Polyolefin alcohol amine polymer, acidic gas adsorbent, and preparation method and application of polyolefin alcohol amine polymer

Abstract

The invention relates to the technical field of gas purification, in particular to a polyolefin alcohol amine polymer, a preparation method of the polyolefin alcohol amine polymer and application of the polyolefin alcohol amine polymer, and the polyolefin alcohol amine polymer contains a structural unit shown in the formula (I), # imgabs0 #, in the formula, R1 is a bond or alkylene containing or not containing heteroatoms; r2 and R3 are respectively and independently selected from hydrogen and alkylene containing or not containing ether bonds. The polyolefin alcohol amine polymer prepared by the method can efficiently absorb harmful gases such as hydrogen sulfide, organic sulfur, carbon dioxide and the like in industrial gases, reduces the influence of raw material gases on the environment and human health, and meets the requirements of industrial gas purification application.

Description

Technical Field

[0001] The present invention relates to the technical field of gas purification, and in particular to a polyolefin alcohol amine polymer, a preparation method of the polyolefin alcohol amine polymer and application thereof, which are used for deeply absorbing carbon dioxide, hydrogen sulfide and organic sulfide in industrial gas. Background Art

[0002] At present, in the applications of industrial gas desulfurization and decarbonization such as natural gas purification and flue gas carbon capture, alcohol amine chemical absorption capture is the most commonly used method, and this method has been carried out in industrial demonstration and commercial operation at home and abroad. However, the problem that needs to be solved urgently is that the absorbent loss needs to be further reduced. At present, the domestic advanced indicator of alcohol amine loss is 0.8kg / tCO2. Under the combined effect of strong oxidation and high temperature atmosphere, the degradation rate needs to be further reduced, and the escape loss needs to be further reduced. Therefore, further development of absorbents is needed. Summary of the invention

[0003] The purpose of the present invention is to overcome the problems of large absorbent loss and low degradation rate in the prior art, and to provide a polyolefin alcohol amine polymer, an acid gas adsorbent, a preparation method of the polyolefin alcohol amine polymer and its application.

[0004] In order to achieve the above object, the present invention provides a polyolefin alcohol amine polymer in a first aspect, wherein the polyolefin alcohol amine polymer contains a structural unit represented by formula (I):

[0005]

[0006] Among them, R 1 is a bond, or an alkylene group which may or may not contain heteroatoms;

[0007] Among them, R 2 , R 3 Each is independently selected from hydrogen, and an alkylene group containing or not containing an ether bond.

[0008] In the present invention, the alkyl group includes a branched alkyl group and / or a straight chain alkyl group.

[0009] A second aspect of the present invention provides a method for preparing a polyolefin alcoholamine polymer, the method comprising the following steps:

[0010] (1) in the presence of a protective atmosphere, a first solvent and an acidic catalyst, polymerizing an olefin amine and a cationic chain transfer agent to obtain a polyolefin amine;

[0011] (2) In the presence of a second solvent and a basic catalyst, the polyolefin amine and the halogenated alcohol are subjected to a substitution reaction to obtain a polyolefin alcohol amine polymer.

[0012] The third aspect of the present invention provides a polyolefin alcoholamine polymer prepared by the method described in the second aspect.

[0013] A fourth aspect of the present invention provides an acidic gas adsorbent, wherein the acidic gas adsorbent contains the polyolefin alcoholamine polymer described in any one of the first and third aspects and an optional organic alcoholamine.

[0014] The fifth aspect of the present invention provides the use of the polyolefin alcohol amine polymer described in the third aspect or the acid gas adsorbent described in the fourth aspect in industrial gas purification, desulfurization and decarbonization.

[0015] Through the above technical solution, the present invention achieves the following technical effects:

[0016] (1) The polyolefin alcohol amine polymer prepared by the present invention has a high amine group loading capacity, and multiple side chain amine groups are suspended from the molecular chain of each polymer. Compared with traditional alcohol amine absorbents, the polymer absorbent designed by the present invention has a higher amine group loading capacity at an equimolar concentration and has a better absorption effect on acidic gases.

[0017] (2) The polyolefin alcohol amine polymer prepared by the present invention has a higher molecular weight and a higher boiling point than the traditional organic amine absorbent, so that the escape loss is further reduced. In addition, the polyolefin alcohol amine polymer of the present invention is also difficult to degrade in the conventional gas purification alkaline system, which can avoid the amine loss and amine liquid degradation problems encountered in the gas purification desulfurization and decarbonization industry at home and abroad.

[0018] (3) The polyolefin alcohol amine polymer prepared by the present invention can be used as an absorbent for gas purification, or it can be compounded with alcohol amines such as methyldiethanolamine, monoethanolamine or diethanolamine for gas purification, thereby achieving the removal of carbon dioxide, hydrogen sulfide and organic sulfur.

[0019] (4) The polyolefin alcohol amine polymer prepared by the present invention does not require complicated equipment and steps during the desulfurization and decarbonization process and can be conveniently applied to actual production. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 It is the GPC chromatogram of the polyolefin and polyolefin alcoholamine prepared in Example 1. DETAILED DESCRIPTION

[0021] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0022] In order to overcome the problems of large absorbent loss and low degradation rate in the prior art in the application of industrial gas desulfurization and decarbonization, the present invention provides a new preparation method and application of an acidic gas adsorbent (polyolefin alcohol amine polymer). The polyolefin alcohol amine polymer can efficiently absorb harmful gases such as hydrogen sulfide, organic sulfur and carbon dioxide in industrial gas, and reduce the impact of raw gas on the environment and human health; at the same time, it has the performance of low escape and low degradation, and can meet the needs of industrial gas purification applications.

[0023] In order to achieve the above object, the technical solution of the present invention is as follows:

[0024] The invention provides a method for synthesizing a polyolefin alcohol amine polymer and a method for deep desulfurization and decarbonization of gas purification, including a method for synthesizing absorbent polyolefin alcohol amine and also includes application of polyolefin alcohol amine in gas purification and removal of sulfide and carbon dioxide.

[0025] The synthesis method is to firstly use cationic reversible addition-fragmentation chain transfer polymerization to control the active controllable polymerization of olefin amine monomers to generate polyolefin amines; and then react with halogenated alcohols to generate polyolefin alcohol amine polymers by nucleophilic substitution reaction. The above reaction steps are shown below.

[0026] Cationic reversible addition-fragmentation chain transfer polymerization:

[0027]

[0028] Substitution reaction:

[0029]

[0030] In order to achieve the above object, the present invention provides a polyolefin alcohol amine polymer in a first aspect, wherein the polyolefin alcohol amine polymer contains a structural unit represented by formula (I):

[0031]

[0032] Among them, R 1 is a bond, or an alkylene group which may or may not contain heteroatoms;

[0033] Among them, R 2 , R 3 Each is independently selected from hydrogen, and an alkylene group containing or not containing an ether bond.

[0034] According to some embodiments of the present invention, wherein R 1 is a bond or a C1-C4 alkylene group; R 2 , R 3 Each is independently selected from C1-C6 alkylene.

[0035] In some embodiments of the present invention, preferably, the structural unit represented by formula (I) can be

[0036]

[0037] According to some embodiments of the present invention, the number average molecular weight of the polyalkene alcoholamine polymer is 100-50000 g / mol.

[0038] A second aspect of the present invention provides a method for preparing a polyolefin alcoholamine polymer, wherein the method comprises the following steps:

[0039] (1) in the presence of a protective atmosphere, a first solvent and an acidic catalyst, polymerizing an olefin amine and a cationic chain transfer agent to obtain a polyolefin amine;

[0040] (2) In the presence of a second solvent and a basic catalyst, the polyolefin amine and the halogenated alcohol are subjected to a substitution reaction to obtain a polyolefin alcohol amine polymer.

[0041] According to some embodiments of the invention, the molar ratio of the olefin amine to the cationic chain transfer agent is (5-500):1, and preferably the molar ratio of the olefin amine to the cationic chain transfer agent is (10-100):1.

[0042] According to some embodiments of the present invention, the polymerization reaction conditions are: temperature of -50°C to -10°C, time of 0.1-10h; preferably -40°C to -10°C, time of 0.1-3h.

[0043] According to some embodiments of the present invention, the first solvent is selected from at least one of n-hexane, diethyl ether, toluene and dichloromethane.

[0044] Preferably, the volume molar ratio of the first solvent to the olefin amine is (0.5-50):1.

[0045] Preferably, the second solvent is selected from water and / or methanol.

[0046] Preferably, the acidic catalyst is selected from at least one of trifluoromethanesulfonic acid, p-toluenesulfonic acid and hydrochloric acid.

[0047] Preferably, the cationic chain transfer agent is at least one selected from dithiocarbonates, trithiocarbonates and dithiocarbamates.

[0048] Preferably, the olefin amine is at least one selected from the group consisting of allylamine, 5-hexen-1-amine, vinylamine and 3-vinyloxypropylamine.

[0049] In the present invention, the cationic chain transfer agent is a conventional reversible addition-fragmentation transfer agent in the art, which is used to control the polymerization reaction and realize living polymerization.

[0050] According to some embodiments of the present invention, the alkaline catalyst is selected from at least one of potassium carbonate, sodium bicarbonate, sodium hydroxide, pyridine and triethylamine.

[0051] Preferably, the halohydrin is selected from 2-bromoethanol and / or 6-bromohexanol;

[0052] Preferably, the molar ratio of the halogenated alcohol to the polyolefin amine is 1:(1-3).

[0053] According to some embodiments of the present invention, the conditions of the substitution reaction are: temperature of 10-100° C., time of 1-24 h; preferably, the temperature is 40° C.-80° C., time of 2-18 h.

[0054] In the present invention, the selection of reaction conditions such as solvent, temperature, time is relevant to the reaction rate, and bad reaction conditions can cause the reaction rate to be significantly reduced or even unreacted. The catalyst is relevant to the rate of polyreaction and substitution reaction, and can also affect the controllability of the polymer product (affecting the molecular weight and molecular weight distribution of the polymer). The selection of raw materials can affect the structure of the final polymer product, and then affect the efficiency of desulfurization and decarbonization. When the conditions of the types of solvent, catalyst, raw materials, etc., polyreaction and substitution reaction meet the above-mentioned range, the reaction rate of polyreaction and substitution reaction is fast, and the polyolefin alcoholamine polymer prepared has high amine group loading, and has better absorption effect to acidic gas.

[0055] The third aspect of the present invention provides a polyolefin alcoholamine polymer prepared by the method described in the second aspect.

[0056] A fourth aspect of the present invention provides an acidic gas adsorbent, wherein the acidic gas adsorbent comprises the polyolefin alcoholamine polymer according to any one of the first and third aspects and an optional organic alcoholamine.

[0057] In the present invention, there is no particular limitation on the preparation method of the acidic gas adsorbent. For example, the polyolefin alcohol amine polymer can be dissolved in water to prepare an aqueous solution, or the polyolefin alcohol amine polymer can be dissolved in an organic solvent to prepare an organic solution for industrial gas purification to remove hydrogen sulfide, organic sulfur and carbon dioxide.

[0058] In the present invention, the acidic gas adsorbent may be a polyolefin alcohol amine polymer alone, or a mixture of a polyolefin alcohol amine polymer and an organic alcohol amine.

[0059] Preferably, the organic alcohol amine is selected from at least one of methyldiethanolamine, monoethanolamine and diethanolamine.

[0060] Preferably, in the acidic gas adsorbent, the weight ratio of the polyolefin alcoholamine polymer to the organic alcoholamine is (0.1-2):1.

[0061] In the present invention, the method for using the acidic gas adsorbent to remove hydrogen sulfide, organic sulfur and carbon dioxide from industrial gas comprises: passing industrial gas containing hydrogen sulfide, organic sulfur and carbon dioxide into the acidic gas adsorbent, wherein the gas-liquid ratio is (50-200):1, the temperature is 0-60°C, the flow rate is 50-500mL / min, and after 2 hours, the content of total sulfur and carbon dioxide in the absorption liquid is detected by a coulometer.

[0062] In the present invention, after the industrial gas is deeply purified by the acid gas absorbent, the total sulfur (in terms of sulfur) in the purified gas is ≤20 mg / m 3 、H2S≤10mg / m 3 , the carbon dioxide content is 0-2vol%.

[0063] The fifth aspect of the present invention provides the use of the polyolefin alcohol amine polymer described in the third aspect or the acid gas adsorbent described in the fourth aspect in industrial gas purification, desulfurization and decarbonization.

[0064] Preferably, the industrial gas is selected from at least one of coalbed methane, natural gas, oilfield gas, flue gas and synthesis gas.

[0065] Preferably, the pressure of the industrial gas is 0-6MPa; based on the total volume of the industrial gas, the content of CO2 is 0-10vol%, the content of hydrogen sulfide is 0-10vol%, the content of organic sulfur is 0-300ppm, and the rest is N2.

[0066] According to a particularly preferred embodiment of the present invention, the method for preparing the polyalkenolamine polymer is as follows:

[0067] In a nitrogen environment, a cationic chain transfer agent, acrylamine, n-hexane, and dichloromethane are added to a reactor, and the molar ratio of the monomer to the cationic chain transfer agent is (10-100):1. Then, a trifluoromethanesulfonic acid ether solution is added through a dry syringe. The reaction is carried out at -40°C to -10°C for 0.1-3h to obtain a polyolefin amine. Then, triethylamine and 2-bromoethanol are added, wherein the molar ratio of 2-bromoethanol to acrylamine is 1:(1-3), heated to 40-80°C and stirred for 2-18h, cooled to room temperature, and the organic phase is precipitated in cold ether, and vacuum dried to obtain a polyolefin alcohol amine polymer product.

[0068] The present invention will be described in detail below through examples.

[0069] The weight average molecular weight, number average molecular weight and molecular weight distribution (PDI) of the polyolefin amine were determined by GPC. The instrument consisted of a constant flow pump (SSI 1500), a gel chromatography column (Waters Styragel HR 2 and Waters Styragel HR 4, 5 μm, 300 mm×7.8 mm), an 18-angle static laser scattering instrument and a differential refractometer.

[0070] Conversion rate of polyolefin amine (%) = (1-molar amount of unreacted polymerization monomer / molar amount of polymerization raw material monomer) x 100%.

[0071] Conversion rate of polyolefin alcoholamine (%) = (1-unreacted substitution monomer molar amount / substitution reaction raw material monomer molar amount) x 100%.

[0072] The contents of H2S and organic sulfur in the gas are determined by chromatography using an Aginlent7890A GCSystem.

[0073] The total sulfur content in the solution was measured by a coulometer, and the instrument model was IF-WK-2000.

[0074] The CO2 content was measured by a flue gas analyzer, the instrument model was MRU VARIOplus-new.

[0075] In the examples, the gas content is measured by volume percentage, and the absorption liquid composition is measured by mass fraction.

[0076] The raw materials in the examples are all commercially available.

[0077] Example 1

[0078] In a nitrogen environment, cationic chain transfer agent (0.3mM), acrylamine (3.0mM), n-hexane (24mL), and dichloromethane (3mL) were added to the reactor, and the molar ratio of monomer to cationic chain transfer agent was 10:1. Then, trifluoromethanesulfonic acid ether solution (0.50mM, 0.30mL) was added through a dry syringe. The reaction was carried out at -40°C for 30 minutes, and the conversion rate was greater than 99%, and the number average molecular weight of the polyolefin polymer was obtained. n The reaction mixture was stirred for 2 hours at 50 °C and the conversion rate was 93%. After cooling to room temperature, the organic phase was precipitated in cold ether and vacuum dried to obtain a polyolefin alcohol amine polymer product (number average molecular weight M n is 2800g / mol).

[0079] The raw gas is at 40℃, with a pressure of 0.5MPa, a H2S content of 4.0%, a CO2 content of 4.5%, an organic sulfur content of 50ppmv, and the rest is N2. The absorption liquid is composed of a polyolefin alcohol amine polymer content of 40%, and the rest is water. Under the condition of a raw gas flow rate of 150mL / min, the sulfur content absorbed by the absorbent is detected by a coulometer. After 2h, the total sulfur content in the solvent is 85mg / L. The H2S content in the instantaneous purified gas is 2.5ppmv, and the CO2 content is 0.2%.

[0080] Example 2

[0081] In a nitrogen environment, cationic chain transfer agent (0.3mM), ethyleneamine (3.0mM), n-hexane (24mL), and dichloromethane (3mL) were added to the reactor, and the molar ratio of monomer to cationic chain transfer agent was 10:1. Then, trifluoromethanesulfonic acid ether solution (0.50mM, 0.30mL) was added through a dry syringe. The reaction was carried out at -40°C for 30 minutes, and the conversion rate was greater than 69%, and the number average molecular weight of the polyolefin polymer was obtained. n The reaction mixture was stirred for 3 hours at 50 °C and the conversion rate was 90%. After cooling to room temperature, the organic phase was precipitated in cold ether and vacuum dried to obtain a polyolefin alcohol amine polymer (number average molecular weight M n is 2700g / mol).

[0082] The raw gas is at 40℃, with a pressure of 0.5MPa, a H2S content of 4.0%, a CO2 content of 4.5%, an organic sulfur content of 50ppmv, and the rest is N2. The composition of the absorption liquid is 40% polymer content and the rest is water. Under the condition of a raw gas flow rate of 150mL / min, the sulfur content absorbed by the absorbent is detected by a coulometer. After 2h, the total sulfur content in the solvent is 74mg / L. The H2S content in the instantaneous purified gas is 3.0ppmv and the CO2 content is 0.3%.

[0083] Example 3

[0084] In a nitrogen environment, cationic chain transfer agent (0.3mM), 3-vinyloxypropylamine (3.0mM), n-hexane (24mL), and dichloromethane (3mL) were added to the reactor. The molar ratio of monomer to cationic chain transfer agent was 10:1. Then, trifluoromethanesulfonic acid ether solution (0.50mM, 0.30mL) was added through a dry syringe. The reaction was carried out at -40°C for 30 minutes. The conversion rate was greater than 99%, and the number average molecular weight of the polyolefin polymer was obtained. nThe reaction mixture was stirred for 3 hours at 50 °C and the conversion rate was 93%. After cooling to room temperature, the organic phase was precipitated in cold ether and vacuum dried to obtain a polyolefin alcohol amine polymer (number average molecular weight M n is 4100g / mol).

[0085] The raw gas is at 40℃, with a pressure of 0.5MPa, a H2S content of 4.0%, a CO2 content of 4.5%, an organic sulfur content of 50ppmv, and the rest is N2. The composition of the absorption liquid is 40% polymer content and the rest is water. Under the condition of a raw gas flow rate of 150mL / min, the sulfur content absorbed by the absorbent is detected by a coulometer. After 2h, the total sulfur content in the solvent is 98mg / L. The H2S content in the instantaneous purified gas is 2.2ppmv and the CO2 content is 0%.

[0086] Example 4

[0087] In a nitrogen environment, cationic chain transfer agent (0.3mM), 5-hexene-1-amine (3.0mM), n-hexane (24mL), and dichloromethane (3mL) were added to the reactor. The molar ratio of monomer to cationic chain transfer agent was 10:1, and then trifluoromethanesulfonic acid ether solution (0.50mM, 0.30mL) was added through a dry syringe. The reaction was carried out at -40°C for 30 minutes, and the conversion rate was greater than 99%, and the number average molecular weight of the polyolefin polymer was obtained. n The reaction mixture was stirred for 3 hours at 50 °C and the conversion rate was 94%. After cooling to room temperature, the organic phase was precipitated in cold ether and vacuum dried to obtain a polyolefin alcohol amine polymer (number average molecular weight M n is 3.6kg / mol).

[0088] The raw gas is at 40℃, with a pressure of 0.5MPa, a H2S content of 4.0%, a CO2 content of 4.5%, an organic sulfur content of 50ppmv, and the rest is N2. The composition of the absorption liquid is 40% polymer content and the rest is water. Under the condition of a raw gas flow rate of 150mL / min, the sulfur content absorbed by the absorbent is detected by a coulometer. After 2h, the total sulfur content in the solvent is 63mg / L. The H2S content in the instantaneous purified gas is 7.8ppmv and the CO2 content is 0.5%.

[0089] Example 5

[0090] In a nitrogen environment, cationic chain transfer agent (0.3mM), acrylamine (6.0mM), n-hexane (24mL), and dichloromethane (3mL) were added to the reactor, and the molar ratio of monomer to cationic chain transfer agent was 20:1. Then, trifluoromethanesulfonic acid ether solution (0.50mM, 0.30mL) was added through a dry syringe. The reaction was carried out at -40°C for 30 minutes, and the conversion rate was greater than 99%, and the number average molecular weight of the polyolefin polymer was obtained. n The molecular weight distribution was 1.26. Then, potassium carbonate and 2-bromoethanol (12.0 mM) were added, and the mixture was heated to 50° C. and stirred for three hours. The conversion rate was 94%. After cooling to room temperature, the organic phase was precipitated in cold ether and vacuum dried to obtain a polyolefin alcohol amine polymer (number average molecular weight M n is 7000g / mol).

[0091] The raw gas is at 40℃, with a pressure of 0.5MPa, a H2S content of 4.0%, a CO2 content of 4.5%, an organic sulfur content of 50ppmv, and the rest is N2. The absorption liquid is composed of 50% polyolefin alcohol amine polymer and the rest is water. Under the condition of a raw gas flow rate of 150mL / min, the sulfur content absorbed by the absorbent is detected by a coulometer. After 2h, the total sulfur content in the solvent is 86mg / L. The H2S content in the instantaneous purified gas is 2.4ppmv and the CO2 content is 0.2%.

[0092] Example 6

[0093] In a nitrogen environment, cationic chain transfer agent (0.3mM), acrylamine (30mM), n-hexane (24mL), and dichloromethane (3mL) were added to the reactor, and the molar ratio of monomer to cationic chain transfer agent was 100:1. Then, trifluoromethanesulfonic acid ether solution (0.50mM, 0.30mL) was added through a dry syringe. The reaction was carried out at -40°C for 6 hours, and the conversion rate was greater than 99%, and the number average molecular weight of the polyolefin polymer was obtained. n The reaction mixture was stirred at 50 °C for 24 hours, and the conversion rate was 89%. After cooling to room temperature, the organic phase was precipitated in cold ether and vacuum dried to obtain a polyolefin alcohol amine polymer (number average molecular weight M n is 33400g / mol).

[0094] The raw gas is at 40℃, with a pressure of 0.5MPa, a H2S content of 4.0%, a CO2 content of 4.5%, an organic sulfur content of 50ppmv, and the rest is N2. The absorption liquid is composed of 50% polyolefin alcohol amine polymer and the rest is water. Under the condition of a raw gas flow rate of 150mL / min, the sulfur content absorbed by the absorbent is detected by a coulometer. After 2h, the total sulfur content in the solvent is 86mg / L. The H2S content in the instantaneous purified gas is 1.8ppmv and the CO2 content is 0.1%.

[0095] Example 7

[0096] In a nitrogen environment, cationic chain transfer agent (0.3mM), acrylamine (3.0mM), n-hexane (24mL), and dichloromethane (3mL) were added to the reactor, and the molar ratio of monomer to cationic chain transfer agent was 10:1. Then, trifluoromethanesulfonic acid ether solution (0.50mM, 0.30mL) was added through a dry syringe. The reaction was carried out at -10°C for 30 minutes, and the conversion rate was greater than 99%, and the number average molecular weight of the polyolefin polymer was obtained. n The reaction mixture was stirred at 50 °C for 2 hours and the conversion rate was 93%. After cooling to room temperature, the organic phase was precipitated in cold ether and vacuum dried to obtain a polyolefin alcohol amine polymer (number average molecular weight M n is 3700g / mol).

[0097] The raw gas is at 40℃, with a pressure of 0.5MPa, a H2S content of 4.0%, a CO2 content of 4.5%, an organic sulfur content of 50ppmv, and the rest is N2. The absorption liquid is composed of 40% polyolefin alcohol amine polymer and the rest is water. Under the condition of a raw gas flow rate of 150mL / min, the sulfur content absorbed by the absorbent is detected by a coulometer. After 2h, the total sulfur content in the solvent is 85mg / L. The H2S content in the instantaneous purified gas is 2.5ppmv and the CO2 content is 0.2%.

[0098] Example 8

[0099] In a nitrogen environment, cationic chain transfer agent (0.3mM), acrylamine (3.0mM), n-hexane (24mL), and dichloromethane (3mL) were added to the reactor, and the molar ratio of monomer to cationic chain transfer agent was 10:1. Then, trifluoromethanesulfonic acid ether solution (0.50mM, 0.30mL) was added through a dry syringe. The reaction was carried out at -50°C for 20 minutes, and the conversion rate was greater than 99%, and the number average molecular weight of the polyolefin polymer was obtained. nThe molecular weight distribution (PDI) was 1300 g / mol and 1.26. Then, triethylamine and 2-bromoethanol (6.0 mM) were added, heated to 50° C. and stirred for 2 h, with a conversion rate of 93%. After cooling to room temperature, the organic phase was precipitated in cold ether and vacuum dried to obtain a polyolefin alcohol amine polymer (number average molecular weight M n is 3.1kg / mol).

[0100] The raw gas is at 40℃, with a pressure of 0.5MPa, a H2S content of 4.0%, a CO2 content of 4.5%, an organic sulfur content of 50ppmv, and the rest is N2. The absorption liquid is composed of 40% polyolefin alcohol amine polymer and the rest is water. Under the condition of a raw gas flow rate of 150mL / min, the sulfur content absorbed by the absorbent is detected by a coulometer. After 2h, the total sulfur content in the solvent is 85mg / L. The H2S content in the instantaneous purified gas is 2.5ppmv and the CO2 content is 0.2%.

[0101] Example 9

[0102] In a nitrogen environment, cationic chain transfer agent (0.3mM), acrylamine (3.0mM), n-hexane (24mL), and dichloromethane (3mL) were added to the reactor, and the molar ratio of monomer to cationic chain transfer agent was 10:1. Then, trifluoromethanesulfonic acid ether solution (0.50mM, 0.30mL) was added through a dry syringe. The reaction was carried out at -40°C for 30 minutes, and the conversion rate was greater than 99%, and the number average molecular weight of the polyolefin polymer was obtained. n The molecular weight distribution (PDI) was 1200 g / mol and 1.24. Then, triethylamine and 6-bromohexanol (6.0 mM) were added, heated to 50° C. and stirred for 2 hours, with a conversion rate of 88%. After cooling to room temperature, the organic phase was precipitated in cold ether and vacuum dried to obtain a polyolefin alcohol amine polymer (number average molecular weight M n is 4900g / mol).

[0103] The raw gas is at 40℃, with a pressure of 0.5MPa, a H2S content of 4.0%, a CO2 content of 4.5%, an organic sulfur content of 50ppmv, and the rest is N2. The absorption liquid is composed of 40% polyolefin alcohol amine polymer and the rest is water. Under the condition of a raw gas flow rate of 150mL / min, the sulfur content absorbed by the absorbent is detected by a coulometer. After 2h, the total sulfur content in the solvent is 45mg / L. The H2S content in the instantaneous purified gas is 13.5ppmv and the CO2 content is 1.8%.

[0104] Example 10

[0105] In a nitrogen environment, cationic chain transfer agent (0.3mM), acrylamine (3.0mM), n-hexane (24mL), and dichloromethane (3mL) were added to the reactor, and the molar ratio of monomer to cationic chain transfer agent was 10:1. Then, trifluoromethanesulfonic acid ether solution (0.50mM, 0.30mL) was added through a dry syringe. The reaction was carried out at -40°C for 30 minutes, and the conversion rate was greater than 99%, and the number average molecular weight of the polyolefin polymer was obtained. n The reaction mixture was stirred at 50 °C for 2 hours and the conversion rate was 93%. After cooling to room temperature, the organic phase was precipitated in cold ether and vacuum dried to obtain a polyolefin alcohol amine polymer (number average molecular weight M n is 2800g / mol).

[0106] The raw gas is at 40℃, with a pressure of 0.5MPa, a H2S content of 4.0%, a CO2 content of 4.5%, an organic sulfur content of 50ppmv, and the rest is N2. The absorption liquid is composed of 40% polymer content and the rest is methanol. Under the condition of a raw gas flow rate of 150mL / min, the sulfur content absorbed by the absorbent is detected by a coulometer. After 2h, the total sulfur content in the solvent is 64mg / L. The H2S content in the instantaneous purified gas is 6.5ppmv and the CO2 content is 0.3%.

[0107] Embodiment 11

[0108] In a nitrogen environment, cationic chain transfer agent (0.3mM), acrylamine (3.0mM), n-hexane (24mL), and dichloromethane (3mL) were added to the reactor, and the molar ratio of monomer to cationic chain transfer agent was 10:1. Then, trifluoromethanesulfonic acid ether solution (0.50mM, 0.30mL) was added through a dry syringe. The reaction was carried out at -40°C for 30 minutes, and the conversion rate was greater than 99%, and the number average molecular weight of the polyolefin polymer was obtained. n The reaction mixture was stirred at 50 °C for 2 hours and the conversion rate was 93%. After cooling to room temperature, the organic phase was precipitated in cold ether and vacuum dried to obtain a polyolefin alcohol amine polymer (number average molecular weight M n is 2800g / mol).

[0109] The raw gas is at 40℃, with a pressure of 0.5MPa, a H2S content of 4.0%, a CO2 content of 4.5%, an organic sulfur content of 50ppmv, and the rest is N2. The absorption liquid is composed of 10% polymer content, 40% methyldiethanolamine content, and the rest is water. Under the condition of a raw gas flow rate of 150mL / min, the sulfur content absorbed by the absorbent is detected by a coulometer. After 2h, the total sulfur content in the solvent is 64mg / L. The H2S content in the instantaneous purified gas is 6.5ppmv, and the CO2 content is 0.3%.

[0110] Example 12

[0111] In a nitrogen environment, cationic chain transfer agent (0.3mM), acrylamine (3.0mM), n-hexane (24mL), and dichloromethane (3mL) were added to the reactor, and the molar ratio of monomer to cationic chain transfer agent was 10:1. Then, trifluoromethanesulfonic acid ether solution (0.50mM, 0.30mL) was added through a dry syringe. The reaction was carried out at -40°C for 30 minutes, and the conversion rate was greater than 99%, and the number average molecular weight of the polyolefin polymer was obtained. n The reaction mixture was stirred at 50 °C for 2 h, and the conversion rate was 93%. After cooling to room temperature, the organic phase was precipitated in cold ether and vacuum dried to obtain a polyolefin alcohol amine polymer (number average molecular weight M n is 2800g / mol).

[0112] The raw gas is at 40℃, with a pressure of 0.5MPa, a H2S content of 4.0%, a CO2 content of 4.5%, an organic sulfur content of 50ppmv, and the rest is N2. The absorption liquid is composed of 10% polymer content, 40% monoethanolamine content, and the rest is water. Under the condition of a raw gas flow rate of 150mL / min, the sulfur content absorbed by the absorbent is detected by a coulometer. After 2h, the total sulfur content in the solvent is 64mg / L. The H2S content in the instantaneous purified gas is 7.6ppmv, and the CO2 content is 0%.

[0113] Example 13

[0114] In a nitrogen environment, cationic chain transfer agent (0.3mM), acrylamine (3.0mM), n-hexane (24mL), and dichloromethane (3mL) were added to the reactor, and the molar ratio of monomer to cationic chain transfer agent was 10:1. Then, trifluoromethanesulfonic acid ether solution (0.50mM, 0.30mL) was added through a dry syringe. The reaction was carried out at -40°C for 30 minutes, and the conversion rate was greater than 99%, and the number average molecular weight of the polyolefin polymer was obtained. nThe reaction mixture was stirred at 50 °C for 2 hours and the conversion rate was 93%. After cooling to room temperature, the organic phase was precipitated in cold ether and vacuum dried to obtain a polyolefin alcohol amine polymer (number average molecular weight M n is 2800g / mol).

[0115] The raw gas is at 40℃, with a pressure of 0.5MPa, a H2S content of 4.0%, a CO2 content of 4.5%, an organic sulfur content of 50ppmv, and the rest is N2. The absorption liquid is composed of 10% polyolefin alcohol amine, 40% diethanolamine, and the rest is water. Under the condition of a raw gas flow rate of 150mL / min, the sulfur content absorbed by the absorbent is detected by a coulometer. After 2h, the total sulfur content in the solvent is 64mg / L. The H2S content in the instantaneous purified gas is 7.3ppmv, and the CO2 content is 0.1%.

[0116] Comparative Example 1

[0117] The raw gas is at 40℃, with a pressure of 0.5MPa, a H2S content of 4.0%, a CO2 content of 4.5%, an organic sulfur content of 50ppm, and the rest is N2. The absorption liquid is composed of 40% MDEA and the rest is water. Under the condition of a raw gas flow rate of 150mL / min, the sulfur content absorbed by the absorbent is detected by a coulometer. After 2h, the total sulfur content in the solvent is 39mg / L. The H2S content in the instantaneous purified gas is 17.4ppm, and the CO2 content is 0.2%.

[0118] Comparative Example 2

[0119] The same method as in Example 1 was used, except that a cationic chain transfer agent (0.3 mM) and acrylamine (1.5 mM) were used. The reaction was carried out at -40°C for 0.5 hours, and the conversion rate was 99%. The polyolefin polymer with a number average molecular weight M n The reaction mixture was stirred for 2 hours at 50 °C and the conversion rate was 93%. After cooling to room temperature, the organic phase was precipitated in cold ether and vacuum dried to obtain a polyolefin alcohol amine polymer product (number average molecular weight M n is 900g / mol).

[0120] The raw gas is at 40℃, with a pressure of 0.5MPa, a H2S content of 4.0%, a CO2 content of 4.5%, an organic sulfur content of 50ppm, and the rest is N2. The absorption liquid is composed of a polyolefin alcohol amine polymer content of 40%, and the rest is water. Under the condition of a raw gas flow rate of 150mL / min, the sulfur content absorbed by the absorbent is detected by a coulometer. After 2h, the total sulfur content in the solvent is 45mg / L. The H2S content in the instantaneous purified gas is 10.5ppm, and the CO2 content is 0.1%.

[0121] Comparative Example 3

[0122] The same method as in Example 1 was used, except that triethylamine and 2-bromoethanol (6.0 mM) were added, heated to 50°C and stirred for 2 hours, and the conversion rate was 98%. After cooling to room temperature, the organic phase was precipitated in cold ether and vacuum dried to obtain a polyolefin alcoholamine polymer product (number average molecular weight M n is 2.0kg / mol).

[0123] The raw gas is at 40℃, with a pressure of 0.5MPa, a H2S content of 4.0%, a CO2 content of 4.5%, an organic sulfur content of 50ppm, and the rest is N2. The absorption liquid is composed of a polyolefin alcohol amine polymer content of 40%, and the rest is water. Under the condition of a raw gas flow rate of 150mL / min, the sulfur content absorbed by the absorbent is detected by a coulometer. After 2h, the total sulfur content in the solvent is 48mg / L. The H2S content in the instantaneous purified gas is 9.8ppm, and the CO2 content is 0%.

[0124] Comparative Example 4

[0125] The same method as in Example 1 was used, except that the polymerization reaction conditions were: reaction at 25° C. for 24 h, the conversion rate was 0%, and no polyolefin polymer was obtained.

[0126] Comparative Example 5

[0127] The same method as in Example 1 was used, except that the conditions for the substitution reaction were: heating to 60° C. and stirring for 24 hours, the conversion rate was 0%, and no polyolefin alcoholamine polymer was obtained.

[0128] Test Example 1

[0129] The polyolefin and polyolefin alcoholamine prepared in Example 1 were subjected to size exclusion chromatography analysis. Figure 1 As shown, as the substitution reaction occurs, the molecular weight of the polymer in the size exclusion chromatogram increases, indicating that the substitution reaction is successfully carried out. It can be seen that the polyolefin polymer and polyolefin alcohol amine polymer are successfully prepared by the method described in the present invention.

[0130] It can be seen from the data of Examples 1-13 and Comparative Examples 1-4 that the polyolefin alcohol amine polymer obtained by the preparation method of the present invention can efficiently absorb harmful gases such as hydrogen sulfide, organic sulfur and carbon dioxide in industrial gases, and the total sulfur content in the solution reaches 98 mg / L, so that the H2S content in the purified gas is lower than 13.5 ppmv, and the CO2 content reaches 0%; while Comparative Example 1 uses MDEA as the absorption liquid, and the desulfurization and decarbonization effects are not as good as the polyolefin alcohol amine polymer of the present invention, the total sulfur content in the solvent is 39 mg / L, the H2S content in the purified gas is 17.4 ppm, and the CO2 content is 0.2%; The molar ratio of the cationic chain transfer agent to acrylamine in Ratio 2 is not within the preferred range of the present invention, resulting in poor desulfurization and decarbonization effects of the adsorbent, the total sulfur content in the solvent is 45 mg / L, the H2S content in the purified gas is 10.5 ppm, and the CO2 content is 0.1%; the molar ratio of the halogenated alcohol to the olefin amine in Comparative Example 3 is not within the range specified by the present invention, resulting in poor desulfurization and decarbonization effects of the adsorbent, and the total sulfur content in the solvent is 48 mg / L; Comparative Example 4 increases the temperature of the polymerization reaction, resulting in a conversion rate of the polyolefin alcoholamine of 0; Comparative Example 5 increases the temperature of the substitution reaction, resulting in a conversion rate of the polyolefin alcoholamine of 0.

[0131] In summary, the polyolefin alcoholamine polymer obtained by the preparation method of the present invention can efficiently absorb harmful gases such as hydrogen sulfide, organic sulfur and carbon dioxide in industrial gases, reduce the impact of raw gas on the environment and human health, and meet the needs of industrial gas purification applications.

[0132] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A polyolefin alcohol amine polymer, characterized in that The polyolefin alcohol amine polymer contains a structural unit represented by formula (I), Among them, R 1 is a bond, or an alkylene group which may or may not contain heteroatoms; Among them, R 2 , R 3 Each is independently selected from hydrogen, and an alkylene group containing or not containing an ether bond.

2. The polymer according to claim 1, wherein R 1 is a bond or a C1-C4 alkylene group; R 2 , R 3 Each is independently selected from C1-C6 alkylene.

3. The polymer according to claim 1 or 2, wherein The number average molecular weight of the polyalkene alcohol amine polymer is 100-50000 g / mol.

4. A method for preparing a polyolefin alcoholamine polymer, characterized in that: The method comprises the following steps: (1) in the presence of a protective atmosphere, a first solvent and an acidic catalyst, polymerizing an olefin amine and a cationic chain transfer agent to obtain a polyolefin amine; (2) In the presence of a second solvent and a basic catalyst, the polyolefin amine and the halogenated alcohol are subjected to a substitution reaction to obtain a polyolefin alcohol amine polymer.

5. The method according to claim 4, wherein: The molar ratio of the olefin amine to the cationic chain transfer agent is (5-500):1, preferably (10-100):

1.

6. The method according to claim 4 or 5, wherein: The polymerization reaction conditions include: temperature of -50°C to -10°C, preferably -40°C to -10°C; time of 0.1-10h, preferably 0.1-3h.

7. The method according to any one of claims 4 to 6, wherein: The first solvent is selected from at least one of n-hexane, ether, toluene and dichloromethane; Preferably, the volume molar ratio of the first solvent to the olefin amine is (0.5-50):1; Preferably, the second solvent is selected from water and / or methanol; Preferably, the acidic catalyst is selected from at least one of trifluoromethanesulfonic acid, p-toluenesulfonic acid and hydrochloric acid; Preferably, the cationic chain transfer agent is selected from at least one of dithiocarbonates, trithiocarbonates and dithiocarbamates; Preferably, the olefin amine is selected from at least one of allylamine, 5-hexen-1-amine, vinylamine and 3-vinyloxypropylamine.

8. The method according to claims 4-7, wherein: The alkaline catalyst is selected from at least one of potassium carbonate, sodium bicarbonate, sodium hydroxide, pyridine and triethylamine; Preferably, the halohydrin is selected from 2-bromoethanol and / or 6-bromo-n-hexanol; Preferably, the molar ratio of the halohydrin to the olefinamine is 1:(1-3).

9. The method according to claims 4-8, wherein: The conditions of the substitution reaction include: temperature of 10-100° C., preferably 40° C.-80° C.; time of 1-24 h, preferably 2-18 h.

10. A polyalkene alcoholamine polymer prepared by the method according to any one of claims 4 to 9.

11. An acid gas adsorbent, characterized in that: The acid gas adsorbent comprises the polyolefin alcohol amine polymer according to any one of claims 1 to 3 and 10 and an optional organic alcohol amine; Preferably, the organic alcohol amine is selected from at least one of methyldiethanolamine, monoethanolamine and diethanolamine; Preferably, the acidic gas adsorbent contains the polyolefin alcoholamine polymer and organic alcoholamine, and the weight ratio of the polyolefin alcoholamine polymer to the organic alcoholamine is (0.1-2):

1.

12. Use of the polyolefin alcohol amine polymer according to claim 10 or the acid gas adsorbent according to claim 11 in industrial gas purification, desulfurization and decarbonization; Preferably, the industrial gas is selected from at least one of coal-bed methane, natural gas, oilfield gas, flue gas and synthesis gas; Preferably, the pressure of the industrial gas is 0-6 MPa; based on the total volume of the industrial gas, the content of CO2 is 0-10 vol%, the content of hydrogen sulfide is 0-10 vol%, the content of organic sulfur is 0-300 ppm, and the rest is N2.

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