solution is bright.
Wherein the hydrogen peroxide of massfraction 30% is with 95% ethanolic soln in after ratio (mass ratio) dilution of 1:5, slowly adds.
Embodiment 5
By 1kg cellulosic material, (wood pulp cellulose and gossypin mass ratio are 0.1:1, wherein the gossypin polymerization degree is 1500, wood pulp cellulose 500) add in kneader (aqueous sodium hydroxide solution mixes in advance with ethanol) with 5.1kg mass concentration 40% aqueous sodium hydroxide solution and the ethanol of 4.0kg mass concentration 95% simultaneously, add after the hydrogen peroxide solution 0.015kg alcohol dilution of mass concentration 30% again, under stirring, be warmed up to 30-45 DEG C, stir 40 minutes.Chloroacetic for 3.0kg ethanolic soln (chloroacetic mass concentration 80%) is sprayed in kneader equably, stir 40 minutes, then etherification reaction is carried out, progressively heat up, 50-76 DEG C of reaction 120 minutes, cooling discharge, neutralization, washing, de-liquid, oven dry, pulverizing obtained the high-purity grade of low sticky Xylo-Mucine of food grade.Substitution value 1.35, Type B (Brookfield) 2% viscosity 10cps, purity 98.1%, CMC solution is bright.
Wherein the hydrogen peroxide of massfraction 30% is with 95% ethanolic soln in after ratio (mass ratio) dilution of 1:10, slowly adds.
Comparative example 1
In reference background technology, application number is 200810035606.3, and publication number is the embodiment 1 in CN 101455286A:
When kneader 30 DEG C of temperature, by mean polymerisation degree be 300 30 parts of wood pulps and 70 parts exquisite cotton in the mixing solutions of the aqueous sodium hydroxide solution and 250 part of 96% (volume) ethanol that evenly to join 136 part 47% for 20 minutes, and under agitation quaternization 80 minutes; Slowly add the Monochloro Acetic Acid ethanolic soln of 140 part 65% in 40 minutes, more evenly added 34 part of 47% aqueous sodium hydroxide solution at 10 minutes, be slowly warmed up to 78 DEG C, etherification reaction 40 minutes under agitation condition, cooling discharge; With remaining sodium hydroxide in system in the acetic acid 11 parts of dropping 20%, 40 minutes are washed with the aqueous ethanolic solution of 2000 part 76% (volume), add 27.5% aqueous hydrogen peroxide solution simultaneously, centrifugation goes out aqueous ethanolic solution, centrifugal rear material uses the aqueous ethanolic solution of 3000 part 70% (volume) to wash 45 minutes again, and the aqueous ethanolic solution that centrifugation goes out uses through recycling Posterior circle.The processes such as reaction mass is drying again, pulverizing obtain Xylo-Mucine product.Above-described embodiment is obtained product by massfraction 2% aqueous solution, with NDJ-79 type viscometer viscosimetric.All the other projects are by " foodstuff additive Xylo-Mucine " GB-1904-2005 standard test, and result is as shown in the table;
| Viscosity mpa.s | Substitution value | Purity % | PH | Moisture % | The sticky ratio of acid | |
| Comparative example 1 | 160 | 1.02 | 98.7 | 7.0 | 9 | 0.85 |
Comparative example 2
In reference background technology, application number is 201110315222.9, and publication number is the embodiment 3 in CN 102367279A:
The 1KG cotton fibre of shredding and the ethanol of 1.25KG 47% aqueous sodium hydroxide solution and 1.5KG 90% are joined in kneader simultaneously, add the hydrogen peroxide ethanolic soln 0.16KG (ethanol accounts for 50%) of 50% again, divide and add for 3 times, stir and be warmed up to 60 DEG C, viscosity reduction 40 minutes.By chloroacetic for 0.65KG ethanolic soln (chloroacetic concentration 60%), spray equably in kneader and carry out carboxymethylation reaction, 78 DEG C of reactions 60 minutes, then 60 DEG C are cooled to, continue interpolation 68% hydrogen peroxide ethanolic soln 0.8KG again, viscosity reduction 60 minutes, add 0.6KG S-WAT powder (based on cotton quality), react 10 minutes, then neutralize according to a conventional method, wash, centrifugal, dry, pulverize and obtain pure low sticky Xylo-Mucine 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 25 DEG C of conditions.
Substitution value (DS): detect according to 5.5 methods in GB 1904-2005 " foodstuff additive Xylo-Mucine ".
Purity: detect sodium-chlor and sodium glycolate content according to 5.8 methods in ASTM D1439-03 standard or GB 1904-2005 " foodstuff additive Xylo-Mucine ", then obtain with minusing.
Product standard: according to GB 1904-2005 " foodstuff additive Xylo-Mucine ".
The testing data contrast of embodiment of the present invention CMC, existing food grade CMC and comparative example CMC sees the following form 1:
The testing data of table 1 Embodiment C MC, existing food grade CMC and comparative example CMC
Can find out in the product of the purity requirement (being greater than 98%) in the standard GB/T 1904-2005 meeting edible CMC from list, our product goes back on substitution value to be all obviously better than other currently available products in viscosity.Although and CMC product viscosity in comparative example 2 is lower, substitution value is not high, and purity is also useless reaches food grade requirement.
Above-described embodiment is one of the present invention preferably scheme, not does any pro forma restriction to the present invention, also has other variant and remodeling under the prerequisite not exceeding the technical scheme described in claim.
Claims (7)
1. the preparation method of food grade high substitution value ultralow-viscosity sodium carboxymethyl cellulose, prepares by the following method:
A. alkalize
By cellulosic material, mass concentration 40-50% aqueous sodium hydroxide solution and mass concentration 85-95% ethanolic soln add stirring in alkalization kneader simultaneously, cellulosic material: aqueous sodium hydroxide solution: the mass ratio of ethanolic soln is 1:(1.9-5.1): (1.5-4.0), aqueous sodium hydroxide solution and ethanolic soln are pre-mixed evenly;
B. viscosity reduction
The viscosity-depression agent adding cellulosic material massfraction 0.3-1.5% again in alkalization kneader carries out viscosity reduction, viscosity reduction process temperature controls at 20-50 DEG C, time is 40-80 minute, hydrogen peroxide solution selected by viscosity reduction viscosity-depression agent used, be, after 1:5-10 dilutes, slowly add by the mass ratio of hydrogen peroxide solution and 95% ethanolic soln;
C. etherificate
Material is entered etherificate kneader from alkalization kneader, etherifying agent sprayed equably on material in 20-40 minute, etherifying agent is the Mono Chloro Acetic Acid ethanolic soln of mass concentration 60-80%, wherein the mass ratio of cellulosic material and etherifying agent is 1:1.8-3.0, the temperature of etherification reaction progressively raises, control at 50-80 DEG C, the reaction times is 60-120 minute, is then cooled to 40-60 DEG C;
D. washing and drying
Cooling discharge, through neutralization, washs more than 2 times with the ethanolic soln of volume percent 70-80%, de-liquid, then obtains the low sticky Xylo-Mucine finished product of food-class high-purity after dried, crushed.
2. the preparation method of food grade high substitution value ultralow-viscosity sodium carboxymethyl cellulose according to claim 1, it is characterized in that: in described steps A, cellulosic material is the mixture of wood pulp cellulose and gossypin, the mass ratio of wood pulp cellulose and gossypin is 0.1-0.3:1, the gossypin polymerization degree used is 500-600, wood pulp cellulose 1000-1500.
3. the preparation method of food grade high substitution value ultralow-viscosity sodium carboxymethyl cellulose according to claim 1, is characterized in that: wherein in steps A, cellulosic material: aqueous sodium hydroxide solution: the mass ratio of ethanolic soln is 1:2.3-2.5:1.75-2.0.
4. the preparation method of food grade high substitution value ultralow-viscosity sodium carboxymethyl cellulose according to claim 1, is characterized in that: the mass concentration of hydrogen peroxide solution described in step B is 30%.
5. the preparation method of food grade high substitution value ultralow-viscosity sodium carboxymethyl cellulose according to claim 1, is characterized in that: wherein in step C, and the mass ratio of cellulosic material and etherifying agent is 1:1.9-2.3.
6. the preparation method of food grade high substitution value ultralow-viscosity sodium carboxymethyl cellulose according to claim 1, is characterized in that: in step D, to be the consumption of 70-80% ethanolic soln be concentration used: cellulosic material and 70-80% ethanolic soln mass ratio are 1:10-20.
7. the preparation method of food grade high substitution value ultralow-viscosity sodium carboxymethyl cellulose according to claim 1, is characterized in that: in step D, the concrete steps of de-liquid are allow Xylo-Mucine be separated with the ethanolic soln of washing by extruding or centrifugal mode.
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| 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 |
| CN113372456A (en) * | 2021-07-13 | 2021-09-10 | 重庆力宏精细化工有限公司 | Ultralow-viscosity carboxymethyl cellulose lithium and preparation method and application thereof |
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| 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 |
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| 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 |
| CN113372456A (en) * | 2021-07-13 | 2021-09-10 | 重庆力宏精细化工有限公司 | Ultralow-viscosity carboxymethyl cellulose lithium and preparation method and application thereof |
| CN113372456B (en) * | 2021-07-13 | 2022-06-10 | 重庆力宏精细化工有限公司 | Ultralow-viscosity carboxymethyl cellulose lithium and preparation method and application thereof |
| CN116655810A (en) * | 2023-06-28 | 2023-08-29 | 重庆力宏精细化工有限公司 | High-permeability ultralow-viscosity sodium carboxymethyl cellulose product and preparation method and application thereof |
| CN118459614A (en) * | 2024-07-12 | 2024-08-09 | 浙江绍兴万德福生物技术有限公司 | Synthesis method for synthesizing carboxymethyl cellulose by slurry method and application thereof |
| CN118459614B (en) * | 2024-07-12 | 2024-09-17 | 浙江绍兴万德福生物技术有限公司 | Synthesis method for synthesizing carboxymethyl cellulose by slurry method and application thereof |
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