CN102584641B - Process for preparing alkylphenol formaldehyde oligomer sulfonate - Google Patents
Process for preparing alkylphenol formaldehyde oligomer sulfonate Download PDFInfo
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- CN102584641B CN102584641B CN2011104316705A CN201110431670A CN102584641B CN 102584641 B CN102584641 B CN 102584641B CN 2011104316705 A CN2011104316705 A CN 2011104316705A CN 201110431670 A CN201110431670 A CN 201110431670A CN 102584641 B CN102584641 B CN 102584641B
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Abstract
The invention discloses a process for preparing alkylphenol formaldehyde oligomer sulfonate. The process comprises the following steps of: adding alkylphenol and a catalyst into a reaction kettle, heating with stirring, dripping a formaldehyde solution or paraformaldehyde, continuously stirring, and raising temperature to reaction temperature, adding residual formaldehyde solution or paraformaldehyde, continuously reacting, and after reaction is finished, adding a sodium hydroxide aqueous solution to adjust pH of a reaction product to be 6.5 to 8.0 to obtain alkylphenol formaldehyde oligomer; and adding the alkylphenol formaldehyde oligomer into the reaction kettle, adding a solvent to dissolve, opening a stirrer, stirring and heating to 30 to 80 DEG C, adding a sulfonating agent, continuously reacting for 30 to 90 minutes, neutralizing a sulfonating product by using alkali until pH is 7 to 8, and evaporating to remove the solvent to obtain the alkylphenol formaldehyde oligomer sulfonate. The process has the advantages that alkylphenol and formaldehyde are used as raw materials, the process is simple, and industrialization is easy to realize.
Description
Technical field
The present invention relates to a kind of technique for preparing alkylphenol formaldehyde oligomer sulfonate with alkylphenol and formaldehyde reaction.
Background technology
Oligomeric-type tensio-active agent (oligomeric surfactant) is that the common strand surfactant molecule more than 2 or 2 is connected together by chamical binding with spacer group (spacer group) at hydrophilic group or near near hydrophilic group.What have the amphiphilic compositions such as 2,3 or 4 in molecule is called as respectively dimerization (dimeric), trimerization (trimeric), four poly-oligomeric-type tensio-active agents such as (tetrameric) simultaneously.With conventional surfactant, compare, the oligomeric-type tensio-active agent has lower micelle-forming concentration, abundanter gathering behavior and more excellent character, especially aspect tertiary oil recovery, has certain application potential.
At present, the research of oligo surfactant mainly concentrated on to dimeric surfactant both at home and abroad, the trimerization that the polymerization degree is slightly high, research four poly-, five tensio-active agents such as poly-mainly concentrate on positively charged ion or nonionic surface active agent, and relevant trimerization, four poly-, five the rarely seen report of anion surfactant such as gather.Such as: Laschewsky, the Argentine Grau of the Esumi of the Zana of France, the Menger of the U.S., Japan and Ikeda, Germany and China Chinese Academy of Sciences chemistry institute, chemical institute of University of Fuzhou, department of chemistry of institute of college of science of University Of Tianjin, chemical engineering institute of Hebei University of Technology etc. all conduct a preliminary study the oligomeric-type tensio-active agent.But above research biases toward the synthetic performance applications that reaches of laboratory lab scale mostly, and raw material is difficult to obtain or high cost, and synthesis step is too complicated, and industrialized feasibility is little.
Alkylphenol formaldehyde oligomer sulfonate is by alkylphenol, the first condensation of formaldehyde, carries out with sulphonating agent the oligomeric-type sulfonate anionic surfactant obtained after sulfonation again.Raw material sources are abundant, and cost is low, and synthetic method is relatively simple, is easy to realize industrialization.At present, after only Zheng of University Of Tianjin Bao Jiang reacts with mol ratio with nonyl phenol and formaldehyde at 2: 1, use the chlorsulfonic acid sulfonation, obtain sulfonate dimer, i.e. two (2-hydroxyl-3-sodium sulfonate group-5-nonyl phenyl) methane.The report that is the synthetic trimerization of raw material, four sulfosalt surfactants such as poly-by alkylphenol, formaldehyde there is not yet.
In the process of by alkylphenol and formaldehyde, carrying out polycondensation synthesis of oligonucleotides thing intermediate, the kind of catalyzer and consumption are very important on the impact of alkylphenol transformation efficiency and the polymerization degree.US3919429 proposes to make with hydrochloric acid, sulfuric acid, phosphoric acid and oxalic acid the catalyzer that alkylphenol reacts with formaldehyde condensation polymer, relies on distillation dehydration to obtain the alkylphenol formaldehyde polycondensate that the polymerization degree is 1～9.CN200510126038.4 proposes to make the synthetic nonyl phenol formaldehyde trimerization intermediate of catalyzer with potassium hydroxide.CN200810152433.3 be take solid super-strong acid and is obtained nonyl phenol formaldehyde trimerization intermediate as catalyzer is synthetic.It is raw material that Hebei University of Technology's chemistry equals to utilize in 2010 nonyl phenol, formaldehyde with the Li Gang of chemical engineering institute, has prepared nonyl phenol formaldehyde dimer or tripolymer with oxalic acid or solid super strong acid as catalyst respectively.
To sum up, there are the following problems for the preparation technology of existing alkylphenol formaldehyde oligomer:
For basic catalyst as potassium hydroxide, nonyl phenol and formaldehyde reaction easily form the oligopolymer of methylol end-blocking, are not the intermediates that this problem is expected, alkali corrosion equipment in addition, contaminate environment.
2. as while with hydrochloric acid, making catalyzer, nonyl phenol and formaldehyde reaction are violent, and in reaction process, hydrochloric acid and formaldehyde easily form the monochloromethyl-ether by product, and this material is considered to potential carcinogens.As with sulfuric acid, made catalyzer, because its dehydration property is too strong, make the polycondensate intramolecular dehydration and loss of activity-OH group, thereby lose the ability of crosslinking reaction.In addition, all there is etching apparatus in the inorganic acid catalysts such as hydrochloric acid, sulfuric acid, the defect of contaminate environment.
For organic acid catalyst as oxalic acid, because of its acidity a little less than, so nonyl phenol and formaldehyde reaction gentle, last long, energy consumption is large.
4. for solid acid catalyst, its preparation process needs high-temperature calcination, time consumption and energy consumption.
5. above-mentioned report is all to reduce pressure and dewater after first polycondensation, and processing step is more, and facility investment is large, long reaction time, and yield is lower.The mode that employing vacuumizes is removed solvent and water, and system viscosity increases, the aftertreatment trouble.
Summary of the invention
The purpose of this invention is to provide and a kind ofly take alkylphenol and formaldehyde as raw material, technique are simple, be easy to the industrialized technique for preparing alkylphenol formaldehyde oligomer sulfonate.
The present invention is under an acidic catalyst exists, alkylphenol and formaldehyde generation polycondensation, obtain by methylene radical alkylphenol at-linear alkyl phenol formaldehyde oligomer (structural formula is shown in formula 1) that the OH ortho position links up, then with sulphonating agent, alkylphenol formaldehyde oligomer is carried out to sulfonation, thereby make alkylphenol formaldehyde oligomer sulfonate.
The present invention is a kind of technique for preparing alkylphenol formaldehyde oligomer sulfonate, and concrete operation step is as follows:
(1) prepare alkylphenol formaldehyde oligomer
Add alkylphenol in reactor, catalyzer, catalyst levels is 0.1%～10.0% of alkylphenol quality, under agitation condition and after being heated to 30～50 ℃, drip 50%～80% of formaldehyde solution or the total sample introduction quality of paraformaldehyde, continue to stir after being warming up to 60～120 ℃ of temperature of reaction and add again remaining formaldehyde solution or paraformaldehyde, the mol ratio of alkylphenol and formaldehyde or paraformaldehyde is 1: 0.5～5, continue reaction 30～240min under this temperature of reaction, reaction finishes rear with adding aqueous sodium hydroxide solution conditioned reaction product to PH=6.5～8.0, obtain alkylphenol formaldehyde oligomer,
(2) prepare alkylphenol formaldehyde oligomer sulfonate
Add alkylphenol formaldehyde oligomer in reactor, after adding dissolution with solvents, unlatching adds sulphonating agent while being heated with stirring to 30～80 ℃, the mol ratio of sulphonating agent and alkylphenol formaldehyde oligomer is 10～1: 1, add rear continuation reaction 30～90min, it is 7～8 that sulfonated products is neutralized to pH with alkali, after steaming desolventizes, obtains alkylphenol formaldehyde oligomer sulfonate.
Alkylphenol R as above
1-OH, R
1For C
8～C
24Straight chain, branched-chain alkyl phenol, or the mixed phenol of different alkane chains etc.
Catalyzer as above can be alkyl aryl sulphonic acid, can be also alkylsulphonic acid etc.
Alkyl aryl sulphonic acid R as above
2-Ar-SO
3H, R2 is C
1～C
16Straight chain, branched-chain alkyl aryl sulfonic acid, or the alkyl aryl sulphonic acid that mixes of different alkane chain etc., Ar is phenyl, naphthyl, phenylbenzene etc.
Alkylsulphonic acid R as above
3-SO
3H, R
3For C
8～C
24Straight chain, branched-chain alkyl sulfonic acid, or the alkylsulphonic acid that mixes of different alkane chain etc.
Solvent as above can be C
6～C
20Alkane (comprising normal paraffin, isoparaffin, branched paraffin, naphthenic hydrocarbon), halohydrocarbon (comprising methylene dichloride, ethylene dichloride, trichloromethane) etc.
Sulphonating agent as above can be oleum, sulfan, gas sulphur trioxide etc.
Sulfan as above can be dissolved in halohydrocarbon (comprising methylene dichloride, ethylene dichloride) and add in reactor again, also can directly add.
Gas sulphur trioxide as above can be the sulphur trioxide/air gas mixture obtained by combustion sulphur method, oleum air lift method, sulfur dioxide liquid catforming or sulfan direct boiling method.
In sulphur trioxide/air gas mixture as above, the volume fraction of sulphur trioxide is in 5～20% scopes.
Alkali used in sulfonation process as above can be mineral alkali, comprises sodium hydroxide, potassium hydroxide etc.; Can be also organic bases, comprise ammoniacal liquor, monoethanolamine, diethanolamine, trolamine, tetra-allkylammonium etc.
Polycondensation as above or sulfonation reaction device be all with agitator, prolong, thermometer etc.
The technique that the present invention prepares alkylphenol formaldehyde oligomer sulfonate has the following advantages:
(1) the alkylphenol formaldehyde oligomer sulfonate technique for preparing of the present invention can obtain the oligomeric-type tensio-active agent that the polymerization degree is suitable, and easy to operate, technique is simple.
(2) the alkylphenol formaldehyde oligomer intermediate technique for preparing of the present invention has been removed solvent, not obvious on the impact of alkylphenol transformation efficiency on the one hand, save on the other hand underpressure distillation and removed solvent, simplified post-treating method, be conducive to energy-conservationly, shorten the operational cycle.
(3) of the present inventionly prepare catalyzer alkyl aryl sulphonic acid in alkylphenol formaldehyde oligomer intermediate technique and itself there is dispersiveness, can make alkylphenol fully contact with formaldehyde solution, improved catalytic activity.
(4) alkylphenol formaldehyde oligomer sulfonate that prepared by the present invention has the performances such as surfactivity is high, the foam ability is strong, high temperature resistant, is highly suitable for preparing Flooding Agent for EOR.
Embodiment
Embodiment 1: in the reactor with thermometer, agitator, prolong, add C
8Straight chained alkyl phenol, catalyzer straight chain Witco 1298 Soft Acid, catalyst levels is 0.1% of alkylphenol quality, after 30 ℃ are stirred and be heated to unlatching, drip 50% of the total sample introduction quality of formaldehyde, continue to stir after being warming up to 60 ℃ of temperature of reaction and add again remaining formaldehyde, the mol ratio of alkylphenol and formaldehyde is 1: 0.5, continues reaction 240min under this temperature of reaction.After reaction finishes with add aqueous sodium hydroxide solution conditioned reaction product to PH be 7.5, finally obtain the tawny gelatinoid, i.e. alkylphenol formaldehyde oligomer.
Add alkylphenol formaldehyde oligomer in the reactor with thermometer, agitator, prolong, after adding octane-iso to dissolve, open while being heated with stirring to 30 ℃ and add appropriate oleum, the SO in oleum
3With the mol ratio of alkylphenol formaldehyde oligomer be 10: 1, add rear continuation reaction 90min, it is 7 that sulfonated products is neutralized to pH with the KOH aqueous solution, after steaming desolventizes, obtains alkylphenol formaldehyde oligomer sulfonate.
Embodiment 2: in the reactor with thermometer, agitator, prolong, add C
9Branched-chain alkyl phenol, catalyzer tosic acid, catalyst levels is 10.0% of alkylphenol quality, after 50 ℃ are stirred and be heated to unlatching, drip 60% of the total sample introduction quality of paraformaldehyde, continue to stir after being warming up to 120 ℃ of temperature of reaction and add again remaining paraformaldehyde, the mol ratio of the formaldehyde in alkylphenol and paraformaldehyde is 1: 5, continues reaction 30min under this temperature of reaction.After reaction finishes with add aqueous sodium hydroxide solution conditioned reaction product to PH be 6.5, finally obtain the tawny gelatinoid, i.e. alkylphenol formaldehyde oligomer.
Add alkylphenol formaldehyde oligomer in the reactor with thermometer, agitator, prolong, after adding cyclohexane to dissolve, open while being heated with stirring to 80 ℃, add appropriate sulphonating agent liquid SO
3, SO
3With the mol ratio of alkylphenol formaldehyde oligomer be 1: 1, add rear continuation reaction 90min, it is 7.5 that sulfonated products is neutralized to pH with monoethanolamine, steams after desolventizing and obtains alkylphenol formaldehyde oligomer sulfonate.
Embodiment 3: in the reactor with thermometer, agitator, prolong, add C
12Branched-chain alkyl phenol, catalyzer isobutyl-naphthene sulfonic acid, catalyst levels is 5.0% of alkylphenol quality, after 40 ℃ are stirred and be heated to unlatching, drip 80% of the total sample introduction quality of formaldehyde, continue to stir after being warming up to 80 ℃ of temperature of reaction and add again remaining formaldehyde, the mol ratio of alkylphenol and formaldehyde is 1: 1.5, continues reaction 90min under this temperature of reaction.After reaction finishes with add aqueous sodium hydroxide solution conditioned reaction product to PH be 7.3, finally obtain the tawny gelatinoid, i.e. alkylphenol formaldehyde oligomer.
Add alkylphenol formaldehyde oligomer in the reactor with thermometer, agitator, prolong, after adding methylene dichloride to dissolve, open while being heated with stirring to 50 ℃ and add again appropriate liquid SO
3/ ethylene dichloride mixture, SO
3With the mol ratio of alkylphenol formaldehyde oligomer be 3: 1, add rear continuation reaction 40min, it is 8 that sulfonated products is neutralized to pH with trolamine, steams after desolventizing and obtains alkylphenol formaldehyde oligomer sulfonate.
Embodiment 4: in the reactor with thermometer, agitator, prolong, add C
18Straight chained alkyl phenol, catalyzer side chain C24 alkylsulphonic acid, catalyst levels is 2.5% of alkylphenol quality, after 50 ℃ are stirred and be heated to unlatching, drip 75% of the total sample introduction quality of formaldehyde, continue to stir after being warming up to 70 ℃ of temperature of reaction and add again remaining formaldehyde, the mol ratio of alkylphenol and formaldehyde is 1: 3, continues reaction 120min under this temperature of reaction.After reaction finishes with add aqueous sodium hydroxide solution conditioned reaction product to PH be 8.0, finally obtain the tawny gelatinoid, i.e. alkylphenol formaldehyde oligomer.
Add alkylphenol formaldehyde oligomer in the reactor with thermometer, agitator, prolong, after adding petroleum ether dissolution, open while being heated with stirring to 40 ℃ and add appropriate sulphonating agent SO
3/ air gas mixture, wherein SO
3Volume fraction be 5%, SO
3With the mol ratio of alkylphenol formaldehyde oligomer be 4: 1, add rear continuation reaction 60min, sulfonated products with ammonia neutralization to pH be 7.7, steam after desolventizing and obtain alkylphenol formaldehyde oligomer sulfonate.
Embodiment 5: in the reactor with thermometer, agitator, prolong, add C
24Branched-chain alkyl phenol, catalyzer diethyl naphthene sulfonic acid, catalyst levels is 6.0% of alkylphenol quality, after 35 ℃ are stirred and be heated to unlatching, drip 55% of the total sample introduction quality of paraformaldehyde, continue to stir after being warming up to 90 ℃ of temperature of reaction and add again remaining paraformaldehyde, the mol ratio of the formaldehyde in alkylphenol and paraformaldehyde is 1: 4.5, continues reaction 160min under this temperature of reaction.After reaction finishes with add aqueous sodium hydroxide solution conditioned reaction product to PH be 6.8, finally obtain the tawny gelatinoid, i.e. alkylphenol formaldehyde oligomer.
Add alkylphenol formaldehyde oligomer in the reactor with thermometer, agitator, prolong, after adding trichloromethane to dissolve, open while being heated with stirring to 70 ℃ and add again appropriate sulphonating agent liquid SO
3/ methylene dichloride, SO
3With the mol ratio of alkylphenol formaldehyde oligomer be 6: 1, add rear continuation reaction 50min, it is 7.2 that sulfonated products is neutralized to pH with the TBuA aqueous solution, after steaming desolventizes, obtains alkylphenol formaldehyde oligomer sulfonate.
Embodiment 6: in the reactor with thermometer, agitator, prolong, add C
14, C
16Straight chained alkyl mixed phenol, catalyzer C
8, C
10Phenylbenzene sulfonic acid, catalyst levels is 8.0% of alkylphenol quality, after 45 ℃ are stirred and be heated to unlatching, drip 60% of the total sample introduction quality of formaldehyde, continue to stir after being warming up to 85 ℃ of temperature of reaction and add again remaining formaldehyde, the mol ratio of alkylphenol and formaldehyde is 1: 1.0, continues reaction 210min under this temperature of reaction.After reaction finishes with add aqueous sodium hydroxide solution conditioned reaction product to PH be 7.6, finally obtain the tawny gelatinoid, i.e. alkylphenol formaldehyde oligomer.
Add alkylphenol formaldehyde oligomer in the reactor with thermometer, agitator, prolong, after adding ethylene dichloride to dissolve, open while being heated with stirring to 50 ℃ and add appropriate sulphonating agent SO
3/ air gas mixture, wherein SO
3Volume fraction be 20%, SO
3With the mol ratio of alkylphenol formaldehyde oligomer be 6: 1, add rear continuation reaction 60min, it is 7.5 that sulfonated products is neutralized to pH with the NaOH aqueous solution, after steaming desolventizes, obtains alkylphenol formaldehyde oligomer sulfonate.
Claims (8)
1. a technique for preparing alkylphenol formaldehyde oligomer sulfonate, is characterized in that comprising the steps:
(1) prepare alkylphenol formaldehyde oligomer
Add alkylphenol in reactor, catalyzer, catalyst levels is 0.1%～10.0% of alkylphenol quality, under agitation condition and after being heated to 30～50 ℃, drip 50%～80% of formaldehyde solution or the total sample introduction quality of paraformaldehyde, continue to stir after being warming up to 60～120 ℃ of temperature of reaction and add again remaining formaldehyde solution or paraformaldehyde, the mol ratio of alkylphenol and formaldehyde or paraformaldehyde is 1:0.5～5, continue reaction 30～240 min under this temperature of reaction, reaction finishes rear with adding aqueous sodium hydroxide solution conditioned reaction product to PH=6.5～8.0, obtain alkylphenol formaldehyde oligomer,
(2) prepare alkylphenol formaldehyde oligomer sulfonate
Add alkylphenol formaldehyde oligomer in reactor, after adding dissolution with solvents, unlatching adds sulphonating agent while being heated with stirring to 30～80 ℃, the mol ratio of sulphonating agent and alkylphenol formaldehyde oligomer is 10～1:1, add rear continuation reaction 30～90min, it is 7～8 that sulfonated products is neutralized to pH with alkali, after steaming desolventizes, obtains alkylphenol formaldehyde oligomer sulfonate;
Described catalyzer is alkyl aryl sulphonic acid or alkylsulphonic acid;
Described alkali is sodium hydroxide, potassium hydroxide, ammoniacal liquor, monoethanolamine or trolamine.
2. a kind of technique for preparing alkylphenol formaldehyde oligomer sulfonate as claimed in claim 1, is characterized in that described alkylphenol is C
8～C
24Straight chain, branched-chain alkyl phenol, or the mixed phenol of different alkane chains.
3. a kind of technique for preparing alkylphenol formaldehyde oligomer sulfonate as claimed in claim 1, is characterized in that described solvent is C
6～C
20Alkane or halohydrocarbon.
4. a kind of technique for preparing alkylphenol formaldehyde oligomer sulfonate as claimed in claim 3, is characterized in that described C
6～C
20Alkane is normal paraffin, isoparaffin, branched paraffin or naphthenic hydrocarbon.
5. a kind of technique for preparing alkylphenol formaldehyde oligomer sulfonate as claimed in claim 3, is characterized in that described halohydrocarbon is methylene dichloride, ethylene dichloride or trichloromethane.
6. a kind of technique for preparing alkylphenol formaldehyde oligomer sulfonate as claimed in claim 1, is characterized in that described sulphonating agent is oleum, sulfan or gas sulphur trioxide.
7. a kind of technique for preparing alkylphenol formaldehyde oligomer sulfonate as claimed in claim 6, is characterized in that
Described gas sulphur trioxide is the sulphur trioxide/air gas mixture obtained by combustion sulphur method, oleum air lift method, sulfur dioxide liquid catforming or sulfan direct boiling method.
8. a kind of technique for preparing alkylphenol formaldehyde oligomer sulfonate as claimed in claim 7, is characterized in that the volume fraction of sulphur trioxide in described sulphur trioxide/air gas mixture is in 5～20% scopes.
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| CN104774645B (en) * | 2014-01-09 | 2017-08-11 | 上海汉遥新材料科技有限公司 | The preparation method of low temperature polyether type thick oil demulsifying agent |
| CN106031854B (en) * | 2015-03-20 | 2018-03-20 | 中国石油化工股份有限公司 | A kind of anionic oligo surfactant and preparation method thereof |
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