CN1157253C - Prepn of lignin surfactant suitable for complex oil displacement - Google Patents
Prepn of lignin surfactant suitable for complex oil displacement Download PDFInfo
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- CN1157253C CN1157253C CNB00131002XA CN00131002A CN1157253C CN 1157253 C CN1157253 C CN 1157253C CN B00131002X A CNB00131002X A CN B00131002XA CN 00131002 A CN00131002 A CN 00131002A CN 1157253 C CN1157253 C CN 1157253C
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- lignin
- active agent
- alkylation
- surface active
- reaction
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Abstract
The present invention relates to a preparation method of a lignin surface active agent by electric oxidation, alkylation and sulfonation. The preparation method of a lignin surface active agent comprises the following steps: the electric oxidation is carried out in a purpose-made reactor, a certain amount of lignin is made into solution with the pH value of 2 to 12 during the reaction, the direct current voltage of 2 to 8 V is applied, and the reaction lasts for 15 to 68 hours; the lignin after the electric oxidation reacts with alkyl halide to generate alkylation lignin, and the alkylation lignin reacts with a sulfonation or sulfomethylation reagent to prepare the lignin surface active agent. The surface active agent can form the ultra low interfacial tension of at most 10<-3> mN/m with aviation coal oil in a compound driving oil system with high mineralization degree and high divalent ionic concentration. Compared with other methods, the preparation method of a lignin surface active agent has no need of high temperature and high pressure to degrade the lignin, mild reaction condition, and no public nuisance generation, and the prepared lignin has the advantages of high surface activity, etc.
Description
The present invention relates to be applicable to the method for the lignin surfactant of complex oil displacing with electroxidation, alkylation, sulfonation preparation.
The method of oil exploitation routine only can the extraction recoverable reserves 33%, want the remaining crude oil of extraction can only lean on tertiary oil recovery technology, in various tertiary oil recovery technologies, confirmed by solution combined technology of reservoir sweep (the abbreviating combination flooding as) development prospect together of alkali, surfactant and polymer best at present, it combines alkali, surfactant, the advantage of the independent displacement of reservoir oil of polymer, be that a kind of cost is low, the efficient height, suitable oil field is technology of reservoir sweep widely, apply a large amount of surfactant of this Technology Need, show according to oil field dense well spacing result of the test, one ton of crude oil of the every volume increase of complex oil displacing technology, need to consume 29.15kg alkali, 9.6kg surfactant, 2.7kg polymer, the petroleum-in-place of verifying according to the existing oil field of measuring and calculating China has nearly 10,000,000,000 tons to adopt to come out, if also can the crude oil of many extraction more than 2,000,000,000 tons with tertiary oil recovery technology.Need to consume 5.8 thousand ten thousand tons of alkali, 1.9 thousand ten thousand tons of surfactants, 5,500,000 tons of polymer as if just meaning with the complex oil displacing technology, so a large amount of surfactants is from being the compound probability of raw material with the oil, both cost an arm and a leg, and formed the recurrent state of recovering the oil with oil again, this is not too rational.With the industrial lignin is that the synthetic lignin surfactant of raw material is considered to the route that cost is cheap, the source is abundant, and around the lignin surfactant of used for tertiary oil recovery, existing many researchs, but all these methods still exist following obstacle at present:
1, because lignin is a network molecular structure, carbon-carbon bond is not easy fracture, makes it be degraded to comparatively difficulty of low molecular compound, and what therefore have will adopt HTHP carbon monoxide or hydrogen reducing technology; What have will adopt for example oxidative degradation technology such as nitric acid of strong oxidant, and the result produces the serious environmental pollution problem;
2, because the lignin surfactant surface-active of preparation is not high enough, need unite use with other surfactant when being used for tertiary oil recovery.
Electroxidation provided by the invention, alkylation and method of sulfonating are made lignin surfactant, have overcome existing variety of problems of said method and obstacle.
Activating agent method for making provided by the invention, lignin are through electroxidation, and alkylation and sulfonation are handled, and specifically comprise the steps:
1), the electroxidation method is lignin liquor to be put into special electro-oxidation reaction device carry out under the DC voltage effect, this reactor is equipped with anode and negative electrode.The all anode materials of the present invention are platinum, gold and plate brown lead oxide on titanium base or nonmetallic materials; Cathode material is lead, iron, stainless steel, nickel, carbon etc., and the DC voltage that adds is the 2-8 volt, and reaction time 15-68 hour, the pH value of solution was 2-12,15 ℃-35 ℃ of reaction temperatures.
2), alkylation provided by the invention is that lignin through electroxidation is reacting under 100 ℃-190 ℃ with alkyl halide under the alkali condition, alkyl halide is the halogen-containing alkane of a class, with C
nH
2n+1X represents that X is a fluorine in the formula, chlorine, and bromine, iodine, n are 4～18 integer.The mol ratio of oxidative lignin and alkyl halide is 1: 0.1 to 1.5: 0.9, solution pH value 8～13,1.5～4 hours reaction time.
3), sulfonation provided by the invention both can carry out sulfomethylation with formaldehyde and water soluble sulfate and lignin, also can use the concentrated sulfuric acid, sulfur trioxide is made sulfonated reagent lignin is carried out sulfonation.Method is lignin and formaldehyde and sulphite reaction preferably, the mol ratio 0.8: 0.1: 1.0 to 1.2: 1.0: 2.5 of lignin, formaldehyde, sulphite during reaction, the reaction solution pH value is 9-12, and reaction temperature is 110 ℃-180 ℃, reaction time 2-6 hour.
Use the lignin surfactant of method preparation provided by the present invention that effect is preferably arranged, at salinity 0.5～8wt%, divalent ion concentration 50ppm～2000ppm, NaOH or Na
2CO
3The lignin surfactant that adds 0.2～1.0wt% concentration in concentration 0.5～1.5wt% system all has higher surface activity with the composite or independent use of mahogany acid salt face, can form≤10 with aviation kerosine
-3The ultralow interfacial tension of mN/m.Method provided by the present invention, compared with prior art, having does not need high temperature, the high pressure lignin degrading, the reaction condition gentleness does not produce the active high advantage of public hazards and gained activating agent.
Embodiment 1:
Wheat straw alkali lignin 25 grams, be made into 8wt% concentration solution with distilled water, transferring pH value with NaOH is 11.0, is injected in the special oxidation reactor, and the anode of this reactor is to plate brown lead oxide on the titanium base, negative electrode is 300 purpose stainless (steel) wires, 5 volts of perfectly straight stream voltages reacted 45 hours product sedimentation and filtration in the aqueous solution of PH3-4 down at 30 ℃, and, be lower than 100 ℃ of following vacuum drying to powder product with the weak acid washing.
Embodiment 2:
0.1 mole of the electroxidation lignin product of example 1 is dissolved in isopropyl alcohol-aqueous solution, is made into 25wt% concentration, add 0.08 mole of bromohexadecane, the solution pH value is adjusted to 10.5, reacts 3 hours down at 175 ℃, is cooled to 70 ℃, add 0.1 moles of formaldehyde, 0.25 the mole sodium sulfite 170 ℃ of reactions 1.5 hours, is cooled to 80 ℃, be lower than 100 ℃ of following decompression distillation, and the dry powder-product that gets.
Embodiment 3:
Lignin surfactant 0.5 gram of example 2, NaCl1.0 gram, NaOH1.0 gram, MgCl
20.14 gram, CaCl
20.17 gram, distilled water 97 grams are made into compound oil displacement agent, and the interfacial tension of this oil displacement agent and aviation kerosine is 8 * 10
-3MN/m.
Embodiment 4:
Add 0.5 gram petroleum sulfonate in embodiment 3, be made into compound oil displacement agent, the interfacial tension of this oil displacement agent and aviation kerosine is 6 * 10
-4MN/m, and the interfacial tension that does not add lignin surfactant is 5 * 10
-3MN/m.
Embodiment 5:
Sodium lignin sulfonate 30 grams.Be made into 10wt% concentration solution with distilled water, transferring pH value with NaOH is 11.5, be injected in the special oxidation reactor, the anode of this reactor is to plate brown lead oxide on plastic filter screen, and negative electrode is 300 purpose stainless (steel) wires, 6 volts of perfectly straight stream voltages, reacted 50 hours down at 30 ℃, reaction finishes afterproduct and precipitates in the aqueous solution of PH3～4, filters, and, be lower than 100 ℃ of following vacuum drying to powder product with the weak acid washing.
Embodiment 6:
0.25 mole of the electroxidation lignin product of example 5 is dissolved in isopropyl alcohol-aqueous solution, is made into 25wt% concentration, add 0.5 mole of bromododecane, the solution pH value is adjusted to 11.5, reacts 2.5 hours down at 170 ℃, is cooled to 70 ℃, add 0.25 moles of formaldehyde, 0.41 the mole sodium hydrogensulfite 160 ℃ of reactions 2 hours, is cooled to 80 ℃, be lower than 100 ℃ of following decompression distillation, and the dry powder-product that gets.
Embodiment 7:
Lignin surfactant 0.3 gram of example 6, NaCl 2.0 grams, NaOH 1.0 grams, MgCl
20.07 gram, CaCl
20.08 gram, distilled water 97 grams are made into compound oil displacement agent, and the interfacial tension of this oil displacement agent and aviation kerosine is 6 * 10
-3MN/m.
Claims (4)
1, a kind of method for making that is applicable to the lignin surfactant of complex oil displacing is characterized in that with lignin that through electroxidation alkylation and sulfonation are handled, and comprise the steps:
1), electroxidation: lignin liquor has been put into the moon, in the electro-oxidation reaction device of anode, fed 2～8 volts of DC voltages, solution PH 2～12 is controlled 15～35 ℃ of temperature, reacts 15～68 hours;
2), alkylation: with 1) in the gained lignin, under alkali condition with the reaction 1.5～4 hours down of 100～190 ℃ of alkyl halides, lignin and alkyl halide mol ratio 1: 0.1～1.5: 0.9, solution PH 8～13;
3), sulfonation: will be through 2) in the lignin handled with formaldehyde and sulphite reaction, 110～180 ℃ of temperature, solution PH 9～12, lignin, formaldehyde, the mol ratio of sulphite 0.8: 0.1: 1.0 to 1.2: 1.0: 2.5 was reacted 2～6 hours.
2, according to the method described in the claim 1, it is characterized in that the cathode material in the electro-oxidation reaction device is lead, iron, stainless steel, nickel or carbon, anode material are gold, platinum, or plate brown lead oxide on titanium base or nonmetallic materials.
3,, it is characterized in that alkyl halide is halogen-containing alkane, with C according to the method described in the claim 1
nH
2n+1X represents that X is a fluorine in the formula, chlorine, and bromine or iodine, n are 4～18 integer.
4, according to the method described in the claim 1, it is characterized in that the sulfonating reaction concentrated sulfuric acid, sulfur trioxide is made sulfonating agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB00131002XA CN1157253C (en) | 2000-12-27 | 2000-12-27 | Prepn of lignin surfactant suitable for complex oil displacement |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB00131002XA CN1157253C (en) | 2000-12-27 | 2000-12-27 | Prepn of lignin surfactant suitable for complex oil displacement |
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| Publication Number | Publication Date |
|---|---|
| CN1360969A CN1360969A (en) | 2002-07-31 |
| CN1157253C true CN1157253C (en) | 2004-07-14 |
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| CNB00131002XA Expired - Fee Related CN1157253C (en) | 2000-12-27 | 2000-12-27 | Prepn of lignin surfactant suitable for complex oil displacement |
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|---|---|---|---|---|
| CN115385828B (en) * | 2022-09-14 | 2023-07-21 | 南京工业大学 | Lignin-based polyester surfactant and preparation method and application thereof |
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2000
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