CN106701050A - Crude oil viscosity reducer, preparation method and application - Google Patents
Crude oil viscosity reducer, preparation method and application Download PDFInfo
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- CN106701050A CN106701050A CN201611146632.4A CN201611146632A CN106701050A CN 106701050 A CN106701050 A CN 106701050A CN 201611146632 A CN201611146632 A CN 201611146632A CN 106701050 A CN106701050 A CN 106701050A
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- formula
- heavy crude
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- thinner
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
- C09K8/524—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning organic depositions, e.g. paraffins or asphaltenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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
- C09K8/588—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 polymers
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17D—PIPE-LINE SYSTEMS; PIPE-LINES
- F17D1/00—Pipe-line systems
- F17D1/08—Pipe-line systems for liquids or viscous products
- F17D1/16—Facilitating the conveyance of liquids or effecting the conveyance of viscous products by modification of their viscosity
Abstract
The invention discloses a crude oil viscosity reducer which is prepared from compounds of formula I, formula II and formula III as shown in the specification through reactions, and in the formulae, n is equal to 13 to 17. The invention further provides a preparation method for the crude oil viscosity reducer, and application of the crude oil viscosity reducer. The crude oil viscosity reducer disclosed by the invention is good in viscosity reduction effect and good in dissolubility, and can be used for collecting and transporting crude oil directly, and in addition, the preparation method of the crude oil viscosity reducer disclosed by the invention is simple in process.
Description
Technical field
The present invention relates to oil gathering-transferring technology field, and in particular to a kind of heavy crude thinner.
Background technology
With the continuous exploitation of oil, in explored petroleum resources, viscous crude proportion is increasing, dilute in the world
Under the situation of oily resource scarcity, viscous crude will be taken over as the important of petroleum resources.During collecting defeated, with thickened oil recovery amount
Increase, its density is big, viscosity is high, poor fluidity characteristic is brought very big difficulty in development and application.Therefore, heavy oil gathering
The advanced and economy of technology directly affects the mixed economy technical indicator of crude oil production.
For a long time, both at home and abroad to viscous crude mainly by the way of traditional heating, viscosity reducing conveying and reducing viscosity by emulsifying conveying.
The former, fuel consumption is big, high cost；The latter, it may appear that post processing problem, and it is not suitable for low water-bearing crude oil.Heavy oil transportation work
Conventional viscosity reducing process in skill also has thin oil blending visbreaking to convey.Thin oil blending visbreaking is conveyed, and is limited by thin oil source, and thin oil valency
Lattice are more expensive, there is a problem of high cost.
Additionally, having drawn thinner viscosity reducing process after research viscous crude structure.In the viscous crude composition of China, colloid, pitch
The too high levels of matter are the high-viscosity main causes of viscous crude, and colloid, asphaltene molecules are in stacking states, make it have high temperature or molten
Under agent effect the characteristics of accumulation horizon gap " loose ".Heavy crude thinner is added, viscosity reduction agent molecule " oozing " is entered colloid or asphalitine point
Between sublayer, play a part of to reduce viscosity of thickened oil, to reduce the condensation point and viscosity of crude oil, make it easier to flowing.But on thick
The thinner search time of oily viscosity reduction is shorter, and desk research and field test stage are only limitted to mostly, and viscosity reducing effect is not notable,
The viscosity reducing effect of high-temperature region is poor.
The content of the invention
In view of this, the application provides a kind of heavy crude thinner.A kind of heavy crude thinner, viscosity reducing effect is good, dissolubility
It is good, also there is preferable universality for different oil fields, thick oil collection and transportation is can be directly used for, synthesis technique is simple.
In order to solve the above-mentioned technical problem, the present invention provides a kind of heavy crude thinner, it is characterised in that the reducing thick oil viscosity
Agent is reacted as Formulas I, Formula II and compound shown in formula III and is obtained；
Wherein n=13~17.
Preferably, the n=13,15,17.
Preferably, the n=17.
The invention provides a kind of preparation method of the heavy crude thinner, including：
A) Formulas I, Formula II and compound shown in formula III mixed, dissolved, obtain mixed solution；
Wherein n=13~17；
B) the heating stepses a) mixed solutions, obtain the heavy crude thinner.
Preferably, the Formulas I, the Formula II and compound mole ratio shown in the formula III are 1：(1~6)：(1~6).
Preferably, the Formulas I, the Formula II and compound mole ratio shown in the formula III are 1：(1~4)：(1~4)
Preferably, the Formulas I, the Formula II and compound mole ratio shown in the formula III are 1：2：2
Preferably, it is one or more in toluene, dimethylbenzene or benzene that solvent is selected in dissolving in the step a).
Preferably, the solution is toluene.
Preferably, the step a) is specially：First by the Formulas I and compound mixed dissolution shown in the Formula II, and instead
Should, add the formula III described in compound reacted, obtain the mixture.
Preferably, the step b) is specially：The mixed solution that the step a) is obtained, then cooled and solidified are heated, is obtained
The heavy crude thinner.
Preferably, the step b) is specially：Heated during catalyst is added into the mixed solution, the mixed solution,
The heavy crude thinner is obtained, it is 0.5%~1.5% that the catalyst accounts for the mixture weight percentage.
Preferably, it is 1.0% that the catalyst accounts for the mixture weight percentage.
Preferably, the catalyst is one or more in sulfuric acid or p-methyl benzenesulfonic acid.
Preferably, the catalyst is p-methyl benzenesulfonic acid.
Preferably, the heating-up temperature in the step b) is 80~140 DEG C.
Preferably, the heating-up temperature in the step b) is 90~120 DEG C.
The invention provides the application of described heavy crude thinner, it is 10000 that the heavy crude thinner is used to reduce viscosity
The viscosity of thickened oil of~50000mPas.
Preferably, the viscosity is 20000~45000mPas.
Preferably, the viscosity is 20000~40000mPas.
Compared with prior art, its detailed description is as follows for the application：
Heavy crude thinner chain alkyl containing C18 and phenyl ring that the present invention is provided.Chain alkyl, on the one hand, form it into comb
Wax eutectic in shaped polymer, with viscous crude, so as to change the brilliant state of wax, makes it be difficult to be formed and the three-dimensional netted knot of expansion space
Structure.On the other hand, chain alkyl increases the steric hindrance of thinner, after thinner has broken asphalitine, colloid structure, resistance
Only when temperature and other conditions change, the intermolecular reconstruction of asphalitine, colloid in viscous crude newly forms hydrogen bond to viscous crude, suppresses pitch
The aggregation of matter and colloid simultaneously reduces absorption and growth of the paraffin on its surface, so as to effectively reduce viscosity of thickened oil.The present invention is provided
Thinner also with phenyl ring presence, be conducive to the interphase interaction of thinner and the colloid with cyclic structure, it is more efficient
Ground reduces viscosity of thickened oil.Viscosity break ratio highest for super-viscous oil can reach 60% so that viscosity of thickened oil is dropped by 30000mPa 〃 s
To 12000mPa 〃 s, hence it is evident that improve the low temperature flow of viscous crude, viscosity reducing effect is compared with the common thinner in market good.
Hydrophobic grouping containing C18 in the molecular structure of the heavy crude thinner that the present invention is provided, need not with good dissolubility
Solvent dissolves, during can be directly used for oil-gas gathering and transportation.
Raw material sources used in the present invention are extensively, with low cost, and will not give it is follow-up in refining equipment cause corruption
Erosion, energy-conserving and environment-protective.
The preparation method that the present invention is provided, the technological process of production is simple, and operating method is easy, and the reaction time is short, Ke Yishi
Existing automatic continuous production, mechanization degree is high, suitable penetration and promotion and industrialized production.
Brief description of the drawings
The infrared spectrogram of the heavy crude thinner that Fig. 1 present invention is provided.
Specific embodiment
In order that those skilled in the art more fully understands technical scheme, with reference to specific embodiment pair
The present invention is described in further detail.
The present invention provides a kind of heavy crude thinner, and the heavy crude thinner is anti-as Formulas I, Formula II and compound shown in formula III
Answer and obtain；
Wherein n=13~17.
Preferably, n=13,15,17, preferred n=17.In some embodiments provided by the present invention, the n=
13；In some embodiments provided by the present invention, the n=15；It is described in other embodiments provided by the present invention
N=17.
The invention provides a kind of preparation method of the heavy crude thinner, including：
A) Formulas I, the Formula II and compound shown in the formula III mixed, dissolved, obtain mixed solution；
B) the heating stepses a) mixed solutions, obtain the heavy crude thinner.
Preferably, the Formulas I, the Formula II and compound mole ratio shown in the formula III are 1：(1~6)：(1~6),
More preferably 1：(1~4)：(1~4), optimal is 1：2：2；In some embodiments provided by the present invention, the mol ratio is excellent
Elect 1 as：1：1；In some embodiments provided by the present invention, the mol ratio is preferably 1：1.5：2.5；Carried in the present invention
In some embodiments for supplying, the mol ratio is preferably 1：2：2；In some embodiments provided by the present invention, described mole
Than being preferably 1：2：4；In some embodiments provided by the present invention, the mol ratio is preferably 1：2.5：2.5；In the present invention
In some embodiments for being provided, the mol ratio is preferably 1：4：2；It is described in some embodiments provided by the present invention
Mol ratio is preferably 1：4：4；In some embodiments provided by the present invention, the mol ratio is preferably 1：4：6；In the present invention
In other embodiments for being provided, the mol ratio is preferably 1：6：4.
Preferably, it is one or more in toluene, dimethylbenzene or benzene that solvent is selected in dissolving in the step a).More preferably
For toluene.
Preferably, the step a) is specially：First by the Formulas I and compound mixed dissolution shown in the Formula II, and instead
Should, add the formula III described in compound reacted, obtain the mixture.
Preferably, the step b) is specially：The mixed solution that the step a) is obtained, then cooled and solidified are heated, is obtained
The heavy crude thinner.
Preferably, the step b) is specially：Heated during catalyst is added into the mixed solution, the mixed solution is anti-
After answering completely, the heavy crude thinner is obtained, it is 0.5%~1.5% that the catalyst accounts for the mixture weight percentage.More
Preferably, 1.0%.
Preferably, the catalyst is one or more in p-methyl benzenesulfonic acid or sulfuric acid；More preferably, to toluene sulphur
Acid.
Preferably, the heating-up temperature in the step c) is 80~140 DEG C；More preferably, 90~120 DEG C.
Present invention also offers the application of described heavy crude thinner, the heavy crude thinner is for reducing viscosity
The viscosity of thickened oil of 10000~50000mPas, it is preferred that the viscosity is 20000~45000mPas；It is furthermore preferred that institute
Viscosity is stated for 20000~40000mPas.
The structural formula of compound described in Formulas I isSo the viscous crude drop that the present invention is provided
Stick compound as described in Formulas I, as crosslinking agent, hasRepeat unit, wherein R1~R4
It can be the substitution base of formula IV~Formula VIII in table 1.
Table 1R1~R4Substitution base situation
-OH
Formula IV
-O-C18H37
Formula V
Hereinafter the solution of the present invention is elaborated with specific embodiment.
Embodiment 1~5
Add Formulas I, Formula II and compound, n=17 shown in formula III in the reactor successively；It is calculated in mass percent, upwards
State 30%~50% mass that gross mass is added in reactant toluene make solvent and reaction raw materials gross mass 1% to first
Benzene sulfonic acid makees catalyst, stirs and reacts 2h in the case where temperature is for 100 DEG C, obtains product liquid, is placed in 5h at room temperature, treats that liquid coagulates
Gu after, heavy crude thinner is obtained.
The viscosity reducing effect of heavy crude thinner is evaluated, is taken first at 1000ml viscous crude is placed on 50 DEG C and is stirred, two hours
After take the 100ml viscous crude, with NDJB-8S type digital display viscosimeters, measure its viscosity size, the as viscosity of viscous crude.
It is the viscous crude of 30000mPas to choose viscosity.The product for adding the embodiment 1 of 50mg to obtain in the viscous crude of 100ml
Thing 1, after then being stirred two hours at 50 DEG C, with NDJB-8S type digital display viscosimeters, surveys its viscosity, that is, obtain adding and produce
The viscosity of viscous crude after thing 1, and calculate viscosity break ratio；The embodiment 1~9 different from the only reaction raw materials mol ratio of embodiment 1 is obtained
Heavy crude thinner, adds viscosity to take viscous crude for 30000mPas, respectively viscous crude after measure viscosity reduction according to the method described above
Viscosity, and calculate viscosity break ratio.The results are shown in Table 2.
Table 2
Embodiment 10~12
It is separately added into shown Formulas I, the Formula II and compound shown in the formula III in the reactor successively, n is respectively
13rd, 15,17, shown Formulas I, the Formula II and compound mole ratio shown in the formula III are 1:2:2；Take chemical combination shown in shown Formulas I
Thing 0.68g, compound shown in the Formula II is taken as table 3, takes compound 1.48g shown in the formula III, is added in above-mentioned reactant
Enter 30% dimethylbenzene and make 1% p-methyl benzenesulfonic acid of solvent and reaction raw materials gross mass to make catalyst, stir in temperature
To react 2h at 100 DEG C, product liquid is obtained, be placed in 5h at room temperature, after after liquid solidification, heavy crude thinner is obtained.
According to the evaluation method of embodiment 1, determine viscosity and product obtained above is added by the viscous crude that takes of 30000mPas
The viscosity of viscous crude after viscosity reduction, and calculate viscosity break ratio.Measurement result is shown in Table 3.
Table 3
In sum, using shown Formulas I, the Formula II and the formula in the heavy crude thinner preparation method that the present invention is provided
Heavy crude thinner prepared by compound shown in III, compound n=13~17 can effectively reduce viscosity of thickened oil shown in the Formula II；
It is optimal using compound n=15~17 viscosity reducing effect shown in the Formula II.Compound n=17 viscosity reductions shown in wherein described Formula II are imitated
Preferably, because compound n=17 shown in the Formula II, is octadecyl alcolol, carbon number is that 18 n-alkane contains to fruit in crude oil
Amount is relatively more, and thinner solute effect now is best, is also easier in playing a role.
Embodiment 13~19
Add compound n=17 shown in Formula II described in compound, 2.70g shown in Formulas I described in 1.36g in the reactor successively
With compound shown in 1.48g formula IIIs；Make solvent and anti-to 30% toluene for adding reaction raw materials gross mass in above-mentioned reactant
Answer the 1.5% of raw material gross mass p-methyl benzenesulfonic acid to make catalyst, stir and reacting 2h at different temperatures respectively, react
Temperature is respectively 80 DEG C, 90 DEG C, 100 DEG C, 110 DEG C, 80 DEG C, 120 DEG C, obtains product liquid, is placed in 5h at room temperature, treats that liquid solidifies
Afterwards, heavy crude thinner is obtained.
According to the evaluation method of embodiment 1, viscosity is determined for the viscous crude of 30000mPas adds product viscosity reduction obtained above
The viscosity of viscous crude afterwards, and calculate viscosity break ratio.Measure structure and be shown in Table 4.
Table 4
In sum, heating-up temperature is 80~140 DEG C in the heavy crude thinner preparation method that the present invention is provided；More preferably
For 90~120 DEG C；Most preferably, 100 DEG C, the heavy crude thinner of preparation can effectively reduce viscosity of thickened oil.
Embodiment 20~24
Successively in the reactor add 1.36g Formulas I shown in compound, compound n=17 shown in Formula II described in 2.70g and
Compound shown in formula III described in 1.48g；To in above-mentioned reactant add reaction raw materials gross mass 30% toluene make solvent and
The p-methyl benzenesulfonic acid of the 1% of reaction raw materials gross mass makees catalyst, stirs and is reacting 2h at 100 DEG C, obtains product liquid,
5h at room temperature is placed in, after after liquid solidification, heavy crude thinner is obtained.
According to the evaluation method of embodiment 1, viscous crude after the viscous crude addition product viscosity reduction obtained above of measure different viscosities
Viscosity, selected viscosity of thickened oil be respectively 10000mPas, 20000mPas, 30000mPas, 40000mPas,
50000mPas, and calculate viscosity break ratio.Measure structure and be shown in Table 5.
Table 5
In sum, the viscosity break ratio highest of the super-viscous oil for 10000~50000mPas of viscosity can reach 60%,
The viscous crude kinematic viscosity in pipeline is substantially reduced, viscosity reducing effect is good.
On be only the preferred embodiment of the present invention, it is noted that above-mentioned preferred embodiment be not construed as to this
The limitation of invention, protection scope of the present invention should be defined by claim limited range.It is general for the art
For logical technical staff, without departing from the spirit and scope of the present invention, some improvements and modifications can also be made, these improvement
Protection scope of the present invention is also should be regarded as with retouching.
Claims (10)
1. a kind of heavy crude thinner, it is characterised in that the heavy crude thinner is reacted as Formulas I, Formula II and compound shown in formula III
And obtain；
Wherein n=13~17.
2. heavy crude thinner according to claim 1, it is characterised in that the n=13,15,17.
3. the preparation method of a kind of heavy crude thinner, it is characterised in that including：
A) Formulas I, Formula II and compound shown in formula III mixed, dissolved, obtain mixed solution；
Wherein n=13~17；
B) the heating stepses a) mixed solutions, obtain the heavy crude thinner.
4. preparation method according to claim 3, it is characterised in that Formulas I, the Formula II and the formula in the step a)
The mol ratio of compound shown in III is 1：(1~6)：(1~6).
5. preparation method according to claim 3, it is characterised in that dissolving is toluene, two from solvent in the step a)
One or more in toluene or benzene.
6. preparation method according to claim 3, it is characterised in that the step b) is specially：The step a) is heated to obtain
The mixed solution for arriving, obtains the heavy crude thinner.
7. preparation method according to claim 3, it is characterised in that the step b) is specially：Catalyst is added described
In mixed solution, heating obtains the heavy crude thinner；The catalyst account for the mixture weight percentage for 0.5%~
1.5%.
8. preparation method according to claim 7, it is characterised in that the catalyst is a kind of in sulfuric acid or p-methyl benzenesulfonic acid
Or it is various.
9. preparation method according to claim 3, it is characterised in that the heating-up temperature in the step c) is 80~140 DEG C.
10. the application of heavy crude thinner described in claim 1, it is characterised in that the heavy crude thinner is used to reduce viscosity and be
The viscous crude of 10000~50000mPas.
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| CN109111367A (en) * | 2018-11-15 | 2019-01-01 | 中国石油大学(华东) | A kind of low-temperature eutectic species heavy crude thinner and its preparation method and application |
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| CN107382720B (en) * | 2017-07-03 | 2020-08-04 | 西南石油大学 | Thick oil viscosity reducer, preparation method and application |
| CN109111367A (en) * | 2018-11-15 | 2019-01-01 | 中国石油大学(华东) | A kind of low-temperature eutectic species heavy crude thinner and its preparation method and application |
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| Publication number | Publication date |
|---|---|
| CN106701050B (en) | 2019-08-16 |
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