CN114540089A - Natural gas desulfurization and decarbonization agent and using method thereof - Google Patents
Natural gas desulfurization and decarbonization agent and using method thereof Download PDFInfo
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- CN114540089A CN114540089A CN202210208841.6A CN202210208841A CN114540089A CN 114540089 A CN114540089 A CN 114540089A CN 202210208841 A CN202210208841 A CN 202210208841A CN 114540089 A CN114540089 A CN 114540089A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
- C10L3/103—Sulfur containing contaminants
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- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/52—Hydrogen sulfide
- B01D53/526—Mixtures of hydrogen sulfide and carbon dioxide
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- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
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- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
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- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/96—Regeneration, reactivation or recycling of reactants
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
- C10L3/104—Carbon dioxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/24—Hydrocarbons
- B01D2256/245—Methane
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- 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
- B01D2257/304—Hydrogen sulfide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
- C10L2290/541—Absorption of impurities during preparation or upgrading of a fuel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Abstract
The invention belongs to the technical field of gas purification, and particularly discloses a natural gas desulfurization and decarbonization agent and a use method thereof. The invention discloses a novel natural gas desulfurization and decarbonization agent which is obtained by compounding liquid non-polymeric aminosilane and an organic solvent, wherein when the novel natural gas desulfurization and decarbonization agent is used, natural gas is directly introduced into a normal-temperature natural gas desulfurization and decarbonization agent and is absorbed for 30-45 min, so that purified natural gas is obtained. The natural gas desulfurization and decarbonization agent has the characteristics of high reaction rate, high absorption capacity, low energy consumption and the like, and can selectively remove H in natural gas2S and CO2. The analysis operation is simple, the energy consumption is low,solvent loss is avoided.
Description
Technical Field
The invention relates to the technical field of gas purification, in particular to a natural gas desulfurization and decarbonization agent and a using method thereof.
Background
With the optimization of the Chinese energy-saving and emission-reducing strategy, the proportion of natural gas in an energy structure is continuously increased, and the natural gas purification technology is widely concerned.
When the natural gas contains acidic components, the natural gas not only can cause corrosion of equipment and pipelines in the processes of mining, processing, storage and transportation, but also can pollute the environment and harm the health of users when used as fuel; when used as chemical raw materials, the catalyst can be poisoned, and the yield and quality of products are influenced. In addition, in the process of freezing and separating natural gas, if CO is generated2The high content of the carbon dioxide can form dry ice, block pipelines and reduce the heat value of the pipelines, thereby causing production accidents. Therefore, when the content of the acidic components in the natural gas exceeds the quality index of the commercial gas or the pipeline requirement, the acidic components must be removed to be within the allowable value by adopting a proper method. The natural gas contains acidic mixture with H as main component2S、CO2And water vapor and small amounts of hydrocarbons.
Removal of H from natural gas2S and CO2The general method of (1): wet, dry, membrane purification and microbial desulfurization. The method using a solution or a solvent as an absorbent is called a wet method. The wet desulfurization and decarburization are classified into a physical solvent absorption method, a chemical solvent absorption method, a physical and chemical solvent absorption method, and the like. Dry desulfurization is a method for natural gas desulfurization by using a solid adsorbent, namely, acidic gas is adsorbed on the surface of a solid desulfurizing agent or the acidic gas reacts with certain components on the surface to achieve the aim of desulfurization. Dry desulfurization, which includes molecular sieve and solid iron oxide processes, is used less often than wet processes.
Physical absorption method for removing natural gas in wet desulfurization and decarbonizationIn the gas H2S and CO2And organic acid (such as mercaptan), but the physical solvent has strong adsorption capacity to heavy hydrocarbon, which not only affects the calorific value of purified gas, but also affects the recovery quality of sulfur in the later period, and the use and operation costs are high. Physical solvents used in industry include propylene carbonate, dimethyl ether of polyethylene glycol, tributyl phosphate and N-methyl pyrrolidone.
The chemical solvent absorption method is that on the basis of reversible reaction, an alkaline solvent and an acid gas are reacted in a raw material gas to generate a compound rich in the acid gas, so that the acid gas is removed; the rich liquid absorbing the acid gas can regenerate the alkaline solution at higher temperature and lower pressure to desorb the acid gas. Among them, the alcohol amine method is the most commonly used method for desulfurization and decarburization of natural gas, and includes Monoethanolamine (MEA), Diethanolamine (DEA), Diglycolamine (DGA), Diisopropanolamine (DIPA), and Methyldiethanolamine (MDEA). Water is generally used as a solvent in the alkanolamine process.
Monoethanolamine (MEA) has the advantages of small molecular weight, good chemical stability, easy desorption of acid gas and the like in the wet desulfurization and decarbonization process of natural gas. But the major disadvantages are MEA and SO2The reaction between them is irreversible, leading to a considerable loss of absorbent and accumulation of product. The MEA has a high vapor pressure and the evaporation loss is high during regeneration of the absorbent.
Diethanolamine (DEA), which is a secondary amine, is similar in application and operation to MEA with natural gas acid gas removal principles. However, DEA reacts with sulfide at a low rate, the product is different, the reaction caused by solvent loss is relatively small, and the corrosiveness is weak. Therefore, it is suitable for refinery gases and artificial gases having a high impurity content.
The Methyldiethanolamine (MDEA) belonging to tertiary amines has the advantages of good chemical stability, small flash evaporation and regeneration loss of an absorbent, weak corrosivity, low regeneration energy consumption and the like in the process of natural gas desulfurization and decarburization. Acid gas mixture (CO)2、H2S), MDEA may be combined with H2S is subjected to a rapid proton transfer reaction; and with CO2The reaction process is complex, the reaction rate is slow, and the selective removal of H is realized2And S. General useAnd using a 30 wt% MDEA water solution as a natural gas desulfurization absorbent.
Physical-chemical solvent absorption processes are used to purify natural gas, and the most typical representative is the sulphonylamine process, in which sulphone is combined with Diisopropanolamine (DIPA) or Methyldiethanolamine (MDEA). It features high acid gas load, high purifying rate and removing H2S and organic sulfur have the advantages of physical absorption and chemical absorption, but the cost of the compound absorbent is high.
The regeneration energy consumption and the loss amount of the absorbent are high, the thermal oxidation stability is not ideal, the corrosion to equipment is serious, and the expanded application of the alcohol amine absorbent in the wet purification of natural gas is limited.
Therefore, how to provide a natural gas desulfurization and decarbonization agent and a using method thereof, which avoid the defects of high viscosity, difficult mass transfer and the like of an absorbent, and reduce the absorption cost is a difficult problem to be solved urgently in the field.
Disclosure of Invention
In view of the above, the invention provides a natural gas desulfurization and decarbonization agent and a using method thereof, the natural gas desulfurization and decarbonization agent disclosed by the invention solves the problems of high viscosity and difficult mass transfer of the traditional absorbent, and the absorbent has the advantages of simple regeneration process and low energy consumption.
In order to achieve the purpose, the invention adopts the following technical scheme:
a natural gas desulfurization and decarbonization agent comprises the following components in parts by weight: 5-50 parts of aminosilane and 50-95 parts of organic solvent;
the structural formula of the aminosilane is
The R is1is-NH2、NH2C2H4NH-、NH2C2H4NHC2H4NH-、-NH(CH2)3N(CH3)2、-N(R2)3Piperazinyl, methylpiperazinyl or cyclohexylamino; the R is2、R3And R4Independently is-H, -CH3、-C2H5、-OCH3、-OCH2CH3or-CH (OCH)3)2。
Preferably, the aminosilane is a liquid non-polymeric aminosilane.
Preferably, the organic solvent is one or more of aliphatic alcohol, diethylene glycol dimethyl ether and sulfolane.
Preferably, the fatty alcohol comprises one or more of monohydric alcohol, dihydric alcohol and trihydric alcohol;
wherein, the molecular general formula of the monohydric alcohol is CnH2n+1OH，4≤n≤9；
The molecular general formula of the dihydric alcohol is CmH2m(OH)2，4≤m≤8；
The molecular general formula of the trihydric alcohol is CxH2x-1(OH)3X is more than or equal to 3 and less than or equal to 8; n, m and x are integers.
The invention also aims to provide a using method of the natural gas desulfurization and decarbonization agent, which comprises the following steps:
will contain H2S and CO2The gas is introduced into a natural gas desulfurization and decarbonization agent for absorption to obtain purified gas.
Preferably, the absorption time is 30-45 min.
Preferably, the natural gas desulfurization and decarbonization agent is used and then analyzed to obtain a regenerated natural gas desulfurization and decarbonization agent, and the regenerated natural gas desulfurization and decarbonization agent can be used for treating the hydrogen-containing component2S and CO2Is absorbed.
Preferably, the temperature of the analysis is 40-70 ℃, and the time of the analysis is 1.5-3 h.
The chemical absorption reaction principle of the invention is as follows:
the natural gas containing acid components passes through a desulfurization and decarbonization device, the natural gas desulfurization and decarbonization agent is simultaneously contacted with the acid components, and in the chemical absorption process, according to the chemical dissolution balance theory, the natural gas desulfurization and decarbonization agent and H2S and CO2Chemical equilibrium is reached. The balance is based on the solubility difference of acid components in different natural gas desulfurization and decarbonization agentsAnd (4) changing. The absorption time of the reaction is reasonably controlled, the chemical absorption efficiency can be further improved, and the method has great significance for purifying natural gas and recycling acid component resources.
The chemical absorption reaction is an exothermic reversible reaction with reduced volume, is favorable for the absorption reaction under low temperature and high pressure, and removes acid components from the natural gas in an absorption tower, thereby realizing the purpose of purifying the natural gas; at high temperature and low pressure, the desorption reaction is facilitated, the acidic components are desorbed from the absorbent in the regeneration tower, and the absorbent is regenerated and recycled.
The principle of selective absorption of natural gas desulfurization and decarbonization agents is as follows:
the solubility of the acid component in the natural gas desulfurization and decarbonization agent containing amino silane with different functional groups is different, the chemical equilibrium is different, and H is controlled by the difference of the solubility2S (or CO)2) The absorption rate of (a) may also be such that the absorbent has the property of selectively absorbing a component of the acid gas to a certain extent.
The aminosilane contains amines with "active" hydrogen, primary and secondary amines depending on the number of nitrogen atoms, the acid component (H) of natural gas being present2S、CO2) All react with 'active' hydrogen, and the selectivity is not obvious. With aminosilanes of secondary amine type with H2S(2)、CO2(1) The reaction of (a) is as follows:
secondary amine aminosilane absorbents with H2S, instantaneous chemical reaction with reaction rate controlled by a gas film; CO 22Solubility lower than H2S, the absorption rate is mainly controlled by a liquid film, and the chemical absorption rate is relatively slow; but from the macroscopic view of chemical absorption, H2S、CO2Has no obvious difference with the reaction rate of the active hydrogen atoms.
Tertiary amine aminosilanes free of "active" hydrogen atoms, absent in the molecule, which react with H to provide a protic hydrogen2S is reacted (3); and with CO2The reaction requires the presence of a protic hydrogen-providing solvent (4, 5).
And H2S reaction:
with CO2Reaction:
(4, Slow reaction)
Thus, tertiary amine aminosilanes can preferentially and relatively rapidly absorb H from acidic components2And S. The invention provides tertiary amine type aminosilane and primary amine type aminosilane containing activated tertiary amine, which can be applied to selectively removing H in natural gas2S、CO2And the method is favorable for independent recovery and reuse of the desorbed acid gas.
According to the technical scheme, compared with the prior art, the invention has the following beneficial effects:
compared with the traditional MEDA and MEA, the natural gas desulfurization and decarbonization agent disclosed by the invention not only has the absorption agent pair H of alkylolamines2S and CO2Has lower saturated vapor pressure, specific heat capacity, high boiling point and good thermal stability, and has high absorption property in H2S and CO2The gas-liquid mass transfer absorption process is less influenced by factors such as gas-liquid entrainment, volatilization, solute loss and the like, and is suitable for H2S and CO2The loading capacity and the absorption rate are high, and the problems that the alcohol amine absorbent is easy to be entrained and volatilized in the absorption process and the desorption temperature is high are avoided.
The invention adopts the compounding of the non-volatile organic solvent with low viscosity and high boiling point and the liquid aminosilane, can adjust the viscosity of the natural gas desulfurization and decarbonization agent,promotion of H2S and CO2The mass transfer absorption, the mass transfer efficiency enhancement, the solvent loss reduction and the H reduction2S and CO2Energy consumption of desorption process. The organic solvent which is not easy to volatilize is used for replacing water, so that energy sources can be greatly saved and the solvent loss can be reduced.
The invention can also realize H2S and CO2The selective absorption of the adsorbent is beneficial to the independent recycling of the desorbed acid gas.
Detailed Description
The invention provides a natural gas desulfurization and decarbonization agent which comprises the following components in parts by weight: 5-50 parts of aminosilane and 50-95 parts of organic solvent;
the structural formula of the aminosilane is
Said R is1is-NH2、NH2C2H4NH-、NH2C2H4NHC2H4NH-、-NH(CH2)3N(CH3)2、-N(R2)3Piperazinyl, methylpiperazinyl or cyclohexylamino; the R is2、R3And R4Independently is-H, -CH3、-C2H5、-OCH3、-OCH2CH3or-CH (OCH)3)2。
In the invention, the optimized parts by weight of the raw materials are 20-40 parts of aminosilane and 60-80 parts of organic solvent; more preferably, the aminosilane is 30 parts and the organic solvent is 70 parts.
In the present invention, the aminosilane is a liquid non-polymeric aminosilane.
In the present invention, the aminosilane is preferably
In the present invention, the organic solvent is preferably one or more of aliphatic alcohol, diethylene glycol dimethyl ether and sulfolane.
In the invention, the fatty alcohol comprises one or more of monohydric alcohol, dihydric alcohol and trihydric alcohol;
wherein, the molecular general formula of the monohydric alcohol is CnH2n+1OH，4≤n≤9；
The molecular general formula of the dihydric alcohol is CmH2m(OH)2，4≤m≤8；
The molecular general formula of the trihydric alcohol is CxH2x-1(OH)3X is more than or equal to 3 and less than or equal to 8; n, m and x are integers.
In the present invention, the organic solvent is preferably monool C8H17OH, Dibutanol C4H8(OH)2Monobasic butanol C4H9OH, ternary Butanol C4H7(OH)3Or monopentyl alcohol C5H11OH。
The invention also provides a using method of the natural gas desulfurization and decarbonization agent, which comprises the following steps:
will contain H2S and CO2The gas is introduced into a natural gas desulfurization and decarbonization agent for absorption to obtain purified gas.
In the invention, the absorption time is 30-45 min, preferably 35 min.
In the present invention, the absorption temperature is preferably room temperature.
In the invention, the natural gas desulfurization and decarbonization agent is used and then is analyzed to obtain the regenerated natural gas desulfurization and decarbonization agent, and the regenerated natural gas desulfurization and decarbonization agent can be used for carrying out the process again on the H-containing natural gas2S and CO2Is absorbed.
In the present invention, the temperature for the analysis is 40 to 70 ℃, preferably 50 to 60 ℃, and more preferably 55 ℃.
In the present invention, the time for the analysis is 1.5 to 3 hours, preferably 2 hours.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparing a natural gas desulfurization decarbonizer: and (3) uniformly mixing 30 parts of N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane and 70 parts of sec-octanol to obtain the natural gas desulfurization and decarbonization agent.
The desulfurization and decarburization rates were measured. H2And (S) determination: GB/T14678-93 air quality-determination of hydrogen sulfide, methyl mercaptan, methyl sulfide and dimethyl disulfide; CO 22And (3) determination: the method for testing carbon dioxide in air in GB/T18204.24-2000 public places comprises the following specific steps:
(1) 0.5g of natural gas (natural gas containing H)2S1500 ppmw (parts per million by mass) and CO21200ppmw, the same below) was added to 10g of zinc acetate-acetic acid solution with a concentration of 0.05486mol/L, an excess iodine solution was added, and after standing for 30min in the dark, titration was performed with 0.01mo1/L sodium thiosulfate solution to test H in natural gas2S content, denoted M0；
(2) Introducing 0.5g of natural gas into a 1L pressure vessel containing 150g of desulfurization and decarburization agent, and standing for 30 min; then using N2Blowing the gas treated by the desulfurization and decarbonization agent into a 1L pressure container (containing 10g of zinc acetate acetic acid solution with the concentration of 0.05486 mol/L), standing for 30min, adding excessive iodine solution, standing for 30min in a dark place, titrating with 0.01mo1/L sodium thiosulfate solution, and testing H in the desulfurized natural gas2The S content, denoted as M;
(3)CO2concentrated absorption solution: 2.8g of barium hydroxide and 0.16g of barium chloride are weighed out and dissolved in 800ml of water, 3ml of n-butanol are added, shaken up and diluted to 1000ml with water.
Oxalic acid standard solution: 0.5637g of oxalic acid solid is weighed, dissolved by water and diluted to 1000 ml;
(4) introducing 0.5g of natural gas into 50ml of CO2In the concentrated absorption liquid, after the absorption liquid is completely precipitated, titrating the content of the residual barium hydroxide by using an oxalic acid standard solution, and testing CO in the natural gas2Content, denoted as mo；
(5) Introducing 0.5g of natural gas into 150g of desulfurization and decarbonization agent, introducing 50ml of carbon dioxide concentrated absorption liquid, titrating the content of residual barium hydroxide by using an oxalic acid standard solution after the absorption liquid is completely precipitated, and testing the content of carbon dioxide in the decarbonized natural gas, wherein the content is recorded as m;
(6) calculating the desulfurization and decarburization rate E (%):
the results are shown in Table 1.
Comparative example 1
The desulfurization and decarburization rate of a 30% by mass aqueous solution of Methyldiethanolamine (MDEA) was measured by the same method as in example 1, and the results are shown in table 1.
Comparative example 2
The desulfurization and decarburization rate of an Ethanolamine (EA) aqueous solution with a mass fraction of 30% was measured by the same method as in example 1, and the results are shown in Table 1.
TABLE 1 desulfurization and decarburization rate of absorbent
As can be seen from Table 1, the aminosilane-based desulfurizing and decarbonizing agents disclosed in the present invention have a higher desulfurizing and decarbonizing rate than the alkanolamine-based desulfurizing and decarbonizing agents.
Example 2
30 parts of N-aminoethyl-3-aminopropylmethyldimethoxysilane (structural formula shown in the specification) and 70 parts of diethylene glycol dimethyl ether are uniformly mixed to obtain the desulfurization and decarburization agent. The desulfurization and decarburization rate was measured in the same manner as in example 1, and the results are shown in Table 2.
Example 3
30 parts of N-aminoethyl-3-aminopropylmethyldimethoxysilane and 70 parts of sec-octanol are uniformly mixed to obtain the desulfurization and decarburization agent. The desulfurization and decarburization rate was measured in the same manner as in example 1, and the results are shown in Table 2.
Example 4
30 parts of 3-dimethylaminopropyl (dimethoxy) methylsilane (structural formula shown below) and 70 parts of sec-octanol are uniformly mixed to obtain the desulfurization and decarburization agent. The desulfurization and decarburization rate was measured in the same manner as in example 1, and the results are shown in Table 2.
TABLE 2 desulfurization and decarburization rates of the absorbent
As can be seen from the analysis of the data in the table 2, the aminosilanes used in the examples 2 and 3 are the same, the solvents are different, the desulfurization and decarburization rate is better by using octanol as the solvent, but the general trend is not obvious in difference; the aminosilane used in example 4 was a tertiary amine type having no active hydrogen, and the desulfurization and decarburization rates were reduced due to the slower absorption reaction rate as compared with the aminosilane containing active hydrogen in example 3.
Example 5
40 parts of 3- (diethoxymethyl silyl) propylamine (with the structural formula shown below) and 60 parts of diethylene glycol dimethyl ether are uniformly mixed to obtain the desulfurization and decarburization agent. The desulfurization and decarburization rate was measured in the same manner as in example 1, and the results are shown in Table 3.
Example 6
And uniformly mixing 50 parts of 3- (diethoxymethylsilyl) propylamine, 40 parts of diethylene glycol dimethyl ether and 10 parts of isopropanol to obtain the desulfurization and decarburization agent. The desulfurization and decarburization rate was measured in the same manner as in example 1, and the results are shown in Table 3.
Example 7
60 parts of 3- (diethoxymethyl silyl) propylamine, 20 parts of sulfolane, 10 parts of isopropanol and 10 parts of diethylene glycol dimethyl ether are uniformly mixed to obtain the desulfurization and decarburization agent. The desulfurization and decarburization rate was measured in the same manner as in example 1, and the results are shown in Table 3.
TABLE 3 desulfurization and decarburization rate of absorbent
The table 3 shows that the natural gas desulfurization and decarbonization agent prepared by the invention has a remarkable desulfurization and decarbonization rate.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. The natural gas desulfurization and decarbonization agent is characterized by comprising the following components in parts by weight: 5-50 parts of aminosilane and 50-95 parts of organic solvent;
the structural formula of the aminosilane is
The R is1is-NH2、NH2C2H4NH-、NH2C2H4NHC2H4NH-、-NH(CH2)3N(CH3)2、-N(R2)2Piperazinyl, methylpiperazinyl or cyclohexylamino; the R is2、R3And R4Independently is-H, -CH3、-C2H5、-OCH3、-OCH2CH3or-CH (OCH)3)2。
2. The natural gas desulfurization and decarbonization agent of claim 1, wherein the aminosilane is a liquid non-polymeric aminosilane.
3. The natural gas desulfurization and decarbonization agent according to claim 1 or 2, wherein the organic solvent is one or more of aliphatic alcohol, diethylene glycol dimethyl ether and sulfolane.
4. The natural gas desulfurization and decarbonization agent according to claim 3, wherein the aliphatic alcohol comprises one or more of monohydric alcohol, dihydric alcohol and trihydric alcohol;
wherein, the molecular general formula of the monohydric alcohol is CnH2n+1OH，4≤n≤9；
The molecular general formula of the dihydric alcohol is CmH2m(OH)2，4≤m≤8；
The molecular formula of the trihydric alcohol is CxH2x-1(OH)3X is more than or equal to 3 and less than or equal to 8; n, m and x are integers.
5. The use method of the natural gas desulfurization and decarbonization agent is characterized by comprising the following steps:
will contain H2S and CO2The gas is introduced into a natural gas desulfurization and decarbonization agent for absorption to obtain purified gas.
6. The use method of the natural gas desulfurization and decarbonization agent is characterized in that the absorption time is 30-45 min.
7. The method of claim 5 or 6, wherein the natural gas desulfurization and decarbonization agent is used and then analyzed to obtain a regenerated natural gas desulfurization and decarbonization agent, and the regenerated natural gas desulfurization and decarbonization agent can be used to regenerate the H-containing components2S and CO2Is absorbed.
8. The use method of the natural gas desulfurization and decarbonization agent is characterized in that the desorption temperature is 40-70 ℃, and the desorption time is 1.5-3 h.
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