CN113731127A - Process for recovering light hydrocarbon from hydrogen-containing gas in refinery - Google Patents
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- CN113731127A CN113731127A CN202010472115.6A CN202010472115A CN113731127A CN 113731127 A CN113731127 A CN 113731127A CN 202010472115 A CN202010472115 A CN 202010472115A CN 113731127 A CN113731127 A CN 113731127A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/229—Integrated processes (Diffusion and at least one other process, e.g. adsorption, absorption)
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/047—Pressure swing adsorption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/12—Liquefied petroleum gas
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0405—Purification by membrane separation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/042—Purification by adsorption on solids
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/048—Composition of the impurity the impurity being an organic compound
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- Oil, Petroleum & Natural Gas (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a process for recovering light hydrocarbon from hydrogen-containing gas in a refinery, which aims to increase the yield of the light hydrocarbon in the refinery as much as possible and improve the economic benefit of the refinery. The method comprises the following steps: 1) hydrogen-containing gas in a refinery enters a membrane separation device for separation into permeation gas rich in hydrogen and tail gas rich in light hydrocarbon; 2) the tail gas rich in light hydrocarbon from the step 1) enters a light hydrocarbon recovery device for light hydrocarbon recovery and product separation, and absorption gas and dry gas are separated to obtain light hydrocarbon products; 3) mixing the absorption gas from the step 2) with the permeation gas rich in hydrogen from the step 1), boosting the pressure to 2.4-2.6 MPag, sending the mixture to a PSA (pressure swing adsorption) device for pressure swing adsorption to obtain high-purity hydrogen, and sending the separated desorption gas to the step 4); 4) the desorbed gas from the step 3) and the dry gas from the step 2) are mixed to be used as refinery fuel gas.
Description
Technical Field
The invention belongs to the field of light hydrocarbon recovery in refineries, and particularly relates to a process for recovering light hydrocarbon from hydrogen-containing gas in refineries.
Background
In recent years, with the continuous and rapid expansion of the oil refining capacity of China, the scale of refineries is continuously increased, the market demand of domestic finished oil is slowly increased, and the yield of the finished oil is far beyond the market demand of China; meanwhile, the elimination speed and the elimination amplitude of the backward oil refining capacity in China are slow, so that the oil refining capacity in China is totally excessive and is in a serious surplus state. In 2018, the crude oil processing amount in China is about 6.05 hundred million tons, and the average operating rate of refineries in China is 72.9 percent, which is the lowest worldwide. By the end of 2020, the oil refining capacity of China is predicted to be increased to 8.82 hundred million tons, and the excess capacity is further aggravated.
With the continuous development of economy in China, the demand of chemical products in ethylene downstream industries is continuously increased. According to statistics, in 2018, the ethylene capacity in China is 2525 ten thousand tons/year, the actual yield is 1841 ten thousand tons/year, the ethylene import amount is 257.6 ten thousand tons/year, and the external dependence is 12.2%. If the downstream products of ethylene such as polyethylene, styrene, ethylene glycol and the like are imported, the total consumption of ethylene equivalent in China in 2018 reaches 4720 ten thousand tons/year, and the ethylene dependence on the outside is higher.
At present, the proportion of naphtha in the ethylene raw material structure in China is over 60 percent and is far higher than the average level of about 40 percent in the world in the same period. Therefore, domestic refineries are continuously optimizing ethylene raw materials and are developing towards light conversion, namely, the conversion from naphtha to gas resources such as light hydrocarbon and ethane is carried out. The production line of ethylene raw material lightening has the advantages of high product yield, low cost, less project investment, low energy consumption, little pollution and the like.
The composition of the hydrogen-containing gas of the existing refinery generally comprises: 10-20 wt% of hydrogen, 30-40 wt% of light hydrocarbon, and the balance of dry gas and C5 +The component accounts for about 40 to 50 weight percent. The conventional refinery hydrogen-containing gas processing flow is as follows: hydrogen-containing gas in the refinery is sent to a PSA (pressure swing adsorption separation) device for hydrogen purification, high-purity hydrogen is produced for a hydrogenation device, and the rest desorbed gas is used as fuel gas of the whole plant.
Under the situation that the oil refining capacity is seriously surplus and the supply and demand gaps of chemical products are increasingly increased at present, for the existing refinery, on the premise of keeping the flow of the existing refinery basically unchanged, the main purposes of the invention are to research how to increase the yield of light hydrocarbon through local optimization of the flow, realize the lightening of ethylene raw materials and improve the economic benefit of the refinery.
Disclosure of Invention
The invention mainly aims to provide a process for recovering light hydrocarbon from hydrogen-containing gas in a refinery so as to increase the yield of the light hydrocarbon in the refinery as much as possible and improve the economic benefit of the refinery. The process of the present invention can recover light hydrocarbon from hydrogen-containing gas in refinery, obtain high purity hydrogen and produce fuel gas as by-product.
The invention provides a process for recovering light hydrocarbon from hydrogen-containing gas in a refinery, which adopts the technical scheme that:
a process for recovering light hydrocarbon from hydrogen-containing gas in refinery is characterized by comprising the following steps:
1) heating hydrogen-containing gas in a refinery, and separating the hydrogen-containing gas in a membrane separation device into permeation gas rich in hydrogen and tail gas rich in light hydrocarbon;
2) sending the tail gas rich in light hydrocarbon from the step 1) to a light hydrocarbon recovery device for light hydrocarbon recovery and product separation, and separating out absorption gas and dry gas to obtain a light hydrocarbon product;
3) mixing the absorption gas from the step 2) with the permeation gas rich in hydrogen from the step 1), boosting the pressure to 2.4-2.6 MPag, sending the mixture to a PSA (pressure swing adsorption) device for pressure swing adsorption to obtain high-purity hydrogen and desorption gas, wherein the desorption gas enters the step 4);
4) the desorbed gas from the step 3) and the dry gas from the step 2) are mixed to be used as refinery fuel gas.
The hydrogen-containing gas in the refinery is preferably heated to 70-90 ℃ and then enters a membrane separation device for separation.
The membrane separation device has the operating pressure of 2.0-2.7 MPag at the temperature of 70-90 ℃.
The PSA device has the operating temperature of 30-50 ℃ and the operating pressure of 0.8-2.6 MPag.
The desorbed gas from the step 3) and the dry gas from the step 2) are mixed and then are boosted to 0.4-0.6 MPag to be used as refinery fuel gas.
The hydrogen content of the hydrogen-containing gas in the refinery is 10-20 wt%, the light hydrocarbon content is 30-40 wt%, and the hydrogen is usually from at least one of various hydrogen consumption devices such as a hydrofining device, a hydrotreating device, a hydrocracking device, a disproportionation device and an isomerization device of the refinery and/or at least one of various dehydrogenation devices such as a propane dehydrogenation device and an isobutane dehydrogenation device.
Compared with the prior art, the invention has the advantages that:
the invention provides a process for recovering light hydrocarbon from hydrogen-containing gas in a refinery, wherein the hydrogen-containing gas in the refinery does not directly enter a PSA (pressure swing adsorption) device to recover hydrogen, membrane separation is firstly carried out to respectively obtain permeate gas rich in hydrogen and non-permeate gas rich in light hydrocarbon, the permeate gas is then sent to the PSA device to be purified to obtain high-purity hydrogen (99.9 mol%), the non-permeate gas rich in light hydrocarbon is sent to a light hydrocarbon recovery device (containing a light hydrocarbon separation part) to obtain propane (purity of not less than 95 wt%), isobutane (purity of not less than 95 wt%) and an n-butane product (purity of not less than 95 wt%); 1) the process can increase the yield of light hydrocarbon (commercial liquefied gas) in a refinery; 2) the propane recovered by the process can be used as an ethylene raw material or a raw material for propane dehydrogenation, so that the yield of ethylene and propylene is increased; 3) the isobutane recovered by the process can be used as a raw material of an alkylation device to produce a gasoline component with a high octane number, and can also be subjected to dehydrogenation to produce isobutene; 4) the n-butane recovered by the process can be used as an ethylene raw material, so that the yield of ethylene and propylene is improved; 5) the process of the invention can effectively increase the economic benefit of refineries.
The invention is described in further detail below with reference to the figures and the detailed description, without limiting the scope of the invention.
Drawings
FIG. 1 is a simplified flow diagram of a process for recovering light hydrocarbons from a hydrogen-containing gas in a refinery according to the present invention.
Wherein:
1-hydrogen-containing gas, 2-membrane separation device, 3-permeation gas, 4-PSA device, 5-hydrogen, 6-desorption gas, 7-tail gas, 8-light hydrocarbon recovery device, 9-absorption gas, 10-dry gas, 11-propane, 12-isobutane, 13-n-butane and 14-C5 +And (4) components.
Detailed Description
As shown in fig. 1, a process for recovering light hydrocarbon from hydrogen-containing gas in a refinery mainly comprises a membrane separation device 2, a PSA device 4 and a light hydrocarbon recovery device 8 (light hydrocarbon-containing separation part). The process for recovering light hydrocarbon from hydrogen-containing gas in a refinery comprises the following steps:
1) heating hydrogen-containing gas 1 in a refinery, and separating the hydrogen-containing gas in a membrane separation device 2 into permeation gas 3 rich in hydrogen and tail gas 7 rich in light hydrocarbon;
2) sending the tail gas 7 rich in light hydrocarbon from the step 1) to a light hydrocarbon recovery device 8 for light hydrocarbon recovery and product separation, separating out absorption gas 9 and dry gas 10 to obtain light hydrocarbon products, such as propane 11, isobutane 12, n-butane 13 and C5 +Component 14, etc.;
3) mixing the absorption gas 9 from the step 2) with the permeation gas 3 rich in hydrogen from the step 1), boosting the pressure to 2.4-2.6 MPag, sending the mixture to a PSA (pressure swing adsorption) device 4 for pressure swing adsorption to obtain high-purity hydrogen 5 and desorption gas 6, wherein the desorption gas 6 enters the step 4);
4) the desorbed gas 6 from the step 3) and the dry gas 10 from the step 2) are mixed to be used as the refinery fuel gas.
The hydrogen-containing gas 1 in the refinery is preferably heated to 70-90 ℃ and then enters the membrane separation device 2 for separation.
The operation temperature of the membrane separation device 2 is 70-90 ℃, and the operation pressure is 2.0-2.7 MPag.
The PSA device has the operating temperature of 30-50 ℃ and the operating pressure of 0.8-2.6 MPag.
The desorbed gas from the step 3) and the dry gas from the step 2) are mixed and then are boosted to 0.4-0.6 MPag to be used as refinery fuel gas.
The light hydrocarbon recovery unit 8 of the present invention generally comprises: 1) the operation temperature of the top of the absorption tower is 10-40 ℃, and the operation pressure of the top of the absorption tower is 0.5-1.0 MPag; 2) the operation temperature at the top of the debutanizer is 50-90 ℃, and the operation pressure at the top of the debutanizer is 1.0-1.3 MPag; 3) the operation temperature at the top of the deethanizer is 30-50 ℃, and the operation pressure at the top of the deethanizer is 3.0-3.3 MPag; 4) a depropanizing tower, wherein the operation temperature at the top of the tower is 40-70 ℃, and the operation pressure at the top of the tower is 1.7-2.0 MPag; 5) the deisobutanizer has the tower top operating temperature of 50-80 ℃ and the tower top operating pressure of 0.8-1.1 MPag; 6) dry gas desulfurization, the operation temperature of the tower top is 30-50 ℃, the operation pressure of the tower top is 0.7-0.9 MPag, 7) liquefied gas desulfurization and mercaptan removal, the operation temperature is 30-50 ℃, the operation pressure is 1.0-2.0 MPag and the like are carried out, and dry gas 10, propane 11, isobutane 12, n-butane 13 and C are respectively obtained5 + Component 14, and the like. The above-mentioned means included in the light hydrocarbon recovery unit 8 may vary according to engineering requirements. The invention is not limited thereto. The specific devices included in light hydrocarbon recovery unit 8 are not shown in fig. 1.
The hydrogen content of the hydrogen-containing gas in the refinery is 10-20 wt%, the light hydrocarbon content is 30-40 wt%, and the hydrogen-containing gas generally comes from various hydrogen consumption devices such as a hydrofining device, a hydrotreating device, a hydrocracking device, a disproportionation device and an isomerization device of the refinery, and various dehydrogenation devices such as propane dehydrogenation and isobutane dehydrogenation.
The process for recovering light hydrocarbon from hydrogen-containing gas in a refinery can increase the yield of light hydrocarbon (commercial liquefied gas) in the refinery by using the process for recovering light hydrocarbon from the hydrogen-containing gas in the refinery, which is described in the figure 1; the propane recovered by the light hydrocarbon recovery device 8 can be used as an ethylene raw material or a raw material for propane dehydrogenation, so that the yield of ethylene and propylene is increased; the isobutane recovered by the light hydrocarbon recovery device 8 can be used as a raw material of an alkylation device to produce a gasoline component with a high octane number, and can also be subjected to dehydrogenation to produce isobutene; the n-butane recovered by the light hydrocarbon recovery device 8 can be used as an ethylene raw material, and the yield of ethylene and propylene is improved.
The process of the invention can effectively increase the economic benefit of refineries, not only can recover light hydrocarbon from hydrogen-containing gas in refineries, but also can obtain high-purity hydrogen and byproduct fuel gas.
Claims (7)
1. A process for recovering light hydrocarbon from hydrogen-containing gas in refinery is characterized by comprising the following steps:
1) heating hydrogen-containing gas in a refinery, and separating the hydrogen-containing gas in a membrane separation device into permeation gas rich in hydrogen and tail gas rich in light hydrocarbon;
2) sending the tail gas rich in light hydrocarbon from the step 1) to a light hydrocarbon recovery device for light hydrocarbon recovery and product separation, and separating out absorption gas and dry gas to obtain a light hydrocarbon product;
3) mixing the absorption gas from the step 2) with the permeation gas rich in hydrogen from the step 1), boosting the pressure to 2.4-2.6 MPag, sending the mixture to a PSA (pressure swing adsorption) device for pressure swing adsorption to obtain high-purity hydrogen and desorption gas, wherein the desorption gas enters the step 4);
4) the desorbed gas from the step 3) and the dry gas from the step 2) are mixed to be used as refinery fuel gas.
2. The process of claim 1, wherein the process comprises the steps of: the hydrogen content of the hydrogen-containing gas in the refinery is 10-20 wt%, and the light hydrocarbon content is 30-40 wt%.
3. The process of claim 1, wherein the process comprises the steps of: the hydrogen-containing gas of the refinery is from at least one of a hydrofining device, a hydrotreating device, a hydrocracking device, a disproportionation device, an isomerization device, a propane dehydrogenation device and an isobutane dehydrogenation device of the refinery.
4. The process of claim 1, wherein the process comprises the steps of: heating the hydrogen-containing gas in the refinery to 70-90 ℃, and then separating the hydrogen-containing gas in a membrane separation device.
5. The process of claim 1, wherein the process comprises the steps of: the operating temperature of the membrane separation device is 70-90 ℃, and the operating pressure is 2.5-2.7 MPag.
6. The process of claim 1, wherein the process comprises the steps of: the PSA device has an operating temperature of 30-50 ℃ and an operating pressure of 2.4-2.6 MPag.
7. The process of claim 1, wherein the process comprises the steps of: and (3) mixing the desorbed gas from the step 3) and the dry gas from the step 2), and boosting the pressure to 0.4-0.6 MPag to be used as refinery fuel gas.
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| CN202010472115.6A CN113731127A (en) | 2020-05-29 | 2020-05-29 | Process for recovering light hydrocarbon from hydrogen-containing gas in refinery |
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| CN202010472115.6A CN113731127A (en) | 2020-05-29 | 2020-05-29 | Process for recovering light hydrocarbon from hydrogen-containing gas in refinery |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104030245A (en) * | 2014-05-23 | 2014-09-10 | 四川天采科技有限责任公司 | Hydrogen purifying method and device for refinery dry gas after recovery of light olefins with high yield and high purity |
| CN104028076A (en) * | 2014-05-23 | 2014-09-10 | 四川天采科技有限责任公司 | Method and device for carrying out membrane separation, pressure swing adsorption and combination recycle on low concentration refinery dry gas |
| CN104692325A (en) * | 2013-12-05 | 2015-06-10 | 北京宜能高科科技有限公司 | System for comprehensively recovering hydrogen and light hydrocarbons through single absorption and double desorption |
| EP3255127A1 (en) * | 2016-06-09 | 2017-12-13 | Linde Aktiengesellschaft | Method of processing a coal seam gas |
| CN109022033A (en) * | 2017-06-09 | 2018-12-18 | 中石化广州工程有限公司 | A kind of group technology that oil refinery dry gas recycling is isolated |
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2020
- 2020-05-29 CN CN202010472115.6A patent/CN113731127A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104692325A (en) * | 2013-12-05 | 2015-06-10 | 北京宜能高科科技有限公司 | System for comprehensively recovering hydrogen and light hydrocarbons through single absorption and double desorption |
| CN104030245A (en) * | 2014-05-23 | 2014-09-10 | 四川天采科技有限责任公司 | Hydrogen purifying method and device for refinery dry gas after recovery of light olefins with high yield and high purity |
| CN104028076A (en) * | 2014-05-23 | 2014-09-10 | 四川天采科技有限责任公司 | Method and device for carrying out membrane separation, pressure swing adsorption and combination recycle on low concentration refinery dry gas |
| EP3255127A1 (en) * | 2016-06-09 | 2017-12-13 | Linde Aktiengesellschaft | Method of processing a coal seam gas |
| CN109022033A (en) * | 2017-06-09 | 2018-12-18 | 中石化广州工程有限公司 | A kind of group technology that oil refinery dry gas recycling is isolated |
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Application publication date: 20211203 |