CN111548824A - Combined process for recovering and separating refinery dry gas - Google Patents
Combined process for recovering and separating refinery dry gas Download PDFInfo
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- CN111548824A CN111548824A CN202010385511.5A CN202010385511A CN111548824A CN 111548824 A CN111548824 A CN 111548824A CN 202010385511 A CN202010385511 A CN 202010385511A CN 111548824 A CN111548824 A CN 111548824A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G70/00—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00
- C10G70/04—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by physical processes
- C10G70/045—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by physical processes using membranes, e.g. selective permeation
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Abstract
The invention discloses a combined process for recovering and separating refinery dry gas in the technical field of petrochemical industry, which adopts a combined process of membrane separation and carbon dioxide recovery to concentrate the dry gas and is characterized by comprising the following steps: 1) the refinery dry gas as a raw material gas enters a membrane separation part, after being pressurized by a compressor, a gas phase enters a membrane separation component, and most of hydrogen, part of methane and trace other components permeate a membrane and are enriched into methane hydrogen gas on a permeation side; a small amount of hydrogen and methane and other components which do not permeate the membrane are enriched into a carbon-rich secondary gas from the non-permeation side of the membrane separation component and sent to a carbon dioxide recovery part; 2) and (3) the carbon-rich secondary gas from the membrane separation part in the step 1) enters a carbon-two recovery part, and after absorption and desorption, a carbon-two concentrated gas and a small amount of fuel gas are obtained. The invention has the following advantages: 1) the process is reasonable, and the carbon dioxide recovery rate is high; 2) the advantages of each unit are fully exerted by adopting a combined process; 3) low energy consumption and low investment.
Description
Technical Field
The invention belongs to the field of petrochemical industry, and particularly relates to a combined process for separating and recovering hydrocarbon and hydrogen from refinery gas.
Background
The refinery dry gas comprises catalytic dry gas, coking dry gas, reforming dry gas, aromatization gas, disproportionation dry gas, PSA tail gas, hydrogenation dry gas and the like, and the main components of the gases comprise H2、CH4、C2H6、C2H4、C3～C5And inert gas components such as nitrogen, which are commonly used as fuel gas by refineries, and further utilization comprises recovering hydrogen in the fuel gas by a pressure swing adsorption process; concentrating ethylene and ethane by an absorption method; and other processes are adopted to recycle the olefin and the like.
Directly adopting a pressure swing adsorption process to recover hydrogen, wherein the content of the hydrogen in the refinery dry gas is different from 10-70 mol%, and the hydrogen contains O2、CO2Heavy hydrocarbon and other impurities, because of low hydrogen content, high impurity concentration, difficult desorption of heavy hydrocarbon, O2The content is difficult to control, so that the quality of the hydrogen is unqualified, the adsorption capacity is reduced after long-term operation, and the investment is high. In the actual production, the pressure swing adsorption process is less adopted to recover hydrogen from refinery gases with high impurity and heavy hydrocarbon content.
The absorption method is adopted to recover the ethylene and the ethane, the raw material adaptability is strong, and the dry gas with high heavy hydrocarbon content can be treated. Chinese patents CN101759516A and CN101759518A disclose a method for oil absorption separation of refinery catalytic dry gas, which uses C five and C four hydrocarbons as absorbents to absorb carbon two fraction and heavier component in the catalytic dry gas after compression and cooling in a main absorption tower, the material flow in the kettle of the main absorption tower is sent to a desorption tower for treatment, and the recovered carbon two concentrated gas is obtained at the top of the desorption tower. The top stream of the main absorption tower enters a reabsorption tower, gasoline is used as an absorbent to absorb a carbon-pentahydrocarbon absorbent in the reabsorption tower, the top gas of the reabsorption tower is sent to a fuel system, and the carbon-two concentrated gas is sent to an ethylene device for refining treatment.
By adopting the methods disclosed in Chinese patents CN101759516A and CN101759518A, because the separation of gas is an absorption desorption method, the absorbent circulates between the absorption tower and the desorption tower, and the circulating amount of the absorbent has decisive influence on the diameters of the absorption tower and the desorption tower, the heat load of a reboiler and the flow of an absorbent circulating pump. The composition of the refinery dry gas comprises hydrogen, methane, ethane, ethylene, carbon four and the like, and the dry gas has large composition difference due to the fact that the dry gas comes from different production devices, particularly the content of light components such as hydrogen, methane and the like, the content of hydrogen is about 5-70% mol, the content of methane is about 2-52% mol, and when the content of the light components is high, the circulation amount of an absorbent is greatly increased, so that the device investment is high, and the energy consumption is high.
Disclosure of Invention
The invention aims to provide a combined process for recovering and separating refinery dry gas, which is a combined process for separating light components such as hydrogen, methane and the like in refinery gas and then carrying out recovery treatment, so as to solve the problems of high content of light components in raw materials, low concentration of effective components, high energy consumption of devices and high investment in the prior art.
In order to solve the technical problems, the invention adopts the technical scheme that:
a combined process for recovering and separating refinery dry gas adopts a combined process of membrane separation and carbon two recovery to concentrate the dry gas, and is characterized by comprising the following steps:
1) the refinery dry gas as a raw material gas enters a membrane separation part, after being pressurized by a compressor, a gas phase enters a membrane separation component, and most of hydrogen, part of methane and trace other components permeate a membrane and are enriched into methane hydrogen gas on a permeation side; a small amount of hydrogen, methane and other components which do not permeate the membrane component are enriched into a carbon-rich secondary gas on the non-permeation side of the membrane separation component and sent to a carbon dioxide recovery part;
2) and (3) the carbon-rich secondary gas from the membrane separation part in the step 1) enters a carbon-two recovery part, and after absorption and desorption, products of carbon-two concentrated gas and a small amount of fuel gas are obtained.
The invention relates to a combined process for recovering and separating refinery dry gas, which is further characterized in that: the refinery dry gas used as the raw material gas is one or more of catalytic dry gas, coking dry gas, reforming dry gas, aromatization gas, disproportionation dry gas, PSA tail gas and hydrogenation dry gas, and can also be gas containing components such as hydrogen, carbon and the like generated by other production devices of a refinery.
The invention relates to a combined process for recovering and separating refinery dry gas, which is further characterized in that: after entering the membrane separation part, the refinery dry gas is firstly pressurized by a compressor, then is cooled and separated, the gas phase enters the membrane separation component, most of hydrogen, partial methane and trace other components permeate the membrane, are enriched into methane hydrogen gas on the permeation side, are discharged from the membrane separation component and are sent out of a boundary area, and can be used as a raw material of a hydrogen recovery device due to the fact that the refinery dry gas contains hydrogen with higher concentration.
The invention relates to a combined process for recovering and separating refinery dry gas, which is further characterized in that: the feed gas enters a gas-liquid separation tank and a coalescing filter after being compressed and cooled in a membrane separation part, a free liquid phase carried in the gas is removed, and the temperature of the gas after liquid removal is about 70-85 ℃ to ensure that the temperature is higher than the dew point when the gas enters a membrane separation component, so that the influence of liquid drops on the performance of a membrane separator is prevented.
The invention relates to a combined process for recovering and separating refinery dry gas, which is further characterized in that: the refinery dry gas as raw material gas can be classified according to composition, several strands with similar hydrogen and methane contents can be combined for membrane separation treatment, and those with larger composition difference can be respectively subjected to membrane separation treatment.
The invention relates to a combined process for recovering and separating refinery dry gas, which is further characterized in that: the pressure of the refinery dry gas as the raw material gas is generally low, the pressure needs to be increased firstly in the membrane separation part, and the pressure can be slightly higher than the pressure required by the absorption tower in the carbon recovery part, and the pressure needs to be determined according to the separation requirement.
The invention relates to a combined process for recovering and separating refinery dry gas, which is further characterized in that: the carbon two recovery part meets the separation requirement, the pressure required by the absorption tower is about 3.5-4.5 MPaG, and the pressure of the raw material gas is increased in the membrane separation part, so that the pressure of the carbon two-rich gas from the membrane separation part is slightly reduced, and the pressure drop is about 0.05-0.2 MPa, so that the carbon two-rich gas can directly enter the absorption tower after entering the carbon two recovery part.
The invention relates to a combined process for recovering and separating refinery dry gas, which is further characterized in that: the pressure of the carbon-rich secondary gas from the membrane separation part is 1.5-5.0 MPaG, preferably 3.5-4.7 MPaG;
the invention relates to a combined process for recovering and separating refinery dry gas, which is further characterized in that: the hydrogen content of the methane hydrogen gas from the membrane separation part is 60-99% v, preferably 80-92% v;
the invention relates to a combined process for recovering and separating refinery dry gas, which is further characterized in that: the carbon content in the carbon dioxide concentrated gas from the carbon dioxide recovery part is 50-99% v, preferably 60-92% v; wherein the proportion of the carbon dioxide in the raw material dry gas is 80-99% v, preferably 85-95% v.
The combined process for recovering and separating the refinery dry gas has the following beneficial effects:
the separation of the refinery dry gas adopts a method of membrane separation and absorption desorption, the raw gas is pressurized, then the pressure of high-pressure gas is utilized, and the hydrogen and part of methane in the gas are separated from the system through membrane separation, so that the content of light components in the carbon-rich secondary gas entering the carbon dioxide recovery part is effectively reduced. The amount of absorbent used in the absorption column is inversely related to the concentration of the carbon dioxide component in the feed, with higher concentrations of the carbon dioxide component requiring less absorbent. Therefore, the amount of the absorbent circulating in the carbon four absorption column and the gasoline absorption column can be reduced, the heat load of the condenser at the top of the carbon four desorption column and the reboiler at the bottom of the carbon four desorption column can be reduced, the equipment size of the column and the heat exchanger can be reduced, and the operation cost can be reduced.
In conclusion, the combined process for recovering and separating the refinery dry gas has the advantages that:
1. the process is reasonable, and the carbon dioxide recovery rate is high;
2. the advantages of each unit are fully exerted by adopting a combined process;
3. low energy consumption and low investment.
Drawings
FIG. 1 is a schematic flow diagram of a combined refinery dry gas recovery process according to the present invention.
The reference symbols shown in the figures are: 1-membrane separation part, 2-carbon two recovery part, 3-refinery dry gas, 4-methane hydrogen, 5-carbon two-rich gas, 6-crude hydrogen gas and 7-carbon two-concentrated gas.
Detailed Description
The invention is described in further detail below with reference to the figures and the specific examples, which do not limit the scope of the invention as claimed.
As shown in figure 1, refinery dry gas 3 enters a membrane separation part 1 and is separated into permeation gas, namely methane hydrogen 4 with high hydrogen and methane content, and non-permeation gas with high pressure, namely carbon-rich gas 5, and the carbon-rich gas 5 enters a carbon-rich recovery part and is subjected to absorption and desorption treatment to obtain crude hydrogen gas 6 and carbon-rich concentrated gas 7.
The refinery dry gas as the raw material gas is one or more of catalytic dry gas, coking dry gas, reforming dry gas, aromatization gas, disproportionation dry gas, PSA tail gas and hydrogenation dry gas, and can also be gas containing components such as hydrogen, carbon and the like generated by other production devices of a refinery.
The pressure of the refinery dry gas as the raw material gas is generally low, the pressure needs to be increased firstly in the membrane separation part, the pressure can be slightly higher than the pressure required by the absorption tower of the carbon two recovery part, the concentration of each component in the permeate gas is influenced by the pressure difference between the raw material gas side and the permeate gas side of the membrane separation and the area of the membrane module, and for the membrane module with a certain area, the larger the pressure difference is, the more the carbon two components enter the permeate gas is, and the lower the recovery rate of the carbon two is. Therefore, it is determined from the recovery rate of carbon dioxide and the properties of the film.
After entering the membrane separation part, the refinery dry gas is firstly pressurized by a compressor, then is cooled and separated, and after being compressed and cooled, the refinery dry gas enters a gas-liquid separation tank and a coalescing filter to remove a free liquid phase carried in the gas, and the temperature of the gas after liquid removal is about 70-85 ℃ to ensure that the temperature of the gas is higher than the dew point when the gas enters a membrane separation component, so that the performance of a membrane separator is prevented from being influenced by liquid drops. The raw material gas enters the membrane separation component in the membrane separation part, the gas phase of the raw material gas permeates the membrane, most of hydrogen, partial methane and trace other components are enriched into methane hydrogen gas on the permeation side, the methane hydrogen gas is discharged from the membrane separation component and is sent out of a boundary region, and the raw material gas can be used as the raw material of a hydrogen recovery device due to the fact that the raw material gas contains hydrogen with higher concentration.
The refinery dry gas as raw material gas can be classified according to composition, several strands with similar hydrogen and methane contents can be combined for membrane separation treatment, and those with larger composition difference can be respectively subjected to membrane separation treatment.
In order to meet the separation requirement in the carbon two recovery part, the pressure required by the absorption tower is about 3.5-4.5 MPaG, and the pressure of the raw material gas is already increased in the membrane separation part, so that the pressure of the carbon two-rich gas from the membrane separation part is slightly reduced, and the pressure is reduced by about 0.05-0.2 MPa, so that the carbon two-rich gas can directly enter the absorption tower after entering the carbon two recovery part. The pressure of the carbon-rich secondary gas from the membrane separation part is preferably 3.5-4.7 MPaG; the carbon content in the carbon dioxide concentrated gas from the carbon dioxide recovery part is 50-99% v, preferably 60-92% v; wherein the proportion of the carbon dioxide in the raw material dry gas is 80-99% v, preferably 85-95% v.
The composition of the refinery dry gas 3 is: 61% v of hydrogen, 0.18% v of carbon monoxide, 12.59% v of methane, 25.74% v of ethane, 0.46% v of ethylene, 0.03% v of the components of carbon five and above, 40 ℃ of temperature and 0.8MPaG of pressure, entering a compressor inlet liquid separation tank of a membrane separation part 1, entering a gas phase into a compressor, compressing the gas, increasing the pressure to 4.5MPaG, cooling to 75 ℃ by a cooler, separating by a liquid separation tank, entering the gas phase into a membrane separator group, separating into a permeable gas, namely hydrogen and methane 4 with high content of hydrogen and methane, and a non-permeable gas, namely carbon-rich gas 5 with high pressure, wherein the carbon-rich gas 5 comprises 9.29% v of hydrogen, 0.32% v of carbon monoxide, 25.26% v of methane, 64.29% v of ethane, 0.81% v of ethylene, 0.03% v of the components of carbon five and above, entering a carbon five, entering a carbon-rich gas recovery part, cooling to 15 ℃ of carbon-rich gas, entering a four-carbon-a four-aG absorption tower, and absorbing tower with 3.03% g of carbon, the temperature of the top of the tower is 16 ℃, the temperature of the bottom of the tower is 126 ℃, an absorbent from the bottom of the carbon four desorption tower enters the top of the carbon four absorption tower after being cooled, materials at the bottom of the carbon four absorption tower enter the carbon four desorption tower, gas at the top of the carbon four desorption tower is condensed and separated, the gas is sent out as a product, namely, a carbon two concentrated gas 7, and the composition of the carbon two concentrated gas 7 is as follows: hydrogen 4.26% v, ethane 88.39% v, ethylene 1.84% v, carbon three 1.8% v, carbon four 3.69% v. And (3) after light components such as hydrogen, methane and the like come out from the top of the carbon four absorption tower, the light components enter a gasoline absorption tower, crude hydrogen gas 6 is obtained from the top of the tower, materials at the bottom of the tower enter a gasoline stabilizing tower, and lean absorbent at the bottom of the tower is recycled to the gasoline absorption tower. The carbon recovery of this example was 97.5%. The heat load of the top condenser and the bottom reboiler of the carbon four desorption tower is reduced by about 50 percent compared with the technology that the refinery dry gas is directly subjected to carbon two recovery treatment without membrane separation.
The technical solution of the present invention is described in detail with reference to the attached drawings, which are only drawn for illustrating the basic contents of the invention, and it does not limit the contents and usage forms of the invention, and in fact, some pipes need to be provided with conventional equipments or pipe elements such as pumps, heat exchangers, etc. according to the specific operation conditions.
Claims (9)
1. A combined process for recovering and separating refinery dry gas adopts a combined process of membrane separation and carbon two recovery to concentrate the dry gas, and is characterized by comprising the following steps:
1) the refinery dry gas as a raw material gas enters a membrane separation part, after being pressurized by a compressor, a gas phase enters a membrane separation component, and most of hydrogen, part of methane and trace other components permeate a membrane and are enriched into methane hydrogen gas on a permeation side; a small amount of hydrogen and methane and other components which do not permeate the membrane are enriched into a carbon-rich secondary gas from the non-permeation side of the membrane separation component and sent to a carbon dioxide recovery part;
2) and (3) the carbon-rich secondary gas from the membrane separation part in the step 1) enters a carbon-two recovery part, and after absorption and desorption, a carbon-two concentrated gas and a small amount of fuel gas are obtained.
2. The refinery dry gas of claim 1, which is one or more of catalytic dry gas, coking dry gas, reforming dry gas, aromatization gas, disproportionation dry gas, PSA tail gas and hydrogenation dry gas.
3. The combined refinery dry gas recovery and separation process of claim 1, wherein: after entering the membrane separation part, the refinery dry gas is pressurized by a compressor, compressed and cooled, and then enters a gas-liquid separation tank and a coalescing filter to remove a free liquid phase carried in the gas.
4. The combined refinery dry gas recovery and separation process of claim 3, wherein: the temperature of the gas after liquid removal is 70-85 ℃.
5. The combined refinery dry gas recovery and separation process of claim 1, wherein: the pressure of the carbon-rich secondary gas from the membrane separation part is 1.5-5.0 MpaG.
6. The combined refinery dry gas recovery and separation process of claim 1, wherein: the pressure of the carbon-rich secondary gas from the membrane separation part is 3.5-4.7 MpaG.
7. The combined refinery dry gas recovery and separation process of claim 1, wherein: and the hydrogen content of the methane hydrogen gas from the membrane separation part is 60-99% v.
8. The combined refinery dry gas recovery and separation process of claim 1, wherein: and the content of carbon two in the carbon two concentrated gas discharged from the carbon two recovery part is 50-99% v.
9. The combined refinery dry gas recovery and separation process of claim 1, wherein: and the proportion of the carbon in the carbon dioxide concentrated gas to the carbon in the raw material dry gas is 80-99% v.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112011357A (en) * | 2020-09-09 | 2020-12-01 | 盘锦浩业化工有限公司 | Refinery gas separation and recovery method and system |
| CN115594150A (en) * | 2022-10-26 | 2023-01-13 | 辽宁北方华锦五洲化工工程设计有限公司（Cn） | Hydrogen recovery system and hydrogen recovery and separation method |
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| 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 |
| CN107986932A (en) * | 2016-10-26 | 2018-05-04 | 中国石油化工股份有限公司 | A kind of apparatus and method that carbon two is recycled in the aromatic hydrocarbons by-product dry gas from methanol |
| 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
- 2020-05-09 CN CN202010385511.5A patent/CN111548824A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107986932A (en) * | 2016-10-26 | 2018-05-04 | 中国石油化工股份有限公司 | A kind of apparatus and method that carbon two is recycled in the aromatic hydrocarbons by-product dry gas from methanol |
| 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112011357A (en) * | 2020-09-09 | 2020-12-01 | 盘锦浩业化工有限公司 | Refinery gas separation and recovery method and system |
| CN115594150A (en) * | 2022-10-26 | 2023-01-13 | 辽宁北方华锦五洲化工工程设计有限公司（Cn） | Hydrogen recovery system and hydrogen recovery and separation method |
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