CN113289458B - Application of amine compound in removing organic sulfide - Google Patents
Application of amine compound in removing organic sulfide Download PDFInfo
- Publication number
- CN113289458B CN113289458B CN202110640696.4A CN202110640696A CN113289458B CN 113289458 B CN113289458 B CN 113289458B CN 202110640696 A CN202110640696 A CN 202110640696A CN 113289458 B CN113289458 B CN 113289458B
- Authority
- CN
- China
- Prior art keywords
- amine compound
- gas
- absorption
- organic
- mixed
- 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
Links
Images
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
- B01D53/1493—Selection of liquid materials for use as absorbents
-
- 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
-
- 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
- B01D53/1468—Removing hydrogen sulfide
-
- 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
- B01D53/1487—Removing organic compounds
-
- 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
-
- 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
-
- 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
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/60—Additives
-
- 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
-
- 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
-
- 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
- B01D2257/306—Organic sulfur compounds, e.g. mercaptans
-
- 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
- B01D2257/308—Carbonoxysulfide COS
Abstract
The invention discloses an application of an amine compound in removing organic sulfides, wherein the amine compound is one or a mixture of benzylamine, benzylethanolamine and derivatives thereof, the amine compound can be directly mixed with water to prepare an aqueous solution with the mass fraction of 5-75% as an absorption solution, or can be mixed with organic ethanolamine firstly and then mixed with water to prepare an aqueous solution with the mass fraction of 5-75% as an absorption solution, and 0-3% of an inhibitor and 0-3% of a regulator are added simultaneously, and the sum of the contents of all components is 1. The absorption solution can simultaneously and efficiently reduce H in logistics such as natural gas, oilfield associated gas, refinery gas, blast furnace gas and the like2S and total sulfur content. Compared with the existing organic alcohol amine compound, the amine compound has higher organic sulfur dissolving performance and removal efficiency, and is beneficial to meeting the desulfurization requirement of feed gas with high organic sulfur content and low absorption pressure.
Description
Technical Field
The invention belongs to the technical field of gas desulfurization and purification, and particularly relates to application of an amine compound in removal of organic sulfides.
Background
The sulfide contained in natural gas, oil field associated gas, refinery gas, blast furnace gas, etc. includes hydrogen sulfide, COS and CS2And organic sulfides such as mercaptans, thioethers, and disulfides. H2The existence of S not only can corrode a conveying pipeline, but also seriously harms the health of a user; COS and mercaptan as main components of organic sulfur in natural gas may result in catalyst poisoning in downstream chemical process with natural gas as material and other poisoningCOS released to the atmosphere can form SO2Promoting photochemical reactions, which poses serious environmental problems. At the same time, these sulfides have an intolerable odor even at very low concentration levels. The natural gas must therefore be freed of the acid components contained, in particular the sulphides, to a specific value before it is piped. For example, newly issued 'Natural gas' standard GB 17820-2018 stipulates H in domestic natural gas2S≤6mg/Nm3Total sulfur is less than or equal to 20mg/Nm3H in natural gas of the second category2S≤20mg/Nm3Total sulfur is less than or equal to 100mg/Nm3。
Refinery gas is one of the products of oil refining equipment, and can be divided into catalytic dry gas and liquefied gas, coking dry gas and liquefied gas, catalytic cracking liquefied gas and the like according to the difference of oil refining processes. Since crude oil contains elemental sulfur, these gas phase products also contain sulfides in various forms, usually H2S and organic sulfur such as COS, mercaptan, thioether and the like. The refinery gas can be used as fuel of heating furnace of refinery process, and also can be used as raw material of downstream chemical process. SO is produced from the combustion of sulfur compounds in refinery gases in a furnace2And the discharge into the atmosphere causes serious air pollution. Sulfides in the refinery gas can also corrode equipment and pipelines, so that the service life of the equipment and the pipelines is shortened, and potential safety hazards are generated. When used as chemical raw materials, sulfides in refinery gas can also cause catalyst poisoning in downstream processes, shorten the operation period of process devices, increase extra production cost, and also pollute downstream products, thus causing the product quality to be not up to standard. The refinery-related gas must therefore also be freed of contained sulphides to a certain level before it can be further processed for use. Wherein the emission Standard of pollutants for oil refining industry GB31570-2015 specifies the SO of the process heating furnace for the refinery2Emission limit of 50mg/m3The total sulfur content in the commercial liquefied gas is definitely not more than 343mg/m as specified in GB 11174-20113The content of hydrogen sulfide is not more than 10mg/m3. In addition, blast furnace gas is an important fuel, and the contained sulfides such as hydrogen sulfide and COS also need to be effectively removed to strictly control the SO in the flue gas discharged from the combustion furnace2And (4) content.
Absorption processes using alkanolamines as solvents are effective for removing these acidic components, and the alkanolamines commonly used are Monoethanolamine (MEA), Diethanolamine (DEA), Methyl Monoethanolamine (MMEA), Diethylethanolamine (DEEA), Triethanolamine (TEA), Diisopropanolamine (DIPA), Diglycolamine (DGA) and N-Methyldiethanolamine (MDEA). Adopts the traditional alcohol amine solvent, and can generally remove H in the raw material gas as long as the device design is reasonable and the process conditions are proper2S and CO2The removal rate of the organic sulfur such as COS, mercaptan and the like is greatly different due to different properties of the solvent, the removal rate of the traditional alcohol amine solvent to the organic sulfur is low, and the removal rates of MEA and DEA with strong alkalinity to methyl mercaptan, ethyl mercaptan and propyl mercaptan are respectively only about 45-50%, 20-25% and 0-10%. In addition, due to H2S and CO2Is more acidic than organic sulfides such as COS and mercaptan, and contains a large amount of H2S and CO2Preferential dissolution of the components in the alcohol amine solvent will further reduce the solubility of the organic sulfur component. Therefore, the acidic petroleum and natural gas simultaneously contains high concentration of H2S and CO2And under the condition of higher concentration of organic sulfides such as COS, mercaptan and the like, the effective removal of high concentration H by using the traditional alcohol amine solvent is generally difficult to achieve2S and CO2While achieving the effective removal of the organic sulfide with higher content.
Although the refinery gas is H2S and CO2Is at a moderate level, but the concentration of organic sulfur such as mercaptans is very high, often H2S、CO2And acidic components such as COS and the like can be effectively removed through chemical absorption, while the content of organic sulfur such as mercaptan and the like which are mainly removed through physical dissolution is difficult to be effectively reduced only through an alcohol amine solvent. At present, aiming at the problem of high content of mercaptan in refinery liquefied gas, a combined process of amine washing and alkali washing is generally adopted by refineries to reduce the content of mercaptan in the liquefied gas within a target range, and H is removed by the amine washing through the process2S、CO2Introducing the liquefied gas after partial organic sulfur into the alkaline tower again, and allowing the alkaline solution to be in countercurrent contact with the liquefied gas, wherein mercaptan and NaOH are subjected to chemical reaction in the process of reacting with each otherIs extracted into alkali liquor, thus reducing the content of mercaptan in the liquefied gas and further reducing the total sulfur content of the liquefied gas. Compared with a pure amine washing process, the process has a remarkable effect on reducing the total sulfur content of the liquefied gas, but has a plurality of disadvantages, namely firstly, the discharge and treatment of the waste alkali, although the alkali liquor in the process can be subjected to in-situ treatment through solvent reverse extraction, the accumulation of sulfur-containing compounds in the alkali liquor can not be avoided, after a period of cyclic regeneration treatment, the efficiency of the regenerated alkali liquor for removing the mercaptan in the liquefied gas is remarkably reduced, the waste alkali liquor and the alkali residues are forced to be replaced, the discharged waste alkali liquor and the alkali residues emit foul odor due to the fact that the waste alkali liquor and the alkali residues contain thioether and other sulfides, and the environmental pollution can be caused by improper treatment due to the fact that the waste alkali liquor and the alkali residues are alkaline. In addition, the disulfide contained in the alkali liquor regeneration process can not be completely removed by the reverse extraction solvent, and when the alkali liquor is returned to the contact tower again to be contacted with the liquefied gas, the disulfide is reversely extracted by the liquefied gas, so that the total sulfur removal effect of the liquefied gas can not be effectively improved. The alkaline washing can only effectively remove the mercaptan organic sulfur, has no obvious effect on removing other organic sulfur and has excessively limited application range. The advantages of this process are further diminished as the types of organic sulfur components in the liquefied gas are complicated and the content rises. In addition, the combined amine and caustic wash process adds complexity to the process flow and capital, operating and maintenance costs.
The improvement of the selective desulfurization performance of the solvent is an effective way for solving the problem of desulfurization of natural gas, oilfield associated gas, refinery gas and blast furnace gas. In order to improve the removal efficiency of the alcohol amine solvent on organic sulfur, most workers improve the removal effect on the organic sulfur by adding a proper amount of auxiliary solvent into the solvent taking MDEA or DIPA as a main body, so as to further reduce the total sulfur content in the purified petroleum and natural gas to meet the related index requirements.
In patent CN 102051244A, considering the high content of organic sulfur such as COS in highly acidic petroleum and natural gas, in order to effectively remove the organic sulfur components such as COS, effective catalytic hydrolysis, chemical absorption and physical dissolution for CO removal are added in the solvent composition designS and active components of organic sulfides such as mercaptan. The high-efficiency purifying desulfurizer for the high-acidity petroleum and natural gas, which is composed of the active components, has good organic sulfur removal performance and can effectively remove high-concentration H2S and high-efficiency removal of high-content organic sulfide show obvious advantages in treatment of high-sulfur-content, particularly high-organic-sulfur-content petroleum and natural gas, however, the organic sulfide dissolving property and the removal efficiency still need to be further improved.
Patent CN102580473A discloses a novel polyamide-amine dendrimer with high desulfurization selectivity and an aqueous solution formed by mixing with alcohol amine as an absorbent, wherein the mass fraction of the polyamide-amine dendrimer is 1% -15%, and the mass fraction of the alcohol amine is 50% -10%. The absorbent has better H than the conventional alcohol amine solvent2S removal selectivity and higher organic sulfur removal rate.
Patent CN101507891B discloses a liquid composition for removing sulfides in gases, which is composed of an absorbent, an auxiliary agent and a defoaming agent; wherein the absorbent consists of a sterically hindered amine and an alkanolamine; the auxiliary agent is one of thiazole, fatty amine and phenols or a mixture thereof; the defoaming agent is siloxane, and the liquid composition can effectively remove organic and inorganic sulfur in gas at the same time.
However, in the above-mentioned methods, alkylol amine (N-methyldiethanolamine, triisopropanolamine) is used as a main solvent, and the removal efficiency of organic sulfur is improved on the basis of the original alkylol amine by preferably using a modifier such as hindered amine; in addition, the organic sulfur content of the treated raw material gas is not more than 1000mg/m3There is no effective method for the effective removal of higher organic sulfur content in the feed gas.
In the treatment of the desulfurization requirement of petroleum and natural gas with higher organic sulfur concentration, in order to maintain the H2While efficiently removing S, the total sulfur content of the feed gas mainly containing methyl mercaptan as organic sulfur is further reduced, and there is still a need for further development of compounds that specifically increase the removal rate of organic sulfur compounds such as methyl mercaptan.
Disclosure of Invention
The invention unexpectedly discovers an amine compound which can efficiently and selectively purify and remove hydrogen sulfide, COS and CS2Organic sulfides such as mercaptan, thioether and disulfide can effectively reduce H in natural gas, oilfield associated gas, refinery gas, blast furnace gas and other material flows aiming at the condition that the content of methyl mercaptan in the petroleum and natural gas is particularly high2S and total sulfur content.
The invention is realized by the following technical scheme:
the application of amine compound in removing organic sulfide is that the amine compound is a compound with the following structural formula and a derivative thereof:
in formula I:
R1is an ammonia or alcohol amine substituent;
R2is H or an oxygen-containing group substituent.
Preferably, the amine compound is one or a mixture of more of benzylamine, benzylethanolamine and derivatives thereof. The amine compound contains 1 amino group, a benzene ring and a methoxyl group or a hydroxyl group in a molecule, the amino group contains 1 or more than 1 hydrogen atom, the amine compound is dissolved in water, the melting point is not higher than 40 ℃, and the boiling point is not lower than 100 ℃.
Further preferably, the amine compound is one or a mixture of more of benzylamine, 4-methoxybenzylamine and N-benzylethanolamine.
Preferably, the amine compound and water are mixed to prepare an aqueous solution with the mass fraction of 5-75% as an absorption solution.
Preferably, the amine compound is mixed with organic alcohol amine, and then mixed with water to prepare an aqueous solution as an absorption solution, wherein the amine compound and the organic alcohol amine are mixed according to the ratio of (1-99): (99-1), mixing with water to prepare a water solution with the mass fraction of 5-75% as an absorption solution, and adding 0-3% of an inhibitor and 0-3% of a regulator.
Preferably, the organic alcohol amine comprises monoethanolamine, diethanolamine, diisopropanolamine, diglycol, N-methyldiethanolamine.
More preferably, the amine compound and diisopropanolamine or N-methyldiethanol are mixed according to the weight ratio of (10-90): (90-10) and preparing into an aqueous solution with the mass fraction of 15-50% for use.
Preferably, the inhibitor is polypropylene glycol ether, and the weight percentage of the inhibitor is 0.01-0.3%.
Preferably, the surface property regulator is polysiloxane, and the weight percentage of the surface property regulator is 0.01-0.3%.
For example, as a specific embodiment, the following composition (all mass fractions) is adopted as the specific components of the absorption solution: 15% of benzylamine, 0.3% of polypropylene glycol ether, 0.01% of polysiloxane and the balance of water, wherein the total content of all the components is 1;
as a specific embodiment, the specific components of the absorption solution adopt the following compositions (all in mass fraction): 50% of N-benzyl ethanolamine, 0.3% of polypropylene glycol ether, 0.01% of polysiloxane and the balance of water, wherein the sum of the contents of all the components is 1;
as a specific embodiment, the specific components of the absorption solution are the following components (all in mass fraction): 20% of 4-methoxybenzylamine, 30% of N-methyldiethanolamine, 0.01% of polypropylene glycol ether, 0.03% of polysiloxane and the balance of water;
as a specific embodiment, the specific components of the absorption solution are the following components (all in mass fraction): 20% of benzylamine, 10% of 4-methoxybenzylamine, 10% of N-benzylethanolamine, 10% of N-methyldiethanolamine, 0.3% of polypropylene glycol ether, 0.1% of polysiloxane and the balance of water, wherein the total content of the components is 1.
The amine compound is used for removing hydrogen sulfide, COS and CS in natural gas, oilfield associated gas, refinery gas and blast furnace gas material flow2The mercaptan, thioether and disulfide with 1-4 carbon atoms, natural gas, oilfield associated gas, refinery gas and blast furnace gas contain up to about 8 (mol)% H2S, about 3000mg (in terms of elemental sulfur)/Nm3Organic sulfur. When natural gas, oilfield associated gas, refinery gas, blast furnace gas and other material flows are processed, the processing load of the raw material gas can be higher, the absorption pressure can be lower, and H in the material flows can be ensured2On the premise that the purification effect of S and COS reaches related indexes, the total sulfur content in the purified gas is remarkably reduced by remarkably increasing the solubility of a desulfurization solvent to organic sulfides such as methyl mercaptan.
Compared with the prior art, the invention has the following advantages:
compared with the existing organic alcohol amine compounds, the amine compound has better organic sulfur reaction activity and stronger interaction between organic sulfur molecules due to the electronic effect of the benzene ring, and is beneficial to improving the organic sulfur dissolving property and the removal efficiency, thereby realizing the aim of stably reaching the standard of the total sulfur content of a purified gas product, meeting the process requirements of natural gas purification and refinery gas desulfurization, and being beneficial to meeting the requirements of raw gas desulfurization with high organic sulfur content and low absorption pressure. The amine compound is mixed with water or an aqueous solution of organic alcohol amine to prepare the absorption solution for removing sulfur, the total organic sulfur removal rate is 2-3 times of that of the existing organic alcohol amine compound, and the absorption solution has obvious technical advantages.
Drawings
FIG. 1 is a flow chart of an experimental scheme for determining the equilibrium solubility of methyl mercaptan in a desulfurization solvent component;
in the figure: 1-a methane gas cylinder; 2-acid gas cylinders; 3-constant temperature water bath; 4-stainless steel reaction kettle; 5-a magnetic stirrer; 6-pressure measurement; 7-temperature measurement and control; 8-needle type valve; 9-a mechanical stirrer;
FIG. 2 is a schematic view of an absorption purification process flow;
in the figure: 1-raw material gas; 2-purifying the gas; 3-flash evaporation gas; 4-acid gas; 5-rich liquid is discharged from the absorption tower; 6-rich liquid is discharged from the flash tank; 7-rich liquid is discharged from the heat exchanger; 8-discharging barren liquor from the regeneration tower; 9-discharging barren liquor from the heat exchanger; 10-discharging the lean solution from the cooler; 11-an absorption column; 12-rich liquid flash tank; 13-a regeneration column; 14-regeneration lean liquid cooler; 15-lean-rich liquor heat exchanger; 16-regeneration of the overhead condenser; 17-regenerator at the bottom of the regeneration column.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
The invention discloses an amine compound which can efficiently and selectively purify and remove organic sulfide, wherein the amine compound is exemplified by benzylamine, 4-methoxybenzylamine and N-benzylethanolamine.
The equilibrium solubility of methyl mercaptan in the desulfurization solvent components is tested, the experimental flow is shown in figure 1, the volume of an equilibrium kettle is 250mL, and the temperature control precision is +/-0.2 ℃. Before the experiment, nitrogen is used for pressure test, 50-100mL of the desulfurization solvent component to be detected is added into the balance reaction kettle, and the nitrogen in the kettle is fully replaced by methane after sealing. And (3) opening the constant-temperature water bath, adjusting the temperature to the temperature required by the experiment, filling certain partial pressure of methyl mercaptan after the temperature is raised to a set value, maintaining the total pressure of the system by methane, and opening gas-liquid dual-drive stirring. After the system reaches each balance point, respectively taking a trace sample to analyze the concentration of the methyl mercaptan in the gas phase and the liquid phase.
Benzylamine, the structural formula is:
the Henry coefficient of the dissolution of methyl mercaptan in the liquid phase at 25 ℃ was 19.21 kPa.L/mol, the Henry coefficient of the dissolution of methyl mercaptan in the liquid phase at 40 ℃ was 33.15 kPa.L/mol, and the Henry coefficient of the dissolution of methyl mercaptan in the liquid phase at 55 ℃ was 47.08 kPa.L/mol.
4-methoxybenzylamine, the structural formula is as follows:
the Henry coefficient of the dissolution of methyl mercaptan in the liquid phase at 25 ℃ is 19.78 kPa.L/mol, the Henry coefficient of the dissolution of methyl mercaptan in the liquid phase at 40 ℃ is 35.61 kPa.L/mol, and the Henry coefficient of the dissolution of methyl mercaptan in the liquid phase at 55 ℃ is 51.44 kPa.L/mol.
N-benzylethanolamine having a structural formula:
at 25 ℃ AThe Henry coefficient of the solution of mercaptan in the liquid phase was 20.46 kPa.L/mol, the Henry coefficient of the solution of methyl mercaptan in the liquid phase was 36.97 kPa.L/mol at 40 ℃ and the Henry coefficient of the solution of methyl mercaptan in the liquid phase was 53.49 kPa.L/mol at 55 ℃.
Preparing amine compounds into absorption solution, removing sulfur in raw material gas by adopting an absorption method, wherein the process flow is shown in figure 2, the raw material gas 1 is in reverse contact with absorption liquid in an absorption tower 11 to remove acidic components and then is discharged from the top of the tower, rich liquid 5 absorbing the acidic components is discharged from the bottom of the tower and enters a rich liquid flash tank 12 to be flashed to obtain dissolved hydrocarbon, the flash-flashed rich liquid 6 exchanges heat with regenerated lean liquid in a heat exchanger 15 and then enters a regeneration tower 13 to be desorbed and regenerated, acidic gas 4 is discharged from the top of the regeneration tower and then is sent to a sulfur recovery device to recover sulfur, the regenerated lean liquid is discharged from the bottom of the tower, and is cooled by a heat exchanger 15 and a cooler 14 and then returns to the absorption tower 11 to be recycled.
The raw material gas composition and the absorption solution composition are specifically adopted as follows:
example 1
The following raw material gases are adopted: total organic sulfur content 3010mg/Nm3(wherein COS 1000 mg/Nm)3And methyl mercaptan of 1500mg/Nm3Ethanethiol 500mg/Nm3)、H2The S content was 2.58% (mol).
The following composition (all mass fractions) of the absorption solution was used: 15 percent of benzylamine, 0.3 percent of polypropylene glycol ether, 0.01 percent of polysiloxane and the balance of water, wherein the total content of all the components is 1. The absorption temperature is 40 ℃, the absorption pressure is 101.325kPa, the feed gas flow is 60.0L/h, and the circulation volume of the absorption liquid is 0.40L/h. Purified gas H2S content 1mg/Nm3The total organic sulfur removal rate was 73.5%.
Example 2
The following raw material gases are adopted: total organosulfur content 2034mg/Nm3(wherein COS 558.0 mg/Nm)3Methyl mercaptan 1046.0mg/Nm3N-propanethiol 430mg/Nm3)，H2S4.95％(mol)。
The following composition (all mass fractions) of the absorption solution was used: 50% of N-benzyl ethanolamine, 0.3% of polypropylene glycol ether, 0.01% of polysiloxane and the balance of waterThe sum of the component contents is 1. The absorption temperature is 40 ℃, the absorption pressure is 101.325kPa, the feed gas flow is 60.0L/h, and the circulation volume of the absorption liquid is 0.30L/h. Purified gas H2S content<1mg/Nm3The total organic sulfur removal rate was 84.8%.
Example 3
The raw material gas comprises the following components: total organic sulfur content 3027mg/Nm3(wherein COS 515 mg/Nm)32010mg/Nm of methyl mercaptan3502mg/Nm of ethanethiol3)、H2The S content was 1.98% (mol).
The following composition (all mass fractions) of the absorption solution was used: 20 percent of 4-methoxybenzylamine, 30 percent of N-methyldiethanolamine, 0.01 percent of polypropylene glycol ether, 0.03 percent of polysiloxane and the balance of water, wherein the sum of the contents of all the components is 1. The absorption temperature is 25 ℃, the absorption pressure is 101.325kPa, the feed gas flow is 60.0L/h, and the circulation volume of the absorption liquid is 0.30L/h. Purified gas H2S content<1mg/Nm3The total organic sulfur removal rate was 78.3%.
Example 4
The following raw material gases are adopted: total organic sulfur content 3327mg/Nm3(wherein COS 715mg/Nm32010mg/Nm of methyl mercaptan3Ethanethiol 602mg/Nm3)、H2The S content was 1.05% (mol).
The following composition (all mass fractions) of the absorption solution was used: 20% of benzylamine, 10% of 4-methoxybenzylamine, 10% of N-benzylethanolamine, 10% of N-methyldiethanolamine, 0.3% of polypropylene glycol ether, 0.1% of polysiloxane and the balance of water, wherein the sum of the contents of the components is 1. The absorption temperature is 40 ℃, the absorption pressure is 101.325kPa, the feed gas flow is 60.0L/h, the absorption liquid circulation is 0.50L/h, and the total organic sulfur removal rate is 89.7 percent.
Comparative example
By using MDEA, the Henry coefficient of methyl mercaptan dissolved in the liquid phase at 25 ℃ is 51.2636 kPa.L/mol, the Henry coefficient of methyl mercaptan dissolved in the liquid phase at 40 ℃ is 85.4156 kPa.L/mol, and the Henry coefficient of methyl mercaptan dissolved in the liquid phase at 55 ℃ is 119.5676 kPa.L/mol.
The following raw material gases are adopted: total organic sulfur content 3027mg/Nm3(wherein COS 515 mg/Nm)32010mg/Nm of methyl mercaptan3502mg/Nm of ethanethiol3)、H2The S content was 2.15% (mol).
The following composition (all mass fractions) of the absorption solution was used: 50% of MDEA and 50% of water. The absorption temperature is 40 ℃, the absorption pressure is 101.325kPa, the feed gas flow is 60.0L/h, the absorption liquid circulation is 0.40L/h, and the total organic sulfur removal rate is 38.10 percent.
Compared with the existing organic alcohol amine compound, the amine compound has higher organic sulfur dissolving performance and removal efficiency, and is beneficial to meeting the requirements of desulfurization of feed gas with high organic sulfur content and low absorption pressure.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (7)
1. The application of the amine compound in removing organic sulfides is characterized in that the amine compound is 4-methoxybenzylamine or N-benzylethanolamine, and the amine compound and water are mixed to prepare an aqueous solution with the mass fraction of 5-75% to serve as an absorption solution, so that sulfides in feed gas are removed.
2. The use of the amine compound for removing organic sulfides according to claim 1, wherein the amine compound is first mixed with the organic alcohol amine, and then mixed with water to prepare an aqueous solution as an absorption solution;
the amine compound and organic alcohol amine are mixed according to the ratio of (1-99): (99-1), mixing with water to prepare a water solution with the mass fraction of 5-75% as an absorption solution, and adding 0-3% of an inhibitor and 0-3% of a regulator.
3. The use of an amine compound for removing organic sulfides according to claim 2, wherein the organic alcohol amine is one of monoethanolamine, diethanolamine, diisopropanolamine, diglycolamine, and N-methyldiethanolamine.
4. The use of the amine compound according to claim 3 for removing organic sulfides, wherein the amine compound is mixed with diisopropanolamine or N-methyldiethanolamine according to the ratio of (10-90): (90-10) and preparing into an aqueous solution with the mass fraction of 15-50% for use.
5. The use of the amine compound for removing organic sulfides according to claim 2, wherein the inhibitor is polypropylene glycol ether, and the weight percentage of the polypropylene glycol ether is 0.01 to 0.3 percent.
6. The use of the amine compound for removing organic sulfides according to claim 2, wherein the modifier is polysiloxane, and the weight percentage of the modifier is 0.01 to 0.3%.
7. The application of the amine compound in removing organic sulfides according to claim 1, wherein the amine compound is used for removing hydrogen sulfide, COS and CS from natural gas, oilfield associated gas, refinery gas and blast furnace gas streams2Thiols, thioethers, disulfides.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110640696.4A CN113289458B (en) | 2021-06-09 | 2021-06-09 | Application of amine compound in removing organic sulfide |
| PCT/CN2021/102913 WO2022257197A1 (en) | 2021-06-09 | 2021-06-29 | Application of amine compound in removing organic sulfides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110640696.4A CN113289458B (en) | 2021-06-09 | 2021-06-09 | Application of amine compound in removing organic sulfide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113289458A CN113289458A (en) | 2021-08-24 |
| CN113289458B true CN113289458B (en) | 2022-07-01 |
Family
ID=77327664
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110640696.4A Active CN113289458B (en) | 2021-06-09 | 2021-06-09 | Application of amine compound in removing organic sulfide |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN113289458B (en) |
| WO (1) | WO2022257197A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114699882A (en) * | 2022-03-11 | 2022-07-05 | 华东理工大学 | Ether amine compound for efficiently absorbing and removing organic sulfur compound and design method and application thereof |
| CN115999335A (en) * | 2023-03-25 | 2023-04-25 | 河北冀隅智能科技有限公司 | Flue gas desulfurizing agent and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5382417A (en) * | 1990-01-03 | 1995-01-17 | Herr Haase, Inc. | Process for removal of selected component gases from multi-component gas streams |
| US5910611A (en) * | 1987-04-09 | 1999-06-08 | Union Carbide Chemicals & Plastics Technology Corporation | Aqueous alkanolamines using an electrodialysis cell with an ion exchange membrane |
| US20070286783A1 (en) * | 2006-05-10 | 2007-12-13 | Pierre-Louis Carrette | Method of deacidizing a gaseous effluent with extraction of the products to be regenerated |
| US20190322948A1 (en) * | 2018-04-19 | 2019-10-24 | Nexgen Oilfield Chemicals, Llc | Methods and compositions for scavenging sulfides and carbon dioxide from petroleum and natural gas |
| CN111925848A (en) * | 2020-07-10 | 2020-11-13 | 中国石油集团工程股份有限公司 | Efficient carbonyl sulfide removal solvent and preparation method thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2161188A6 (en) * | 1971-06-08 | 1973-07-06 | Inst Francais Du Petrole | |
| JP2014073449A (en) * | 2012-10-04 | 2014-04-24 | Toagosei Co Ltd | Carbonyl sulfide absorbent and method of processing carbonyl sulfide |
| US20150367281A1 (en) * | 2013-08-29 | 2015-12-24 | Commonwealth Scientific And Industrial Research Organisation | Absorbent solution for absorption of acid gas and process for absorption of acid gas |
| WO2014194376A1 (en) * | 2013-08-29 | 2014-12-11 | Commonwealth Scientific And Industrial Research Organisation | Benzylamine, benzylamine derivatives and benzylamine mixtures for co2 removal from gas streams |
| FR3011746B1 (en) * | 2013-10-15 | 2016-09-30 | Ifp Energies Now | USE OF AN ABSORBENT SOLUTION IN A GAS DEACIDIFICATION PROCESS TO LIMIT CORROSION OF LOW-ALLOY STEEL EQUIPMENT |
| AU2015218491A1 (en) * | 2014-08-29 | 2016-03-17 | Commonwealth Scientific And Industrial Research Organisation | Absorbent solution for absorption of acid gas and process for absorption of acid gas |
| 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 |
| CN106540512A (en) * | 2015-09-18 | 2017-03-29 | 中国石油化工股份有限公司 | The absorbent of sulfide in a kind of selectively removing natural gas |
-
2021
- 2021-06-09 CN CN202110640696.4A patent/CN113289458B/en active Active
- 2021-06-29 WO PCT/CN2021/102913 patent/WO2022257197A1/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5910611A (en) * | 1987-04-09 | 1999-06-08 | Union Carbide Chemicals & Plastics Technology Corporation | Aqueous alkanolamines using an electrodialysis cell with an ion exchange membrane |
| US5382417A (en) * | 1990-01-03 | 1995-01-17 | Herr Haase, Inc. | Process for removal of selected component gases from multi-component gas streams |
| US20070286783A1 (en) * | 2006-05-10 | 2007-12-13 | Pierre-Louis Carrette | Method of deacidizing a gaseous effluent with extraction of the products to be regenerated |
| US20190322948A1 (en) * | 2018-04-19 | 2019-10-24 | Nexgen Oilfield Chemicals, Llc | Methods and compositions for scavenging sulfides and carbon dioxide from petroleum and natural gas |
| CN111925848A (en) * | 2020-07-10 | 2020-11-13 | 中国石油集团工程股份有限公司 | Efficient carbonyl sulfide removal solvent and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| XDS 溶剂常压吸收脱除高酸性石油天然气中的有机硫效果;章建华 等;《华东理工大学学报（自然科学版）》;20090630;357-362 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113289458A (en) | 2021-08-24 |
| WO2022257197A1 (en) | 2022-12-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113289458B (en) | Application of amine compound in removing organic sulfide | |
| CN1754947B (en) | Process and installation for the treatment of DSO | |
| CN101745289B (en) | Method for selectively removing H2S from gas mixture containing CO2 | |
| CN101993750A (en) | Method for refining liquefied petroleum gas | |
| CN102958877A (en) | Process for removing one or more sulfur compounds from stream | |
| CN101844035A (en) | High-efficient desulfurizing agent for removing hydrogen sulfide and organic mercaptan from mixed gas | |
| US10071339B2 (en) | Process for purifying gaseous mixtures containing acidic gases | |
| CN105695018B (en) | A kind of additive and its application method of liquid gas sweetening | |
| JPS62106987A (en) | Removal of sulfur from hydrocarbon | |
| CN108310915B (en) | Composite desulfurizing agent and method for deep desulfurization of sulfur-containing gas | |
| CN108355463B (en) | Desulfurization method and device for sulfur tail gas | |
| CN104789290B (en) | The method of liquefied petroleum gas deep desulfuration | |
| CN113318586B (en) | Application of amine compound in improvement of organic sulfur dissolution and absorption removal | |
| CN108467757A (en) | Reduce COS and CS2Method | |
| CN104403688A (en) | Deep desulfurization and refining combined technology for liquefied petroleum gas | |
| CN101676018A (en) | Method for selectively removing COS from acid gas flow | |
| CN110385022B (en) | Desulfurizing agent and application thereof, and method for light hydrocarbon desulfurization processing | |
| CN1775924A (en) | Liquefied gas desulfurizing and refining method | |
| CN110628476B (en) | Pretreatment method and purifying agent for refinery rich gas and desulfurization method for dry gas and/or liquefied gas | |
| CN102343204A (en) | Method for removing sulfides from acidic gas flow | |
| CN104371781A (en) | Desulfurization method and device of liquefied petroleum gas | |
| CN114699882A (en) | Ether amine compound for efficiently absorbing and removing organic sulfur compound and design method and application thereof | |
| CN110628475B (en) | Process for pretreating rich gas in refinery and process for desulfurizing dry gas and/or liquefied gas | |
| CN111770783B (en) | Improved impurity removal process | |
| CN116103067A (en) | Alkoxypropylamine compound and application thereof in organic sulfur absorption and removal |
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 |