CN115400549B - Morpholine cyclic amine desulfurizing agent with high regeneration cycle performance and preparation method thereof - Google Patents

Morpholine cyclic amine desulfurizing agent with high regeneration cycle performance and preparation method thereof Download PDF

Info

Publication number
CN115400549B
CN115400549B CN202211067817.1A CN202211067817A CN115400549B CN 115400549 B CN115400549 B CN 115400549B CN 202211067817 A CN202211067817 A CN 202211067817A CN 115400549 B CN115400549 B CN 115400549B
Authority
CN
China
Prior art keywords
morpholine
absorption
desulfurizing agent
hem
hydroxyethyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202211067817.1A
Other languages
Chinese (zh)
Other versions
CN115400549A (en
Inventor
李建军
张洪伟
程灿
刘勤
郭家秀
舒松
岑望来
刘勇军
楚英豪
吴光宇
陈亚玲
张心怡
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sichuan University
Original Assignee
Sichuan University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sichuan University filed Critical Sichuan University
Priority to CN202211067817.1A priority Critical patent/CN115400549B/en
Publication of CN115400549A publication Critical patent/CN115400549A/en
Application granted granted Critical
Publication of CN115400549B publication Critical patent/CN115400549B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1456—Removing acid components
    • B01D53/1481—Removing sulfur dioxide or sulfur trioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1493—Selection of liquid materials for use as absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/202—Alcohols or their derivatives
    • B01D2252/2023—Glycols, diols or their derivatives
    • B01D2252/2026—Polyethylene glycol, ethers or esters thereof, e.g. Selexol
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines
    • B01D2252/20436—Cyclic amines
    • B01D2252/20452—Cyclic amines containing a morpholine-ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/50—Combinations of absorbents
    • B01D2252/504—Mixtures of two or more absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/302—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treating Waste Gases (AREA)
  • Gas Separation By Absorption (AREA)

Abstract

The invention provides a morpholine cyclic amine desulfurizing agent with high regeneration cycle performance and a preparation method thereof. The morpholine cyclic amine desulfurizing agent is prepared by mixing N- (2-hydroxyethyl) morpholine (HEM) as a solute and polyethylene glycol dimethyl ether (NHD) as a solvent. The desulfurizing agent provided by the invention not only has good absorption effect on SO 2, which is obviously higher than organic liquid desulfurizing agents such as Cansolv amine liquid in commercial industrial application, but also has excellent multiple-cycle absorption effect on SO 2 with higher concentration condition, and the preparation method has the characteristics of lower cost and suitability for continuous production in process steps, and has industrial production prospect.

Description

Morpholine cyclic amine desulfurizing agent with high regeneration cycle performance and preparation method thereof
Technical Field
The invention belongs to the field of desulfurizing agents for industrial flue gas, and relates to a morpholine cyclic amine desulfurizing agent with high regeneration cycle performance and a preparation method thereof.
Background
China is a country rich in coal, lean in oil and less in gas, and is a large country with extremely high energy requirements. The Chinese coal yield and the demand are huge, and are the first world. In the combustion process, traditional energy sources such as coal and the like can generate various atmospheric pollutants including sulfur dioxide (molecular formula SO 2), SO 2 discharged into the atmosphere can cause acid rain pollution, SO that plants are maldeveloped and slow in growth, and further, the plants are rapidly withered and dead, and the health of human beings and the survival of various animals and plants can be endangered; acid rain can also corrode buildings, machinery and municipal facilities, causing significant economic losses and possibly other safety concerns. In addition, atmospheric SO 2 can be oxidized to SO 3, and finally sulfuric acid mist is formed, which causes more serious damage.
According to investigation, in 2020, the total discharge amount of SO 2 in China reaches 318.2 ten thousand tons, wherein the discharge amount of industrial sources reaches 253.2 ten thousand tons, and the ratio is close to 80%. In view of the severe emission conditions of SO 2 in China and the market demands of economic development situation, the national and industrial production enterprises all put forward higher requirements on the industrial flue gas desulfurization process. In general, the means commonly used in the prior desulfurization process are wet desulfurization, (semi) dry desulfurization, ionic liquid desulfurization, organic amine desulfurization and the like. The wet desulfurization process has the characteristics of high reaction rate and high desulfurization rate, but can generate a large amount of waste water and waste liquid, and the problems of proper treatment of waste water and easy secondary pollution are also the main problems in the current industrial application; the byproducts of the dry desulfurization process are solid, which is beneficial to comprehensive application, but the reaction rate is relatively slow, and the desulfurization rate is low; in recent years, the commonly used semi-dry desulfurization absorbent has high utilization rate and no wastewater, but also has the problems of high content of smoke dust particles after desulfurization and the like, thereby limiting popularization and use in actual environment; the ionic liquid desulfurization has the advantages of mild conditions, simple operation, short time consumption, low energy consumption and the like. The organic amine desulfurization is an emerging application of ionic liquid, and has the characteristics of high absorptivity, easy recycling, economy, environmental protection and the like. However, the technology has no obvious advantages in the aspects of economy and the like due to the preparation difficulty, the specific difficulties of recycling and the like at present, and is also a key problem for preventing the development and the application of the desulfurization technology.
Specifically, the organic amine method is used as an absorption technology, and the structure and composition of an absorbent directly determine the absorption regeneration performance. Four types of organic amine desulfurizing agents are commonly used: chain monoamines, chain diamines, cyclic amines and mixed amines. Wherein, the chain monoamine is easy to degrade and deteriorate, is difficult to regenerate, and has little selectivity on the absorption of SO 2; the chain diamine solves the problem of high regeneration energy consumption of the chain monoamine, but the cost of the used patent amine liquid is higher, and the method still has great improvement space. Currently, a lot of cyclic amines represented by Piperazine (PZ) and derivatives thereof are reported, the cyclic amines have better absorption capacity than diamines such as alcohol amine and EDA, and Chinese patent CN202011025636.3 discloses an organic amine desulfurizing agent, a preparation method and application thereof, and the functions of improving the recovery rate of sulfur dioxide, reducing the loss of the desulfurizing agent and the like are expected by adding a composite antioxidant inhibitor into piperazine organic amine. Chinese patent CNCN201610745489.4 discloses that the absorption-analysis comprehensive performance of a composite piperazine organic amine desulfurizer is improved by adding fatty amine, aromatic amine and the like to a dihydroxyalkyl piperazine system to assist an absorber, an additive and the like. However, in practical application, the desorption rate is still relatively low, and the problem of high regeneration energy consumption limits the popularization of the market.
In view of the above-mentioned current situation, the preparation of the organic liquid desulfurizing agent of SO 2 with higher SO 2 absorption efficiency, good regeneration cycle performance and lower cost is a problem to be solved in the current engineering application of removing SO 2 in flue gas.
Disclosure of Invention
The invention provides a morpholine cyclic amine desulfurizing agent with high regeneration cycle performance and a preparation method thereof, aiming at solving the problems in the background art. The method has the advantages of good absorption effect on SO 2, obviously higher than that of organic liquid desulfurizing agents such as Cansolv amine liquid applied in the market, excellent multi-cycle absorption effect on SO 2 with higher concentration, low cost and suitability for continuous production in process steps, and has industrial production prospect.
In order to achieve the above object, the present invention is realized by adopting the technical scheme comprising the following technical measures.
In one aspect, the invention provides a morpholine cyclic amine desulfurizer with high regeneration cycle performance, which is prepared by mixing N- (2-hydroxyethyl) morpholine (HEM) as a solute and polyethylene glycol dimethyl ether (NHD) as a solvent.
The invention is based on the research of the inventor, and the morpholine cyclic amine is selected as one organic solvent of a desulfurizing agent in the prior art literature because of the desulfurizing function and a certain sulfur capacity, and is generally used as one of alternatives of the organic solvent in the desulfurizing agent together with alcohol reagents, ether reagents, sulfone reagents and the like; or on the premise of small addition, the sulfur-tolerant agent is used as a reinforcing agent or a synergistic agent of the desulfurizing agent so as to improve the desulfurizing and sulfur-tolerant effects of the desulfurizing agent.
In the above-mentioned research literature, morpholine cyclic amines include morpholine, N- (2-hydroxyethyl) morpholine (HEM), N-formylmorpholine, N-methylmorpholine and the like, which are the predominant choices.
However, the currently disclosed desulfurizing agent formula with high desulfurizing performance is basically prepared by compounding a plurality of components, or has a preparation mode with a relatively complex process, so that the excellent desulfurizing performance is ensured, and the application cost of the desulfurizing agent is increased virtually and rapidly. However, since the industrial use of desulfurizing agents is generally based on high dosage and high consumption, a plurality of new desulfurizing agent patents can only exist in the verification stage of a laboratory and cannot be put into practical industrial application. Based on the thought of reducing industrial cost, the inventor of the invention verifies whether morpholine cyclic amine can be used as a main desulfurization functional component of a single-component non-compound desulfurizing agent through design experiments:
It was found by preliminary experiments that when the organic solvent is selected as conventional Sulfolane (SUL) (with extremely low viscosity and saturated vapor pressure, and extremely low absorption capacity for SO 2, SO as not to interfere with the results of the experiments), morpholine (MP), N- (2-hydroxyethyl) morpholine (HEM), N-formylmorpholine, N-methylmorpholine all have good desulfurization adsorption capacity, with the highest desulfurization adsorption capacity. The design test also includes N- (2-aminoethyl) morpholine (AEM) which is not mentioned in the above research literature, and the desulfurization adsorption capacity of the N- (2-aminoethyl) morpholine (AEM) is found to be remarkably poor, so that the reason that the N- (2-aminoethyl) morpholine is not adopted in the desulfurization industry is proved.
However, in a regeneration cycle test for further developing a desulfurizing agent, it was found that Morpholine (MP) is difficult to regenerate by analytical heat, and the desulfurizing adsorption performance is close to one-time, so that it cannot be used as a main desulfurizing functional component of a desulfurizing agent requiring multiple regeneration cycles. The N- (2-hydroxyethyl) morpholine (HEM), the N-formyl morpholine and the N-methyl morpholine all show better regeneration cycle performance, and the total sulfur absorption amount difference of the three after 5 times of regeneration cycle absorption is smaller, wherein the N- (2-hydroxyethyl) morpholine (HEM) is only slightly better than the N-formyl morpholine and the N-methyl morpholine.
The previous test contents and conclusions of the design test are described in the published papers of the inventor (The absorption of SO2 by morpholine cyclic amines with sulfolane as the solvent for flue gas[J].Journal of Hazardous Materials,2021,408:124462.).
Based on the above-described studies, the inventors of the present invention have found that in the post-test, in order to further reduce the industrial production cost and to improve the desulfurization performance of the desulfurizing agent when N- (2-hydroxyethyl) morpholine (HEM) is used as a solute, a large number of tests are conducted to obtain an optimal, optimally matched organic solvent selection. In the experiment, organic solvents most widely used in the prior desulfurization technique were selected, and dibasic ester solvents represented by dimethyl succinate (DMSu), dimethyl glutarate (DMG) and dimethyl adipate (DMA), ether reagents represented by polyethylene glycol dimethyl ether (NHD) and triethylene glycol monomethyl ether (TEM), sulfone reagents represented by dimethyl sulfoxide (DMSO) and Sulfolane (SUL), and alcohol reagents represented by ethanol (EtOH) and glycerol (Gly) were selected, respectively.
The mixed solution prepared by the organic solvents and N- (2-hydroxyethyl) morpholine (HEM) respectively in the same concentration ratio is used, and the first desulfurization adsorption test shows that when glycerol (Gly), triethylene glycol monomethyl ether (TEM) and dimethyl sulfoxide (DMSO) are used as solvents, the first absorption capacity of the mixed solution is remarkably higher than that of other organic solvents.
However, after the total sulfur absorption after 5 times of regeneration cycle absorption was counted, it was surprisingly found that when polyethylene glycol dimethyl ether (NHD) was used as a solvent, the total sulfur absorption after 5 times of regeneration cycle absorption was significantly higher than other organic solvent selections. The sulfur absorption amount of the organic solvents with the highest primary absorption capacity during 5 times of regeneration cycle absorption has a more obvious trend of reduction, so that the total sulfur absorption amount is obviously lower than that of polyethylene glycol dimethyl ether (NHD); and triethylene glycol monomethyl ether (TEM) which is also an ether reagent, and the total sulfur absorption is obviously lower than polyethylene glycol dimethyl ether (NHD).
This occasional discovery is clearly extremely advantageous for the construction of low cost N- (2-hydroxyethyl) morpholine (HEM) single component non-compounded desulfurizing agents for production and practical industrial applications. In addition, through repeated regeneration cycle desulfurization tests, the sulfur absorption amount of each regeneration cycle is more uniform and stable than other solvents under the collocation of N- (2-hydroxyethyl) morpholine (HEM) and polyethylene glycol dimethyl ether (NHD), and the better industrial application prospect of the catalyst is fully demonstrated.
The morpholine cyclic amine desulfurizing agent is prepared by mixing N- (2-hydroxyethyl) morpholine (HEM) as a solute and polyethylene glycol dimethyl ether (NHD) as a solvent. It is emphasized that the morpholine cyclic amine desulfurizing agent of the invention is prepared by mixing N- (2-hydroxyethyl) morpholine (HEM) and polyethylene glycol dimethyl ether (NHD) only, and forms a homogeneous solution after the solute is uniformly dispersed, thereby being beneficial to long-term preservation. Whether the sulfur absorption stability of the repeated regeneration cycle of the compound desulfurizing agent is influenced by adding other auxiliary agents, fillers, reinforcing agents and the like is not known for a long time, and the homogeneous phase property of the compound desulfurizing agent can be possibly damaged.
In one technical scheme, the mass percentage of the N- (2-hydroxyethyl) morpholine (HEM) serving as a solute in the morpholine cyclic amine desulfurizing agent is 20-50%.
It should be noted that, on the premise that the solute and solvent components are provided in the present invention, a person skilled in the art may refer to the prior art to obtain a specific method for preparing a mixed solution according to the conventional principle of the mixed solution. Therefore, the technical solutions provided below of the present invention are not meant to be a unique specification or limitation of the preparation method of the present invention.
The preparation method of the morpholine cyclic amine desulfurizing agent with high regeneration cycle performance mainly comprises the following steps:
(1) Mixing N- (2-hydroxyethyl) morpholine (HEM) as a solute and polyethylene glycol dimethyl ether (NHD) as a solvent to obtain a mixed solution;
(2) And (3) uniformly dispersing the N- (2-hydroxyethyl) morpholine in the mixed solution obtained in the step (1) at normal temperature or at the temperature of 20-40 ℃ by stirring, thus obtaining the morpholine cyclic amine desulfurizer with high regeneration cycle performance.
The mixed absorbent of morpholine and cyclic amine prepared finally by the technical proposal has strong repeated cyclic absorption capacity to SO 2 with higher concentration under the conditions that the temperature window is 293.15K-333.15K and the gas flow is certain, and can achieve better effect.
When the temperature is 293.15K and the gas flow is 700ml/min, the first adsorption can reach 192.18mg/g and the absorption capacity for 5 times can reach more than 4800mg/g under the condition of simulating SO 2 with the concentration of 8580mg/m 3 in flue gas.
The invention has the following beneficial effects:
1. The morpholine cyclic amine desulfurizer provided by the invention can reach a considerable level on the repeated cyclic absorption capacity of SO 2 under a higher concentration condition at a certain temperature, the repeated multiplexing effect of the preferable technical scheme is higher than that of Cansolv amine liquid which is already industrially applied under the similar experimental condition, and the morpholine cyclic amine desulfurizer has excellent selectivity on the absorption of SO 2 under the condition that various flue gas components such as SO 2、NOx, O 2 and the like coexist, and the water in wet flue gas has little influence on the absorption efficiency of the wet flue gas, thereby being particularly suitable for absorbing SO 2 -containing waste gas discharged by steel sintering and pellet industry.
2. The morpholine cyclic amine desulfurizer absorbent provided by the invention has the advantages of high desulfurization efficiency, simple and reliable operation and maintenance, and good thermal stability and chemical stability of the absorbent; and at the same time, as a homogeneous liquid, has the advantage of long-term storage.
3. The preparation method has the characteristics of lower cost, simple and convenient process steps and the like, has the advantages of less regeneration energy consumption and low energy consumption cost, has good engineering application economy, has lower cost compared with the traditional desulfurization method, and has excellent market application prospect.
Drawings
FIG. 1 is a graph showing the first absorption capacity of SO 2 in the desulfurization absorption test versus the bar graph of example 1 and comparative examples 1 to 8 according to the present invention.
FIG. 2 is a graph showing the comparison of SO 2 absorption capacities of example 1 and comparative examples 1 to 8 according to the present invention, which were regenerated 5 times in the desulfurization absorption test.
FIG. 3 is a graph showing the comparison of the mass loss rate of the solution in the regeneration cycle 5 times in the desulfurization absorption test in example 1 and comparative examples 1 to 8 of the present invention.
FIG. 4 is a photograph showing the apparent delamination of HEM-NHD-40 prepared in example 1 of the present invention after absorption of SO 2.
FIG. 5 is a FTIR comparison of the supernatant and underlying liquid of HEM-NHD-40 prepared in example 1 of the present invention prior to absorption and after the first absorption of SO 2. In the figure, the uppermost spectral line corresponds to the supernatant liquid after the first absorption of SO 2, the middle spectral line corresponds to the lower liquid after the first absorption of SO 2.
FIG. 6 is a graph comparing FTIR of HEM-NHD-40 prepared in example 1 of the present invention before absorption with that after 5 regeneration cycles. In the figure, the uppermost line corresponds to HEM-NHD-40 desorbed again after 5 regeneration cycles before absorption, and the lowermost line corresponds to HEM-NHD-40.
FIG. 7 is a NMR spectrum of HEM-NHD-40 prepared in example 1 of the invention before absorption and after 5 regeneration cycles. The left graph (a) is a 1H NMR spectrum, the uppermost spectrum corresponds to HEM-NHD-40 desorbed again after 5 regeneration cycles before absorption, and the lowermost spectrum corresponds to HEM-NHD-40 desorbed again after 5 regeneration cycles; the right panel (b) shows the 13C NMR spectrum with the uppermost line corresponding to HEM-NHD-40 desorbed again after 5 regeneration cycles before absorption and the lowermost line corresponding to absorption.
FIG. 8 is a photograph showing the HEM-TEM-40 of comparative example 6 of the present invention showing no delamination after absorbing SO 2.
FIG. 9 is a graph comparing FTIR of HEM-TEM-40 prepared in comparative example 6 of the invention, before absorption, after the first absorption of SO 2, with after 5 regeneration cycles. In the figure, the uppermost spectral line corresponds to HEM-TEM-40 desorbed again after 5 regeneration cycles after the first absorption of SO 2 and the middle spectral line corresponds to SO 2.
FIG. 10 is a chart showing the NMR spectra of HEM-TEM-40 prepared in comparative example 6 of the invention, before absorption, after the first absorption of SO 2, and after 5 regeneration cycles. The left graph (a) is a 1H NMR spectrum, the uppermost spectrum corresponds to HEM-TEM-40 desorbed again after the first absorption of SO 2 and the lowermost spectrum corresponds to the regeneration cycle after 5 times; the right panel (b) shows the 13C NMR spectrum, the uppermost line corresponding to HEM-TEM-40 desorbed again after 5 regeneration cycles, after the first absorption of SO 2, the middle line corresponding to SO 2.
FIG. 11 is a graph showing the comparison of SO 2 absorption capacities of examples 1 to 3 according to the present invention in 5 regeneration cycles in repeated desulfurization absorption tests.
FIG. 12 is a schematic flow chart of an experiment for absorbing SO 2 in the test method of the present invention.
FIG. 13 is a schematic flow chart of an experiment for desorbing SO 2 in the test method of the present invention.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention and are not limiting of the invention claims. Those skilled in the art can, with the benefit of this disclosure, suitably modify the process parameters to achieve this. It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and are deemed to be included within the present invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those skilled in the relevant art that variations and modifications can be made in the methods and applications described herein, and in the practice and application of the techniques of this invention, without departing from the spirit or scope of the invention. While the following terms are believed to be well understood by those of ordinary skill in the art, the following definitions are set forth to aid in the description of the presently disclosed subject matter.
In one aspect, the invention provides a morpholine cyclic amine desulfurizer with high regeneration cycle performance, which is prepared by mixing N- (2-hydroxyethyl) morpholine (HEM) as a solute and polyethylene glycol dimethyl ether (NHD) as a solvent.
The morpholine cyclic amine desulfurizing agent is prepared by mixing N- (2-hydroxyethyl) morpholine (HEM) as a solute and polyethylene glycol dimethyl ether (NHD) as a solvent. It is emphasized that the morpholine cyclic amine desulfurizing agent of the invention is prepared by mixing N- (2-hydroxyethyl) morpholine (HEM) and polyethylene glycol dimethyl ether (NHD) only, and forms a homogeneous solution after the solute is uniformly dispersed, thereby being beneficial to long-term preservation. Whether the sulfur absorption stability of the repeated regeneration cycle of the compound desulfurizing agent is influenced by adding other auxiliary agents, fillers, reinforcing agents and the like is not known for a long time, and the homogeneous phase property of the compound desulfurizing agent can be possibly damaged.
In one embodiment, the mass percentage of N- (2-hydroxyethyl) morpholine (HEM) as a solute in the above-mentioned cyclic amine desulfurizing agent is 1% -99%, for example 1%, 2%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 98%, 99%.
In a preferred embodiment, the mass percentage of N- (2-hydroxyethyl) morpholine (HEM) as solute in the morpholino cyclic amine desulfurizing agent is 20% -50%, such as 21%, 22%, 24%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, 44%, 45%, 46%, 48%, 49%. It is found through comparative experiments that when the solute addition amount exceeds 50wt%, physical properties such as viscosity and the like are affected, and absorption of SO 2 is hindered. More preferably 30 to 40%.
It should be noted that, on the premise that the solute and solvent components are provided in the present invention, a person skilled in the art may refer to the prior art to obtain a specific method for preparing a mixed solution according to the conventional principle of the mixed solution. Therefore, the technical solutions provided below of the present invention are not meant to be a unique specification or limitation of the preparation method of the present invention.
The preparation method of the morpholine cyclic amine desulfurizing agent with high regeneration cycle performance mainly comprises the following steps:
(1) Mixing N- (2-hydroxyethyl) morpholine (HEM) as a solute and polyethylene glycol dimethyl ether (NHD) as a solvent to obtain a mixed solution;
(2) And (3) uniformly dispersing the N- (2-hydroxyethyl) morpholine in the mixed solution obtained in the step (1) at normal temperature or at the temperature of 20-40 ℃ by stirring, thus obtaining the morpholine cyclic amine desulfurizer with high regeneration cycle performance.
In one embodiment, the stirring means in step (2) is mechanical stirring, and the person skilled in the art can stir according to the general knowledge in the art or by referring to conventional mechanical stirring means for organic reagents in the chemical industry, for example, conventional industrial stirrers such as a propeller stirrer, a turbine stirrer, a paddle stirrer, an anchor stirrer, etc.
In one embodiment, the stirring means in step (2) is magnetic stirring, and the person skilled in the art may refer to conventional magnetic stirring means for organic reagents in chemical laboratories, according to common general knowledge in the art.
In one preferred embodiment, the stirring means in step (2) is magnetic stirring at a rate of 200-400 r/min for more than 1min under the condition that the total mass of the reagent is not more than 1kg, so that the N- (2-hydroxyethyl) morpholine (HEM) is fully dissolved in polyethylene glycol dimethyl ether (NHD).
The present application will be explained in further detail with reference to examples. However, those skilled in the art will appreciate that these examples are provided for illustrative purposes only and are not intended to limit the present application.
Examples
Embodiments of the present application will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present application and should not be construed as limiting the scope of the present application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention. All amounts listed are described in weight percent based on total weight unless otherwise indicated. The application should not be construed as being limited to the particular embodiments described.
1. Selecting reagent
The main experimental reagents and raw materials are shown in table 1.
Table 1 experiment reagent and raw material summary table
Table1 The summary table of experimental reagents and raw materials.
2. Test method
Absorption SO 2 experiment:
According to the different absorption dose sizes required by the experiment, a Monte-Carlo gas cylinder with two specifications of 5ml and 50ml is selected for containing the desulfurizer samples used by the experiment. The bottle stopper of the gas washing bottle is wound with a raw material belt to make gas sealing measures. The air cylinder was then weighed with a balance, and the mass was recorded as M 0. And taking a certain mass of solvent and solute into a gas washing bottle by using a rubber head dropper, shaking uniformly, weighing by using a balance, and recording the total mass as M T.
The flow chart of the device for SO 2 absorption experiment is shown in FIG. 12. The required gas enters a mass flow controller from a gas cylinder through a pipeline to control the flow rate of each gas, and enters a gas mixing device to mix the gases, and the total flow rate of the gases is controlled to be 700ml/min. The pipeline is cut into a bypass, the mixed gas directly enters the flue gas analyzer after being dried, and the gas flow ratio is adjusted to enable the concentration value of SO 2 of the flue gas analyzer to be stabilized within 2% of the required concentration value of SO 2. And connecting the gas washing bottle after sample filling into an absorption experiment device, immersing into a digital display constant-temperature oil bath to control and stabilize the experiment temperature, and switching a pipeline from a bypass to a main circuit. The experiment adopts a bubbling method to blow the prepared mixed gas into a gas washing bottle filled with the mixed absorbent, and uses Gasboard-3000PLUS flue gas analyzer to detect the SO 2 outlet concentration in the simulated flue gas on line. The absorption capacity of the absorbent can be calculated by the following formulas (4) and (5):
M＝MT-M0 (4)
desorption of SO 2 experiment:
The flow chart of the apparatus for SO 2 desorption experiments is shown in FIG. 13. After the absorption experiment was completed, the absorption liquid was desorbed under a 353.15K oil bath and 700ml/min nitrogen gas blow. Considering that the concentration of SO 2 generated by the absorption liquid at the beginning of desorption may exceed the measuring range of a flue gas analyzer, the amount of SO 2 desorbed in each period of time is measured by adopting a hydrochloric acid titration method. As shown in FIG. 3, 30ml of NaOH standard solution of a proper concentration was prepared for collecting SO 2 obtained by desorption. To the NaOH standard solution of (2) 3-5 drops of 30% H 2O2 solution are added to oxidize the sulfite formed. The solution in the SO 2 collection bottle was titrated with a HCl standard solution of a certain concentration, and the amount of desorbed SO 2 was calculated over a certain period of time using formulas (6) and (7).
On the basis of the above absorption and desorption experiments, absorption-desorption cycle experiments were performed using the desulfurizing agents (mixed absorbent) of each example and comparative example, and 5 cycle absorption experiments were performed under the condition that the absorption and desorption temperatures were constant.
Example 1, comparative examples 1 to 8
Examples 1 and comparative examples 1 to 8 were respectively bivalent acid ester solvents represented by dimethyl succinate (DMSu), dimethyl glutarate (DMG) and dimethyl adipate (DMA), ether reagents represented by polyethylene glycol dimethyl ether (NHD) and triethylene glycol monomethyl ether (TEM), sulfone reagents represented by dimethyl sulfoxide (DMSO) and Sulfolane (SUL), alcohol reagents represented by ethanol (EtOH) and glycerol (Gly) as solvents, and the total absorption capacity of SO 2 after 5 regeneration cycles in desulfurization absorption test (absorption SO 2 test) was studied by comparative experiments with the desulfurizing agent prepared when N- (2-hydroxyethyl) morpholine (HEM) was used as a solute (40 wt%).
Laboratory simulated flue gas conditions: SO 2 concentration=8580mg/m 3, nitrogen as carrier gas, gas flow 700ml/min, reaction temperature 293.15K, water content 0%.
As shown in fig. 1, the first absorption capacity of SO 2 of the desulfurizing agent of different solvents is different, wherein when glycerol (Gly), triethylene glycol monomethyl ether (TEM) and dimethyl sulfoxide (DMSO) are used as solvents, the first absorption capacity of the desulfurizing agent is obviously higher than that of other organic solvents. Specific absorption data are shown in table 2 below:
Table 2 list of first SO 2 absorption capacities of mixed absorbents
Sequence number Name of the name SO 2 absorption capacity (mg/g)
Comparative example 1 1 HEM-EtOH-40 80.84
Comparative example 2 2 HEM-Gly-40 230.3
Comparative example 3 3 HEM-DMSu-40 194.1
Comparative example 4 4 HEM-DMG-40 177.57
Comparative example 5 5 HEM-DMA-40 163.8
Example 1 6 HEM-NHD-40 196.73
Comparative example 6 7 HEM-TEM-40 225.75
Comparative example 7 8 HEM-DMSO-40 213.9
Comparative example 8 9 HEM-SUL-40 192.18
As shown in fig. 2, it was surprisingly found that, of the total absorption capacity after 5 regeneration cycles of the desulfurizing agent of different solvents, the total absorption amount of sulfur after 5 regeneration cycles was significantly higher than other organic solvent selections when polyethylene glycol dimethyl ether (NHD) was used as the solvent.
TABLE 3 total SO 2 absorption profile after 5 regeneration cycles of the mixed absorbent
Sequence number Name of the name 5 Cycles of SO 2 absorption capacity (mg)
Comparative example 1 1 HEM-EtOH-40 /
Comparative example 2 2 HEM-Gly-40 /
Comparative example 3 3 HEM-DMSu-40 4173.96
Comparative example 4 4 HEM-DMG-40 3979.92
Comparative example 5 5 HEM-DMA-40 3930.08
Example 1 6 HEM-NHD-40 5012.09
Comparative example 6 7 HEM-TEM-40 4533.85
Comparative example 7 8 HEM-DMSO-40 /
Comparative example 8 9 HEM-SUL-40 4317.45
As shown in fig. 3, the mass loss rate of the solution after 5 times of regeneration cycles of the desulfurizing agent of different solvents was compared, wherein the difference from the other several solvents was not significant when polyethylene glycol dimethyl ether (NHD) was used as the solvent.
Fig. 4 shows that obvious layering phenomenon (b) occurs after SO 2 is absorbed when polyethylene glycol dimethyl ether (NHD) is used as a solvent, and on the basis, the supernatant liquid and the lower liquid of the pre-reaction absorbent and the post-reaction absorbent are characterized by FT-IR, and the details are shown in fig. 5 and 6 of the specification. First, the weighted addition of FTIR lines to the NHD showed very high similarity to HEM-NHD-40 and no new peak was generated, indicating that the NHD is dominated by the physical solvent effect in the absorber. Second, the molecular vibration of S and O, which correspond to absorption peaks at 455, 602 and 947cm -1, which are sulfite characteristic absorption peaks, indicate that the system components undergo a chemical reaction to cause SO 2 absorption. More importantly, after 5 absorption-desorption cycles, each absorption peak of the HEM-NHD-40 is almost unchanged, and the spectrum is almost the same as that before absorption, which shows that the HEM-NHD-40 absorbent has excellent regeneration performance, and after the absorption-desorption cycles, the absorbent is highly regenerated. In the characterization of the 1H NMR and 13CNMR nuclear magnetic resonance of the absorbent after 5 absorption-desorption cycles, delta phase difference values of all characteristic peaks are almost about 0.02ppm, and the detailed description is shown in figure 7 of the specification, which also shows that the HEM-NHD-40 structure has good recovery strength and excellent regeneration performance, and is completely matched with experimental results.
The same characterization was performed for triethylene glycol monomethyl ether (TEM), which is also an ether reagent, and the desulfurizing agent was configured to have no delamination after the desulfurization adsorption test, as shown in fig. 8. On the basis of the experiment, the characterization of the absorbent before and after the reaction by means of FT-IR is shown in figure 9 of the description. The weighted addition of FTIR lines by HEM and TEM is very similar to HEM-TEM-40 and does not produce a new peak, indicating that TEM is dominated by the physical solvent effect in the absorbent. Next, characteristic absorption peaks of sulfite corresponding to 455 and 1020cm -1. Flexural vibration of the SO 2 molecule at 505, 548 and 646cm -1, corresponding to the twist in HEM-SO 2, indicates that the system components chemically react to cause SO 2 absorption. After 5 absorption-desorption cycles, each absorption peak of HEM-TEM-40 has a certain change, the same phenomenon can be observed in the characterization of nuclear magnetic resonance of the absorbent 1HNMR and 13CNMR after 5 absorption-desorption cycles, the delta value of each characteristic peak has a large height change, and the detailed description is shown in figure 10 of the specification, which also shows that the absorbent can not completely recover the original state after desorption, the regeneration performance is not ideal, the absorption capacity of the recycled HEM-TEM-40 is affected to a certain extent, and the phenomenon that the stability of the HEM-TEM-40 is slightly insufficient in the cycle experiment is explained.
The characterization of the absorber before and after the reaction, and the characterization of the 1HNMR, 13C NMR nuclear magnetic resonance were also performed for other solvent selections, and the total absorption of sulfur after 5 times of absorption based on other solvent selection regeneration cycles was lower than that of comparative example 6, which was omitted in view of the description.
Examples 1 to 3
The procedure of example 1 was repeated to verify the standard deviation of the sulfur absorption amount for 5 times of the regeneration cycle, and the results are shown in FIG. 11 of the specification.
It is obvious that in repeated experiments, the specific embodiment using polyethylene glycol dimethyl ether (NHD) as the solvent shows extremely high repeatability, and the sulfur absorption amount of each regeneration cycle tends to be uniform and stable compared with other solvents, so that the method has better industrial application prospect.
The following examples respectively examine the influence of four influencing factors, namely the reaction temperature, the solute mass percent, the SO 2 concentration and the flue gas water content, on the morpholine cyclic amine desulfurizing agent with high regeneration cycle performance, and a three-level optimization orthogonal experiment of the four influencing factors is designed by taking the first sulfur absorption as an evaluation index.
Example 4
In example 4, the mass percentage of N- (2-hydroxyethyl) morpholine was 30%, the SO 2 concentration=5720mg/m 3, nitrogen gas as carrier gas, the gas flow rate was 700ml/min, the reaction temperature was 293.15K, the water content was 10%, and the absorption capacity of SO 2 was 972.37mg.
Example 5
In example 5, the mass percentage of N- (2-hydroxyethyl) morpholine was 20%, the SO 2 concentration=2860 mg/m 3, nitrogen gas as carrier gas, the gas flow rate was 700ml/min, the reaction temperature was 293.15K, the water content was 20%, and the first absorption capacity of SO 2 was 896.78mg.
Example 6
In example 6, the mass percentage of N- (2-hydroxyethyl) morpholine was 40%, the SO 2 concentration=5720mg/m 3, nitrogen gas as carrier gas, the gas flow rate was 700ml/min, the reaction temperature was 313.15K, the water content was 20%, and the first absorption capacity of SO 2 was 518.5mg.
Example 7
In example 7, the mass percentage of N- (2-hydroxyethyl) morpholine was 30%, the concentration of SO 2 =2860 mg/m 3, the flow rate of nitrogen gas as carrier gas was 700ml/min, the reaction temperature was 313.15K, the water content was 0%, and the first absorption capacity of SO 2 was 318.89mg.
Example 8
In example 8, the mass percentage of N- (2-hydroxyethyl) morpholine was 20%, the SO 2 concentration=8580mg/m 3, nitrogen gas as carrier gas, the gas flow rate was 700ml/min, the reaction temperature was 313.15K, the water content was 10%, and the first absorption capacity of SO 2 was 519.85mg.
Example 9
In example 9, the mass percentage of N- (2-hydroxyethyl) morpholine was 40%, the concentration of SO 2 = 2860mg/m 3, the flow rate of nitrogen gas as carrier gas was 700ml/min, the reaction temperature was 333.15K, the water content was 10%, and the first absorption capacity of SO 2 was 172.77mg.
Example 10
In example 10, the mass percentage of N- (2-hydroxyethyl) morpholine was 30%, the SO 2 concentration=8580mg/m 3, nitrogen gas as carrier gas, the gas flow rate was 700ml/min, the reaction temperature was 333.15K, the water content was 20%, and the first absorption capacity of SO 2 was 246.5mg.
Example 11
In example 11, the mass percentage of N- (2-hydroxyethyl) morpholine was 30%, the SO 2 concentration=5720mg/m 3, nitrogen gas as carrier gas, the gas flow rate was 700ml/min, the reaction temperature was 333.15K, the water content was 0%, and the first absorption capacity of SO 2 was 178.6mg.
The foregoing examples are illustrative of the present invention and are not intended to be limiting, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principles of the invention are intended to be equivalent and are within the scope of the present invention.

Claims (5)

1. A morpholine cyclic amine desulfurizing agent with high regeneration cycle performance is characterized in that the desulfurizing agent is prepared by mixing N- (2-hydroxyethyl) morpholine serving as a solute and polyethylene glycol dimethyl ether serving as a solvent, wherein the mass percentage of the N- (2-hydroxyethyl) morpholine serving as the solute is 20% -50%.
2. The morpholino cyclic amine desulfurizing agent according to claim 1, characterized in that: the mass percentage of the N- (2-hydroxyethyl) morpholine serving as a solute in the morpholine cyclic amine desulfurizing agent is 30% -40%.
3. The preparation method of the morpholine cyclic amine desulfurizer with high regeneration cycle performance is characterized by mainly comprising the following steps:
(1) Mixing N- (2-hydroxyethyl) morpholine serving as a solute and polyethylene glycol dimethyl ether serving as a solvent, wherein the mass percentage of the N- (2-hydroxyethyl) morpholine serving as the solute is 20% -50% as a mixed solution;
(2) And (3) uniformly dispersing the N- (2-hydroxyethyl) morpholine in the mixed solution obtained in the step (1) at normal temperature or at the temperature of 20-40 ℃ by stirring, so as to obtain the morpholine cyclic amine desulfurizer with high regeneration cycle performance.
4. A method of preparation according to claim 3, characterized in that: the mass percentage of the N- (2-hydroxyethyl) morpholine serving as a solute in the mixed solution is 30% -40%.
5. The use of the morpholine cyclic amine desulfurizing agent with high regeneration cycle performance as claimed in claim 1 in the field of organic amine desulfurization.
CN202211067817.1A 2022-09-01 2022-09-01 Morpholine cyclic amine desulfurizing agent with high regeneration cycle performance and preparation method thereof Active CN115400549B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211067817.1A CN115400549B (en) 2022-09-01 2022-09-01 Morpholine cyclic amine desulfurizing agent with high regeneration cycle performance and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211067817.1A CN115400549B (en) 2022-09-01 2022-09-01 Morpholine cyclic amine desulfurizing agent with high regeneration cycle performance and preparation method thereof

Publications (2)

Publication Number Publication Date
CN115400549A CN115400549A (en) 2022-11-29
CN115400549B true CN115400549B (en) 2024-04-16

Family

ID=84163967

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211067817.1A Active CN115400549B (en) 2022-09-01 2022-09-01 Morpholine cyclic amine desulfurizing agent with high regeneration cycle performance and preparation method thereof

Country Status (1)

Country Link
CN (1) CN115400549B (en)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4482529A (en) * 1983-01-07 1984-11-13 Air Products And Chemicals, Inc. Catalytic hydrolysis of COS in acid gas removal solvents
US4524050A (en) * 1983-01-07 1985-06-18 Air Products And Chemicals, Inc. Catalytic hydrolysis of carbonyl sulfide
US6342091B1 (en) * 1999-01-22 2002-01-29 Krupp Uhde Gmbh Method of removing carbon dioxide, sulphur compounds, water and aromatic and higher aliphatic hydrocarbons from industrial gases
CN102657998A (en) * 2012-04-25 2012-09-12 中国石油化工股份有限公司 Mixed solvent for removing acid gas
CN104548903A (en) * 2013-10-09 2015-04-29 中国石油化工股份有限公司 Organic amine solvent for capturing carbon dioxide
CN105126576A (en) * 2015-07-29 2015-12-09 中国石油集团工程设计有限责任公司 High-efficiency composite desulphurization solvent and system and method for removing acidic gas and organic sulfur
CN112023662A (en) * 2020-08-04 2020-12-04 宁波中一石化科技有限公司 Composite desulfurizer for purifying petroleum and natural gas

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103357261B (en) * 2013-06-24 2016-04-27 宜兴汉光高新石化有限公司 A kind of composite desulfurizing agent and preparation method thereof
CN114317054A (en) * 2021-12-29 2022-04-12 宁波中一石化科技有限公司 Device and method for eliminating back-vulcanization effect in liquefied gas desulfurization process

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4482529A (en) * 1983-01-07 1984-11-13 Air Products And Chemicals, Inc. Catalytic hydrolysis of COS in acid gas removal solvents
US4524050A (en) * 1983-01-07 1985-06-18 Air Products And Chemicals, Inc. Catalytic hydrolysis of carbonyl sulfide
US6342091B1 (en) * 1999-01-22 2002-01-29 Krupp Uhde Gmbh Method of removing carbon dioxide, sulphur compounds, water and aromatic and higher aliphatic hydrocarbons from industrial gases
CN102657998A (en) * 2012-04-25 2012-09-12 中国石油化工股份有限公司 Mixed solvent for removing acid gas
CN104548903A (en) * 2013-10-09 2015-04-29 中国石油化工股份有限公司 Organic amine solvent for capturing carbon dioxide
CN105126576A (en) * 2015-07-29 2015-12-09 中国石油集团工程设计有限责任公司 High-efficiency composite desulphurization solvent and system and method for removing acidic gas and organic sulfur
CN112023662A (en) * 2020-08-04 2020-12-04 宁波中一石化科技有限公司 Composite desulfurizer for purifying petroleum and natural gas

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Study on absorption and spectral properties of H2S in carboxylate protic ionic liquids with low viscosity;Tianxiang Zhao;Journal of Molecular Liquids;第806-813页 *
The absorption of SO2 by morpholine cyclic amines with sulfolane as the solvent for flue gas;Can Cheng;Journal of Hazardous Materials;第1-12页 *
张巧玲.化工工艺学.北京：国防工业出版社,2015,第62-63页. *
炭基脱硫剂再生研究综述;贺尧祖;化工技术与开发;第45卷(第5期);第44-46页 *

Also Published As

Publication number Publication date
CN115400549A (en) 2022-11-29

Similar Documents

Publication Publication Date Title
CN105289209B (en) One kind traps CO by phase transformation2、SO2The mixed organic solvents of sour gas
AU2010209661B2 (en) Absorbent containing cyclic amines for removing acid gases
EP2618914B1 (en) Solvent composition for carbon dioxide recovery
CN107715845B (en) Flue gas desulfurization and denitrification adsorbent and preparation and use methods thereof
CN101745289B (en) Method for selectively removing H2S from gas mixture containing CO2
CN101612509A (en) Capture the composite decarbonizing solution of carbon dioxide in the mist
CN1125158A (en) Method for the removal of hydrogen sulfide present in gases
CN102179132A (en) Absorbent for catching or separating dioxide carbon
EP3378550A1 (en) Carbon dioxide adsorbent and carbon dioxide separation and recovery system
WO2012162944A1 (en) Composite decarburized solution for capturing carbon dioxide in mixed gas
CN104853830B (en) It is a kind of containing 2-amino-2-methyl-1-propanol and the aqueous CO of 3- aminopropanols or 2-amino-2-methyl-1-propanol and 4- amino butanols2Absorbent
CN102284227A (en) Method for capturing carbon dioxide in mixed gas by using composite decarbonizing solution
Meng et al. A comparative study of the effects of aqueous mixed amines on biogas upgrading based on 13C nuclear magnetic resonance (NMR) analysis
CN113101782B (en) Functionalized ionic liquid absorption liquid and preparation method and application thereof
CN115069068A (en) Rapid low-energy-consumption CO capture by catalyzing tertiary amine solvent with hydrotalcite catalyst 2 Method (2)
CN115400549B (en) Morpholine cyclic amine desulfurizing agent with high regeneration cycle performance and preparation method thereof
KR101094327B1 (en) Absorbents for separation of acidic gas
CN111821813B (en) Ternary eutectic solvent and method for adsorbing sulfur dioxide by using same
CN116212591A (en) Low-corrosiveness phase change absorbent and application thereof in carbon dioxide capturing
Yokoyama et al. Hitachi’s carbon dioxide scrubbing technology with new absorbent for coal fired power plants
CN109420409A (en) It is selectively removed from air-flow containing H2S and CO2Sour gas absorbent and method
EP3673973A1 (en) Decarbonization solution for capturing carbon dioxide in mixed gas and capable of reducing impact of hygroscopicity
KR100259461B1 (en) Tertiary alkanolamine absorbent containing ethylene amine promoter
CN112540021A (en) Device and method for rapidly evaluating emission reduction effect of emission reduction device on VOCs (volatile organic compounds)
CN114540089B (en) Natural gas desulfurization decarbonization agent and use method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant