CN114196445A - Method for desulfurizing sulfur-containing synthesis gas in megaton coal chemical engineering project - Google Patents
Method for desulfurizing sulfur-containing synthesis gas in megaton coal chemical engineering project Download PDFInfo
- Publication number
- CN114196445A CN114196445A CN202111298669.XA CN202111298669A CN114196445A CN 114196445 A CN114196445 A CN 114196445A CN 202111298669 A CN202111298669 A CN 202111298669A CN 114196445 A CN114196445 A CN 114196445A
- Authority
- CN
- China
- Prior art keywords
- sulfur
- synthesis gas
- desulfurization
- heated
- desulfurizing agent
- 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.)
- Pending
Links
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 133
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 122
- 239000011593 sulfur Substances 0.000 title claims abstract description 122
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 114
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 113
- 238000000034 method Methods 0.000 title claims abstract description 89
- 230000003009 desulfurizing effect Effects 0.000 title claims abstract description 48
- 239000003245 coal Substances 0.000 title claims abstract description 14
- 238000003889 chemical engineering Methods 0.000 title abstract description 5
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 146
- 230000023556 desulfurization Effects 0.000 claims abstract description 146
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 50
- 125000001741 organic sulfur group Chemical group 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000005864 Sulphur Substances 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 20
- 230000007062 hydrolysis Effects 0.000 claims description 17
- 238000006460 hydrolysis reaction Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 230000001502 supplementing effect Effects 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 6
- 239000007789 gas Substances 0.000 description 94
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 22
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 150000003568 thioethers Chemical class 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- -1 alkyl alcohol amines Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 230000000153 supplemental effect Effects 0.000 description 2
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/20—Purifying combustible gases containing carbon monoxide by treating with solids; Regenerating spent purifying masses
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/34—Purifying combustible gases containing carbon monoxide by catalytic conversion of impurities to more readily removable materials
Abstract
The present invention relates to a method for desulphurizing sulphur-containing synthesis gas in a megaton coal chemical project, wherein the method comprises: and based on the type of the sulfur-containing component and the content of the organic sulfur-containing component, heating the sulfur-containing synthesis gas to obtain heated synthesis gas, then sending the heated synthesis gas to a desulfurization reactor containing a desulfurizing agent and arranged in parallel, and removing sulfide to obtain the desulfurized synthesis gas. The method realizes the desulfurization precision required by megaton-level coal chemical engineering projects.
Description
Technical Field
The application belongs to the field of coal chemical industry, and particularly relates to a fine desulfurization method for removing sulfides in synthesis gas in megaton coal chemical engineering projects.
Background
At present, in the conversion and utilization processes of coal-to-oil, coal-to-synthesis gas/natural gas and the like, sulfides in feed gas need to be removed. For a million ton coal-to-liquids project, the fresh synthesis gas from the purification unit contains H2S and COS, C2H5Sulfides such as SH and the like can not only cause catalyst poisoning of Fischer-Tropsch synthesis but also cause corrosion of downstream equipment and environmental pollution if the sulfides are not subjected to high-precision desulfurization treatment. It is therefore necessary to remove the sulphide from the synthesis gas before it enters the fischer-tropsch synthesis reactor.
With respect to H2S and COS, C2H5Many treatment technologies are developed at home and abroad at present for removing sulfides such as SH, and the adopted desulfurization technologies comprise dry desulfurization and wet desulfurization. The wet desulfurization is to absorb sulfide in gas by using a liquid desulfurizer, and the sulfide-containing liquid desulfurizer is recycled after being decomposed or resolved to obtain sulfide. The existing wet desulphurization method mainly comprises an amine desulphurization method and the like, and the commonly used desulphurization agent is alkyl alcohol amines, such as monoethanolamine, diethanolamine, diglycolamine and the like. Wet desulfurization is generally used for gas H at normal and low temperatures2High S content, low requirement for desulfurization precision, low desulfurization temperature, high gas treatment capacity, and high content of H in gas to be treated2High S content, and the desulfurizing agent can be recycled. The dry desulfurization is carried out by taking metal oxide as active component and reacting with H2S and COS, C2H5The sulfide such as SH reacts to generate metal sulfide to achieve the aim of desulfurization, or active carbon is used as an adsorbent to adsorb H in gas phase2S and other sulfides are oxidized into elemental sulfur in the adsorption layer to achieve the aim of desulfurization. The dry desulfurization includes an iron method, an iron oxide method, a zinc oxide method, an activated carbon method, an analytical sieve method, an ion exchange method, and the like. With the continuous innovation of desulfurizer, the dry desulfurization technology is widely applied in the low-temperature and medium-high temperature environment at present, and is particularly suitable for low-sulfur gas and the rectification precisionHigh environment is required.
Although the wet desulphurization has wider application range and can adapt to the desulphurization requirement of higher load, the process flow is more complicated than that of dry desulphurization, and the desulphurization precision of the wet desulphurization is lower than that of the dry desulphurization. As for the current fine desulfurization technology, the desulfurization precision of the general fine desulfurization agent can reach that the total sulfur content after fine desulfurization is less than or equal to 0.05ppm, and even the H of the outlet gas2The S content is less than or equal to 0.005ppm, and simultaneously, effective gases CO + H in the crude synthesis gas2Can not be lost. For a million-ton coal-to-oil project, because fresh synthesis gas before entering a Fischer-Tropsch synthesis reactor has the characteristics of large flow, high pressure, high desulfurization precision requirement and the like, a fine desulfurization technology suitable for fine desulfurization at high airspeed and high pressure needs to be developed. The art has not heretofore developed technology that can be adapted for large scale desulfurization in megaton coal chemical projects.
Disclosure of Invention
The application aims to purify fresh synthesis gas (containing H) at the outlet of a device in megaton coal chemical engineering projects (including projects of coal-made natural gas, coal-made olefin, coal-made oil and the like)2S、COS、CS2、C2H5Sulfides such as SH (mercaptan) and the like) are desulfurized through a fine desulfurization process, so that the total sulfur content in the fresh synthesis gas is less than a certain value, and the intake requirement of a subsequent process can be met.
To achieve the above objects and additional other objects or benefits, the present application relates to a method for desulphurizing sulphur-containing synthesis gas in a megaton coal chemical project, wherein the method comprises:
(1) heating the sulfur-containing synthesis gas to 70-90 ℃ or 90-200 ℃ based on the sulfur-containing component type and the content of the organic sulfur-containing component to obtain the heated synthesis gas;
(2) and (3) sending the heated synthesis gas to desulfurization reactors which are arranged in parallel and contain a desulfurizing agent, and removing sulfide to obtain the desulfurized synthesis gas.
The inventor discovers, through research, the types of sulfur-containing components in the sulfur-containing synthesis gas and COS and CS2Thiol and the like areThe proportion of the organic sulfur to the total sulfur content of the sulfur-containing components can heat the sulfur-containing synthesis gas to different specific temperature ranges, thereby realizing the desulfurization precision meeting the requirements of the application. In addition, different amounts of desulfurization reactors are flexibly arranged in parallel in the desulfurization process according to the amount of sulfur-containing synthesis gas to be treated, so that the desulfurization efficiency is higher under a reasonable cost-benefit ratio, the desulfurized synthesis gas can meet the air inlet requirement of the Fischer-Tropsch synthesis process (the total sulfur content is less than or equal to 0.05ppm), the desulfurized synthesis gas does not contain oxygen, and meanwhile, the total pressure drop of the whole desulfurization process device is less than or equal to 0.03 MPa; thereby enabling megaton-level coal chemical projects to be continuously and efficiently carried out industrially.
Drawings
FIG. 1 shows a flow diagram of an exemplary method for low temperature fine desulfurization of a megaton coal-to-liquids project.
FIG. 2 illustrates a flow diagram of an exemplary method for high temperature fine desulfurization of a megaton coal-to-liquids project.
Detailed Description
The following exemplary embodiments are only for explaining the aspects of the present invention, and are not intended to limit the scope of protection of the present application in any way.
In the present application, unless otherwise indicated, the term "total sulfur content" refers to the total sulfur content in the synthesis gas to be subjected to desulfurization treatment, and for the purposes of the present application, refers to the sum of the contents of organic and inorganic sulfur.
In the present application, unless otherwise specified, the term "sulfur capacity" refers to the mass of sulfur adsorbed per unit mass of the desulfurizing agent, expressed by a percentage in terms of sulfur.
In one embodiment, the present application relates to a method for desulfurizing sulfur-containing syngas in a megaton coal chemical project, wherein the method comprises:
(1) heating the sulfur-containing synthesis gas to 70-90 ℃ or 90-200 ℃ based on the sulfur-containing component type and the content of the organic sulfur-containing component to obtain the heated synthesis gas;
(2) and (3) sending the heated synthesis gas to desulfurization reactors which are arranged in parallel and contain a desulfurizing agent, and removing sulfide to obtain the desulfurized synthesis gas.
In a preferred embodiment, the sour syngas is passed to a desulfurization heater and heated with a heating medium (e.g., steam). The desulfurization ability of the subsequent desulfurizing agent can be further increased by raising the temperature of the sulfur-containing synthesis gas to the above-specified range by heating.
In a preferred embodiment, the sulfur-containing syngas has a total sulfur content of 0.1 to 1 ppm.
In a preferred embodiment, the sulfur capacity of the desulfurizing agent is 5% or more.
In a preferred embodiment, the desulfurizing agent may be any desulfurizing agent known in the art, including but not limited to: desulfurizer such as JX-4B, JX-9E produced by Beijing environmental protection new trimerization material GmbH (the two desulfurizer can be used in the high temperature fine desulfurization method and the low temperature fine desulfurization method of the invention, and can be used singly or in combination). And calculating the initial loading of the desulfurizing agent according to the airspeed, and calculating the loading according to the total sulfur capacity of the desulfurizing agent under the high sulfide concentration under the extreme working condition.
In a preferred embodiment, the desulfurization efficiency of the desulfurization agent is > 95% with respect to the amount of heated syngas.
In exemplary embodiments of the present application, the composition of the sulfur-containing component of the sulfur-containing syngas and H2S, COS, and the ratio of the sulfur content of organic sulfur such as mercaptan to the total sulfur content of sulfur-containing components, in order to achieve the desulfurization accuracy required by the present application, the sulfur-containing synthesis gas can be heated to different temperature ranges, and the corresponding desulfurization methods are referred to as a high-temperature fine desulfurization method and a low-temperature fine desulfurization method, respectively.
Low-temperature fine desulfurization method
In a preferred embodiment, the sulfur-containing component of the sulfur-containing syngas is predominantly H2Sulfides such as S and COS, and COS and CS2And the RSH fraction relative to the total sulphur content is low,for example not exceeding 1/3, the sulfur-containing synthesis gas is heated to 70-90 ℃, thereby carrying out fine desulfurization treatment on the sulfur-containing synthesis gas by using a low-temperature fine desulfurization method.
In a further preferred embodiment, the sour syngas is passed to a desulphation heater and heated with steam to a temperature in the range 70 ℃ to 90 ℃. More preferably, the sulfur-containing synthesis gas with the temperature of 30-50 ℃ enters a desulfurization heater.
In a preferred embodiment, in the sulfur-containing syngas, H is2The molar ratio of S to COS is 2-4.
In an exemplary embodiment, the heated syngas is sent to a desulfurization reactor containing a desulfurizing agent arranged in parallel to remove H2S and COS.
In a preferred embodiment, the heated synthesis gas is supplemented with steam before being sent to a desulfurization reactor containing a desulfurizing agent arranged in parallel. At this time, the purpose of supplementing the water vapor is to hydrolyze organic sulfur (e.g., COS); in the presence of water, COS can be hydrolyzed to CO2And H2S, then removing H by a desulfurizing agent2And S, achieving the purification purpose. In a further preferred embodiment, the mass flow rate of the supplemented water vapor is greater than the amount of organic sulfur (e.g., COS) in the syngas and is 3 to 6 times the content of the organic sulfur (e.g., COS).
Or, in another preferred embodiment, the temperature of the heated synthesis gas is further increased to 90-120 ℃ before the heated synthesis gas is sent to the desulfurization reactors containing the desulfurizing agent, which are arranged in parallel.
In a further preferred embodiment, in the desulfurization reactor, a hydrolysis catalyst and a desulfurizing agent are disposed in series. More preferably, the upper half section of the desulfurization reactor is filled with a hydrolysis catalyst (for catalyzing the hydrolysis of COS to H2S and CO2Thereby removing COS; e.g., JX-6B, etc.), a desulfurizing agent (for removing H) is charged in the lower half of the desulfurization reactor2S)。
In a further preferred embodiment, the hydrolysis catalyst and the desulfurizer which are arranged in series satisfy high-precision desulfurization effects at high space velocity (less than or equal to 7000/h) and high pressure (3.0-4.5MPaG), the pressure loss of the desulfurizer per 10 m is less than or equal to 4Kpa, and the total sulfur content of the purified synthesis gas obtained by desulfurization is less than or equal to 0.05 ppm.
The process selects high-quality desulfurizer, and the sulfur capacity of the selected desulfurizer is more than or equal to 5%.
In a further preferred embodiment, the desulphurised synthesis gas is passed to a downstream fischer-tropsch synthesis unit and/or catalyst reduction unit.
The low-temperature fine desulfurization method has the following characteristics and advantages:
(1) for which the sulfur-containing component is predominantly H2The sulfur-containing synthesis gas of S + COS adopts a low-temperature fine desulfurization method to solve the fine desulfurization of synthesis feed gas with very low sulfide content at the inlet, high space velocity and high desulfurization fine requirement.
(2) In the low-temperature fine desulfurization method, the hydrolysis catalyst and the desulfurizer are connected in series in the desulfurization reactors arranged in parallel, so that the high-precision desulfurization effect (on H) under high airspeed and high pressure can be met2The S and the COS have good removal efficiency); under normal working conditions, the total sulfur content of the obtained synthesis gas is less than or equal to 0.05ppm by desulfurization treatment on the synthesis gas with the total sulfur content of 0.1-1 ppm; under abnormal working conditions (such as the sulfur content of the synthesis gas sent to the fine desulfurization device by an upstream device exceeds the value in normal operation) and short desulfurization treatment time (within 24 hours), aiming at the sulfur-containing synthesis gas with the total sulfur content of 1-2 ppm, water vapor is supplemented or the temperature of the synthesis gas is further increased before desulfurization, so that the total sulfur content of the synthesis gas obtained after desulfurization can be guaranteed to be less than or equal to 0.05 ppm.
(3) The low-temperature fine desulfurization method has simple flow, can control the equipment pressure drop of the desulfurization reactor through the filling mode of the desulfurizer, the airspeed of the reactor and the like, enables the total pressure of the device to drop by less than or equal to 0.03MPa, and reduces energy loss.
High-temperature fine desulfurization method
In a preferred embodiment, the sulfur-containing component of the sulfur-containing syngasIs H2S、COS、CS2And RSH (mercaptan), etc., and COS, CS2And when the ratio of RSH relative to the total sulfur content is high, such as exceeding 1/3, heating the sulfur-containing synthesis gas to 90-200 ℃, thereby carrying out fine desulfurization treatment on the sulfur-containing synthesis gas by using a high-temperature fine desulfurization method.
The inventor finds that the organic sulfur is decomposed and absorbed less effectively at 30-90 ℃ than at 90-200 ℃, so that the sulfur-containing component of the sulfur-containing synthesis gas used as the raw material gas of the desulfurization process is mainly H2S、COS、CS2And when the ratio of the total sulfur content of the organic sulfur is more than 1/3, the high-temperature fine desulfurization method is more suitable to be selected.
In a further preferred embodiment, the total sulfur content of the sulfur-containing syngas is 0.1 to 1 ppm. Further preferably, the sulfur-containing synthesis gas is fed into a desulfurization heater, and the sulfur-containing synthesis gas is heated to 90 ℃ to 200 ℃ with steam. More preferably, the sulfur-containing synthesis gas with the temperature of 30-50 ℃ enters a desulfurization heater.
In an exemplary embodiment, the heated syngas is sent to a desulfurization reactor containing a desulfurizing agent arranged in parallel to remove H2S、COS、CS2And sulfides such as mercaptans.
In a preferred embodiment, in the sulfur-containing syngas, H is2The molar ratio of S/organic sulfur is 1-2.
In a preferred embodiment, the heated synthesis gas is supplemented with steam before being sent to a desulfurization reactor containing a desulfurizing agent arranged in parallel. At this time, the purpose of supplementing the water vapor is to hydrolyze organic sulfur (e.g., COS); in the presence of water, COS can be hydrolyzed to CO2And H2S, then removing H by a desulfurizing agent2And S, achieving the purification purpose. In a further preferred embodiment, the mass flow rate of the supplemented steam is greater than the amount of organic sulfur in the syngas and is 3 to 6 times the organic sulfur content.
In a further preferred embodiment, in the desulfurization reactor, water is arranged in seriesA decomposition catalyst and a desulfurizing agent. More preferably, the upper half section of the desulfurization reactor is filled with a hydrolysis catalyst (for catalyzing the hydrolysis of COS to H2S and CO2Thereby removing COS; such as JX-6B, etc.), a desulfurizing agent (for removing H) is filled in the lower half section of the desulfurization reactor2S、CS2And-thiols).
In a further preferred embodiment, the hydrolysis catalyst and the desulfurizer which are arranged in series satisfy high-precision desulfurization effects at high temperature (90-200 ℃), high space velocity (7000/h or less) and high pressure (3.0-4.5MPaG), the pressure loss of the desulfurizer per 10 m needs to satisfy 4Kpa or less, and the total sulfur content of the purified synthesis gas obtained by desulfurization is 0.05ppm or less.
In a further preferred embodiment, the sulfur capacity of the desulfurizing agent is more than or equal to 5 percent, so that the desulfurizing agent can treat COS and CS2And organic sulfur such as mercaptan shows good removal efficiency.
In a further preferred embodiment, the desulphurised synthesis gas (also referred to as "clean gas" or "cleaned synthesis gas") is sent to a downstream fischer-tropsch synthesis unit and/or catalyst reduction unit.
The technical scheme of the high-temperature fine desulfurization method has the following characteristics and advantages:
(1) for which the sulfur-containing component is predominantly H2S、COS、CS2And sulfur-containing synthesis gas of mercaptan, and the fine desulfurization of synthesis feed gas with low inlet sulfide content, high organic sulfur ratio (relative to the total sulfur content), high space velocity and high desulfurization fine requirement can be realized by adopting a high-temperature fine desulfurization method.
(2) In the high-temperature fine desulfurization method, the hydrolysis catalyst and the desulfurizer are connected in series in the desulfurization reactors which are arranged in parallel, so that the high-precision desulfurization effect (good removal efficiency on organic sulfur such as COS, CS2 and mercaptan) under high temperature, high space velocity and high pressure can be met; under normal working conditions, the total sulfur content of the obtained synthesis gas is less than or equal to 0.05ppm by desulfurization treatment on the synthesis gas with the total sulfur content of 0.1-1 ppm; under abnormal working conditions and in short-time (within 24 hours) desulfurization treatment, aiming at the sulfur-containing synthesis gas with the total sulfur content as high as 1-2 ppm, the total sulfur content of the synthesis gas obtained after desulfurization can be ensured to be less than or equal to 0.05ppm by increasing the removal temperature of the sulfur-containing synthesis gas, increasing the sulfur capacity of a desulfurizing agent, accelerating the desulfurization reaction rate, supplementing water vapor before desulfurization and the like.
(3) The high-temperature fine desulfurization method has simple flow, can control the equipment pressure drop of the fine desulfurization reactor through the filling mode of the desulfurizer, the airspeed of the reactor and the like, so that the total pressure drop of the device is less than or equal to 0.03MPa, and the energy loss is reduced.
In the present application, based on the kind of sulphur-containing components in the sulphur-containing synthesis gas and the COS, CS2And the proportion of the organic sulfur such as mercaptan to the total sulfur content of the sulfur-containing components can be respectively heated to different specific temperature ranges for desulfurization treatment, so that the desulfurization precision meeting the requirements of the application is realized. In addition, the desulfurization reactors with corresponding amount are flexibly arranged in parallel according to needs in the desulfurization process, so that the desulfurization efficiency is higher under a reasonable cost-benefit ratio, and the desulfurized synthesis gas can meet the air inlet requirement of the Fischer-Tropsch synthesis process, so that megaton-level coal chemical industry, such as coal-to-oil projects, can be continuously and efficiently carried out industrially.
In the present application, the amount of gas treated by the desulfurization method shown in fig. 1 and 2 is 200 ten thousand tons per year of syngas of coal-to-oil; if the project is a project of 100 ten thousand per year coal-to-oil and 400 ten thousand per year coal-to-oil, the fine desulfurization reactors arranged in parallel only need to be increased or decreased in proportion, so that the desulfurization method related to the invention has more flexible and simpler process flow and can be adjusted at any time according to the industrial production requirement.
Exemplary aspects of the present invention may be illustrated by the following numbered paragraphs, but the scope of the present invention is not limited thereto:
1. a method for desulphurizing sulphur-containing synthesis gas in a megaton coal chemical project, wherein the method comprises:
(1) heating the sulfur-containing synthesis gas to 70-90 ℃ or 90-200 ℃ based on the sulfur-containing component type and the content of the organic sulfur-containing component to obtain the heated synthesis gas;
(2) and (3) sending the heated synthesis gas to desulfurization reactors which are arranged in parallel and contain a desulfurizing agent, and removing sulfide to obtain the desulfurized synthesis gas.
2. The method of paragraph 1 wherein the sulfur containing syngas is passed into a desulfurization heater and the sulfur containing syngas is heated with a heating medium.
3. The method of paragraph 1 or 2, wherein the total sulfur content of the sulfur-containing syngas is 0.1 to 1 ppm.
4. The method of any of paragraphs 1-3, wherein the sulfur capacity of the desulfurizing agent is greater than or equal to 5%.
5. The method of any of paragraphs 1-4, wherein the desulfurizing agent is at least one of a JX-4B desulfurizing agent and a JX-9E desulfurizing agent.
6. The method of any of paragraphs 1-5, wherein the desulfurization efficiency of the desulfurization agent is > 95% relative to the amount of gas of the heated syngas.
7. The method of any of paragraphs 1-6, wherein the sulfur-containing component of the sulfur-containing syngas is predominantly H2S and COS, CS2And the ratio of RSH to total sulfur content does not exceed 1/3, heating the sulfur-containing synthesis gas to 70-90 ℃.
8. The method of paragraph 7, wherein the sulfur-containing syngas is passed into a desulfurization heater, which heats the sulfur-containing syngas to 70 ℃ to 90 ℃ with steam.
9. The method of paragraph 8, wherein the sulfur-containing syngas at a temperature of 30-50 ℃ is passed into the desulfurization heater.
10. The method of any of paragraphs 7-9, wherein, in the sour syngas, H2The molar ratio of S to COS is 2-4.
11. The method of any of paragraphs 7-10, wherein the heated syngas is supplemented with steam before being sent to a desulfurization reactor containing a desulfurizing agent arranged in parallel.
12. The method of paragraph 11, wherein the mass flow of the supplemental steam is greater than the amount of organic sulfur in the syngas and is 3-6 times the organic sulfur content.
13. The method of any of paragraphs 7-10, wherein the heated syngas is further increased in temperature to 90-120 ℃ before being sent to a desulfurization reactor containing a desulfurizing agent arranged in parallel.
14. The method of any of paragraphs 1-6, wherein the sulfur-containing component of the sulfur-containing syngas is predominantly H2S、COS、CS2And RSH, and COS, CS2And RSH in excess of 1/3 with respect to total sulfur content, heating the sulfur-containing syngas to 90 ℃ to 200 ℃.
15. The method of paragraph 14 wherein the sulfur containing syngas is passed into a desulfurization heater and the sulfur containing syngas is heated with steam to a temperature of 90 ℃ to 200 ℃.
16. The method of paragraph 15, wherein the sulfur-containing syngas at a temperature of 30-50 ℃ is passed into the desulfurization heater.
17. The method of any of paragraphs 14-16, wherein, in the sour syngas, H2The molar ratio of S to organic sulfur is 1-2.
18. The method of any of paragraphs 14-17, wherein the heated syngas is supplemented with steam before being sent to a desulfurization reactor containing a desulfurizing agent arranged in parallel.
19. The method of paragraph 18, wherein the mass flow of the supplemental steam is greater than the amount of organic sulfur in the syngas and is 3-6 times the organic sulfur content.
20. The method of any of paragraphs 1-19, wherein in the desulfurization reactor, a hydrolysis catalyst and a desulfurizing agent are disposed in series.
21. The method of any of paragraphs 1-20, wherein the desulfurization reactor is charged with a hydrolysis catalyst in the upper half and a desulfurizing agent in the lower half.
22. The method of paragraph 20 or 21, wherein the hydrolysis catalyst is JX-6B.
23. The method of any of paragraphs 1-22, wherein the desulfurized syngas is sent to a downstream fischer-tropsch synthesis unit and/or catalyst reduction unit.
Examples
The following description of exemplary embodiments of the invention, including various details of the embodiments of the invention to assist understanding, is to be construed as exemplary only and not limiting the scope of the invention. Accordingly, those of ordinary skill in the art will recognize that various changes and modifications of the embodiments described herein can be made without departing from the scope and spirit of the invention. Also, descriptions of well-known functions and constructions are omitted in the following description for clarity and conciseness.
Reagents, consumables, raw materials, apparatuses, and the like used in the following examples are commercially available or can be prepared by those skilled in the art based on the ordinary technical knowledge in the art, unless otherwise specified.
Example 1
As shown in FIG. 1, 62000kmol/h of a synthesis gas (temperature 30 ℃, pressure 3.2 MpaG; composition and properties of the feed gas are shown in tables 1 and 2 below) from an upstream apparatus was fed to a fine desulfurization heater and heated to 80 ℃ with steam in a fine desulfurization heater I. Supplementing steam to the obtained heated synthesis gas, wherein the mass flow of the supplemented steam is 4 times of the content of COS, and then sending the supplemented steam to fine desulfurization reactors I, II, III and IV (wherein the upper half section of each desulfurization reactor is filled with a JX-6B hydrolysis catalyst, and the lower half section is filled with a JX-4B desulfurizer) arranged in parallel for desulfurization treatment. And measuring the desulfurized synthesis gas by using a sulfur detector, wherein the total sulfur content is less than or equal to 0.05ppm, and sending the synthesis gas to a downstream Fischer-Tropsch synthesis unit and a downstream catalyst reduction unit. In the whole desulfurization treatment process, the total pressure of the whole device is reduced to be less than or equal to 0.03 MPa.
TABLE 1 feed gas composition
TABLE 2 physical Properties of the feed gases
Example 2
As shown in FIG. 2, 62000kmol/h of a synthesis gas (temperature 30 ℃, pressure 3.2 MpaG; composition and physical properties of the feed gas are shown in tables 3 and 4 below) from an upstream apparatus was fed to a fine desulfurization heater and heated to 140 ℃ with steam in a fine desulfurization heater II. Supplementing steam to the obtained heated synthesis gas, wherein the mass flow of the supplemented steam is 4 times of the content of COS, and then sending the supplemented steam to fine desulfurization reactors V, VI, VII and VIII which are arranged in parallel (wherein the upper half section of each desulfurization reactor is filled with a JX-6B hydrolysis catalyst, and the lower half section is filled with a JX-9E desulfurizer) for desulfurization treatment. And measuring the desulfurized synthesis gas by using a sulfur detector, wherein the total sulfur content is less than or equal to 0.05ppm, and sending the synthesis gas to a downstream Fischer-Tropsch synthesis unit and a downstream catalyst reduction unit. In the whole desulfurization treatment process, the total pressure of the whole device is reduced to be less than or equal to 0.03 MPa.
TABLE 3 feed gas composition
TABLE 4 physical Properties of raw Material gases
Numerous modifications and variations will readily occur to those skilled in the art based upon this disclosure without departing from the basic spirit of the invention. All such variations and modifications are intended to be within the scope of the present invention.
Claims (10)
1. A method for desulphurizing sulphur-containing synthesis gas in a megaton coal chemical project, wherein the method comprises:
(1) heating the sulfur-containing synthesis gas to 70-90 ℃ or 90-200 ℃ based on the sulfur-containing component type and the content of the organic sulfur-containing component to obtain the heated synthesis gas;
(2) and (3) sending the heated synthesis gas to desulfurization reactors which are arranged in parallel and contain a desulfurizing agent, and removing sulfide to obtain the desulfurized synthesis gas.
2. The method of claim 1, wherein the sour syngas is passed to a desulfurization heater and heated with a heating medium.
3. The method according to claim 1 or 2, wherein the total sulphur content of the sulphur-containing synthesis gas is between 0.1 and 1 ppm.
4. The method according to any one of claims 1 to 3, wherein the sulfur capacity of the desulfurizing agent is 5% or more.
5. The process of any one of claims 1-4, wherein the desulfurizing agent is at least one of a JX-4B desulfurizing agent and a JX-9E desulfurizing agent.
6. The process of any of claims 1-5, wherein the desulfurization efficiency of the desulfurization agent is > 95% relative to the amount of gas of the heated syngas.
7. The process of any of claims 1-6, wherein the sulfur-containing component of the sulfur-containing syngas is predominantly H2S and COS, CS2And RSH in a ratio not exceeding 1/3 relative to the total sulphur content, heating the sulphur-containing synthesis gas to 70 ℃ to 90 ℃;
preferably, the sulfur-containing synthesis gas is fed into a desulfurization heater, and the sulfur-containing synthesis gas is heated to 70 ℃ to 90 ℃ by using steam;
preferably, enabling the sulfur-containing synthesis gas with the temperature of 30-50 ℃ to enter the desulfurization heater;
preferably, in the sulfur-containing syngas, H2The molar ratio of S to COS is 2-4;
preferably, before sending the heated synthesis gas to the desulfurization reactors containing the desulfurizing agent arranged in parallel, supplementing water vapor to the heated synthesis gas;
preferably, the mass flow of the supplemented water vapor is greater than the amount of organic sulfur in the synthesis gas and is 3-6 times of the content of the organic sulfur;
preferably, the temperature of the heated synthesis gas is further increased to 90-120 ℃ before the heated synthesis gas is sent to desulfurization reactors containing a desulfurizing agent, which are arranged in parallel.
8. The process of any of claims 1-6, wherein the sulfur-containing component of the sulfur-containing syngas is predominantly H2S、COS、CS2And RSH, and COS, CS2And RSH in excess of 1/3 relative to the total sulfur content, heating the sulfur-containing syngas to 90-200 ℃;
preferably, the sulfur-containing synthesis gas enters a desulfurization heater, and the sulfur-containing synthesis gas is heated to 90-200 ℃ by steam;
preferably, enabling the sulfur-containing synthesis gas with the temperature of 30-50 ℃ to enter the desulfurization heater;
preferably, in the sulfur-containing syngas, H2The molar ratio of S to organic sulfur is 1-2;
preferably, before sending the heated synthesis gas to the desulfurization reactors containing the desulfurizing agent arranged in parallel, supplementing water vapor to the heated synthesis gas;
preferably, the mass flow of the supplemented water vapor is greater than the amount of organic sulfur in the synthesis gas and is 3-6 times of the content of the organic sulfur.
9. The process of any one of claims 1-8, wherein in the desulfurization reactor, a hydrolysis catalyst and a desulfurizing agent are disposed in series;
preferably, a hydrolysis catalyst is filled in the upper half section of the desulfurization reactor, and a desulfurizing agent is filled in the lower half section of the desulfurization reactor;
preferably, the hydrolysis catalyst is JX-6B.
10. The process of any one of claims 1 to 9, wherein the desulphurised synthesis gas is passed to a downstream fischer-tropsch synthesis unit and/or catalyst reduction unit.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111298669.XA CN114196445A (en) | 2021-11-04 | 2021-11-04 | Method for desulfurizing sulfur-containing synthesis gas in megaton coal chemical engineering project |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111298669.XA CN114196445A (en) | 2021-11-04 | 2021-11-04 | Method for desulfurizing sulfur-containing synthesis gas in megaton coal chemical engineering project |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114196445A true CN114196445A (en) | 2022-03-18 |
Family
ID=80646798
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111298669.XA Pending CN114196445A (en) | 2021-11-04 | 2021-11-04 | Method for desulfurizing sulfur-containing synthesis gas in megaton coal chemical engineering project |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114196445A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0066307A2 (en) * | 1981-05-26 | 1982-12-08 | Shell Internationale Researchmaatschappij B.V. | Process for the removal of acid gases from gaseous streams |
| JP2001011476A (en) * | 1999-06-29 | 2001-01-16 | Babcock Hitachi Kk | Dry desulfurization equipment for coal gasification gas |
| CN104531233A (en) * | 2014-12-22 | 2015-04-22 | 史惠元 | Waste biomass gas purification method and device |
| CN106947539A (en) * | 2017-05-08 | 2017-07-14 | 淄博赢信达知识产权咨询服务有限公司 | The technique for preparing low hydrogen CO gas |
| CN112226249A (en) * | 2020-10-26 | 2021-01-15 | 中冶节能环保有限责任公司 | Integrated catalytic hydrolysis desulfurization tower, integrated dry purification device and method |
-
2021
- 2021-11-04 CN CN202111298669.XA patent/CN114196445A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0066307A2 (en) * | 1981-05-26 | 1982-12-08 | Shell Internationale Researchmaatschappij B.V. | Process for the removal of acid gases from gaseous streams |
| JP2001011476A (en) * | 1999-06-29 | 2001-01-16 | Babcock Hitachi Kk | Dry desulfurization equipment for coal gasification gas |
| CN104531233A (en) * | 2014-12-22 | 2015-04-22 | 史惠元 | Waste biomass gas purification method and device |
| CN106947539A (en) * | 2017-05-08 | 2017-07-14 | 淄博赢信达知识产权咨询服务有限公司 | The technique for preparing low hydrogen CO gas |
| CN112226249A (en) * | 2020-10-26 | 2021-01-15 | 中冶节能环保有限责任公司 | Integrated catalytic hydrolysis desulfurization tower, integrated dry purification device and method |
Non-Patent Citations (2)
| Title |
|---|
| 乌云主编, 北京理工大学出版社 * |
| 王小宝主编: "《无机化学工艺学》", 31 May 2000, 化学工业出版社 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7569199B1 (en) | Method to remove sulfur or sulfur-containing species from a source | |
| JP5694957B2 (en) | Method for removing SOx in gas with polyethylene glycol | |
| JPS627960B2 (en) | ||
| CN101918104A (en) | Method for treating a process gas flow containing CO2 | |
| EP0227259A1 (en) | Sulfur removal from hydrocarbons | |
| JPH0345118B2 (en) | ||
| CN108531223A (en) | Coke oven gas desulfurization hydroconversion process method | |
| PL107862B1 (en) | METHOD OF PROCESSING GASES CONTAINING HYDROGEN SULFIDE | |
| CN110982566A (en) | Process for removing organic sulfur in natural gas | |
| CN109195686B (en) | Device, method and catalyst for dehydrating gaseous hydrocarbon raw material and removing hydrogen sulfide and mercaptan | |
| EP3247484B1 (en) | Solvent and method for removing acid gases from a gaseous mixture | |
| CN114196445A (en) | Method for desulfurizing sulfur-containing synthesis gas in megaton coal chemical engineering project | |
| Kwong et al. | Rounding up sulfur | |
| CN105344220A (en) | Method for desulphurization and standard-reached emission of Claus tail gas | |
| CN104073288A (en) | Method removing sulphur from fluid | |
| JP7423320B2 (en) | Method for removing sulfur oxides from gas containing carbon dioxide as the main component | |
| CA2830498C (en) | Process and system for removing sulfur from sulfur-containing gaseous streams | |
| WO2010138281A2 (en) | Process for treating a gas stream or effluent | |
| CN108144318B (en) | Associated gas desulfurization system | |
| CN113877405B (en) | Waste lubricating oil hydrogenation gas treatment and discharge process | |
| CN113332845B (en) | Dry desulfurization and purification process for ethylene-rich gas | |
| Faizullayevna et al. | DEVELOPMENT OF TECHNOLOGICAL METHODS FOR OBTAINING AMINE ABSORBENTS BASED ON LOCAL RAW MATERIALS FOR OIL AND GAS PROCESSING PLANTS | |
| CN100384516C (en) | Improved method for removing sulfur by vanadium based wet-type oxidization | |
| CN101522562A (en) | Process for disposal of mercaptans | |
| Mukhtor et al. | THE INFLUENCE OF DIFFERENT PARAMETERS IN THE PROCESSES OF AMINE PURIFICATION OF NATURAL GASES |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220318 |
|
| RJ01 | Rejection of invention patent application after publication |