CN102994258A - Preparation method of composition for alpha-sulfo-group fatty acid alkyl ester salt-containing detergent - Google Patents
Preparation method of composition for alpha-sulfo-group fatty acid alkyl ester salt-containing detergent Download PDFInfo
- Publication number
- CN102994258A CN102994258A CN2012105577853A CN201210557785A CN102994258A CN 102994258 A CN102994258 A CN 102994258A CN 2012105577853 A CN2012105577853 A CN 2012105577853A CN 201210557785 A CN201210557785 A CN 201210557785A CN 102994258 A CN102994258 A CN 102994258A
- Authority
- CN
- China
- Prior art keywords
- sulfo
- fatty acid
- alpha
- alkyl ester
- acid alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention discloses a preparation method of composition for alpha-sulfo-group fatty acid alkyl ester salt-containing detergent, and the preparation method comprises the following steps of: spraying a non-ionic surface active agent onto powdery alpha-sulfo-group fatty acid alkyl ester salt in the manner of spraying, spraying and stirring to be formed into a compound of the non-ionic surface active agent and the powdery alpha-sulfo-group fatty acid alkyl ester salt and formed into a layer of liquid non-ionic film-packed layer on a surface; and adding zeolite, and evenly mixing into the composition for detergent. The flowability of the composition for the detergent prepared by the method is obviously higher than that of the alpha-sulfo-group fatty acid alkyl ester salt per se, the detergent is hard to bond to be clustered, and is stable in property, the requirement of the stable discharge in a production technology can be met, and the generation of the bad smell when the alpha-sulfo-group fatty acid alkyl ester salt-containing powdery detergent is stored can be effectively restrained.
Description
Technical field
The present invention relates to a kind of preparation method of composition for detergent, be specifically related to a kind of preparation method who contains the composition for detergent of alpha-sulfo-fatty acid alkyl ester salt (MES).
Background technology
Alpha-sulfo-fatty acid alkyl ester salt (MES), to adopt natural matter renewable resources Oleum Cocois, palm wet goods glyceride stock is through sulfonation, the product that obtains after the neutralization, it is a kind of well behaved tensio-active agent, has excellent lime soap dispersing power, low irritant and good biological degradability, compare in cost performance with the tensio-active agent of present use and to possess suitable advantage, and has an environment protection significance, be used for the Application and Development of petroleum replacing by product alkyl benzene sulphonate (ABS) at aspects such as washing composition and personal care articles, solving the industry, to rely on for a long time the common problem of oil significant, has broad prospects in the washing sector application.
At present, alpha-sulfo-fatty acid alkyl ester salt is applied to the alpha-sulfo-fatty acid alkyl ester salt that needs in the rear allotment of labor skill of washing powder sheet through special disintegrating process, and forming could be composite in washing powder behind the powdery.But since alpha-sulfo-fatty acid alkyl ester salt itself to have easy bonding agglomerating, poor fluidity and in the characteristic that just is in molten state more than 45 ℃, cause in feed bin, building bridge easily, latch up phenomenon, be difficult to guarantee to reach the requirement of stable processing technique blanking.The powdery alpha-sulfo-fatty acid alkyl ester salt produces false caking easily through transportation with after piling pressure, needs the process processing will become crumby material powder to be broken into tiny particle and can use, if storage period is longer, serious agglomeration problems can occur.Have data to show that MES is applied in the washing powder, the product stock time has been grown and offending smell can occur.
Summary of the invention
The object of the present invention is to provide a kind of preparation method who contains the composition for detergent of alpha-sulfo-fatty acid alkyl ester salt.The composition for detergent flowability that process the method makes is apparently higher than alpha-sulfo-fatty acid alkyl ester salt itself, and it is agglomerating to be difficult for bonding, stable in properties, satisfy the requirement of stable processing technique blanking, and can contain the unhappy smell generation of alpha-sulfo-fatty acid alkyl ester salt powdered detergent in storage process by establishment.
The objective of the invention is to be achieved through the following technical solutions: a kind of preparation method who contains the composition for detergent of alpha-sulfo-fatty acid alkyl ester salt may further comprise the steps:
(1) adopt spray pattern that nonionogenic tenside evenly is sprayed on the powdery alpha-sulfo-fatty acid alkyl ester salt, stir in order to form the mixture that ionic surfactant pack is wrapped up in the powdery alpha-sulfo-fatty acid alkyl ester salt while spraying, a described nonionogenic tenside part is by the internal penetration of osmosis to the MES particle, another part has formed liquid nonionic film integument on the composite particles surface, this nonionic film integument is kept apart MES and external environment, stop extraneous moisture to the MES effect, and as the required binding agent of the attached polymer molding in the subsequent handling;
(2) in the middle mixture that forms of step (1), add zeolite, be mixed into composition for detergent, the solid-state integument of mixture outside formation that nodulizing forms in step (1) occurs under the effect of the lip-deep liquid nonionic film integument of composite particles that described zeolite forms in step (1), liquid nonionic with the composite surface of formation in the step (1) adsorbs simultaneously, makes composition not have adhesive.The adsorption of zeolite has improved the flowability of the mixture that forms in the step (1).
The described zeolite of step of the present invention (2) is the 4A zeolite.
The present invention also comprises step (3): the composition for detergent that described step (2) obtains is through the processing of sieving, and acquisition meets the composition for detergent powder of the particle diameter of production requirement.
The order number that adopts when the composition for detergent in the step of the present invention (3) sieves is the above sieves of 16 orders, and preferred order number is the above sieves of 20 orders.
The present invention can adopt drum tumbler to produce continuously, also can adopt batch production.And in batch production, for fear of larger coarse particles occurring, operation below concrete the employing;
(1) to 3 ~ 5 minutes nonionogenic tenside of powdery alpha-sulfo-fatty acid alkyl ester salt sprinkling, stirs while spraying, in order to form the mixture that ionic surfactant pack is wrapped up in the powdery alpha-sulfo-fatty acid alkyl ester salt;
(2) add the part zeolite, mixed 10 ~ 15 minutes, to being uniformly dispersed;
(3) repeating step (1) and step (2) until the nonionogenic tenside in same batch and zeolite interpolation are complete, can obtain to contain the composition for detergent of alpha-sulfo-fatty acid alkyl ester salt.
The described zeolite of step of the present invention (2) is the 4A zeolite.
The present invention also comprises step (4): the composition for detergent that described step (3) obtains is through the processing of sieving, and acquisition meets the composition for detergent powder of the particle diameter of production requirement.
The order number that adopts when the composition for detergent in the step of the present invention (4) sieves is the above sieves of 16 orders, and preferred order number is the above sieves of 20 orders.
The present invention compared with prior art has the following advantages:
The present invention forms the solid-state integument of one deck by using by the effect of liquid non-ionic surfactant so that the zeolite of dryness can nodulizing occur on the surface of MES particle, thereby reaches the purpose that MES is isolated from the outside.Be coated in the MES particle surface liquid state nonionogenic tenside some penetrate into the MES granule interior by osmosis, form mixture with MES, a part forms solid-state integument with the surface that zeolite acts on composite particles.Be equivalent to again the MES surface by the MES composition of processing and established the protective layer of twice: the outside be solid-state zeolite layer together, mainly play improving liquidity, next plays and stops moisture, basic material that the effect of MES particle is caused that MES is hydrolyzed into the reaction of undesirable product disodium salt; The inside be the nonionogenic tenside layer together, mainly utilize nonionogenic tenside and water directly to contact the character that forms easily gel, stop moisture to enter into the hydrolysis that the MES layer causes MES by simple osmosis, moisture is inner by the molecular sieve structure that outer field zeolite adsorption enters zeolite under the obstruction of nonionogenic tenside layer.
MES after treatment can effectively protect under the effect of protective layer the MES particle of the inside to avoid the impact of extraneous chemical substance outside, can the establishment alpha-sulfo-fatty acid alkyl ester salt be applied in the generation of unpleasant peculiar smell in storage process behind the washing powder product; And can effectively avoid agglomerating, the powdery alpha-sulfo-fatty acid alkyl ester salt false caking after transportation and heap pressure of bonding between the MES particle.
The flowability of the composition of the present invention's preparation occurs significantly to change, and flowability significantly is better than raw material powdery MES.Tiny MES(mainly is that particle diameter is less than 100 purpose MES particles) aggregate that nodulizing forms larger particles occurs in particle under the effect of nonionogenic tenside, the dust that MES is caused is reduced significantly, efficiently solves the dust problem that exists in the powdery MES use procedure; Within the shelf lives of short-term, reduce the tendency of material clumps, thereby solved the problem of material blanking difficulty in the washing powder production process, improved the in-situ production environment of washing powder.
Embodiment
Below in conjunction with embodiment and test example the present invention is set forth.
The preparation method of following examples 1 ~ 6 can adopt the consecutive production mode, also can adopt the intermittent mode of production.
Produce continuously:
(1) gets nonionogenic tenside, powdery alpha-sulfo-fatty acid alkyl ester salt (MES) and zeolite by proportioning.
(2) powdery MES by bin blanking to the below conveying belt, through being delivered in the drum tumbler after the metering, the nonionic spraying gun is installed near drum tumbler feeding mouth place, nonionogenic tenside utilizes pipeline to be transported to be installed in the drop that forms atomizing on the atomizing nozzle in the drum tumbler by volumetric pump pressurization, be dispersed in the powdery MES particle, stir into the mixture of nonionogenic tenside and powdery MES while spraying, a described nonionogenic tenside part is by the internal penetration of osmosis to the MES particle, another part has formed the liquid nonionic film of one deck integument on the composite particles surface, this nonionic film integument is kept apart MES and external environment, stop extraneous moisture to the MES effect, and as the required binding agent of the attached polymer molding in the subsequent handling.
(3) add the 4A zeolite from the drum tumbler stage casing, on the composite particles surface of the second half section of drum tumbler 4A zeolite agglomeration at MES and nonionogenic tenside, mix and obtain composition for detergent, nodulizing occurs and forms solid-state integument in the 4A zeolite under the effect of the lip-deep liquid nonionic film integument of composite particles that step (2) forms, MES is wrapped up, make not have adhesive between composition grain.
(4) 16 mesh sieves or 20 mesh sieves are adopted in the composition for detergent that step (3) the is obtained processing of sieving when sieving, obtain to meet the composition for detergent powder of the particle diameter of production requirement.
Batch production:
(1) gets nonionogenic tenside, powdery alpha-sulfo-fatty acid alkyl ester salt (MES) and zeolite by proportioning.
(2) powdery MES is placed mixing equipment, opening device, by atomisation unit nonionogenic tenside is atomized, nonionogenic tenside drop after the atomizing is dispersed in the powdery MES particle, and at the liquid nonionic film of the surface of MES particle formation one deck, stir while spraying, this process exists tiny powdery MES generation nodulizing phenomenon to form oarse-grained agglomerate.The nonionogenic tenside spraying time is controlled in 3 ~ 5 minutes scopes.
(2) add the part zeolite, mixed 10 ~ 15 minutes, to being uniformly dispersed;
(3) repeating step (1) and step (2), until the nonionogenic tenside in same batch and zeolite interpolation are complete, can obtain to contain the composition for detergent of alpha-sulfo-fatty acid alkyl ester salt, part nonionogenic tenside and powdery alpha-sulfo-fatty acid alkyl ester salt form mixture, and at the liquid nonionic film integument of powdery alpha-sulfo-fatty acid alkyl ester salt surface formation, zeolite and remainder nonionogenic tenside form solid-state integument on described composite particles surface, and the powdery alpha-sulfo-fatty acid alkyl ester salt is isolated from the outside.
(4) composition for detergent that obtains of described step (3) adopts 16 mesh sieves or 20 mesh sieves through the processing of sieving when sieving, and obtains to meet the composition for detergent powder of the particle diameter of production requirement.
Proportioning between nonionogenic tenside described in the above-mentioned preparation, powdery alpha-sulfo-fatty acid alkyl ester salt and the zeolite is:
Nonionogenic tenside 1.0 ~ 6.0%
Powdery alpha-sulfo-fatty acid alkyl ester salt 65 ~ 94%
Zeolite 5 ~ 34%;
Above-mentioned nonionogenic tenside adopts ethoxylated alcohol nonionic surfactant.Ethoxylated alcohol nonionic surfactant comprises that average degree of ethoxylation is the C of 3 ~ 10 ethoxylation
10 ~ 16Alcohol, as: AEO7, AEO9, XL-80, SA-9, FMEE, TO-10 etc.Further, the preferred average degree of ethoxylation of the present invention is the C of 7 ~ 9 ethoxylation
10 ~ 16Straight chain alcohol or branched-chain alcoho, as: AEO7, AEO9, XL-80 etc.
The general formula of above-mentioned alpha-sulfo-fatty acid alkyl ester salt is:
Wherein, R
1That average carbon atom number is 8～20 alkyl, R
2Be that average carbon atom number is 1～4 alkyl, n=1 or 2, M are selected from Na
+, K
+, Li
+, NH
4 +, Ca
2+, Mg
2+Or their mixture.Preferred R
1That average carbon atom number is 14～16 alkyl, R
2Be methyl, M is Na
+
For the index of balance flowability and solvability two aspects proposes the granularity requirement.The particle size large fluidity is good, dust is few, but solvability is relatively poor, otherwise solvability is good, dust is large, poor fluidity, easily conglomeration, be unfavorable for production operation.Therefore, the size of powdery alpha-sulfo-fatty acid alkyl ester salt of the present invention require be: 90%(weight) above alpha-sulfo-fatty acid alkyl ester salt particle size in 20 orders ~ 100 order scopes.Further, the size of described powdery alpha-sulfo-fatty acid alkyl ester salt requires to be preferably: 90%(weight) above alpha-sulfo-fatty acid alkyl ester salt particle size in 30 orders ~ 90 order scopes.
Adopt the benefit of 4A zeolite to be: the 4A zeolite is present most widely used phosphorus-free adjuvant, itself has water-insoluble characteristic, inner trickle cage structure can be limited in the internal space with the part moisture that absorbs, can prevent effectively that composition from because of the moisture absorption deliquescence occuring in storage process, conglomeration, simultaneously, the 4A zeolite also has stronger adsorptive liquid material (nonionogenic tenside, such as AEO7, AEO9) ability, can make composition have dry and comfortable state, being in above characteristic 4A zeolite, that composition is had is mobile preferably with respect to single powdery MES.
Testing method
2.1. fluidity testing method:
With reference to the measurement at GB 11986-89 surfactant powders and particle slope of repose (corresponding national standard number and title).Slope of repose according to the definition powder at slope of repose is less, shows that the frictional force between powder granule is less, and also just the flowability of less powder is also just better for the resistance that powder runs in the process that flows.It is generally acknowledged good fluidity when θ≤30 °, can satisfy the need for liquidity in the production process during θ≤40 °, the result is referring to table 1.
Store smell 2.2. improve the washing powder finished product
Get the composition for detergent of embodiment 3 in the table 1 for the preparation of washing powder, Comparative Examples 1 ~ 4 is that two kinds of washing powder carry out accelerated test with the washing powder of direct usefulness 85% MES preparation, investigates the storage smell whether the present invention can improve washing powder.
1 ~ 7 starting material in the preparation method of washing powder: embodiment 7 ~ 10 and the Comparative Examples 1 ~ 4 all are prepared into the washing powder base-material by the mode of high tower spray drying, 8 ~ 12 starting material all add in the washing powder base-material in the rear allotment of labor's order stage by the washing powder production technique, finally obtain the washing powder finished product.
The accelerated test method: the PET clear vial of testing sample with 80 milliliters of volumes installed, reach the effect of sealing by covering tightly lid, the amount of sample accounts for 2/3rds of bottle volumetric quantity.Sample is placed 45 ℃/60% humidity, carry out the accelerated test in 4 weeks under 48 ℃ of two different conditions.Sample after the test is judged the character of smell by sense of smell, the results are shown in Table 2 and table 3.
Above embodiment only is used for setting forth the present invention, and protection scope of the present invention is not only to be confined to above embodiment.Those skilled in the art all can realize purpose of the present invention according to above content disclosed by the invention and scope that each parameter is got.
Claims (8)
1. a preparation method who contains the composition for detergent of alpha-sulfo-fatty acid alkyl ester salt is characterized in that, may further comprise the steps:
(1) adopt spray pattern that nonionogenic tenside is sprayed on the powdery alpha-sulfo-fatty acid alkyl ester salt, stir in order to help form the mixture of nonionogenic tenside and powdery alpha-sulfo-fatty acid alkyl ester salt while spraying, a described nonionogenic tenside part is by the internal penetration of osmosis to the MES particle, and another part has formed the liquid nonionic film of one deck integument on the surface of composite particles;
(2) add zeolite in the mixture in step (1), be mixed into composition for detergent, described zeolite forms solid-state integument by on the surface nodulizing occuring under the effect of the lip-deep liquid nonionic film integument of composite particles that forms in step (1).
2. the preparation method who contains the composition for detergent of alpha-sulfo-fatty acid alkyl ester salt according to claim 1, it is characterized in that, also comprise step (3): the detergent composition that described step (2) the obtains processing of sieving obtains to meet the composition for detergent powder of the particle diameter of production requirement.
3. the preparation method who contains the composition for detergent of alpha-sulfo-fatty acid alkyl ester salt according to claim 2 is characterized in that, the order number that adopts when the mixture in the described step (3) sieves is the above sieves of 16 orders.
4. according to claim 1 and 2 or the 3 described preparation methods that contain the composition for detergent of alpha-sulfo-fatty acid alkyl ester salt, it is characterized in that described zeolite is the 4A zeolite.
5. a preparation method who contains the composition for detergent of alpha-sulfo-fatty acid alkyl ester salt is characterized in that, may further comprise the steps:
(1) to 3 ~ 5 minutes nonionogenic tenside of powdery alpha-sulfo-fatty acid alkyl ester salt sprinkling, stirs while spraying, in order to form the mixture that ionic surfactant pack is wrapped up in the powdery alpha-sulfo-fatty acid alkyl ester salt;
(2) add the part zeolite, mixed 10 ~ 15 minutes, to being uniformly dispersed;
(3) repeating step (1) and step (2) until the nonionogenic tenside in same batch and zeolite interpolation are complete, can obtain to contain the composition for detergent of alpha-sulfo-fatty acid alkyl ester salt.
6. the preparation method who contains the composition for detergent of alpha-sulfo-fatty acid alkyl ester salt according to claim 5, it is characterized in that, also comprise step (4): the detergent composition that described step (3) the obtains processing of sieving obtains to meet the composition for detergent powder of the particle diameter of production requirement.
7. the preparation method who contains the composition for detergent of alpha-sulfo-fatty acid alkyl ester salt according to claim 6 is characterized in that, the order number that adopts when the mixture in the described step (3) sieves is the above sieves of 16 orders.
8. according to claim 5 or the 6 or 7 described preparation methods that contain the composition for detergent of alpha-sulfo-fatty acid alkyl ester salt, it is characterized in that described zeolite is the 4A zeolite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210557785.3A CN102994258B (en) | 2012-12-20 | 2012-12-20 | Preparation method of composition for alpha-sulfo-group fatty acid alkyl ester salt-containing detergent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210557785.3A CN102994258B (en) | 2012-12-20 | 2012-12-20 | Preparation method of composition for alpha-sulfo-group fatty acid alkyl ester salt-containing detergent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102994258A true CN102994258A (en) | 2013-03-27 |
| CN102994258B CN102994258B (en) | 2014-08-20 |
Family
ID=47923374
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210557785.3A Active CN102994258B (en) | 2012-12-20 | 2012-12-20 | Preparation method of composition for alpha-sulfo-group fatty acid alkyl ester salt-containing detergent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102994258B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106795453A (en) * | 2014-10-01 | 2017-05-31 | 狮王株式会社 | Coating alpha sulfo-fatty acid alkyl ester salt particle swarm and its manufacture method, and powder detergent |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1371361A (en) * | 1999-06-25 | 2002-09-25 | 狮王株式会社 | Process for producing alpha-sulfo-fatty acid alkyl ester salt |
| WO2010058599A1 (en) * | 2008-11-21 | 2010-05-27 | ライオン株式会社 | METHOD FOR PRODUCING AQUEOUS α-SULFO FATTY ACID ALKYL ESTER SALT SOLUTION |
-
2012
- 2012-12-20 CN CN201210557785.3A patent/CN102994258B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1371361A (en) * | 1999-06-25 | 2002-09-25 | 狮王株式会社 | Process for producing alpha-sulfo-fatty acid alkyl ester salt |
| WO2010058599A1 (en) * | 2008-11-21 | 2010-05-27 | ライオン株式会社 | METHOD FOR PRODUCING AQUEOUS α-SULFO FATTY ACID ALKYL ESTER SALT SOLUTION |
Non-Patent Citations (1)
| Title |
|---|
| 邓龙辉 等: "MES在浓缩洗衣粉中的应用研究", 《日用化学品科学》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106795453A (en) * | 2014-10-01 | 2017-05-31 | 狮王株式会社 | Coating alpha sulfo-fatty acid alkyl ester salt particle swarm and its manufacture method, and powder detergent |
| US10407645B2 (en) | 2014-10-01 | 2019-09-10 | Lion Corporation | Coated [alpha]-sulfofatty acid alkyl ester salt particle group, method for producing same, and powder detergent |
| CN106795453B (en) * | 2014-10-01 | 2020-04-03 | 狮王株式会社 | Coated α -sulfofatty acid alkyl ester salt particle group, method for producing same, and powder detergent |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102994258B (en) | 2014-08-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101659581A (en) | Anti-caking additive with slow release effect | |
| CN102153408A (en) | Antiblocking agent for macroelement water-dissolvable fertilizer, as well as preparation and application of the antiblocking agent | |
| KR20100028586A (en) | Solid dialysis preparation | |
| CN102994257B (en) | Composition for alpha-sulfo fatty acid alkyl ester salt-containing detergent, and application thereof | |
| JPS61188497A (en) | Additive for detergent and cleaner | |
| CN102994258B (en) | Preparation method of composition for alpha-sulfo-group fatty acid alkyl ester salt-containing detergent | |
| CN105330783B (en) | A kind of preparation method of silane-modified concrete inner curing agent | |
| CN112500936B (en) | Washing powder and production process thereof, granulating powder and granulating process of granulating powder | |
| US8916214B2 (en) | Process for preparing a free-flowing powder containing a deliquescent quaternary ammonium compound | |
| JP4417195B2 (en) | Production method of granular anionic surfactant | |
| CN103664376A (en) | Preparation method of coated controlled-release compound fertilizer | |
| CN100569227C (en) | Acetaminophen DC90 fine grained and preparation method thereof | |
| CN102504977B (en) | Color particle composition for powdery, flaky or particulate fabric washing agent | |
| CN102690143A (en) | Method for producing granular potassium chloride | |
| CN102618218B (en) | Special dust suppressor for bin for calcined coke finished products and preparation method for special dust suppressor | |
| CN102428921A (en) | Clodinafop-propargyl water dispersible granule and preparation method thereof | |
| CN104559123B (en) | Rubber vulcanizing accelerator CBS granulation specialist additive, the preparation method of the additive and prilling process | |
| JP2009091534A (en) | Method for producing powdery agent | |
| CN104341604B (en) | A kind of easily scattered preparation method without dust guar gum particle | |
| CN104884405A (en) | Wetting and hydrophobing additives | |
| CN109232682B (en) | Auxiliary agent composition for validamycin fermentation liquor spray drying and application thereof | |
| CN102618091A (en) | Method for preparing free-flowing granular iron oxide yellow pigment | |
| CN108530159A (en) | A kind of coating method of granulated fertilizer | |
| CN1062302C (en) | Method for continuously producing high-density powdery cleaner with good fluidity | |
| WO2012043699A1 (en) | Powder detergent composition and method for producing same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230703 Address after: 511455 No. 8 Xiaohu South Third Road, Xiaohu Island, Huangge Town, Nansha District, Guangzhou City, Guangdong Province Patentee after: GUANGZHOU LANGQI DAILY NECESSITIES CO.,LTD. Address before: No. 128, Huangpu Avenue East, Tianhe District, Guangzhou, Guangdong 510660 Patentee before: GUANGZHOU LONKEY INDUSTRIAL Co.,Ltd. |
|
| TR01 | Transfer of patent right |