CN101381440A - Preparation method of polyacrylamide phenolic resin crosslinking agent for improving oilfield recovery - Google Patents
Preparation method of polyacrylamide phenolic resin crosslinking agent for improving oilfield recovery Download PDFInfo
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- CN101381440A CN101381440A CNA2007101213166A CN200710121316A CN101381440A CN 101381440 A CN101381440 A CN 101381440A CN A2007101213166 A CNA2007101213166 A CN A2007101213166A CN 200710121316 A CN200710121316 A CN 200710121316A CN 101381440 A CN101381440 A CN 101381440A
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Abstract
The invention provides a method for preparing a polyacrylamide phenolic resin cross linking agent used for improving the recovery ratio of an oil field, which relates to a method for preparing a cross linking agent used for improving the recovery ratio of the oil field. In the method, phenol and formaldehyde are used as materials and prepared by the condensation reaction, the mixture of alkali metal hydroxide and alkaline earth metal hydroxide is used as a catalyst, and the weight ratio of the alkali metal hydroxide to the alkaline earth metal hydroxide is between 1 to 1 and 7; on the basis of the weight of reactants, the consumption of the catalyst is between 0.04 and 0.1 percent, the mol ratio of the phenol to the formaldehyde is between 1 to 2 and 1 to 3, the reaction temperature is controlled to between 60 and 80 DEG C, and the reaction time is controlled to between 4 and 9 hours; and the alkali metal hydroxid is sodium hydroxide, and the alkaline earth metal hydroxide is calcium hydroxide. The method has the advantages that the preparation process is simple; the cross linking agent has good storage stability, and can be stably stored for more than 180 days at the normal temperature, so that the cross linking agent is safely and conveniently used; moreover, the cross linking agent has the advantages of wide gel forming concentration range, low consumption and stable performance of the formed gel system.
Description
Technical field
The present invention relates to a kind of oil field and improve the preparation method of recovery ratio linking agent, the preparation method of recovery ratio polyacrylamide gel with phenolic resin crosslinking agent improved in particularly a kind of oil field.
Background technology
Linking agent is that one of recovery ratio common chemical agent is improved in the oil field, and it can generate the gelinite with different shape with the effect of polyacrylamide base polymer, is applied to profile control, water blockoff and the displacement technology in oil field.Polyacrylamide amine crosslinker commonly used at present mainly contains high volence metal ion (as chromium, aluminium) class and organic synthesis (as resol) class.
" research of deep profile controlling displacement of reservoir oil linking agent " (Speciality Petrochemicals progress .2003,4 (8) .-30-32,38), for improving the serious in-place oil recovery ratio of nonuniformity, synthesized 4 kinds of linking agents that are used for polymer flooding, and the system that type of polymer, consumption and itself and linking agent are formed has been estimated.40 ℃ of following aluminum crosslinker gel viscosities are low, do not become glue under the phenolic resin crosslinking agent low temperature, and organic chromium linking agent (J2) and organic varies (J3) cross-linking effect are good.
(oilfield chemistry .2002,19 (3) .-360-364,271) have studied the influence to HPAM microgel thermostability of polymkeric substance, linking agent, stablizer, dosing water quality and temperature " to improve the polyacrylamide microgel Research on Thermal Stability ".
Phenolic resin crosslinking agent is a kind of water soluble phenol resin, belongs to the first rank product of resol, contains methylol functional group or dimethylene diether linkage structure on its molecule, and has the self cure performance.Because the methylol functional group on the phenyl ring has very strong reactive behavior, its under certain condition can with amide group generation dehydration condensation, therefore, the linking agent that can be used as polyacrylamide is applied to the oil field.
As the linking agent of polyacrylamide, resol must have good water-solubility, high crosslinking activity and good storage stability.Preparation method commonly used at present is:, sodium hydroxide excessive at aldehyde is under the situation of catalyzer, is prepared by phenol and formaldehyde reaction.But the subject matter that the prepared phenolic resin crosslinking agent of present technology exists is that relative molecular mass is bigger, the product package stability is poor, that is to say that the linking agent product must produce before use, will autohemagglutination when placing for a long time form insoluble or the second rank of not melting or the third rank polymer and lose crosslinking activity.Can not long storage, directly affect linking agent applying at the scene, oil field.
People such as Shi Jihuai, Li Gang, Qian Xiaolin study the preparation of phenolic resin crosslinking agent respectively and report, but it all adopts the preparation of polystep reaction method, and technological process is complicated.People such as Li Gang investigate the package stability of prepared phenolic resin crosslinking agent, only can preserve two weeks at 25 ℃, and the product package stability is poor.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method with polyacrylamide gel phenolic resin crosslinking agent of crosslinking activity height, product excellent storage stability, characteristics such as safe in utilization.
The preparation method of recovery ratio with polyacrylamide phenolic resin crosslinking agent improved in a kind of oil field, with phenol and formaldehyde is that raw material makes through condensation reaction, with the mixture of alkali metal hydroxide and alkaline earth metal hydroxides as catalyzer, the weight proportion of alkali metal hydroxide and alkaline earth metal hydroxides is 1: 1～7, and catalyst consumption is that benchmark is 0.04～0.1% with the weight of reactant.
The mol ratio of phenol and formaldehyde is 1:2～1:3.
Temperature of reaction is controlled at 60 ℃～80 ℃.
Reaction times was controlled at 4 hours～9 hours, and the reaction times is preferably 6 hours～and 8 hours.
Described alkali metal hydroxide is a sodium hydroxide, and alkaline earth metal hydroxides is a calcium hydroxide.
The present invention adopts composite catalyst, and preparation technology is simple, the product excellent storage stability.
Concrete preparation process is:
1. in reactor, add phenol and formaldehyde with mol ratio 1:2～1:3;
2. under agitation add 0～0.07% alkali metal hydroxide and 0.01%～0.1% alkaline earth metal hydroxides or its oxide compound, preferred proportion alkali metal hydroxide 0.01%～0.05%, alkaline earth metal hydroxides or its oxide compound 0.03%～0.07%;
3. heat temperature raising to 60 ℃～80 ℃ isothermal reaction is 4 hours～9 hours, best 6 hours～8 hours.
Under alkaline condition, three active sites are arranged, only one of two at ortho position, contraposition in the phenol molecule.If the adjacency pair position is active the same, the probability of reaction equates that again then adjacent hydroxymethyl phenol should be compared many one times of hydroxymethyl phenol.But under general alkaline condition, in fact the activity of contraposition is much larger than adjacent activity (ortho position electron density 4.048, contraposition electron density 4.063), so be big to the ratio of hydroxymethyl phenol than aforementioned proportion.When using alkaline-earth metal to make catalyzer, because divalent metal forms " chelating shape complex compound " thereby helps generating the ortho position methylol, promptly so-called " high ortho position " resol between phenol and formaldehyde in catalytic process.Therefore, the composite use of alkali metal hydroxide and alkaline earth metal hydroxides (or its oxide compound) helps formaldehyde addition reaction on three active sites of phenol ortho para and generates tri hydroxy methyl phenol, improves the crosslinking activity and the storage stability of linking agent.
The present invention has following characteristics:
1. preparation technology is simple.The present invention adopts single stage method synthetic, and preparation process is simple to operate, is easy to control.
2. linking agent excellent storage stability.This clearly demarcated linking agent can be stablized storage more than 180 days at normal temperatures.
3. linking agent is safe and convenient to use.Linking agent of the present invention is liquid, and irritating smell is little, and is on-the-spot safe and convenient to use, avoided high concentration phenol and formaldehyde to the harm of human body and the pollution of environment.
4. linking agent becomes the gum concentration wide ranges, and usage quantity is low.When the HPAM working concentration is 1000mg/L, all can form the stable gel system during greater than 400mg/L at the linking agent dosage.
5. the gelling system stable performance of Xing Chenging.The formed gelling system of linking agent of the present invention and HPAM can be stablized more than 90 days under 80 ℃, sudden and violent oxygen condition.
Embodiment
Embodiment 1:
Prepare raw material: phenol, 37% formaldehyde solution, sodium hydroxide, calcium hydroxide.
Place the magnetic agitation control-temperature electric heating to put the 250mL there-necked flask that magnetic agitation, reflux exchanger, thermometer are housed, in adding flask, add 18.82g phenol and 48.70g formaldehyde solution, add 0.0203g calcium hydroxide and 0.0068g sodium hydroxide after stirring 5min, continue to stir and be warming up to 60 ℃, isothermal reaction 8h, cooling promptly obtains the 67.52g linking agent.
Embodiment 2:
Prepare raw material: phenol, 37% formaldehyde solution, sodium hydroxide, calcium hydroxide.
Place the magnetic agitation control-temperature electric heating to put the 250mL there-necked flask that magnetic agitation, reflux exchanger, thermometer are housed, in adding flask, add 18.82g phenol and 48.70g formaldehyde solution, add 0.0473g calcium hydroxide and 0.0203g sodium hydroxide after stirring 5min, continue to stir and be warming up to 60 ℃, isothermal reaction 8h, cooling promptly obtains the 67.52g linking agent.
Embodiment 3:
Prepare raw material: phenol, 37% formaldehyde solution, sodium hydroxide, calcium hydroxide.
Place the magnetic agitation control-temperature electric heating to put the 250mL there-necked flask that magnetic agitation, reflux exchanger, thermometer are housed, in adding flask, add 18.82g phenol and 48.70g formaldehyde solution, add 0.0203g calcium hydroxide and 0.0203g sodium hydroxide after stirring 5min, continue to stir and be warming up to 60 ℃, isothermal reaction 8h, cooling promptly obtains the 67.52g linking agent.
Embodiment 4:
Prepare raw material: phenol, 37% formaldehyde solution, sodium hydroxide, calcium hydroxide.
Place the magnetic agitation control-temperature electric heating to put the 250mL there-necked flask that magnetic agitation, reflux exchanger, thermometer are housed, in adding flask, add 18.82g phenol and 48.70g formaldehyde solution, add 0.0473g calcium hydroxide and 0.0068g sodium hydroxide after stirring 5min, continue to stir and be warming up to 60 ℃, isothermal reaction 8h, cooling promptly obtains the 67.52g linking agent.
Embodiment 5:
Prepare raw material: phenol, 37% formaldehyde solution, sodium hydroxide, calcium hydroxide.
Place the magnetic agitation control-temperature electric heating to put the 250mL there-necked flask that magnetic agitation, reflux exchanger, thermometer are housed, in adding flask, add 23.53g phenol and 40.58g formaldehyde solution, add 0.0192g calcium hydroxide and 0.0128g sodium hydroxide after stirring 5min, continue to stir and be warming up to 80 ℃, isothermal reaction 6h, cooling promptly obtains the 64.14g linking agent.
Embodiment 6:
Prepare raw material: industrial phenol, industrial formol, sodium hydroxide, calcium hydroxide.
In the heated enamel reaction still of the 2000L that mechanical stirring, reflux exchanger, thermometer are housed, add 400kg phenol and 1100kg formaldehyde solution, add 0.75kg calcium hydroxide and 0.3kg sodium hydroxide after stirring 10min, continue to stir and be warming up to 60 ℃, isothermal reaction 6h, cooling promptly obtains 1500kg linking agent product.
Comparative Examples 7:
Following table provides synthetic cross-linking agent stability of sample under the different catalysts, and be that sample loses flowability or the stratified time steady time.As seen, use NaOH and Ca (OH)
2The storage stability of linking agent is greatly improved during as catalysts.
| Catalyzer | 40 ℃ of steady times |
| NaOH | 14 days |
| Ca(OH) 2 | 20 days |
| NaOH+Ca(OH) 2 | Greater than 146 days |
Claims (6)
1, the preparation method of recovery ratio with polyacrylamide phenolic resin crosslinking agent improved in a kind of oil field, with phenol and formaldehyde is that raw material makes through condensation reaction, it is characterized in that, with the mixture of alkali metal hydroxide and alkaline earth metal hydroxides as catalyzer, the weight proportion of alkali metal hydroxide and alkaline earth metal hydroxides is 1: 1～7, and catalyst consumption is that benchmark is 0.04～0.1% with the weight of reactant.
2, the preparation method of polyacrylamide phenolic resin crosslinking agent according to claim 1 is characterized in that: the mol ratio of phenol and formaldehyde is 1:2～1:3.
3, the preparation method of polyacrylamide phenolic resin crosslinking agent according to claim 1 is characterized in that: temperature of reaction is controlled at 60 ℃～80 ℃.
4, the preparation method of polyacrylamide phenolic resin crosslinking agent according to claim 1 is characterized in that: the reaction times was controlled at 4 hours～9 hours.
5, preparation method according to claim 4 is characterized in that, the reaction times is 6 hours～8 hours.
6, preparation method according to claim 1 is characterized in that, alkali metal hydroxide is a sodium hydroxide, and alkaline earth metal hydroxides is a calcium hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNA2007101213166A CN101381440A (en) | 2007-09-04 | 2007-09-04 | Preparation method of polyacrylamide phenolic resin crosslinking agent for improving oilfield recovery |
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| CNA2007101213166A CN101381440A (en) | 2007-09-04 | 2007-09-04 | Preparation method of polyacrylamide phenolic resin crosslinking agent for improving oilfield recovery |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101979420A (en) * | 2010-10-12 | 2011-02-23 | 山东圣泉化工股份有限公司 | Method for preparing phenolic resin |
| CN102153999A (en) * | 2011-01-21 | 2011-08-17 | 西安石油大学 | Profile modification agent for amphion jelly |
| CN103214639A (en) * | 2013-04-24 | 2013-07-24 | 新疆华油技术服务股份有限公司 | Production method of water-soluble phenolic resin cross-linking agent used for water shut-off and profile control of oil field |
| CN104140795A (en) * | 2014-07-17 | 2014-11-12 | 陕西延长石油(集团)有限责任公司研究院 | Composite plugging agent used for oil well water plugging and preparing method thereof |
| CN106398672A (en) * | 2016-09-07 | 2017-02-15 | 中国石油化工股份有限公司 | Preparation method of water soluble phenolic resin crosslinking agent for temporary plugging steering acidizing |
| CN107057667A (en) * | 2017-04-28 | 2017-08-18 | 中国石油天然气集团公司 | A kind of modified phenolic crosslinking agent and its preparation method and application |
| CN108250376A (en) * | 2017-12-18 | 2018-07-06 | 常熟东南塑料有限公司 | Water-soluble Cementing preparation method of phenolic resin and its device |
| CN108841369A (en) * | 2018-07-02 | 2018-11-20 | 陕西科技大学 | A kind of preparation method of polyacrylamide Weak Gels |
| CN109111557A (en) * | 2018-07-30 | 2019-01-01 | 兰州理工大学 | The preparation method of agent for improving oilfield recovery low solubility phenolic resin |
| CN111909671A (en) * | 2020-08-14 | 2020-11-10 | 天津新翔油气技术有限公司 | Preparation method and application of phenolic resin cross-linking agent |
| CN111978496A (en) * | 2020-09-04 | 2020-11-24 | 科迪特能源科技(北京)有限公司 | Preparation method of profile control system cross-linking agent with physical and chemical functions |
| CN113136195A (en) * | 2020-01-20 | 2021-07-20 | 中国海洋石油集团有限公司 | Oligomeric polyphenol resin cross-linking agent for improving recovery ratio of oil field and preparation method thereof |
| CN114456784A (en) * | 2021-12-07 | 2022-05-10 | 中国海洋石油集团有限公司 | Long-storage phenolic resin cross-linking agent and high-temperature high-salt gel prepared from same |
| CN115181229A (en) * | 2022-09-09 | 2022-10-14 | 克拉玛依市正诚有限公司 | Modified urea-formaldehyde resin cross-linking agent and preparation method thereof |
-
2007
- 2007-09-04 CN CNA2007101213166A patent/CN101381440A/en active Pending
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101979420A (en) * | 2010-10-12 | 2011-02-23 | 山东圣泉化工股份有限公司 | Method for preparing phenolic resin |
| CN102153999A (en) * | 2011-01-21 | 2011-08-17 | 西安石油大学 | Profile modification agent for amphion jelly |
| CN102153999B (en) * | 2011-01-21 | 2012-11-21 | 西安石油大学 | Profile modification agent for amphion jelly |
| CN103214639A (en) * | 2013-04-24 | 2013-07-24 | 新疆华油技术服务股份有限公司 | Production method of water-soluble phenolic resin cross-linking agent used for water shut-off and profile control of oil field |
| CN104140795A (en) * | 2014-07-17 | 2014-11-12 | 陕西延长石油(集团)有限责任公司研究院 | Composite plugging agent used for oil well water plugging and preparing method thereof |
| CN106398672A (en) * | 2016-09-07 | 2017-02-15 | 中国石油化工股份有限公司 | Preparation method of water soluble phenolic resin crosslinking agent for temporary plugging steering acidizing |
| CN107057667B (en) * | 2017-04-28 | 2020-04-21 | 中国石油天然气集团公司 | Modified phenolic crosslinking agent and preparation method and application thereof |
| CN107057667A (en) * | 2017-04-28 | 2017-08-18 | 中国石油天然气集团公司 | A kind of modified phenolic crosslinking agent and its preparation method and application |
| CN108250376A (en) * | 2017-12-18 | 2018-07-06 | 常熟东南塑料有限公司 | Water-soluble Cementing preparation method of phenolic resin and its device |
| CN108841369A (en) * | 2018-07-02 | 2018-11-20 | 陕西科技大学 | A kind of preparation method of polyacrylamide Weak Gels |
| CN109111557A (en) * | 2018-07-30 | 2019-01-01 | 兰州理工大学 | The preparation method of agent for improving oilfield recovery low solubility phenolic resin |
| CN109111557B (en) * | 2018-07-30 | 2021-06-22 | 兰州理工大学 | Preparation method of low-solubility phenolic resin for improving recovery ratio of oil field |
| CN113136195A (en) * | 2020-01-20 | 2021-07-20 | 中国海洋石油集团有限公司 | Oligomeric polyphenol resin cross-linking agent for improving recovery ratio of oil field and preparation method thereof |
| CN111909671A (en) * | 2020-08-14 | 2020-11-10 | 天津新翔油气技术有限公司 | Preparation method and application of phenolic resin cross-linking agent |
| CN111978496A (en) * | 2020-09-04 | 2020-11-24 | 科迪特能源科技(北京)有限公司 | Preparation method of profile control system cross-linking agent with physical and chemical functions |
| CN114456784A (en) * | 2021-12-07 | 2022-05-10 | 中国海洋石油集团有限公司 | Long-storage phenolic resin cross-linking agent and high-temperature high-salt gel prepared from same |
| CN115181229A (en) * | 2022-09-09 | 2022-10-14 | 克拉玛依市正诚有限公司 | Modified urea-formaldehyde resin cross-linking agent and preparation method thereof |
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Open date: 20090311 |