CN110128553A - A kind of cellulose gum and its preparation method and application - Google Patents
A kind of cellulose gum and its preparation method and application Download PDFInfo
- Publication number
- CN110128553A CN110128553A CN201910402616.4A CN201910402616A CN110128553A CN 110128553 A CN110128553 A CN 110128553A CN 201910402616 A CN201910402616 A CN 201910402616A CN 110128553 A CN110128553 A CN 110128553A
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- China
- Prior art keywords
- cellulose
- preparation
- water
- cellulose powder
- basifier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920002134 Carboxymethyl cellulose Polymers 0.000 title claims abstract description 38
- 235000010948 carboxy methyl cellulose Nutrition 0.000 title claims abstract description 38
- 239000001768 carboxy methyl cellulose Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 71
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229920002678 cellulose Polymers 0.000 claims abstract description 50
- 235000010980 cellulose Nutrition 0.000 claims abstract description 50
- 239000001913 cellulose Substances 0.000 claims abstract description 41
- 235000013361 beverage Nutrition 0.000 claims abstract description 29
- 235000013365 dairy product Nutrition 0.000 claims abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 230000002378 acidificating effect Effects 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 47
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 239000003513 alkali Substances 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 19
- 229920000875 Dissolving pulp Polymers 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 12
- 238000007873 sieving Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000003381 stabilizer Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000006266 etherification reaction Methods 0.000 claims description 6
- 229920001131 Pulp (paper) Polymers 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 4
- 102000004169 proteins and genes Human genes 0.000 claims description 4
- 108090000623 proteins and genes Proteins 0.000 claims description 4
- 238000010298 pulverizing process Methods 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- -1 monohaloalkyl acetate Chemical compound 0.000 claims description 3
- 241001343274 Dichrostachys spicata Species 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 235000011054 acetic acid Nutrition 0.000 claims 2
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 claims 1
- 150000001243 acetic acids Chemical class 0.000 claims 1
- 150000002431 hydrogen Chemical group 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims 1
- 229910001950 potassium oxide Inorganic materials 0.000 claims 1
- 239000003292 glue Substances 0.000 abstract description 11
- 238000005119 centrifugation Methods 0.000 abstract description 4
- 239000000725 suspension Substances 0.000 abstract description 4
- 235000013373 food additive Nutrition 0.000 abstract description 2
- 239000002778 food additive Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 52
- 238000001816 cooling Methods 0.000 description 20
- 235000019441 ethanol Nutrition 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 18
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 14
- 229940106681 chloroacetic acid Drugs 0.000 description 13
- 239000000843 powder Substances 0.000 description 11
- 235000011121 sodium hydroxide Nutrition 0.000 description 11
- 239000012153 distilled water Substances 0.000 description 10
- 238000004886 process control Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 7
- 238000004898 kneading Methods 0.000 description 6
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 5
- 238000013019 agitation Methods 0.000 description 5
- 230000001404 mediated effect Effects 0.000 description 5
- 230000001376 precipitating effect Effects 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 238000011017 operating method Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound 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 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 1
- 241001391926 Neea Species 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical class [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23C—DAIRY PRODUCTS, e.g. MILK, BUTTER OR CHEESE; MILK OR CHEESE SUBSTITUTES; MAKING THEREOF
- A23C9/00—Milk preparations; Milk powder or milk powder preparations
- A23C9/152—Milk preparations; Milk powder or milk powder preparations containing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
- C08B1/08—Alkali cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/02—Alkyl or cycloalkyl ethers
- C08B11/04—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals
- C08B11/10—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals
- C08B11/12—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals substituted with carboxylic radicals, e.g. carboxymethylcellulose [CMC]
Abstract
The invention discloses a kind of cellulose gums and its preparation method and application.The preparation method of the cellulose gum includes the following steps: that (1) in the presence of water and isopropanol, cellulose powder and basifier are stirred, and reaction obtains alkalinized celluloses；The mass ratio of water and cellulose powder is (1.50-3.80): 1；The mass ratio of basifier and cellulose powder is (0.60-0.70): 1；(2) in the presence of etherifying agent, by the alkalinized celluloses in step (1) it is etherified reaction to get；The mass ratio of basifier and cellulose powder is (0.70-0.80): 1.Food-grade cellulose element glue produced by the present invention is under the premise of meeting as food additives, it can ensure albumen centrifugation≤1.5% in acidic dairy prod beverage, and the placement of acidic dairy prod beverage 21 days not stratified, plays the role of extraordinary suspension and stablizes lactoprotein.
Description
Technical field
The present invention relates to a kind of cellulose gums and its preparation method and application.
Background technique
Acidic dairy prod beverage cellulose gum or food-grade cellulose element glue on market today, (carboxymethyl is fine by also referred to as CMC
Tie up plain sodium), the problem of stability difference is always existed in acidic dairy prod beverage products use process, and it is steady to be especially embodied in albumen
It on qualitative, be embodied in and be also easy to produce lactoprotein precipitating (> 2.0%), be not easy to store, long-term place is also easy to produce precipitating etc., it is difficult to
Meets the needs of present field of food is growing for additive.
Therefore, how to improve stability of the food-grade CMC in the application of acidic dairy prod beverage products, allow food-grade CMC
Albumen precipitation is reduced in acidic dairy prod beverage, is the content that acidic dairy prod beverage is paid close attention to the most；In addition, can allow acid newborn
It is also the effect that this field is pursued always that product beverage can keep longer time under normal temperature conditions.
Summary of the invention
Technical problem to be solved by the present invention lies in overcome existing food-grade cellulose element glue to be applied to acidic dairy prod
When in beverage, it is also easy to produce the defect that lactoprotein precipitating (> 2.0%) and long term storage are easily layered, and provides a kind of cellulose gum
And its preparation method and application.Food-grade cellulose element glue produced by the present invention can ensure that albumen is centrifuged in acidic dairy prod beverage
Precipitating≤1.5%, and the placement of acidic dairy prod beverage 21 days are not stratified, realize long-time stable.
The present invention provides a kind of preparation methods of cellulose gum comprising following steps:
(1) in the presence of water and isopropanol, cellulose powder and basifier are stirred, reacts, obtains alkalinized celluloses；
The mass ratio of the water and the cellulose powder is (1.50-3.80): 1；
The mass ratio of the basifier and the cellulose powder is (0.60-0.70): 1；
(2) in the presence of etherifying agent, by alkalinized celluloses described in step (1) it is etherified reaction to get；
The mass ratio of the etherifying agent and the cellulose powder is (0.70-0.80): 1.
In step (1), the method that this field routine can be used in the cellulose powder is made, such as by cellulose through powder
It is broken to get；Preferably, also operating through sieving after the crushing, such as cross 40 meshes.
In step (1), the cellulose in the cellulose powder can be used for preparing carboxymethyl fibre for this field routine
Tie up the cellulose of plain sodium, such as dissolving pulp.
In this field, the dissolving pulp generally refers to " dissolving grade chemical wood pulp ", at 20 DEG C, immerses mass concentration
After one hour in 18% sodium hydroxide solution, by weight, alkali wood pulp or sulfuric acid containing 92% or more insoluble fraction
Salt wood pulp；Or the sulphite wood pulp of the insoluble fraction containing 88% or more, and by weight, content of ashes is no more than
0.15%.
Preferably, the dissolving pulp is tembec company, the Canada fiber produced made of natural needlebush
Element.
Preferably, the average degree of polymerization of the dissolving pulp is 1200-1600, such as 1452.
In this field, isopropanol easily forms azeotropic mixture with water, it is difficult to obtain the isopropyl raw polyol that purity is 99.9% or more.
Thus, in step (2), the isopropanol is practical, and volumetric concentration can be used is 88-94% (such as 88%, 89%, 91%, 92%
Or 93%) isopropanol, rest part are water, specific dosage can convert by its volumetric concentration.
In step (1), the mass ratio of the water and the cellulose powder is preferably (1.67-3.67): 1, such as
2.35:1,3.67:1,1.67:1,2.48:1 or 2.42:1.
In step (1), the mass ratio of the isopropanol and the cellulose powder is preferably >=10:1；More preferably it is
(10-18): 1, such as 13.32:1,17.04:1,10.95:1,16.21:1 or 11.23:1.
In step (1), preferably, (such as the alcohols such as methanol, ethyl alcohol are molten without containing other alcohols solvents other than isopropanol
Agent)；More preferably, without containing other solvents other than water and isopropanol.
In step (1), the basifier can be the basifier of this field routine, such as potassium hydroxide and/or sodium hydroxide.
The sodium hydroxide is preferably the sodium hydroxide of purity >=98%, and percentage refers to mass percent.
In step (1), the mass ratio of the basifier and the cellulose powder is preferably (0.61-0.70): 1, example
Such as 0.61:1,0.64:1,0.66:1,0.68:1 or 0.70:1.
In step (1), mass concentration of the basifier in the water is preferably 15-30%, such as 22%,
16%, 27% or 21%.
In step (1), preferably, the basifier is first dissolved in the water, then mixed with the cellulose powder.
Wherein, the temperature of the dissolution is preferably 10-35 DEG C.
Wherein, the time of the dissolution is preferably 20-60min.
In step (1), described be stirred preferably is carried out using uniaxial double-blade blender.
In step (1), the time being stirred is preferably 50-120min, for example, 50min, 60min, 80min,
100min or 120min.
In step (1), the revolving speed being stirred is preferably 160-170r/min, such as 166r/min.
In step (1), the temperature being stirred is preferably 15-30 DEG C, such as 20-25 DEG C.
In step (2), the etherifying agent can be the etherifying agent of this field routine, such as monohaloalkyl acetic acid or monohaloalkyl acetic acid
Salt, then such as monoxone.
Wherein, the etherifying agent when in use, can generally be configured to solution use, such as monoxone aqueous isopropanol.
Preferably, chloroacetic mass fraction is 70% in the monoxone aqueous isopropanol.More preferably, by monoxone
After dissolving with isopropanol by weight 3:2, reusing isopropanol to quality of chloroacetic acid score is 70%.
In step (2), preferably, the mass ratio of the etherifying agent and the cellulose powder is (0.74-0.80): 1, example
Such as 0.75:1,0.80:1,0.77:1 or 0.74:1.
In step (2), the addition manner of the etherifying agent can be by the addition manner of this field routine, it is however generally that, by institute
Etherifying agent is stated slowly to be homogeneously added into the alkalinized celluloses.
Wherein, described to be slowly homogeneously added into and carry out in the steps below, under the conditions of 25-60 DEG C (such as 30-40 DEG C),
The etherifying agent is slowly added into alkali cellulose in 25-60min (such as 20min, 25min, 40min or 45min).
Wherein, the etherifying agent can be added by acid-resistant pipeline, pass through valve controlling flow amount.
In step (2), the etherification reaction is preferably carried out in the reaction kettle with agitating function.
In step (2), the etherification reaction can carry out in the steps below: stir under the conditions of 25-60 DEG C (such as 30-40 DEG C)
After mixing 10-25min (such as 10min, 15min, 20min or 25min), 15-30min (such as 15min, 20min, 25min or
It is warming up to 75-78 DEG C (such as 75-76 DEG C, 76-77 DEG C or 77-78 DEG C) in 30min), constant temperature 35-90min (such as 35min,
45min, 70min, 80min or 90min).
Wherein, after the completion of reaction, temperature of charge can be down to≤50 DEG C by this field routine operation.
In step (2), after the etherification reaction, can also by this field routine operation by the cellulose gum through adjusting
PH, drying and processing.
Wherein, the reagent for adjusting pH is the pH adjusting agent of this field routine, such as aqueous acetic acid, preferably matter
Measure the aqueous acetic acid of concentration 30-40%, the more preferably aqueous acetic acid for mass concentration 30%.Preferably, adjust pH value to
6.8-8.0。
Wherein, carrying out washing treatment can be also carried out before the adjusting pH, and/or after the adjusting pH.The washing it is molten
Agent is the solvent of this field routine, such as volume fraction is the alcohol water blend of 60-76%.
Centrifugal dewatering should be generally carried out before and after the washing.The number of the washing can be multiple, it is however generally that, washing is extremely
The purity of material is up to 99.5%.
Wherein, the drying can be carried out by the process conditions of this field routine, preferably, being dried to the cellulose gum
Water content is 5-8%, and percentage refers to mass percent.
Wherein, preferably, also carrying out pulverization process after the drying.It can also routinely be grasped by this field after the pulverization process
Sieving processing is carried out, such as crosses 80 meshes.
The present invention also provides one kind cellulose gums as made from above-mentioned preparation method.
Cellulose gum 1%B type range of viscosities produced by the present invention is in 300-600mPas, in acidic dairy prod beverage
It can ensure that albumen centrifugation≤1.5%, and the placement of acidic dairy prod beverage 21 days not stratified.As it can be seen that produced by the present invention
Cellulose gum can play the role of extraordinary suspension in acidic dairy prod beverage and stablize lactoprotein.
It is described the present invention also provides a kind of above-mentioned cellulose gum as the application of stabilizer in acidic dairy prod beverage
Stabilizer is preferably protein stabiliser.
On the basis of common knowledge of the art, above-mentioned each optimum condition, can any combination to get each preferable reality of the present invention
Example.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is that:
The present invention, as solvent, is added basifier and is uniformly mixed with isopropanol to cellulose progress alkali using isopropyl alcohol and water
Pretreatment, obtains alkali cellulose before changing, and then acid adding, etherificate obtain the good acidic dairy prod beverage cellulose of uniformity again
Glue.Its stability is more preferable, is suitble to use in the environment of pH value 3.0-8.5, under the premise of meeting as food additives,
It can ensure albumen centrifugation≤1.5% in acidic dairy prod beverage, and the placement of acidic dairy prod beverage 21 days are not stratified,
Play the role of extraordinary suspension and stablizes lactoprotein.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to the reality
It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient
The selection of product specification.
In following embodiments and comparative example, dissolving pulp is purchased from tembec company, Canada.
Embodiment 1
(1) under agitation, the solid caustic soda of 0.67kg 98.2% (being calculated as 0.66kg with pure quality) is dissolved in 0.67kg
Distilled water and and 15kg volume fraction be 91% isopropanol (wherein the quality of isopropanol is 13.32kg, and the quality of water is
It 1.68kg) is added in stirred autoclave and stirs evenly together, be then added thereto the dissolving pulp that the 1kg degree of polymerization is 1452,
Control temperature is stirred alkalization 80min under 20-25 DEG C, 166r/min state, obtains uniform alkali cellulose.
(2) to the chloroethene that addition quality of chloroacetic acid content is 70% in the reaction kettle for having formed uniform alkali cellulose
Sour aqueous isopropanol 1.07kg, is uniformly slowly added into 45min, while the process control reaction temperature is at 30-40 DEG C.
(3) by material under the conditions of 30-40 DEG C cooling and stirring 15min, then material is warming up to 76-77 DEG C in 15min,
And constant temperature 70min, material is cooled to 50 DEG C or less again to the end of reacting.
(4) material of the cooling after good is put into alcohol water blend, is adjusted with the aqueous acetic acid that mass concentration is 30%
PH value is to 6.8-8.0.
(5) it will be pulverized into powder after drying materials, it is fine with acidic dairy prod beverage is just obtained after the sieving of 80 mesh screens
Tie up plain glue.
Embodiment 2
(1) under agitation, the solid caustic soda of 0.71kg 98.2% (being calculated as 0.70kg with pure quality) is dissolved in 0.71kg
Distilled water and and 20kg volume fraction be 88% isopropanol (wherein the quality of isopropanol is 17.04kg, and the quality of water is
It 2.96kg) is added in stirred autoclave and stirs evenly together, be then added thereto the dissolving pulp that the 1kg degree of polymerization is 1452,
Control temperature is stirred alkalization 50min under 20-25 DEG C, 166r/min state, obtains uniform alkali cellulose.
(2) to the chloroethene that addition quality of chloroacetic acid content is 70% in the reaction kettle for having formed uniform alkali cellulose
Sour aqueous isopropanol 1.14kg, is uniformly slowly added into 20min, while the process control reaction temperature is at 30-40 DEG C.
(3) by material under the conditions of 30-40 DEG C cooling and stirring 20min, then material is warming up to 77-78 DEG C in 30min,
And constant temperature 35min, material is cooled to 50 DEG C or less again to the end of reacting.
(4) material of the cooling after good is put into alcohol water blend, is adjusted with the aqueous acetic acid that mass concentration is 30%
PH value is to 6.8-8.0.
(5) it will be pulverized into powder after drying materials, it is fine with acidic dairy prod beverage is just obtained after the sieving of 80 mesh screens
Tie up plain glue.
Embodiment 3
(1) under agitation, the solid caustic soda of 0.62kg 98.2% (being calculated as 0.61kg with pure quality) is dissolved in 0.62kg
Distilled water and and 12kg volume fraction be 93% isopropanol (wherein the quality of isopropanol is 10.95kg, and the quality of water is
It 1.05kg) is added in stirred autoclave and stirs evenly together, be then added thereto the dissolving pulp that the 1kg degree of polymerization is 1452,
Control temperature is stirred alkalization 120min under 20-25 DEG C, 166r/min state, obtains uniform alkali cellulose.
(2) to the chloroethene that addition quality of chloroacetic acid content is 70% in the reaction kettle for having formed uniform alkali cellulose
Sour aqueous isopropanol 1kg, is uniformly slowly added into 20min, while the process control reaction temperature is at 30-40 DEG C.
(3) by material under the conditions of 30-40 DEG C cooling and stirring 10min, then material is warming up to 75-76 DEG C in 15min,
And constant temperature 90min, material is cooled to 50 DEG C or less again to the end of reacting.
(4) material of the cooling after good is put into alcohol water blend, is adjusted with the aqueous acetic acid that mass concentration is 30%
PH value is to 6.8-8.0.
(5) it will be pulverized into powder after drying materials, it is fine with acidic dairy prod beverage is just obtained after the sieving of 80 mesh screens
Tie up plain glue.
Embodiment 4
(1) under agitation, the solid caustic soda of 0.69kg 98.2% (being calculated as 0.68kg with pure quality) is dissolved in 0.69kg
Distilled water and and 18kg volume fraction be 92% isopropanol (wherein the quality of isopropanol is 16.21kg, and the quality of water is
It 1.79kg) is added in stirred autoclave and stirs evenly together, be then added thereto the dissolving pulp that the 1kg degree of polymerization is 1452,
Control temperature is stirred alkalization 100min under 20-25 DEG C, 166r/min state, obtains uniform alkali cellulose.
(2) to the chloroethene that addition quality of chloroacetic acid content is 70% in the reaction kettle for having formed uniform alkali cellulose
Sour aqueous isopropanol 1.1kg, is uniformly slowly added into 40min, while the process control reaction temperature is at 30-40 DEG C.
(3) by material under the conditions of 30-40 DEG C cooling and stirring 25min, then material is warming up to 76-77 DEG C in 25min,
And constant temperature 80min, material is cooled to 50 DEG C or less again to the end of reacting.
(4) material of the cooling after good is put into alcohol water blend, is adjusted with the aqueous acetic acid that mass concentration is 30%
PH value is to 6.8-8.0.
(5) it will be pulverized into powder after drying materials, it is fine with acidic dairy prod beverage is just obtained after the sieving of 80 mesh screens
Tie up plain glue.
Embodiment 5
(1) under agitation, the solid caustic soda of 0.65kg 98.2% (being calculated as 0.64kg with pure quality) is dissolved in 0.65kg
Distilled water and and 13kg volume fraction be 89% isopropanol (wherein the quality of isopropanol is 11.23kg, and the quality of water is
It 1.77kg) is added in stirred autoclave and stirs evenly together, be then added thereto the dissolving pulp that the 1kg degree of polymerization is 1452,
Control temperature is stirred alkalization 60min under 20-25 DEG C, 166r/min state, obtains uniform alkali cellulose.
(2) to the chloroethene that addition quality of chloroacetic acid content is 70% in the reaction kettle for having formed uniform alkali cellulose
Sour aqueous isopropanol 1.05kg, is uniformly slowly added into 25min, while the process control reaction temperature is at 30-40 DEG C.
(3) by material under the conditions of 30-40 DEG C cooling and stirring 15min, then material is warming up to 75-76 DEG C in 20min,
And constant temperature 45min, material is cooled to 50 DEG C or less again to the end of reacting.
(4) material of the cooling after good is put into alcohol water blend, is adjusted with the aqueous acetic acid that mass concentration is 30%
PH value is to 6.8-8.0.
(5) it will be pulverized into powder after drying materials, it is fine with acidic dairy prod beverage is just obtained after the sieving of 80 mesh screens
Tie up plain glue.
Comparative example 1
(1) method is mediated using traditional handicraft and prepares sample, according to the feeding quantity of embodiment 1, by consolidating for 0.67kg98.2%
Alkali is dissolved in 0.67kg distilled water and is added in kneader together with the alcohol water blend of 2.5kg 91% and stirs evenly, and then will
The dissolving pulp that the 1kg degree of polymerization is 1452 is added thereto, and control temperature carries out kneading alkali under 20-25 DEG C, 166r/min state
Change 80min, obtains alkali cellulose.
(2) the monoxone wine that quality of chloroacetic acid content is 70% is added into the kneader in the alkali cellulose formed
Smart solution 1.07kg, is uniformly slowly added into 45min, while the process control reaction temperature is at 30-40 DEG C.
(3) by material, cooling and stirring kneads 15min under the conditions of 30-40 DEG C, then material is warming up to 76- in 15min
77 DEG C, and constant temperature 70min, material is cooled to 50 DEG C or less again to the end of reacting.
(4) material of the cooling after good is put into alcohol water blend, is adjusted with the aqueous acetic acid that mass concentration is 30%
PH value is to 6.8-8.0.
(5) it will be pulverized into powder after drying materials, just obtain sample after being sieved with 80 mesh screens.
Comparative example 2
(1) method is mediated using traditional handicraft and prepares sample, according to the feeding quantity of embodiment 2, by consolidating for 0.71kg98.2%
Alkali be dissolved in 0.71kg distilled water and be 88% with 2.8kg mass fraction alcohol water blend be added in kneader together stir it is equal
It is even, then by the 1kg degree of polymerization be 1452 dissolving pulp be added thereto, control temperature under 20-25 DEG C, 166r/min state into
Row kneading alkalization 50min, obtains alkali cellulose.
(2) the monoxone wine that quality of chloroacetic acid content is 70% is added into the kneader in the alkali cellulose formed
Smart solution 1.14kg, is uniformly slowly added into 20min, while the process control reaction temperature is at 30-40 DEG C.
(3) by material, cooling and stirring kneads 20min under the conditions of 30-40 DEG C, then material is warming up to 77- in 30min
78 DEG C, and constant temperature 35min, material is cooled to 50 DEG C or less again to the end of reacting.
(4) material of the cooling after good is put into alcohol water blend, is adjusted with the aqueous acetic acid that mass concentration is 30%
PH value is to 6.8-8.0.
(5) it will be pulverized into powder after drying materials, just obtain sample after being sieved with 80 mesh screens.
Comparative example 3
(1) method is mediated using traditional handicraft and prepares sample, according to the feeding quantity of embodiment 3, by consolidating for 0.62kg98.2%
Alkali be dissolved in 0.62kg distilled water and be 93% with 2.3kg mass fraction alcohol water blend be added in kneader together stir it is equal
It is even, then by the 1kg degree of polymerization be 1452 dissolving pulp be added thereto, control temperature under 20-25 DEG C, 166r/min state into
Row kneading alkalization 120min, obtains alkali cellulose.
(2) the monoxone wine that quality of chloroacetic acid content is 70% is added into the kneader in the alkali cellulose formed
Smart solution 1kg, is uniformly slowly added into 20min, while the process control reaction temperature is at 30-40 DEG C.
(3) by material, cooling and stirring kneads 10min under the conditions of 30-40 DEG C, then material is warming up to 75- in 15min
76 DEG C, and constant temperature 90min, material is cooled to 50 DEG C or less again to the end of reacting.
(4) material of the cooling after good is put into alcohol water blend, is adjusted with the aqueous acetic acid that mass concentration is 30%
PH value is to 6.8-8.0.
(5) it will be pulverized into powder after drying materials, just obtain sample after being sieved with 80 mesh screens.
Comparative example 4
(1) method is mediated using traditional handicraft and prepares sample, according to the feeding quantity of embodiment 4, by consolidating for 0.69kg98.2%
Alkali be dissolved in 0.69kg distilled water and be 92% with 2.6kg mass fraction alcohol water blend be added in kneader together stir it is equal
It is even, then by the 1kg degree of polymerization be 1452 dissolving pulp be added thereto, control temperature under 20-25 DEG C, 166r/min state into
Row kneading alkalization 100min, obtains alkali cellulose.
(2) the monoxone wine that quality of chloroacetic acid content is 70% is added into the kneader in the alkali cellulose formed
Smart solution 1.1kg, is uniformly slowly added into 40min, while the process control reaction temperature is at 30-40 DEG C.
(3) by material, cooling and stirring kneads 25min under the conditions of 30-40 DEG C, then material is warming up to 76- in 25min
77 DEG C, and constant temperature 80min, material is cooled to 50 DEG C or less again to the end of reacting.
(4) material of the cooling after good is put into alcohol water blend, is adjusted with the aqueous acetic acid that mass concentration is 30%
PH value is to 6.8-8.0.
(5) it will be pulverized into powder after drying materials, just obtain sample after being sieved with 80 mesh screens.
Comparative example 5
(1) method is mediated using traditional handicraft and prepares sample, according to the feeding quantity of embodiment 5, by consolidating for 0.65kg98.2%
Alkali be dissolved in 0.65kg distilled water and be 89% with 2.4kg mass fraction alcohol water blend be added in kneader together stir it is equal
It is even, then by the 1kg degree of polymerization be 1452 dissolving pulp be added thereto, control temperature under 20-25 DEG C, 166r/min state into
Row kneading alkalization 60min, obtains alkali cellulose.
(2) the monoxone wine that quality of chloroacetic acid content is 70% is added into the kneader in the alkali cellulose formed
Smart solution 1.05kg, is uniformly slowly added into 25min, while the process control reaction temperature is at 30-40 DEG C.
(3) by material, cooling and stirring kneads 15min under the conditions of 30-40 DEG C, then material is warming up to 75- in 20min
76 DEG C, and constant temperature 45min, material is cooled to 50 DEG C or less again to the end of reacting.
(4) material of the cooling after good is put into alcohol water blend, is adjusted with the aqueous acetic acid that mass concentration is 30%
PH value is to 6.8-8.0.
(5) it will be pulverized into powder after drying materials, just obtain sample after being sieved with 80 mesh screens.
Comparative example 6
Corresponding product is made according to the operating method of the embodiment 7 in existing patent CN 102822204A.
Comparative example 7
Corresponding product is made according to the operating method of the embodiment 12 in existing patent CN 102822204A.
Comparative example 8
The dosage of solid caustic soda is 0.50kg in step (1), remaining is the same as embodiment 3.
Comparative example 9
The dosage of solid caustic soda is 0.80kg in step (1), remaining is the same as embodiment 3.
Comparative example 10
The dosage for the monoxone aqueous isopropanol that quality of chloroacetic acid content is 70% in step (2) is 0.8kg, remaining is the same as real
Apply example 3.
Comparative example 11
The dosage for the monoxone aqueous isopropanol that quality of chloroacetic acid content is 70% in step (2) is 1.5kg, remaining is same
Embodiment 3.
Comparative example 12
Corresponding product is made according to the operating method of the embodiment 10 in existing patent CN 102822204A.
Effect example 1
(1) by cellulose gum obtained by embodiment and comparative example and the cellulose gum of commercial source, according to food-grade
It is as follows that cellulose gum national standard detects its degree of substitution, pH value and 30min viscosity, detection method:
GB 1886.232-2016 is detected degree of substitution according to national standards；
30min viscosity is with the embodiment of 1%B type viscosity, and GB1886.232-2016 is detected according to national standards.
(2) by cellulose gum obtained by embodiment and comparative example and the cellulose gum of commercial source, it is used to prepare acid
Property dairy beverage (pH of finished product be 4.3, protein content 4.2%), detection is (in the item of 4000rpm after configuration is complete
It is centrifuged 20 minutes under part) its albumen precipitation amount (with volume percentage), room temperature places 21 days for a long time, and whether the observation period is layered.
Above-mentioned data result is as shown in table 1 below.
1 food-grade cellulose element glue performance indicator of table, precipitation capacity and Detection of Stability result
Pass through correlation data, it is known that:
(1) in the application of acidic dairy prod beverage, the albumen precipitation amount of cellulose gum produced by the present invention is obviously than passing
Cellulose gum made from system method wants much lower, and albumen centrifugation≤1.5% (with volume percentage), this index changes
Into the quality limit that changes original traditional handicraft and can not go beyond；
(2) during the test of the storage Stratified stability of acidic dairy prod beverage, cellulose gum energy produced by the present invention
Holding is stablized not stratified in 21 days, and conventionally (is carried out using ethyl alcohol as solvent, by kneading method in comparative example 1-5
Alkalization) made from cellulose gum be then difficult to realize it is not stratified in 21 days, generally storage 7 days later just it is obvious occur layering (on
Layer has the suspension of white protein object), all (upper layer is clear liquid, and lower layer is then milky white chromoprotein) is layered when 14 days；
(3) by comparing cellulose gum obtained by preparation method in the prior art, referring specifically to comparative example 6,7 and
10, even if inventor's discovery improves the viscosity of cellulose gum, it can not also effectively realize albumen in acidic dairy prod beverage
Stablizing, inventor speculates, may be related with the position of substitution of sodium carboxymethylcellulose, even if viscosity is promoted, if but in acid item
Cellulose is reduced under part, it is also difficult to the effect of playing stably；
(4) pass through comparative example 8-11 it is found that when basifier, etherifying agent dosage not within the scope of this application when, it is made
The cellulose gum obtained is difficult to remain protein stabilized in acid condition, and long-term place 14 days is layered.
Claims (10)
1. a kind of preparation method of cellulose gum, which is characterized in that it includes the following steps:
(1) in the presence of water and isopropanol, cellulose powder and basifier are stirred, reacts, obtains alkalinized celluloses；
The mass ratio of the water and the cellulose powder is (1.50-3.80): 1；
The mass ratio of the basifier and the cellulose powder is (0.60-0.70): 1；
(2) in the presence of etherifying agent, by alkalinized celluloses described in step (1) it is etherified reaction to get；
The mass ratio of the etherifying agent and the cellulose powder is (0.70-0.80): 1.
2. the preparation method of cellulose gum as described in claim 1, which is characterized in that in step (1), the cellulose powder
Using following methods be made, by cellulose crushed to get；Preferably, also operated through sieving after the crushing, preferably
40 meshes；
And/or in step (1), the cellulose in the cellulose powder is dissolving pulp, preferably, the cellulose powder
In cellulose be tembec company, the Canada cellulose produced made of natural needlebush；Preferably, the dissolution
The average degree of polymerization of wood pulp is 1200-1600, is more preferably 1452；
And/or in step (1), the mass ratio of the water and the cellulose powder is (1.67-3.67): 1, preferably
2.35:1,3.67:1,1.67:1,2.48:1 or 2.42:1；
And/or in step (1), the mass ratio of the isopropanol and the cellulose powder is >=10:1；Preferably (10-
18): 1, it is more preferably 13.32:1,17.04:1,10.95:1,16.21:1 or 11.23:1；
And/or in step (1), without containing other alcohols solvents other than isopropanol；Preferably, without containing water and isopropanol with
Other outer solvents.
3. the preparation method of cellulose gum as described in claim 1, which is characterized in that in step (1), the basifier is hydrogen
Potassium oxide and/or sodium hydroxide；
And/or in step (1), the mass ratio of the basifier and the cellulose powder is (0.61-0.70): 1, preferably
For 0.61:1,0.64:1,0.66:1,0.68:1 or 0.70:1；
Or, in step (1), mass concentration of the basifier in the water is 15-30%, preferably 22%, 16%,
27% or 21%；
And/or in step (1), the basifier is first dissolved in the water, then mix with the cellulose powder；Wherein, institute
The temperature for stating dissolution is preferably 10-35 DEG C, and the time of the dissolution is preferably 20-60min；
It is described to be stirred to be carried out using uniaxial double-blade blender and/or in step (1)；
And/or in step (1), the time being stirred be 50-120min, preferably 50min, 60min, 80min,
100min or 120min；
And/or in step (1), the revolving speed being stirred is 160-170r/min, preferably 166r/min；
And/or in step (1), the temperature being stirred is 15-30 DEG C, preferably 20-25 DEG C.
4. the preparation method of cellulose gum as described in claim 1, which is characterized in that in step (2), the etherifying agent is single
Halogenated acetic acids or monohaloalkyl acetate, preferably monoxone；
And/or in step (2), the mass ratio of the etherifying agent and the cellulose powder is (0.74-0.80): 1, preferably
For 0.75:1,0.80:1,0.77:1 or 0.74:1.
5. the preparation method of cellulose gum as described in claim 1, which is characterized in that in step (2), the etherifying agent is added
Enter into the alkalinized celluloses；Preferably, the etherifying agent is added in the alkalinized celluloses using following step:
Under the conditions of 25-60 DEG C, the etherifying agent is all added in the alkali cellulose in 25-60min；Preferably, the ether
Agent is added by acid-resistant pipeline, passes through valve controlling flow amount；
And/or in step (2), the etherification reaction carries out in the reaction kettle with agitating function；
And/or in step (2), the etherification reaction carries out in the steps below: after stirring 10-25min under the conditions of 25-60 DEG C,
75-78 DEG C is warming up in 15-30min, constant temperature 35-90min.
6. the preparation method of cellulose gum as described in claim 1, which is characterized in that in step (2), the etherification reaction knot
Shu Hou, by the cellulose gum through adjusting pH and/or drying and processing.
7. the preparation method of cellulose gum as claimed in claim 6, which is characterized in that the reagent for adjusting pH is acetic acid water
Solution, the preferably aqueous acetic acid of mass concentration 30-40%, the more preferably aqueous acetic acid for mass concentration 30%；
And/or the adjusting pH is to adjust pH value to 6.8-8.0；
And/or also progress carrying out washing treatment before the adjusting pH, and/or after the adjustings pH, the solvent of the washing compared with
It goodly is the alcohol water blend that volume fraction is 60-76%；
And/or the drying is 5-8% to be dried to the water content of the cellulose gum, percentage refers to mass percent；
And/or pulverization process is also carried out after the drying, preferably, also carrying out the processing of 80 meshes after the pulverization process.
8. cellulose gum obtained by a kind of preparation method such as cellulose gum according to any one of claims 1 to 7.
9. a kind of cellulose gum as claimed in claim 8 is in acidic dairy prod beverage as the application of stabilizer.
10. cellulose gum as claimed in claim 9 is in acidic dairy prod beverage as the application of stabilizer, the stabilizer
For protein stabiliser.
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| CN101033256A (en) * | 2007-03-09 | 2007-09-12 | 北京理工大学 | Method of preparing high viscosity carboxymethyl cellulose by slurry method |
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| CN102822204A (en) * | 2010-03-30 | 2012-12-12 | 陶氏环球技术有限责任公司 | New high viscosity carboxymethyl cellulose and method of preparation |
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| CN101033256A (en) * | 2007-03-09 | 2007-09-12 | 北京理工大学 | Method of preparing high viscosity carboxymethyl cellulose by slurry method |
| CN101548732A (en) * | 2008-04-03 | 2009-10-07 | 上海长光企业发展有限公司 | Preparation method for low-viscosity sodium carboxymethyl cellulose for foodstuff |
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| CN103724436A (en) * | 2013-12-06 | 2014-04-16 | 济南圣泉集团股份有限公司 | Preparation method of cellulose ether |
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