CN101619209A - New application and composition of amide sodium sulfonate as oil field additive - Google Patents
New application and composition of amide sodium sulfonate as oil field additive Download PDFInfo
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Abstract
The invention discloses application of amide sulphonic acid presented in a general expression I or salt thereof to the reduction of crude oil viscosity, a composition containing the amide sulphonic acid or the salt thereof and a chemical reagent selected from triethylamine, lignosulphonates or polyoxyethylene polyoxypropylene alkyl phenol ether presented in a general expression II, application of the composition to the reduction of the crude oil viscosity, and a method of reducing the crude oil viscosity by using the amide sulphonic acid presented in the general expression I or the salt thereof. R1-R3 and M in the general expression I and R and a/b in the general expression II are defined in the text.
Description
Technical field
The present invention relates to amide group sulfonic acid or its salt and the composition that contains amide group sulfonic acid or its salt and their purposes in crude oil production, pit shaft lifting and conveying, particularly their purposes in the preparation oil field additive.
Background technology
Colloid that contains in the underground crude oil of containing and bitum quantity directly influence the viscosity of crude oil.Crude oil in the crude oil of China more than 60% belongs to and contains colloid and bitum viscous crude.The viscous crude field that has been found that at present mainly is distributed in oil fields such as the Liaohe River, Xinjiang, triumph, Henan, huge port, Jilin.
In crude oil production, pit shaft lifting and course of conveying, because viscosity of crude is big, particularly when crude oil contained certain water, along with crude oil flow, it is more and more thicker that crude oil can become.Because viscosity of crude is big, in exploitation, pit shaft lifting and course of conveying, it adsorbs consumingly to bottom and wall, and this not only makes the resistance of crude oil production and conveying increase, and has had a strong impact on the recovery ratio and the transport efficiency of crude oil.
Along with increasing rapidly of Chinese national economy, the demand of oil is also being increased day by day.To reducing viscosity of crude and crude oil production and transporting resistance, improve oil recovery factor and transport efficiency and have higher requirement.
Although the method for having developed polytype reduction viscosity of crude is to be used for exploitation, pit shaft lifting and conveying crude oil, for example, mix thin oil method, heating method and chemical viscosity reduction method, but still need the viscosity that new viscosity reducing process and new viscosity-depression agent reduce crude oil badly, change the flowability of crude oil, to be easy to exploitation, pit shaft lifting and conveying crude oil.
Summary of the invention
One aspect of the present invention relates to the amide group sulfonic acid shown in the general formula I or its salt reducing viscosity of crude, particularly reduces the purposes in the viscosity of thickened oil,
General formula I
R
1For containing C straight chain or side chain of at least one two key
12-C
25Thiazolinyl;
R
2C for straight or branched
1-C
8Alkyl;
R
3C for straight or branched
1-C
8Alkylidene group;
M is selected from hydrogen, ammonium ion and metallic cation, and described metallic cation is selected from sodium, potassium, lithium, calcium, magnesium, aluminium, iron, zinc, copper and manganese.
In one embodiment, R
1C for the straight or branched that contains two keys
12-C
25Thiazolinyl; R
2C for straight or branched
1-C
8Alkyl; R
3C for straight or branched
1-C
8Alkylidene group; M is selected from hydrogen, ammonium ion and metallic cation, and described metallic cation is selected from sodium, potassium, lithium, calcium and magnesium.
In another embodiment, R
1C for the straight or branched that contains two keys
15-C
23Thiazolinyl; R
2C for straight or branched
1-C
6Alkyl; R
3C for straight or branched
1-C
6Alkylidene group; M is selected from hydrogen, ammonium ion and metallic cation, and described metallic cation is selected from sodium and potassium.
The present invention relates to composition on the other hand, the chemical reagent that it comprises the amide group sulfonic acid shown in as hereinbefore defined the general formula I or its salt and is selected from the polyoxyethylene polyoxypropylene alkylbenzene phenolic ether shown in triethylamine, Sulfite lignin or the general formula I I,
General formula I I
R：H
3C-(CH
2)n-????n＝7-17
a/b＝50％～100％。
In one embodiment, described composition comprises the amide group sulfonic acid shown in the above defined general formula I or its salt and triethylamine, and based on the gross weight of described composition, the content of described amide group sulfonic acid or its salt is the about 99w/w% of about 70w/w%-, the preferred about 96w/w% of about 77w/w%-, the more preferably from about about 92w/w% of 82w/w%-.
In another embodiment, described composition comprises the amide group sulfonic acid shown in the above defined general formula I or its salt and Sulfite lignin, and based on the gross weight of described composition, the content of described amide group sulfonic acid or its salt is the about 95w/w% of about 5w/w%-, the preferred about 70w/w% of about 35w/w%-, the more preferably from about about 60w/w% of 40w/w%-.
In another embodiment, described composition comprises the polyoxyethylene polyoxypropylene alkylbenzene phenolic ether shown in the amide group sulfonic acid shown in the above defined general formula I or its salt and the general formula I I, and based on the gross weight of described composition, the content of described amide group sulfonic acid or its salt is the about 95w/w% of about 5w/w%-, the preferred about 75w/w% of about 30w/w%-, the more preferably from about about 60w/w% of 40w/w%-.
In another embodiment, in the polyoxyethylene polyoxypropylene alkylbenzene phenolic ether shown in the described general formula I I, n=7-11 and a/b=50%～95%.
The present invention relates to above-mentioned composition on the other hand reducing viscosity of crude, particularly reduces the purposes in the viscosity of thickened oil.
Another aspect of the present invention also relates to the method that reduces viscosity of crude, and described method comprises the steps:
(1) the amide group sulfonic acid shown in the general formula I defined above or its salt are mixed with water, form the aqueous solution;
(2) aqueous solution that obtains in the step (1) is mixed with crude oil to reduce viscosity of crude.
In one embodiment, also comprise the step of adding the polyoxyethylene polyoxypropylene alkylbenzene phenolic ether shown in triethylamine, Sulfite lignin or the general formula I I defined above in the described step (1).
In one embodiment, the total concn of the aqueous solution that obtains in the step (1) is about 5.0% (w/w) of about 0.01%-, and preferably about 0.02%-is about 3.0%, and more preferably from about 0.04%-is about 2.0%, and most preferably from about 0.04%-about 1.5%.
In another embodiment, the aqueous solution that obtains in crude oil and the step (1), is more preferably less than the mass ratio that equals about 65: 35 and mixes preferably smaller or equal to about 75: 25 with smaller or equal to about 90: 10.
Detailed description of the invention
In the above-mentioned definition and embodiment hereinafter described of the amide group sulfonic acid shown in the general formula I or its salt, term used herein has following implication:
Term " thiazolinyl " is meant the aliphatic hydrocarbon group of the straight or branched of being made up of carbon atom and hydrogen atom that contains at least one unsaturated double-bond, and it is connected with the rest part of molecule by singly-bound.Described thiazolinyl has about 12 to about 25 carbon atoms, preferred 15-23 carbon atom, more preferably 15-20 carbon atom.Described thiazolinyl preferably has a unsaturated double-bond.The limiting examples of described thiazolinyl includes but not limited to tridecylene base, tetradecene base, hexadecylene base, icosa alkene base, two tetradecene bases, 24 pentaene bases or the like.
Term " alkyl " is meant the aliphatic hydrocarbon group of the saturated straight or branched of being made up of carbon atom and hydrogen atom, and it is connected with the rest part of molecule by singly-bound.Described alkyl has 1-8 carbon atom, preferred 1-6 carbon atom, more preferably 1-4 carbon atom, most preferably 1-2 carbon atom.The limiting examples of described alkyl includes but not limited to such as methyl, ethyl, propyl group, 2-propyl group, normal-butyl, isobutyl-, tert-butyl, just-amyl group, 2-methyl butyl, neo-pentyl, n-hexyl, 2-methyl hexyl or the like.
Term " alkylidene group " only is meant the bivalent hydrocarbon chain of the saturated straight or branched of the rest part of the link molecule of being made up of carbon atom and hydrogen atom and residue group.Described alkylidene group has 1-8 carbon atom, and preferred 1-6 is carbon atom, more preferably 1-4 carbon atom.Described alkylidene group is preferably the alkylidene group of straight chain.The limiting examples of described alkyl includes but not limited to methylene radical, ethylidene, propylidene, butylidene, pentylidene, hexylidene, inferior heptyl and octylene or the like.
Term " ammonium ion " is meant formula-NH
4Group.
Term " Sulfite lignin " is meant ammonium salt, an alkali metal salt and the alkaline earth salt of lignosulfonic acid.The limiting examples of Sulfite lignin comprises ammonium lignin sulfonate, sodium lignosulfonate, lignin sulfonic acid potassium, lignosulfonic acid magnesium, calcium lignosulfonate or the like.
An aspect of of the present present invention relates to the amide group sulfonic acid shown in the general formula I or its salt reducing viscosity of crude, particularly reduces the purposes in the viscosity of thickened oil,
Wherein
R
1For containing C straight chain or side chain of at least one two key
12-C
25Thiazolinyl;
R
2C for straight or branched
1-C
8Alkyl;
R
3C for straight or branched
1-C
8Alkylidene group;
M is selected from hydrogen, ammonium ion and metallic cation, and described metallic cation is selected from sodium, potassium, lithium, calcium, magnesium, aluminium, iron, zinc, copper and manganese.
In one embodiment, R
1For containing C straight chain or side chain of at least one two key
15-C
23Thiazolinyl; In another embodiment, R
1For containing C straight chain or side chain of at least one two key
15-C
20Thiazolinyl; In another embodiment, R
1For containing C straight chain or side chain of two keys
12-C
25Thiazolinyl; In another embodiment, R
1For containing C straight chain or side chain of two keys
15-C
23Thiazolinyl; In another embodiment, R
1For containing C straight chain or side chain of two keys
15-C
20Thiazolinyl; In another embodiment, R
1C for the straight chain that contains two keys
12-C
25Thiazolinyl; In another embodiment, R
1C for the straight chain that contains two keys
15-C
23Thiazolinyl; In another embodiment, R
1C for the straight chain that contains two keys
15-C
20Thiazolinyl.
In one embodiment, R
2C for straight or branched
1-C
6Alkyl; In another embodiment, R
2C for straight or branched
1-C
4Alkyl; In another embodiment, R
2C for straight chain
1-C
8Alkyl; In another embodiment, R
2C for straight chain
1-C
6Alkyl; In another embodiment, R
2C for straight chain
1-C
4Alkyl; In another embodiment, R
2Be C
1-C
2Alkyl.
In one embodiment, R
3C for straight or branched
1-C
6Alkylidene group; In another embodiment, R
3C for straight or branched
1-C
4Alkylidene group; In another embodiment, R
3C for straight chain
1-C
8Alkylidene group; In another embodiment, R
3C for straight chain
1-C
6Alkylidene group; In another embodiment, R
3C for straight chain
1-C
4Alkylidene group.In another embodiment, R
3Be C
1-C
2Alkylidene group.
In one embodiment, M is selected from hydrogen, ammonium ion and described metal ion, and described metallic cation is selected from sodium, potassium, lithium, calcium, magnesium and aluminium.In one embodiment, M is selected from hydrogen, ammonium ion and described metal ion, and described metallic cation is selected from sodium, potassium, lithium, calcium and magnesium.In one embodiment, M is selected from hydrogen, ammonium ion and described metal ion, and described metallic cation is selected from sodium and potassium.In one embodiment, M is selected from hydrogen, ammonium ion and described metal ion, and described metallic cation is selected from sodium.
In one embodiment, R
1C for the straight or branched that contains two keys
12-C
25Thiazolinyl; R
2C for straight or branched
1-C
8Alkyl; R
3C for straight or branched
1-C
8Alkylidene group; M is hydrogen, ammonium ion or metallic cation, and described metallic cation is selected from sodium, potassium, lithium, calcium and magnesium.
In another embodiment, R
1C for the straight or branched that contains two keys
15-C
23Thiazolinyl; R
2C for straight or branched
1-C
6Alkyl; R
3C for straight or branched
1-C
6Alkylidene group; M is hydrogen, ammonium ion or metallic cation, and described metallic cation is selected from sodium, potassium, lithium, calcium and magnesium.
In another embodiment, R
1C for the straight or branched that contains two keys
15-C
20Thiazolinyl; R
2C for straight or branched
1-C
4Alkyl; R
3C for straight or branched
1-C
4Alkylidene group; M is hydrogen, ammonium ion or metallic cation, and described metallic cation is selected from sodium and potassium.
In one embodiment, R
1C for the straight chain that contains two keys
12-C
25Thiazolinyl; R
2C for straight chain
1-C
8Alkyl; R
3C for straight chain
1-C
8Alkylidene group; M is hydrogen, ammonium ion or metallic cation, and described metallic cation is selected from sodium, potassium, lithium, calcium and magnesium.
In another embodiment, R
1C for the straight chain that contains two keys
15-C
23Thiazolinyl; R
2C for straight chain
1-C
6Alkyl; R
3C for straight chain
1-C
6Alkylidene group; M is hydrogen, ammonium ion or metallic cation, and described metallic cation is selected from sodium, potassium, lithium, calcium and magnesium.
In another embodiment, R
1C for the straight chain that contains two keys
15-C
20Thiazolinyl; R
2C for straight chain
1-C
4Alkyl; R
3C for straight chain
1-C
4Alkylidene group; M is hydrogen, ammonium ion or metallic cation, and described metallic cation is selected from sodium and potassium.
Amide group sulfonic acid shown in the general formula I or its salt are water-soluble good, have very strong surfactivity, can obviously change oil water interfacial tension.With N-oleoyl-N methyl taurine sodium is example, uses JZHY-180 type surface tension instrument, measures the surface tension of N-oleoyl-N methyl taurine sodium water solution by suspension ring method conventional in this area.In distilled water, the micelle-forming concentration of N-oleoyl-N methyl taurine sodium is about 0.16g/L; At the about 15000mg/L of NaCl, Ca
2+About 800mg/L, Mg
2+In the simulated formation water of about 200mg/L, the micelle-forming concentration of N-oleoyl-N methyl taurine sodium is about 0.024g/L; Under this concentration, surface tension is about 26.7mN/m.
The contriver is surprised to find that to have that the amide group sulfonic acid shown in the very strong surface-active general formula I or its salt are used for crude oil production, pit shaft lifting and when carrying, especially for the exploitation of viscous crude, pit shaft lifting with when carrying, can significantly reduce the viscosity of crude oil, particularly viscous crude.Therefore, available its preparation oil field additive particularly prepares the oil field viscosity-depression agent.
When the amide group sulfonic acid shown in the general formula I or its salt are used viscosity-depression agent and are reduced viscosity of crude in the preparation oil field, it has following advantage: (1) is to crude oil, the wide accommodation of viscous crude particularly, it all has good viscosity reducing effect to common heavy oil, special viscous crude and super viscous crude, is specially adapted to viscosity and is about 1000-46 * 10
4The viscous crude of mPa.s; (2) good salt tolerance is applicable to NaCl about 20 * 10
4Mg/L, calcium+magnesium about 2 * 10
4The high salinity highrank fuel salinity water of mg/L; (3) to crude oil, viscous crude particularly, viscosity reduction efficient height and consumption are low, concentration just can be with crude oil for the aqueous solution of about 0.01%-1.0%, particularly the viscosity drop of viscous crude is low to moderate below about 500mPa.s, preferably be reduced to below about 300mPa.s, more preferably be reduced to below about 150mPa.s, also more preferably be reduced to below the 50mPa.s; (4) the Applicable temperature scope is wide, and＜150 ℃ condition is all applicable; (5) good water solubility, its aqueous stability is good, is not subjected to the influence of storage period, even its long-time placement does not influence its viscosity reducing effect to crude oil yet; (6) behind the reduction viscosity of crude, formed crude oil emulsion good stability.
Preparing the oil field with the amide group sulfonic acid shown in the general formula I or its salt comprises with viscosity-depression agent or the process that reduces viscosity of crude the amide group sulfonic acid shown in the general formula I or its salt are mixed the step that forms the aqueous solution with water.
Amide group sulfonic acid shown in the general formula I or its salt in the preparation oil field with viscosity-depression agent or when reducing viscosity of crude, those skilled in the art can according to himself technical knowledge and the disclosure can according to usage determine the preparation oil field with viscosity-depression agent the concentration of the aqueous solution of the amide group sulfonic acid shown in the general formula I or its salt and suitable crude oil and the ratio of this aqueous solution during with the reduction viscosity of crude.
For example, being used to prepare the oil field is about 5.0% (w/w) of about 0.01%-with viscosity-depression agent or the concentration that reduces the aqueous solution of the amide group sulfonic acid shown in the general formula I of viscosity of crude or its salt, preferred about 0.02%-is about 3.0%, and more preferably from about 0.04%-is about 2.0%, and most preferably from about 0.04%-about 1.5%.
For another example, the mass ratio of crude oil and this aqueous solution is smaller or equal to about 90: 10, preferably smaller or equal to about 75: 25, is more preferably less than and equals about 65: 35.But those skilled in the art are appreciated that also the concentration of aqueous solution that exceeds above-mentioned scope and the ratio of the crude oil and the aqueous solution remain acceptable.
Be used to prepare the described aqueous solution water kind without limits, can be tap water, also can be oilfield sewage, preferred oilfield sewage.
Amide group sulfonic acid shown in the general formula I or its salt compound can use suitable reaction raw materials by but be not limited to following reaction scheme and synthesize.Those skilled in the art can be according to technical knowledge and disclosure suitable reaction temperature, reaction times and the reaction solvent that can according to usage determine following reaction scheme of himself.
1. hydroxy sulfonate is synthetic
(reaction conditions can be referring to Kunka, I.; Wirpsza, Z. " Preparation and reactions ofmonosulfomethylmelamine. " Tetrahedron (1984), 40 (10), 1855-6; Igawa, Manabu; Fukushi, Yasuko; Hayashita, Takashi; Hoffmann, Michael R. " Selective transport of aldehydes across an anion-exchange membrane via theformation of bisulfite adducts. " Industrial ﹠amp; Engineering Chemistry Research (1990), 29 (5), 857-61; People such as Ceng Renquan " study on the synthesis of aminomethanesulfonic acid ", " Sichuan chemical industry ", 2005 the 8th the 2nd phases of volume)
(reaction conditions can be referring to Lauer, Walter M.; Hill, Archie., " Addition of sodiumbisulfite to alkylene oxides. " Journal of the American Chemical Society (1936), 581873-4)
(reaction conditions can be referring to Cao Zhanmei, the synthetic and anticorrosion-antiscaling property research of 2-hydroxy-propanesulfonic acid (EDHPS) " quadrol is two-", " Treatment of Industrial Water ", (2006), 26 (1), 24-27; People such as Chen Zhengguo " study on the synthesis of 3-chloro-2-hydroxypropionate sodium ", " colloid and polymkeric substance ", 2003 the 21st the 2nd phases of volume)
2. alkyl amino sulfonate is synthetic
RNH
2+HOCH
2SO
3Na→RNHCH
2SO
3Na+H
2O
RNH
2+HOCH
2CH
2SO
3Na→RNHCH
2CH
2SO
3Na+H
2O
(reaction conditions can be referring to Hellmann, people such as Heinrich " The mechanism of theaminomethylation reaction.II.The aminomethylating agent. " ChemischeBerichte (1956), 8981-95)
(reaction conditions is translated " contemporary methodology of organic synthesis " (ModernMethods of Organic Synthesis (4th), original work: William Carruthers referring to Wang Quan is auspicious with Li Zhiming, Iain Coldham), press of East China University of Science, on March 1st, 2006 published, the 443rd page)
(reaction conditions can be referring to Young, Rodney C.; Ganellin, C.Robin; Graham, Michael J.; Mitchell, Robert C.; Roantree, Michael L.; " Zwitterionic analogsof cimetidine as H2 receptor antagonists ", Journal of Medicinal Chemistry (1987), 30 (7), 1150-6)
3. final compound is synthetic
(reaction conditions is translated " contemporary methodology of organic synthesis " (ModernMethods of Organic Synthesis (4th), original work: William Carruthers referring to Wang Quan is auspicious with Li Zhiming, Iain Coldham), press of East China University of Science, on March 1st, 2006 published, the 443rd page)
The present invention also relates to composition on the other hand, the chemical reagent that it comprises the amide group sulfonic acid shown in the above defined general formula I or its salt and is selected from the polyoxyethylene polyoxypropylene alkylbenzene phenolic ether shown in triethylamine, Sulfite lignin or the general formula I I:
General formula I
R
1-R
3With M all as hereinbefore defined;
General formula I I
R：H
3C-(CH
2)n-??????n＝7-17
a/b＝50％～100％。
In one embodiment, described composition comprises the amide group sulfonic acid shown in the above defined general formula I or its salt and the chemical reagent that is selected from triethylamine.Based on the gross weight of said composition, the content of the amide group sulfonic acid shown in the general formula I or its salt is about 99% (w/w) of about 70%-, and preferably about 77%-is about 96%, and more preferably from about 82%-about 92%.
In one embodiment, described composition comprises the amide group sulfonic acid shown in the above defined general formula I or its salt and the chemical reagent that is selected from Sulfite lignin, particularly sodium lignosulfonate and lignin sulfonic acid potassium.Based on the gross weight of said composition, the content of the amide group sulfonic acid shown in the general formula I or its salt is about 95% (w/w) of about 5%-, and preferably about 35%-is about 70%, and more preferably from about 40%-about 60%.
In one embodiment, described composition comprises the amide group sulfonic acid shown in the above defined general formula I or its salt and the chemical reagent that is selected from the polyoxyethylene polyoxypropylene alkylbenzene phenolic ether shown in the general formula I I.Based on the gross weight of said composition, the content of the amide group sulfonic acid shown in the general formula I or its salt is about 95% (w/w) of about 5%-, and preferably about 30%-is about 75%, and more preferably from about 40%-about 60%:
General formula I I
R:H
3C-(CH
2) n-n=7-17, preferred n=7-11,
A/b=50%～100%, preferred a/b=50%～95%.
One aspect of the present invention also relates to above-mentioned composition to be used viscosity-depression agent and reduces viscosity of crude in the preparation oil field, particularly reduces the purposes in the viscosity of thickened oil.The preparation oil field comprises with the process that reduces viscosity of crude with viscosity-depression agent mixes the step that forms the aqueous solution with above-mentioned composition with water.
Similarly, those skilled in the art can according to usage be identified for preparing oil field viscosity-depression agent and the concentration of the aqueous solution of the present composition that reduces viscosity of crude and the mass ratio of crude oil and this aqueous solution according to the technical knowledge and the disclosure of himself.
For example, being used to prepare the oil field is about 5.0% (w/w) of about 0.01%-with viscosity-depression agent and the concentration of aqueous solution that reduces the above-mentioned composition of viscosity of crude, and preferably about 0.02%-is about 3.0%, and more preferably from about 0.04%-is about 2.0%, and most preferably from about 0.04%-about 1.5%.
For another example, the mass ratio of crude oil and this aqueous solution is as smaller or equal to about 90: 10, preferably smaller or equal to about 75: 25, be more preferably less than and equal about 65: 35, but it will be appreciated by those skilled in the art that the concentration of aqueous solution that exceeds above-mentioned scope and the ratio of the crude oil and the described aqueous solution remain acceptable.
Be used to prepare the described aqueous solution water kind without limits, can be tap water, also can be oilfield sewage, preferred oilfield sewage.
The present invention also relates to the reduction viscosity of crude on the other hand, particularly reduces the method for viscosity of thickened oil, and described method comprises the steps:
(1) the amide group sulfonic acid shown in the general formula I defined above or its salt are mixed with water, form the aqueous solution;
(2) aqueous solution that obtains in the step (1) is mixed with crude oil to reduce viscosity of crude.
In another embodiment, also comprise the step of adding the chemical reagent that is selected from the polyoxyethylene polyoxypropylene alkylbenzene phenolic ether shown in triethylamine or Sulfite lignin or the general formula I I defined above in the described step (1).
Those skilled in the art can understand the step of adding above-mentioned chemical reagent and can implement as follows: above-mentioned chemical reagent with after water mixes, is mixed with the amide group sulfonic acid shown in the general formula I or its salt again; Perhaps the amide group sulfonic acid shown in the general formula I or its salt and above-mentioned chemical reagent are mixed with water together; Perhaps with the amide group sulfonic acid shown in the general formula I or its salt with after water mixes, mix with above-mentioned chemical reagent again.
When adding triethylamine, the mass ratio of the amide group sulfonic acid shown in the general formula I or its salt and triethylamine is about 70: about 99: 1 of 30-, preferably about 77: about 96: 4 of 23-, more preferably from about 82: about 92: 8 of 18-.
When adding Sulfite lignin, when preferred sodium lignosulfonate and lignin sulfonic acid potassium, the mass ratio of the amide group sulfonic acid shown in the general formula I or its salt and Sulfite lignin is about 5: about 95: 5 of 95-, preferably about 35: about 70: 30 of 65-, more preferably from about 40: about 60: 40 of 60-.
When the polyoxyethylene polyoxypropylene alkylbenzene phenolic ether shown in the interpolation general formula I I defined above, the mass ratio of the polyoxyethylene polyoxypropylene alkylbenzene phenolic ether shown in the amide group sulfonic acid shown in the general formula I or its salt and the general formula I I is about 5: about 95: 5 of 95-, preferred about 30: about 75: 25 of 70-, more preferably from about 40: about 60: 40 of 60-.
In one embodiment, in the polyoxyethylene polyoxypropylene alkylbenzene phenolic ether shown in the described general formula I I, n is preferably 7-11, and a/b is preferably 50%～95%.
In one embodiment, the total concn of the aqueous solution that obtains in the step (1) is about 5.0% (w/w) of about 0.01%-, and preferably about 0.02%-is about 3.0%, and more preferably from about 0.04%-is about 2.0%, and most preferably from about 0.04%-about 1.5%.
In another embodiment, the aqueous solution that obtains in crude oil and the step (1), is more preferably less than the mass ratio that equals about 65: 35 and mixes preferably smaller or equal to about 75: 25 with smaller or equal to about 90: 10.
Embodiment
Can understand the present invention better by following specific embodiment, but given specific embodiment should not be construed as the present invention and only limits to following specific embodiment just for exemplary illustration the present invention.Except as otherwise noted, employed per-cent all is weight percentage in following examples.Used crude oil sample all after the KDM-2 type ultrasonic crude-oil dehydrating apparatus dehydration degassing that Heze, Shandong electron temperature-control technical institute produces, is for experiment.Used reagent or obtain or prepare according to synthetic schemes disclosed herein by being purchased.
Active constituent content is to the influence of viscosity of crude in embodiment 1 viscosity-depression agent
1.1 in distilled water, active constituent content is to the influence of viscosity of crude in the viscosity-depression agent
Crude oil sample: the special viscous crude of old 375 wells, recording its viscosity under 60 ℃ with ordinary method is 13900mPas;
Viscosity-depression agent: effective constituent is example with N-oleoyl-N methyl taurine sodium, is mixed with solution in different concentration in distilled water;
The mass ratio of crude oil and viscosity-depression agent: 7: 3;
Treatment temp: 60 ℃;
The special viscous crude of a certain amount of old 375 wells of weighing places Yongxing, Shandong instrument plant Water Tank with Temp.-controlled at 60 ℃ of following constant temperature 6h in the 125ml wide-necked bottle then.Be mixed with the N-oleoyl-N methyl taurine sodium water solution (being viscosity-depression agent) of different concns with distilled water; and after placing 60 ℃ thermostat(t)ed water constant temperature 0.5h; pour in the above-mentioned oil sample by the mass ratio of 7: 3 crude oil and viscosity-depression agent, stir, form milk sap with glass stick.Viscosity with BROOKFILD DV-III+ type rheometer measurement milk sap.Viscosity of crude and viscosity break ratio after the processing are as shown in table 1:
In table 1 distilled water, N-oleoyl-N methyl taurine sodium water solution concentration is to the influence of viscosity of crude
| N-oleoyl-N methyl taurine sodium water | Handle back viscosity of crude/mPas (shearing rate 10sec -1) | Viscosity break ratio/% (shearing rate 10sec -1) | Handle back viscosity of crude/mPas (shearing rate 5sec -1) | Viscosity break ratio/% (shearing rate 5sec -1) |
| Strength of solution (w/w) | ||||
| ??0.4％ | ?760 | ??94.5 | ??875 | ??93.7 |
| ??0.5％ | ?210 | ??98.5 | ??250 | ??98.2 |
| ??0.7％ | ?190 | ??98.6 | ??210 | ??98.5 |
| ??1.0％ | ?80 | ??99.4 | ??75 | ??99.5 |
By in the above-mentioned table 1 as can be known, when N-oleoyl-N methyl taurine sodium water solution concentration increased, when promptly active constituent content increased in the viscosity-depression agent, milk sap viscosity reduced.
1.2 in oilfield sewage, active constituent content is to the influence of viscosity of crude in the viscosity-depression agent
Except use has the N-oleoyl-N methyl taurine sodium water solution of oilfield sewage preparation different concns of following composition; similar condition in employing and the foregoing description 1.1; evaluation is in oilfield sewage, and active constituent content is to the influence of viscosity of crude in the viscosity-depression agent.
Table 2 oilfield sewage Analysis Results of Water Quality
In table 3 oilfield sewage, N-oleoyl-N methyl taurine sodium water solution concentration is to the influence of viscosity of crude
| N-oleoyl-N-N-methyltaurine sodium water solution concentration (w/w) | Handle back viscosity of crude/mPas (shearing rate 10sec -1) | Viscosity break ratio/% (shearing rate 10sec -1) | Handle back viscosity of crude/mPas (shearing rate 5sec -1) | Viscosity break ratio/% (shearing rate 5 sec -1) |
| ??0.4％ | ??58.7 | ??99.6 | ??75 | ??99.5 |
| ??0.5％ | ??69 | ??99.5 | ??74 | ??99.5 |
| ??0.6％ | ??39.5 | ??99.7 | ??55.2 | ??99.6 |
| ??0.8％ | ??40.5 | ??99.7 | ??45.2 | ??99.7 |
By in the above-mentioned table 3 as can be known, when using the identical viscosity-depression agent of active constituent content, be better than the effect of distilled water emulsified crude oil with the effect of oilfield sewage emulsified crude oil.
1.3 in hypersalinity water, active constituent content is to the influence of the viscosity of dissimilar crude oil in the viscosity-depression agent
Use contains NaCl 15 * 10
3Mg/L, Ca
2+600mg/L and Mg
2+N-oleoyl-N methyl taurine the sodium water solution of the hypersalinity water preparation different concns of 200mg/L; similar experiment condition in employing and the foregoing description 1.1; estimating in hypersalinity water under the different temperature, active constituent content is to the influence of the viscosity of dissimilar crude oil in the viscosity-depression agent.
Table 4 is in high mineral water, and N-oleoyl-N methyl taurine sodium water solution concentration is to the influence of the viscosity of dissimilar crude oil
By in the above-mentioned table 4 as can be known, in hypersalinity water, the viscosity-depression agent with different active constituent contents all has good viscosity reducing effect to the dissimilar crude oil with different viscosity.
The mass ratio of embodiment 2 crude oil and viscosity-depression agent is to reducing the influence of viscosity of crude
2.1 different active constituent contents are to reducing the influence of viscosity of crude in different crude oil and the mass ratio of viscosity-depression agent and the viscosity-depression agent
Crude oil sample: 21 10-13 wells of Bohai Sea common heavy oil, recording its viscosity under 50C with ordinary method is 3769mPas;
Viscosity-depression agent: effective constituent is example with N-oleoyl-N methyl taurine sodium, is containing NaCl15000mg/L, Ca
2++ Mg
2+Be mixed with solution in different concentration in the hypersalinity water for 400mg/L;
The mass ratio of crude oil and viscosity-depression agent: as shown in table 5;
Treatment temp: 50 ℃;
Adopt the similar experiment condition described in the embodiment 1.1, different active constituent contents influence the viscosity reduction of 21 10-13 wells of Bohai Sea common heavy oil in the 50 ℃ of mass ratioes of measuring different crude oil and viscosity-depression agent down and viscosity-depression agent.
Different active constituent contents are to the influence of viscosity of crude in the mass ratio of the different crude oil of table 5 and viscosity-depression agent and the viscosity-depression agent
By in the above-mentioned table 5 as can be known, in the emulsification of crude oil process, under the condition that active constituent content is identical in viscosity-depression agent, the increase of viscosity-depression agent consumption helps the reduction of crude oil emulsion viscosity.
2.2 in oilfield sewage, the different crude oil and the mass ratio of viscosity-depression agent are to the influence of viscosity of crude
Crude oil sample: the oblique 139 well common heavy oils of stake, recording its viscosity under 50 ℃ with ordinary method is 6028mPa.s;
Viscosity-depression agent: effective constituent is example with N-oleoyl-N methyl taurine sodium, is mixed with 0.4% the aqueous solution in oilfield sewage;
The mass ratio of crude oil and viscosity-depression agent: as shown in table 6 below;
Treatment temp: 50 ℃;
Adopt the similar experiment condition described in the embodiment 1.1, measure quality at different crude oil and viscosity-depression agent down than under the condition, to the viscosity reduction influence of the oblique 139 well common heavy oils of stake at 50 ℃.
The crude oil that table 6 is different and the mass ratio of viscosity-depression agent are to the influence of viscosity of crude
| The mass ratio of crude oil and viscosity-depression agent | Viscosity of crude after the processing (mPa.s) |
| ??9∶1 | ??6000 |
| ??8∶2 | ??500 |
| ??7∶3 | ??28 |
| ??65∶35 | ??14 |
| ??5∶5 | ??12 |
| ??3∶7 | ??12 |
| ??2∶8 | ??14 |
| ??1∶9 | ??10 |
By table 6 as seen, the consumption of viscosity-depression agent increases, and viscosity of crude obviously reduces, and viscosity reducing effect is good, considers that from production cost the mass ratio of crude oil and viscosity-depression agent is 65/35 o'clock the best.
The stability of embodiment 3 viscosity-depression agents
Crude oil sample: the special viscous crude of old 375 wells, recording its viscosity under 60 ℃ with ordinary method is 13900mPas;
Viscosity-depression agent: effective constituent is example with N-oleoyl-N methyl taurine sodium, is mixed with 0.7% the aqueous solution in containing the water of NaCl15000mg/L;
The mass ratio of crude oil and viscosity-depression agent: 7: 3;
Treatment temp: 60 ℃;
After viscosity-depression agent (being N-oleoyl-N methyl taurine sodium water solution) is placed different time as shown in table 7; adopt the similar experiment condition described in the embodiment 1.1, the viscosity-depression agent after 60 ℃ different time is placed in measurement down is to the influence of the special viscosity of thickened oil of old 375 wells.
The viscosity-depression agent of table 7 different storage periods is to the influence of viscosity of crude
| The storage period of viscosity-depression agent | Viscosity of crude after the processing (mPas) |
| ??5h | ??61 |
| ??1d | ??60 |
| ??5d | ??64 |
| ??10d | ??60 |
| 1 month | ??66 |
| 2 months | ??67 |
| 6 months | ??71 |
| 1 year | ??68 |
| 2 years | ??69 |
By in the above-mentioned table 7 as can be seen, along with the prolongation of storage period of viscosity-depression agent,, do not influence the effect that viscosity-depression agent reduces viscosity of crude even place 2 years.This shows that viscosity-depression agent is stable.
The stability of crude oil emulsion after embodiment 4 emulsifications
Crude oil sample: the special viscous crude of old 375 wells, recording its viscosity under 60 ℃ with ordinary method is 13900mPas;
Viscosity-depression agent: effective constituent is example with N-oleoyl-N methyl taurine sodium, is mixed with 0.7% the aqueous solution in containing the water of NaCl15000mg/L;
The mass ratio of crude oil and viscosity-depression agent: 7: 3;
Treatment temp: 60 ℃;
Adopt the similar experiment condition described in the embodiment 1.1, measure the influence of viscosity-depression agent to the special viscosity of thickened oil of old 375 wells down at 60 ℃, find that viscous crude by viscosity-depression agent emulsification, is form of emulsion, this moment, viscosity was 61mPas.After leaving standstill 14 hours under 60 ℃, find viscous oil emulsion by the breakdown of emulsion layering subsequently, the upper strata is an oil phase, and lower floor is a water, and upper oil phase viscosity is 5362mPas.Viscous oil emulsion after will leaving standstill then stirs again, is form of emulsion once more, and viscosity is 64mPas.
Embodiment 5 present compositions are to the influence of viscosity of crude
5.1 general formula I+triethylamine
Crude oil sample: the special viscous crude of old 375 wells, recording its viscosity under 60 ℃ with ordinary method is 13900mPas;
Viscosity-depression agent 1: contain (1) N-oleoyl-N methyl taurine sodium, containing NaCl15000mg/L, Mg
2+200mg/L and Ca
2+Be mixed with 0.5% and 0.7% the aqueous solution in the water of 600mg/L respectively; And (2) triethylamine, its concentration in above-mentioned hypersalinity water is as shown in table 7
The mass ratio of crude oil and viscosity-depression agent: 7: 3;
Treatment temp: 60 ℃;
Adopt the similar experiment condition described in the embodiment 1.1,60 ℃ of influences of measuring 1 pair of viscosity of crude of viscosity-depression agent down.
The influence of 1 pair of viscosity of crude of table 8 viscosity-depression agent
By in the table 8 as can be known, N-oleoyl-when N methyl taurine sodium consumption is high, triethylamine is little to the viscosity of crude influence; When N-oleoyl-N methyl taurine sodium consumption hanged down, triethylamine was big to the viscosity of crude influence.
5.2 general formula I+Sulfite lignin
Crude oil sample: the special viscous crude of old 375 wells, recording its viscosity under 60 ℃ with ordinary method is 13900mPas;
Viscosity-depression agent 2: contain (1) N-oleoyl-N methyl taurine sodium, it is containing NaCl15000mg/L, Mg
2+200mg/L and Ca
2+Be mixed with 0.4% the aqueous solution in the water of 600mg/L; And (2) Sulfite lignin are example with the sodium lignosulfonate, and the mass ratio of itself and N-oleoyl-N methyl taurine sodium is as shown in table 9
The mass ratio of crude oil and viscosity-depression agent: 7: 3;
Treatment temp: 60 ℃;
Adopt the similar experiment condition described in the embodiment 1.1,60 ℃ of influences of measuring 2 pairs of viscosity of crude of viscosity-depression agent down.
The influence of 2 pairs of viscosity of crude of table 9 viscosity-depression agent
| N-oleoyl-N methyl taurine sodium: sodium lignosulfonate (w/w) | Viscosity break ratio (%) |
| ??10∶0 | ??94 |
| ??9∶1 | ??94 |
| ??8∶2 | ??95 |
| ??7∶3 | ??97 |
| ??6∶4 | ??99 |
| ??5∶5 | ??99 |
| ??4∶6 | ??99 |
| ??3∶7 | ??96 |
| ??2∶8 | ??95 |
| ??1∶9 | ??94 |
By in the table 9 as can be known, contain N-and have good viscosity reducing effect by the viscosity-depression agent of acyl group-N methyl taurine sodium and sodium lignosulfonate.When the two mass ratio is 6: 4-4: in the time of 6, viscosity reducing effect is best.5.3 general formula I+general formula I I
Crude oil sample: the special viscous crude of old 375 wells, recording its viscosity under 60 ℃ with ordinary method is 13900mPas;
Viscosity-depression agent 3: containing (1) compound of Formula I is example with N-oleoyl-N methyl taurine sodium, and it is containing NaCl 15000mg/L, Mg
2+200mg/L and Ca
2+Be mixed with 0.4% the aqueous solution in the water of 600mg/L; And the polyoxyethylene polyoxypropylene alkylbenzene phenolic ether shown in (2) general formula I I, wherein a/b=1: 1, R=CH
3-(CH
2)
8-, the mass ratio of itself and N-oleoyl-N methyl taurine sodium is as shown in table 10;
The mass ratio of crude oil and viscosity-depression agent: 7: 3;
Treatment temp: 60 ℃;
Adopt the similar experiment condition described in the embodiment 1.1,60 ℃ of influences of measuring 3 pairs of viscosity of crude of viscosity-depression agent down.
The influence of 3 pairs of viscosity of crude of table 10 viscosity-depression agent
| General formula I: general formula I I (w/w) | Viscosity break ratio (%) |
| ??10∶0 | ??94 |
| ??9∶1 | ??95 |
| ??8∶2 | ??96 |
| ??7∶3 | ??98 |
| ??6∶4 | ??99 |
| ??5∶5 | ??99 |
| ??4∶6 | ??99 |
| ??3∶7 | ??97 |
| ??2∶8 | ??96 |
| ??1∶9 | ??95 |
By in the table 10 as can be known, the viscosity-depression agent that contains the polyoxyethylene polyoxypropylene alkylbenzene phenolic ether shown in N-oleoyl-N methyl taurine sodium and the general formula I I has good viscosity reducing effect.When the two ratio is 6: 4-4: in the time of 6, viscosity reducing effect is best.
Claims (10)
1. the amide group sulfonic acid shown in the general formula I or its salt purposes in reducing viscosity of crude,
General formula I
R
1For containing C straight chain or side chain of at least one two key
12-C
25Thiazolinyl;
R
2C for straight or branched
1-C
8Alkyl;
R
3C for straight or branched
1-C
8Alkylidene group;
M is selected from hydrogen, ammonium ion and metallic cation, and described metallic cation is selected from sodium, potassium, lithium, calcium, magnesium, aluminium, iron, zinc, copper and manganese.
2. purposes as claimed in claim 1, R
1C for the straight or branched that contains two keys
12-C
25Thiazolinyl, described metallic cation is selected from sodium, potassium, lithium, calcium and magnesium.
3. as the described purposes of claim 1-2, R
1C for the straight or branched that contains two keys
15-C
23Thiazolinyl, R
2C for straight or branched
1-C
6Alkyl, R
3C for straight or branched
1-C
6Alkylidene group, described metallic cation is selected from sodium and potassium.
4. composition, the chemical reagent that it comprises the amide group sulfonic acid shown in the described general formula I of arbitrary claim or its salt among the claim 1-3 and is selected from the polyoxyethylene polyoxypropylene alkylbenzene phenolic ether shown in triethylamine, Sulfite lignin or the general formula I I,
General formula I
R
1-R
3With M all such as among the claim 1-3 definition;
General formula I I
R：H
3C-(CH
2)n-????n＝7-17
a/b＝50％～100％。
5. composition as claimed in claim 4, described chemical reagent is selected from triethylamine, and based on the gross weight of described composition, the content of the amide group sulfonic acid shown in the described general formula I of arbitrary claim or its salt is the about 99w/w% of about 70w/w%-among the claim 1-3, the preferred about 96w/w% of about 77w/w%-, the more preferably from about about 92w/w% of 82w/w%-.
6. composition as claimed in claim 4, described chemical reagent is selected from Sulfite lignin, and based on the gross weight of described composition, the content of the amide group sulfonic acid shown in the described general formula I of arbitrary claim or its salt is about 95% (w/w) of about 5%-among the claim 1-3, preferred about 35%-is about 70%, and more preferably from about 40%-about 60%.
7. composition as claimed in claim 4, described chemical reagent is selected from the polyoxyethylene polyoxypropylene alkylbenzene phenolic ether shown in the general formula I I, and based on the gross weight of described composition, the content of the amide group sulfonic acid shown in the described general formula I of arbitrary claim or its salt is about 95% (w/w) of about 5%-among the claim 1-3, preferred about 30%-is about 75%, and more preferably from about 40%-about 60%.
8. the purposes of the described composition of arbitrary claim in reducing viscosity of crude among the claim 4-7.
9. reduce the method for viscosity of crude, described method comprises the steps:
(1) the amide group sulfonic acid shown in the defined general formula I of arbitrary claim or its salt among the claim 1-3 are mixed with water, form the aqueous solution;
(2) aqueous solution that obtains in the step (1) is mixed with crude oil to reduce viscosity of crude.
10. the method for reduction viscosity of crude as claimed in claim 9, described step (1) also comprise adds the polyoxyethylene polyoxypropylene alkylbenzene phenolic ether shown in triethylamine, Sulfite lignin or the general formula I I:
General formula I I
R：H
3C-(CH
2)n-?????????n＝7-17，
a/b＝50％～100％。
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Address after: 257000 No. 188, three West Road, Shandong, Dongying Patentee after: Petroleum works Institute for Research and Technology of Shengli Oil Field branch company of Sinopec Group Address before: 257000 No. 188, three West Road, Shandong, Dongying Patentee before: SINOPEC Shengli Oilfield Drilling Technology Institute |
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Granted publication date: 20130508 Termination date: 20190731 |