CN113307747A - Fine-particle-size fatty alcohol disodium sulfosuccinate powder and production method thereof - Google Patents
Fine-particle-size fatty alcohol disodium sulfosuccinate powder and production method thereof Download PDFInfo
- Publication number
- CN113307747A CN113307747A CN202110479974.2A CN202110479974A CN113307747A CN 113307747 A CN113307747 A CN 113307747A CN 202110479974 A CN202110479974 A CN 202110479974A CN 113307747 A CN113307747 A CN 113307747A
- Authority
- CN
- China
- Prior art keywords
- fatty alcohol
- reaction
- reaction kettle
- fine
- disodium
- 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.)
- Pending
Links
- 239000000843 powder Substances 0.000 title claims abstract description 41
- -1 fatty alcohol disodium sulfosuccinate Chemical class 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 83
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 59
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 28
- 239000008213 purified water Substances 0.000 claims abstract description 27
- 238000005886 esterification reaction Methods 0.000 claims abstract description 21
- 235000010265 sodium sulphite Nutrition 0.000 claims abstract description 20
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 19
- 238000001694 spray drying Methods 0.000 claims abstract description 17
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 12
- 230000032050 esterification Effects 0.000 claims abstract description 11
- 230000032683 aging Effects 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000011049 filling Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 238000004321 preservation Methods 0.000 claims abstract description 10
- 238000005086 pumping Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000010419 fine particle Substances 0.000 claims abstract description 7
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 claims abstract description 4
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims abstract 6
- 239000000463 material Substances 0.000 claims description 31
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 26
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- 239000001632 sodium acetate Substances 0.000 claims description 8
- 235000017281 sodium acetate Nutrition 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- 239000006071 cream Substances 0.000 claims description 6
- 238000013329 compounding Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000002453 shampoo Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 2
- 239000008257 shaving cream Substances 0.000 claims description 2
- 229940023462 paste product Drugs 0.000 abstract 1
- 238000005485 electric heating Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 239000007788 liquid Substances 0.000 description 9
- 239000000498 cooling water Substances 0.000 description 7
- 238000010790 dilution Methods 0.000 description 7
- 239000012895 dilution Substances 0.000 description 7
- 238000005286 illumination Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000001815 facial effect Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
- A61K8/466—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfonic acid derivatives; Salts
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/10—Washing or bathing preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/02—Preparations for cleaning the hair
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q9/00—Preparations for removing hair or for aiding hair removal
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/17—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing carboxyl groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Dermatology (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a production method of fine-particle-size fatty alcohol disodium sulfosuccinate powder, which comprises the following steps: s1, adding fatty alcohol into the esterification reaction kettle, adding maleic anhydride and a catalyst under the stirring condition, and obtaining an esterification intermediate 1 after the reaction is finished; s2, adding purified water into the sulfonation reaction kettle, and adding sodium sulfite to dissolve; s3, adding the esterification intermediate 1, and finishing the reaction when the reaction system is clear and transparent to obtain an intermediate 2; s4, filling the intermediate 2 into a wide-mouth barrel, and naturally cooling and aging for 2-3 days; and S5, putting the aged intermediate 2 into a reaction kettle, adding purified water for burdening, filtering by a filter bag, and then pumping into a heat preservation tank for spray drying. The advantages are that: the method can prepare the disodium fatty alcohol sulfosuccinate powder with fine particle size, and solves the problems that the application of the conventional paste product in the market is relatively single, particularly the paste becomes hard after the temperature in winter is reduced, the use is extremely inconvenient, and the addition amount in the formula of a downstream product is limited.
Description
Technical Field
The invention relates to a production process of fatty alcohol disodium sulfosuccinate, in particular to a production process of fine-particle-size fatty alcohol disodium sulfosuccinate powder.
Background
The fatty alcohol disodium sulfosuccinate is an anionic surfactant, belongs to sulfosuccinate series, and has fine and rich foam, no greasy feeling and easy cleaning; the detergent has strong detergency and low degreasing power, and belongs to common mild surfactants; can be combined with other surfactants and reduce the irritation. Can be widely used for preparing hand washing cream (liquid), foam face cleaning cream and foam shaving cream, and can also be used for preparing smooth and clean foam shower gel and pearly shampoo without greasy. At present, a conventional product in the market is a paste with a concentration of 50%, the application is relatively single, particularly, after the temperature is reduced in winter, the paste becomes hard, the use is extremely inconvenient, the market demand of high-end green, safe and environment-friendly cosmetics is increased along with the improvement of the living standard of people, and the original product limits the application range of the product and the addition amount in the formula of downstream products. At present, no domestic fine powder production enterprises are seen, no related powder finished product production process reports exist, academic documents are research on liquid and paste synthesis technologies, powder products are supplied abroad, and related patents and production processes are not issued for a while due to technical secrecy. Domestic powdery products are mainly imported and expensive, the price is 10 times higher than that of 50 percent paste, and the market demand is increased year by year. In order to solve the application field, increase the usage amount in the formula and meet the requirement of diversified development of the product, the invention discloses a production method of a powder product with the water content of less than 5 percent, fills the gap of the domestic powder production technology of the product, has huge economic benefit and has good application prospect.
Disclosure of Invention
In order to solve the technical problem that the application range of the fatty alcohol disodium sulfosuccinate paste in the prior art is narrow, the invention provides fine-particle-size fatty alcohol disodium sulfosuccinate powder and a production method thereof.
The technical scheme adopted by the invention is as follows: the production method of the fine-particle-size fatty alcohol disodium sulfosuccinate powder is characterized by comprising the following steps of:
s1, adding fatty alcohol into an esterification reaction kettle, adding maleic anhydride and a catalyst under the stirring condition, controlling the reaction temperature at 65-75 ℃ and reacting for 2-3 hours, and obtaining an esterification intermediate 1 after the reaction is finished; the molar ratio of the fatty alcohol to the maleic anhydride is 1: 1.0-1.05; the catalyst is prepared by compounding sodium carbonate, urea and sodium acetate according to the mass ratio of 1: 0.1-1: 1.5-2.5, and the dosage of the catalyst accounts for 0.08-0.12% of the total mass of the feed;
s2, adding purified water into the sulfonation reaction kettle at one time according to a 50% solid content reaction system, controlling the temperature of the reaction kettle to be 40-50 ℃, adding sodium sulfite under stirring to dissolve, and dissolving for 1-1.5 h; the molar ratio of the sodium sulfite to the maleic anhydride is 1: 1;
s3, adding the esterified intermediate 1 into the sulfonation reaction kettle under the stirring condition, controlling the reaction temperature at 75-85 ℃ to react for 1-2 h, and finishing the reaction when the reaction system is clear and transparent to obtain an intermediate 2;
s4, filling the intermediate 2 into a wide-mouth barrel, and naturally cooling and aging for 2-3 days;
s5, putting the aged intermediate 2 into a reaction kettle, adding 22-32 kg of purified water for each 100kg of material, heating to 70-80 ℃, filtering by a filter bag, and then pumping into a heat preservation tank for spray drying until the water content is lower than 5% to obtain the finished product.
As a further improvement of the present invention, the molar ratio of the fatty alcohol to the maleic anhydride in step S1 is 1: 1.035.
As a further improvement of the invention, in the step S5, the aperture of the filter bag is 0.08-0.12 micron.
As a further improvement, the fatty alcohol is one or two selected from dodecanol and tetradecanol.
The invention also discloses fine-particle-size fatty alcohol disodium sulfosuccinate powder, which is prepared by the production method of the fine-particle-size fatty alcohol disodium sulfosuccinate powder.
The invention also discloses a production method of the washing and caring product, which is characterized in that the production raw material comprises the fine-particle-size fatty alcohol disodium sulfosuccinate powder.
It will be readily appreciated that the toiletries of the present invention include, but are not limited to, hand creams, hand lotions, facial cleansers, shaving creams, body washes, shampoos, and the like.
The invention also discloses a washing and protecting product which is prepared by the production method of the washing and protecting product.
The invention has the beneficial effects that: the method can prepare the fine-particle-size fatty alcohol disodium sulfosuccinate powder, overcomes the problems that the conventional paste products in the market are relatively single in application, particularly, after the temperature in winter is reduced, the paste becomes hard, the use is extremely inconvenient, and the addition amount in the downstream product formula is limited, and meets the requirements of diversified development of products. The invention discloses a production method of a powder product with the water content of less than 5 percent, which fills the domestic gap of powder production technology of the product, has huge economic benefit and has good application prospect.
Detailed Description
The present invention will be further described with reference to the following examples.
The first embodiment is as follows:
producing a fine-particle-size fatty alcohol disodium sulfosuccinate powder product according to the following steps:
adding dodecanol into an esterification reaction kettle, adding maleic anhydride and a catalyst under the stirring condition, controlling the reaction temperature at 70 ℃ and reacting for 2.5 hours to obtain an esterification intermediate 1 after the reaction is finished; the molar ratio of the dodecanol to the maleic anhydride is 1: 1.035; the catalyst is prepared by compounding sodium carbonate, urea and sodium acetate according to the mass ratio of 1:0.3:2, and the dosage of the catalyst accounts for 0.1% of the total mass of the feed;
s2, adding purified water into the sulfonation reaction kettle at one time according to a 50% solid content reaction system, controlling the temperature of the reaction kettle to be 45 ℃, adding sodium sulfite to dissolve under the stirring condition, and dissolving for 1.5 h; the molar ratio of the sodium sulfite to the maleic anhydride is 1: 1;
s3, adding the esterified intermediate 1 into the sulfonation reaction kettle under the stirring condition, controlling the reaction temperature at 80 ℃ for reaction for 2 hours, and ending the reaction when the reaction system is clear and transparent to obtain an intermediate 2;
s4, filling the intermediate 2 into a wide-mouth barrel, and naturally cooling and aging for 3 days;
s5, putting the aged intermediate 2 into a reaction kettle, adding 28kg of purified water for each 100kg of material, heating to 80 ℃, filtering by a 0.1 micron filter bag, and then pumping into a heat preservation tank for spray drying to obtain the product.
The spray drying comprises the following specific operation steps:
first, preparation work
1. The compressed air is turned on and the atomizer is turned on to cool the water.
2. And checking whether the pipeline is sealed or not, whether the charging basket is installed or not and whether the tower door is closed or not.
3. The dilution was melted in the ratio of the material and the purified water in step S5, and the diluted liquid was maintained at 75 ℃.
Second, the starting sequence
1. The atomizer was turned on and the frequency was adjusted.
2. And opening the induced draft fan.
3. The electric heating is switched on.
4. Turn on the illumination, turn on the air hammer.
5. After the outlet temperature rises to 90 ℃, adding water, starting a screw pump, adjusting the frequency to be 15Hz, waiting for hot water to be added to 13cm below the tower top, switching materials after a feeding pipe is scalded, slowly adjusting the feeding frequency, controlling the inlet temperature to be 150 ℃ and the outlet temperature to be 95 ℃.
Third, shutdown sequence
1. After the material is sprayed, the water is switched, and after 5 minutes of watering, the electric heating pipe is closed.
2. When the inlet temperature is reduced to 140 ℃, the feeding pump is closed.
3. And (5) waiting for the inlet and outlet temperatures to be reduced to 90 ℃, and closing the induced draft fan.
4. The atomizer was turned off.
5. And closing the air hammer and closing the illuminating lamp.
6. The cooling water is turned off and the compressed air is turned off.
S6, the performance of the obtained powder product is detected, and the result is shown in Table 1.
Example two:
producing a fine-particle-size fatty alcohol disodium sulfosuccinate powder product according to the following steps:
adding tetradecanol into an esterification reaction kettle, adding maleic anhydride and a catalyst under the stirring condition, controlling the reaction temperature at 65 ℃ for 2 hours, and obtaining an esterification intermediate 1 after the reaction is finished; the molar ratio of the tetradecanol to the maleic anhydride is 1: 1.05; the catalyst is prepared by compounding sodium carbonate, urea and sodium acetate according to the mass ratio of 1:0.5:1.5, and the dosage of the catalyst accounts for 0.12% of the total mass of the feed;
s2, adding purified water into the sulfonation reaction kettle at one time according to a 50% solid content reaction system, controlling the temperature of the reaction kettle to be 50 ℃, adding sodium sulfite to dissolve under the stirring condition, and dissolving for 1.5 h; the molar ratio of the sodium sulfite to the maleic anhydride is 1: 1;
s3, adding the esterified intermediate 1 into the sulfonation reaction kettle under the stirring condition, controlling the reaction temperature at 75 ℃ for reaction for 2 hours, and ending the reaction when the reaction system is clear and transparent to obtain an intermediate 2;
s4, filling the intermediate 2 into a wide-mouth barrel, and naturally cooling and aging for 2 days;
s5, putting the aged intermediate 2 into a reaction kettle, adding 30kg of purified water for each 100kg of material, heating to 80 ℃, filtering by a 0.1 micron filter bag, and then pumping into a heat preservation tank for spray drying to obtain the product.
The spray drying comprises the following specific operation steps:
first, preparation work
1. The compressed air is turned on and the atomizer is turned on to cool the water.
2. And checking whether the pipeline is sealed or not, whether the charging basket is installed or not and whether the tower door is closed or not.
3. The dilution was melted in the ratio of the material and the purified water in step S5, and the diluted liquid was maintained at 75 ℃.
Second, the starting sequence
1. The atomizer was turned on and the frequency was adjusted.
2. And opening the induced draft fan.
3. The electric heating is switched on.
4. Turn on the illumination, turn on the air hammer.
5. After the outlet temperature rises to 90 ℃, adding water, starting a screw pump, adjusting the frequency to be 15Hz, waiting for hot water to be added to 13cm below the tower top, switching materials after a feeding pipe is scalded, slowly adjusting the feeding frequency, controlling the inlet temperature to be 150 ℃ and the outlet temperature to be 95 ℃.
Third, shutdown sequence
1. After the material is sprayed, the water is switched, and after 5 minutes of watering, the electric heating pipe is closed.
2. When the inlet temperature is reduced to 140 ℃, the feeding pump is closed.
3. And (5) waiting for the inlet and outlet temperatures to be reduced to 90 ℃, and closing the induced draft fan.
4. The atomizer was turned off.
5. And closing the air hammer and closing the illuminating lamp.
6. The cooling water is turned off and the compressed air is turned off.
S6, the performance of the obtained powder product is detected, and the result is shown in Table 1.
Example three:
producing a fine-particle-size fatty alcohol disodium sulfosuccinate powder product according to the following steps:
adding mixed alcohol consisting of dodecanol and tetradecanol according to a molar ratio of 3:1 into an esterification reaction kettle, adding maleic anhydride and a catalyst under a stirring condition, controlling the reaction temperature at 75 ℃ for reacting for 3 hours, and obtaining an esterification intermediate 1 after the reaction is finished; the molar ratio of the mixed alcohol to the maleic anhydride is 1: 1; the catalyst is prepared by compounding sodium carbonate, urea and sodium acetate according to the mass ratio of 1:0.8:2.5, and the dosage of the catalyst accounts for 0.09% of the total mass of the feed;
s2, adding purified water into the sulfonation reaction kettle at one time according to a 50% solid content reaction system, controlling the temperature of the reaction kettle to be 50 ℃, adding sodium sulfite to dissolve under the stirring condition, and dissolving for 1.5 h; the molar ratio of the sodium sulfite to the maleic anhydride is 1: 1;
s3, adding the esterified intermediate 1 into the sulfonation reaction kettle under the stirring condition, controlling the reaction temperature at 75 ℃ for reaction for 2 hours, and ending the reaction when the reaction system is clear and transparent to obtain an intermediate 2;
s4, filling the intermediate 2 into a wide-mouth barrel, and naturally cooling and aging for 3 days;
s5, putting the aged intermediate 2 into a reaction kettle, adding 23kg of purified water for each 100kg of material, heating to 80 ℃, filtering by a 0.1 micron filter bag, and then pumping into a heat preservation tank for spray drying to obtain the product.
The spray drying comprises the following specific operation steps:
first, preparation work
1. The compressed air is turned on and the atomizer is turned on to cool the water.
2. And checking whether the pipeline is sealed or not, whether the charging basket is installed or not and whether the tower door is closed or not.
3. The dilution was melted in the ratio of the material and the purified water in step S5, and the diluted liquid was maintained at 75 ℃.
Second, the starting sequence
1. The atomizer was turned on and the frequency was adjusted.
2. And opening the induced draft fan.
3. The electric heating is switched on.
4. Turn on the illumination, turn on the air hammer.
5. After the outlet temperature rises to 90 ℃, adding water, starting a screw pump, adjusting the frequency to be 15Hz, waiting for hot water to be added to 13cm below the tower top, switching materials after a feeding pipe is scalded, slowly adjusting the feeding frequency, controlling the inlet temperature to be 150 ℃ and the outlet temperature to be 95 ℃.
Third, shutdown sequence
1. After the material is sprayed, the water is switched, and after 5 minutes of watering, the electric heating pipe is closed.
2. When the inlet temperature is reduced to 140 ℃, the feeding pump is closed.
3. And (5) waiting for the inlet and outlet temperatures to be reduced to 90 ℃, and closing the induced draft fan.
4. The atomizer was turned off.
5. And closing the air hammer and closing the illuminating lamp.
6. The cooling water is turned off and the compressed air is turned off.
S6, the performance of the obtained powder product is detected, and the result is shown in Table 1.
Comparative example one:
this comparative example is a control experiment of example one, designed according to the same procedure and experimental conditions as example one, and differs only in that: in step S1, no catalyst is added, and the specific steps are as follows:
producing a fine-particle-size fatty alcohol disodium sulfosuccinate powder product according to the following steps:
adding dodecanol into an esterification reaction kettle, adding maleic anhydride under the stirring condition, controlling the reaction temperature at 70 ℃ and reacting for 2.5 hours to obtain an esterification intermediate 1 after the reaction is finished; the molar ratio of the dodecanol to the maleic anhydride is 1: 1.035;
s2, adding purified water into the sulfonation reaction kettle at one time according to a 50% solid content reaction system, controlling the temperature of the reaction kettle to be 45 ℃, adding sodium sulfite to dissolve under the stirring condition, and dissolving for 1.5 h; the molar ratio of the sodium sulfite to the maleic anhydride is 1: 1;
s3, adding the esterified intermediate 1 into the sulfonation reaction kettle under the stirring condition, controlling the reaction temperature at 80 ℃ for reaction for 2 hours, and ending the reaction when the reaction system is clear and transparent to obtain an intermediate 2;
s4, filling the intermediate 2 into a wide-mouth barrel, and naturally cooling and aging for 3 days;
s5, putting the aged intermediate 2 into a reaction kettle, adding 28kg of purified water for each 100kg of material, heating to 80 ℃, filtering by a 0.1 micron filter bag, and then pumping into a heat preservation tank for spray drying to obtain the product.
The spray drying comprises the following specific operation steps:
first, preparation work
1. The compressed air is turned on and the atomizer is turned on to cool the water.
2. And checking whether the pipeline is sealed or not, whether the charging basket is installed or not and whether the tower door is closed or not.
3. The dilution was melted in the ratio of the material and the purified water in step S5, and the diluted liquid was maintained at 75 ℃.
Second, the starting sequence
1. The atomizer was turned on and the frequency was adjusted.
2. And opening the induced draft fan.
3. The electric heating is switched on.
4. Turn on the illumination, turn on the air hammer.
5. After the outlet temperature rises to 90 ℃, adding water, starting a screw pump, adjusting the frequency to be 15Hz, waiting for hot water to be added to 13cm below the tower top, switching materials after a feeding pipe is scalded, slowly adjusting the feeding frequency, controlling the inlet temperature to be 150 ℃ and the outlet temperature to be 95 ℃.
Third, shutdown sequence
1. After the material is sprayed, the water is switched, and after 5 minutes of watering, the electric heating pipe is closed.
2. When the inlet temperature is reduced to 140 ℃, the feeding pump is closed.
3. And (5) waiting for the inlet and outlet temperatures to be reduced to 90 ℃, and closing the induced draft fan.
4. The atomizer was turned off.
5. And closing the air hammer and closing the illuminating lamp.
6. The cooling water is turned off and the compressed air is turned off.
S6, the performance of the obtained powder product is detected, and the result is shown in Table 1.
Comparative example two:
this comparative example is a control experiment of example one, designed according to the same procedure and experimental conditions as example one, and differs only in that: in the step S1, the catalyst is sodium carbonate, and the specific steps are as follows:
producing a fine-particle-size fatty alcohol disodium sulfosuccinate powder product according to the following steps:
adding dodecanol into an esterification reaction kettle, adding maleic anhydride and a catalyst under the stirring condition, controlling the reaction temperature at 70 ℃ and reacting for 2.5 hours to obtain an esterification intermediate 1 after the reaction is finished; the molar ratio of the dodecanol to the maleic anhydride is 1: 1.035; the catalyst is sodium carbonate, and the using amount of the catalyst accounts for 0.1 percent of the total mass of the feed;
s2, adding purified water into the sulfonation reaction kettle at one time according to a 50% solid content reaction system, controlling the temperature of the reaction kettle to be 45 ℃, adding sodium sulfite to dissolve under the stirring condition, and dissolving for 1.5 h; the molar ratio of the sodium sulfite to the maleic anhydride is 1: 1;
s3, adding the esterified intermediate 1 into the sulfonation reaction kettle under the stirring condition, controlling the reaction temperature at 80 ℃ for reaction for 2 hours, and ending the reaction when the reaction system is clear and transparent to obtain an intermediate 2;
s4, filling the intermediate 2 into a wide-mouth barrel, and naturally cooling and aging for 3 days;
s5, putting the aged intermediate 2 into a reaction kettle, adding 28kg of purified water for each 100kg of material, heating to 80 ℃, filtering by a 0.1 micron filter bag, and then pumping into a heat preservation tank for spray drying to obtain the product.
The spray drying comprises the following specific operation steps:
first, preparation work
1. The compressed air is turned on and the atomizer is turned on to cool the water.
2. And checking whether the pipeline is sealed or not, whether the charging basket is installed or not and whether the tower door is closed or not.
3. The dilution was melted in the ratio of the material and the purified water in step S5, and the diluted liquid was maintained at 75 ℃.
Second, the starting sequence
1. The atomizer was turned on and the frequency was adjusted.
2. And opening the induced draft fan.
3. The electric heating is switched on.
4. Turn on the illumination, turn on the air hammer.
5. After the outlet temperature rises to 90 ℃, adding water, starting a screw pump, adjusting the frequency to be 15Hz, waiting for hot water to be added to 13cm below the tower top, switching materials after a feeding pipe is scalded, slowly adjusting the feeding frequency, controlling the inlet temperature to be 150 ℃ and the outlet temperature to be 95 ℃.
Third, shutdown sequence
1. After the material is sprayed, the water is switched, and after 5 minutes of watering, the electric heating pipe is closed.
2. When the inlet temperature is reduced to 140 ℃, the feeding pump is closed.
3. And (5) waiting for the inlet and outlet temperatures to be reduced to 90 ℃, and closing the induced draft fan.
4. The atomizer was turned off.
5. And closing the air hammer and closing the illuminating lamp.
6. The cooling water is turned off and the compressed air is turned off.
S6, the performance of the obtained powder product is detected, and the result is shown in Table 1.
Comparative example three:
this comparative example is a control experiment of example one, designed according to the same procedure and experimental conditions as example one, and differs only in that: in the step S1, the catalyst is urea, and the specific steps are as follows:
producing a fine-particle-size fatty alcohol disodium sulfosuccinate powder product according to the following steps:
adding dodecanol into an esterification reaction kettle, adding maleic anhydride and a catalyst under the stirring condition, controlling the reaction temperature at 70 ℃ and reacting for 2.5 hours to obtain an esterification intermediate 1 after the reaction is finished; the molar ratio of the dodecanol to the maleic anhydride is 1: 1.035; the catalyst is urea, and the using amount of the catalyst accounts for 0.1 percent of the total mass of the fed materials;
s2, adding purified water into the sulfonation reaction kettle at one time according to a 50% solid content reaction system, controlling the temperature of the reaction kettle to be 45 ℃, adding sodium sulfite to dissolve under the stirring condition, and dissolving for 1.5 h; the molar ratio of the sodium sulfite to the maleic anhydride is 1: 1;
s3, adding the esterified intermediate 1 into the sulfonation reaction kettle under the stirring condition, controlling the reaction temperature at 80 ℃ for reaction for 2 hours, and ending the reaction when the reaction system is clear and transparent to obtain an intermediate 2;
s4, filling the intermediate 2 into a wide-mouth barrel, and naturally cooling and aging for 3 days;
s5, putting the aged intermediate 2 into a reaction kettle, adding 28kg of purified water for each 100kg of material, heating to 80 ℃, filtering by a 0.1 micron filter bag, and then pumping into a heat preservation tank for spray drying to obtain the product.
The spray drying comprises the following specific operation steps:
first, preparation work
1. The compressed air is turned on and the atomizer is turned on to cool the water.
2. And checking whether the pipeline is sealed or not, whether the charging basket is installed or not and whether the tower door is closed or not.
3. The dilution was melted in the ratio of the material and the purified water in step S5, and the diluted liquid was maintained at 75 ℃.
Second, the starting sequence
1. The atomizer was turned on and the frequency was adjusted.
2. And opening the induced draft fan.
3. The electric heating is switched on.
4. Turn on the illumination, turn on the air hammer.
5. After the outlet temperature rises to 90 ℃, adding water, starting a screw pump, adjusting the frequency to be 15Hz, waiting for hot water to be added to 13cm below the tower top, switching materials after a feeding pipe is scalded, slowly adjusting the feeding frequency, controlling the inlet temperature to be 150 ℃ and the outlet temperature to be 95 ℃.
Third, shutdown sequence
1. After the material is sprayed, the water is switched, and after 5 minutes of watering, the electric heating pipe is closed.
2. When the inlet temperature is reduced to 140 ℃, the feeding pump is closed.
3. And (5) waiting for the inlet and outlet temperatures to be reduced to 90 ℃, and closing the induced draft fan.
4. The atomizer was turned off.
5. And closing the air hammer and closing the illuminating lamp.
6. The cooling water is turned off and the compressed air is turned off.
S6, the performance of the obtained powder product is detected, and the result is shown in Table 1.
Comparative example four:
this comparative example is a control experiment of example one, designed according to the same procedure and experimental conditions as example one, and differs only in that: in the step S1, the catalyst is sodium acetate, and the specific steps are as follows:
producing a fine-particle-size fatty alcohol disodium sulfosuccinate powder product according to the following steps:
adding dodecanol into an esterification reaction kettle, adding maleic anhydride and a catalyst under the stirring condition, controlling the reaction temperature at 70 ℃ and reacting for 2.5 hours to obtain an esterification intermediate 1 after the reaction is finished; the molar ratio of the dodecanol to the maleic anhydride is 1: 1.035; the catalyst is sodium acetate, and the using amount of the catalyst accounts for 0.1% of the total mass of the feed;
s2, adding purified water into the sulfonation reaction kettle at one time according to a 50% solid content reaction system, controlling the temperature of the reaction kettle to be 45 ℃, adding sodium sulfite to dissolve under the stirring condition, and dissolving for 1.5 h; the molar ratio of the sodium sulfite to the maleic anhydride is 1: 1;
s3, adding the esterified intermediate 1 into the sulfonation reaction kettle under the stirring condition, controlling the reaction temperature at 80 ℃ for reaction for 2 hours, and ending the reaction when the reaction system is clear and transparent to obtain an intermediate 2;
s4, filling the intermediate 2 into a wide-mouth barrel, and naturally cooling and aging for 3 days;
s5, putting the aged intermediate 2 into a reaction kettle, adding 28kg of purified water for each 100kg of material, heating to 80 ℃, filtering by a 0.1 micron filter bag, and then pumping into a heat preservation tank for spray drying to obtain the product.
The spray drying comprises the following specific operation steps:
first, preparation work
1. The compressed air is turned on and the atomizer is turned on to cool the water.
2. And checking whether the pipeline is sealed or not, whether the charging basket is installed or not and whether the tower door is closed or not.
3. The dilution was melted in the ratio of the material and the purified water in step S5, and the diluted liquid was maintained at 75 ℃.
Second, the starting sequence
1. The atomizer was turned on and the frequency was adjusted.
2. And opening the induced draft fan.
3. The electric heating is switched on.
4. Turn on the illumination, turn on the air hammer.
5. After the outlet temperature rises to 90 ℃, adding water, starting a screw pump, adjusting the frequency to be 15Hz, waiting for hot water to be added to 13cm below the tower top, switching materials after a feeding pipe is scalded, slowly adjusting the feeding frequency, controlling the inlet temperature to be 150 ℃ and the outlet temperature to be 95 ℃.
Third, shutdown sequence
1. After the material is sprayed, the water is switched, and after 5 minutes of watering, the electric heating pipe is closed.
2. When the inlet temperature is reduced to 140 ℃, the feeding pump is closed.
3. And (5) waiting for the inlet and outlet temperatures to be reduced to 90 ℃, and closing the induced draft fan.
4. The atomizer was turned off.
5. And closing the air hammer and closing the illuminating lamp.
6. The cooling water is turned off and the compressed air is turned off.
S6, the performance of the obtained powder product is detected, and the result is shown in Table 1.
TABLE 1 product performance test result table for fine particle size fatty alcohol disodium sulfosuccinate powder
| Fine powder active (%) | Sodium sulfite (％) | |
| Example one | 89.8 | 0.1 |
| Example two | 90.2 | 0.15 |
| EXAMPLE III | 90.3 | 0.08 |
| COMPARATIVE EXAMPLE I (without catalyst) | 78.8 | 0.75 |
| Comparative example No. two (sodium carbonate as catalyst) | 82.6 | 0.52 |
| COMPARATIVE EXAMPLE III (Urea as catalyst) | 83.5 | 0.40 |
| Comparative example No. four (catalyst is sodium acetate) | 84.8 | 0.46 |
Claims (8)
1. The production method of the fine-particle-size fatty alcohol disodium sulfosuccinate powder is characterized by comprising the following steps of:
s1, adding fatty alcohol into an esterification reaction kettle, adding maleic anhydride and a catalyst under the stirring condition, controlling the reaction temperature at 65-75 ℃ and reacting for 2-3 hours, and obtaining an esterification intermediate 1 after the reaction is finished; the molar ratio of the fatty alcohol to the maleic anhydride is 1: 1.0-1.05; the catalyst is prepared by compounding sodium carbonate, urea and sodium acetate according to the mass ratio of 1: 0.1-1: 1.5-2.5, and the dosage of the catalyst accounts for 0.08-0.12% of the total mass of the feed;
s2, adding purified water into the sulfonation reaction kettle at one time according to a 50% solid content reaction system, controlling the temperature of the reaction kettle to be 40-50 ℃, adding sodium sulfite under stirring to dissolve, and dissolving for 1-1.5 h; the molar ratio of the sodium sulfite to the maleic anhydride is 1: 1;
s3, adding the esterified intermediate 1 into the sulfonation reaction kettle under the stirring condition, controlling the reaction temperature at 75-85 ℃ to react for 1-2 h, and finishing the reaction when the reaction system is clear and transparent to obtain an intermediate 2;
s4, filling the intermediate 2 into a wide-mouth barrel, and naturally cooling and aging for 2-3 days;
s5, putting the aged intermediate 2 into a reaction kettle, adding 22-32 kg of purified water for each 100kg of material, heating to 70-80 ℃, filtering by a filter bag, and then pumping into a heat preservation tank for spray drying until the water content is lower than 5% to obtain the finished product.
2. The method for producing disodium fine particle size fatty alcohol sulfosuccinate powder according to claim 1, wherein: in step S1, the molar ratio of the fatty alcohol to the maleic anhydride is 1: 1.035.
3. The method for producing disodium fine particle size fatty alcohol sulfosuccinate powder according to claim 1, wherein: in the step S5, the aperture of the filter bag is 0.08-0.12 micron.
4. The method for producing disodium fine particle size fatty alcohol sulfosuccinate powder according to claim 1, wherein: the fatty alcohol is one or two of dodecanol and tetradecanol.
5. The fine particle size disodium fatty alcohol sulfosuccinate powder produced by the method for producing a fine particle size disodium fatty alcohol sulfosuccinate powder according to any one of claims 1 to 4.
6. A production method of a washing and caring product is characterized in that: the production raw material comprises the fine-particle-size fatty alcohol disodium sulfosuccinate powder of claim 5.
7. A process for the production of a laundry care product according to claim 6, characterized in that: the washing and caring product comprises hand washing cream, hand sanitizer, face cleaning cream, shaving cream, shower gel and shampoo.
8. A laundry product made by the process of claim 6 or 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110479974.2A CN113307747A (en) | 2021-04-30 | 2021-04-30 | Fine-particle-size fatty alcohol disodium sulfosuccinate powder and production method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110479974.2A CN113307747A (en) | 2021-04-30 | 2021-04-30 | Fine-particle-size fatty alcohol disodium sulfosuccinate powder and production method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113307747A true CN113307747A (en) | 2021-08-27 |
Family
ID=77371407
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110479974.2A Pending CN113307747A (en) | 2021-04-30 | 2021-04-30 | Fine-particle-size fatty alcohol disodium sulfosuccinate powder and production method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113307747A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116947711A (en) * | 2023-09-19 | 2023-10-27 | 广州宏度精细化工有限公司 | Preparation method of fatty alcohol sulfosuccinic acid monoester disodium salt |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4039562A (en) * | 1975-02-21 | 1977-08-02 | Rewo Chemische Werke G.M.B.H. | Process for preparing sulfosuccinates |
| US4056558A (en) * | 1971-12-06 | 1977-11-01 | Colgate-Palmolive Company | Sulfosuccinates of polyhydroxy tertiary amines as new detergent-softener compounds |
| CN102391158A (en) * | 2011-08-04 | 2012-03-28 | 浙江合诚化学有限公司 | Preparation method of isooctanol polyoxypropylene ether sodium sulfosuccinate diester |
| CN102503866A (en) * | 2011-09-29 | 2012-06-20 | 无锡青苹果工程勘察设计院 | Method for preparing sodium fatty acid methyl ester sulfonate with low content of disodium salt |
| CN106748911A (en) * | 2016-11-29 | 2017-05-31 | 四川花语精细化工有限公司 | A kind of method for efficiently synthesizing sulfosuccinic acid ethyoxyl ether alkyl monoester disodium salt |
| CN106750261A (en) * | 2017-01-12 | 2017-05-31 | 温州大学 | A kind of preparation method of the polymer fatliquoring agent with sulfosuccinate ester salt structure |
| CN109796378A (en) * | 2018-12-28 | 2019-05-24 | 广州花语精细化工有限公司 | A kind of preparation method of fatty alcohol sulfoacetic acid ester sodium |
| CN110526838A (en) * | 2019-09-24 | 2019-12-03 | 山东泰和水处理科技股份有限公司 | A kind of production method of sodium diethylhexyl sulfosuccinate |
| CN111087328A (en) * | 2019-11-07 | 2020-05-01 | 广州宏茂实业有限公司 | Preparation method of fatty alcohol sulfosuccinic acid monoester disodium salt |
-
2021
- 2021-04-30 CN CN202110479974.2A patent/CN113307747A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4056558A (en) * | 1971-12-06 | 1977-11-01 | Colgate-Palmolive Company | Sulfosuccinates of polyhydroxy tertiary amines as new detergent-softener compounds |
| US4039562A (en) * | 1975-02-21 | 1977-08-02 | Rewo Chemische Werke G.M.B.H. | Process for preparing sulfosuccinates |
| CN102391158A (en) * | 2011-08-04 | 2012-03-28 | 浙江合诚化学有限公司 | Preparation method of isooctanol polyoxypropylene ether sodium sulfosuccinate diester |
| CN102503866A (en) * | 2011-09-29 | 2012-06-20 | 无锡青苹果工程勘察设计院 | Method for preparing sodium fatty acid methyl ester sulfonate with low content of disodium salt |
| CN106748911A (en) * | 2016-11-29 | 2017-05-31 | 四川花语精细化工有限公司 | A kind of method for efficiently synthesizing sulfosuccinic acid ethyoxyl ether alkyl monoester disodium salt |
| CN106750261A (en) * | 2017-01-12 | 2017-05-31 | 温州大学 | A kind of preparation method of the polymer fatliquoring agent with sulfosuccinate ester salt structure |
| CN109796378A (en) * | 2018-12-28 | 2019-05-24 | 广州花语精细化工有限公司 | A kind of preparation method of fatty alcohol sulfoacetic acid ester sodium |
| CN110526838A (en) * | 2019-09-24 | 2019-12-03 | 山东泰和水处理科技股份有限公司 | A kind of production method of sodium diethylhexyl sulfosuccinate |
| CN111087328A (en) * | 2019-11-07 | 2020-05-01 | 广州宏茂实业有限公司 | Preparation method of fatty alcohol sulfosuccinic acid monoester disodium salt |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116947711A (en) * | 2023-09-19 | 2023-10-27 | 广州宏度精细化工有限公司 | Preparation method of fatty alcohol sulfosuccinic acid monoester disodium salt |
| CN116947711B (en) * | 2023-09-19 | 2024-02-09 | 广州宏度精细化工有限公司 | Preparation method of fatty alcohol sulfosuccinic acid monoester disodium salt |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102978048B (en) | Weakly acidic transparent soap and preparation method thereof | |
| US20100081716A1 (en) | Process for production of ether carboxylates | |
| CN103484264B (en) | High concentrated paste-shaped detergent | |
| CN103012220B (en) | Method for preparing powdery Alpha-olefin sulfonate and preparation device | |
| CN113307747A (en) | Fine-particle-size fatty alcohol disodium sulfosuccinate powder and production method thereof | |
| CN102787037A (en) | Transparent soap | |
| CN114133344A (en) | Method for preparing N-fatty acyl amino acid surfactant by high-temperature melting direct condensation | |
| CN1923852A (en) | One-step method of preparing oxidated carboxymethyl starch sodium from sweet potato starch | |
| CN105130805A (en) | Alcohol ether carboxylate preparation method | |
| JPH029853A (en) | N-alkoxyalkylamides of hydroxyacid and skin treatment composition containing the same | |
| CN102174503A (en) | Spray drying micro-capsulation process for high-yield alkaline protease | |
| CN104556116B (en) | A kind of method of aerosol auxiliary synthesis TS-1 molecular sieve | |
| CN111333531B (en) | Preparation process of lauroyl sarcosine sodium and application of lauroyl sarcosine sodium in daily chemical field | |
| CN102584642B (en) | Preparation method for ethoxyl sodium sulfonate fatty acid ester | |
| CN1078243C (en) | Non-phosphate high-effect liquid laundry detergent | |
| CN109369475A (en) | A kind of preparation method of double taurine based surfactants | |
| CN106821863A (en) | A kind of environment-friendly type bacterium-suppressing shower lotion and preparation method thereof | |
| CN112143588A (en) | Production process of high-efficiency fluffy sodium bicarbonate cleaning agent | |
| JP2000154163A (en) | Production of ether carboxylate | |
| CN109810798A (en) | Main lotion of cold washing for textile and preparation method thereof | |
| CN115836981A (en) | Upgraded children shower gel and preparation method thereof | |
| CN103449988B (en) | A kind of production method of 2-sub-borneol alkene base propionic aldehyde | |
| CN106350323A (en) | Perfumed soap grain production formula capable of improving bar output speed in perfumed soap grain forming process | |
| CN117243828A (en) | Double-layer cleaning composition and preparation method thereof | |
| CN117165376A (en) | Full-effect multifunctional neutral perfumed soap and processing technology 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 | ||
| CB02 | Change of applicant information |
Address after: 7th Floor, Building 4, Nan'an Science and Technology New Zone, Zigong City, Sichuan Province, 643000 Applicant after: SICHUAN FLOWER'S SONG FINE CHEMICAL CO.,LTD. Address before: 643000 12 floor, science and technology building, Huidong hi tech Zone, Zigong, Sichuan Applicant before: SICHUAN FLOWER'S SONG FINE CHEMICAL CO.,LTD. |
|
| CB02 | Change of applicant information | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210827 |
|
| RJ01 | Rejection of invention patent application after publication |