Process for selective removal of acid gases from fluid streams using a hybrid solvent mixture
10940432 ยท 2021-03-09
Assignee
Inventors
- John R. Dowdle (Lake Jackson, TX, US)
- Timothy D. Halnon (Lake Jackson, TX, US)
- Christophe R. Laroche (Lake Jackson, TX, US)
- Diego Ortiz Vega (Houston, TX, US)
- Linda L. Pirtle (Brazoria, TX, US)
- Gerardo PADILLA (Lake Jackson, TX, US)
Cpc classification
B01D53/1493
PERFORMING OPERATIONS; TRANSPORTING
B01D2252/2023
PERFORMING OPERATIONS; TRANSPORTING
B01D2252/504
PERFORMING OPERATIONS; TRANSPORTING
B01D2252/20489
PERFORMING OPERATIONS; TRANSPORTING
Y02C20/40
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
B01D2257/306
PERFORMING OPERATIONS; TRANSPORTING
B01D2257/408
PERFORMING OPERATIONS; TRANSPORTING
B01D53/96
PERFORMING OPERATIONS; TRANSPORTING
B01D2252/202
PERFORMING OPERATIONS; TRANSPORTING
International classification
Abstract
Disclosed is a process for regenerating a hybrid solvent used to remove contaminants from a fluid stream and to provide an improved yield of purified fluid. Said process comprises at least two purification units and at least one regeneration unit wherein regenerated lean hybrid solvent and condensed water from the regeneration unit is used to reclaim additional purified fluid in the second purification unit.
Claims
1. A process for treating a hydrocarbon fluid stream containing one or more acid gas comprising the steps of: i) absorbing one or more acid gas from the hydrocarbon fluid stream in a first purification unit by counter currently contacting the fluid stream with a lean hybrid solvent comprising a chemical solvent, a physical solvent, and water to produce a first purified hydrocarbon fluid stream and a first rich hybrid solvent containing hybrid solvent, hydrocarbons, and acid gas(es); ii) passing the first rich hybrid solvent to a separation unit to separate hydrocarbons from the first rich hybrid solvent providing a second hydrocarbon stream and a second rich hybrid solvent with a hydrocarbon content lower than the first rich hybrid solvent; iii) passing the second rich hybrid solvent to a regenerating unit to produce a gas stream containing acid gas(es) and water vapor which is condensed and a regenerated lean hybrid solvent; and iv) passing the second hydrocarbon stream to a second purification unit wherein the second hydrocarbon stream is counter currently contacted with the regenerated lean hybrid solvent and the condensed water from the regenerating unit to produce a second purified hydrocarbon stream and a third rich hybrid solvent.
2. The process of claim 1 further comprising the steps: v) combining the second rich hybrid solvent from the separation unit with the third rich hybrid solvent from the second purification unit; and vi) passing the combined rich solvents through the regenerating unit.
3. The process of claim 1 further comprising the steps of: ix) passing the second purified hydrocarbon stream to a compressor to provide a compressed purified hydrocarbon stream; and x) passing the compressed purified hydrocarbon stream through a cooler.
4. The process of claim 1 further comprising the step of: xi) combining the first purified hydrocarbon stream and the second purified hydrocarbon fluid stream.
5. The process of claim 1 wherein the fluid stream is derived from natural gas and is a gas, a liquid, or mixtures thereof.
6. The process of claim 1 wherein the physical solvent consists of dimethyl ether of polyethylene glycol; propylene carbonate; N-methyl-2-pyrrolidone; methanol; N-acetylmorpholine; N-formylmorpholine; 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone; methoxytriglycol; glycerol; sulfolane; ethylene glycol; or blends thereof.
7. The process of claim 1 wherein the chemical solvent consists of monoethanolamine, methylethanolamine, monoisopropanolamine, diisopropanolamine, 2-hydroxyethylpiperazine, piperazine, 1-methylpiperazine, 2-methylpiperazine, 2-(2-aminoethoxy) ethanol; 2-(2-tertiarybutylamino)propoxyethanol, 2-(2-tertiarybutylamino)ethoxyethanol, 2-(2-isopropylamino)propoxyethanol, tertiaryamylaminoethoxyethanol, (1-methyl-2-ethylpropylamino)ethoxyethanol; tris(2-hydroxyethyl)amine (triethanolamine, TEA); tris(2-hydroxypropyl)amine (triisopropanol); tributanolamine; bis(2-hydroxyethyl)methylamine (methyldiethanolamine, MDEA); 2-diethylaminoethanol (diethylethanolamine, DEEA); 2-dimethylaminoethanol (dimethylethanolamine, DMEA); 3-dimethylamino-1-propanol; 3-diethylamino-1-propanol; 2-diisopropylaminoethanol (DIEA); N,N-bis(2-hydroxypropyl)methylamine (methyldiisopropanolamine, MDIPA); N,N-bis(2-hydroxyethyl)piperazine (dihydroxyethylpiperazine, DiHEP)); diethanolamine (DEA); 2-(tert-butylamino)ethanol; 2-(tert-butylaminoethoxy)ethanol; 1-amino-2-methylpropan-2-ol; 2-amino-2-methyl-1-propanol (AMP), 2-(2-aminoethoxy)ethanol, and blends thereof.
8. The process of claim 1 wherein the lean hybrid solvent comprises 5 to 40 weight percent water based on the total weight of the hybrid solvent.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1)
(2)
(3)
DETAILED DESCRIPTION OF THE INVENTION
(4) The invention relates to treatment of fluids to remove acid gases, in which the fluid stream is contacted with a hybrid solvent which preferentially absorbs the acid gases. More particularly, the invention is concerned with the regeneration of a hybrid solvent of the type specified for reuse and maximizing the amount of purified fluid stream produced.
(5) Fluid streams treatable by the process of the present invention may be a gas, a liquid, or mixtures thereof, for example gases produced by a gasifier comprising hydrogen, carbon dioxide, and carbon monoxide; a syngas stream comprising hydrogen, carbon dioxide, and carbon monoxide; natural gas; refinery gas; hydrocarbon gases from shale pyrolysis; synthesis gas; and liquids such as liquefied petroleum gas (LPG) and natural gas liquids (NGL). For example, fluid streams derived from natural gas reservoirs, petroleum, or coal, comprise methane (CH.sub.3) and commonly exist in mixtures with other hydrocarbons, principally ethane (C.sub.2H.sub.6), propane (C.sub.3H.sub.8), butanes (C.sub.4H.sub.10), pentanes (C.sub.5H.sub.12), and to a lesser extent, heavier hydrocarbons. Such fluid streams comprise a variety of impurities such as hydrogen (H.sub.2), water (H.sub.2O), carbon monoxide (CO), nitrogen (N.sub.2), and acid gases, for example carbon dioxide (CO.sub.2), hydrogen sulfide (H.sub.2S), sulfur dioxide (SO.sub.2), carbon disulfide (CS.sub.2), ammonia (NH.sub.3), hydrogen cyanide (HCN), carbonyl sulfide (COS), and/or mercaptans. In one embodiment, the term contaminant refers generally to one or more of C.sub.2 or heavier hydrocarbons, impurities, acid gases, and mixtures thereof to be removed from a fluid stream.
(6) The term hybrid solvent, as used herein, shall mean a solution comprising a combined chemical solvent and physical solvent with some water, which solutions are capable of absorbing acid gases. Suitable hybrid solvents useful in the process of the present invention may remove one or more of the above listed contaminants from the fluid stream. Solvents may be non-selective, i.e., remove one or more heavier hydrocarbon/impurity/acid gas or selective, i.e., they may target specific heavier hydrocarbons/impurities/acid gas(es).
(7) Preferably, the chemical solvent is one or more amino compound. Suitable amino compounds may be selected from a primary amine, a secondary amine, a tertiary amine, or blends thereof. Alkanolamines are suitable, especially those having 1 to 4 and preferably 2 to 3 carbon atoms per alkanol radical, while dialkanolamines are particularly advantageous. Amino compounds useful in the process of the present invention include, but are not limited to, monoethanolamine, methylethanolamine, monoisopropanolamine, diisopropanolamine, 2-hydroxyethylpiperazine, piperazine, 1-methylpiperazine, 2-methylpiperazine, 2-(2-aminoethoxy) ethanol; 2-(2-tertiarybutylamino)propoxyethanol, 2-(2-tertiarybutylamino)ethoxyethanol, 2-(2-isopropylamino)propoxyethanol, tertiaryamylaminoethoxyethanol, (1-methyl-2-ethylpropylamino)ethoxyethanol; tris(2-hydroxyethyl)amine (triethanolamine, TEA); tris(2-hydroxypropyl)amine (triisopropanol); tributanolamine; bis(2-hydroxyethyl)methylamine (methyldiethanolamine, MDEA); 2-diethylaminoethanol (diethylethanolamine, DEEA); 2-dimethylaminoethanol (dimethylethanolamine, DMEA); 3-dimethylamino-1-propanol; 3-diethylamino-1-propanol; 2-diisopropylaminoethanol (DIEA); N,N-bis(2-hydroxypropyl)methylamine (methyldiisopropanolamine, MDIPA); N,N-bis(2-hydroxyethyl)piperazine (dihydroxyethylpiperazine, DiHEP)); diethanolamine (DEA); 2-(tert-butylamino)ethanol; 2-(tert-butylaminoethoxy)ethanol; 1-amino-2-methylpropan-2-ol; 2-amino-2-methyl-1-propanol (AMP), 2-(2-aminoethoxy)ethanol, and blends thereof.
(8) A hybrid solvent suitable for use in the present invention comprises a chemical solvent in an amount of equal to or less than 70 weight percent, preferably equal to or less than 60 weight percent, more preferably equal to or less than 50, and more preferably equal to or less than 40 weight percent weight percent based on the total weight of the hybrid solvent. Preferably the amount of the chemical solvent present in the hybrid solvent is an amount of equal to or greater than 5 weight percent, more preferably equal to or greater than 10 weight percent, more preferably equal to or greater than 20, and preferably equal to or greater than 30 weight percent based on the total weight of the hybrid solvent.
(9) Suitable physical solvents include, but are not limited to, one or more of dimethyl ether of polyethylene glycol (DMPEG), propylene carbonate (PC), N-methyl-2-pyrrolidone (NMP), methanol (MeOH), blends of N-acetylmorpholine and N-formylmorpholine, 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (DMTP), methoxytriglycol (MTG), glycerol, sulfolane, ethylene glycol, and blends thereof.
(10) DMPEG is a mixture of dimethyl ethers of polyethylene glycol (CH.sub.3O(C.sub.2H.sub.4O).sub.nCH.sub.3 (n is from 2 to 9) used in what is referred to as the SELEXOL process to physically absorb H.sub.2S, CO.sub.2, and mercaptans from gas streams, for example see U.S. Pat. No. 6,203,599 which is incorporated herein in its entirety. Solvents containing DMPEG are licensed and/or manufactured by several companies including Coastal Chemical Company (as COASTAL AGR) and Dow (SELEXOL). Other process suppliers such as Clariant GmbH of Germany offer similar solvents. Clariant solvents are a family of dialkyl ethers of polyethylene glycol under the GENOSORB. DMPEG can be used for selective H.sub.2S removal which requires stripping, vacuum stripping, or a reboiler.
(11) A hybrid solvent suitable for use in the present invention comprises a physical solvent in an amount of equal to or less than 70 weight percent, preferably equal to or less than 60 weight percent, more preferably equal to or less than 50, and more preferably equal to or less than 40 weight percent based on the total weight of the hybrid solvent. Preferably the amount of the physical solvent present in the hybrid solvent is an amount of equal to or greater than 5 weight percent, more preferably equal to or greater than 10 weight percent more preferably equal to or greater than 15 weight percent, and more preferably equal to or greater than 25 weight percent based on the total weight of the hybrid solvent.
(12) A hybrid solvent suitable for use in the present invention comprises a condensed stripping solvent, preferably water, that when heated the condensed stripping solvent vaporizes to become a condensable stripping gas, in the case for water it becomes steam. Preferably the amount of condensed stripping gas (in liquid form) is present in the solvent in an amount of equal to or less than 50 weight percent, preferably equal to or less than 40 weight percent, more preferably equal to or less than 30 weight percent based on the total weight of the hybrid solvent. Preferably the amount of condensed stripping gas (in liquid form) is present in the solvent in an amount of equal to or greater than 5 weight percent, more preferably equal to or greater than 15 weight percent and more preferably equal to or greater than 25 weight percent based on the total weight of the hybrid solvent.
(13) A conventional solvent process for removing contaminants from a fluid stream is shown in
(14)
(15) In many instances, the contact between the solvent and the contaminated fluid, such as a hydrocarbon fluid stream, occurs in unit 12 in counter-current fashion as shown in
(16) As used herein, the term lean with respect to a solvent shall mean that the concentration of contaminants in the solvent is sufficiently low such that mass transfer of contaminant from the fluid being treated to the solvent will occur when the solvent and contaminated fluid are contacted. In one embodiment, a lean solvent includes a regenerated hybrid solvent solution that has been treated to remove contaminant content from a rich hybrid solvent solution, optionally fresh solvent introduced to the system that has not yet been used for purification, and/or a combination of these. In another embodiment, a lean solvent includes a regenerated solvent that has been treated to remove contaminant content from a rich solvent, optionally fresh solvent introduced to the system that has not yet been used for purification, and/or a combination of these. Fresh solvent shall refer to a solvent that is being introduced into the treatment system 10 for the first time from a suitable source. Fresh solvent also is lean with respect to contaminants. The term rich with respect to a solvent shall refer to a solvent that has picked up contaminants relative to the lean solvent during the course of a purification treatment.
(17) After the rich solvent exits the first purification unit 12, it is desirable to regenerate the solvent so that the solvent can be recycled back to the first purification unit 12 for more cycle(s) of treatment. Accordingly, a first pathway 26 is used to convey the rich solvent to a separation unit, preferably a flash tank 28, where depressurization takes place, thereby desorbing a major part of the absorbed hydrocarbons 29. The rich solvent with lower hydrocarbon content is passed from the flash tank 28 via line 30 through a heat exchanger 31 and line 32 then introduced into the top of a regeneration column, preferably a stripper column 40 where the lean solvent is regenerated from the rich solvent. For purposes of illustration,
(18) As used herein, and with respect to a column, the terms upper and lower should be understood as relative to each other. For example, withdrawal or addition of a stream from an upper portion of a column means that the withdrawal or addition is at a higher position (relative to the ground when the column is in operation) than a stream withdrawn or added from a lower region of the same column. Viewed from another perspective, the term upper may thus refer to the upper half of a column, whereas the term lower may refer to the lower half of a column. Similarly, where the term middle is used, it is to be understood that a middle portion of the column is intermediate to an upper portion and a lower portion. However, where upper, middle, and lower are used to refer to a column, it should not be understood that such column is strictly divided into thirds by these terms.
(19) In other embodiments of the prior art and the present invention, the stripper column 40 may comprise as many vapor-liquid contacting sections as needed to provide lean solvent, for example as many as 1 to 20 sections or more (2 to 20 section not depicted in
(20) As used herein, with respect to vapor-liquid contacting sections, the term portion of a section should be understood to mean that there may be a location within the section wherein some part or fraction of the section is above that location and some part or fraction of the section is below that location.
(21) In other modes of practice of the prior art and the present invention, the first portion of the regeneration stage may include a plurality of stripper units with at least two sections and/or reboiler units in which corresponding regeneration action takes place. The multiple units may be the same or different. In addition to the stripper column 40, other kinds of regeneration equipment can be used to help regenerate lean solvent if desired.
(22) As shown in
(23) Stripped contaminants exit the top of the stripper column 40 via line 49 with the condensable stripper gas (for example steam) as an admixture of contaminants, steam and possibly solvent. The admixture is directed to a condenser 60. In condenser 60, solvent, condensed stripper gas (for example condensed water vapor), and other compounds that may leave the top the stripper column 40 together with stripped contaminants are condensed. The stripped contaminants are discharged from the condenser to line 61 for further downstream processing or disposal as desired. At least part of the condensed stripping gas, e.g., water vapor, and/or solvent and other compounds that may have condensed is returned via line 62 to the upper portion of the stripper column 40 at or above the same location of the rich feed at the return position 63 and is used to aid in stripping the contaminants from the solvent being regenerated.
(24) Solvent leaving the bottom of the stripper column through line 51 passes to a reboiler 50 which is connected back to the stripper column by return line 52 and reenters the stripper column at location 53. The solvent circulating through the reboiler 50 is heated to produce additional steam which is feed back into the stripper column 40. Solvent will have an extended residence time in these units 40 and 50 until a portion of the solvent exits reboiler 50 via line 54 through the heat exchanger 31 and back to the purification unit 12.
(25) The hot solvent leaving reboiler 50 via line 54 heats up the solvent being transported to the stripper column 40 via line 30 in the heat exchanger 31, while the relatively cooler solvent being conveyed to the stripper column 40 in line 31 cools the relatively hot solvent leaving reboiler 50 in line 54. An additional cooling unit 56 may be incorporated into line 55 to further cool the lean solvent prior to the solvent being introduced to the purification unit 12 via inlet 16.
(26) One of the objects of the process of the present invention is to improve the efficiency of the regeneration step, specifically the saving of energy required for regenerating the hybrid solvent. This is accomplished by reducing the stripping solvent, i.e., water, content recycled into the regeneration column, preferably a stripper column 40,
(27) In addition, the reduced proportion of water in the hybrid solvent reduces the strength of the chemical bond between the hybrid solvent and the acid gas, which lowers the resistance of the absorbed gases to stripping
(28) For the invention to make a significant effect on the energy consumption required for regeneration of a hybrid solvent, the hybrid solvent should not contain so much water that its removal from the regeneration zone does not substantially alter the thermodynamic and chemical conditions obtaining there. Some water/steam should, nevertheless, remain in the regenerator as this is necessary for the removal of the acid gases from the regenerator. Furthermore, sufficient water should be present in the hybrid solvent that a significant proportion of it can be withdrawn from the regenerator without the temperature at the bottom of the regenerator becoming unstable due to excessively low partial pressure of the remaining water; a remedy for this phenomenon is, however, proposed below.
(29) A second object of the process of the present invention is to maximize the amount of purified gas. This is accomplished by the use of a second purification unit 70. The desorbed hydrocarbon stream 29 from the flash tank 28 is fed into the lower end of the second purification unit 70. In one embodiment (not shown in the drawings) the hydrocarbon stream is subjected to one or more compression/cooling operations prior to entering the second purification unit. Lean regenerated hybrid solvent 73 enters the second purification unit 70 at an upper end via inlet 74. The water from condenser 60 is fed into the second purification unit 70 via line 71 and enters the second purification unit 70 at inlet 72, which is preferably lower on the column than the lean regenerated hybrid solvent inlet 74. Preferably the condensed water 71 and the regenerated absorbent solvent 73 are not mixed together prior to entering the second purification unit 70.
(30) The absorbed hydrocarbon stream moves through unit 70 in the opposite direction of the regenerated hybrid solvent and exits in more pure form from upper end via pathway 77 and may be kept separate from and/or combined with the purified stream 23 from the first purification unit 12. When the purified fluid is a gas, the purified gas might entrain vaporized solvent, water vapor, or the like. It may be desirable to separate the purified gas from such entrained components. Consequently, the purified gas may be directed to an optional condenser (not illustrated in the figure), where the vaporized solvent or water vapor exiting the unit 70 is condensed. After having absorbed contaminants from the fluid being treated, the resultant rich hybrid solvent exits the second purification unit 70 at a lower end via an outlet 76 and is combined with the rich hybrid solvent 30 from the flash tank 28 and is then fed to the stripper column 40 for regeneration.
(31) In one embodiment of the process of the present invention, the hydrocarbon stream 29 leaving the flash tank 28 is subjected to one or more compression/cooling operations. In one embodiment (not shown in the drawings) the hydrocarbon stream 29 leaving the flash tank 28 is passed through one or more compression unit (not shown in the drawings) followed by one or more cooler (not shown in the drawings) before entering the second purification unit 70.
(32) In another embodiment of the process of the present invention, the purified stream 77 leaving the second purification unit 70 is subjected to one or more compression/cooling operations. In one embodiment, as shown in
(33) The present invention provides for plant and process to treat a fluid stream which (1) is more energy efficient and/or cost effective by lowering the amount of energy required to produce a lean solvent stream from a rich solvent stream and (2) provides a higher yield of the purified fluid stream.
EXAMPLES
(34) Simulation of a Stripping Column with Condenser Feed Modification.
(35) Two different systems are simulated and compared. In Comparative Example A, a conventional gas treating process is modeled (e.g., as in
(36) The process conditions and composition for the feed gas is shown in Table 1.
(37) TABLE-US-00001 TABLE 1 CONDITIONS Flow Rate kmol/s 1.29 Temperature K 305 Pressure kPa 6920 COMPOSITION Water Mole fraction 0.0008 CO.sub.2 Mole fraction 0.0555 H.sub.2S Mole fraction 0.0393 Methane Mole fraction 0.8213 Ethane Mole fraction 0.0527 Propane Mole fraction 0.0208 Butane Mole fraction 0.0093 Methyl mercaptan ppmv 119 Ethyl mercaptan ppmv 85 Propyl mercaptan ppmv 27 n-Butyl mercaptan ppmv 3
(38) The process conditions and composition for the lean hybrid solvent is shown in Table 2. In Table 2, MDEA is methyldiethanolamine, MTG is methoxytriglycol, and Loading for a given acid gas species is defined as the ratio of the amount of moles of that species in solution to the amount of moles of alkanolamine in solution. MTG is methoxytriglycol.
(39) In Table 3, hydrocarbon loss and mercaptan removal are defined as the molar percentage of hydrocarbons or mercaptans, respectively, from the feed gas stream that are not recovered in the purified gas stream. In Comparative Example A, this difference is between purified gas stream 23 and the feed gas stream 21 in
(40) TABLE-US-00002 TABLE 2 CONDITIONS Flow Rate kmol/s 1.14 Temperature K 318 Pressure kPa 6950 COMPOSITION Water Mass fraction 0.2200 MDEA Mass fraction 0.4100 MTG Mass fraction 0.3700 CO.sub.2 Loading 0.0000 H.sub.2S Loading 0.0002
(41) In the cases of Comparative Example A and Example 1, the processes are designed for selectively removing sulfur, and therefore it is desired to minimize hydrocarbon losses and maximize CO.sub.2 slip while removing as much of the sulfur-containing compounds as possible. In the case of Comparative Example A, Product gas refers to purified gas stream 23 in
(42) As shown in Table 3, the simulation of the present invention, Example 1, performed significantly better than the traditional simulation, Comparative Example A. There is a 25% percent reduction in the amount of energy required by the reboiler to achieve the same lean loading, and an order of magnitude reduction in the amount of hydrocarbon lost.
(43) TABLE-US-00003 TABLE 3 Com. Ex. A Example 1 Total Hydrocarbon Loss mol % 1.1 0.1 Total Mercaptan Removal mol % 87 82 CO.sub.2 Slip mol % 40 45 CO.sub.2 Concentration in mol % 2.4 2.7 Product Gas H.sub.2S Concentration in ppmv 11 11 Product Gas Total Mercaptan ppmv 32 47 Concentration in Product Gas Reboiler Duty GJ/hr 45 35 Total Duty GJ/hr 87 68