CN116574521B - Preparation method of plant hydrolyzed protein amino acid derivative surfactant - Google Patents
Preparation method of plant hydrolyzed protein amino acid derivative surfactant Download PDFInfo
- Publication number
- CN116574521B CN116574521B CN202310571181.2A CN202310571181A CN116574521B CN 116574521 B CN116574521 B CN 116574521B CN 202310571181 A CN202310571181 A CN 202310571181A CN 116574521 B CN116574521 B CN 116574521B
- Authority
- CN
- China
- Prior art keywords
- amino acid
- surfactant
- hydrolyzed protein
- drying
- acid derivative
- 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
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 49
- 150000003862 amino acid derivatives Chemical class 0.000 title claims abstract description 39
- 102000004169 proteins and genes Human genes 0.000 title claims abstract description 25
- 108090000623 proteins and genes Proteins 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 235000010469 Glycine max Nutrition 0.000 claims abstract description 57
- 244000068988 Glycine max Species 0.000 claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- 239000008367 deionised water Substances 0.000 claims abstract description 32
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 32
- 238000001035 drying Methods 0.000 claims abstract description 32
- 239000003531 protein hydrolysate Substances 0.000 claims abstract description 30
- 108010073771 Soybean Proteins Proteins 0.000 claims abstract description 28
- 150000001413 amino acids Chemical class 0.000 claims abstract description 26
- 238000005406 washing Methods 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 22
- 229940001941 soy protein Drugs 0.000 claims abstract description 22
- 241000196324 Embryophyta Species 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 17
- 238000005303 weighing Methods 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 11
- 102000057297 Pepsin A Human genes 0.000 claims abstract description 10
- 108090000284 Pepsin A Proteins 0.000 claims abstract description 10
- 229940111202 pepsin Drugs 0.000 claims abstract description 10
- 230000007062 hydrolysis Effects 0.000 claims abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 6
- 238000007873 sieving Methods 0.000 claims abstract description 6
- 238000010298 pulverizing process Methods 0.000 claims abstract description 3
- 239000004005 microsphere Substances 0.000 claims description 67
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 66
- 239000000243 solution Substances 0.000 claims description 43
- FLVFLHZPYDNHJE-UHFFFAOYSA-N chloro hypochlorite;hafnium Chemical compound [Hf].ClOCl FLVFLHZPYDNHJE-UHFFFAOYSA-N 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 28
- 238000001914 filtration Methods 0.000 claims description 23
- 229910000449 hafnium oxide Inorganic materials 0.000 claims description 23
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims description 23
- 235000018102 proteins Nutrition 0.000 claims description 22
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 17
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 14
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 14
- 239000004327 boric acid Substances 0.000 claims description 14
- 239000001632 sodium acetate Substances 0.000 claims description 14
- 235000017281 sodium acetate Nutrition 0.000 claims description 14
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 13
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 11
- 108090000790 Enzymes Proteins 0.000 claims description 10
- 102000004190 Enzymes Human genes 0.000 claims description 10
- 229940088598 enzyme Drugs 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 7
- 229960000541 cetyl alcohol Drugs 0.000 claims description 6
- 239000007822 coupling agent Substances 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 239000012460 protein solution Substances 0.000 claims description 6
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 6
- 235000019710 soybean protein Nutrition 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 108010009736 Protein Hydrolysates Proteins 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000002779 inactivation Effects 0.000 claims 1
- 235000013311 vegetables Nutrition 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 20
- 108010064851 Plant Proteins Proteins 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 235000021118 plant-derived protein Nutrition 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000005619 boric acid group Chemical group 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(iv) oxide Chemical compound O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/28—Aminocarboxylic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/30—Proteins; Protein hydrolysates
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P13/00—Preparation of nitrogen-containing organic compounds
- C12P13/04—Alpha- or beta- amino acids
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P21/00—Preparation of peptides or proteins
- C12P21/06—Preparation of peptides or proteins produced by the hydrolysis of a peptide bond, e.g. hydrolysate products
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Zoology (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Molecular Biology (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Biotechnology (AREA)
- Biochemistry (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Peptides Or Proteins (AREA)
Abstract
The invention discloses a preparation method of a surfactant of a plant hydrolyzed protein amino acid derivative, which comprises the following steps: (1) Weighing the peeled soybeans, washing the soybeans, and drying the soybeans; (2) Grinding, pulverizing, and sieving to obtain soybean powder; (3) Mixing soybean powder with deionized water, adding pepsin until hydrolysis is finished, and obtaining soybean hydrolyzed protein liquid; (4) Heating and drying the soy protein hydrolysate to obtain soy protein hydrolysate amino acid; (5) Adding fatty alcohol into a reaction flask, adding soy protein hydrolysate amino acid and a catalyst, and reacting to obtain the amino acid derivative surfactant. The novel catalyst is used for catalyzing and synthesizing the amino acid derivative surfactant, has higher catalytic activity, and can generate fewer byproducts in the catalytic process, thereby avoiding the defects of the traditional surfactant for synthesizing the amino acid derivative.
Description
Technical Field
The invention relates to the field of surfactants, in particular to a preparation method of a surfactant of an amino acid derivative of a plant hydrolyzed protein.
Background
The amino acid type surfactant is a novel green environment-friendly surfactant derived from renewable biomass, and is an upgrading product of the traditional surfactant. The amino acid type surfactant has the advantages of wide sources of biomass raw materials, small toxic and side effects, mild performance, small irritation and good biodegradability, and good emulsifying, wetting, solubilizing, dispersing, foaming and other performances are paid attention to by people at present, so that the amino acid type surfactant is gradually applied to various fields such as washing, personal care, food industry and the like.
Amino acid surfactants include N-alkyl amino acid surfactants and N-acyl amino acid surfactants, and many amino acid surfactants including N-alkyl amino acid surfactants and N-acyl amino acid surfactants are currently studied, wherein N-acyl amino acid surfactants have been developed very well and have been industrially produced by using fatty acid chloride and amino acid reaction in the production process, however, the preparation of fatty acid chloride and its purification and purification of the reaction product with amino acid produce a large amount of by-products and three wastes, and in addition, the method can only produce anionic surfactants and can only be blended with anionic or nonionic surfactants.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a preparation method of a surfactant of amino acid derivatives of plant hydrolyzed protein.
The aim of the invention is realized by adopting the following technical scheme:
the preparation method of the plant hydrolyzed protein amino acid derivative surfactant comprises the following steps:
(1) Weighing the peeled soybeans, washing the soybeans with clear water, drying the soybeans in an oven, taking out the soybeans, and then placing the soybeans in a drying oven for standby;
(2) Placing dried soybean in a grinding machine, grinding, pulverizing, and sieving to obtain soybean powder;
(3) Mixing soybean powder with deionized water, uniformly dispersing by ultrasonic, adding pepsin, adjusting the temperature and the pH, and stirring the reaction solution until the hydrolysis is finished to obtain soybean hydrolyzed protein solution;
(4) Heating the soy protein hydrolysate, centrifuging to remove solids, and performing freeze drying or vacuum drying treatment to obtain soy protein hydrolysate amino acid;
(5) Adding fatty alcohol into a reaction flask, heating to melt, adding soybean protein hydrolysate amino acid, adding a catalyst, reacting for 4-6h under the stirring action of 90-120 ℃, stopping heating, cooling to room temperature, filtering and removing impurities to obtain the amino acid derivative surfactant.
Preferably, in the step (1), the temperature is increased to 80-100 ℃ in the oven, and the drying treatment time is 3-6h.
Preferably, in the step (2), the diameter of the sieve holes of the sieve is 2-4mm.
Preferably, in the step (3), the mass ratio of the soybean powder to the deionized water is 20-30:100.
Preferably, in the step (3), the addition amount of pepsin is 5000-10000U/g, the temperature is regulated to 30-40 ℃, the pH is 1.5-2.5, and the stirring reaction time is 2-4h.
Preferably, in the step (4), the temperature of the soy protein hydrolysate is raised to 80-100 ℃ so as to inactivate enzymes and facilitate removal, and the time for heat preservation after the temperature is raised is 20-30min.
Preferably, in the step (5), the fatty alcohol comprises lauryl alcohol or cetyl alcohol, and the molar ratio of the fatty alcohol to the amino acid of the soy protein hydrolysate is 1.8-2.2:1.
Preferably, in the step (5), the catalyst is HfO 2 -NH 2 -BO 3 The addition amount of the microspheres is 0.5% -1% of the mass of the fatty alcohol.
Preferably, the catalyst HfO 2 -NH 2 -BO 3 The preparation method of the microsphere comprises the following steps:
s1, weighing hafnium oxychloride and PEG-400, mixing into deionized water, fully stirring until the hafnium oxychloride and the PEG-400 are completely dissolved, adding sodium acetate, pouring into a reaction kettle, reacting at 160-180 ℃ for 6-12h, filtering out product solids after the reaction is finished, washing with deionized water for three times, and drying to obtain hafnium oxide microspheres;
s2, adding the hafnium oxide microspheres into an ethanol solution, adding an aminosilane coupling agent and ammonia water, stirring uniformly at room temperature, heating to boil, reacting for 8-10 hours under the condition of condensing and refluxing, filtering out liquid, washing with pure water, and drying to obtain HfO 2 -NH 2 A microsphere;
s3, mixing boric acid in ethanol solution, and then adding HfO 2 -NH 2 Heating the microspheres to boiling, reacting for 5-8h under the condition of condensing and refluxing, filtering out liquid, washing with pure water, and drying to obtain HfO 2 -NH 2 -BO 3 And (3) microspheres.
Preferably, in the S1, the mass ratio of the hafnium oxychloride, the PEG-400 and the deionized water is 1:1.2-2.6:10-20.
Preferably, in the S1, the mass ratio of the sodium acetate to the hafnium oxychloride is 1.3-2.6:1.
Preferably, in the step S2, the mass concentration of the ethanol solution is 55% -75%, and the mass ratio of the hafnium oxide microspheres to the ethanol solution is 1:20-40.
Preferably, in the step S2, the aminosilane coupling agent is KH-570, the concentration of ammonia water is 25%, and the mass ratio of the aminosilane coupling agent to the ammonia water to the ethanol solution is 0.4-0.8:1-2:10-20.
Preferably, in the S3, the mass concentration of the ethanol solution is 55% -75%, boric acid and HfO 2 -NH 2 The mass ratio of the microspheres to the ethanol solution is 0.6-1.2:2-4:20-40.
The beneficial effects of the invention are as follows:
1. the invention uses the way of enzymolysis of soybean protein to obtain soybean protein hydrolysate, then removes enzyme and impurities at high temperature to obtain soybean protein hydrolysate amino acid, and directly carries out esterification and combination reaction on the soybean protein hydrolysate amino acid and fatty alcohol (laurinol or cetyl alcohol) to obtain the amino acid derivative surfactant. By the reaction arrangement of the invention, the purity of the synthesized product is higher, three wastes can not be generated, and the concept of green chemistry is more compounded.
2. The novel catalyst is used for catalyzing and synthesizing the amino acid derivative surfactant, has higher catalytic activity, and can generate fewer byproducts in the catalytic process, thereby avoiding the defects of the traditional surfactant for synthesizing the amino acid derivative.
3. HfO prepared by the invention 2 -NH 2 -BO 3 The microsphere catalyst is prepared by firstly preparing hafnium oxide microspheres by taking hafnium oxychloride as a precursor, and then modifying-NH on the surfaces of the hafnium oxide microspheres 2 Thereby obtaining HfO 2 -NH 2 Microspheres, finally, through combining with boric acid, the catalyst HfO is constructed 2 -NH 2 -BO 3 And (3) microspheres.
Detailed Description
The technical features, objects and advantages of the present invention will be more clearly understood from the following detailed description of the technical aspects of the present invention, but should not be construed as limiting the scope of the invention.
The invention is further described with reference to the following examples.
Example 1
The preparation method of the plant hydrolyzed protein amino acid derivative surfactant comprises the following steps:
(1) Weighing the peeled soybeans, washing the soybeans with clear water, drying the soybeans in an oven at the temperature of 100 ℃ for 4 hours, taking out the soybeans, and then placing the soybeans in a drying oven for standby;
(2) Placing dried soybean in a grinding machine, grinding, sieving to obtain soybean powder with mesh diameter of 3 mm;
(3) Mixing soybean powder and deionized water, wherein the mass ratio of the soybean powder to the deionized water is 25:100, adding pepsin after ultrasonic dispersion is uniform, wherein the adding amount of the pepsin is 8000U/g, adjusting the temperature to 35 ℃, the pH value to 2, stirring the reaction solution, and stirring the reaction solution for 3 hours until the hydrolysis is finished, thereby obtaining soybean hydrolyzed protein solution;
(4) Heating the soy protein hydrolysate to 90 ℃ to deactivate the enzyme for convenient removal, centrifuging to remove solid enzyme, and performing freeze drying or vacuum drying treatment to obtain soy protein hydrolysate amino acid;
(5) Adding fatty alcohol into a reaction flask, heating to melt, adding soy protein hydrolysate amino acid, wherein the fatty alcohol comprises lauryl alcohol or cetyl alcohol, the molar ratio of the fatty alcohol to the soy protein hydrolysate amino acid is 2:1, and adding a catalyst HfO 2 -NH 2 -BO 3 The microsphere is added in an amount of 0.8 percent of the mass of fatty alcohol, and reacts for 5 hours under the stirring effect of 100 ℃, then the temperature is stopped rising, the microsphere is cooled to the room temperature, and the amino acid derivative surfactant is obtained after filtration and impurity removal.
Of the above, the catalyst HfO 2 -NH 2 -BO 3 The preparation method of the microsphere comprises the following steps:
s1, weighing hafnium oxychloride and PEG-400, mixing into deionized water, fully stirring until the hafnium oxychloride and the PEG-400 are completely dissolved, adding sodium acetate, pouring the mixture into a reaction kettle, reacting at a high temperature of 170 ℃ for 10 hours, filtering out product solids after the reaction is finished, washing the product solids with deionized water for three times, and drying the product solids to obtain hafnium oxide microspheres;
wherein, the mass ratio of the hafnium oxychloride, the PEG-400 and the deionized water is 1:1.8:15, and the mass ratio of the sodium acetate to the hafnium oxychloride is 1.9:1.
S2, adding the hafnium oxide microspheres into an ethanol solution with the mass concentration of 65%, adding KH-570 and ammonia water with the mass concentration of 25%, stirring uniformly at room temperature, heating to boil, performing heat preservation reaction for 9 hours under the condition of condensation reflux, filtering out liquid, washing with pure water, and drying to obtain HfO 2 -NH 2 A microsphere;
wherein, the mass ratio of the hafnium oxide microsphere to the ethanol solution is 1:30, and the mass ratio of KH-570 and the ammonia water to the ethanol solution is 0.6:1.5:15.
S3, mixing boric acid in an ethanol solution with the mass concentration of 65%, and then adding HfO 2 -NH 2 Heating the microspheres to boiling, reacting for 6 hours under the condition of condensing and refluxing, filtering liquid, washing with pure water, and drying to obtain HfO 2 -NH 2 -BO 3 Microspheres with a particle size of 800-1200nm.
Wherein, boric acid, hfO 2 -NH 2 The mass ratio of the microspheres to the ethanol solution is 0.9:3:20.
Example 2
The preparation method of the plant hydrolyzed protein amino acid derivative surfactant comprises the following steps:
(1) Weighing the peeled soybeans, washing the soybeans with clear water, drying the soybeans in an oven at 80 ℃ for 6 hours, taking out the soybeans, and then placing the soybeans in a drying oven for standby;
(2) Placing dried soybean in a grinding machine, grinding, sieving to obtain soybean powder with mesh diameter of 2 mm;
(3) Mixing soybean powder and deionized water, wherein the mass ratio of the soybean powder to the deionized water is 20:100, adding pepsin after ultrasonic dispersion is uniform, wherein the addition amount of the pepsin is 5000U/g, adjusting the temperature to 30 ℃, and the pH value to be 1.5, stirring the reaction solution, and stirring the reaction solution for 2 hours until the hydrolysis is finished, thereby obtaining soybean hydrolyzed protein solution;
(4) Heating the soy protein hydrolysate to 80 ℃ to deactivate the enzyme for convenient removal, centrifuging to remove solid enzyme, and performing freeze drying or vacuum drying treatment to obtain soy protein hydrolysate amino acid;
(5) Adding fatty alcohol into a reaction flask, heating to melt, adding soy protein hydrolysate amino acid, wherein the fatty alcohol comprises lauryl alcohol or cetyl alcohol, the molar ratio of the fatty alcohol to the soy protein hydrolysate amino acid is 1.8:1, and adding a catalyst HfO 2 -NH 2 -BO 3 The microsphere is added in an amount of 0.5 percent of the mass of fatty alcohol, and reacts for 4 hours under the stirring effect at 90 ℃, then the temperature is stopped rising, the microsphere is cooled to the room temperature, and the amino acid derivative surfactant is obtained after filtration and impurity removal.
Catalyst HfO 2 -NH 2 -BO 3 The preparation method of the microspheres is the same as that of example 1.
Example 3
The preparation method of the plant hydrolyzed protein amino acid derivative surfactant comprises the following steps:
(1) Weighing the peeled soybeans, washing the soybeans with clear water, drying the soybeans in an oven at the temperature of 100 ℃ for 3 hours, taking out the soybeans, and then placing the soybeans in a drying oven for standby;
(2) Placing dried soybean in a grinding machine, grinding, sieving to obtain soybean powder with mesh diameter of 4 mm;
(3) Mixing soybean powder and deionized water, wherein the mass ratio of the soybean powder to the deionized water is 30:100, adding pepsin with the addition amount of 10000U/g after ultrasonic dispersion, adjusting the temperature to 40 ℃, and the pH value to 2.5, stirring the reaction solution, and stirring the reaction solution for 4 hours until the hydrolysis is finished, thereby obtaining soybean hydrolyzed protein solution;
(4) Heating the soy protein hydrolysate to 100 ℃ to deactivate the enzyme and remove the enzyme conveniently, centrifuging to remove the solid enzyme, and performing freeze drying or vacuum drying treatment to obtain the soy protein hydrolysate amino acid;
(5) Adding fatty alcohol into a reaction flask, heating to melt, adding soy protein hydrolysate amino acid, wherein the fatty alcohol comprises lauryl alcohol or cetyl alcohol, the molar ratio of the fatty alcohol to the soy protein hydrolysate amino acid is 2.2:1, and adding a catalyst HfO 2 -NH 2 -BO 3 The microsphere is added in an amount of 1% of the weight of fatty alcohol, and reacts for 6 hours under the stirring action of 120 ℃, then the temperature is stopped rising, the microsphere is cooled to room temperature, and the amino acid derivative surfactant is obtained after filtration and impurity removal.
Catalyst HfO 2 -NH 2 -BO 3 The preparation method of the microspheres is the same as that of example 1.
Example 4
A method for preparing a surfactant of a plant hydrolyzed protein amino acid derivative, which is the same as in example 1, except that the catalyst HfO 2 -NH 2 -BO 3 The preparation methods of the microspheres are slightly different.
Catalyst HfO 2 -NH 2 -BO 3 The preparation method of the microsphere comprises the following steps:
s1, weighing hafnium oxychloride and PEG-400, mixing into deionized water, fully stirring until the hafnium oxychloride and the PEG-400 are completely dissolved, adding sodium acetate, pouring into a reaction kettle, reacting at 160 ℃ for 12 hours, filtering out product solids after the reaction is finished, washing the product solids with deionized water for three times, and drying to obtain hafnium oxide microspheres;
wherein, the mass ratio of the hafnium oxychloride, the PEG-400 and the deionized water is 1:1.2:10, and the mass ratio of the sodium acetate to the hafnium oxychloride is 1.3:1.
S2, adding the hafnium oxide microspheres into an ethanol solution with the mass concentration of 55%, adding KH-570 and ammonia water with the mass concentration of 25%, stirring uniformly at room temperature, heating to boil, performing heat preservation reaction for 8 hours under the condition of condensation reflux, filtering out liquid, washing with pure water, and drying to obtain HfO 2 -NH 2 A microsphere;
wherein, the mass ratio of the hafnium oxide microsphere to the ethanol solution is 1:20, and the mass ratio of KH-570 and the ammonia water to the ethanol solution is 0.4:1:10.
S3, mixing boric acid in an ethanol solution with the mass concentration of 55% -75%, and then adding HfO 2 -NH 2 Heating the microspheres to boiling, reacting for 5-8h under the condition of condensing and refluxing, filtering out liquid, washing with pure water, and drying to obtain HfO 2 -NH 2 -BO 3 And (3) microspheres.
Wherein, boric acid, hfO 2 -NH 2 The mass ratio of the microspheres to the ethanol solution is 0.6:2:20.
Example 5
A method for preparing a surfactant of a plant hydrolyzed protein amino acid derivative, which is the same as in example 1, except that the catalyst HfO 2 -NH 2 -BO 3 The preparation methods of the microspheres are slightly different.
Catalyst HfO 2 -NH 2 -BO 3 The preparation method of the microsphere comprises the following steps:
s1, weighing hafnium oxychloride and PEG-400, mixing into deionized water, fully stirring until the hafnium oxychloride and the PEG-400 are completely dissolved, adding sodium acetate, pouring into a reaction kettle, reacting for 6 hours at a high temperature of 180 ℃, filtering out product solids after the reaction is finished, washing with deionized water for three times, and drying to obtain hafnium oxide microspheres;
wherein, the mass ratio of the hafnium oxychloride, the PEG-400 and the deionized water is 1:2.6:20, and the mass ratio of the sodium acetate to the hafnium oxychloride is 2.6:1.
S2, adding the hafnium oxide microspheres into an ethanol solution with the mass concentration of 75%, adding KH-570 and ammonia water with the mass concentration of 25%, stirring uniformly at room temperature, heating to boil, performing heat preservation reaction for 10 hours under the condition of condensation reflux, filtering out liquid, washing with pure water, and drying to obtain HfO 2 -NH 2 A microsphere;
wherein, the mass ratio of the hafnium oxide microsphere to the ethanol solution is 1:20-40, and the mass ratio of KH-570 and the ammonia water to the ethanol solution is 0.4-0.8:1-2:10-20.
S3, mixing boric acid in an ethanol solution with the mass concentration of 55% -75%, and then adding HfO 2 -NH 2 Heating the microspheres to boiling, reacting for 5-8h under the condition of condensing and refluxing, filtering out liquid, washing with pure water, and drying to obtain HfO 2 -NH 2 -BO 3 And (3) microspheres.
Wherein, boric acid, hfO 2 -NH 2 The mass ratio of the microspheres to the ethanol solution is 0.6-1.2:2-4:20-40.
Comparative example 1
The preparation method of the plant hydrolyzed protein amino acid derivative surfactant is the same as in example 1, except that the catalyst used in the comparative example is hafnium oxide microsphere, and the preparation method is as follows:
s1, weighing hafnium oxychloride and PEG-400, mixing into deionized water, fully stirring until the hafnium oxychloride and the PEG-400 are completely dissolved, adding sodium acetate, pouring the mixture into a reaction kettle, reacting at a high temperature of 170 ℃ for 10 hours, filtering out product solids after the reaction is finished, washing the product solids with deionized water for three times, and drying the product solids to obtain hafnium oxide microspheres;
wherein, the mass ratio of the hafnium oxychloride, the PEG-400 and the deionized water is 1:1.8:15, and the mass ratio of the sodium acetate to the hafnium oxychloride is 1.9:1.
Comparative example 2
A method for preparing a surfactant of a plant protein hydrolysate amino acid derivative is the same as in example 1, except that the catalyst used in this comparative example is HfO 2 -NH 2 The microsphere is prepared by the following steps:
s1, weighing hafnium oxychloride and PEG-400, mixing into deionized water, fully stirring until the hafnium oxychloride and the PEG-400 are completely dissolved, adding sodium acetate, pouring the mixture into a reaction kettle, reacting at a high temperature of 170 ℃ for 10 hours, filtering out product solids after the reaction is finished, washing the product solids with deionized water for three times, and drying the product solids to obtain hafnium oxide microspheres;
wherein, the mass ratio of the hafnium oxychloride, the PEG-400 and the deionized water is 1:1.8:15, and the mass ratio of the sodium acetate to the hafnium oxychloride is 1.9:1.
S2, adding the hafnium oxide microspheres into an ethanol solution with the mass concentration of 65%, adding KH-570 and ammonia water with the mass concentration of 25%, stirring uniformly at room temperature, heating to boil, performing heat preservation reaction for 9 hours under the condition of condensation reflux, filtering out liquid, washing with pure water, and drying to obtain HfO 2 -NH 2 A microsphere;
wherein, the mass ratio of the hafnium oxide microsphere to the ethanol solution is 1:30, and the mass ratio of KH-570 and the ammonia water to the ethanol solution is 0.6:1.5:15.
Comparative example 3
A method for preparing a surfactant which is a plant protein hydrolysate amino acid derivative is the same as in example 1, except that the catalyst used in this comparative example is boric acid of equal mass purchased in the market.
Comparative example 4
A method for preparing a surfactant which is a plant protein hydrolysate amino acid derivative is the same as in example 1, except that the catalyst used in this comparative example is a commercially available hafnium oxide powder (1 μm) of equal quality.
Experimental example
1. Yield and purity of product detection:
in order to more clearly illustrate the content of the present invention, the yields and purities of the amino acid derivatives of plant hydrolyzed proteins obtained in examples 1 to 3 and comparative examples 1 to 4 were examined, and the results were shown in Table 1 below:
TABLE 1 yields and purities of amino acid derivatives obtained by different methods
| Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Yield (%) | 98.4 | 97.1 | 98.9 | 92.3 | 94.6 | 95.2 | 90.5 |
| Purity (%) | 97.6 | 96.5 | 97.0 | 94.5 | 95.1 | 89.6 | 93.8 |
As can be seen from Table 1, the plant protein hydrolysate amino acid derivatives prepared in examples 1 to 3 of the present invention have very high yields, up to 98.9% of example 3, and at the same time, high purities, up to 97.6% of example 1, and example 1 was selected as the best embodiment in view of the addition amount of the catalyst and the yields and purities. In the comparative experiments based on example 1, comparative example 1 and comparative example 4 were both hafnium oxide, except that one was prepared microsphere and one was directly purchased pellet, although the yield and purity of comparative example 1 were slightly higher, but there was a large difference from example 1; the yield of comparative example 2 is superior to that of comparative example 1, probably due to the-NH on the surface thereof 2 The catalyst can be more uniformly dispersed in the reaction liquid; comparative example 3 was boric acid alone as a catalyst, and although it had a yield exceeding 95%, the purity was poor and the recyclability of boric acid alone was poor.
2. Catalyst recoverability detection:
the catalyst HfO prepared in example 1 was prepared 2 -NH 2 -BO 3 After the microspheres are reacted for the first time, the microspheres are centrifugally separated and recycled, ethanol is used as a catalyst for the second reaction after being ultrasonically cleaned and dried, and after the reaction is repeated for five times, the yield of the last detection can still reach more than 95%, which indicates that the catalyst has high catalytic efficiency and strong reusability.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The preparation method of the plant hydrolyzed protein amino acid derivative surfactant is characterized by comprising the following steps of:
(1) Weighing the peeled soybeans, washing the soybeans with clear water, drying the soybeans in an oven, taking out the soybeans, and then placing the soybeans in a drying oven for standby;
(2) Placing dried soybean in a grinding machine, grinding, pulverizing, and sieving to obtain soybean powder;
(3) Mixing soybean powder with deionized water, uniformly dispersing by ultrasonic, adding pepsin, adjusting the temperature and the pH, and stirring the reaction solution until the hydrolysis is finished to obtain soybean hydrolyzed protein solution;
(4) Heating the soy protein hydrolysate, centrifuging to remove solids, and performing freeze drying or vacuum drying treatment to obtain soy protein hydrolysate amino acid;
(5) Adding fatty alcohol into a reaction flask, heating to melt, adding soybean protein hydrolysate amino acid, adding a catalyst, reacting for 4-6h under the stirring action of 90-120 ℃, stopping heating, cooling to room temperature, filtering and removing impurities to obtain the amino acid derivative surfactant.
2. The method for preparing a surfactant of amino acid derivatives of plant hydrolyzed protein according to claim 1, wherein in the step (1), the temperature is raised to 80-100 ℃ in the oven, and the drying treatment time is 3-6h.
3. The method for preparing a surfactant of amino acid derivative of plant hydrolyzed protein according to claim 1, wherein in the step (2), the diameter of the sieve opening is 2-4mm.
4. The method for preparing a surfactant of amino acid derivatives of plant hydrolyzed protein according to claim 1, wherein the mass ratio of soybean powder to deionized water in the step (3) is 20-30:100.
5. The method for preparing a surfactant of amino acid derivatives of plant hydrolyzed protein according to claim 1, wherein in the step (3), the added amount of pepsin is 5000-10000U/g, the temperature is adjusted to 30-40 ℃, the pH is 1.5-2.5, and the stirring reaction time is 2-4 hours.
6. The method for preparing a surfactant of amino acid derivatives of plant hydrolyzed protein according to claim 1, wherein in the step (4), the temperature of the hydrolyzed soy protein solution is raised to 80-100 ℃ for convenient removal by enzyme inactivation, and the time for heat preservation after the temperature rise is 20-30min.
7. The method for preparing a surfactant of amino acid derivative of vegetable hydrolyzed protein according to claim 1, wherein in the step (5), the fatty alcohol comprises lauryl alcohol or cetyl alcohol, and the molar ratio of fatty alcohol to amino acid of soybean hydrolyzed protein is 1.8-2.2:1.
8. The method for preparing a surfactant of amino acid derivatives of plant hydrolyzed protein according to claim 1, wherein in the step (5), the catalyst is HfO2-NH2-BO3 microsphere, and the addition amount is 0.5% -1% of the mass of fatty alcohol.
9. The method for preparing the plant hydrolyzed protein amino acid derivative surfactant according to claim 1, wherein the method for preparing the catalyst HfO2-NH2-BO3 microsphere comprises the following steps:
s1, weighing hafnium oxychloride and PEG-400, mixing into deionized water, fully stirring until the hafnium oxychloride and the PEG-400 are completely dissolved, adding sodium acetate, pouring into a reaction kettle, reacting at 160-180 ℃ for 6-12h, filtering out product solids after the reaction is finished, washing with deionized water for three times, and drying to obtain hafnium oxide microspheres;
s2, adding the hafnium oxide microspheres into an ethanol solution, adding an aminosilane coupling agent and ammonia water, stirring uniformly at room temperature, heating to boil, reacting for 8-10 hours under the condition of condensing and refluxing, filtering out liquid, washing with pure water, and drying to obtain HfO2-NH2 microspheres;
s3, mixing boric acid in an ethanol solution, adding HfO2-NH2 microspheres, heating to boiling, performing heat preservation reaction for 5-8 hours under a condensing reflux condition, filtering out liquid, washing with pure water, and drying to obtain the HfO2-NH2-BO3 microspheres.
10. The method for preparing the plant hydrolyzed protein amino acid derivative surfactant according to claim 9, wherein in S1, the mass ratio of hafnium oxychloride, PEG-400 to deionized water is 1:1.2-2.6:10-20;
in the step S1, the mass ratio of the sodium acetate to the hafnium oxychloride is 1.3-2.6:1;
in the step S2, the mass concentration of the ethanol solution is 55% -75%, and the mass ratio of the hafnium oxide microspheres to the ethanol solution is 1:20-40;
in the step S2, the aminosilane coupling agent is KH-570, the concentration of ammonia water is 25%, and the mass ratio of the aminosilane coupling agent to the ammonia water to the ethanol solution is 0.4-0.8:1-2:10-20;
in the step S3, the mass concentration of the ethanol solution is 55% -75%, and the mass ratio of the boric acid, the HfO2-NH2 microspheres and the ethanol solution is 0.6-1.2:2-4:20-40.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310571181.2A CN116574521B (en) | 2023-05-20 | 2023-05-20 | Preparation method of plant hydrolyzed protein amino acid derivative surfactant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310571181.2A CN116574521B (en) | 2023-05-20 | 2023-05-20 | Preparation method of plant hydrolyzed protein amino acid derivative surfactant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116574521A CN116574521A (en) | 2023-08-11 |
| CN116574521B true CN116574521B (en) | 2023-10-27 |
Family
ID=87537375
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310571181.2A Active CN116574521B (en) | 2023-05-20 | 2023-05-20 | Preparation method of plant hydrolyzed protein amino acid derivative surfactant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116574521B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IN192824B (en) * | 1999-10-11 | 2004-05-22 | Council Scient Ind Res | |
| CN1617670A (en) * | 2001-12-21 | 2005-05-18 | 拉伊西奥比尼考有限公司 | Protein hydrolysate and plant sterol containing composition for improving serum lipid profile and preventing atherosclerosis |
| CN102978269A (en) * | 2012-12-26 | 2013-03-20 | 东北农业大学 | Method for preparing soybean peptides from carrier-free immobilized enzyme |
| CN113477177A (en) * | 2020-10-15 | 2021-10-08 | 百葵锐(天津)生物科技有限公司 | Biosurfactant and preparation method thereof |
| CN114133344A (en) * | 2021-11-29 | 2022-03-04 | 江苏奥洁生物科技有限公司 | Method for preparing N-fatty acyl amino acid surfactant by high-temperature melting direct condensation |
| JP2023025603A (en) * | 2021-08-10 | 2023-02-22 | 不二製油株式会社 | Method of producing emulsifier |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9951171B2 (en) * | 2014-08-20 | 2018-04-24 | Resinate Materials Group, Inc. | Polyester polyols from recycled polymers and waste streams |
-
2023
- 2023-05-20 CN CN202310571181.2A patent/CN116574521B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IN192824B (en) * | 1999-10-11 | 2004-05-22 | Council Scient Ind Res | |
| CN1617670A (en) * | 2001-12-21 | 2005-05-18 | 拉伊西奥比尼考有限公司 | Protein hydrolysate and plant sterol containing composition for improving serum lipid profile and preventing atherosclerosis |
| CN102978269A (en) * | 2012-12-26 | 2013-03-20 | 东北农业大学 | Method for preparing soybean peptides from carrier-free immobilized enzyme |
| CN113477177A (en) * | 2020-10-15 | 2021-10-08 | 百葵锐(天津)生物科技有限公司 | Biosurfactant and preparation method thereof |
| JP2023025603A (en) * | 2021-08-10 | 2023-02-22 | 不二製油株式会社 | Method of producing emulsifier |
| CN114133344A (en) * | 2021-11-29 | 2022-03-04 | 江苏奥洁生物科技有限公司 | Method for preparing N-fatty acyl amino acid surfactant by high-temperature melting direct condensation |
Non-Patent Citations (1)
| Title |
|---|
| 化学改性大豆蛋白质高分子材料研究进展;吴溪;陈国;阚成友;;现代化工(10);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116574521A (en) | 2023-08-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2020113975A1 (en) | High-purity rice protein powder and preparation method therefor and use thereof | |
| CN101012471A (en) | Method for extracting rice bran protein by complex enzyme | |
| CN109575028B (en) | Method for hydrolyzing adenosine by cation exchange resin catalysis-separation coupling technology | |
| CN1561814A (en) | River crab flavouring and its preparing method | |
| CN105733800A (en) | Preparation method of special virgin sesame seed oil | |
| CN116574521B (en) | Preparation method of plant hydrolyzed protein amino acid derivative surfactant | |
| CN114438072B (en) | Production method of trehalose | |
| CN114457132B (en) | Method for preparing starch and non-heat-denaturation protein powder by taking rice as raw material | |
| CN117210971A (en) | Method for preparing high-water-holding capacity and high-oil-holding capacity nano citrus fiber | |
| CN109468356B (en) | Preparation method of rice protein | |
| CN111235206A (en) | Method for preparing shellfish high F value oligopeptide by subcritical water-assisted enzyme method | |
| CN109971811A (en) | A kind of enzymatic isolation method prepares the method for corn functional peptides and the corn functional peptides of preparation | |
| CN108157582A (en) | It is a kind of that the method for improving sesame protein gelation is modified using immobilised enzymes | |
| CN111280291B (en) | Preparation method of squid soybean compound protein particles | |
| CN113907367A (en) | Preparation method of shaddock soluble dietary fiber | |
| JP4044422B2 (en) | Production method of feed obtained from barley shochu distillation residue | |
| CN112851724A (en) | Preparation method of vegetarian D-glucosamine hydrochloride | |
| CN116947711B (en) | Preparation method of fatty alcohol sulfosuccinic acid monoester disodium salt | |
| CN114868808B (en) | Preparation method of strong-flavor beef tallow and product thereof | |
| CN114181069B (en) | Method for efficiently preparing bis (salicylic acid) palladium (II) acid | |
| US3855062A (en) | Process for preparation of derivatives of l-tyrosine | |
| CN116478054A (en) | Preparation method and reaction system of feed additive glycine complex zinc | |
| CN108208308B (en) | Method for extracting thermal denaturation rice bran protein | |
| CN117051069B (en) | Extraction method and application of peony antioxidant peptide | |
| CN112921060B (en) | Method for synthesizing sucrose fatty acid ester by lipase catalysis in organic solvent |
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 |