CN1174229A - Phosphate oil-base pressure cracked liquid gelatinizer and its preparation - Google Patents
Phosphate oil-base pressure cracked liquid gelatinizer and its preparation Download PDFInfo
- Publication number
- CN1174229A CN1174229A CN 97116660 CN97116660A CN1174229A CN 1174229 A CN1174229 A CN 1174229A CN 97116660 CN97116660 CN 97116660 CN 97116660 A CN97116660 A CN 97116660A CN 1174229 A CN1174229 A CN 1174229A
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- Prior art keywords
- phosphate
- base pressure
- gelatinizer
- oil
- dialkyl
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Abstract
The said gelatinizer enables kerosine, diesel oil and petroleum to form gel. It consists of dialkyl phosphate with long carbon chain alkyl, dimethylbenzene and kerosine; and its preparation process includes the reaction of triethyl phosphate with P2O5 to produce intermediate polyphosphate and the reaction of polyphosphate with alcohol mixture comprising butyl alcohol, octyl alcohol, C16-C18 alcohol at 88-98 deg. c for 8-10 hr to produce dialkyl phosphate.
Description
The present invention relates to a kind of fracturing fluid additive that in petroleum exploration and development, uses and preparation method thereof, particularly a kind of phosphate oil-base pressure cracked liquid gelatinizer that is used for water sensitivity hydrocarbon zone fracturing reform and preparation method thereof.
U.S. Pat 4877894 discloses a kind of phosphate oil-base pressure cracked liquid gelatinizer and preparation method thereof.This phosphate oil-base pressure cracked liquid gelatinizer is by short carbon chain alkyl (C
1-C
4) and moderate-length alkyl chain length (C
6-C
10) dialkyl phosphate and the base fluid (kerosene, diesel oil etc.) thereof formed form, it is made by following steps: (1). and triethyl phosphate and Vanadium Pentoxide in FLAKES be 80 ℃ of reactions 2 hours, generation poly phosphate intermediate; (2). the mixture of poly phosphate intermediate and hexanol, octanol, decyl alcohol generates dialkyl phosphate 121-127 ℃ of reaction 2 hours; (3). in dialkyl phosphate, add a certain amount of kerosene, diesel oil etc. and make solvent, be mixed with phosphate oil-base pressure cracked liquid gelatinizer.The weak point of this invention is: (1). lack the alkyl of long carbochain in the dialkyl phosphate oil-base pressure cracked liquid gelatinizer of generation, more how long it can not make contains that the crude oil of carbochain alkyl forms frozen glue; (2). it is lower that above-mentioned preparation method generates the dialkyl phosphate reaction yield, has only about 80%; (3). above-mentioned preparation method has used expensive hexanol and decyl alcohol, the production cost height.
It is lower to the purpose of this invention is to provide a kind of production cost, can make kerosene, diesel oil and more how long contain that the crude oil of carbochain alkyl forms phosphate oil-base pressure cracked liquid gelatinizer of good frozen glue and preparation method thereof, this method can also improve the productive rate that generates phosphate oil-base pressure cracked liquid gelatinizer simultaneously.
The objective of the invention is to realize by following technical scheme:
A kind of phosphate oil-base pressure cracked liquid gelatinizer comprises dialkyl phosphate, dimethylbenzene and kerosene, is characterized in: dialkyl phosphate wherein is by short carbon chain alkyl (C
1-C
4) and moderate-length alkyl chain length (C
6-C
10) dialkyl phosphate and the short carbon chain alkyl (C that form
1-C
4) and long alkyl chain length (C
12-C
18) dialkyl phosphate formed forms.The shared weight ratio of dialkyl phosphate is 35-80% in this jelling agent.
The preparation method of above-mentioned phosphate oil-base pressure cracked liquid gelatinizer comprises: (1) triethyl phosphate and Vanadium Pentoxide in FLAKES reaction generate the poly phosphate intermediate; (2) reaction of poly phosphate intermediate and alcohol mixture generates dialkyl phosphate; (3) mixture as solvent of a certain amount of dimethylbenzene of adding and kerosene in dialkyl phosphate is mixed with phosphate oil-base pressure cracked liquid gelatinizer.Be characterized in: poly phosphate intermediate and the alcohol mixtures reaction generation dialkyl phosphate of forming to stearyl alcohol by butanols, octanol, 16.
In above-mentioned preparation method: triethyl phosphate and Vanadium Pentoxide in FLAKES react down at 82-88 ℃ and generated the poly phosphate intermediate in 4-5 hour.Mol ratio when triethyl phosphate and Vanadium Pentoxide in FLAKES reaction is 1.3: 1-1: 1.Poly phosphate intermediate and alcohol mixture react down at 88-98 ℃ and generated dialkyl phosphate in 8-10 hour.The mol ratio of alcohol mixture and Vanadium Pentoxide in FLAKES is 4: 1-2: 1, and it is that butanols accounts for 8-17.5% that the quality of alcohol mixture is formed, and octanol accounts for 12.5-52%, and 16 account for 32.5-72% to stearyl alcohol.
The present invention proves by a large amount of experimental studies:
(1). contain short carbon chain alkyl (C
1-C
4) and moderate-length alkyl chain length (C
6-C
10) dialkyl phosphate and the short carbon chain alkyl (C that form
1-C
4) and long alkyl chain length (C
12-C
18) the mixing dialkyl phosphate oil-base pressure cracked liquid gelatinizer of the dialkyl phosphate formed can make kerosene, diesel oil etc. form frozen glue, can make the crude oil that contains longer carbochain alkyl form frozen glue again.
(2). because the reaction of poly phosphate intermediate and alcohol mixture is thermopositive reaction, therefore reduce temperature of reaction, chemical equilibrium is moved to the direction that generates dialkyl phosphate, promptly reduce temperature of reaction, can improve the concentration of reacting dialkyl phosphate when reaching balance, reduce the speed of response that temperature will reduce poly phosphate and alcohol mixture on the other hand, make the time lengthening that reaches chemical equilibrium.Therefore, suitable reduction temperature also prolongs the reaction times, can improve the productive rate that generates dialkyl phosphate.In the prior art, the temperature of reaction of the alcohol mixture of poly phosphate intermediate and hexanol, octanol and decyl alcohol is 121-127 ℃, and the reaction times is 2 hours, and the productive rate of reaction is about 80%.And poly phosphate intermediate of the present invention and butanols, octanol, 16 temperature of reaction to the alcohol mixture of stearyl alcohol are 88-98 ℃, and the reaction times is 8-10 hour, and the productive rate of reaction is 85.7-87.3%.Compared with prior art, temperature of reaction of the present invention is lower, and the productive rate of reaction improves.
(3) raw material of the present invention has used low-cost butanols, 16 to 18 alcohol mixtures, and does not use expensive hexanol and decyl alcohol, thereby production cost is lower.
Embodiment 1:
1. in a 250ml there-necked flask that mechanical stirrer, prolong, thermometer be housed, add 47.3g triethyl phosphate and 28.4g Vanadium Pentoxide in FLAKES,, be cooled to and promptly obtain the poly phosphate intermediate about 50 ℃ 83 ℃ of reactions 5 hours;
2. be that 256.7 Alcohol Cetylicuset Stearylicus mixes with the molecular-weight average of 8.1g butanols, 33.9g octanol and 59.1g, and be heated to about 50 ℃, the 101.1g alcohol mixture;
3. will join by the 101.1g alcohol mixture of step 2 gained by in the step 1 gained poly phosphate,, obtain 153g dialkyl phosphate (reaction yield is 86.5%) 95 ℃ of reactions 9 hours;
4. in by the dialkyl phosphate of step 3 gained, add a certain amount of dimethylbenzene and kerosene and make solvent, be made into the solution that contains 60% dialkyl phosphate, promptly get phosphate oil-base pressure cracked liquid gelatinizer;
5. tell at 100ml and breathe out in the crude oil (paraffin that contains 9-18%), add phosphate oil-base pressure cracked liquid gelatinizer and a certain amount of sulfuric acid and the sodium aluminate of 1.67g, placed 1-2 hour, promptly get the oil base gelled fracturing fluid by step 4 gained;
6. use the RV30 rotary viscosity design determining by the oil base gelled fracturing fluid of step 5 gained through 100 ℃, 170s
-1Shear the viscosity after 1 hour, basic viscosity is 139mPa.s..
Embodiment 2-5:
According to the experiment condition of table 1, repeat the experiment in the 1st to the 6th step of embodiment 1, the result who obtains is as shown in table 2.
The experiment condition of table 1. embodiment 2-5
| Embodiment | ????2 | ????3 | ????4 | ????5 |
| Vanadium Pentoxide in FLAKES dosage (g) | ????28.42 | ????28.4 | ????28.4 | ????28.4 |
| Triethyl phosphate dosage (g) | ????41.2 | ????43.7 | ????43.7 | ????36.4 |
| Vanadium Pentoxide in FLAKES and triethyl phosphate temperature of reaction (℃) | ????82 | ????88 | ????88 | ????82 |
| Vanadium Pentoxide in FLAKES and triethyl phosphate reaction times (h) | ????5 | ????4 | ????5 | ????4 |
| The dosage of butanols (g) | ????8.8 | ????16.4 | ????23.1 | ????4.8 |
| The dosage of octanol (g) | ????22.1 | ????46.8 | ????16.5 | ????31.4 |
| The dosage of Alcohol Cetylicuset Stearylicus (g) | ????79.5 | ????30.4 | ????92.4 | ????21.2 |
| The temperature of reaction of poly phosphate and alcohol mixture (℃) | ????88 | ????98 | ????98 | ????88 |
| The reaction times of poly phosphate and alcohol mixture (h) | ????8 | ????10 | ????10 | ????8 |
| The content of actives (g/100ml) during preparing fracturing fluid | ????1 | ????1 | ????1 | ????1 |
The experimental result of table 2. embodiment 2-5
| Embodiment | ????2 | ????3 | ????4 | ????5 |
| Reaction yield (%) | ????87.3 | ????86.8 | ????85.7 | ????86.5 |
| The content of actives (%) in the jelling agent | ????35 | ????80 | ????50 | ????75 |
| Of the fracturing fluid viscosity (mPa.s) | ????58 | ????75 | ????107 | ????93 |
Claims (7)
1. a phosphate oil-base pressure cracked liquid gelatinizer comprises dialkyl phosphate, and dimethylbenzene and kerosene is characterized in that: dialkyl phosphate wherein is by short carbon chain alkyl (C
1-C
4) and moderate-length alkyl chain length (C
6-C
10) dialkyl phosphate and the short carbon chain alkyl (C that form
1-C
4) and long alkyl chain length (C
12-C
18) dialkyl phosphate formed forms.
2. phosphate oil-base pressure cracked liquid gelatinizer according to claim 1 is characterized in that: the shared weight ratio of dialkyl phosphate is 35-80% in this jelling agent.
3. the preparation method of the described phosphate oil-base pressure cracked liquid gelatinizer of claim 1 comprises:
(1) reaction of triethyl phosphate and Vanadium Pentoxide in FLAKES generates the poly phosphate intermediate;
(2) reaction of poly phosphate intermediate and alcohol mixture generates dialkyl phosphate;
(3) mixture as solvent of a certain amount of dimethylbenzene of adding and kerosene in dialkyl phosphate is mixed with phosphate oil-base pressure cracked liquid gelatinizer,
It is characterized in that:
The poly phosphate intermediate with generate dialkyl phosphates by butanols, octanol, 16 alcohol mixtures reactions to stearyl alcohol.
4. the preparation method of phosphate oil-base pressure cracked liquid gelatinizer according to claim 3 is characterized in that: poly phosphate intermediate and alcohol mixture 88-98 ℃ down reaction generated dialkyl phosphate in 8-10 hour.
5. according to the preparation method of claim 3 or 4 described phosphate oil-base pressure cracked liquid gelatinizers, it is characterized in that: when poly phosphate intermediate and alcohol mixture reaction, the mol ratio of alcohol mixture and Vanadium Pentoxide in FLAKES is 4: 1-2: 1, it is that butanols accounts for 8-17.5% that the quality of alcohol mixture is formed, octanol accounts for 12.5-52%, and 16 account for 32.5-72% to stearyl alcohol.
6. the preparation method of phosphate oil-base pressure cracked liquid gelatinizer according to claim 3 is characterized in that: triethyl phosphate and Vanadium Pentoxide in FLAKES 82-88 ℃ down reaction generated the poly phosphate intermediate in 4-5 hour.
7. according to the preparation method of claim 3 or 6 described phosphate oil-base pressure cracked liquid gelatinizers, it is characterized in that: the mol ratio when triethyl phosphate and Vanadium Pentoxide in FLAKES reaction is 1.3: 1-1: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97116660A CN1055112C (en) | 1997-08-07 | 1997-08-07 | Phosphate oil-base pressure cracked liquid gelatinizer and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97116660A CN1055112C (en) | 1997-08-07 | 1997-08-07 | Phosphate oil-base pressure cracked liquid gelatinizer and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1174229A true CN1174229A (en) | 1998-02-25 |
| CN1055112C CN1055112C (en) | 2000-08-02 |
Family
ID=5174009
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97116660A Expired - Fee Related CN1055112C (en) | 1997-08-07 | 1997-08-07 | Phosphate oil-base pressure cracked liquid gelatinizer and its preparation |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1078609C (en) * | 1999-09-03 | 2002-01-30 | 清华大学 | Process for preparing lubricating oil of high-speed jewel bearing |
| CN102212358A (en) * | 2010-04-09 | 2011-10-12 | 新疆荣森农业科技有限公司 | Preparation of hydrocarbon-based fracturing fluid thickening agent for oil production |
| CN103665383A (en) * | 2013-11-07 | 2014-03-26 | 江苏雅克科技股份有限公司 | Oligomeric phosphate compound and preparation method |
| CN104232072A (en) * | 2013-06-21 | 2014-12-24 | 中国石油天然气股份有限公司 | Phosphate anhydrous fracturing fluid gelling agent and preparation and applications thereof |
| CN104293335A (en) * | 2014-10-14 | 2015-01-21 | 西南石油大学 | Anhydrous fracturing fluid suitable for shale gas and preparation method of anhydrous fracturing fluid |
| CN104371694A (en) * | 2013-08-15 | 2015-02-25 | 中国石油天然气股份有限公司 | Water phase-free fracturing fluid system preparation method |
| CN104498017A (en) * | 2014-12-22 | 2015-04-08 | 中国石油天然气股份有限公司 | Fracturing fluid cross-linking agent and preparation method and application thereof |
| CN105086988A (en) * | 2015-09-02 | 2015-11-25 | 西南石油大学 | Low-carbon-hydrocarbon anhydrous fracturing fluid gelling agent and preparation method thereof |
| CN108285782A (en) * | 2017-01-10 | 2018-07-17 | 中国石油化工股份有限公司 | A kind of lower carbon number hydrocarbons gelling agent of polyalcohol synergy and preparation method thereof |
| CN109666463A (en) * | 2017-10-14 | 2019-04-23 | 新沂市中诺新材料科技有限公司 | A kind of preparation method of oil base drilling fluid thickening extracting and cutting agent |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4877894A (en) * | 1988-01-11 | 1989-10-31 | Nalco Chemical Company | Hydrocarbon geller and method for making the same |
| CN1019073B (en) * | 1989-10-30 | 1992-11-18 | 西南合成制药厂 | Baffle-less roll daubing type thin-membrane short-range distiller |
| JP2642204B2 (en) * | 1989-12-14 | 1997-08-20 | シャープ株式会社 | Drive circuit for liquid crystal display |
-
1997
- 1997-08-07 CN CN97116660A patent/CN1055112C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1078609C (en) * | 1999-09-03 | 2002-01-30 | 清华大学 | Process for preparing lubricating oil of high-speed jewel bearing |
| CN102212358A (en) * | 2010-04-09 | 2011-10-12 | 新疆荣森农业科技有限公司 | Preparation of hydrocarbon-based fracturing fluid thickening agent for oil production |
| CN104232072A (en) * | 2013-06-21 | 2014-12-24 | 中国石油天然气股份有限公司 | Phosphate anhydrous fracturing fluid gelling agent and preparation and applications thereof |
| CN104371694A (en) * | 2013-08-15 | 2015-02-25 | 中国石油天然气股份有限公司 | Water phase-free fracturing fluid system preparation method |
| CN103665383A (en) * | 2013-11-07 | 2014-03-26 | 江苏雅克科技股份有限公司 | Oligomeric phosphate compound and preparation method |
| CN104293335A (en) * | 2014-10-14 | 2015-01-21 | 西南石油大学 | Anhydrous fracturing fluid suitable for shale gas and preparation method of anhydrous fracturing fluid |
| CN104498017A (en) * | 2014-12-22 | 2015-04-08 | 中国石油天然气股份有限公司 | Fracturing fluid cross-linking agent and preparation method and application thereof |
| CN104498017B (en) * | 2014-12-22 | 2018-09-04 | 中国石油天然气股份有限公司 | A kind of fracturing liquid cross-linking agent and its preparation and application |
| CN105086988A (en) * | 2015-09-02 | 2015-11-25 | 西南石油大学 | Low-carbon-hydrocarbon anhydrous fracturing fluid gelling agent and preparation method thereof |
| CN108285782A (en) * | 2017-01-10 | 2018-07-17 | 中国石油化工股份有限公司 | A kind of lower carbon number hydrocarbons gelling agent of polyalcohol synergy and preparation method thereof |
| CN109666463A (en) * | 2017-10-14 | 2019-04-23 | 新沂市中诺新材料科技有限公司 | A kind of preparation method of oil base drilling fluid thickening extracting and cutting agent |
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| CN1055112C (en) | 2000-08-02 |
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