CN107760292A - A kind of lower carbon number hydrocarbons gelling agent of polyalcohol synergy and preparation method thereof - Google Patents
A kind of lower carbon number hydrocarbons gelling agent of polyalcohol synergy and preparation method thereof Download PDFInfo
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- CN107760292A CN107760292A CN201610669658.0A CN201610669658A CN107760292A CN 107760292 A CN107760292 A CN 107760292A CN 201610669658 A CN201610669658 A CN 201610669658A CN 107760292 A CN107760292 A CN 107760292A
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- polyalcohol
- gelling agent
- carbon number
- alcohol
- lower carbon
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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
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/64—Oil-based compositions
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- 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
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
- C08G79/04—Phosphorus linked to oxygen or to oxygen and carbon
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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
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/70—Compositions for forming crevices or fractures characterised by their form or by the form of their components, e.g. foams
Abstract
The present invention relates to the lower carbon number hydrocarbons gelling agent of a kind of polyalcohol synergy in efficient gelling agent synthesis field and preparation method thereof.The lower carbon number hydrocarbons gelling agent of the polyalcohol synergy of the present invention, includes polyphosphate intermediate, monohydric alcohol and polyalcohol；The polyphosphate intermediate and the ratio of weight and number of monohydric alcohol total amount, polyalcohol are 150~190:95~100:1~5.Cross-linked speed can be improved about 30% by the very small amount addition of polyalcohol, will largely solve the problems, such as that lower carbon number hydrocarbons fracturing fluid cross-linked speed is slow, it is used in conjunction with being formed the lower carbon number hydrocarbons fracturing fluid system with Quick cross-linking speed with efficient crosslinking agent.Without using solvent in phosphate gelling agent synthetic route described herein, and reaction temperature is more gentle, is green, environmentally friendly, the production line of low energy consumption.
Description
Technical field
The present invention relates to efficient gelling agent to synthesize field, furtherly, is related to a kind of lower carbon number hydrocarbons pressure of polyalcohol synergy
Split liquid gelling agent and preparation method thereof.
Background technology
In terms of international market, lower carbon number hydrocarbons fracturing fluid has reached industrial applications.For domestic market, lower carbon number hydrocarbons fracturing fluid
The laboratory research stage is still in, its subject matter is that cross-linked speed is slow, it is difficult to meet the needs of live continuous mixture.
Patent CN105154056A describes a kind of anhydrous pressure break liquid and preparation method thereofs of LPG suitable for unconventional reservoir with answering
With its phosphate gelling agent is by monohydric alcohol, dihydric alcohol, polyalcohol or its mixture in phosphate intermediate and C2~C18
Occur under certain condition made from esterification.The preparation method of phosphate gelling agent described by the patent is：(1) phosphoric acid
Triethyl and phosphoric acid are anti-as solvent using normal heptane, dimethylbenzene, toluene or their mixture under the conditions of 80 DEG C~95 DEG C
Answer 2~4 hour generation polyphosphate intermediates；(2) by the polyphosphate intermediate in step (1) and C2~C18 unitary
Alcohol, dihydric alcohol, polyalcohol or their mixture react 4~6 hour generation phosphates under the conditions of 120 DEG C~135 DEG C
Gelling agent.In the art, one of the component of polyalcohol as mixed alcohol, phosphorus is provided commonly for common monohydric alcohol and dihydric alcohol
The synthesis of acid esters, but the influence of the species to polyalcohol and dosage to gelling agent performance is not studied.And the synthetic route
A large amount of poisonous, high price solvent uses, such as dimethylbenzene are relate to, reaction temperature is 120 DEG C~135 DEG C.
The content of the invention
In order to solve the above-mentioned problems in the prior art, the present invention proposes a kind of lower carbon number hydrocarbons pressure break of polyalcohol synergy
Liquid gelling agent and preparation method thereof.This invention address that proposing a kind of suitable polyalcohol synergist, there is high crosslinking with synthesis
The gelling agent of speed.
A kind of lower carbon number hydrocarbons gelling agent of polyalcohol synergy of one of the object of the invention, includes among polyphosphate
Body, mixed alcohol；Wherein, the mixed alcohol includes monohydric alcohol and polyalcohol；The polyphosphate intermediate and monohydric alcohol total amount,
The ratio of weight and number of polyalcohol is (150~190):(95~100):(1~5), preferably (160~180):(95~100):(1~
5)；The ratio of weight and number of monohydric alcohol total amount and polyalcohol is (95~100) in the mixed alcohol:(1~5).The gelling agent is close
Degree can be 1.02~1.08g/cm3。
Combination property and price consider, the monohydric alcohol may be selected ethanol, normal propyl alcohol, n-butanol, n-amyl alcohol, n-hexyl alcohol,
Any one or a few mixing in n-octyl alcohol, Decanol, n-dodecanol, tetradecanol, positive hexadecanol and positive octadecyl alcolol,
In preferred alcohol, n-butanol, n-octyl alcohol, Decanol, n-dodecanol, positive hexadecanol, positive octadecyl alcolol any one or a few
Mixing.
The polyalcohol may be selected from polyol molecule pentaerythrite and/or bipentaerythrite.
By consulting literatures and exploitative experiment, the method for the polyphosphate intermediate may include following steps：Filling
Have and 100~120 parts by weight of phosphoric acid triethyls and 50~70 parts by weight are added in the 250mL three-necked flasks of mechanical agitation and thermometer
Phosphorus pentoxide, it is well mixed, being down to room temperature after 5~8h of reaction at 85~95 DEG C obtains polyphosphate intermediate.
The introducing of polyphosphate intermediate in the application can improve esterification yield；Monohydric alcohol is as phosphate
Main composition part, form the skeleton of gelling agent；A small amount of polyalcohol is added on this basis, is simultaneously participated in two or more
In the structure of phosphate, play a part of bridging, increase molecular dimension, molecular weight is improved, so as to improve cross-linked speed.
A kind of preparation method of the lower carbon number hydrocarbons gelling agent of polyalcohol synergy of the two of the object of the invention, including it is following
Step：
1) polyphosphate intermediate is synthesized；
2) mixed alcohol is added into the polyphosphate intermediate, 4~7h is reacted at 75~105 DEG C, then be down to room temperature and obtain
To the lower carbon number hydrocarbons gelling agent of the polyalcohol synergy.
Under normal circumstances, polyalcohol price is higher, is not suitable for being widely used in phosphate synthesis.However, polyalcohol
A small amount of addition in mixed alcohol can significantly improve the performance of gelling agent.Therefore, the application focuses on the species of polyalcohol and added
Influence of the dosage to gelling agent performance, in the hope of the excellent gelling agent of the addition processability with a small amount of polyalcohol.The application is retouched
Without using solvent in the phosphate gelling agent synthetic route stated, and reaction temperature is more gentle, be 75~105 DEG C, be green,
Environmental protection, the production line of low energy consumption.
In order to improve cross-linked speed, larger polynary of two kinds of sizes, degree of functionality, molecular weight differences is have selected in the present invention
Alcohol molecule pentaerythrite and bipentaerythrite, using the parts by weight of monohydric alcohol total amount and polyalcohol total amount as 95~100:1~5
Addition, which is added in mixed alcohol, to be participated in having synthesized the gelling agent containing polyalcohol.Very small amount addition can improve cross-linked speed
About 30%, will largely solve the problems, such as that lower carbon number hydrocarbons fracturing fluid cross-linked speed is slow, it is common with efficient crosslinking agent
Using the lower carbon number hydrocarbons fracturing fluid system with Quick cross-linking speed can be formed.Lower carbon number hydrocarbons according to present invention synthesis polyalcohol synergy
During gelling agent, it is only necessary to a small amount of polyalcohol is added into original synthetic system, device and reaction condition do not change
Become, prepare simple, excellent effect, be worthy of popularization.
Brief description of the drawings
Fig. 1 is the cross-linked speed curve ratio of the lower carbon number hydrocarbons gelling agent of polyalcohol synergy prepared by the embodiment of the present invention
Compared with figure.
Embodiment
With reference to embodiment, the present invention is further illustrated.But the present invention is not restricted by the embodiments.
Embodiment institute is commercially available using chemical reagent.
Embodiment 1
47.30g triethyl phosphates are added in the 250mL three-necked flasks equipped with mechanical agitation and thermometer, then 1~
Point three batches add 28.40g phosphorus pentoxides in 1.5h, are reacted at 85 DEG C and are down to room temperature after 5h and obtain among polyphosphate
Body.Mixed alcohol is added into system (including 5.61g ethanol, 15.02g n-octyl alcohols, the positive hexadecanols of 26.75g and 0.82g seasons
Penta tetrol), reaction 6h is down to room temperature and obtains the lower carbon number hydrocarbons gelling agent E of polyalcohol synergy at 95 DEG C1, density is
1.03g/cm3。
Embodiment 2
47.30g triethyl phosphates are added in the 250mL three-necked flasks equipped with mechanical agitation and thermometer, then 1~
Point three batches add 28.40g phosphorus pentoxides in 1.5h, are reacted at 85 DEG C and are down to room temperature after 5h and obtain among polyphosphate
Body.It is (double including 5.61g ethanol, 15.02g n-octyl alcohols, the positive hexadecanols of 26.75g and 1.52g that mixed alcohol is added into system
Pentaerythrite), reaction 6h is down to room temperature and obtains the lower carbon number hydrocarbons gelling agent E of polyalcohol synergy at 95 DEG C2, density is
1.05g/cm3。
Embodiment 3
47.30g triethyl phosphates are added in the 250mL three-necked flasks equipped with mechanical agitation and thermometer, then 1~
Point three batches add 28.40g phosphorus pentoxides in 1.5h, are reacted at 85 DEG C and are down to room temperature after 5h and obtain among polyphosphate
Body.Mixed alcohol is added into system (including 7.10g ethanol, 14.10g n-octyl alcohols, the positive hexadecanols of 26.01g and 0.48g seasons
Penta tetrol), reaction 6h is down to room temperature and obtains the lower carbon number hydrocarbons gelling agent E of polyalcohol synergy at 95 DEG C3, density is
1.02g/cm3。
Embodiment 4
56.76g triethyl phosphates are added in the 250mL three-necked flasks equipped with mechanical agitation and thermometer, then 1~
Point three batches add 31.69g phosphorus pentoxides in 1.5h, are reacted at 85 DEG C and are down to room temperature after 5h and obtain among polyphosphate
Body.Mixed alcohol is added into system (including 4.73g ethanol, 14.10g n-octyl alcohols, the positive hexadecanols of 26.01g and 2.2g seasons penta
Tetrol), reaction 6h is down to room temperature and obtains the lower carbon number hydrocarbons gelling agent E of polyalcohol synergy at 85 DEG C4, density 1.08g/
cm3。
Embodiment 5
47.30g triethyl phosphates are added in the 250mL three-necked flasks equipped with mechanical agitation and thermometer, then 1~
Point three batches add 23.65g phosphorus pentoxides in 1.5h, are reacted at 85 DEG C and are down to room temperature after 5h and obtain among polyphosphate
Body.It is (double including ethanol 4.73g, 14.10g n-octyl alcohols, the positive hexadecanols of 26.01g and 0.71g that mixed alcohol is added into system
Pentaerythrite), reaction 4h is down to room temperature and obtains the lower carbon number hydrocarbons gelling agent E of polyalcohol synergy at 105 DEG C5, density is
1.03g/cm3。
Embodiment 6
47.30g triethyl phosphates are added in the 250mL three-necked flasks equipped with mechanical agitation and thermometer, then 1~
Point three batches add 33.11g phosphorus pentoxides in 1.5h, are reacted at 85 DEG C and are down to room temperature after 5h and obtain among polyphosphate
Body.It is (double including 4.73g ethanol, 14.10g n-octyl alcohols, the positive hexadecanols of 26.01g and 2.36g that mixed alcohol is added into system
Pentaerythrite), reaction 4h is down to room temperature and obtains the lower carbon number hydrocarbons gelling agent E of polyalcohol synergy at 95 DEG C6, density is
1.03g/cm3。
Embodiment 7
47.30g triethyl phosphates are added in the 250mL three-necked flasks equipped with mechanical agitation and thermometer, then 1~
Point three batches add 28.40g phosphorus pentoxides in 1.5h, are reacted at 95 DEG C and are down to room temperature after 5h and obtain among polyphosphate
Body.Mixed alcohol is added into system (including 4.73g butanol, 18.92g Decanols, the positive octadecyl alcolols of 21.29g and 1.42g seasons
Penta tetrol), reaction 6h is down to room temperature and obtains the lower carbon number hydrocarbons gelling agent E of polyalcohol synergy at 75 DEG C7, density is
1.05g/cm3。
Embodiment 8
47.30g triethyl phosphates are added in the 250mL three-necked flasks equipped with mechanical agitation and thermometer, then 1~
Point three batches add 28.40g phosphorus pentoxides in 1.5h, are reacted at 85 DEG C and are down to room temperature after 8h and obtain among polyphosphate
Body.It is (double including 7.10g ethanol, 11.83g n-octyl alcohols, 28.38g n-dodecanols and 2.36g that mixed alcohol is added into system
Pentaerythrite), reaction 7h is down to room temperature and obtains the lower carbon number hydrocarbons gelling agent E of polyalcohol synergy at 75 DEG C8, density is
1.04g/cm3。
Comparative example
47.30g triethyl phosphates are added in the 250mL three-necked flasks equipped with mechanical agitation and thermometer, then 1~
Point three batches add 28.40g phosphorus pentoxides in 1.5h, are reacted at 85 DEG C and are down to room temperature after 5h and obtain among polyphosphate
Body.Mixed alcohol (including 5.61g ethanol, 15.02g n-octyl alcohols, the positive hexadecanols of 26.75g) is added into system, at 95 DEG C
Reaction 6h is down to room temperature and obtains blank control group gelling agent E, density 1.03g/cm3。
Effect example
Cross-linked speed assay method：Under 200rpm mechanical agitations, by the lower carbon number hydrocarbons gelling agent of polyalcohol synergy
E1、E2And blank control group gelling agent E is dissolved in 100mL petroleum ethers respectively, a certain amount of crosslinking agent is added after dissolving completely.Use
Six fast viscosimeter measure gelatin viscosities simultaneously record the measurement moment, are mapped with viscosity over time, i.e. the crosslinking agent or crosslinking accelerator
Cross-linked speed under dosage.
As can be seen that the addition of pentaerythrite and bipentaerythrite can effectively improve cross-linked speed from Fig. 1, with crosslinking
Exemplified by time t=3min, the viscosity for being not added with the gelling agent system of polyalcohol is 50mPas, addition pentaerythrite and double Ji Wusi
The viscosity of the gelling agent system of alcohol is 130mPas, i.e. the cross-linked speed of polyalcohol gelling agent system is about common gelling agents
1.3 times of system.
The molecular weight of lower carbon number hydrocarbons gelling agent is 200~400g/mol, belongs to small-molecule substance, crosslinking molecule at initial stage
Amount increase is more slow, and macro manifestations are that viscosity rises slowly.Pentaerythrite and bipentaerythrite molecular functionality and molecule chi
It is very little placed in the middle, have the function that to improve cross-linked speed during with this both as synergist synthetic gelling agentses.
Claims (9)
1. a kind of lower carbon number hydrocarbons gelling agent of polyalcohol synergy, includes polyphosphate intermediate and mixed alcohol；Wherein, institute
State mixed alcohol and include monohydric alcohol and polyalcohol；The ratio of weight and number of the polyphosphate intermediate and monohydric alcohol, polyalcohol is
150~190:95~100:1~5.
A kind of 2. lower carbon number hydrocarbons gelling agent of polyalcohol synergy according to claim 1, it is characterised in that：It is described poly-
The ratio of weight and number of phosphate intermediate and monohydric alcohol, polyalcohol is 160~180:95~100:1~5.
A kind of 3. lower carbon number hydrocarbons gelling agent of polyalcohol synergy according to claim 1, it is characterised in that：Described one
First alcohol is selected from ethanol, normal propyl alcohol, n-butanol, n-amyl alcohol, n-hexyl alcohol, n-octyl alcohol, Decanol, n-dodecanol, tetradecanol, positive ten
At least one of six alcohol and positive octadecyl alcolol.
A kind of 4. lower carbon number hydrocarbons gelling agent of polyalcohol synergy according to claim 3, it is characterised in that：Described one
First alcohol is selected from least one of ethanol, n-butanol, n-octyl alcohol, Decanol, n-dodecanol, positive hexadecanol, positive octadecyl alcolol.
A kind of 5. lower carbon number hydrocarbons gelling agent of polyalcohol synergy according to claim 1, it is characterised in that：It is described poly-
Phosphate intermediate is prepared by the method including comprising the following steps：
100~120 parts by weight of phosphoric acid triethyls and 50~70 parts by weight phosphorus pentoxides are well mixed, reacted at 85~95 DEG C
Room temperature is down to after 5~8h and obtains polyphosphate intermediate.
6. a kind of lower carbon number hydrocarbons gelling agent of polyalcohol synergy according to any one of Claims 1 to 5, its feature
It is：
The polyalcohol is selected from pentaerythrite and/or bipentaerythrite.
A kind of 7. preparation of the lower carbon number hydrocarbons gelling agent of polyalcohol synergy according to any one of claim 1~6
Method, it is characterised in that comprise the following steps：
1) polyphosphate intermediate is synthesized；
2) mixed alcohol is added into the polyphosphate intermediate, reacted at 75~105 DEG C, then be down to room temperature obtain it is described
The lower carbon number hydrocarbons gelling agent of polyalcohol synergy.
8. a kind of preparation method of the lower carbon number hydrocarbons gelling agent of polyalcohol synergy according to claim 7, its feature
It is：
The mixed alcohol includes monohydric alcohol and polyalcohol；The polyphosphate intermediate and monohydric alcohol, the parts by weight of polyalcohol
Number is than being 150~190:95~100:1~5.
9. a kind of preparation method of the lower carbon number hydrocarbons gelling agent of polyalcohol synergy according to claim 8, its feature
It is：
The ratio of weight and number of the polyphosphate intermediate and monohydric alcohol, polyalcohol is 160~180:95~100:1~5.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5190675A (en) * | 1985-12-12 | 1993-03-02 | Dowell Schlumberger Incorporated | Gelling organic liquids |
| US20050189112A1 (en) * | 2004-02-26 | 2005-09-01 | Taylor Robert S. | Compositions and methods for treating subterranean formations with liquefied petroleum gas |
| CN104004506A (en) * | 2014-06-18 | 2014-08-27 | 西安石油大学 | Anhydrous fracturing fluid suitable for unconventional reservoir fracturing and preparing method of anhydrous fracturing fluid |
| CN105154056A (en) * | 2015-09-02 | 2015-12-16 | 西南石油大学 | Preparation method of LPG (Liquefied Petroleum Gas) anhydrous fracturing fluid suitable for unconventional reservoir stratum and application |
-
2016
- 2016-08-15 CN CN201610669658.0A patent/CN107760292A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5190675A (en) * | 1985-12-12 | 1993-03-02 | Dowell Schlumberger Incorporated | Gelling organic liquids |
| US20050189112A1 (en) * | 2004-02-26 | 2005-09-01 | Taylor Robert S. | Compositions and methods for treating subterranean formations with liquefied petroleum gas |
| CN104004506A (en) * | 2014-06-18 | 2014-08-27 | 西安石油大学 | Anhydrous fracturing fluid suitable for unconventional reservoir fracturing and preparing method of anhydrous fracturing fluid |
| CN105154056A (en) * | 2015-09-02 | 2015-12-16 | 西南石油大学 | Preparation method of LPG (Liquefied Petroleum Gas) anhydrous fracturing fluid suitable for unconventional reservoir stratum and application |
Non-Patent Citations (2)
| Title |
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| 罗灿，等: "一种能连续压裂施工的无水压裂液胶凝剂的合成及性能评价", 《2014中国功能材料科技与产业高层论坛摘要集》 * |
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Application publication date: 20180306 |