CN109207139A - A kind of non-crosslinked plant gum fracturing fluid and preparation method thereof - Google Patents
A kind of non-crosslinked plant gum fracturing fluid and preparation method thereof Download PDFInfo
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- CN109207139A CN109207139A CN201811220640.8A CN201811220640A CN109207139A CN 109207139 A CN109207139 A CN 109207139A CN 201811220640 A CN201811220640 A CN 201811220640A CN 109207139 A CN109207139 A CN 109207139A
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- guar gum
- fracturing fluid
- hydroxypropanone
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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
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
- C08B37/0087—Glucomannans or galactomannans; Tara or tara gum, i.e. D-mannose and D-galactose units, e.g. from Cesalpinia spinosa; Tamarind gum, i.e. D-galactose, D-glucose and D-xylose units, e.g. from Tamarindus indica; Gum Arabic, i.e. L-arabinose, L-rhamnose, D-galactose and D-glucuronic acid units, e.g. from Acacia Senegal or Acacia Seyal; Derivatives thereof
- C08B37/0096—Guar, guar gum, guar flour, guaran, i.e. (beta-1,4) linked D-mannose units in the main chain branched with D-galactose units in (alpha-1,6), e.g. from Cyamopsis Tetragonolobus; Derivatives thereof
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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
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/90—Compositions based on water or polar solvents containing organic compounds macromolecular compounds of natural origin, e.g. polysaccharides, cellulose
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Abstract
The invention belongs to fracturing fluid gelatinizer technical fields, and in particular to a kind of non-crosslinked plant gum fracturing fluid and preparation method thereof.For in the prior art, cross-linking type guar gum includes insoluble residue as fracturing fluid gelatinizer and uses the problem of heavy metal is as crosslinking agent, technical solution of the present invention includes modifyed guar gum, the modification mode of the modifyed guar gum is to increase modified group on guar gum strand, the modified group is one of 3- hydroxypropanone- base, 1- hydroxypropanone- base, 1,3- hydroxypropanone- base or glycollic aldehyde base or a variety of.In addition, also including the method being modified to above-mentioned modifyed guar gum in the present invention.The present invention is suitable for the pressure break of oil/gas well.
Description
Technical field
The invention belongs to fracturing fluid gelatinizer technical fields, and in particular to a kind of non-crosslinked plant gum fracturing fluid and its preparation
Method.
Background technique
The main function of fracturing fluid is: seam and taking sand.Fracturing fluid and formation rock and reservoir fluid want compatibility and right
Proppant permeability injury is minimum.Its major function is seam and conveys proppant, therefore the viscosity of liquid along the crack of opening
It is most important.Successful fracturing work requires liquid in addition to viscosity with higher in crack, also wants that glue can be broken rapidly；Make
It being capable of the row of returning rapidly after industry；Fluid loss can be controlled well；Frictional resistance is lower during pumping；Economically feasible is also wanted simultaneously.By
Have the characteristics that inexpensive, property is good and easily controllable in water base fluid, it has also become the fracturing fluid being most widely used.For being thickened pressure break
The polymer of liquid first is that guar gum.Guar gum polymer has very strong hydrophily, and melon glue powder is added to the water, and the particle of guar gum will
Be swollen and and hydrate, i.e. guar gum polymer molecule and many associated water molecules, be unfolded in the solution and extend.To increase
The viscosity of solution.
Guar gum and its modified product have improved and maturation in fracturing yield increasing technology very much as fracturing fluid gelatinizer.But as
Storey increase design measure, the insoluble residue introduced in operation by it (including residue itself and crosslinking after breaking gel insoluble matter) is often to throwing
It provides great operation and causes fatal risk.
And environmental requirement at present is higher and higher.But guar gum crosslinking agent uses the heavy metals such as boron, zirconium, titanium often to increase and hand over
The intensity of connection, to increase difficulty and risk for subsequent environmental protection treatment.
Summary of the invention
For in the prior art, cross-linking type guar gum as fracturing fluid gelatinizer include insoluble residue and use heavy metal as
The problem of crosslinking agent, the present invention provide a kind of non-crosslinked plant gum fracturing fluid and preparation method thereof, its object is to: to guar gum into
Row is modified, and makes its viscosity i.e. with higher, to meet the requirement as fracturing fluid thickener, while reducing consolidating after breaking gel again
Body residue, and do not include heavy metal component.
The technical solution adopted by the invention is as follows:
A kind of non-crosslinked plant gum fracturing fluid, including modifyed guar gum, the modification mode of the modifyed guar gum are in guar gum point
Increase modified group in subchain, the modified group is 3- hydroxypropanone- base, 1- hydroxypropanone- base, 1,3- hydroxypropanone- base or hydroxyl
One of ethylhexanal base is a variety of.
Preferably, the number of the quantity of the modified group on modifyed guar gum strand and the hydroxyl on guar gum strand before modified
The ratio of amount is 1:5-1:1.
The present invention also provides the preparation methods of above-mentioned non-crosslinked plant gum fracturing fluid, before preparing fracturing fluid, to guar gum into
Row modification, the modification include the following steps:
[1] guar gum is configured to aqueous solution, catalyst is added, and be passed through oxygen, oxidation reaction occurs, so that guar gum molecule
Part of hydroxyl on chain is converted into ketone group；
[2] by the solution filtering by step [1] reaction, catalyst is removed；Then modifying agent and alkali are added into solution
Catalyst, heating reaction；The modifying agent is one of 1- hydroxypropanone-, 1,3- hydroxypropanone- or hydroxyl ethanol or a variety of；
[3] solution by step [2] reaction is dried, crushed to get to for the powdered of preparing fracturing fluid
Modifyed guar gum.
Preferably, catalyst described in step [1] is Cu, Ag, Pd, MnO2Or TiO2One of.
Preferably, the temperature of heating process described in step [1] is controlled at 70-90 DEG C.
Preferably, base catalyst described in step [2] is oxide, hydroxide, the carbonic acid of alkali or alkaline earth metal
One of hydrogen salt, carbonate or carboxylate.
Preferably, the temperature of heating process described in step [2] is controlled at 60-90 DEG C.
After technical solution of the present invention, fracturing fluid is configured to using modified guar gum.In modified guar gum, change
Property group be characterized in comprising with α hydroxyl carbonyl, while on guar gum strand itself have a large amount of hydroxyl.It is above-mentioned to have
The carbonyl and hydroxyl of α hydroxyl can form seven-members ring structure by hydrogen bond.By taking 3- hydroxypropanone- base as an example, the heptatomic ring knot of formation
Structure is as follows:
Wherein, R3、R4、R5And R6Represent a part of modifyed guar gum strand.
In the cyclic structure of organic molecule, five-membered ring, hexatomic ring not comprising hydrogen bond usually have stable structure；And
In the case where there is hydrogen bond participation, hexatomic ring and heptatomic ring usually have stable structure.Due to being deposited in modifyed guar gum strand
The modified group and hydroxyl of stable heptatomic ring can be largely being mutually formed, thus can passed through between modifyed guar gum strand
It forms a large amount of seven-members ring structure and generates more strong active force, eventually led to fracturing fluid viscosity with higher, reached
To requirement.
In conclusion by adopting the above-described technical solution, the beneficial effects of the present invention are:
1. the cross-linking type guar gum in compared with the prior art, the modifyed guar gum in the technical solution is easier by gel breaker
(such as ammonium persulfate) is oxidized to small molecule, so that residue content is lower (being lower than 162mg/L) after breaking gel.
2. cross-linking type guar gum in the prior art needs to add the heavy metals such as boron, zirconium, titanium as crosslinking agent, and the present invention is kept away
Exempt from using heavy metal, it is environmentally friendly.
3. by adjusting the quantitative proportion of modified group and hydroxyl, so that the fracturing fluid viscosity being finally configured to is adjustable and takes
Sand stability is good, has the function of significantly to drop resistance compared with guar gum fracturing fluid, it is made to be more suitable for fracturing fluid gelatinizer.
4. traditional plant glue because colloform texture is relatively weak, takes sand stability difference and broken glue is often not thorough, row is returned for the later period
Production is asked to have larger impact, but the exploitation of the modifyed guar gum in the present invention overcomes this defect, and modified resistance and stability
It is stronger, it might even be possible to seawater is directly prepared, and is returned drain and be can be used directly after supplementing concentration, greatly reduce construction cost and
The pressure of environmental protection treatment.
Specific embodiment
All features disclosed in this specification or disclosed all methods or in the process the step of, in addition to mutually exclusive
Feature and/or step other than, can combine in any way.
A kind of non-crosslinked plant gum fracturing fluid, including modifyed guar gum, the modification mode of the modifyed guar gum are in guar gum point
Increase modified group in subchain, the modified group is 3- hydroxypropanone- base, 1- hydroxypropanone- base, 1,3- hydroxypropanone- base or hydroxyl
One of ethylhexanal base is a variety of.
Preferably, the number of the quantity of the modified group on modifyed guar gum strand and the hydroxyl on guar gum strand before modified
The ratio of amount is 1:5-1:1.
The present invention also provides the preparation methods of above-mentioned non-crosslinked plant gum fracturing fluid, before preparing fracturing fluid, to guar gum into
Row modification, the modification include the following steps:
[1] guar gum is configured to aqueous solution, catalyst is added, and be passed through oxygen, oxidation reaction occurs, so that guar gum molecule
Part of hydroxyl on chain is converted into ketone group；
[2] by the solution filtering by step [1] reaction, catalyst is removed；Then modifying agent and alkali are added into solution
Catalyst, heating reaction；The modifying agent is one of 1- hydroxypropanone-, 1,3- hydroxypropanone- or hydroxyl ethanol or a variety of；
[3] solution by step [2] reaction is dried, crushed to get to for the powdered of preparing fracturing fluid
Modifyed guar gum.
It is the citing of 3- hydroxypropanone- base with modified group, modified reaction process is as follows:
Wherein, R1And R2Respectively a part of guar gum strand before modified, R3And R4Respectively modified guar gum strand
A part.
Preferably, catalyst described in step [1] is Cu, Ag, Pd, MnO2Or TiO2One of.
Preferably, the temperature of heating process described in step [1] is controlled at 70-90 DEG C.
Preferably, base catalyst described in step [2] is oxide, hydroxide, the carbonic acid of alkali or alkaline earth metal
One of hydrogen salt, carbonate or carboxylate.
Preferably, the temperature of heating process described in step [2] is controlled at 60-90 DEG C.
Above-mentioned technical proposal is illustrated below by specific embodiment.
Embodiment 1
The present embodiment provides the modifyed guar gums on a kind of strand with 3- hydroxypropanone- base, and in strand, 3- hydroxyl
The ratio of the quantity of the quantity and hydroxyl of acetonyl is 1:5.
Its synthesis step is as follows:
[1] guar gum is configured to the aqueous solution of mass fraction 40%, Cu is added as catalyst, and be passed through oxygen, heats
Reflux, 70-75 DEG C of temperature control, generation oxidation reaction, the reaction time 2 hours, so that the part of hydroxyl on guar gum strand turns
Turn to ketone group；
[2] by the solution filtering by step [1] reaction, Cu is removed；Then into solution be added 1- hydroxypropanone- and
The additional amount of NaOH, 1- hydroxypropanone- is that the additional amount of 50%, NaOH of guar gum quality is the 10% of guar gum quality, in order to reduce
Aldol condensation between 1- hydroxypropanone- itself reduces by-product.1- hydroxypropanone- can be divided into 3-5 parts to add by several times,
It can be added dropwise with dropping funel.In the present embodiment, 1- hydroxypropanone- is divided into 3 parts and is added in three times, every time between addition
It is spaced 1h, in reaction process, is heated and refluxed for, temperature is controlled at 60-65 DEG C, after last time adds 1- hydroxypropanone- 1h, instead
It should complete.
[3] solution by step [2] reaction is cooled down, dried and is crushed to get to for preparing fracturing fluid
Powdered modified guar gum.
The aqueous solution that modifyed guar gum in the present embodiment is configured to mass fraction 0.15% measures parameter as fracturing fluid
It is as follows:
| Project | The index that should meet | Measured data |
| Apparent viscosity: mPa.s | ≥15 | 16 |
| Residue content: mg/L | ≤300 | 162 |
| Dynamic fluid loss coefficient: m/min0.5 | 1×10-3 | 0.935×10-3 |
| Leak-off permeability injury rate: % | ≤20 | 16.5 |
| Resistance-reducing yield: % | ≥60 | 63.1 |
| Broken adhesiveness: mPa.s | ≤5 | 3 |
| Breaking glue solution surface tension: mN/m | ≤25 | 24.12 |
Embodiment 2
The present embodiment provides the modifyed guar gums on a kind of strand with 1,3- hydroxypropanone- base, and in strand, and 1,3-
The ratio of the quantity of the quantity and hydroxyl of hydroxypropanone- base is 1:1.
Its synthesis step is as follows:
[1] guar gum is configured to the aqueous solution of mass fraction 40%, Ag is added as catalyst, and be passed through oxygen, heats
Reflux, 85-90 DEG C of temperature control, generation oxidation reaction, the reaction time 2 hours, so that the part of hydroxyl on guar gum strand turns
Turn to ketone group；
[2] by the solution filtering by step [1] reaction, Ag is removed；Then into solution be added 1,3- hydroxypropanone- and
NaOH, the additional amount that the additional amount of 1,3- hydroxypropanone- is 40%, NaOH of guar gum quality is the 10% of guar gum quality, in order to subtract
Aldol condensation between few 1- hydroxypropanone- itself, reduces by-product.1- hydroxypropanone- can be divided into 3-5 parts to add by several times,
It can also be added dropwise with dropping funel.In the present embodiment, 1,3- hydroxypropanone- is divided into 5 parts and is added in five times, added every time
Between be spaced 30min, in reaction process, be heated and refluxed for, temperature is controlled at 85-90 DEG C, and last time adds 1,3- hydroxyl third
After ketone 1h, reaction is completed.
[3] solution by step [2] reaction is cooled down, dried and is crushed to get to for preparing fracturing fluid
Powdered modified guar gum.
The aqueous solution that modifyed guar gum in the present embodiment is configured to mass fraction 0.15% measures parameter as fracturing fluid
It is as follows:
| Project | The index that should meet | Measured data |
| Apparent viscosity: mPa.s | ≥15 | 16 |
| Residue content: mg/L | ≤300 | 168 |
| Dynamic fluid loss coefficient: m/min0.5 | 1×10-3 | 0.897×10-3 |
| Leak-off permeability injury rate: % | ≤20 | 17.1 |
| Resistance-reducing yield: % | ≥60 | 62.3 |
| Broken adhesiveness: mPa.s | ≤5 | 3 |
| Breaking glue solution surface tension: mN/m | ≤25 | 23.77 |
The actual measurement parameter of the property of the modifyed guar gum provided from embodiment 1 and embodiment 2 is it is found that embodiment 1 and implementation
Example 2 meets the index that should meet as fracturing fluid practical application.
The specific embodiment of the application above described embodiment only expresses, the description thereof is more specific and detailed, but simultaneously
The limitation to the application protection scope therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, under the premise of not departing from technical scheme design, various modifications and improvements can be made, these belong to this
The protection scope of application.
Claims (7)
1. a kind of non-crosslinked plant gum fracturing fluid, it is characterised in that: including modifyed guar gum, the modification mode of the modifyed guar gum is
Increase modified group on guar gum strand, the modified group is 3- hydroxypropanone- base, 1- hydroxypropanone- base, 1,3- hydroxyl third
One of ketone group or glycollic aldehyde base are a variety of.
2. a kind of non-crosslinked plant gum fracturing fluid described in accordance with the claim 1, it is characterised in that: the modifyed guar gum strand
On the quantity of modified group and the ratio of the quantity of the hydroxyl on guar gum strand before modified be 1:5-1:1.
3. a kind of preparation method of non-crosslinked plant gum fracturing fluid described in accordance with the claim 1, which is characterized in that pressed preparing
Before splitting liquid, processing is modified to guar gum, the modification includes the following steps:
[1] guar gum is configured to aqueous solution, catalyst is added, and be passed through oxygen, oxidation reaction occurs for heating, so that guar gum molecule
Part of hydroxyl on chain is converted into ketone group；
[2] by the solution filtering by step [1] reaction, catalyst is removed；Then modifying agent and base catalysis are added into solution
Agent, heating reaction；The modifying agent is one of 1- hydroxypropanone-, 1,3- hydroxypropanone- or hydroxyl ethanol or a variety of；
[3] solution by step [2] reaction is dried, crushed to get to for the powdered modified of preparing fracturing fluid
Guar gum.
4. a kind of preparation method of non-crosslinked plant gum fracturing fluid described in accordance with the claim 3, it is characterised in that: step [1]
Described in catalyst be Cu, Ag, Pd, MnO2Or TiO2One of.
5. a kind of preparation method of non-crosslinked plant gum fracturing fluid described in accordance with the claim 3, it is characterised in that: step [1]
Described in heating process temperature control at 70-90 DEG C.
6. a kind of preparation method of non-crosslinked plant gum fracturing fluid described in accordance with the claim 3, it is characterised in that: step [2]
Described in base catalyst be in the oxide of alkali or alkaline earth metal, hydroxide, bicarbonate, carbonate or carboxylate
It is a kind of.
7. a kind of preparation method of non-crosslinked plant gum fracturing fluid described in accordance with the claim 3, it is characterised in that: step [2]
Described in heating process temperature control at 60-90 DEG C.
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| CN201811220640.8A CN109207139A (en) | 2018-10-19 | 2018-10-19 | A kind of non-crosslinked plant gum fracturing fluid and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2010086482A1 (en) * | 2009-01-29 | 2010-08-05 | Consejo Superior De Investigaciones Científicas (Csic) | Chemoenzymatic method for the synthesis of 1-deoxy-d-xylulose |
| CN106701723A (en) * | 2016-12-21 | 2017-05-24 | 浙江大学 | D-fructose-6-phosphate aldolase A mutant, recombinant expression vector, genetically engineered bacterium and application and reaction product thereof |
| WO2018017390A1 (en) * | 2016-07-18 | 2018-01-25 | Isp Investments Llc | A hair care composition, process for preparing the same and method of use thereof |
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2018
- 2018-10-19 CN CN201811220640.8A patent/CN109207139A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010086482A1 (en) * | 2009-01-29 | 2010-08-05 | Consejo Superior De Investigaciones Científicas (Csic) | Chemoenzymatic method for the synthesis of 1-deoxy-d-xylulose |
| WO2018017390A1 (en) * | 2016-07-18 | 2018-01-25 | Isp Investments Llc | A hair care composition, process for preparing the same and method of use thereof |
| CN106701723A (en) * | 2016-12-21 | 2017-05-24 | 浙江大学 | D-fructose-6-phosphate aldolase A mutant, recombinant expression vector, genetically engineered bacterium and application and reaction product thereof |
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| Title |
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| 何敬文: "《药物合成反应》", 31 December 1995, 中国医药科技出版社 * |
| 姜子奇等: "Cu(Ⅱ)络合物催化氧化环己醇的研究 ", 《催化学报》 * |
| 林凯峰等: "在Cu_2(OH)PO_4催化剂上温和条件下H_2O_2对醇类化合物的催化氧化 ", 《吉林大学学报(理学版)》 * |
| 林淑勤等: "正己醇催化氧化制备正己醛 ", 《精细石油化工》 * |
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Application publication date: 20190115 |