CN110128553B - Cellulose gum and preparation method and application thereof - Google Patents
Cellulose gum and preparation method and application thereof Download PDFInfo
- Publication number
- CN110128553B CN110128553B CN201910402616.4A CN201910402616A CN110128553B CN 110128553 B CN110128553 B CN 110128553B CN 201910402616 A CN201910402616 A CN 201910402616A CN 110128553 B CN110128553 B CN 110128553B
- Authority
- CN
- China
- Prior art keywords
- stirring
- cellulose
- chloroacetic acid
- temperature
- materials
- 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.)
- Active
Links
- 229920002134 Carboxymethyl cellulose Polymers 0.000 title claims abstract description 47
- 239000001768 carboxy methyl cellulose Substances 0.000 title claims abstract description 47
- 235000010948 carboxy methyl cellulose Nutrition 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 61
- 238000003756 stirring Methods 0.000 claims abstract description 61
- 229920002678 cellulose Polymers 0.000 claims abstract description 45
- 239000001913 cellulose Substances 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims description 58
- 238000006243 chemical reaction Methods 0.000 claims description 57
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 51
- 239000003513 alkali Substances 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 38
- 239000007864 aqueous solution Substances 0.000 claims description 28
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 28
- 229940106681 chloroacetic acid Drugs 0.000 claims description 28
- 238000001816 cooling Methods 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 28
- 230000002378 acidificating effect Effects 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 229920001131 Pulp (paper) Polymers 0.000 claims description 23
- 235000013361 beverage Nutrition 0.000 claims description 21
- 235000013365 dairy product Nutrition 0.000 claims description 21
- KJJPESOHTCIVIS-UHFFFAOYSA-N 2-chloroacetic acid propan-2-ol Chemical compound C(C)(C)O.ClCC(=O)O KJJPESOHTCIVIS-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 18
- 238000007873 sieving Methods 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- 239000012153 distilled water Substances 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 16
- 239000003795 chemical substances by application Substances 0.000 abstract description 14
- 239000002253 acid Substances 0.000 abstract description 10
- 235000019543 dairy drink Nutrition 0.000 abstract description 10
- 230000006920 protein precipitation Effects 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 6
- 238000006266 etherification reaction Methods 0.000 abstract description 5
- 230000000087 stabilizing effect Effects 0.000 abstract description 4
- 102000014171 Milk Proteins Human genes 0.000 abstract description 3
- 108010011756 Milk Proteins Proteins 0.000 abstract description 3
- 235000021239 milk protein Nutrition 0.000 abstract description 3
- 235000013373 food additive Nutrition 0.000 abstract description 2
- 239000002778 food additive Substances 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 18
- 238000004898 kneading Methods 0.000 description 13
- 235000011121 sodium hydroxide Nutrition 0.000 description 9
- 239000000047 product Substances 0.000 description 7
- 235000018102 proteins Nutrition 0.000 description 7
- 102000004169 proteins and genes Human genes 0.000 description 7
- 108090000623 proteins and genes Proteins 0.000 description 7
- 238000005406 washing Methods 0.000 description 6
- 230000001476 alcoholic effect Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 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
- 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 description 3
- 230000003113 alkalizing effect Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000010979 pH adjustment Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 239000005456 alcohol based solvent Substances 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- PTHCMJGKKRQCBF-UHFFFAOYSA-N Cellulose, microcrystalline Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC)C(CO)O1 PTHCMJGKKRQCBF-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 229940124272 protein stabilizer Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 239000000725 suspension Substances 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 cellulose gum and a preparation method and application thereof. The preparation method of the cellulose gum comprises the following steps: (1) in the presence of water and isopropanol, stirring and mixing cellulose powder and an alkalizer, and reacting to obtain alkalized cellulose; the mass ratio of water to cellulose powder is (1.50-3.80): 1; the mass ratio of the alkalizer to the cellulose powder is (0.60-0.70) to 1; (2) in the presence of an etherifying agent, carrying out etherification reaction on the alkalized cellulose in the step (1) to obtain the alkalized cellulose; the mass ratio of the alkalizer to the cellulose powder is (0.70-0.80): 1. The food-grade cellulose gum prepared by the invention can ensure that the centrifugal precipitation of protein is less than or equal to 1.5 percent in the acid dairy drink on the premise of serving as a food additive, and the acid dairy drink is not layered after being placed for 21 days, thereby playing a very good role in suspending and stabilizing the milk protein.
Description
Technical Field
The invention relates to a cellulose gum and a preparation method and application thereof.
Background
Cellulose gum or food grade cellulose gum, also called CMC (sodium carboxymethylcellulose), for acidic dairy drinks in the market has the problem of poor stability in the use process of acidic dairy drink products, and is particularly reflected in protein stability, and specifically has the characteristics of easy generation of lactoprotein precipitate (more than 2.0%), difficult storage, easy generation of precipitate after long-term storage and the like, so that the increasing requirements of the current food field on additives are difficult to meet.
Therefore, how to improve the stability of the food-grade CMC in the application of the acid dairy beverage products and reduce protein precipitation of the food-grade CMC in the acid dairy beverage is the most concerned content of the acid dairy beverage; in addition, it is also an effect of the present invention to keep the acidic dairy beverage at room temperature for a long time.
Disclosure of Invention
The invention aims to overcome the defects that the existing food-grade cellulose gum is easy to generate lactoprotein precipitate (more than 2.0 percent) and is easy to delaminate after being stored for a long time when being applied to acidic dairy beverages, and provides the cellulose gum as well as a preparation method and application thereof. The food-grade cellulose gum prepared by the invention can ensure that the centrifugal precipitation of protein is less than or equal to 1.5 percent in the acid dairy drink, and the acid dairy drink is not layered after being placed for 21 days, thereby realizing long-time stability.
The invention provides a preparation method of cellulose gum, which comprises the following steps:
(1) in the presence of water and isopropanol, stirring and mixing cellulose powder and an alkalizer, and reacting to obtain alkalized cellulose;
the mass ratio of the water to the cellulose powder is (1.50-3.80): 1;
the mass ratio of the alkalizer to the cellulose powder is (0.60-0.70) to 1;
(2) in the presence of an etherifying agent, carrying out etherification reaction on the alkalized cellulose in the step (1) to obtain the alkalized cellulose;
the mass ratio of the etherifying agent to the cellulose powder is (0.70-0.80): 1.
In the step (1), the cellulose powder can be prepared by adopting a conventional method in the field, for example, the cellulose is crushed to obtain the cellulose powder; preferably, the pulverization is followed by a sieving operation, such as 40 mesh sieving.
In step (1), the cellulose in the cellulose powder may be cellulose conventionally used in the art for preparing sodium carboxymethyl cellulose, such as dissolving wood pulp.
In the art, the dissolving wood pulp is generally referred to as "dissolving grade chemical wood pulp" which contains more than 92% by weight of insoluble fraction of alkali wood pulp or sulfate wood pulp after immersion in 18% by mass sodium hydroxide solution at 20 ℃ for one hour; or sulfite wood pulp containing an insoluble fraction of 88% or more and having an ash content of not more than 0.15% by weight.
Preferably, the dissolving wood pulp is cellulose made from natural softwood, produced by tembec corporation, canada.
Preferably, the average degree of polymerization of the dissolved wood pulp is 1200-1600, such as 1452.
In the art, isopropanol easily forms an azeotrope with water, and it is difficult to obtain an isopropanol raw material with a purity of 99.9% or more. Thus, in step (2), the isopropanol may be used in a concentration of 88-94% (e.g., 88%, 89%, 91%, 92% or 93%) by volume, and the remainder may be water, and the specific amount may be converted by volume.
In step (1), the ratio of the mass of the water and the cellulose powder is preferably (1.67-3.67):1, for example 2.35:1, 3.67:1, 1.67:1, 2.48:1 or 2.42: 1.
In the step (1), the mass ratio of the isopropanol to the cellulose powder is preferably not less than 10: 1; more preferably (10-18):1, e.g., 13.32:1, 17.04:1, 10.95:1, 16.21:1 or 11.23: 1.
In the step (1), it is preferable that alcohol solvents other than isopropyl alcohol (for example, alcohol solvents such as methanol and ethanol) are not contained; more preferably, no solvents other than water and isopropanol are present.
In step (1), the alkalizer may be a conventional alkalizer in the art, such as potassium hydroxide and/or sodium hydroxide. The sodium hydroxide is preferably sodium hydroxide with the purity of more than or equal to 98 percent, and the percentage refers to the mass percentage.
In step (1), the ratio of the mass of the alkalizing agent and the cellulose powder is preferably (0.61-0.70):1, for example, 0.61:1, 0.64:1, 0.66:1, 0.68:1 or 0.70: 1.
In step (1), the mass concentration of the alkalizer in the water is preferably 15 to 30%, for example, 22%, 16%, 27% or 21%.
In the step (1), preferably, the alkalizer is dissolved in the water and then mixed with the cellulose powder.
Wherein the temperature of the dissolution is preferably 10-35 ℃.
Wherein the dissolving time is preferably 20-60 min.
In the step (1), the stirring and mixing are preferably performed by using a single-shaft double-blade stirrer.
In step (1), the stirring and mixing time is preferably 50-120min, such as 50min, 60min, 80min, 100min or 120 min.
In step (1), the rotation speed of the stirring and mixing is preferably 160-170r/min, such as 166 r/min.
In step (1), the temperature for the stirring and mixing is preferably 15 to 30 ℃, for example, 20 to 25 ℃.
In step (2), the etherifying agent may be an etherifying agent conventional in the art, such as monohaloacetic acid or monohaloacetate, further such as chloroacetic acid.
Wherein, the etherifying agent is generally prepared into a solution for use, such as a chloroacetic acid isopropanol solution.
Preferably, the mass fraction of chloroacetic acid in the chloroacetic acid isopropanol solution is 70%. More preferably, after the chloroacetic acid and the isopropanol are dissolved according to the weight ratio of 3:2, the chloroacetic acid and the isopropanol are diluted by using the isopropanol until the mass fraction of the chloroacetic acid is 70%.
In step (2), the mass ratio of the etherifying agent to the cellulose powder is preferably (0.74-0.80):1, for example, 0.75:1, 0.80:1, 0.77:1 or 0.74: 1.
In the step (2), the addition manner of the etherifying agent may be a conventional addition manner in the art, and generally, the etherifying agent is slowly and uniformly added to the alkalized cellulose.
Wherein the slowly and uniformly adding can be carried out by slowly adding the etherifying agent to the alkali cellulose within 25-60min (e.g., 20min, 25min, 40min or 45min) at 25-60 deg.C (e.g., 30-40 deg.C).
Wherein the etherifying agent may be added through an acid resistant pipe, with flow controlled by a valve.
In the step (2), the etherification reaction is preferably performed in a reaction kettle with a stirring function.
In the step (2), the etherification reaction may be performed by the following steps: stirring at 25-60 deg.C (e.g. 30-40 deg.C) for 10-25min (e.g. 10min, 15min, 20min or 25min), heating to 75-78 deg.C (e.g. 75-76 deg.C, 76-77 deg.C or 77-78 deg.C) within 15-30min (e.g. 15min, 20min, 25min or 30min), and keeping at constant temperature for 35-90min (e.g. 35min, 45min, 70min, 80min or 90 min).
Wherein, after the reaction is finished, the temperature of the materials can be reduced to less than or equal to 50 ℃ according to the conventional operation in the field.
In the step (2), after the etherification reaction is finished, the cellulose gum can be subjected to pH adjustment and drying treatment according to conventional operations in the field.
Wherein, the reagent for adjusting pH is a pH adjusting agent which is conventional in the art, such as an aqueous acetic acid solution, preferably an aqueous acetic acid solution with a mass concentration of 30-40%, and more preferably an aqueous acetic acid solution with a mass concentration of 30%. Preferably, the pH is adjusted to 6.8-8.0.
Wherein, the washing treatment can be carried out before the pH adjustment and/or after the pH adjustment. The solvent for washing is a solvent conventional in the art, such as 60-76% by volume of an aqueous alcohol solution.
The washing is generally performed by centrifugation before and after the washing. The washing times can be multiple times, and generally speaking, the washing is carried out until the purity of the material reaches 99.5%.
Wherein, the drying can be carried out according to the conventional process conditions in the field, preferably, the drying is carried out until the water content of the cellulose gum is 5-8 percent, and the percentage refers to the mass percentage.
Wherein, preferably, the drying is further followed by a crushing treatment. The pulverization may be followed by a sieving treatment according to conventional procedures in the art, such as 80 mesh sieving.
The invention also provides the cellulose gum prepared by the preparation method.
The viscosity range of the 1% B type cellulose gel prepared by the invention is 300-600 mPas, the centrifugal precipitation of protein in the acidic dairy beverage is less than or equal to 1.5%, and the acidic dairy beverage is not layered after being placed for 21 days. Therefore, the cellulose gum prepared by the invention can play a very good role in suspending and stabilizing milk protein in the acidic dairy beverage.
The invention also provides the application of the cellulose gum in acidic dairy drinks as a stabilizer, and the stabilizer is preferably a protein stabilizer.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
the invention adopts isopropanol and water as solvents, adds alkalizer and isopropanol to be mixed uniformly to carry out pretreatment before alkalization on cellulose to obtain alkali cellulose, and then adds acid and etherifies to obtain cellulose gum for acidic dairy drinks with good uniformity. The stability is better, the protein suspension agent is suitable for being used in an environment with a pH value of 3.0-8.5, on the premise of serving as a food additive, centrifugal precipitation of protein in the acidic dairy beverage is not more than 1.5 percent, and the acidic dairy beverage is not layered after being placed for 21 days, thereby playing a very good role in suspending and stabilizing the milk protein.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
In the following examples and comparative examples, the dissolved wood pulp was obtained from tembec, canada.
Example 1
(1) Under the stirring condition, 0.67kg of 98.2% solid caustic soda (0.66 kg calculated by pure mass) is dissolved in 0.67kg of distilled water and is added into a stirring reaction kettle together with 15kg of isopropanol with the volume fraction of 91% (wherein the mass of the isopropanol is 13.32kg, and the mass of the water is 1.68kg), the stirring is carried out uniformly, then 1kg of dissolved wood pulp with the polymerization degree of 1452 is added into the stirring reaction kettle, the stirring and alkalization are carried out for 80min under the condition that the temperature is controlled to be 20-25 ℃ and the 166r/min state, and the uniform alkali cellulose is obtained.
(2) 1.07kg of chloroacetic acid isopropanol solution with chloroacetic acid mass content of 70 percent is added into a reaction kettle which already forms uniform alkali cellulose, and the chloroacetic acid isopropanol solution is uniformly and slowly added within 45min, and the reaction temperature is controlled to be 30-40 ℃ in the process.
(3) Cooling and stirring the materials at 30-40 deg.C for 15min, heating to 76-77 deg.C within 15min, maintaining the temperature for 70min, and cooling to below 50 deg.C after the reaction.
(4) And (3) putting the cooled material into an alcohol aqueous solution, and adjusting the pH value to 6.8-8.0 by using an acetic acid aqueous solution with the mass concentration of 30%.
(5) And drying the materials, crushing the dried materials into powder, and sieving the powder by using a 80-mesh sieve to obtain the cellulose gum for the acidic dairy beverage.
Example 2
(1) Under the condition of stirring, 0.71kg of 98.2% solid caustic soda (0.70 kg of pure mass) is dissolved in 0.71kg of distilled water and is added into a stirring reaction kettle together with 20kg of 88% volume fraction isopropanol (wherein the mass of the isopropanol is 17.04kg, and the mass of water is 2.96kg), and then 1kg of dissolved wood pulp with the polymerization degree of 1452 is added into the stirring reaction kettle, and stirring and alkalization are carried out for 50min under the condition that the temperature is controlled to be 20-25 ℃ and 166r/min, so as to obtain uniform alkali cellulose.
(2) 1.14kg of chloroacetic acid isopropanol solution with chloroacetic acid mass content of 70 percent is added into a reaction kettle which already forms uniform alkali cellulose, and the chloroacetic acid isopropanol solution is uniformly and slowly added within 20min, and the reaction temperature is controlled to be 30-40 ℃ in the process.
(3) Cooling and stirring the materials at 30-40 deg.C for 20min, heating to 77-78 deg.C within 30min, holding the temperature for 35min, and cooling to below 50 deg.C after the reaction is finished.
(4) And (3) putting the cooled material into an alcohol aqueous solution, and adjusting the pH value to 6.8-8.0 by using an acetic acid aqueous solution with the mass concentration of 30%.
(5) And drying the materials, crushing the dried materials into powder, and sieving the powder by using a 80-mesh sieve to obtain the cellulose gum for the acidic dairy beverage.
Example 3
(1) Under the stirring condition, 0.62kg of 98.2% solid caustic soda (0.61 kg calculated by pure mass) is dissolved in 0.62kg of distilled water and is added into a stirring reaction kettle together with 12kg of isopropanol with the volume fraction of 93% (wherein the mass of the isopropanol is 10.95kg, and the mass of the water is 1.05kg), the stirring is carried out uniformly, then 1kg of dissolved wood pulp with the polymerization degree of 1452 is added into the stirring reaction kettle, the stirring and alkalization are carried out for 120min under the condition that the temperature is controlled to be 20-25 ℃ and the 166r/min state, and the uniform alkali cellulose is obtained.
(2) 1kg of chloroacetic acid isopropanol solution with the chloroacetic acid mass content of 70 percent is added into a reaction kettle which already forms uniform alkali cellulose, and the chloroacetic acid isopropanol solution is uniformly and slowly added within 20min, and the reaction temperature is controlled to be 30-40 ℃ in the process.
(3) Cooling and stirring the materials at 30-40 deg.C for 10min, heating to 75-76 deg.C within 15min, holding the temperature for 90min, and cooling to below 50 deg.C after the reaction.
(4) And (3) putting the cooled material into an alcohol aqueous solution, and adjusting the pH value to 6.8-8.0 by using an acetic acid aqueous solution with the mass concentration of 30%.
(5) And drying the materials, crushing the dried materials into powder, and sieving the powder by using a 80-mesh sieve to obtain the cellulose gum for the acidic dairy beverage.
Example 4
(1) Under the stirring condition, 0.69kg of 98.2% solid caustic soda (0.68 kg of pure mass) is dissolved in 0.69kg of distilled water and is added into a stirring reaction kettle together with 18kg of isopropanol with the volume fraction of 92% (wherein the mass of the isopropanol is 16.21kg, and the mass of the water is 1.79kg), and then 1kg of dissolved wood pulp with the polymerization degree of 1452 is added into the stirring reaction kettle, and the stirring and alkalization are carried out for 100min under the condition that the temperature is controlled to be 20-25 ℃ and the 166r/min state, so as to obtain uniform alkali cellulose.
(2) 1.1kg of chloroacetic acid isopropanol solution with the chloroacetic acid mass content of 70 percent is added into a reaction kettle which already forms uniform alkali cellulose, and the chloroacetic acid isopropanol solution is uniformly and slowly added within 40min, and the reaction temperature is controlled to be 30-40 ℃ in the process.
(3) Cooling and stirring the materials at 30-40 deg.C for 25min, heating to 76-77 deg.C within 25min, maintaining the temperature for 80min, and cooling to below 50 deg.C after the reaction.
(4) And (3) putting the cooled material into an alcohol aqueous solution, and adjusting the pH value to 6.8-8.0 by using an acetic acid aqueous solution with the mass concentration of 30%.
(5) And drying the materials, crushing the dried materials into powder, and sieving the powder by using a 80-mesh sieve to obtain the cellulose gum for the acidic dairy beverage.
Example 5
(1) Under the stirring condition, 0.65kg of 98.2% solid caustic soda (0.64 kg calculated by pure mass) is dissolved in 0.65kg of distilled water and is added into a stirring reaction kettle together with 13kg of isopropanol with the volume fraction of 89% (wherein the mass of the isopropanol is 11.23kg, and the mass of the water is 1.77kg), the stirring is carried out uniformly, then 1kg of dissolved wood pulp with the polymerization degree of 1452 is added into the stirring reaction kettle, the stirring and alkalization are carried out for 60min under the condition that the temperature is controlled to be 20-25 ℃ and the 166r/min state, and the uniform alkali cellulose is obtained.
(2) 1.05kg of chloroacetic acid isopropanol solution with chloroacetic acid mass content of 70 percent is added into a reaction kettle which already forms uniform alkali cellulose, and the chloroacetic acid isopropanol solution is uniformly and slowly added within 25min, and the reaction temperature is controlled to be 30-40 ℃ in the process.
(3) Cooling and stirring the materials at 30-40 deg.C for 15min, heating to 75-76 deg.C within 20min, maintaining the temperature for 45min, and cooling to below 50 deg.C after the reaction.
(4) And (3) putting the cooled material into an alcohol aqueous solution, and adjusting the pH value to 6.8-8.0 by using an acetic acid aqueous solution with the mass concentration of 30%.
(5) And drying the materials, crushing the dried materials into powder, and sieving the powder by using a 80-mesh sieve to obtain the cellulose gum for the acidic dairy beverage.
Comparative example 1
(1) A sample is prepared by adopting a kneading method of a traditional process, according to the feeding amount of example 1, 0.67kg of 98.2 percent solid alkali is dissolved in 0.67kg of distilled water and added into the kneader together with 2.5kg of 91 percent alcohol water solution to be uniformly stirred, then 1kg of dissolved wood pulp with the polymerization degree of 1452 is added into the kneader, and the kneading and alkalization are carried out for 80min under the condition that the temperature is controlled to be 20-25 ℃ and 166r/min, so as to obtain alkali cellulose.
(2) 1.07kg of chloroacetic acid alcoholic solution with chloroacetic acid content of 70% by mass is added into a kneader of the formed alkali cellulose, and is added uniformly and slowly within 45min, and the reaction temperature is controlled to be 30-40 ℃ in the process.
(3) Cooling, stirring and kneading the materials at 30-40 deg.C for 15min, heating to 76-77 deg.C within 15min, holding the temperature for 70min, and cooling to below 50 deg.C after the reaction is finished.
(4) And (3) putting the cooled material into an alcohol aqueous solution, and adjusting the pH value to 6.8-8.0 by using an acetic acid aqueous solution with the mass concentration of 30%.
(5) And drying the materials, crushing the dried materials into powder, and sieving the powder by using a 80-mesh sieve to obtain a sample.
Comparative example 2
(1) A sample is prepared by adopting a kneading method of a traditional process, according to the feeding amount of the example 2, 0.71kg of 98.2 percent solid alkali is dissolved in 0.71kg of distilled water and is added into the kneader together with 2.8kg of 88 percent alcohol water solution by mass fraction to be uniformly stirred, then 1kg of dissolved wood pulp with 1452 of polymerization degree is added into the kneader, and the mixture is kneaded and alkalized for 50min under the condition of controlling the temperature to be 20-25 ℃ and 166r/min, so that the alkali cellulose is obtained.
(2) 1.14kg of chloroacetic acid alcoholic solution with chloroacetic acid content of 70% by mass is added into a kneader of the formed alkali cellulose, and is added uniformly and slowly within 20min, and the reaction temperature is controlled to be 30-40 ℃ in the process.
(3) Cooling, stirring and kneading the materials at 30-40 deg.C for 20min, heating to 77-78 deg.C within 30min, holding the temperature for 35min, and cooling to below 50 deg.C after the reaction is finished.
(4) And (3) putting the cooled material into an alcohol aqueous solution, and adjusting the pH value to 6.8-8.0 by using an acetic acid aqueous solution with the mass concentration of 30%.
(5) And drying the materials, crushing the dried materials into powder, and sieving the powder by using a 80-mesh sieve to obtain a sample.
Comparative example 3
(1) A sample is prepared by adopting a kneading method of a traditional process, according to the feeding amount of example 3, 0.62kg of 98.2% solid alkali is dissolved in 0.62kg of distilled water and is added into the kneader together with 2.3kg of 93% alcohol water solution by mass fraction to be uniformly stirred, then 1kg of dissolved wood pulp with 1452 polymerization degree is added into the kneader, and kneading and alkalization are carried out for 120min under the condition of controlling the temperature to be 20-25 ℃ and 166r/min, so as to obtain alkali cellulose.
(2) 1kg of chloroacetic acid alcoholic solution with chloroacetic acid content of 70% by mass is added into a kneader of the formed alkali cellulose, and is added uniformly and slowly within 20min, and the reaction temperature is controlled to be 30-40 ℃ in the process.
(3) Cooling, stirring and kneading the materials at 30-40 deg.C for 10min, heating to 75-76 deg.C within 15min, holding the temperature for 90min, and cooling to below 50 deg.C after the reaction is finished.
(4) And (3) putting the cooled material into an alcohol aqueous solution, and adjusting the pH value to 6.8-8.0 by using an acetic acid aqueous solution with the mass concentration of 30%.
(5) And drying the materials, crushing the dried materials into powder, and sieving the powder by using a 80-mesh sieve to obtain a sample.
Comparative example 4
(1) A sample is prepared by adopting a kneading method of a traditional process, according to the feeding amount of example 4, 0.69kg of 98.2 percent solid alkali is dissolved in 0.69kg of distilled water and is added into the kneader together with 2.6kg of 92 percent alcohol water solution by mass fraction to be uniformly stirred, then 1kg of dissolved wood pulp with 1452 of polymerization degree is added into the kneader, and the mixture is kneaded and alkalized for 100min under the condition of controlling the temperature to be 20-25 ℃ and 166r/min, so that the alkali cellulose is obtained.
(2) 1.1kg of chloroacetic acid alcoholic solution with chloroacetic acid content of 70% by mass is added into a kneader of the formed alkali cellulose, and is added uniformly and slowly within 40min, and the reaction temperature is controlled to be 30-40 ℃ in the process.
(3) Cooling, stirring and kneading the materials at 30-40 deg.C for 25min, heating to 76-77 deg.C within 25min, holding the temperature for 80min, and cooling to below 50 deg.C after the reaction is finished.
(4) And (3) putting the cooled material into an alcohol aqueous solution, and adjusting the pH value to 6.8-8.0 by using an acetic acid aqueous solution with the mass concentration of 30%.
(5) And drying the materials, crushing the dried materials into powder, and sieving the powder by using a 80-mesh sieve to obtain a sample.
Comparative example 5
(1) A sample is prepared by adopting a kneading method of a traditional process, according to the feeding amount of example 5, 0.65kg of 98.2 percent solid alkali is dissolved in 0.65kg of distilled water and is added into the kneader together with 2.4kg of 89 percent alcohol water solution by mass percent to be uniformly stirred, then 1kg of dissolved wood pulp with 1452 of polymerization degree is added into the kneader, and the mixture is kneaded and alkalized for 60min under the condition of controlling the temperature to be 20-25 ℃ and 166r/min, so that the alkali cellulose is obtained.
(2) 1.05kg of chloroacetic acid alcoholic solution with chloroacetic acid content of 70% by mass is added into a kneader of the formed alkali cellulose, and is added uniformly and slowly within 25min, and the reaction temperature is controlled to be 30-40 ℃ in the process.
(3) Cooling, stirring and kneading the materials at 30-40 deg.C for 15min, heating to 75-76 deg.C within 20min, holding the temperature for 45min, and cooling to below 50 deg.C after the reaction is finished.
(4) And (3) putting the cooled material into an alcohol aqueous solution, and adjusting the pH value to 6.8-8.0 by using an acetic acid aqueous solution with the mass concentration of 30%.
(5) And drying the materials, crushing the dried materials into powder, and sieving the powder by using a 80-mesh sieve to obtain a sample.
Comparative example 6
The corresponding product was obtained according to the procedure of example 7 of the prior patent CN 102822204A.
Comparative example 7
The corresponding product was obtained according to the procedure of example 12 of the prior patent CN 102822204A.
Comparative example 8
The amount of solid caustic used in step (1) was 0.50kg, as in example 3.
Comparative example 9
The amount of solid caustic used in step (1) was 0.80kg, as in example 3.
Comparative example 10
The amount of the chloroacetic acid isopropyl alcohol solution having a chloroacetic acid content of 70% by mass in the step (2) was 0.8kg, and the rest was the same as in example 3.
Comparative example 11
The amount of the chloroacetic acid isopropyl alcohol solution having a chloroacetic acid content of 70% by mass in the step (2) was 1.5kg, and the rest was the same as in example 3.
Comparative example 12
The corresponding product was obtained according to the procedure of example 10 of the prior patent CN 102822204A.
Effect example 1
(1) The cellulose gum prepared in the examples and the comparative examples and the cellulose gum from commercial sources are tested for the substitution degree, the pH value and the 30min viscosity according to the national standard of food-grade cellulose gum, and the testing method is as follows:
the degree of substitution is detected according to the national standard GB 1886.232-2016;
the 30min viscosity is expressed as a 1% type B viscosity, which is measured according to the national standard GB 1886.232-2016.
(2) The cellulose gums prepared in examples and comparative examples and a commercially available cellulose gum were used to prepare an acidic dairy drink (final product pH 4.3, protein content 4.2%), and after preparation, the amount of protein precipitation (in volume percent) was measured (centrifugation at 4000rpm for 20 minutes), and the product was allowed to stand for a long period of 21 days at room temperature to observe whether or not the product was delaminated.
The results of the above data are shown in table 1 below.
TABLE 1 detection results of Performance index, precipitation amount and stability of food grade cellulose gum
By comparing the data, it can be seen that:
(1) in the application of the acidic dairy beverage, the protein precipitation amount of the cellulose gum prepared by the invention is obviously much lower than that of the cellulose gum prepared by the traditional method, and the centrifugal precipitation of the protein is less than or equal to 1.5 percent (by volume percentage), so the improvement of the index changes the quality limit which cannot be exceeded by the traditional process;
(2) in the storage layering stability test process of the acidic dairy beverage, the cellulose gum prepared by the invention can be kept stable and does not layer within 21 days, while the cellulose gum prepared by the conventional method (using ethanol as a solvent and alkalizing by a kneading method) in the comparative examples 1-5 is difficult to realize non-layering within 21 days, generally, layering (white protein suspension on the upper layer) is obvious after 7 days of storage, and the cellulose gum is completely layered (the upper layer is a clear liquid, and the lower layer is opalescent protein) in 14 days;
(3) by comparing cellulose gums prepared by the preparation methods in the prior art, specifically referring to comparative examples 6, 7 and 10, the inventors found that even if the viscosity of the cellulose gum is increased, the protein in the acidic dairy drink cannot be effectively stabilized, and the inventors speculated that, in relation to the substitution position of sodium carboxymethyl cellulose, even if the viscosity is increased, if the cellulose gum is reduced to cellulose under acidic conditions, the stabilizing effect is difficult to exert;
(4) as is clear from comparative examples 8 to 11, when the amounts of the alkalizing agent and the etherifying agent were out of the ranges of the present application, the resulting cellulose gum was difficult to maintain protein stability under acidic conditions, and delamination occurred for 14 days after long-term storage.
Claims (4)
1. The preparation method of the cellulose gum is characterized by comprising the following steps:
(1) under the stirring condition, 0.67kg of 98.2% solid alkali is dissolved in 0.67kg of distilled water and added into a stirring reaction kettle together with 15kg of isopropanol with the volume fraction of 91% to be uniformly stirred, then 1kg of dissolved wood pulp with the polymerization degree of 1452 is added into the stirring reaction kettle, the stirring and alkalization are carried out for 80min under the condition that the temperature is controlled to be 20-25 ℃ and the 166r/min state, and uniform alkali cellulose is obtained;
(2) adding 1.07kg of chloroacetic acid isopropanol solution with chloroacetic acid mass content of 70% into a reaction kettle which already forms uniform alkali cellulose, and uniformly and slowly adding the chloroacetic acid isopropanol solution within 45min, wherein the reaction temperature is controlled to be 30-40 ℃ in the process;
(3) cooling and stirring the materials at 30-40 deg.C for 15min, heating to 76-77 deg.C within 15min, maintaining the temperature for 70min, and cooling to below 50 deg.C after reaction;
(4) putting the cooled material into an alcohol aqueous solution, and adjusting the pH value to 6.8-8.0 by using an acetic acid aqueous solution with the mass concentration of 30%;
(5) and drying the materials, crushing the dried materials into powder, and sieving the powder by using a 80-mesh sieve to obtain the cellulose gum for the acidic dairy beverage.
2. The preparation method of the cellulose gum is characterized by comprising the following steps:
(1) under the stirring condition, 0.71kg of 98.2% solid alkali is dissolved in 0.71kg of distilled water and added into a stirring reaction kettle together with 20kg of isopropanol with the volume fraction of 88% to be uniformly stirred, then 1kg of dissolved wood pulp with the polymerization degree of 1452 is added into the stirring reaction kettle, the stirring and alkalization are carried out for 50min under the condition that the temperature is controlled to be 20-25 ℃ and the 166r/min state, and uniform alkali cellulose is obtained;
(2) adding 1.14kg of chloroacetic acid isopropanol solution with chloroacetic acid mass content of 70% into a reaction kettle which already forms uniform alkali cellulose, and uniformly and slowly adding the chloroacetic acid isopropanol solution within 20min, wherein the reaction temperature is controlled to be 30-40 ℃ in the process;
(3) cooling and stirring the materials at 30-40 deg.C for 20min, heating to 77-78 deg.C within 30min, holding the temperature for 35min, and cooling to below 50 deg.C after reaction;
(4) putting the cooled material into an alcohol aqueous solution, and adjusting the pH value to 6.8-8.0 by using an acetic acid aqueous solution with the mass concentration of 30%;
(5) and drying the materials, crushing the dried materials into powder, and sieving the powder by using a 80-mesh sieve to obtain the cellulose gum for the acidic dairy beverage.
3. The preparation method of the cellulose gum is characterized by comprising the following steps:
(1) under the stirring condition, 0.69kg of 98.2% solid alkali is dissolved in 0.69kg of distilled water and is added into a stirring reaction kettle together with 18kg of isopropanol with the volume fraction of 92% to be uniformly stirred, then 1kg of dissolved wood pulp with the polymerization degree of 1452 is added into the stirring reaction kettle, the stirring and alkalization are carried out for 100min under the condition that the temperature is controlled to be 20-25 ℃ and the 166r/min state, and uniform alkali cellulose is obtained;
(2) adding 1.1kg of chloroacetic acid isopropanol solution with chloroacetic acid mass content of 70% into a reaction kettle which already forms uniform alkali cellulose, and uniformly and slowly adding the chloroacetic acid isopropanol solution within 40min, wherein the reaction temperature is controlled to be 30-40 ℃ in the process;
(3) cooling and stirring the materials at 30-40 deg.C for 25min, heating to 76-77 deg.C within 25min, maintaining the temperature for 80min, and cooling to below 50 deg.C after reaction;
(4) putting the cooled material into an alcohol aqueous solution, and adjusting the pH value to 6.8-8.0 by using an acetic acid aqueous solution with the mass concentration of 30%;
(5) and drying the materials, crushing the dried materials into powder, and sieving the powder by using a 80-mesh sieve to obtain the cellulose gum for the acidic dairy beverage.
4. The preparation method of the cellulose gum is characterized by comprising the following steps:
(1) under the stirring condition, 0.65kg of 98.2% solid alkali is dissolved in 0.65kg of distilled water and added into a stirring reaction kettle together with 13kg of isopropanol with the volume fraction of 89% to be uniformly stirred, then 1kg of dissolved wood pulp with the polymerization degree of 1452 is added into the stirring reaction kettle, the stirring and alkalization are carried out for 60min under the condition that the temperature is controlled to be 20-25 ℃ and the 166r/min state, and uniform alkali cellulose is obtained;
(2) adding 1.05kg of chloroacetic acid isopropanol solution with chloroacetic acid mass content of 70% into a reaction kettle which already forms uniform alkali cellulose, and uniformly and slowly adding the chloroacetic acid isopropanol solution within 25min, wherein the reaction temperature is controlled to be 30-40 ℃ in the process;
(3) cooling and stirring the materials at 30-40 deg.C for 15min, heating to 75-76 deg.C within 20min, keeping the temperature for 45min, and cooling to below 50 deg.C after the reaction;
(4) putting the cooled material into an alcohol aqueous solution, and adjusting the pH value to 6.8-8.0 by using an acetic acid aqueous solution with the mass concentration of 30%;
(5) and drying the materials, crushing the dried materials into powder, and sieving the powder by using a 80-mesh sieve to obtain the cellulose gum for the acidic dairy beverage.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910402616.4A CN110128553B (en) | 2019-05-15 | 2019-05-15 | Cellulose gum and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910402616.4A CN110128553B (en) | 2019-05-15 | 2019-05-15 | Cellulose gum and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110128553A CN110128553A (en) | 2019-08-16 |
| CN110128553B true CN110128553B (en) | 2022-04-29 |
Family
ID=67574195
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910402616.4A Active CN110128553B (en) | 2019-05-15 | 2019-05-15 | Cellulose gum and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110128553B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104448009A (en) * | 2014-12-05 | 2015-03-25 | 上海申光食用化学品有限公司 | Preparation method of food-grade acid-resisting sodium carboxymethyl cellulose |
-
2019
- 2019-05-15 CN CN201910402616.4A patent/CN110128553B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110128553A (en) | 2019-08-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU2010234846B2 (en) | Tartaric salt stabilizer for wine | |
| CN104448010A (en) | Instant polyanionic cellulose and preparation method thereof | |
| CN110128553B (en) | Cellulose gum and preparation method and application thereof | |
| WO2019217489A1 (en) | Seaweed meal and method of making the same | |
| CN104473318B (en) | Harm-reducing and tar-lowering recombined tobacco and producing method thereof | |
| CN104387477B (en) | The preparation method of food stage high substituted degree ultralow-viscosity sodium carboxymethyl cellulose | |
| CN102524857A (en) | Production method for crystal wrappers | |
| CN111171344B (en) | Preparation method of alcohol-induced low-alkali konjac gel | |
| CN111758949B (en) | Synthesis method of novel edible betel nut brine | |
| CN104387476B (en) | The preparation method of food-class high-purity viscosity higher sodium carboxymethyl cellulose | |
| JPH11187826A (en) | Dispersion-stabilizing composition and dispersion-stabilized food using the same | |
| CN104448009A (en) | Preparation method of food-grade acid-resisting sodium carboxymethyl cellulose | |
| CN117186248A (en) | Cellulose gum and preparation method and application thereof | |
| CN113683902B (en) | Method for preparing caramel pigment, caramel pigment and application thereof | |
| JPS62184002A (en) | Production of low-molecular weight water-soluble chitosan | |
| CN101524095A (en) | Melon and fruit preservation solution and preparation method thereof | |
| CN105380236A (en) | Compound low-methoxyl pectin and preparation method and application thereof | |
| JP3751948B2 (en) | Sodium carboxymethylcellulose for milk-containing beverages | |
| CN114680178B (en) | Composite for improving water retention rate of yoghurt | |
| CN115806680A (en) | Guar gum and carrageenan compound and preparation method and application thereof | |
| CN114686021A (en) | Caramel color production process by using common method and caramel color | |
| SU1755773A1 (en) | Marmalade preparation method | |
| CN1348704A (en) | New year cake color protecting agent and New Year cake producing process | |
| CN115073617A (en) | Preparation method of mixed anhydride crosslinked starch | |
| CN109965176A (en) | Agar-agar eats suspending agent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 201512 Shanghai City, Jinshan District Jinshanwei town old Weiqing Road No. 898 Patentee after: SHANGHAI EVERBRIGHT ENTERPRISE DEVELOPMENT CO.,LTD. Patentee after: Shandong Yangzi Biotechnology Co.,Ltd. Address before: 201512 Shanghai City, Jinshan District Jinshanwei town old Weiqing Road No. 898 Patentee before: SHANGHAI EVERBRIGHT ENTERPRISE DEVELOPMENT CO.,LTD. Patentee before: Yangtze Chemical Technology (Yantai) Co.,Ltd. |
|
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20190816 Assignee: Yantai Yida Financial Leasing Co.,Ltd. Assignor: Shandong Yangzi Biotechnology Co.,Ltd. Contract record no.: X2022980010023 Denomination of invention: A cellulose glue and its preparation method and Application Granted publication date: 20220429 License type: Exclusive License Record date: 20220708 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A cellulose glue and its preparation method and Application Effective date of registration: 20220712 Granted publication date: 20220429 Pledgee: Yantai Yida Financial Leasing Co.,Ltd. Pledgor: Shandong Yangzi Biotechnology Co.,Ltd. Registration number: Y2022980010326 |
|
| EC01 | Cancellation of recordation of patent licensing contract | ||
| EC01 | Cancellation of recordation of patent licensing contract |
Assignee: Yantai Yida Financial Leasing Co.,Ltd. Assignor: Shandong Yangzi Biotechnology Co.,Ltd. Contract record no.: X2022980010023 Date of cancellation: 20230907 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20230907 Granted publication date: 20220429 Pledgee: Yantai Yida Financial Leasing Co.,Ltd. Pledgor: Shandong Yangzi Biotechnology Co.,Ltd. Registration number: Y2022980010326 |