CN101302175B - Process for preparing alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate - Google Patents
Process for preparing alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate Download PDFInfo
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- CN101302175B CN101302175B CN200810055355.5A CN200810055355A CN101302175B CN 101302175 B CN101302175 B CN 101302175B CN 200810055355 A CN200810055355 A CN 200810055355A CN 101302175 B CN101302175 B CN 101302175B
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- alkyl
- phenol ether
- alkyl phenol
- sulphonate
- ethoxylated
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 125000005233 alkylalcohol group Chemical group 0.000 title claims abstract description 38
- 125000000217 alkyl group Chemical group 0.000 title claims description 74
- 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 title claims description 64
- LRMHFDNWKCSEQU-UHFFFAOYSA-N ethoxyethane;phenol Chemical compound CCOCC.OC1=CC=CC=C1 LRMHFDNWKCSEQU-UHFFFAOYSA-N 0.000 title claims description 33
- 238000004519 manufacturing process Methods 0.000 title 1
- -1 alkyl phenol ether Chemical compound 0.000 claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000002904 solvent Substances 0.000 claims abstract description 28
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 21
- 238000010992 reflux Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 3
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 33
- 238000005516 engineering process Methods 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 19
- 239000001103 potassium chloride Substances 0.000 claims description 19
- 235000011164 potassium chloride Nutrition 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 11
- 125000004964 sulfoalkyl group Chemical group 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 150000003460 sulfonic acids Chemical class 0.000 claims description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 230000018044 dehydration Effects 0.000 claims description 7
- 238000006297 dehydration reaction Methods 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 125000005037 alkyl phenyl group Chemical group 0.000 claims description 4
- 229910052728 basic metal Inorganic materials 0.000 claims description 4
- 150000003818 basic metals Chemical class 0.000 claims description 4
- 239000012188 paraffin wax Substances 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229910000102 alkali metal hydride Inorganic materials 0.000 claims description 2
- 150000008046 alkali metal hydrides Chemical class 0.000 claims description 2
- 150000004703 alkoxides Chemical class 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 abstract description 3
- RZXLPPRPEOUENN-UHFFFAOYSA-N Chlorfenson Chemical compound C1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C=C1 RZXLPPRPEOUENN-UHFFFAOYSA-N 0.000 abstract 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 abstract 2
- 238000003756 stirring Methods 0.000 description 12
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000002191 fatty alcohols Chemical class 0.000 description 5
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 description 3
- XCIXBINTPHGFFK-UHFFFAOYSA-N 2-hydroxyethanesulfonic acid;potassium Chemical compound [K].OCCS(O)(=O)=O XCIXBINTPHGFFK-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229940045998 sodium isethionate Drugs 0.000 description 2
- LADXKQRVAFSPTR-UHFFFAOYSA-M sodium;2-hydroxyethanesulfonate Chemical compound [Na+].OCCS([O-])(=O)=O LADXKQRVAFSPTR-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical group O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- BKXAWCWTSBWIRG-UHFFFAOYSA-N 4-hydroxybutane-1-sulfonic acid;sodium Chemical compound [Na].OCCCCS(O)(=O)=O BKXAWCWTSBWIRG-UHFFFAOYSA-N 0.000 description 1
- UMJJNXFVAMHNIE-UHFFFAOYSA-N ClCC[Na] Chemical compound ClCC[Na] UMJJNXFVAMHNIE-UHFFFAOYSA-N 0.000 description 1
- CLALDLKARGDSEE-UHFFFAOYSA-N OC[K] Chemical compound OC[K] CLALDLKARGDSEE-UHFFFAOYSA-N 0.000 description 1
- BSMWUNYNFLXPNB-UHFFFAOYSA-N [H]OC([H])([H])C([H])([H])C[K] Chemical compound [H]OC([H])([H])C([H])([H])C[K] BSMWUNYNFLXPNB-UHFFFAOYSA-N 0.000 description 1
- GHVZOJONCUEWAV-UHFFFAOYSA-N [K].CCO Chemical compound [K].CCO GHVZOJONCUEWAV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a process for making alkyl alcohol ether sulfonate or alkyl phenol ether sulfonate, comprising the steps of: reacting alkyl alcohol ether or alkyl phenol ether with equal molar ratio with strong alkali or alkali metal to generate sodium salt or potassium salt of the alkyl alcohol ether or the alkyl phenol ether; adding hydroxyalkyl sulfonate and an alkaline catalyst to the sodium salt or the potassium salt of the alkyl alcohol ether or the alkyl phenol ether at a room temperature; adding solvent at the same time; reacting for 0.5 to 5 hours between 100 and 220 DEG C by means of azeotropy refluxing or evacuation, removing water which is generated by reaction, and obtaining alkyl alcohol ether sulfonate or alkyl phenol ether sulfonate. The invention has the advantages of convenient operation, simple process, easy control and low cost and so on.
Description
Technical field
The present invention relates to a kind of technology with alkyl ethoxylated or alkyl phenol ether and hydroxyalkylated sulfonic acid salt generation sulfoalkyl prepared in reaction alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate.
Background technology
Alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate are a kind of for adapting to the NEW TYPE OF COMPOSITE tensio-active agent that Development of Tertiary Oil Recovery Technology produces.At present, the technological line for preparing alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate in the world mainly contains sulphite sulfonation method and sulfoalkyl method.Wherein the sulphite sulfonation method always can relate to a kind of halogen-containing reactive group, can produce some poisonous and harmfuls and have corrosive material, not only contaminate environment but also etching apparatus in its preparation process.The sulfoalkyl method is alkyl ethoxylated or alkyl phenol ether R-O-(R in the presence of certain temperature, pressure and catalyzer
1O)
nH and sulfoalkyl agent generation homogeneous phase or inhomogeneous reaction, on its molecule, introduce the anion sulfoacid base of a strong hydrophilicity type, thereby make alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate, reaction principle is sulfoalkyl agent and alkyl ethoxylated or alkyl phenol ether R-O-(R
1O)
nNucleophilic substitution reaction between H.The sulfoalkyl agent of current application mainly is propane sultone, chloroethyl sodium sulfonate, sodium vinyl sulfonate, sodium isethionate etc.The pertinent literature report that synthesizes and use about alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate, as the patent US4226807 of U.S. Texaco company application in 1980, employing vacuumizes, the method for logical rare gas element, sulfonic acid and sulfonate by fatty alcohol-ether and hydroxyl have made alkyl alcohol ether sulphonate under the katalysis of alkali aqueous solution, produce a large amount of foams in the reaction process, and later stage system thickness very; The patent US4978780 of Germany BASF AG nineteen ninety application is in the presence of the phase-transfer catalyst tri-n-octyl methyl ammonium chloride, synthesized the fatty alcohol-ether sodium sulfonate by sodium vinyl sulfonate and fatty alcohol-polyoxyethylene ether, and proposed to obtain the alkyl alcohol ether sulphonate of different performance by the material ratio that changes alcohol ether and sodium vinyl sulfonate; The synthetic report of domestic relevant alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate is less.
There is following problem in the existing technology by alkyl ethoxylated or alkyl phenol ether and hydroxyalkylated sulfonic acid salt generation sulfoalkyl prepared in reaction alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate:
(1) there are a large amount of foams to produce in the technological process;
(2) the reaction later stage system very thickness that becomes;
(3) adopt the mode that vacuumizes to react, have a small amount of lower boiling raw material and moisture and taken away together, both wasted raw material, can influence the composition of product again, and difficult control of temperature.
Summary of the invention
The purpose of this invention is to provide that a kind of preparation technology is easy, the preparation alkyl alcohol ether sulphonate of easy handling or the technology of alkyl phenol ether sulphonate.
The present invention is a kind of technology for preparing alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate, and the concrete operations step is as follows:
(1) sodium salt or the sylvite of preparation alkyl ethoxylated or alkyl phenol ether
The sodium salt or the sylvite of preparation alkyl ethoxylated or alkyl phenol ether mainly contain following 4 kinds of methods:
A, etc. alkyl ethoxylated or the alkyl phenol ether and the highly basic azeotropic dehydration of mol ratio, azeotropic 2～5 hours complete reactions that reflux in the presence of solvent steam solvent fully, obtain the sodium salt or the sylvite of alkyl ethoxylated or alkyl phenol ether;
B, etc. alkyl ethoxylated or the alkyl phenol ether and the alkali-metal hydride azeotropic dehydration of mol ratio, azeotropic 2～5 hours complete reactions that reflux in the presence of solvent steam solvent fully, obtain the sodium salt or the sylvite of alkyl ethoxylated or alkyl phenol ether;
C, etc. the alkyl ethoxylated of mol ratio or alkyl phenol ether and basic metal under protection of inert gas, obtained the sodium salt or the sylvite of alkyl ethoxylated or alkyl phenol ether in 1～24 hour in 0 ℃～120 ℃ reactions;
D, etc. the alkyl ethoxylated of mol ratio or alkyl phenol ether and alkali-metal short chain alkoxide pure permutoid reaction takes place, by distillation the short chain alcohol that generates is steamed simultaneously, reach until temperature till the boiling point of alkyl ethoxylated or alkyl phenol ether, obtain the sodium salt or the sylvite of alkyl ethoxylated or alkyl phenol ether;
Used highly basic is potassium hydroxide or sodium hydroxide among the A as mentioned above.
Used basic metal is potassium or sodium among B, C, the D as mentioned above.
Used short chain alcohol is methyl alcohol or ethanol among the D as mentioned above.
(2) sulfoalkyl reaction
At room temperature add hydroxyalkylated sulfonic acid salt, basic catalyst in the sodium salt of alkyl ethoxylated that any one method makes in by step (1) or alkyl phenol ether or the sylvite, add solvent simultaneously, the mode that adopts azeotropic to reflux or vacuumize was in 100～220 ℃ of reactions 0.5～5 hour, remove the water that reaction generates, obtain alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate;
Wherein the mol ratio of alkyl ethoxylated or alkyl phenol ether and hydroxyalkylated sulfonic acid salt is 0.6～5: 1, and the mol ratio of alkyl ethoxylated or alkyl phenol ether and basic catalyst is 10～1: 1.
The present invention also is included in step (2) the reaction forward reaction still and adds alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate, and add-on is 0.5%～50% of alkyl ethoxylated or an alkyl phenol ether quality, can further improve productive rate, shortens the reaction times.
Aforesaid vacuumizing is logical rare gas element, and vacuum tightness is 0.001～0.1Mpa.
Before carrying out the sulfoalkyl reaction, must earlier alkyl ethoxylated or alkyl phenol ether be made corresponding sodium salts or sylvite as mentioned above.
The structural formula of aforesaid alkyl ethoxylated or alkyl phenol ether is R-O-(R
1O)
nH, wherein R is C
8-C
24Alkyl or alkyl phenyl, R
1Be C
2-C
4Alkylidene group, n is 0-30.
The structural formula of aforesaid hydroxyalkylated sulfonic acid salt is HO-R
2-SO
3M, wherein R
2Be C
1-C
4Alkyl, M is sodium or potassium.
Aforesaid basic catalyst can be potassium hydroxide, sodium hydroxide etc., and directly adds with solid state.
Aforesaid solvent can be C
6～C
20Alkane (comprising normal paraffin, isoparaffin, branched paraffin, naphthenic hydrocarbon), whiteruss, 190
#Solvent oil, 200
#The solvent wet goods.
The hydroxyalkylated sulfonic acid salt of Jia Ruing can be granular as mentioned above, also can be pulverous.
Aforesaid reactor has whipping appts.
Aforesaid experimental installation all is equipped with moisture eliminator at the position that communicates with air.
Compare with existing preparation alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate technology, the present invention prepares alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate technology has the following advantages:
(1) preparation alkyl alcohol ether sulphonate of the present invention or alkyl phenol ether sulphonate technology can adopt the mode that azeotropic refluxes, and easy to operate, technology is simple, be easy to control, and cost reduce greatly;
(2) added solvent in preparation alkyl alcohol ether sulphonate of the present invention or the alkyl phenol ether sulphonate technology, the effect that not only has azeotropic to reflux, and the diluting reaction system arranged, improve the effect of reaction yield, thereby solved reaction later stage system heavy-gravity problem, the solvent that is added simultaneously also has the effect of the foamy of inhibition;
(3) catalyzer alkali adopts solid state directly to add in preparation alkyl alcohol ether sulphonate of the present invention or the alkyl phenol ether sulphonate technology, brings water into when having avoided with aqueous solution form adding system, makes reaction faster, more convenient operation;
(4) alkyl alcohol ether sulphonate or the alkyl phenol ether sulphonate yield that obtain of the present invention is higher, has extensive applicability, especially aspect tertiary oil recovery.
Embodiment
Embodiment 1: at first have stirring at one, be equipped with in the 500ml reactor of water trap and add C
8-C
10Natural fat alcohol ether R-O-(EO)
30H 0.5mol, potassium hydroxide 0.5mol, hexanaphthene 60ml open and stir and heating, and azeotropic reflux dewatering 2 hours is clarified to water trap, and water layer no longer changes and finishes, and makes it fully generate C
8-C
10The sylvite of natural fat alcohol ether.Secondly water trap is removed, water distilling apparatus is installed the hexanaphthene in the reactor is fully steamed.Adding 0.1mol methylol potassium sulfonate, 0.05mol catalyzer potassium hydroxide, 100ml n-decane azeotropic reflux and obtained C in 0.5 hour in reactor then
8-C
10Natural fatty alcohol ether sulfonic acid potassium.
Embodiment 2: at first have stirring at one, be equipped with in the 500ml reactor of water trap and add C
24Alkyl phenol ether R-O-(EO)
9H 0.3mol, sodium Metal 99.5 0.3mol, octane 50ml, logical rare gas element reaction 24 hours makes it fully generate C
24The sodium salt of alkyl phenol ether.Adding 0.5mol sodium isethionate, 0.3mol catalyzer sodium hydroxide, 130ml whiteruss in reactor vacuumize dehydration under the vacuum tightness of 200～220 ℃ temperature, logical rare gas element, 0.001～0.006Mpa then, react to obtain C in 5 hours
24The alkyl phenol ether sodium sulfonate, productive rate about 55%.
Embodiment 3: at first have stirring at one, be equipped with in the 500ml reactor of water trap and add C
14Alkyl ethoxylated R-O-(CH
2CH
2CH
2CH
2O)
18H 0.3mol, 0.3mol sodium hydride, toluene 80ml open stirring and are heated to 120 ℃, and azeotropic reflux dewatering 3.5 hours is clarified to water trap, and water layer no longer changes and finishes, and makes it fully generate C
14The sodium salt of alkyl ethoxylated.Secondly water trap is removed, water distilling apparatus is installed the solvent in the reactor is steamed.In reactor, add 0.2mol hydroxypropyl azochlorosulfonate acid sodium, 0.1mol catalyzer potassium hydroxide, 60ml dodecane then, with C
18The product of alkyl ethoxylated quality meter 20%, azeotropic reflux and obtained C in 2 hours
11Alkyl ethoxylated sodium sulfonate, productive rate are 62%.
Embodiment 4: at first have stirring at one, be equipped with in the 500ml reactor of water trap and add C
16-C
18Natural fatty alcohol 0.5mol, 0.5mol sodium hydroxide, normal hexane 80ml open stirring and are heated to 90 ℃, and azeotropic reflux dewatering 3 hours is clarified to water trap, and water layer no longer changes and finishes, and makes it fully generate C
16-C
18The sodium salt of natural fatty alcohol.Secondly water trap is removed, water distilling apparatus is installed the solvent in the reactor is steamed.In reactor, add 0.7mol hydroxyl butyl sulfonic acid sodium, 0.1mol catalyzer sodium hydroxide, 90ml 200# solvent oil then, with C
16-C
18The product of natural fatty alcohol quality meter 50% vacuumizes dehydration under the vacuum tightness of 100～120 ℃ of temperature, 0.09～0.1Mpa, react to obtain C in 1.5 hours
16-C
18Natural fatty alcohol sodium sulfonate, productive rate are 64%.
Embodiment 5: at first have stirring at one, be equipped with and add nonyl phenol poly(propylene oxide) (10) 0.5mol, 0.5mol potassium metal, toluene 60ml in the 500ml reactor of branch device, logical rare gas element reaction 24 hours makes it fully generate the sylvite of nonyl phenol poly(propylene oxide) (10).Secondly water trap is removed, water distilling apparatus is installed the solvent in the reactor is steamed.In reactor, add 0.8mol hydroxyethylsulfonic acid potassium, 0.2mol catalyzer potassium hydroxide, 90ml nonane then, in the product of nonyl phenol poly(propylene oxide) (10) quality 0.5%, azeotropic refluxes and obtained nonyl phenol poly(propylene oxide) (10) potassium sulfonate in 3 hours, and productive rate is 61%.
Embodiment 6: at first have stirring at one, be equipped with in the 500ml reactor of water trap and add C
15Alkyl ethoxylated R-O-(CH
2CH
2CH
2O)
20H 0.7mol, 0.7mol sodium methylate fully react it, the methyl alcohol that generates is steamed, thereby make C
15The sodium salt of alkyl ethoxylated.Secondly water trap is removed, water distilling apparatus is installed the solvent in the reactor is steamed.In reactor, add 0.8mol hydroxypropyl potassium sulfonate, 0.2mol catalyzer potassium hydroxide, 90ml eicosane then, with C
15The product of alkyl ethoxylated quality meter 15% vacuumizes dehydration under the vacuum tightness of 175～185 ℃ of temperature, 0.04～0.06Mpa, react to obtain C in 4.5 hours
15Alkyl ethoxylated potassium sulfonate, productive rate are 57%.
Embodiment 7: at first have stirring at one, be equipped with and add octylphenol ether R-O-(EO) in the 500ml reactor of water trap
6H 1.2mol, potassium ethylate 1.2mol fully react it, the ethanol that generates is steamed, thereby make the sylvite of octylphenol ether.Secondly water trap is removed, water distilling apparatus is installed the solvent in the reactor is steamed.Add 0.8mol hydroxyl butyl sulfonic acid potassium, 0.3mol catalyzer potassium hydroxide, 160ml 190# solvent oil then in reactor, azeotropic refluxes and obtained the octylphenol ether potassium sulfonate in 3.5 hours, and productive rate is 58%.
Embodiment 8: at first have stirring at one, be equipped with in the 500ml reactor of water trap and add C
16Alkyl ethoxylated R-O-(EO)
6H 1.8mol, potassium hydride KH 1.8mol, hexanaphthene 80ml opens stirring and is heated to 100 ℃, and azeotropic reflux dewatering 5 hours is clarified to water trap, and water layer no longer changes and finishes, and makes it fully generate C
16The sylvite of alkyl ethoxylated.Secondly water trap is removed, water distilling apparatus is installed the solvent in the reactor is steamed.Add 1.6mol hydroxyethylsulfonic acid potassium, 0.4mol catalyzer potassium hydroxide, 140ml 190# solvent oil then in reactor, azeotropic refluxes and obtained C in 4 hours
16Alkyl ethoxylated potassium sulfonate, productive rate are 61%.
Claims (10)
1. a technology for preparing alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate is characterized in that comprising the steps:
(1) sodium salt or the sylvite of preparation alkyl ethoxylated or alkyl phenol ether
The sodium salt or the sylvite of preparation alkyl ethoxylated or alkyl phenol ether have following 4 kinds of methods:
A, etc. alkyl ethoxylated or the alkyl phenol ether and the highly basic azeotropic dehydration of mol ratio, azeotropic 2～5 hours complete reactions that reflux in the presence of solvent steam solvent fully, obtain the sodium salt or the sylvite of alkyl ethoxylated or alkyl phenol ether;
B, etc. alkyl ethoxylated or the alkyl phenol ether and the alkali-metal hydride azeotropic dehydration of mol ratio, azeotropic 2～5 hours complete reactions that reflux in the presence of solvent steam solvent fully, obtain the sodium salt or the sylvite of alkyl ethoxylated or alkyl phenol ether;
C, etc. the alkyl ethoxylated of mol ratio or alkyl phenol ether and basic metal under protection of inert gas, obtained the sodium salt or the sylvite of alkyl ethoxylated or alkyl phenol ether in 1～24 hour in 0 ℃～120 ℃ reactions;
D, etc. the alkyl ethoxylated of mol ratio or alkyl phenol ether and alkali-metal short chain alkoxide pure permutoid reaction takes place, by distillation the short chain alcohol that generates is steamed simultaneously, reach until temperature till the boiling point of alkyl ethoxylated or alkyl phenol ether, obtain the sodium salt or the sylvite of alkyl ethoxylated or alkyl phenol ether;
(2) sulfoalkyl reaction
At room temperature add hydroxyalkylated sulfonic acid salt, basic catalyst in the sodium salt of alkyl ethoxylated that any one method makes in by step (1) or alkyl phenol ether or the sylvite, add solvent simultaneously, the mode that adopts azeotropic to reflux or vacuumize was in 100～220 ℃ of reactions 0.5～5 hour, remove the water that reaction generates, obtain alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate;
Wherein the mol ratio of alkyl ethoxylated or alkyl phenol ether and hydroxyalkylated sulfonic acid salt is 0.6～5: 1, and the mol ratio of alkyl ethoxylated or alkyl phenol ether and basic catalyst is 10～1: 1;
Described solvent is C
6～C
20Alkane, whiteruss, 190
#Solvent oil or 200
#Solvent oil.
2. a kind of technology for preparing alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate as claimed in claim 1, it is characterized in that reacting adding alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate in the forward reaction still, add-on is 0.5%～50% of alkyl ethoxylated or an alkyl phenol ether quality.
3. a kind of technology for preparing alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate as claimed in claim 1 or 2 is characterized in that described highly basic is potassium hydroxide or sodium hydroxide.
4. a kind of technology for preparing alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate as claimed in claim 1 or 2 is characterized in that described basic metal is potassium or sodium.
5. a kind of technology for preparing alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate as claimed in claim 1 or 2 is characterized in that described short chain alcohol is methyl alcohol or ethanol.
6. a kind of technology for preparing alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate as claimed in claim 1 or 2 is characterized in that described vacuumizing is logical rare gas element, and vacuum tightness is 0.001～0.1Mpa.
7. a kind of technology for preparing alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate as claimed in claim 1 or 2, the structural formula that it is characterized in that described alkyl ethoxylated or alkyl phenol ether is R-O-(R
1O)
nH, wherein R is C
8-C
24Alkyl or alkyl phenyl, R
1Be C
2-C
4Alkylidene group, n is 0-30.
8. a kind of technology for preparing alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate as claimed in claim 1 or 2, the structural formula that it is characterized in that described hydroxyalkylated sulfonic acid salt is HO-R
2-SO
3M, wherein R
2Be C
1-C
4Alkyl, M is sodium or potassium.
9. a kind of technology for preparing alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate as claimed in claim 1 or 2 is characterized in that described basic catalyst is potassium hydroxide or sodium hydroxide.
10. a kind of technology for preparing alkyl alcohol ether sulphonate or alkyl phenol ether sulphonate as claimed in claim 1 or 2 is characterized in that described C
6～C
20Alkane is normal paraffin, isoparaffin, branched paraffin or naphthenic hydrocarbon.
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|---|---|---|---|
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| CN101302175B true CN101302175B (en) | 2011-01-05 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103897677A (en) * | 2012-12-27 | 2014-07-02 | 中国石油化工股份有限公司 | Oil-based drilling fluid adopting phenol ether sulfonate composite oil-based emulsifier, and preparation method thereof |
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| CN102120197B (en) * | 2010-11-26 | 2013-05-01 | 昆明孚锐特经贸有限公司 | Mineral floatation foaming agent and preparation method thereof |
| CN102943288A (en) * | 2012-11-19 | 2013-02-27 | 湖北吉和昌化工科技有限公司 | Carrier brightening agent for potassium chloride galvanization and preparation method thereof |
| CN105483762B (en) * | 2015-11-30 | 2018-10-26 | 武汉奥克特种化学有限公司 | A method of preparing Potassium Chloride Zinc Plating carrier brightener with block polyether |
| CN112175601A (en) * | 2020-12-03 | 2021-01-05 | 山东新港化工有限公司 | Low-tension thick oil viscosity reduction washing oil agent for cold production of common thick oil and preparation method and application thereof |
| CN115069199A (en) * | 2022-07-14 | 2022-09-20 | 山东大明精细化工有限公司 | Preparation process of sodium alkyl polyoxyethylene ether sulfonate |
| CN115386359B (en) * | 2022-11-01 | 2023-01-17 | 山东东方盛嘉石油科技有限责任公司 | Viscous oil cold production dispersing huff and puff viscosity reducer and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4226807A (en) * | 1979-06-07 | 1980-10-07 | Texaco Development Corp. | Process for making ether sulfonates |
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2008
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4226807A (en) * | 1979-06-07 | 1980-10-07 | Texaco Development Corp. | Process for making ether sulfonates |
Non-Patent Citations (1)
| Title |
|---|
| 张锁兵.脂肪醇聚氧乙烯醚系列磺酸盐的泡沫性能研究.日用化学工业.2007,37(3),172-175. * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103897677A (en) * | 2012-12-27 | 2014-07-02 | 中国石油化工股份有限公司 | Oil-based drilling fluid adopting phenol ether sulfonate composite oil-based emulsifier, and preparation method thereof |
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|---|---|
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