阅读说明：本技术 一种生物质无污染油田解堵剂 (Biomass pollution-free oilfield blocking remover ) 是由 王泽晨 于 2021-08-02 设计创作，主要内容包括：本发明公开了一种生物质无污染油田解堵剂,其包含：解堵主剂、酸性调节剂、渗透调节剂；所述解堵剂按质量分数计包含：10-20%的聚天冬氨酸、1-5%的木质素磺酸钠、1-5%的羧甲基氧化琥珀酸钠、10-30%的多羧酸基团聚合物,及余量水。本发明提供的生物质无污染油田解堵剂所使用的主体原料均可从动植物中提取,且可降解为有机物质,因此具有环境友好的效果,另外,还具有非常低的表面张力,渗透性好,并且应用于油田中时,可以显著降低了油田沉积物的粘度,因此具有较好的解堵效果,能够适用于不同油田的复杂环境。(The invention discloses a biomass pollution-free oilfield blocking remover, which comprises: a blockage removal main agent, an acidity regulator and a permeation regulator; the blocking remover comprises the following components in percentage by mass: 10-20% of polyaspartic acid, 1-5% of sodium lignosulfonate, 1-5% of sodium carboxymethyl oxysuccinate, 10-30% of polycarboxylic acid group polymer and the balance of water. The main raw materials used by the biomass pollution-free oilfield blocking remover provided by the invention can be extracted from animals and plants, and can be degraded into organic substances, so that the biomass pollution-free oilfield blocking remover has an environment-friendly effect, has very low surface tension and good permeability, and can obviously reduce the viscosity of oilfield sediments when being applied to an oilfield, so that the biomass pollution-free oilfield blocking remover has a good blockage removing effect, and can be applied to complex environments of different oilfields.)

1. The biomass pollution-free oilfield blockage relieving agent is characterized by comprising a blockage relieving main agent, an acid regulator and a permeation regulator; the blockage removing main agent comprises the following components in parts by mass:

10-20% of polyaspartic acid

1 to 5 percent of sodium lignosulfonate

1-5% of sodium carboxymethyl oxysuccinate

10-30% of polycarboxylic acid group polymer

And the balance of water.

2. The blockage removing agent for the biomass pollution-free oil field according to claim 1, wherein the blockage removing main agent comprises the following components in percentage by mass:

10-15% of polyaspartic acid

1 to 3 percent of sodium lignosulfonate

1-3% of sodium carboxymethyl oxysuccinate

Polycarboxylic acid group polymer 20-30%

And the balance of water.

3. The plugging agent for a biomass pollution-free oil field as claimed in claim 1, wherein the molecular weight of said polyaspartic acid is 10000-.

4. The biomass pollution-free oilfield unblocking agent according to claim 1, wherein the polycarboxylic acid group polymer is formed by free radical polymerization of one or more unsaturated carboxylic acids selected from one or more of oleic acid, erucic acid, linolenic acid, linoleic acid and eicosapentaenoic acid.

5. The biomass pollution-free oilfield unblocking agent according to claim 4, wherein the preparation method of the polycarboxylic acid group polymer comprises the following steps:

(1): dissolving unsaturated carboxylic acid by using an organic solvent, adding azobisisobutyronitrile, stirring until the mixture is completely dissolved to obtain a dropwise added solution for later use;

(2): adding an organic solvent into a reactor provided with a condenser in advance, heating the solvent in the reactor to 75-85 ℃, slowly dropwise adding the solution obtained in the step (1) into the reactor while keeping the temperature at 75-85 ℃, heating the reaction solution to 95-105 ℃ after dropwise adding, curing, and stopping the reaction;

(3): and (3) concentrating the reaction liquid obtained in the step (2) under reduced pressure to obtain the polycarboxylic acid group polymer.

6. The blockage relieving agent for the biomass pollution-free oil field as claimed in claim 1, wherein the acidity regulator is a polyene polyamine component.

7. The blockage relieving agent for the biomass-free oil field according to claim 6, wherein the polyene polyamine component is selected from one or more of diethylenetriamine, triethylene tetramine and tetraethylene pentamine.

8. The biomass pollution-free oilfield blockage removing agent as claimed in claim 1, wherein the permeation regulator is a fluorine-containing macromolecular polymer.

9. The biomass pollution-free oilfield blockage relieving agent as claimed in claim 8, wherein the fluorine-containing macromolecular polymer is prepared by ring-opening lactide from perfluoropolyether monoalcohol or perfluoropolyether diol.

10. The blockage removing agent for the biomass pollution-free oil field as claimed in claim 1, wherein the mass ratio of the blockage removing main agent to the acidity regulator to the permeability regulator is 100:1-5: 0.1-1.

Technical Field

The invention relates to the field of oilfield chemistry, in particular to a biomass pollution-free oilfield blocking remover.

Background

Petroleum is an important energy source, and a series of reservoir damages are easily caused because external fluid enters a reservoir in the process of drilling, oil production and well repair operation. Solid-phase particles in external working fluid invade into a hydrocarbon reservoir, possibly causing reservoir blockage; meanwhile, if the external working fluid is incompatible with the physical properties of reservoir rocks, sensitive damages such as water sensitivity, salt sensitivity, alkali sensitivity and the like and wetting reversal phenomena are easily caused; in addition, if the external working fluid is incompatible with the reservoir fluid, inorganic salt precipitation is easily generated, water lock effect is generated, and reservoir damage such as emulsification blockage, bacterial blockage and the like is generated. Oil and gas well reservoirs are damaged, and production is reduced or even stopped. Therefore, it has very important significance to provide various blockage removal and production increase technologies aiming at different reservoir damage. At present, the domestic methods and technologies for treating reservoir blockage are various, and can be summarized into four methods, namely a chemical method, a physical-chemical method, a microbial method and the like. The chemical blockage removal method has the advantages of strong pertinence, simple, flexible and convenient construction, low operation cost relative ratio, small damage to a well body structure, high success rate, effective time of several months to one or two years and the like, and is the most common blockage removal method. The chemical blockage removing method adopts a composite chemical blockage removing agent which takes a strong oxidant as a main component to remove blockage, wherein the oxidant can degrade crosslinked polymer coagulated agglomerates, kill and decompose microorganisms and metabolites, dissolve iron sulfide, clay minerals and the like, degrade large-particle gel agglomerates into small fragments and solution, enter the deep part of the stratum along with injected fluid, and dredge the stratum pore canals in blast holes and near-wellbore zones, thereby achieving the purpose of removing blockage.

The preparation of the blocking remover is the key in the chemical blocking removal method, and the preparation is specific according to different wells; secondly, the construction procedure needs to be carried out safely, reasonably and continuously; and thirdly, the dosage of the blocking remover is injected, and generally cannot be less than the damaged radius of the hydrocarbon reservoir. The continuous improvement of the preparation of the blocking remover and the reduction of the construction cost are the directions of continuous efforts of the chemical blocking removal method.

At present, the chemical blocking remover needs to consider more environmental protection problems, so that more and more new directions appear. Chinese patent application publication No. CN110776892A discloses a microemulsion neutral blocking remover, which is neutral, but uses a large amount of surfactant to achieve acidic blocking removal effect, so it does not solve the pollution problem though it reduces the use of acid. Also, for example, chinese patent application publication No. CN112778991A discloses a bio-enzyme composite blocking remover and a preparation method thereof, which uses bio-enzyme as a catalytic substance to obtain a certain effect, but the catalysis of bio-enzyme has a relatively large limitation, and the variety of bio-enzyme needs to be continuously changed, and the environment of an oil field is complex, and bio-enzyme is easily polluted and loses effect. Therefore, the development of chemical blocking removers is still a technical problem.

Disclosure of Invention

The purpose of the invention is as follows: aiming at the defects of the prior art, the invention aims to provide an environment-friendly biomass pollution-free oilfield blockage removing agent with a good blockage removing effect.

The technical scheme of the invention is as follows:

in order to realize the aim, the invention provides a biomass pollution-free oilfield blocking remover, which comprises a blocking remover main agent, an acid regulator and a permeation regulator; the blockage removing main agent comprises the following components in parts by mass:

as a further scheme of the invention, the blockage removing main agent used by the invention comprises the following components in percentage by mass:

as a further embodiment of the present invention, the molecular weight of the polyaspartic acid is 10000-20000.

The polyaspartic acid is a polymeric amino acid with a carboxylic acid side chain, and peptide bonds on the structural main chain of the polyaspartic acid are easily broken under the action of microorganisms, fungi and the like, and finally, degradation products are water and carbon dioxide which are harmless to the environment, so the polyaspartic acid is an environment-friendly and pollution-free material.

As a further scheme of the invention, the polycarboxylic acid group polymer used by the biomass pollution-free oilfield blocking remover is prepared by the reaction of one or more unsaturated carboxylic acids through free radical polymerization.

As a further scheme of the invention, the unsaturated carboxylic acid used by the biomass pollution-free oilfield unblocking agent is selected from one or more of oleic acid, erucic acid, linolenic acid, linoleic acid and eicosapentaenoic acid.

As a further scheme of the invention, the preparation method of the polycarboxylic acid group polymer used by the biomass pollution-free oilfield blocking remover comprises the following steps:

(1): dissolving unsaturated carboxylic acid by using an organic solvent, adding azobisisobutyronitrile, stirring until the mixture is completely dissolved to obtain a dropwise added solution for later use;

(2): adding an organic solvent into a reactor provided with a condenser in advance, heating the solvent in the reactor to 75-85 ℃, slowly dropwise adding the solution obtained in the step (1) into the reactor while keeping the temperature at 75-85 ℃, heating the reaction solution to 95-105 ℃ after dropwise adding, curing, and stopping the reaction;

(3): and (3) concentrating the reaction liquid obtained in the step (2) under reduced pressure to obtain the polycarboxylic acid group polymer.

As a further embodiment of the present invention, the acidity regulator used in the present invention is a polyene polyamine component selected from one or more of diethylenetriamine, triethylenetetramine and tetraethylenepentamine. Specifically, the polyene polyamine component can form a macromolecular salt compound through the reaction of an amino group and a carboxylic acid group, so that the overall acid value can be reduced, and the aim of adjusting the acid value is fulfilled.

In a further embodiment of the present invention, the permeation enhancer used in the present invention is a fluorine-containing macromolecular polymer obtained by ring-opening lactide from perfluoropolyether monoalcohol or perfluoropolyether diol.

Specifically, the fluorine-containing macromolecular polymer is generated by catalyzing perfluoropolyether and lactide with an organotin catalyst.

More specifically, the organic tin catalyst is one or more selected from stannous octoate, stannous dichloride and dibutyltin dilaurate.

As a further scheme of the invention, the molecular weight of the fluorine-containing macromolecular polymer used by the biomass pollution-free oilfield blocking remover is 2000-5000.

As a further scheme of the invention, the mass ratio of the blockage removing main agent, the acidity regulator and the permeation regulator in the biomass pollution-free oilfield blockage removing agent provided by the invention is 100:1-5: 0.1-1.

Has the advantages that:

the main raw materials used by the biomass pollution-free oilfield blocking remover provided by the invention can be extracted from animals and plants, and can be degraded into organic substances, so that the biomass pollution-free oilfield blocking remover has an environment-friendly effect, has very low surface tension and good permeability, and can obviously reduce the viscosity of oilfield sediments when being applied to an oilfield, so that the biomass pollution-free oilfield blocking remover has a good blockage removing effect, and can be applied to complex environments of different oilfields.

Detailed description of the invention

The present invention will be further described below by way of specific examples.

In the following examples, those whose operations are not subject to the conditions indicated, are carried out according to the conventional conditions or conditions recommended by the manufacturer. The raw materials used in the scheme of the invention are purchased from Chinese medicine reagents and an Allantin reagent.

Synthesis example 1 of polycarboxylic acid group Polymer

Adding 100g of oleic acid, 150g of linoleic acid, 50g of linolenic acid and 2g of azobisisobutyronitrile into a mixed solvent consisting of 100g of butyl acetate and 100g of toluene, and stirring until the mixture is completely dissolved to obtain a dropwise added solution for later use;

a mixed solvent composed of 50g of butyl acetate and 50g of toluene was previously charged into a reactor equipped with a condenser, the mixed solvent in the reactor was heated to 80 ℃ and the titration solution was slowly added dropwise to the reactor over 6 hours while maintaining the temperature at 80 ℃, after completion of the dropwise addition, the reaction solution was heated to 100 ℃ to effect aging for 3.5 hours, and then the reaction was stopped. The reaction solution was concentrated under reduced pressure to obtain a polycarboxylic acid group polymer 1, whose weight average molecular weight was 7890 as measured by the SES method.

Synthesis example 2 of polycarboxylic acid group Polymer

Adding 150g of erucic acid, 150g of linoleic acid and 1.5g of azobisisobutyronitrile into a mixed solvent consisting of 100g of butyl acetate and 100g of toluene, and stirring until the mixture is completely dissolved to obtain a dropwise added solution for later use;

a mixed solvent composed of 50g of butyl acetate and 50g of toluene was previously charged into a reactor equipped with a condenser, the mixed solvent in the reactor was heated to 80 ℃ and the titration solution was slowly added dropwise to the reactor over 6 hours while maintaining the temperature at 80 ℃, after completion of the dropwise addition, the reaction solution was heated to 100 ℃ to effect aging for 2.5 hours, and then the reaction was stopped.

The reaction solution was concentrated under reduced pressure to obtain a polycarboxylic acid group polymer 2, whose weight average molecular weight was 8240 by SES method.

Synthesis example 3 of polycarboxylic acid group Polymer

Adding 100g of oleic acid, 150g of erucic acid, 50g of linolenic acid and 1g of azobisisobutyronitrile into a mixed solvent consisting of 100g of butyl acetate and 100g of toluene, and stirring until the mixture is completely dissolved to obtain a dropwise added solution for later use;

a mixed solvent composed of 50g of butyl acetate and 50g of toluene was previously charged into a reactor equipped with a condenser, the mixed solvent in the reactor was heated to 80 ℃ and the titration solution was slowly dropped into the reactor over 6 hours while maintaining the temperature at 80 ℃, after completion of the dropping, the reaction solution was heated to 100 ℃ to effect aging for 4 hours, and then the reaction was stopped.

The reaction solution was concentrated under reduced pressure to obtain a polycarboxylic acid group polymer 3, whose weight average molecular weight was 7780 as measured by SES method.

Synthesis example 4 of polycarboxylic acid group Polymer

100g of eicosapentaenoic acid, 100g of linoleic acid, 100g of linolenic acid and 2g of azobisisobutyronitrile are added into a mixed solution of 100g of butyl acetate and 100g of toluene, and stirred until complete dissolution is achieved, so as to obtain a dropwise added solution for later use.

A mixed solvent composed of 50g of butyl acetate and 50g of toluene was previously charged into a reactor equipped with a condenser, the temperature of the mixed solvent system in the reactor was slowly raised to 80 ℃, the titrated solution was slowly dropped into the reactor over 6 hours while maintaining the temperature at 80 ℃, after completion of dropping, the reaction solution was heated to 100 ℃ to be aged for 3.5 hours, and then the reaction was stopped.

The reaction solution was concentrated under reduced pressure to obtain polycarboxylic acid group polymer 4, whose weight average molecular weight was 7370 by SES method.

Synthesis example 1 of fluoropolymer

Adding 100g of perfluoropolyether diol (purchased from Suwei, model number E10H) and 144g of lactide into a reactor, uniformly stirring, heating the system to 100 ℃, adding 0.5g of stannous octoate to start reaction, slowly changing the system from milky turbid to a semitransparent state, stopping the reaction until the lactide residue is less than 5% after 6 hours of reaction, obtaining the fluorine-containing macromolecular polymer 1, and measuring the weight average molecular weight of the fluorine-containing macromolecular polymer 1 by using an SES method to be 3300.

Synthesis example 2 of fluoropolymer

Adding 80g of perfluoropolyether diol (purchased from Suwei, model D2) and 144g of lactide into a reactor, uniformly stirring, heating the system to 100 ℃, adding 0.4g of stannous octoate to start reaction, slowly changing the system from milky turbid to a semitransparent state, stopping the reaction until the lactide residue is less than 5% after the reaction is carried out for 4 hours, and obtaining the fluorine-containing macromolecular polymer 2, wherein the weight average molecular weight of the fluorine-containing macromolecular polymer is 3500 by using an SES method.

Synthesis example 3 of fluoropolymer

100g of perfluoropolyether monoalcohol (molecular weight is 2200, purchased from Suzhou Bingmu New Material Co., Ltd.) and 144g of lactide are added into a reactor, after uniform stirring, the system is heated to 100 ℃, 0.4g of stannous octoate is added to start reaction, the system slowly changes from milky turbid to semitransparent, the residual amount of the lactide is less than 5% after 9 hours of reaction, the reaction is stopped, and the fluorine-containing macromolecular polymer 3 is obtained, and the weight-average molecular weight of the fluorine-containing macromolecular polymer is 4200 measured by an SES method.

Example 1

15g of polyaspartic acid, 3g of sodium lignosulfonate, 3g of sodium hydroxymethyloxydisuccinate and 25g of polycarboxylic acid group polymer 4 were added to 54g of deionized water and dissolved at 50 ℃ until clear and transparent.

2g of diethylenetriamine was added as an acidity regulating component, and 0.1g of fluorine-containing macromolecular polymer 1 was added as an osmosis regulating component. And mixing the mixture by using an emulsifying machine at the rotating speed of 10000 r/min to finally obtain blue-emitting slightly turbid liquid.

Example 2

15g of polyaspartic acid, 3g of sodium lignosulfonate, 3g of sodium hydroxymethyloxydisuccinate and 25g of polycarboxylic acid group polymer 3 were added to 54g of deionized water and dissolved at 50 ℃ until clear and transparent.

1g of tetraethylenepentamine was added as an acidity regulating component, and 0.5g of a fluorine-containing macromolecular polymer 3 was added as an osmosis regulating component. Mixing was carried out using an emulsifying machine at 10000 rpm to obtain a white slightly turbid liquid.

Example 3

20g of polyaspartic acid, 1g of sodium lignosulfonate, 1g of sodium hydroxymethyloxydisuccinate and 15g of polycarboxylic acid group polymer 1 are added to 63g of deionized water and dissolved at 50 ℃ until clear and transparent.

4g of triethylene tetramine was added as an acid adjusting component, and 0.5g of fluoropolymer 2 was added as an osmotic adjusting component. Mixing was carried out using an emulsifying machine at 10000 rpm to obtain a white slightly turbid liquid.

Example 4

13g of polyaspartic acid, 2g of sodium lignosulfonate, 2g of sodium hydroxymethyloxydisuccinate and 30g of polycarboxylic acid polymer 3 were added to 53g of deionized water and dissolved at 50 ℃ until clear and transparent.

3g of tetraethylenepentamine was added as an acidity regulating component, and 0.4g of fluoropolymer 3 was added as a permeation regulating component. Mixing was carried out using an emulsifying machine at 10000 rpm to obtain a white slightly turbid liquid.

Example 5

20g of polyaspartic acid, 5g of sodium lignosulfonate, 2g of sodium hydroxymethyloxydisuccinate and 30g of polycarboxylic acid polymer 3 were added to 43g of deionized water and dissolved at 50 ℃ until clear and transparent.

5g of triethylene tetramine was added as an acid adjusting component, and 0.8g of fluoropolymer 3 was added as an osmotic adjusting component. Mixing was carried out using an emulsifying machine at 10000 rpm to obtain a white slightly turbid liquid.

Example 6

20g of polyaspartic acid, 5g of sodium lignosulfonate, 2g of sodium hydroxymethyloxydisuccinate and 30g of polycarboxylic acid polymer 3 were added to 43g of deionized water and dissolved at 50 ℃ until clear and transparent.

5g of triethylene tetramine was added as an acid adjusting component, and 0.1g of fluoropolymer 3 was added as an osmotic adjusting component. And mixing the mixture by using an emulsifying machine at the rotating speed of 10000 r/min to finally obtain the blue-emitting slightly turbid liquid.

The deblocking agents prepared in examples 1-6 were applied to field a and field B, respectively, and the surface tension of each example and the rate of decrease in viscosity (25 ℃) of the oil after application to two different fields were tested.

The main component contents of the sediments in the oil field A and the oil field B are analyzed according to the analysis of soluble organic matters in rock and crude oil family components as follows:

	aromatic hydrocarbons	Glue	Asphaltenes	Inorganic substance
					Oilfield a sediments	20.51％	6.51％	52.11％	7.60％
Oilfield B-sediment	23.07％	8.92％	37.15％	14.66％

The surface tension was measured using a platinum plate method.

The test method of the viscosity reduction rate is as follows: the viscosity at 25 ℃ of the oilfield sediment test is taken as the initial viscosity, 5g of the blocking remover of each embodiment is added into 100g of oilfield sediment, stirred for 30min and then kept stand, and the viscosity at 25 ℃ of the upper layer test is taken as the test viscosity.

Viscosity reduction rate (initial viscosity-test viscosity)/initial viscosity

The above table shows that the biomass pollution-free oilfield blockage removing agent prepared by the invention has very low surface tension and good permeability, and in addition, when the biomass pollution-free oilfield blockage removing agent is applied to an oilfield, the viscosity of oilfield sediments is obviously reduced, so that the biomass pollution-free oilfield blockage removing agent has a good blockage removing effect and can be suitable for complex environments of different oilfields.

The above-mentioned embodiments are merely illustrative of the principles and effects of the present invention, and some embodiments may be used, not restrictive; it should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the inventive concept of the present invention, and these changes and modifications belong to the protection scope of the present invention.