ZA200101985B - Process for the preparation of calcium hydroxyalkane sulphonates. - Google Patents
Process for the preparation of calcium hydroxyalkane sulphonates. Download PDFInfo
- Publication number
- ZA200101985B ZA200101985B ZA200101985A ZA200101985A ZA200101985B ZA 200101985 B ZA200101985 B ZA 200101985B ZA 200101985 A ZA200101985 A ZA 200101985A ZA 200101985 A ZA200101985 A ZA 200101985A ZA 200101985 B ZA200101985 B ZA 200101985B
- Authority
- ZA
- South Africa
- Prior art keywords
- calcium
- process according
- olefins
- mixture
- olefin
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 22
- 229910052791 calcium Inorganic materials 0.000 title claims description 15
- 239000011575 calcium Substances 0.000 title claims description 15
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims description 14
- 238000002360 preparation method Methods 0.000 title claims description 7
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 title description 8
- 150000001336 alkenes Chemical class 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 25
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical group O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 24
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 19
- 238000006386 neutralization reaction Methods 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical group [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 6
- 239000000920 calcium hydroxide Substances 0.000 claims description 6
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000002585 base Substances 0.000 description 6
- 239000003599 detergent Substances 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- GGQQNYXPYWCUHG-RMTFUQJTSA-N (3e,6e)-deca-3,6-diene Chemical compound CCC\C=C\C\C=C\CC GGQQNYXPYWCUHG-RMTFUQJTSA-N 0.000 description 4
- 239000011552 falling film Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- -1 aliphatic monoolefin Chemical class 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000010687 lubricating oil Substances 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000010763 heavy fuel oil Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- LCCNCVORNKJIRZ-UHFFFAOYSA-N parathion Chemical compound CCOP(=S)(OCC)OC1=CC=C([N+]([O-])=O)C=C1 LCCNCVORNKJIRZ-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000008053 sultones Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 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
-
- 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
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
- C07C303/06—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Lubricants (AREA)
Description
' La . 7 WO 00/15607 PCT/EP99/06723 - 1 =
PROCESS FOR THE PREPARATION OF
CALCIUM HYDROXYALKANE SULPHONATES
The present invention relates to a process for the production of calcium hydroxyalkane sulphonates, which are suitable for use as fuel and lubricating oil additives.
The use of hydroxyalkyl sulphonates in detergent compositions is well-known. For example, US-A-3896057 discloses the use of water-soluble salts and acids of alkene sulphonates and hydroxyalkyl sulphonates in laundry detergents. US-A-3883583 discloses high
C10 molecular weight, oil-soluble, anionic surface active . agents consisting of sulphonates of an aliphatic monoolefin having a carbon number in the range of 32-40.
The surface active agents are said to be good reagents for dry-cleaning detergents.
EP-A-0537840 discloses a lubricating oil composition comprising a major proportion of a lubricating oil and a minor proportion of an alkaline earth metal salt selected from calcium and magnesium salts of a hydroxyalkyl sulphonic acid. The compounds are formed by the sulphonation of internal olefins which are disclosed as Cip - Ci; olefins, with Cis - Cy olefins with an average molecular weight of 230 being preferred.
EP-A-0351928 discloses a process for the preparation of internal olefin sulphonates which comprises reacting in a film reactor an internal olefin having from 8 to 26 carbon atoms with a sulphonating agent, in a molar ratio of sulphonating agent to internal olefin of 1:1 to 1.25:1, while cooling the reactor with a cooling means having a temperature not
- 2 = exceeding 35°C, and neutralising and hydrolysing the Co reaction product of the sulphonating step.
The successful preparation of hydroxyalkane sulphonates depends very much on the efficiency of the neutralisation/hydrolysis reactions. If these reactions - are not carried out efficiently, immediately following sulphonaticn, the reverse reaction to olefins and sulphur trioxide can occur, resulting in poor yields or poor quality products.
However, in each of the above publications the olefins are relatively pure, without contaminating materials present which may interfere with the various two-phase reactions and/or with the reaction products.
For example, high levels of paraffins would be detrimental to the effectiveness of sulphonation, neutralisation and hydrolysis, as the paraffins have the effect of slowing down the reactions. It is expected that high levels of paraffins negatively affect direct neutralisation (ring opening) of the beta-sultones ) produced in the sulphonation reaction. This may give : rise to unacceptably low conversicns to hydroxyalkane sulphonates, due to the reverse-reaction to sulphur trioxide and internal olefin.
This 1s expected to be even greater if bases of limited solubility in water, such as calcium hydroxide, are used in the neutralisation step.
US-A-5488148 discloses a process for sulphonating internal olefins in the presence of a hydrocarbon solvent but wherein the intermediate sulphonated compounds are neutralised with an aqueous solution of an alkali metal hydroxide, such as sodium hydroxide. The reverse-reaction to olefins and sulphur trioxide is counteracted by the use of an excess of the alkali metal hydroxide.
Co , ‘WO 00/15607 PCT/EP99/06723 - 3 =
The present invention is based on the realisation that mixtures of olefins and paraffins which emerge from a dehydrogenation plant, such as a PACOL-(OLEX) unit or a wax cracker unit fed with paraffins, or from a
Fischer-Tropsch unit fed with natural gas, other : hydrocarbons, or ccal, may be utilised directly as a feedstock in the production of calcium hydroxyalkane sulphonates.
Therefore in accordance with the present invention there is provided a process for the preparation of calcium hydroxyalkane sulphonates from a mixture comprising at least 20% by weight paraffins and at least 10% by weight olefins, comprising reacting the mixture with a sulphonating agent in a reactor, and neutralising and hydrolysing the reaction product in the presence of a calcium-containing base.
Preferably the olefins in said mixture are Cg_30 olefins, more preferably Ciy-3y olefins, particularly
Ci4-20 Olefins. Said base is preferably selected from
A 20 calcium hydroxide, calcium carbonate, calcium acetate i and calcium oxide. Particularly preferred is calcium hydroxide. The mixture may also comprise 1 to 25% by weight of oxygenated products, as for example found in the Fischer-Tropsch olefin/paraffin products.
The reaction product is suitable as a detergent in fuel and lubricant compositions.
In the process of the present invention, said mixture is typically reacted with a sulphonating agent in a reaction vessel with a subsequent reaction in a stirred neutralisation vessel. A final heating step may be carried out to hydrolyse any residual sultones produced by the reaction.
The feedstock that is typically used in the process mimics those produced from a PACOL~ (OLEX)
dehydrogenation plant, from a wax cracker after double ’ bond isomerisation, both fed with paraffins and, more particularly, those from a Fischer-Tropsch unit, e.g. from the Shell Middle Distillate Synthesis (SMDS) unit prior to hydrocracking, fed with methane, naphtha, residual fuel, or coal using a suitable Fischer-Tropsch catalyst, if required after double-bond isomerisation.
Said mixture preferably comprises 10% to 80% by weight olefins.
In a preferred embodiment of the present invention, the olefins present in the mixture are internal olefins.
The molar ratio of sulphonating agent to olefin is preferably in the range of 1:1 to 1.25:1.
The sulphonation of the olefins is preferably carried out with sulphur trioxide, preferably in a film reactor. The reactor is preferably cooled to a temperature not exceeding 35°C, more preferably in the range 10-30°C.
The neutralisation/hydrolysis is preferably carried out with the calcium-containing base in aqueous medium. LN
The neutralisation of the reaction product is preferably ) carried out with a molar excess of calcium-containing base, preferably at a base:olefin molar ratio of at least 1.2:1, more preferably a molar ratio of at least 1.5:1. Preferably, neutralisation is carried out at a temperature in the range 0°C to 80°C, more preferably 30 to 40°C.
The hydrolysing step is preferably carried out at a temperature in the range of 100°C to 250°C, more preferably 130°C to 200°C.
The process may be carried out batch wise, semi- continuously or continuously. The reaction is generally performed in a falling-film reactor (ffr) which is cooled by flowing water on the outside walls of the
Cn wo 00715607 PCT/EP99/06723 reactor. At the inner walls of the reactor, the mixture’ flows in a downward direction. The sulphur trioxide is diluted with a stream of nitrogen, air or any other inert gas into the reactor. The concentration of sulphur trioxide is generally 1-4 % by volume with respect to the carrier gas. The neutralisation reaction should be carried out immediately after the sulphonation reaction under high shear mixing conditions.
The following Examples illustrate the present invention.
Example 1
A mixture comprising 76.8% by weight paraffins, 3% by weight oxygenates and 20.2% by weight internal olefins (having a chain length distribution of: Cis 5%;
Cis 22.3%; Cis 31.8%; Cy7 23.8%; Cig 11.7%; Cig 4.3%; and
C20 1% w/w), was sulphonated in a continuous falling- film reactor having a diameter of 0.5 cm and a length of lm.
Sulphur trioxide was prepared by reacting sulphur a 20 dioxide with oxygen (dry air) over a vanadium pentoxide catalyst at about 450°C. a The mixture flowed along the inner part of the reactor walls as a flowing film in a downward direction and reacted with the sulphur trioxide (molar ratio sulphur trioxide:olefins was 1.2:1). The temperature of the reaction mixture was approximately 15°C. After the sulphonation process had been carried out, the reaction products were fed to a stirred slurry of calcium hydroxide in water (about 1.5 equivalents calcium hydroxide with respect to the amount of olefin feed).
The mixture was stirred vigorously {using an
Ultraturrax high-shear mixer) at about 40°C for at least 2 hours and subsequently transferred into a hydrolysis reactor and heated at 160°C for 1 hour.
Examples 2 and 3 : oo
Example 1 was repeated but using a pure olefin mixture instead of an olefin/paraffin mixture. In
Example 3, a larger falling-film reactor was used.
A comparison of the sulphonation conditions in i
Examples 1-3 is shown in Table 1 and an analysis of the reaction products is shown in Table 2.
Table 1
Sulphonation reactor ffr ffr ffr length (m) 1.0 1.0 6 diameter {cm) 0.5 0.5 2.54 temperature (°C) 15 15 23-24 conc. SOs; (%vol) 1 3 2.5 olefin C14-Ca2o Ci15—Cis C15-Cis mw olefin 224 230 230 mw sulphonate 674 686 686 iP throughput (mol/hour) 0.42 1.5 71.3 LE
SO;:0lefin molar ratio 1.2 1.2 1.06 :
Neutralisation/Hydrolysis
OH:olefin molar ratio 1.5 1.4 1.5
Taking account of the fact that the sulphur trioxide concentration in Example 1 was lowered to accommodate the longer residence time of the dilute olefin in the falling film reactor, Table 1 shows that the sulphonation and neutralisation conditions in all three Examples are similar, the sulphur trioxide:olefin 135 molar ratio being within the desired range.
oo WO 0015607 PCT/EP99/06723 pu 7 —_
Table 2 oo
Mass product (gq) 2058 307 450,000
Mass AM (g) 203.4 54.3 109,000
Yield (% mol/mol) 71 81 85
Table 2 shows that the yield of the calcium hydroxyalkane sulphonate, using olefin/paraffin mixtures (Ex 1) was comparable to those obtained using a pure
Ci5—-Ci9 internal olefin mixture (Ex 2 and 3). This shows that mixtures comprising high levels of paraffins are suitable feedstocks for the preparation of calcium hydroxyalkane sulphonates, which are suitable detergents for use in fuel and lubricant compositions.
Claims (12)
1. A process for the preparation of calcium hydroxy alkane sulphonates from a mixture comprising at least . 20% by weight paraffins and at least 10% by weight olefins, comprising reacting the mixture with a sulphonating agent in a reactor, and neutralising and hydrolysing the reaction product in the presence of a calcium-containing base.
2. A process according to claim 1, wherein the olefins in the mixture are Cg.3; olefins.
3. A process according to claim 1 or 2, wherein the mixture comprises 10 to 80% by weight olefins.
4. A process according to any one of the preceding claims, wherein the molar ratio of sulphonating agent to olefin is 1:1 to 1.25:1.
5. A process according to any one of the preceding : claims, wherein the reactor is cooled to a temperature not exceeding 35°C.
6. A process according to any one of the preceding > claims, wherein neutralisation is carried out at a AN temperature in the range 0 to 80°C.
7. A process according to any one of the preceding claims, wherein the hydrolysing step is carried out at a temperature in the range 100°C to 250°C.
8. A process according to any one of the preceding claims, wherein the sulphonating agent is sulphur trioxide.
9. A process according to any one of the preceding claims, wherein the calcium-containing base is present at a base:olefin molar ratio of at least 1.2:1.
10. A process according to any one of the preceding claims, wherein the calcium-containing base is calcium hydroxide.
-8/A ’ 11. A process according to claim 1, substantially as herein described and . exemplified.
12. Products when produced by the process of any one of the preceding claims. AMENDED SHEET
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP98307385 | 1998-09-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| ZA200101985B true ZA200101985B (en) | 2002-04-09 |
Family
ID=8235057
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| ZA200101985A ZA200101985B (en) | 1998-09-11 | 2001-03-09 | Process for the preparation of calcium hydroxyalkane sulphonates. |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP1109778A1 (en) |
| KR (1) | KR20010073142A (en) |
| AU (1) | AU5976899A (en) |
| CA (1) | CA2343025A1 (en) |
| CZ (1) | CZ2001860A3 (en) |
| ID (1) | ID27550A (en) |
| NZ (1) | NZ510204A (en) |
| PL (1) | PL346536A1 (en) |
| WO (1) | WO2000015607A1 (en) |
| ZA (1) | ZA200101985B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2542336B1 (en) * | 2010-03-05 | 2016-11-23 | H R D Corporation | High shear process for the production of halogenated and/or sulfonated paraffins |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8817293D0 (en) * | 1988-07-20 | 1988-08-24 | Shell Int Research | Process for preparation of internal olefin sulphonates |
| DE69212265T2 (en) * | 1991-10-07 | 1996-12-12 | Shell Int Research | Lubricant compositions containing overbased alkaline earth metal salts of hydroxyalkyl sulfonic acid |
| US5488148A (en) * | 1993-09-01 | 1996-01-30 | Vista Chemical Company | Process for sulfonating internal olefins |
-
1999
- 1999-09-09 AU AU59768/99A patent/AU5976899A/en not_active Abandoned
- 1999-09-09 PL PL99346536A patent/PL346536A1/en unknown
- 1999-09-09 CA CA002343025A patent/CA2343025A1/en not_active Abandoned
- 1999-09-09 EP EP99969086A patent/EP1109778A1/en not_active Withdrawn
- 1999-09-09 KR KR1020017003053A patent/KR20010073142A/en not_active Application Discontinuation
- 1999-09-09 CZ CZ2001860A patent/CZ2001860A3/en unknown
- 1999-09-09 WO PCT/EP1999/006723 patent/WO2000015607A1/en not_active Application Discontinuation
- 1999-09-09 ID IDW20010565A patent/ID27550A/en unknown
- 1999-09-09 NZ NZ510204A patent/NZ510204A/en not_active Application Discontinuation
-
2001
- 2001-03-09 ZA ZA200101985A patent/ZA200101985B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| KR20010073142A (en) | 2001-07-31 |
| AU5976899A (en) | 2000-04-03 |
| EP1109778A1 (en) | 2001-06-27 |
| WO2000015607A1 (en) | 2000-03-23 |
| ID27550A (en) | 2001-04-12 |
| CZ2001860A3 (en) | 2001-08-15 |
| NZ510204A (en) | 2002-08-28 |
| PL346536A1 (en) | 2002-02-11 |
| CA2343025A1 (en) | 2000-03-23 |
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