CN105419766A - Technology method of synthesizing heavy oil sulfonate surfactant with sulfonation promoter - Google Patents
Technology method of synthesizing heavy oil sulfonate surfactant with sulfonation promoter Download PDFInfo
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- CN105419766A CN105419766A CN201510985129.7A CN201510985129A CN105419766A CN 105419766 A CN105419766 A CN 105419766A CN 201510985129 A CN201510985129 A CN 201510985129A CN 105419766 A CN105419766 A CN 105419766A
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
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Abstract
The invention relates to a technology method of synthesizing a heavy oil sulfonate surfactant with a sulfonation promoter and mainly solves the problem of difficult stirring, serious coking and low sulfonic acid conversion rate in a heavy oil sulfonation process in synthesis of the heavy oil sulfonate surfactant. The technology method comprises the following steps: 1) dehydrating heavy oil to obtain dehydrated heavy oil; 2) mixing the sulfonation promoter with the dehydrated heavy oil according to proportion, feeding a mixed gas composed of SO3 and nitrogen when the temperature reaches an initial temperature being 65-85 DEG C, and carrying out a reaction for 20-60 min, wherein the initial reaction temperature increases and then the temperature is reduced in a middle stage and finally is reduced to 90-110 DEG C through natural constant-temperature treatment; and 3) aging the reaction product, adding alkaline liquid to neutralize the reaction product, and adding prepared mixed alcohol after neutralization with uniform stirring to obtain the heavy oil sulfonate surfactant which is 50% in concentration and is used for oil displacement. The technology method, in which the sulfonation promoter is used for synthesizing the heavy oil sulfonate surfactant, is high in the sulfonic acid conversion rate, low in reaction coking and is good in interface performance of a synthesized product.
Description
Technical field
The present invention relates to a kind of processing method adopting sulfonation promotor to synthesize heavy crude oil sulfonates tensio-active agent, belong to the technical field of surfactant that oil field chemical uses.
Background technology
Current oil field surfactant oil displacement mainly contains heavy alkylbenzene sulfonate and the large class of sulfonated petro-leum two, and while tensio-active agent demand increases, raw material heavy alkyl benzene price but goes up year by year, and production cost also rises thereupon.Aromaticity content more than 30% in viscous crude, is suitable for producing heavy crude oil sulfonates surfactant oil displacement.At present, heavy crude oil sulfonates is not all specifically applied to the relevant report of surfactant oil displacement aspect both at home and abroad.
The method of synthesis heavy crude oil sulfonates mainly adopts that oleum is sulphonating agent catalysis sulfonation method, sulphur trioxide is sulphonating agent method.During current viscous crude Direct Sulfonation, reaction system stirs difficulty, and coking is serious, and sulfonic acid low conversion rate, synthetic product poorly water-soluble, does not reach the technical requirements of oil field surfactant oil displacement.
Summary of the invention
The invention reside in that viscous crude sulfonation process coking in the synthesis heavy crude oil sulfonates tensio-active agent technique overcoming and exist in background technology is serious, the problem of sulfonic acid low conversion rate and synthetic product interface performance difference, and to provide
oneplant the processing method adopting sulfonation promotor synthesis heavy crude oil sulfonates tensio-active agent.The processing method of this employing sulfonation promotor synthesis heavy crude oil sulfonates tensio-active agent, sulfonic acid transformation efficiency is high, and reaction coking is few, and synthetic product interface performance is good.
The present invention solves its problem and reaches by following technical scheme: a kind of processing method adopting sulfonation promotor to synthesize heavy crude oil sulfonates tensio-active agent, comprises the following steps:
1), first processed is carried out to viscous crude, obtain the viscous crude that dewaters;
2), by sulfonation promotor and above-mentioned dehydration viscous crude be mixed in proportion, after the starting temperature that temperature reaches 65 ~ 85 DEG C, pass into SO
3and nitrogen mixed gas, react 20 ~ 60 minutes; Initial reaction temperature rise, mid-term temperature drops back, natural constant temperature to 90 ~ 110 DEG C, add after aging alkali lye neutralization, add the alcohol mixture of preparation after neutralization, stir, obtain the displacement of reservoir oil heavy crude oil sulfonates tensio-active agent of concentration 50%.
Described sulfonation promotor is boiling range 220 ~ 300 DEG C of fulvene diesel oil or C
14~ C
22lipid acid, or boiling range 220 ~ 300 DEG C of fulvene diesel oil mix with the heavy alkyl benzene of boiling range 300 ~ 400 DEG C, or C
14~ C
22lipid acid mixes with the heavy alkyl benzene of boiling range 300 ~ 400 DEG C.
The heavy alkyl benzene blending ratio of described boiling range 220 ~ 300 DEG C of fulvene diesel oil and boiling range 300 ~ 400 DEG C is 1:1 ~ 1:3; Described C
14~ C
22the heavy alkyl benzene blending ratio of lipid acid and boiling range 300 ~ 400 DEG C is 1:1 ~ 1:3.
The present invention can have following beneficial effect compared with above-mentioned background technology: this employing sulfonation promotor synthesizes the processing method of heavy crude oil sulfonates tensio-active agent, has the following advantages:
(1) the present invention synthesis heavy crude oil sulfonates product water dissolubility and interface performance good, meet the basic demand of oil field surfactant oil displacement product;
(2) heavy crude oil sulfonates process for sulfonation of the present invention adopts a charging, and viscous crude is without the need to carrying out pre-treatment, and product, without the need to aftertreatment, decreases processing step, and synthetic method is simple;
(3) sulfonic acid transformation efficiency of the present invention is high, and reaction coking is few;
(4) the heavy crude oil sulfonates tensio-active agent of the present invention's synthesis is domestic initiation in surfactant oil displacement field, has broad application prospects.
embodiment:
Below in conjunction with specific embodiment, the invention will be further described:
Comparative example 1
First carry out processed to viscous crude, take the four-hole boiling flask that 30g adds the 250mL being furnished with electric mixer, constant speed stirs, and four-hole boiling flask inserts constant temperature oil bath; After reaching the starting temperature of 65 ~ 85 DEG C in bottle, pass into SO in the dense ratio 2-7% of gas
3and nitrogen mixed gas, react 20 ~ 60 minutes; Reaction steep temperature rise, viscosity sharply increases, and stir more and more difficult, coking is serious.
Embodiment 1
Mix in 1:2 ratio with dehydration viscous crude for sulfonation promotor with the fulvene diesel oil of boiling range 220 ~ 300 DEG C, take the four-hole boiling flask that 50g adds the 250mL being furnished with electric mixer, constant speed stirs, and four-hole boiling flask inserts constant temperature oil bath; After reaching the starting temperature of 75 DEG C in bottle, pass into SO in the dense ratio of 3.5% gas
3and nitrogen mixed gas, react 40 minutes; Initial reaction stage has red cigarette, and punching temperature is little; Initial reaction temperature rise, the viscous crude sulfonation degree of depth progressively improves, mid-term temperature drops back, natural constant temperature is to 90 DEG C, without obvious coking, digestion time 2h, weightening finish ratio is 18%, in weightening finish ratio 1.3 ratios add 20% alkali lye neutralization, neutral temperature controls at 95 DEG C, in and time 2h; Add propyl carbinol and the alcohol mixture prepared by 1:1 of n-Octanol of 16% after neutralization, stir, obtain the displacement of reservoir oil heavy crude oil sulfonates tensio-active agent of concentration 50%.This product water dissolubility is better than viscous crude Direct Sulfonation product, still has unsulfonated oil floating on a small quantity in 5% solution; Interface performance is 10
-2the order of magnitude.
Embodiment 2
Mix as sulfonation promotor using the heavy alkyl benzene of the fulvene diesel oil of boiling range 220 ~ 300 DEG C and boiling range 300 ~ 400 DEG C in 1:1 ratio, above-mentioned sulfonation promotor mixes in 1:2 ratio with dehydration viscous crude, take the four-hole boiling flask that 50g adds the 250mL being furnished with electric mixer, constant speed stirs, and four-hole boiling flask inserts constant temperature oil bath; After reaching the starting temperature of 75 DEG C in bottle, pass into SO in the dense ratio of 3.5% gas
3and nitrogen mixed gas, react 40 minutes; Initial reaction stage has-drop of obviously leaping high, natural constant temperature to about 95 DEG C, without obvious coking, digestion time 2h, weightening finish is than 20%, and add 20% alkali lye neutralization in 1.3 ratios of weightening finish ratio, neutral temperature controls at 95 DEG C, in and time 2h; Add propyl carbinol and the alcohol mixture prepared by 1:1 of n-Octanol of 16% after neutralization, stir, obtain the displacement of reservoir oil heavy crude oil sulfonates tensio-active agent of concentration 50%.This product water dissolubility is better than embodiment 1, but still has unsulfonated oil floating on a small quantity in 5% solution; Interface performance is 10
-2the order of magnitude.
Embodiment 3
With C
14~ C
22lipid acid to be sulfonation promotor mix in 1:2 ratio with dehydration viscous crude, take the four-hole boiling flask that 50g adds the 250mL being furnished with electric mixer, constant speed stirring, four-hole boiling flask inserts constant temperature oil bath; After reaching the starting temperature of 80 DEG C in bottle, pass into SO in the dense ratio of 3.5% gas
3and nitrogen mixed gas, react 30 minutes; Initial reaction stage rushes temperature fast, subsequently temperature drops back, and natural constant temperature is to 96 DEG C, and system viscosity increases, but without obvious coking, latter temperature falls after rise, stopped reaction, and the reaction times shortens.Digestion time 2h, weightening finish is than 22%, and add 20% alkali lye neutralization in 1.35 ratios of weightening finish ratio, neutral temperature controls at 95 DEG C, in and time 2h; Add propyl carbinol and the alcohol mixture prepared by 1:1 of n-Octanol of 16% after neutralization, stir, obtain the displacement of reservoir oil heavy crude oil sulfonates tensio-active agent of concentration 50%.This product good water solubility, 5% solution is homogeneous; Interface performance reaches 10
-3the order of magnitude.
Embodiment 4
With C
14~ C
22lipid acid and boiling range 300 ~ 400 DEG C heavy alkyl benzene in 1:1 ratio mixing as sulfonation promotor, described sulfonation promotor mixes in 1:2 ratio with dehydration viscous crude, take the four-hole boiling flask that 50g adds the 250mL being furnished with electric mixer, constant speed stirs, and four-hole boiling flask inserts constant temperature oil bath; After reaching the starting temperature of 80 DEG C in bottle, pass into SO in the dense ratio of 3.5% gas
3and nitrogen mixed gas, react 30 minutes; Initial reaction stage rushes temperature fast, subsequently temperature drops back, and natural constant temperature is to 96 DEG C, and system viscosity increases, but without obvious coking, latter temperature falls after rise, stopped reaction, and the reaction times shortens.Digestion time 2h, weightening finish ratio is 23%, and sulfonic acid transformation efficiency improves; In weightening finish ratio 1.35 ratios add 20% alkali lye neutralization, neutral temperature controls at 95 DEG C, in and time 2h.Add propyl carbinol and the alcohol mixture prepared by 1:1 of n-Octanol of 16% after neutralization, stir, obtain the displacement of reservoir oil heavy crude oil sulfonates tensio-active agent of concentration 50%.This product good water solubility, 5% solution is homogeneous; Its weak base ternary system equilibrium interfacial tension reaches 10
-3the mN/m order of magnitude, meets the technical requirements of oil field displacement of reservoir oil type weak alkali surfactant.
From above-described embodiment 1-4 and comparative example 1, use as boiling range 220 ~ 300 DEG C of fulvene diesel oil or C
14~ C
22lipid acid, or boiling range 220 ~ 300 DEG C of fulvene diesel oil mix with the heavy alkyl benzene of boiling range 300 ~ 400 DEG C, or C
14~ C
22four kinds of sulfonation promotor that lipid acid mixes with the heavy alkyl benzene of boiling range 300 ~ 400 DEG C synthesize processing method and the viscous crude Direct Sulfonation process ration of heavy crude oil sulfonates tensio-active agent, the technological process reaction coking of the heavy crude oil sulfonates of the present invention's synthesis is few, sulfonic acid transformation efficiency is high, product water dissolubility and interface performance good, meet the basic demand of oil field surfactant oil displacement product; Adopt a charging, viscous crude is without the need to carrying out pre-treatment, and product, without the need to aftertreatment, decreases processing step, and synthetic method is simply efficient.
Claims (6)
1. adopt sulfonation promotor to synthesize a processing method for heavy crude oil sulfonates tensio-active agent, it is characterized in that: comprise the following steps:
1), first processed is carried out to viscous crude, obtain the viscous crude that dewaters;
2), by sulfonation promotor and above-mentioned dehydration viscous crude be mixed in proportion, after the starting temperature that temperature reaches 65 ~ 85 DEG C, pass into SO
3and nitrogen mixed gas, react 20 ~ 60 minutes; Initial reaction temperature rise, mid-term temperature drops back, natural constant temperature to 90-110 DEG C, add after aging alkali lye neutralize, add the alcohol mixture of preparation after neutralization, stir, obtain the displacement of reservoir oil heavy crude oil sulfonates tensio-active agent of concentration 50%.
2. a kind of processing method adopting sulfonation promotor to synthesize heavy crude oil sulfonates tensio-active agent according to claim 1, is characterized in that: described sulfonation promotor is boiling range 220 ~ 300 DEG C of fulvene diesel oil or C
14~ C
22lipid acid.
3. a kind of processing method adopting sulfonation promotor to synthesize heavy crude oil sulfonates tensio-active agent according to claim 1, is characterized in that: described sulfonation promotor is that boiling range 220 ~ 300 DEG C of fulvene diesel oil mix with the heavy alkyl benzene of boiling range 300 ~ 400 DEG C; Or C
14~ C
22lipid acid mixes with the heavy alkyl benzene of boiling range 300 ~ 400 DEG C.
4. a kind of processing method adopting sulfonation promotor to synthesize heavy crude oil sulfonates tensio-active agent according to claim 3, is characterized in that: the heavy alkyl benzene blending ratio of described boiling range 220 ~ 300 DEG C of fulvene diesel oil and boiling range 300 ~ 400 DEG C is 1:1 ~ 1:3; Described C
14~ C
22the heavy alkyl benzene blending ratio of lipid acid and boiling range 300 ~ 400 DEG C is 1:1 ~ 1:3.
5. a kind of processing method adopting sulfonation promotor to synthesize heavy crude oil sulfonates tensio-active agent according to claim 1, is characterized in that: described alcohol mixture is propyl carbinol and the n-Octanol of 10% ~ 20%, and propyl carbinol and n-Octanol blending ratio are 5:1 ~ 1:1.
6. a kind of processing method adopting sulfonation promotor to synthesize heavy crude oil sulfonates tensio-active agent according to claim 1, it is characterized in that: described sulfonation promotor and above-mentioned dehydration viscous crude blending ratio are 1:1 ~ 1:5, digestion time 2h, aging rear weightening finish, than 15 ~ 25%, adds 20% alkali lye neutralization in 1.1 ~ 1.5 ratios of weightening finish ratio; Described SO
3ratio 2-7% dense with the gas of nitrogen mixed gas.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109439304A (en) * | 2018-11-01 | 2019-03-08 | 中国石油天然气集团有限公司 | Using C14~C22The technique of fatty acid synthesis heavy crude oil sulfonates surfactant |
| CN111286314A (en) * | 2019-12-09 | 2020-06-16 | 大庆石油管理局有限公司 | Heavy oil sulfonate and synthesis method of heavy oil sulfonate surfactant |
| CN117304074A (en) * | 2023-09-22 | 2023-12-29 | 安徽金桐精细化学有限公司 | High-carbon barium alkylbenzenesulfonate, preparation method and application |
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| US3169142A (en) * | 1960-05-25 | 1965-02-09 | Stepan Chemical Co | Method for sulfonation and sulfation of organic compounds |
| US4148821A (en) * | 1974-10-16 | 1979-04-10 | Stepan Chemical Company | Process for sulfonation |
| CN101955451A (en) * | 2010-09-03 | 2011-01-26 | 中国石油大学(华东) | Method for preparing petroleum sulfonate surfactant by falling film sulfonation |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109439304A (en) * | 2018-11-01 | 2019-03-08 | 中国石油天然气集团有限公司 | Using C14~C22The technique of fatty acid synthesis heavy crude oil sulfonates surfactant |
| CN111286314A (en) * | 2019-12-09 | 2020-06-16 | 大庆石油管理局有限公司 | Heavy oil sulfonate and synthesis method of heavy oil sulfonate surfactant |
| CN117304074A (en) * | 2023-09-22 | 2023-12-29 | 安徽金桐精细化学有限公司 | High-carbon barium alkylbenzenesulfonate, preparation method and application |
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