CN1116400C - Process for mfg. high density detergent granules - Google Patents
Process for mfg. high density detergent granules Download PDFInfo
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- CN1116400C CN1116400C CN96180269A CN96180269A CN1116400C CN 1116400 C CN1116400 C CN 1116400C CN 96180269 A CN96180269 A CN 96180269A CN 96180269 A CN96180269 A CN 96180269A CN 1116400 C CN1116400 C CN 1116400C
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Abstract
The present invention discloses a method for preparing freely flowing washing agent agglomerates containing high-concentration anionic surface active agents by a method of using a builder with ultra-fine grains.
Description
Technical field
The present invention relates to prepare the method for the high activity detergent agglomerate of unrestricted flow performance with improvement.
Background of the present invention
The cloth-washing detergent particle comprises one or more tensio-active agents (being generally anionic) and one or more washing assistants (being generally phosphoric acid salt, carbonate, zeolite etc.).Generally also this slurry spraying drying is formed particle and make detergent particles by the slurry for preparing various detergent ingredients.Also can be by in mixing tank, the mixture agglomeration of tensio-active agent and washing assistant being made these products.In agglomeration process, in can using and the anion surfactant of form or be incorporated into its form in the agglomeration process and neutralized by alkaline matter (as yellow soda ash) on the spot with acid.Optional detergent materials such as whitening agent, stain remover etc. can or can mix with it after agglomerate forms with tensio-active agent and washing assistant agglomeration.Generally speaking, come compared with those Betengent products of being produced by spraying drying, nodulizing can be produced more highdensity Betengent product.
It is gluing (the promptly poor free-flowing property) that is easy to show to a certain degree that various detergent agglomerates, particularly those surfactant concentrations are not less than the problem that 20% detergent agglomerate often runs into.In order to relax this problem, use various glidants such as clay, talcum, zeolite or silicon-dioxide usually.
Each relevant with the agglomeration method that is used to produce detergent particles has the representative instance of patent to be earlier: United States Patent (USP) 5,133,924 (Appel), United States Patent (USP) 5,164,108 (Appel), United States Patent (USP) 5,160,657 (Bartolloti), English Patent 1,517,713 (Unilever), European specification sheets 451,894 (Curis), United States Patent (USP) 5,108,646 (people such as Beerse), European patent specification 351,937 (people such as Hollingsworth) and United States Patent (USP) 5,205,958.
Target of the present invention provides the method for the detergent agglomerate that is used to produce the free-flowing character with high surfactant concentration and improvement.
Summary of the present invention
The present invention relates to comprise the method for following steps:
(a) mixture of each component of preparing washing agent in mixing tank, described each component comprises:
(1) compound of the acidic precursor that is selected from anion surfactant and anion surfactant of about 20%-about 35%;
(2) about 0%-'s about 65% is selected from polyphosphate, pyrophosphate salt and composition thereof
The particle phosphate builders;
(3) particle that is selected from yellow soda ash, salt of wormwood and composition thereof of about 6%-about 60%
Carbonate is wherein before using the acidity of anion surfactant in (a) (1)
During body, the amount of carbonate is be enough to neutralize at least 2 times of amount of described acidic precursor; Wherein, component (2) and (3) total amount at least about 20% satisfy 97% particle less than 50 microns and medium size be the 5-20 micron the granularity specification requirement and
(b) in second mixing tank, the mixture of step (a) is carried out agglomeration to produce detergent agglomerate.The present invention describes in detail
According to the present invention, we find to have high anionic surfactant concentration (promptly being not less than 20%) and contain in the process of anionic detergent agglomerate of carbonate and optional phosphate builders in preparation, satisfy 97% particle less than 50 microns and medium grain size during, the free-flowing character that can be improved if be used to prepare at least 20% of the granulated carbon hydrochlorate of described agglomerate/phosphatic total (promptly mixing) amount for the specification requirement of 5-20 micron.Raw material
Anion surfactant is the basal component by the composition of present method preparation.This class tensio-active agent is well-known in the art.Useful in the present invention anion surfactant is preferably basic metal (being sodium and potassium) salt or its mixture of alkylbenzene sulfonate or alkyl-sulphate.The example of other also useful anion surfactant is an alkali metal salt of alkane sulfonate, alkyl glycidyl ether sulfonate and sulfated alkyl ether (all have about 8-Yue 18 carbon atoms on its alkyl chain).It is about 1.0% that anion surfactant starting material moisture content preferably is less than, more preferably less than about 0.5%.Based on the total amount meter of the raw material that is added in the inventive method process, the amount of anion surfactant is about 35% for about 20-, is preferably about 20%-about 30%.
Be preferred for alkylbenzene sulfonate in present method and comprise that those have moieties is straight or branched, preferably have about 8-Yue 18 carbon atoms, more preferably have the alkylbenzene sulfonate of about 16 carbon atoms of about 10-.The mean chain length of the alkyl chain of alkylbenzene sulfonate is preferably about 11-Yue 14 carbon atoms.The alkylbenzene sulfonate that comprises branched-chain alkyl is called as ABS.What preferably be called as LAS is the alkylbenzene sulfonate of straight chain all, because its readily biodegradable more.
Be preferred for alkyl-sulphate in present method and comprise that those have moieties is straight or branched, preferably have about 8-Yue 24 carbon atoms, more preferably have about 20 carbon atoms of about 10-, be more preferably alkyl-sulphate with about 18 carbon atoms of about 12-.The mean chain length of the alkyl chain of alkyl-sulphate is preferably about 14-Yue 16 carbon atoms.Alkyl chain is preferably straight chain.Usually by will be, particularly reduce the fatty alcohol sulphuric acidization that makes and obtain alkyl-sulphate from the fat of fatty oil or Oleum Cocois and/or oily glyceryl ester from natural origin.
The mixture that preferred useful in the methods of the invention anion surfactant also can be alkylbenzene sulfonate and alkyl-sulphate (no matter being mixed together or adding respectively in mixing process).The ratio that preferably has alkylbenzene sulfonate and alkyl-sulphate is about 20: the mixture that 80-is about 80: 20, more preferably those to have ratio be about 40: the mixture that 60-is about 60: 40.Other disclosure of negatively charged ion synthetic surfactant can be found in United States Patent (USP) 3,664, and (Norris, on May 23rd, 1972 authorized) incorporates this paper herein by reference in 961.In implementing this method, anion surfactant can be imported with the form of its neutralization (being basic metal) or with the form of its unneutralized acidic precursor, as after this discussing, acidic precursor is neutralized by excessive alkaline carbonate under latter event.
Can randomly phosphoric acid salt be used as according to the washing assistant in the prepared composition of this prescribing method.Useful in the methods of the invention phosphate builders raw material is with the particulate form, and is made up of water-soluble salt (as sodium salt and sylvite) or its mixture of polyphosphate (as tri-polyphosphate, hexametaphosphate etc.) or pyrophosphate salt basically.The moisture content of phosphate builders raw material be preferably be less than about 2%, more preferably less than about 1%.Based on the total amount meter of the raw material that is added in the inventive method, it is about 65% that the amount of phosphate builders is generally about 5%-, and it is about 55% to be preferably about 15%-, more preferably about 25%-about 45%.The phosphate builders raw material generally by its manufacturer with pulverous form supply, having medium size usually is about 25 microns-Yue 50 microns.The carbonate raw material generally by its manufacturer with granular form supply, having granularity usually is about 25 microns-Yue 150 microns.For " same as before (asis) " medium size of polyphosphate and carbonate with the different supply places of production and different suppliers and different.For multi-phosphate detergent builders and/or carbonate are used for the present invention, be ground into phosphoric acid salt/carbonate particle total amount of being used for present method at least about 20%, preferably satisfying 97% particle at least about 40% is the 5-20 micron less than 50 microns (preferably less than 40 microns) and medium size, is preferably the granularity of the specification requirement of 10-20 micron.A kind of or both in carbonate, the phosphoric acid salt can be ground to obtain a certain amount of total phosphoric acid salt/carbonate particle in desired particle size requires.Preferably at least 40%, more preferably at least 70% particle should satisfy required specification.All particles that are generally used for phosphoric acid salt in present method and carbonate will be in total magnitude range of 5-300 micron.Grinding can be finished in conventional powder grinding plant such as ACM size classification mill (HosokawaMicron Powder Systems).During the grinding or after grinding, as needs, can be with gradation to guarantee that stand-by abrasive grains is in desired specification limit.Can use MicronPulsaire Classifier (Hosokawa Powder Systems) to be used for classification.
Preferably using phosphate builders in the method is tripoly phosphate sodium STPP (STPP), and STPP can buy from for example FMC Corp..Another kind of preferred phosphate builders is tetrasodium pyrophosphate (TSPP), and TSPP can buy from for example FMC Corp..
The inventive method is used the preferred granulated alkali metal carbonate of being made up of yellow soda ash or salt of wormwood or its mixture basically as washing assistant.If use the acidic precursor of anion surfactant in the method, then carbonate also plays the work of neutralizing agent in order to acidic precursor is changed into an alkali metal salt.It is about 2% that the moisture content of alkaline carbonate raw material preferably is less than, more preferably less than about 1%.Based on the gross weight meter that adds the raw material in the inventive method to, the amount of alkaline carbonate is about 60% for about 6%-, and it is about 50% to be preferably about 10%-, more preferably about 30%-about 40%.
For the acidic precursor of neutralize anionic surfactant, each carbonate ion (CO
3 =) must with two acidic hydrogen (H
+) reaction.From this reaction, need in theory can to determine the amount of the carbonate of neutralize anionic surfactant acid precursor.When using the acidic precursor of anion surfactant in the method, the amount that adds the carbonate in this process be neutralize in theory this acid aequum at least about 2 times.The amount of preferred carbonate is in needing and about 4 times-Yue 12 times of the amount of acidic precursor, more preferably from about 6 times-Yue 12 times.
In the methods of the invention, when through after the described process, in fact be present in only water in the material and be the moisture that is present on a small quantity in the raw material and by in the anionic surfactant acid precursor and the water that is produced.In the whole process, it is about 10% that the maximum value of the water content in institute's material processed is preferably, more preferably about 7%, is more preferably approximately 5%, most preferably is about 3%.The detergent agglomerate that is made by present method has water absorbability to a certain degree, and obtains moisture from atmosphere.
The detergent agglomerate that derives from the inventive method generally has about 200 microns-Yue 800 microns, more preferably about 300 microns-Yue 700 microns, is more preferably about 400 microns-Yue 600 microns mean particle size.
An advantage of the inventive method is to reduce or to cancel the use of glidant such as silicon-dioxide, clay, diatomite, silico-aluminate (as zeolite), perlite and calcite in fact.Method steps
The present invention can carry out with continuous or batch-wise mode.Preferred processing continuously.The present method of carrying out is described below in a continuous manner:
The first step of present method is preferably carried out in high speed, high shear mixer.The mixing tank that is applicable to this step comprises for example Loedige CB
, Shugi Granulator
And Drais K-TTP
The preferred mixing tank that is used for first step is Loedige CB
In general, to have diameter be cylindrical mixing section for the about 1m of about 0.3m-, length for the about 3.5m of about 1m-to super mixer substantially.The preferred mixing tank that is used for first step has an axis that connects blender blade, preferred axis is with the about 1800rpm of about 300rpm-, more preferably from about the about 1250rpm of 350rpm-is more preferably the speed rotation of the about 1000rpm of about 400rpm-, and is lower for the common speed of bigger mixing tank.Super mixer is preferably with water jacket, make cooling-water flowing through the mixing tank chuck to remove the heat that neutralization reaction is produced.
First step for present method, generally various basic raw materials (being the acid precursor of tensio-active agent or tensio-active agent, carbonate and phosphoric acid salt (if you are using)) are sent to super mixer and closely mix during by mixing section when it at the end near cylindrical mixing section, and mixture is from the other end discharge near cylindrical mixing section.The through-put rate of average is about 0.2 Kilograms Per Second-Yue 17 Kilograms Per Seconds, especially is about 2 Kilograms Per Seconds-Yue 13 Kilograms Per Seconds, uses bigger mixing tank can obtain higher through-put rate.The mean residence time of raw material in the first step mixing tank was preferably about 2 seconds-Yue 30 seconds, more preferably about 5 seconds-Yue 20 seconds, was more preferably about 10 seconds-Yue 15 seconds.
When using the acidic precursor of anion surfactant, in the first step of present method, most acid is neutralized by carbonate.Preferred all basically neutralizing effects all take place in first step.Yet neutralization reaction can be finished after the first step mixing tank is discharged at mixture.Acid is neutralized basically fully during this process.Preferably be that about 5 ℃-Yue 25 ℃ water coolant is sent in the water jacket of super mixer with temperature.The temperature of the mixture of discharging from super mixer is generally about 35 ℃-Yue 70 ℃, is preferably about 45 ℃-Yue 55 ℃.
The raw material of discharging from the first step mixing tank is generally sent into the mixing tank of second step immediately.The mean residence time of raw material between two mixing tanks preferably was less than about 5 minutes, more preferably less than about 1 minute.
Second step of the inventive method is preferably carried out in moderate-speed mixers.The mixing tank that is applicable to this step comprises the ploughshare mixing tank, for example Loedige KM
And Drais K-T
LoedigeKM
It is the preferred mixing tank that is used for the inventive method second step.In general, to have diameter be cylindrical mixing section for the about 2m of about 0.6m-, length for the about 5m of about 2m-to moderate-speed mixers substantially.Preferred mixing tank has an axis that connects blender blade, and preferred axis is with the about 160rpm of about 40rpm-, and more preferably from about the about 140rpm of 45rpm-is more preferably the speed rotation of the about 100rpm of about 50rpm-, and is lower for the common speed of bigger mixing tank.Moderate-speed mixers is preferably with water jacket, make cooling-water flowing through the mixing tank chuck the product temperature in moderate-speed mixers is remained on approximately its feeding temperature.
Second step for present method, usually the mixture of the various raw materials that will discharge from the first step mixing tank is sent into the moderate-speed mixers at the end near cylindrical mixing section, mixed when it passes through mixing section, and in the other end discharge near cylindrical mixing section.In general, the through-put rate of second step and first step is the same.The mean residence time of raw material in the second step mixing tank was preferably about 0.5 minute-Yue 10 minutes, more preferably about 0.5 minute-Yue 5 minutes, was more preferably about 1 minute-Yue 4 minutes.
The temperature of the mixture of discharging from moderate-speed mixers is generally about 35 ℃-Yue 70 ℃, is preferably about 45 ℃-Yue 55 ℃.
The purpose that can be used for " same as before " washing composition by the agglomerate of present method production herein.But being usually included in other various materials in the detergent composition can be included in fact in the agglomerate itself or in one or more follow-up mixing steps and mix with agglomerate.These materials include organic polymer washing assistant such as polycarboxylate (referring to United States Patent (USP) 4,144,226Diehl), as being disclosed in United States Patent (USP) 3,159,581,3,213,030,3,422,021,3,442,137,3,400, phosphonic acids washing assistant in 176 and 3,400,148, as being disclosed in United States Patent (USP) 4, alkalimetal silicate in 605,509, zeolite builders, SYNTHETIC OPTICAL WHITNER, bleach-activating agent, soil-suspending agent, enzyme, spices, sequestrant and other tensio-active agent such as alkyl polyethoxye compound, ethoxylated fatty amine etc.
Except as otherwise noted, otherwise all percentage ratios and ratio in this patent file are " by weight ".This paper is all incorporated in patent that all confirm herein and patent application by reference into.
The present invention will describe by following examples, but should think limitation of the present invention in no instance.
Example I
In this embodiment, the following agglomeration composition of preparation.
| A | B | |
| Sodium alkyl benzene sulfonate | 27.5％ * | 27.5％ * |
| Yellow soda ash | 40.0 ** | 32.0 *** |
| Tri-polyphosphate | 21.9 | 19.6 |
| Sodium sulfate | 0.6 | 0.7 |
| Zeolite | 7.2 | 15.2 |
| Moisture | 1.9 | 4.7 |
| Other material | To 100 | To 100 |
*26.5% is unneutralized alkyl benzene sulphonate (ABS).
*Preceding 44% alkyl benzene sulphonate (ABS) neutralizes.
* *Preceding 36% alkyl benzene sulphonate (ABS) neutralizes.
Use the acidic precursor of alkyl benzene sulfonate surfactant to make composition A according to the inventive method.Use Loedige CB mixing tank in step 1, and use the LoedigeKM mixing tank in step 2.All raw materials (except that zeolite) add in step 1, and 20% zeolite (i.e. 1.44 weight parts) adds in step 2.To " obtain " 97% granularity is that all yellow soda ash of 50 microns grind and are 10 micron specification requirement to satisfy 97% less than 40 microns and medium size by size classification less than about 200 microns and medium size." obtaining " 97% granularity that tripolyphosphate has be 50 microns less than 200 microns and medium size.This tripolyphosphate need not grind and size classification before using.Therefore, 67% the 44 weight part carbonate that are used for preparing the phosphoric acid salt of composition and carbonate total amount are carried out pre-treatment to satisfy the requirement of granularity specification required for the present invention.
Make composition B in the mode identical, different carbonate and phosphatic " obtaining " granularities used simultaneously with composition A.In addition, in composition B, add 90% of zeolite, and add 10% (i.e. 1.52 weight parts) of zeolite in step 2 in step 1.
Composition A has excellent free-flowing character, and composition B has relatively poor free-flowing character.
Two kinds of compositions are all carried out " arch test ".In this test, can determine existing potential flowability problem in transportation equipment and storage warehouse in formation arcual ability under the pressure with a kind of agglomerate product.In this test, the agglomerate product is pressed into the arcual shape in cylindrical vessel, arch is smashed the tackiness that needed power is estimated product by measuring.Product is adhesion more, and then required power is just big more.Need 1.5 kilograms power for composition A, then need the power of 3-5 kilogram for composition B.
Claims (8)
1. be used for process for making detergent agglomerates, it may further comprise the steps:
(a) mixture of each component of preparing washing agent in mixing tank, described mixing tank have with the axis of 300rpm-1800rpm rotation and 2 seconds-30 seconds mean residence time, and described each component comprises:
(1) surfactant compounds of the acidic precursor that is selected from anion surfactant and anion surfactant of about 20%-about 35%;
(2) about 0%-'s about 65% is selected from polyphosphate, pyrophosphate salt and composition thereof
The particle phosphate builders;
(3) particle that is selected from yellow soda ash, salt of wormwood and composition thereof of about 6%-about 60%
Carbonate is wherein before using the acidity of anion surfactant in (a) (1)
During body, the amount of carbonate be enough to neutralize described surfactant acid amount at least
2 times; Wherein, component (2) and (3) total amount to satisfy 97% particle at least about 20% be the requirement of the granularity specification of 5-20 micron less than 50 microns and medium size, the temperature of the mixture of discharge be 35 ℃-70 ℃ and
(b) in moderate-speed mixers, the mixture of step (a) is carried out agglomeration to produce detergent agglomerate, described mixing tank has with the axis of 40rpm-160rpm rotation and 0.5 minute-10 minutes mean residence time, and the temperature of the mixture of discharge is 35 ℃-70 ℃.
2. the process of claim 1 wherein that the amount of component (a) (1) is about 20%-about 30%.
3. the process of claim 1 wherein that the amount of component (a) (2) is about 5%-about 65%.
4. the process of claim 1 wherein that component (a) (1) is the acidic precursor of anion surfactant, and the amount of component (a) (3) be in and about 4 times-Yue 12 times of the required amount of component (a) (1).
5. the method for claim 1, wherein component (a) (1) is the acidic precursor of anion surfactant, the amount of component (a) (1) is about 20%-about 30%, the amount of component (a) (2) is about 55% for about 15%-, and the amount of component (a) (3) be in and about 4 times-Yue 12 times of the required amount of component (a) (1).
6. each method among the claim 1-5, wherein component (a) (2) and (a) (3) total amount at least 40% to satisfy 97% particle be the requirement of the granularity specification of 5-20 micron less than 50 microns and medium size.
7. the method for claim 6, wherein component (a) (2) and (a) at least 70% requirement of satisfying the granularity specification of claim 6 of (3) total amount.
8. the method for claim 6, wherein 97% described particle is less than 40 microns.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96180269A CN1116400C (en) | 1996-02-29 | 1996-02-29 | Process for mfg. high density detergent granules |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96180269A CN1116400C (en) | 1996-02-29 | 1996-02-29 | Process for mfg. high density detergent granules |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1217019A CN1217019A (en) | 1999-05-19 |
| CN1116400C true CN1116400C (en) | 2003-07-30 |
Family
ID=5127777
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96180269A Expired - Lifetime CN1116400C (en) | 1996-02-29 | 1996-02-29 | Process for mfg. high density detergent granules |
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|---|---|
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070249513A1 (en) * | 2006-04-20 | 2007-10-25 | Mort Paul R | Solid particulate laundry detergent composition comprising aesthetic particle |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0351937A1 (en) * | 1988-07-21 | 1990-01-24 | Unilever Plc | Detergent compositions and process for preparing them |
| EP0420317A1 (en) * | 1989-09-29 | 1991-04-03 | Unilever N.V. | Process for preparing high bulk density detergent compositions |
| EP0555622A1 (en) * | 1992-02-14 | 1993-08-18 | The Procter & Gamble Company | Process for making detergent granules by neutralisation of sulphonic acids |
-
1996
- 1996-02-29 CN CN96180269A patent/CN1116400C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0351937A1 (en) * | 1988-07-21 | 1990-01-24 | Unilever Plc | Detergent compositions and process for preparing them |
| EP0420317A1 (en) * | 1989-09-29 | 1991-04-03 | Unilever N.V. | Process for preparing high bulk density detergent compositions |
| EP0555622A1 (en) * | 1992-02-14 | 1993-08-18 | The Procter & Gamble Company | Process for making detergent granules by neutralisation of sulphonic acids |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1217019A (en) | 1999-05-19 |
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