阅读说明：本技术 一种超支化多胺二氧化碳吸收剂及其制备方法和应用 (Hyperbranched polyamine carbon dioxide absorbent, and preparation method and application thereof ) 是由 柳沛丰 刘磊 周晓寒 于 2021-07-16 设计创作，主要内容包括：本发明公开了一种超支化多胺二氧化碳吸收剂,具有-A-C-或-B-C-的重复结构单元,A、B、C的结构式如下：其制备方法为：季戊四醇或丙三醇与三溴化磷反应得到四溴季戊醇或三溴丙三醇；在碱作用下四溴季戊醇或三溴丙三醇与通式为P1的化合物反应得到具有A或B结构式的化合物；在还原剂作用下,具有A或B结构式的化合物与具有C结构式的化合物反应,得到超支化多胺二氧化碳吸收剂。本发明制备的超支化多胺二氧化碳吸收剂含氮量(氮密度高)、二氧化碳吸收能力强、吸收速度快；吸收二氧化碳后得到一种富碳流体,可以用于提高石油采收率,降低了CCS的运行成本,对碳中和、碳减排具有非常重要的理论和现实意义。(The invention discloses a hyperbranched polyamine carbon dioxide absorbent, which has a repeating structural unit of-A-C-or-B-C-, wherein A, B, C has the following structural formula: the preparation method comprises the following steps: pentaerythritol or glycerol reacts with phosphorus tribromide to obtain tetrabromo-pentaerythritol or tribromoglycerol; tetrabromo-pentaerythritol or tribromoglycerol reacts with a compound with a general formula of P1 under the action of alkali to obtain a compound with A or B structural formula; under the action of a reducing agent, the compound with the structural formula A or B reacts with the compound with the structural formula C to obtain the hyperbranched polyamine carbon dioxide absorbent. The hyperbranched polyamine carbon dioxide absorbent prepared by the invention has high nitrogen content (high nitrogen density) and dioxygenThe absorption capacity of the carbonized carbon is strong, and the absorption speed is high; the carbon-rich fluid obtained after carbon dioxide absorption can be used for improving the oil recovery rate and reducing the operation cost of CCS, and has very important theoretical and practical significance for carbon neutralization and carbon emission reduction.)

1. The hyperbranched polyamine carbon dioxide absorbent is characterized in that the structural formula of the hyperbranched polyamine carbon dioxide absorbent has a repeating structural unit of-A-C-or-B-C-, and A, B, C has the following structural formula:

R₁,R₂,R₃,R₄each independently represents-Ar-or C1-C8 unsubstituted or substituted alkyl, wherein Ar is a divalent aromatic group; n is 0 to 4.

2. The hyperbranched polyamine carbon dioxide absorbent according to claim 1, wherein,

the R is₁,R₂,R₃,R₄Respectively independent representationOr C1-C5 unsubstituted or substituted alkyl, wherein X represents O or S.

3. The method for preparing the hyperbranched polyamine carbon dioxide absorbent according to claim 1 or 2, comprising the steps of:

(1) in an organic solvent, pentaerythritol or glycerol reacts with phosphorus tribromide to obtain tetrabromo-pentaerythritol or tribromoglycerol;

(2) in an organic solvent, tetrabromophytiol or tribromoglycerol reacts with a compound with a general formula of P1 under the action of alkali to obtain a compound with an A or B structural formula; the compound with the general formula P1 has the following structural formula:

wherein R represents-Ar-or C1-C8 unsubstituted or substituted alkyl;

(3) in an organic solvent, under the action of a reducing agent, a compound with a structural formula A or B reacts with a compound with a structural formula C to obtain the hyperbranched polyamine carbon dioxide absorbent.

4. The method according to claim 3, wherein in step (1), the molar ratio of pentaerythritol to phosphorus tribromide is 1: (4.4-6.0); the molar ratio of the glycerol to the phosphorus tribromide is 1: (3.3-5.0); preferably, the reaction is carried out for 1-24 h at the temperature of 100-200 ℃; after the reaction is finished, pouring reaction liquid obtained by reacting pentaerythritol or glycerol with phosphorus tribromide into ice water to adjust the pH of the solution to 7-10, and performing suction filtration to obtain tetrabromophytiol or tribromoglycerol; preferably, the organic solvent is selected from N, N-dimethylformamide or N, N-dimethylacetamide.

5. The preparation method according to claim 3, wherein in the step (2), the molar ratio of the compound with the general formula P1 to the base is 1 (1.2-2.0), and the compound with the general formula P1 and the base are reacted at 50-100 ℃ for 1-10 h; preferably, the base is selected from sodium hydroxide, potassium hydroxide, sodium ethoxide or potassium carbonate; preferably, the organic solvent is selected from N, N-dimethylformamide or acetonitrile.

6. The process according to claim 3 or 5, wherein in the step (2), the molar ratio of tetrabromopentaerythritol to the compound of formula P1 is 1: (4.4-8.0); preferably, the molar ratio of the tribromoglycerol to the compound of formula P1 is 1: (3.3-6.0); preferably, the reaction time of the tetrabromopentaerythritol or the tribromoglycerol and the P1 compound with the general formula is 15-48 h.

7. The method according to claim 3, wherein in the step (3), the molar ratio of the compound of formula A to the compound of formula C is 1: (2.0-4.0); the molar ratio between the compound of formula B and the compound of formula C is 1: (1.5-3.0); preferably, the molar ratio between the reducing agent and the compound of formula a is 1: (4.0-6.0); the molar ratio between the reducing agent and the compound having the structural formula B is 1: (3.0-5.0).

8. The production method according to claim 3 or 7, wherein in the step (3), the reaction is: carrying out a reduction ammoniation reaction for 4-24 h at the temperature of-10-30 ℃; preferably, the organic solvent is selected from one or two of water, methanol or tetrahydrofuran; preferably, the reducing agent is selected from sodium borohydride, potassium borohydride or sodium cyanoborohydride.

9. Use of the hyperbranched polyamine carbon dioxide absorbent according to claim 1 or 2 for absorbing carbon dioxide.

10. A carbon-rich fluid obtained by reacting the hyperbranched polyamine carbon dioxide absorbent according to claim 1 or 2 after absorbing carbon dioxide.

Technical Field

The invention relates to the technical field of carbon dioxide absorption, in particular to a hyperbranched polyamine carbon dioxide absorbent, and a preparation method and application thereof.

Background

Climate change caused by greenhouse effect in recent decades seriously affects the development of environment, society and economy. In which the contribution of carbon dioxide to the greenhouse effect occupies a considerable proportion, which is one of the main components in greenhouse gases, the separation and capture of which has become a hot spot of global research.

The existing carbon dioxide separation and capture technology has many problems, such as: large equipment size, high regeneration energy consumption, potential environmental pollution and the like. The key to the solution of the above problem lies in the development of new absorbents. The absorbents currently used in carbon capture processes mainly include physical absorbents and chemical absorbents. The physical absorbent absorbs carbon dioxide through physical action between absorbent molecules and carbon dioxide molecules, and has the advantages of easy regeneration, but generally smaller absorption amount; the chemical absorbent absorbs the carbon dioxide through a chemical reaction with the carbon dioxide, and due to the generation of chemical bonds in the reaction process, the chemical bonds are broken by large heat when the absorbent is regenerated, so that the absorbent is relatively difficult to regenerate.

The physical properties of the absorbent, such as absorption capacity, absorption rate, heat of reaction, viscosity, density, volatility and the like, are directly related to the absorption efficiency of carbon dioxide, the capture energy consumption and the operation cost of the whole carbon dioxide capture and sequestration technology (CCS) device. Amine compounds are used as ideal carbon dioxide absorbents, most researched, most mature and most widely applied, and are mainly divided into primary amine, secondary amine and tertiary amine absorbents. Although many effective absorbents have been developed, there are problems to be solved, such as low nitrogen content, insufficient carbon dioxide absorption capacity, slow absorption rate, and low viscosity of the absorbent. Therefore, the development of a novel absorbent with high nitrogen content (high nitrogen density), strong carbon dioxide absorption capacity, high absorption speed, simple synthesis method and easy industrial production has very important theoretical and practical significance for carbon neutralization and carbon emission reduction.

Disclosure of Invention

Aiming at the prior art, the invention aims to provide a hyperbranched polyamine carbon dioxide absorbent, and a preparation method and application thereof. The hyperbranched polyamine carbon dioxide absorbent prepared by the invention has high nitrogen content (nitrogen density), strong carbon dioxide absorption capacity and high absorption speed, and the synthesis method is simple and has very important theoretical and practical significance for carbon neutralization and carbon emission reduction.

In order to achieve the purpose, the invention adopts the following technical scheme:

in a first aspect of the present invention, there is provided a hyperbranched polyamine carbon dioxide absorbent, wherein the structural formula of the hyperbranched polyamine carbon dioxide absorbent has a repeating structural unit of-a-C-or-B-C-, and A, B, C has the following structural formula:

R₁,R₂,R₃,R₄each independently represents-Ar-or C1-C8 unsubstituted or substituted alkyl, wherein Ar is a divalent aromatic group; n is 0 to 4.

Preferably, said R is₁,R₂,R₃,R₄Respectively independent representationOr C1-C5 unsubstituted or substituted alkyl, wherein X represents O or S.

In a second aspect of the present invention, a method for preparing a hyperbranched polyamine carbon dioxide absorbent is provided, which comprises the following steps:

(1) in an organic solvent, pentaerythritol or glycerol reacts with phosphorus tribromide to obtain tetrabromo-pentaerythritol or tribromoglycerol;

(2) in an organic solvent, tetrabromophytiol or tribromoglycerol reacts with a compound with a general formula of P1 under the action of alkali to obtain a compound with an A or B structural formula; the compound with the general formula P1 has the following structural formula:

wherein R represents-Ar-or C1-C8 unsubstituted or substituted alkyl;

(3) in an organic solvent, under the action of a reducing agent, a compound with a structural formula A or B reacts with a compound with a structural formula C to obtain the hyperbranched polyamine carbon dioxide absorbent.

Preferably, the compound of formula P1 has the following structure:

preferably, in step (1), the molar ratio of pentaerythritol to phosphorus tribromide is 1: (4.4-6.0); the molar ratio of the glycerol to the phosphorus tribromide is 1: (3.3-5.0).

Preferably, in the step (1), the reaction is carried out for 1-24 h at the temperature of 100-200 ℃; after the reaction is finished, pouring reaction liquid obtained by reacting pentaerythritol or glycerol with phosphorus tribromide into ice water to adjust the pH of the solution to 7-10, and performing suction filtration to obtain tetrabromophytiol or tribromoglycerol;

preferably, the organic solvent is selected from N, N-dimethylformamide or N, N-dimethylacetamide.

Preferably, the pH value of the solution is adjusted to 7-10 by adding an alkaline solution, wherein the alkaline solution is one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium bicarbonate, sodium carbonate, sodium bicarbonate, potassium carbonate or potassium bicarbonate; the concentration of the alkaline solution is 0.01-3 mol L^-1。

Preferably, in the step (2), the molar ratio of the compound with the general formula of P1 to the base is 1 (1.2-2.0), and the compound with the general formula of P1 reacts with the base at 50-100 ℃ for 1-10 h;

preferably, the molar ratio of tetrabromo pentaerythritol to the compound of formula P1 is 1: (4.4-8.0);

preferably, the molar ratio of the tribromoglycerol to the compound of formula P1 is 1: (3.3-6.0);

preferably, the reaction time of the tetrabromopentaerythritol or the tribromoglycerol and the P1 compound with the general formula is 15-48 h.

Preferably, in step (2), the base is selected from sodium hydroxide, potassium hydroxide, sodium ethoxide or potassium carbonate;

preferably, the organic solvent is selected from N, N-dimethylformamide or acetonitrile.

Preferably, in step (3), the molar ratio between the compound of formula a and the compound of formula C is 1: (2.0-4.0); the molar ratio between the compound of formula B and the compound of formula C is 1: (1.5-3.0);

preferably, the molar ratio between the reducing agent and the compound of formula a is 1: (4.0-6.0); the molar ratio between the reducing agent and the compound having the structural formula B is 1: (3.0-5.0).

Preferably, in step (3), the reaction is: carrying out a reduction ammoniation reaction for 4-24 h at the temperature of-10-30 ℃;

preferably, the organic solvent is selected from one or two of water, methanol or tetrahydrofuran;

preferably, the reducing agent is selected from sodium borohydride, potassium borohydride or sodium cyanoborohydride.

In a third aspect of the present invention, an application of the hyperbranched polyamine carbon dioxide absorbent in carbon dioxide absorption and capture is provided. The hyperbranched polyamine carbon dioxide absorbent is prepared with water to obtain an aqueous solution before use, and then the aqueous solution is used for absorbing carbon dioxide.

In a fourth aspect of the present invention, a carbon-rich fluid is provided, which is obtained by absorbing carbon dioxide with a hyperbranched polyamine carbon dioxide absorbent.

The product of the hyperbranched polyamine carbon dioxide absorbent absorbing carbon dioxide is called as carbon-rich fluid, and the carbon-rich fluid obtained by the invention can be used as an oil displacement agent in the fields of secondary and tertiary recovery of petroleum and the like.

The invention has the beneficial effects that:

1. the hyperbranched polyamine absorbent provided by the invention has the advantages of high nitrogen content, strong carbon dioxide absorption capacity, high absorption speed and high absorption efficiency; in addition, the absorbent has the advantages of simple structure, strong modifiability, adjustable performance, easy preparation, purification and batch synthesis, and good application prospect in the aspect of carbon dioxide absorption and capture.

2. The hyperbranched polyamine absorbent prepared by the invention absorbs carbon dioxide and then reacts to generate carbon-rich fluid, and the carbon-rich fluid can be used for improving the recovery ratio of petroleum and has very important theoretical and practical significance for carbon neutralization and carbon emission reduction.

Drawings

FIG. 1: and (3) testing the absorption performance of the hyperbranched polyamine carbon dioxide absorbent.

FIG. 2: the product (carbon-rich fluid) of the hyperbranched polyamine carbon dioxide absorbent absorbing carbon dioxide can enhance the effect of polymer flooding.

Detailed Description

It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.

As described in the background section, amine-based compounds, which are the most studied, mature and widely used as the ideal carbon dioxide absorbents, are mainly classified into primary, secondary and tertiary amine absorbents. Although many absorbents having sufficient effects have been developed, there are problems such as low nitrogen content, insufficient absorption capacity of carbon dioxide, and slow absorption rate.

Based on the above, one of the objectives of the present invention is to provide a hyperbranched polyamine carbon dioxide absorbent, and a preparation method and applications thereof. The structural formula of the hyperbranched polyamine carbon dioxide absorbent has a repeating structural unit of-A-C-or-B-C-, and the structural formula of A, B, C is as follows:

the hyperbranched polyamine carbon dioxide absorbent with-A-C-repeating structural units is prepared by the following method:

1) in an organic solvent, pentaerythritol reacts with phosphorus tribromide to obtain tetrabromo-pentaerythritol:

2) in an organic solvent, tetrabromo-pentaerythritol reacts with a compound with a general formula P1 under the action of alkali to obtain a compound with a structural formula A, wherein R and R in the general formula P1₁、R₂、R₃、R₄The expression ranges of (c) are consistent:

3) in an organic solvent, obtaining the hyperbranched polyamine carbon dioxide absorbent- (A-C) with-A-C-repetitive structural unit by the compound with the structural formula A and the compound with the structural formula C under the action of a reducing agent_n-：

The hyperbranched polyamine carbon dioxide absorbent with the-B-C-repeating structural unit is prepared by the following method:

1) in an organic solvent, glycerol reacts with phosphorus tribromide to obtain tribromoglycerol:

2) in an organic solvent, tribromoglycerol reacts with a compound with a general formula P1 under the action of alkali to obtain a compound with a structural formula B, wherein R and R in the general formula P1₁、R₂、R₃、R₄The expression ranges of (c) are consistent:

3) in an organic solvent, under the action of a reducing agent, the compound with the structural formula B and the compound with the structural formula C obtain a hyperbranched polyamine carbon dioxide absorbent- (B-C) with a-B-C-repeating structural unit_n-：

In the prior art, carbon dioxide is generally separated after the carbon dioxide is absorbed by a carbon dioxide absorbing material, and the separated carbon dioxide is sealed; making the carbon dioxide capture and sequestration costly. And the storage of carbon dioxide not only comprises the introduction of CO₂Stored deep underground and leakage monitored. Oil and gas fields have been extensively analyzed for geological purposes, and are most suitable for storing CO₂The site of (a) is an exhausted oil and gas field. The hyperbranched polyamine absorbent disclosed by the invention absorbs carbon dioxide and then reacts to obtain a carbon-rich fluid, and the inventor finds through experiments that the carbon-rich fluid can be used as an oil displacement agent for oil exploitation, so that the oil recovery rate is improved, and the absorbed CO can be used for oil exploitation₂The carbon is sealed and stored in the deep underground, thereby achieving multiple purposes, reducing the cost of carbon capture and sealing, and having very important theoretical and practical significance for carbon neutralization and carbon emission reduction.

In order to make the technical solutions of the present application more clearly understood by those skilled in the art, the technical solutions of the present application will be described in detail below with reference to specific embodiments.

The test materials used in the examples of the present invention are all conventional in the art and commercially available.

Example 1

A repeating unit of the formula-A-C-, andpreparation of compound P4-1 with n-2;

the structural formula of P4-1 is:

1) pentaerythritol (13.6g, 0.1mol) was dissolved in dry N, N-dimethylformamide (200mL) and phosphorus tribromide (133g, 0.5mol) was added in portions at 25 ℃. After stirring for 20 minutes, the temperature was slowly raised to 125 ℃ for 12 hours. After completion of the reaction, the reaction mixture was poured into ice water (500mL), and sodium hydroxide solution (0.2mol L) was added^-1) The pH was adjusted to 8 and the residue was suction filtered to give tetrabromobisphenol (24.6g, 64%).¹H NMR(CDCl₃,400MHz):δ3.20(s,8H).¹³C NMR(CDCl₃,100MHz):δ146.1,37.9.HR-MS(MALDI):m/z[M]⁺cacld for C5H8Br4,383.7860；found,387.7319.

2) Tetrabromoquaternary amyl alcohol (19.2g, 0.05mol) prepared in step 1), 4-hydroxybenzaldehyde (26.8g, 0.220mol), and potassium carbonate (41.4g, 0.30mol) were added to N, N-dimethylformamide (250mL) and the temperature was raised to 100 ℃ for reaction for 16 hours. The reaction was poured into ice water (500mL) and the residue was suction filtered to give intermediate A-1(22.9g, 83%).¹H NMR(CDCl₃,400MHz):δ3.82(s,8H),7.17(d,J＝8.0Hz,8H),7.78(d,J＝8.0Hz,8H),10.02(s,4H).¹³C NMR(CDCl₃,100MHz):δ191.11,165.23,131.92,128.56,114.97,61.23,40.26.HR-MS(MALDI):m/z[M]⁺cacld for C33H28O8,552.1784；found,553.1790.

3) The intermediate a-1(27.6g, 0.05mol) prepared in step 2) and C-1(n ═ 2) triethylene tetramine (14.6g, 0.10mol) were added to methanol (100mL), and sodium borohydride (7.6g,0.20mol) was added slowly in portions at 0 to 10 ℃. After the addition, the reaction mixture was warmed to room temperature and reacted for 5 hours. The solvent was distilled off under reduced pressure, and the residue was dissolved in chloroform and filtered. The filtrate was distilled off under reduced pressure to give hyperbranched polyamine P4-1(33.4g, 86%).¹H NMR(CDCl₃,400MHz):δ2.52-2.66(m,48H),3.74(s,8H),3.80(s,8H),7.12(d,J＝8.0Hz,8H),7.54(d,J＝8.0Hz,8H).¹³C NMR(CDCl₃,100MHz):δ157.71,156.63,131.82,130.26,127.17,114.20,61.23,52.33,51.20,49.12,48.25,41.26.

Example 2

A repeating unit of the formula-A-C-, andpreparation of compound P4-2 with n-3;

the structural formula of P4-2 is:

1) tetrabromo-neopentyl alcohol (19.2g, 0.05mol) and 3-hydroxybenzaldehyde (26.8g, 0.220mol), potassium carbonate (41.4g, 0.30mol) were added to N, N-dimethylformamide (250mL), and the temperature was raised to 100 ℃ for reaction for 16 hours. The reaction was poured into ice water (500mL) and the residue was suction filtered to give intermediate A-2(20.9g, 76%).¹H NMR(CDCl₃,400MHz):δ3.823(s,8H),7.22(d,J＝8.0Hz,4H),7.35(s,4H),7.56(d,J＝8.0Hz,4H),7.65-7.72(m,4H),9.82(s,4H).¹³C NMR(CDCl₃,100MHz):δ191.08,165.63,137.52,129.86,121.54,12.78,115.97,61.23,40.56.HR-MS(MALDI):m/z[M]⁺cacld for C33H28O8,552.1784；found,553.1786.

2) The intermediate product a-2(27.6g, 0.05mol) prepared in step 1) and C-2(n ═ 3) tetraethylenepentamine (19.4g, 0.10mol) were added to methanol (100mL), and sodium borohydride (7.6g,0.20mol) was slowly added in portions at 0 to 10 ℃. After the addition, the reaction mixture was warmed to room temperature and allowed to react for 8 hours. The solvent was distilled off under reduced pressure, and the residue was dissolved in chloroform and filtered. The filtrate was distilled off under reduced pressure to give hyperbranched polyamine P4-1(37.4g, 84%).¹H NMR(CDCl₃,400MHz):δ2.49-2.63(m,48H),3.76(s,8H),3.81(s,8H),J＝8.0Hz,4H),7.35(s,4H),7.56(d,J＝8.0Hz,4H),7.65-7.72(m,4H).¹³C NMR(CDCl₃,100MHz):δ157.21,137.82,129.16,112.70,112.10,61.23,52.63,51.20,48.92,41.12.

Example 3

General formula (VII)Is a-B-C-repeating unit, andpreparation of compound P6-1 with n-2 the structural formula of P6-1 is:

1) glycerol (9.2g, 0.1mol) was dissolved in dry N, N-dimethylformamide (200mL) and phosphorus tribromide (106.4g, 0.4mol) was added in portions at 25 ℃. After stirring for 20 minutes, the temperature was slowly raised to 120 ℃ for 12 hours. After completion of the reaction, the reaction mixture was poured into ice water (500mL), and sodium hydroxide solution (0.2mol L) was added^-1) The pH was adjusted to 8 and the residue was suction filtered to give tribromoglycerol (17.6g, 63%).¹H NMR(CDCl₃,400MHz):δ4.60-4.65(m,1H),3.74(d,J＝8.0Hz 4H).¹³C NMR(CDCl₃,100MHz):δ48.9,34.7.HR-MS(MALDI):m/z[M]⁺cacld for C3H5Br3,277.7941；found,279.7921.

2) Tribromoglycerol (13.9g, 0.05mol) prepared in step 1), 4-hydroxybenzaldehyde (19.9g, 0.16mol) and potassium carbonate (27.6g, 0.20mol) were added to N, N-dimethylformamide (200mL), and the mixture was heated to 100 ℃ to react for 16 hours. The reaction was poured into ice water (500mL) and the residue was filtered off with suction to give intermediate B-1(17.2g, 85%).¹H NMR(CDCl₃,400MHz):δ4.20-4.25(m,1H),4.72(s,4H),7.15(d,J＝8.0Hz,6H),7.60(d,J＝8.0Hz,6H),9.89(s,3H).¹³C NMR(CDCl₃,100MHz):δ191.01,165.23,163.21,131.90,128.46,114.92,81.85,67.53.HR-MS(MALDI):m/z[M]⁺cacld for C24H20O6,404.1260；found,405.1265.

3) Adding the intermediate product B-1(20.2g, 0.05mol) prepared in the step 2) and C-1 (n-2) triethylene tetramine (11.0g, 0.075mol) into methanol (100mL), and slowly adding sodium borohydride (5.7g,0.15mol) in portions at 0-10 ℃. After the addition, the reaction mixture was warmed to room temperature and reacted for 5 hours. The solvent was distilled off under reduced pressure, and the residue was dissolved in chloroform and filtered. The filtrate was distilled off under reduced pressure to obtain hyperbranched polyamine P6-1(27.4g, 89%).¹H NMR(CDCl₃,400MHz):δ2.50-2.55(m,36H),3.76(s,6H),4.17(d,J＝6.8Hz,4H),4.68-4.75(m,1H),7.12(d,J＝8.0Hz,6H),7.56(d,J＝8.0Hz,6H).¹³C NMR(CDCl₃,100MHz):δ157.73,155.76,131.85,131.21,114.25,81.87,67.54,52.36,51.22,49.02,46.32,41.16.

Test example: the hyperbranched polyamine carbon dioxide absorption performance test adopts a constant volume combined gas chromatography (Chenjian, Luowei, Libreak, the research progress of thermodynamics and kinetics of organic amine absorbing carbon dioxide, journal of chemical industry, 2014, 65: 12-21.) to measure the absorption performance of carbon dioxide, and the specific test process is as follows:

1) the hyperbranched polyamine carbon dioxide absorbent prepared in the example 1-3 is respectively prepared with water into 30 wt% absorbent solutions (respectively marked as P4-1, P4-2 and P6-1) for standby.

2) About 100ml of the prepared absorbent solution prepared in example 1 was injected into a reaction vessel with a syringe, and after the solution was stabilized at a desired temperature of 313.15K, the temperature T was recorded₀And pressure P₀。

3) Introducing proper amount of CO₂When the pressure is stable and the reaction reaches equilibrium, the temperature value T is recorded_iAnd a pressure value P_iAnd repeating the steps until the required measuring pressure is reached.

4) After the reaction kettle is cooled to room temperature, discharging gas and liquid in the kettle, and cleaning the kettle by using clear water;

5) steps 2) to 4) were repeated using the absorbent solutions prepared in examples 2 and 3, respectively.

Solubility of CO absorbed by liquids₂And the molar ratio of the polyamine solution, alpha_CO2＝n’_CO2/n_amineIts unit is mol CO₂And/mol amine. Wherein, n'_CO2Is CO in liquid phase₂Amount of substance(s), n'_CO2Equal to the introduction of CO₂Total amount of (2)_CO2Minus its quantity n in the gas phase^g _CO2。n_CO2And n^g _CO2Can be obtained by a P-R equation and temperature and pressure data recorded by experiments.

The gas phase composition was analyzed by gas chromatography, and the results of the hyperbranched polyamine carbon dioxide absorption performance test are shown in FIG. 1. As can be seen from FIG. 1, the three hyperbranched polyamine absorbents prepared in examples 1-3 exhibited good absorption rate and absorption amount for carbon dioxide at a temperature of 313.15K.

Application example: carbon-rich fluid for enhancing polymer flooding effect

CO absorption by hyperbranched polyamine carbon dioxide absorbent P4-1 prepared in example 1₂Taking the carbon-rich fluid (Fortane) obtained later as an example, polyacrylamide (HPAM, Beijing carbofuran) is selected as the oil displacement polymer, and aqueous solutions of HPAM (2000ppm), HPAM (2000ppm) + Fortane (1000ppm), HPAM (2000ppm) + Fortane (1500ppm) and HPAM (2000ppm) + Fortane (2000ppm) are respectively prepared for the test of polymer oil displacement. The specific test process is as follows:

adopting simulated crude oil and simulated water; oil reservoir temperature 60 ℃ and porosity>20%, permeability about 1500 mD; the total mineralization of the simulated water is about 2500mg/L, wherein, NaCl 2300mg/L, CaCl₂200 mg/L; the experimental oil was a simulated oil, i.e., dehydrated crude oil/kerosene (vol): 6:4, and had an apparent viscosity of 20.4 mPa-s (60 ℃, shear rate of 7.34 s)^-1)。

The physical model is a quartz sand epoxy resin bonded two-dimensional longitudinal heterogeneous artificial core, and the physical dimension is as follows: height × width × length ═ 4.5 × 4.5 × 30cm³Comprises 3 penetration layers with gas permeability of 3000 × 10^-3、1500×10^-3And 500X 10^-3μm²。

The displacement experiment comprises the following specific steps: firstly, vacuumizing a rock core at room temperature, saturating simulated water, and obtaining the pore volume of the rock core; secondly, saturating the core with simulated oil at 60 ℃, and calculating the oil saturation; thirdly, water is driven to 70 percent of water content, and water drive recovery ratio is obtained; fourthly, injecting an oil displacement agent, driving the water content to 98 percent by the follow-up water, and calculating the recovery ratio. The injection rate for the above experimental procedure was 0.3 mL/min.

The result of the carbon-rich fluid enhanced polymer flooding is shown in figure 2, and it can be seen from figure 2 that the recovery degree of the polymer HPAM flooding synergy is increased along with the increase of the addition amount of the carbon-rich fluid Fortane. Description of the inventionThe hyperbranched polyamine carbon dioxide absorbent prepared by the invention absorbs CO₂The obtained carbon-rich fluid can improve the recovery ratio of petroleum and can simultaneously convert CO₂Sealed in oil and gas field to reduce CO₂The capture and sequestration cost has very important theoretical and practical significance for carbon neutralization and carbon emission reduction.

The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.