Renewable high efficient desulfurization process using a suspension bed
10471387 ยท 2019-11-12
Assignee
Inventors
Cpc classification
Y02P70/10
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
C10L2290/12
CHEMISTRY; METALLURGY
C10L2290/10
CHEMISTRY; METALLURGY
B01D53/80
PERFORMING OPERATIONS; TRANSPORTING
C10L2290/541
CHEMISTRY; METALLURGY
B01D1/289
PERFORMING OPERATIONS; TRANSPORTING
B01D53/96
PERFORMING OPERATIONS; TRANSPORTING
International classification
B01D53/96
PERFORMING OPERATIONS; TRANSPORTING
C10L3/10
CHEMISTRY; METALLURGY
B01D53/80
PERFORMING OPERATIONS; TRANSPORTING
Abstract
Provided is a renewable high efficient desulfurization process using a suspension bed, comprising mixing the desulfurization slurry with a hydrogen sulfide containing gas to obtain a first mixture, and passing the first mixture into a suspension bed reactor from bottom to top, with controlling the first mixture to have a dwell time of 5-60 minutes in the suspension bed reactor to allow they contact and react sufficiently with each other; and subjecting a second mixture obtained from the reaction to gas liquid separation to produce a rich solution and a purified gas, feeding the purified gas into a fixed bed reactor for carrying out a second desulfurization to obtain a second purified gas, subjecting the resulting rich solution to flash evaporation and then reacting with an oxygen-containing gas for carrying out regeneration. The process may reduce the sulfur content in the hydrogen sulfide containing gas from 2.4-140 g/Nm.sup.3 to 50 ppm or less by using a suspension bed, and further reduce the sulfur content to less than 10 ppm in conjunction with a fixed bed. The invention achieves high efficient desulfurization by combining the suspension bed with the fixed bed connected in series. The present invention has high regeneration efficiency, and the barren solution may be recycled for being used as the desulfurization slurry, without generating secondary pollution, which is very suitable for industrial promotion.
Claims
1. A renewable highly efficient desulfurization process using a suspension bed, comprising the following steps: (1), mixing a desulfurizer with water uniformly to prepare a desulfurization slurry; (2), mixing the desulfurization slurry with a hydrogen sulfide containing gas to obtain a first mixture, and passing the first mixture into a suspension bed reactor from bottom to top, with controlling the first mixture to have a dwell time of 5-60 minutes in the suspension bed reactor to allow the desulfurization slurry to contact and react sufficiently with the hydrogen sulfide containing gas; and (3), discharging a second mixture from the top of the suspension bed reactor, and subjecting the second mixture to gas liquid separation to produce a purified gas and a rich solution; (4), feeding the purified gas into a fixed bed reactor for carrying out a second desulfurization to obtain a second purified gas, wherein the fixed bed reactor comprises a desulfurizer selected from the group consisting of amorphous iron oxide hydroxide, iron oxide, iron hydroxide, copper oxide, zinc oxide, and any mixture thereof, and wherein the fixed bed reactor has a gas flow rate of from 1 to 20 m/s; (5), subjecting the rich solution to flash evaporation and then reacting with an oxygen-containing gas to realize regeneration to produce a barren solution which is then recycled to the Step (2) for being used as the desulfurization slurry.
2. The renewable highly efficient desulfurization process of claim 1, wherein, the desulfurization slurry has a desulfurizer concentration of 2-3 wt %.
3. The renewable highly efficient desulfurization process of claim 1, wherein, the desulfurization slurry has a desulfurizer concentration of 1-5 wt %.
4. The renewable highly efficient desulfurization process of claim 1, wherein, the hydrogen sulfide containing gas is selected from a group consisting of biogas, coke oven gas, oilfield associated gas, natural gas, petrochemical gas or any mixture thereof.
5. The renewable highly efficient desulfurization process of claim 1, further comprising: pre-treating the hydrogen sulfide containing gas to remove heavy components above C5 in prior to mixing the hydrogen sulfide containing gas with the desulfurization slurry in the Step (2).
6. The renewable highly efficient desulfurization process of claim 1, wherein the flash evaporation has a pressure drop of 0.1-0.4 MPa in the step (5).
7. The renewable highly efficient desulfurization process of claim 1, wherein the oxygen-containing gas has an actual introduction amount which is 5-15 times of a theoretical consumption amount thereof, and the regeneration lasts for a period of 30-60 minutes.
8. The renewable highly efficient desulfurization process of claim 1, wherein at least a part of the rich solution is replaced with fresh desulfurization slurry when the rich solution reaches a sulfur capacity of 300% or more; and wherein the replaced part of the rich solution is subjected to solid-liquid separation to produce solid sulfur and a liquid phase, wherein the solid sulfur is delivered out and the liquid phase is returned to an oxidation regeneration tank for being used as a recycling supplementary moisture.
9. The renewable highly efficient desulfurization process of claim 1, wherein, in step (1), the desulfurizer has a particle size of no greater than 20 m, and wherein, the desulfurizer is selected from a group consisting of amorphous iron oxide hydroxide, iron oxide, iron hydroxide or any mixture thereof.
10. The renewable highly efficient desulfurization process of claim 9, wherein, the desulfurization slurry has a desulfurizer concentration of 2-3 wt %.
11. The renewable highly efficient desulfurization process of claim 9, wherein, the desulfurization slurry has a desulfurizer concentration of 1-5 wt %.
12. The renewable highly efficient desulfurization process of claim 9, wherein, the hydrogen sulfide containing gas is selected from a group consisting of biogas, coke oven gas, oilfield associated gas, natural gas, petrochemical gas or any mixture thereof.
13. The renewable highly efficient desulfurization process of claim 9, further comprising pre-treating the hydrogen sulfide containing gas to remove heavy components above C5 in prior to mixing the hydrogen sulfide containing gas with the desulfurization slurry in the Step (2).
14. The renewable highly efficient desulfurization process of claim 9, wherein the flash evaporation has a pressure drop of 0.1-0.4 MPa in the step (5).
15. The renewable highly efficient desulfurization process of claim 9, wherein the oxygen-containing gas has an actual introduction amount which is 5-15 times of a theoretical consumption amount thereof, and the regeneration lasts for a period of 30-60 minutes.
16. The renewable highly efficient desulfurization process of claim 9, wherein at least a part of the rich solution is replaced with fresh desulfurization slurry when the rich solution reaches a sulfur capacity of 300% or more; and wherein the replaced part of the rich solution is subjected to solid-liquid separation to produce solid sulfur and a liquid phase, wherein the solid sulfur is delivered out and the liquid phase is returned to an oxidation regeneration tank for being used as a recycling supplementary moisture.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) The above and other features of the present invention or the technical solutions in the prior art will now be described in detail with reference to certain example embodiments thereof illustrated in the accompanying drawings. It should be understood that the embodiments and drawings are given hereinbelow by way of illustration only, and thus are not limitative of the present invention, and apparent modifications can be made by those skilled in the art without paying any creative work, and wherein:
(2)
(3) The reference numerals are as follows:
(4) 1coalescer; 2suspension bed reactor; 3gas liquid separation tank; 4flash evaporation tank; 5oxidation regeneration tank; 6fixed bed reactor; 7blower; 8aerator; 9aeration pump; 10venturi mixer; 11barren solution pump; 12saturated slurry pump; 13first sprinkler means; 14second sprinkler means; 15third sprinkler means; 16fourth sprinkler means.
DETAILED DESCRIPTION OF EMBODIMENTS
(5) The technical solution of the present invention will now be described in detail with reference to the accompanying drawings. Obviously, the described embodiments are exemplary embodiments of the invention, rather than all embodiments. Based on embodiments in the present invention, all other embodiments obtained by those skilled in the art without making creative work are within the scope of the present invention.
(6) In the description of the present invention, unless otherwise expressly stated and defined, the terms connected and connected should be broadly understood, for example, it may be a fixed connection, a detachable connection or an integral connection; it may be either directly connected or indirectly connected through an intermediate medium, or may be an internal communication between the two elements. It will be apparent to those skilled in the art that the specific meaning of the above terms in the present invention may be understood depending on the actual situation. In addition, the technical features described in different embodiments of the present invention described below may be recombined with each other as long as they do not form a conflict with each other.
(7) In the following embodiments, the desulfurization efficiency of the suspension bed=(total mass of hydrogen sulfide in a feed gasmass of hydrogen sulfide in the gas after the desulfurization with the suspension bed)/the total mass of the hydrogen sulfide in the feed gas; regeneration efficiency=mass of sulfur/(mass of the catalyst+mass of sulfur).
Embodiment 1
(8) The renewable high efficient desulfurization process using a suspension bed provided by the present embodiment comprises the following steps:
(9) (1) mixing magnetism ferric oxide having a particle size of 1-20 m with water uniformly to prepare a desulfurization slurry having a concentration of 1 wt %;
(10) (2) mixing a biogas having a H.sub.2S content of 71.2 g/Nm.sup.3 with the desulfurization slurry to obtain a first mixture, and passing the first mixture into a first suspension bed reactor having an empty tower gas velocity of 0.3 m/s from bottom to top, and controlling the first mixture to have a dwell time of 5-7 min in the first suspension bed reactor, then discharging a second mixture from the top of the first suspension bed reactor, and passing the second mixture into a second suspension bed reactor having an empty tower gas velocity of 0.3 m/s from the bottom thereof, and controlling the second mixture to have a dwell time of 5 minutes in the second suspension bed reactor, such that the biogas contacts and reacts sufficiently with desulfurization slurry in the two suspension bed reactors connected in series;
(11) (3) discharging a gas-solid-liquid three-phase mixture from the top of the second suspension bed reactor and subjecting the mixture to gas liquid separation to produce a rich solution and a purified gas, wherein the purified gas was determined to have a H.sub.2S content of 45 ppm;
(12) (4) feeding the purified gas into a fixed bed reactor filled with iron hydroxide as desulfurizer for carrying out a second desulfurization, with keeping a gas flow rate of 3 m/s in the fixed bed reactor, to obtain a second purified gas which was determined to have a H.sub.2S content of 8 ppm;
(13) (5) feeding the rich solution into a flash evaporation tank having a pressure drop of 0.2 MPa for undergoing flash evaporation to remove light hydrocarbon, and then feeding the rich solution into a regeneration tank for undergoing reaction with air for 50 minutes, wherein the introduction amount of air during the reaction is 10 times of a theoretical consumption amount thereof, to produce a barren solution, wherein the regeneration efficiency is 72%; and the barren solution is then recycled to the Step (2) for being used as the desulfurization slurry.
Embodiment 2
(14) The renewable high efficient desulfurization process using a suspension bed provided by the present embodiment comprises the following steps:
(15) (1) mixing the ferric hydroxide with a particle size of 5-15 m with water uniformly to prepare a desulfurization slurry having a concentration of 2 wt %;
(16) (2) mixing coke oven gas having a H.sub.2S content of 2.4 g/Nm.sup.3 with the desulfurization slurry to obtain a first mixture, and passing the first mixture into a suspension bed reactor with an empty tower gas velocity of 0.15 m/s from bottom to top, and controlling the first mixture to have a dwell time of 6-8 minutes in the suspension bed reactor to allow the coke oven gas contacts and reacts sufficiently with the desulfurization slurry;
(17) (3) discharging a gas-solid-liquid three-phase mixture from the top of the suspension bed reactor and subjecting the mixture to gas liquid separation to produce a rich solution and a purified gas, wherein the purified gas was determined to have a H.sub.2S content of 50 ppm;
(18) (4) feeding the purified gas into a fixed bed reactor filled with magnetic iron oxide as desulfurizer for carrying out a second desulfurization, with keeping a gas flow rate of 6 m/s in the fixed bed reactor, to obtain a second purified gas which was determined to have a H.sub.2S content of 3 ppm;
(19) (5) feeding the rich solution into a flash evaporation tank having a pressure drop of 0.15 MPa for undergoing flash evaporation to remove the light hydrocarbon, and then feeding the rich solution into a regeneration tank for undergoing reaction with air for 45 minutes to realize regeneration to produce a barren solution, wherein the introduction amount of air during the reaction is 12.5 times of a theoretical consumption amount thereof. It has been determined that the regeneration efficiency is 83%. The barren solution is then recycled to the Step (2) for being used as the desulfurization slurry.
Embodiment 3
(20) As shown in
(21) (1) mixing amorphous iron oxide hydroxide having a particle size of 5-20 m with water uniformly to prepare a desulfurization slurry having a concentration of 2.5 wt %;
(22) (2) feeding a natural gas having a H.sub.2S content of 140 g/Nm.sup.3 into a coalescer tank to remove heavy components above C5, and mixing the natural gas discharged from the coalescer tank with the desulfurization slurry to obtain a first mixture, and passing the first mixture into a suspension bed reactor having an empty tower gas velocity of 0.2 m/s from bottom to top, and controlling the first mixture to have a dwell time of 30-35 minutes in the suspension bed reactor such that the natural gas contacts and reacts sufficiently with the desulfurization slurry;
(23) (3) discharging a gas-solid-liquid three-phase mixture from the top of the suspension bed reactor, and subjecting the mixture to gas liquid separation to produce a rich solution and a purified gas, wherein the purified gas was determined to have a H.sub.2S content of 41 ppm;
(24) (4) feeding the purified gas into a fixed bed reactor filled with amorphous iron oxide hydroxide as desulfurizer for carrying out a second desulfurization, with keeping a gas flow rate of 1.8 m/s in the fixed bed reactor, to obtain a second purified gas which was determined to have a H.sub.2S content of 3 ppm;
(25) (5) feeding the rich solution into a flash evaporation tank having a pressure drop of 0.17 MPa for undergoing flash evaporation to remove light hydrocarbon, and then feeding the rich solution into a regeneration tank for undergoing reaction with air for 55 minutes, wherein the introduction amount of air during the reaction is 11 times of a theoretical consumption amount thereof, to produce a barren solution, wherein the regeneration efficiency is 78%; and the barren solution is then recycled to the Step (2) for being used as the desulfurization slurry; replacing half of the rich solution in the regeneration tank with fresh desulfurization slurry when the rich solution reaches a sulfur capacity of 300%, considered as saturated, and subjecting the replaced rich solution to solid-liquid separation to produce solid sulfur and a liquid phase, wherein the solid sulfur is delivered out and the liquid phase is returned to the oxidation regeneration tank for being used as a recycling supplementary moisture.
Embodiment 4
(26) As shown in
(27) (1) mixing amorphous iron oxide hydroxide having a particle size of 1-20 m with water uniformly to prepare a desulfurization slurry having a concentration of 3 wt %;
(28) (2) feeding an oilfield associated gas having a H.sub.2S content of 108 g/Nm.sup.3 into a coalescer tank to remove heavy components above C5, and mixing the oilfield associated gas discharged from the coalescer tank with the desulfurization slurry to obtain a first mixture, and passing the first mixture into a suspension bed reactor having an empty tower gas velocity of 0.05 m/s from bottom to top, and controlling the first mixture to have a dwell time of 20 minutes in the suspension bed reactor such that the oilfield associated gas contacts and reacts sufficiently with the desulfurization slurry;
(29) (3) discharging a gas-solid-liquid three-phase mixture from the top of the suspension bed reactor, and subjecting the mixture to gas liquid separation to produce a rich solution and a purified gas, wherein the purified gas was determined to have a H.sub.2S content of 43 ppm;
(30) (4) feeding the purified gas into a fixed bed reactor filled with amorphous iron oxide hydroxide as desulfurizer for carrying out a second desulfurization, with keeping a gas flow rate of 4 m/s in the fixed bed reactor, to obtain a second purified gas which was determined to have a H.sub.2S content of 5 ppm;
(31) (5) feeding the rich solution into a flash evaporation tank having a pressure drop of 0.23 MPa for undergoing flash evaporation to remove light hydrocarbon, and then feeding the rich solution into a regeneration tank for undergoing reaction with air for 50 minutes, wherein the introduction amount of air during the reaction is 15 times of a theoretical consumption amount thereof, to realize regeneration to produce a barren solution, wherein the regeneration efficiency is 66%; and the barren solution obtained by regeneration is then recycled to the Step (2) for being used as the desulfurization slurry; replacing all of the rich solution in the regeneration tank with fresh desulfurization slurry when the rich solution reaches a sulfur capacity of 300%, considered as saturated, and subjecting the replaced rich solution to solid-liquid separation to produce solid sulfur and a liquid phase, wherein the solid sulfur is delivered out and the liquid phase is returned to the oxidation regeneration tank for being used as a recycling supplementary moisture.
Embodiment 5
(32) As shown in
(33) (1) mixing amorphous iron oxide hydroxide having a particle size of 10-15 m with water uniformly to prepare a desulfurization slurry with a concentration of 5 wt %;
(34) (2) feeding a petrochemical gas having a H.sub.2S content of 35 g/Nm.sup.3 into a coalescer tank to remove heavy components above C5, and mixing the petrochemical gas discharged from the coalescer tank with the desulfurization slurry to obtain a first mixture, and passing the first mixture into a suspension bed reactor having an empty tower gas velocity of 0.3 m/s from bottom to top, and controlling the first mixture to have a dwell time of 40 minutes in the suspension bed reactor such that the petrochemical gas contacts and reacts sufficiently with the desulfurization slurry;
(35) (3) discharging a gas-solid-liquid three-phase mixture from the top of the suspension bed reactor, and subjecting the mixture to gas liquid separation to produce a rich solution and a purified gas, wherein the purified gas was determined to have a H.sub.2S content of 46 ppm;
(36) (4) feeding the purified gas into a fixed bed reactor filled with amorphous iron oxide hydroxide as desulfurizer for carrying out a second desulfurization, with keeping a gas flow rate of 5 m/s in the fixed bed reactor, to obtain a second purified gas which was determined to have a H.sub.2S content of 4 ppm;
(37) (5) feeding the rich solution into a flash evaporation tank having a pressure drop of 0.3 MPa for undergoing flash evaporation to remove light hydrocarbon, and then feeding the rich solution into a regeneration tank for undergoing reaction with air for 60 minutes, wherein the introduction amount of air during the reaction is 13 times of a theoretical consumption amount thereof, to produce a barren solution, wherein the regeneration efficiency is 81%; and the barren solution is then recycled to the Step (2) for being used as the desulfurization slurry; replacing all of the rich solution in the regeneration tank with fresh desulfurization slurry when the rich solution reaches a sulfur capacity of 300%, considered as saturated, and subjecting the replaced rich solution to solid-liquid separation to produce solid sulfur and a liquid phase, wherein the solid sulfur is delivered out and the liquid phase is returned to the oxidation regeneration tank for being used as a recycling supplementary moisture.
Embodiment 6
(38) As shown in
(39) (1) mixing amorphous iron oxide hydroxide having a particle size of 10-15 m with water uniformly to prepare a desulfurization slurry having a concentration of 1.5 wt %;
(40) (2) feeding a petrochemical gas having a H.sub.2S content of 123 g/Nm.sup.3 into a coalescer tank to remove heavy components above C5, and mixing the petrochemical gas discharged from the coalescer tank with the desulfurization slurry to obtain a first mixture, and passing the first mixture into a suspension bed reactor having an empty tower gas velocity of 0.1 m/s from bottom to top, and controlling the first mixture to have a dwell time of 10-15 minutes in the suspension bed reactor such that the petrochemical gas contacts and reacts sufficiently with the desulfurization slurry;
(41) (3) discharging a gas-solid-liquid three-phase mixture from the top of the suspension bed reactor, and subjecting the mixture to gas liquid separation to produce a rich solution and a purified gas, wherein the purified gas was determined to have a H.sub.2S content of 48 ppm;
(42) (4) feeding the purified gas into a fixed bed reactor filled with zinc oxide as desulfurizer for carrying out a second desulfurization, with keeping a gas flow rate of 10 m/s in the fixed bed reactor, to obtain a second purified gas which was determined to have a H.sub.2S content of 8 ppm;
(43) (5) feeding the rich solution into a flash evaporation tank having a pressure drop of 0.1 MPa for undergoing flash evaporation to remove light hydrocarbon, and then feeding the rich solution into a regeneration tank for undergoing reaction with air for 35 minutes, wherein the introduction amount of air during the reaction process is 8 times of a theoretical consumption amount thereof, to produce a barren solution, wherein the regeneration efficiency is 65%; and the barren solution is then recycled to the Step (2) for being used as the desulfurization slurry; replacing all of the rich solution in the regeneration tank with fresh desulfurization slurry when the rich solution reaches a sulfur capacity of 300%, considered as saturated, and subjecting the replaced rich solution to solid-liquid separation to produce solid sulfur and a liquid phase, wherein the solid sulfur is delivered out and the liquid phase is returned to the oxidation regeneration tank for being used as a recycling supplementary moisture.
Embodiment 7
(44) As shown in
(45) (1) mixing amorphous iron oxide hydroxide having a particle size of 1-10 m with water uniformly to prepare a desulfurization slurry having a concentration of 2.5 wt %;
(46) (2) feeding a petrochemical gas having a H.sub.2S content of 89 g/Nm.sup.3 into a coalescer tank to remove heavy components above C5, and mixing the petrochemical gas discharged from the coalescer tank with the desulfurization slurry to obtain a first mixture, and passing the first mixture into a suspension bed reactor having an empty tower gas velocity of 0.03 m/s from bottom to top, and controlling the first mixture to have a dwell time of 50-60 minutes in the suspension bed reactor such that the petrochemical gas contacts and reacts sufficiently with the desulfurization slurry;
(47) (3) discharging a gas-solid-liquid three-phase mixture from the top of the suspension bed reactor, and subjecting the mixture to gas liquid separation to produce a rich solution and a purified gas, wherein the purified gas was determined to have a H.sub.2S content of 45 ppm;
(48) (4) feeding the purified gas into a fixed bed reactor filled with copper oxide as desulfurizer for carrying out a second desulfurization, with keeping a gas flow rate of 20 m/s in the fixed bed reactor, to obtain a second purified gas which was determined to have a H.sub.2S content of 7.5 ppm;
(49) (5) feeding the rich solution into a flash evaporation tank having a pressure drop of 0.4 MPa for undergoing flash evaporation to remove light hydrocarbon, and then feeding the rich solution into a regeneration tank for undergoing reaction with air for 30-40 minutes, wherein the introduction amount of air during the reaction is 5 times of a theoretical consumption amount thereof, to produce a barren solution, wherein the regeneration efficiency is 80%; and the barren solution is then recycled to the Step (2) for being used as the desulfurization slurry; replacing all of the rich solution in the regeneration tank with fresh desulfurization slurry when the rich solution reaches a sulfur capacity of 300%, considered as saturated, and subjecting the replaced rich solution to solid-liquid separation to produce solid sulfur and a liquid phase, wherein the solid sulfur is delivered out and the liquid phase is returned to the oxidation regeneration tank for being used as a recycling supplementary moisture.
Embodiment 8
(50) The desulfurization process provided by the above embodiments 1-7 of the present invention is carried out by using an integrated system as shown in
(51) It is obvious that the above embodiments are given by way of illustration only, and thus are not limitative of the present invention. Those skilled in the art should understand, any equivalent alternatives derived on the basis of the present invention should be embraced within the protection scope of the present invention.