CN111547691A - Equipment and process for extracting helium from BOG gas with high hydrogen content - Google Patents
Equipment and process for extracting helium from BOG gas with high hydrogen content Download PDFInfo
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- CN111547691A CN111547691A CN202010347730.4A CN202010347730A CN111547691A CN 111547691 A CN111547691 A CN 111547691A CN 202010347730 A CN202010347730 A CN 202010347730A CN 111547691 A CN111547691 A CN 111547691A
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- C01B23/001—Purification or separation processes of noble gases
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Abstract
The invention discloses a device and a process for extracting helium from BOG gas with high hydrogen content, which relates to the field of devices and processes for extracting helium from BOG gas, and comprises a catalytic dehydrogenation reactor, a cooler, a molecular sieve dryer, a feed gas compressor, a heat exchanger, a membrane separator, a vacuum pump, a buffer tank, a crude helium compressor, a helium purifier, a helium supercharger, a digital display type gas supply busbar device and a helium bottle, wherein the device adopts a mode of pressurization before a membrane and vacuumizing after the membrane to increase the permeability coefficient of gas molecules, uses less membrane area to achieve higher yield and purity, does not have phase change in the membrane separation process of extracting crude helium from BOG feed gas, reduces equipment investment and operation cost, increases the recovery rate of helium before the analysis gas of the helium purifier returns to the feed gas compressor, the helium yield of the whole device is up to 99 percent, and performs the concentration of helium from BOG feed gas by adding an interface on the original BOG fuel gas pipeline, the non-permeation gas loss after passing through the membrane separator is less than 5%.
Description
Technical Field
The invention relates to equipment for extracting helium from BOG gas and a process field thereof, in particular to equipment for extracting helium from BOG gas with high hydrogen content and a process thereof.
Background
The BOG gas refers to gas which cannot be liquefied or noncondensable gas evaporated from a liquefied natural gas storage tank in the process of producing LNG by liquefying natural gas, the BOG gas flow is considerable, and can account for about 8% of the flow of the raw material gas to the maximum extent, so the BOG gas can be recovered by a special recovery process in the LNG production process flow, the BOG gas in an LNG storage tank is compressed to medium pressure by a BOG compressor, one part of gas is combusted as fuel gas, the rest part of gas is further compressed to the same pressure as the raw material gas by the BOG compressor, and the BOG gas is liquefied again before being merged back to the raw material gas pretreatment or after the raw material gas pretreatment according to the condition of an LNG device.
The BOG is circulated for many times, the non-condensable gases such as helium, hydrogen and the like in the BOG are concentrated and enriched continuously, helium in the BOG is still enriched to 1% -3% under the condition that a part of the BOG is burnt, and at the moment, if the BOG gas is used for extracting the helium, the helium extraction device has very low helium extraction energy consumption and completely has the industrial development value of purifying the helium.
The low-temperature condensation method is a method widely adopted for extracting helium from natural gas in various countries in the world at present. Firstly, impurities such as hydrogen sulfide, carbon dioxide, moisture and even mercury in a helium-containing gas source need to be purified before entering a low-temperature device, then natural gas is secondarily condensed to prepare crude helium with the helium content of about 60%, hydrogen which is difficult to liquefy in the natural gas is concentrated in the crude helium along with the concentration of the helium and needs to be removed before refining, in the process of removing the hydrogen from the crude helium, the content of the hydrogen reaches more than 10%, so the temperature rise in the catalytic combustion process of the hydrogen in the crude helium is high, which is not beneficial to the control of reaction, a common mode is to dilute the concentration of the hydrogen by adding excessive air or carry out multi-stage catalytic combustion, the concentration of the helium is diluted by the first process, the helium needs to be concentrated again, and the multi-stage hydrogen catalytic reactor of the second process has more equipment, large equipment investment and large occupied area.
Disclosure of Invention
In order to solve the problems in the prior art, the invention discloses equipment and a process for extracting helium from BOG gas with high hydrogen content, wherein the equipment comprises the following contents:
in a first aspect, the invention provides a device for extracting helium from BOG gas with high hydrogen content, which comprises a catalytic dehydrogenation reactor, a cooler, a molecular sieve dryer, a feed gas compressor, a heat exchanger, a membrane separator, a vacuum pump, a buffer tank, a crude helium compressor, a helium purifier, a helium supercharger, a digital display type gas supply busbar device and a helium bottle, wherein the output end of the catalytic dehydrogenation reactor is connected with the input end of the cooler, the output end of the cooler is connected with the input end of the molecular sieve dryer, the output end of the molecular sieve dryer is connected with the input end of the feed gas compressor, the output end of the feed gas compressor is connected with the input end of the heat exchanger, the output end of the heat exchanger is connected with the input end of the membrane separator, the permeation gas end of the membrane separator is connected with the vacuum pump, the output end of the vacuum pump is connected, the output end of the coarse helium compressor is connected with the input end of the helium purifier, the output end of the helium purifier for analyzing gas is connected with the input end of the feed gas compressor, the output end of the helium purifier for purifying gas is connected with the input end of the helium supercharger, the output end of the helium supercharger is connected with the input end of the digital display type gas supply bus device, and the output end of the digital display type gas supply bus device is connected with the helium bottle.
Preferably, a BOG raw gas helium removal device hand valve is fixedly installed at the input end of the catalytic dehydrogenation reactor, a BOG raw gas fuel gas pipe network hand valve is fixedly installed at one side, located at the BOG raw gas helium removal device hand valve, of the input end of the catalytic dehydrogenation reactor, and a membrane separator non-permeation gas BOG fuel gas removal hand valve is fixedly installed at the non-permeation gas end of the membrane separator.
Preferably, the cooler is one of a water cooler and an air cooler.
Preferably, the heat exchanger is one of a steam heater or an electric heater.
Preferably, the membrane separator is one of a single-stage membrane separation device, a two-stage membrane separation device or a multi-stage membrane separation device.
Preferably, the helium purifier comprises a pressure swing adsorption purifier and a cryogenic condensation purifier.
In a second aspect, the present invention provides a process for extracting helium from BOG gas with high hydrogen content, comprising the following steps:
step 1: mixing BOG raw material gas from an original BOG fuel gas pipe network with air, and then, dehydrogenating the mixture in a catalytic dehydrogenation reactor at the temperature of 200 ℃;
step 2: cooling the dehydrogenated gas in the step one to below 40 ℃ through a cooler, conveying the cooled gas to a molecular sieve dryer for dehydration, reducing the dew point of the dehydrated gas to below-60 ℃, and compressing the dehydrated gas in a feed gas compressor, wherein the pressure of the compressed gas is 0.8 MPaG;
and step 3: conveying the gas compressed in the step 2 to a heat exchanger with the temperature of 65 ℃ for heating;
and 4, step 4: conveying the gas heated in the step (3) to a membrane separator, conveying non-permeation gas of the membrane separator into an original BOG fuel gas pipe network to a boiler for combustion, generating crude helium from the permeation gas of the membrane separator, conveying the crude helium into a vacuum pump, and conveying the crude helium into a buffer tank for buffering through the vacuum pump;
and 5: conveying the crude helium buffered in the step (4) to a crude helium compressor, compressing the crude helium to 0.4MPaG by the crude helium compressor, and conveying the crude helium to a helium purifier for purification;
step 6: and (4) mixing the desorption gas generated in the purification process of the helium purifier in the step (5) with the gas after dehydrogenation compression before the desorption gas enters a feed gas compressor, pressurizing the purified gas helium of the helium purifier to 16.0MPaG through a helium supercharger, and filling the helium cylinder through a digital display type gas supply bus device.
Preferably, the BOG feed gas pressure from the raw BOG fuel gas grid in step 1 is 0.02 MPaG.
Preferably, the molecular sieve dryer in the step 2 adopts porous aluminosilicate crystals.
Preferably, the inlet pressure of the vacuum pump in the step 4 is-0.09 MPaG, and the outlet pressure of the vacuum pump is 0.05 MPaG.
Advantageous effects
The equipment and the process for extracting the helium from the BOG gas with high hydrogen content, which are manufactured by the technical scheme of the invention;
1. BOG raw material gas is adopted for direct catalytic dehydrogenation, the content of hydrogen in the BOG gas is 0.4-1% (v), the combustion reaction temperature is controllable, and nitrogen and oxygen are introduced into the front section. The introduced impurity gases can be removed together by the subsequent treatment process.
2. The invention adopts the mode of pressurizing before the membrane and vacuumizing after the membrane to increase the permeability coefficient of gas molecules and uses less membrane area to ensure that helium gas achieves higher yield and purity.
3. The invention has no phase change in the membrane separation process of concentrating crude helium from BOG feed gas, and reduces equipment investment and operation cost.
4. The desorption gas of the helium purifier is returned to the raw material gas compressor, so that the recovery rate of helium is increased, and the helium yield of the whole device is as high as 99%.
5. The invention adds a new interface on the original BOG fuel gas pipeline to concentrate helium in BOG raw material gas, and the loss of non-permeable gas after passing through a membrane separator is less than 5 percent.
Drawings
FIG. 1 is a block flow diagram of the present invention;
in the figure, 1-a catalytic dehydrogenation reactor; 2-a cooler; 3-a molecular sieve dryer; 4-a feed gas compressor; 5-a heat exchanger; 6-membrane separator; 7-a vacuum pump; 8-a buffer tank; 9-crude helium compressor; 10-helium purifier; 11-helium booster; 12-digital display type gas supply bus device; 13-helium tank; 14-BOG raw material gas helium extraction device hand valve; 15-BOG raw material gas is sent to a fuel gas pipe network hand valve; the 16-membrane separator non-permeate gas goes to BOG fuel gas hand valve.
Detailed Description
The present invention will be described in further detail with reference to examples.
A device for extracting helium from BOG gas with high hydrogen content comprises a catalytic dehydrogenation reactor 1, a cooler 2, a molecular sieve dryer 3, a feed gas compressor 4, a heat exchanger 5, a membrane separator 6, a vacuum pump 7, a buffer tank 8, a crude helium compressor 9, a helium purifier 10, a helium supercharger 11, a digital display type gas supply busbar device 12 and a helium bottle 13, wherein the output end of the catalytic dehydrogenation reactor 1 is connected with the input end of the cooler 2, the output end of the cooler 2 is connected with the input end of the molecular sieve dryer 3, the output end of the molecular sieve dryer 3 is connected with the input end of the feed gas compressor 4, the output end of the feed gas compressor 4 is connected with the input end of the heat exchanger 5, the output end of the heat exchanger 5 is connected with the input end of the membrane separator 6, the permeation gas end of the membrane separator 6 is connected with the vacuum pump 7, the output end, the output end of the buffer tank 8 is connected with the input end of a crude helium compressor 9, the output end of the crude helium compressor 9 is connected with the input end of a helium purifier 10, the analytic gas output end of the helium purifier 10 is connected with the input end of a feed gas compressor 4, the purified gas output end of the helium purifier 10 is connected with the input end of a helium booster 11, the output end of the helium booster 11 is connected with the input end of a digital display type gas supply busbar device 12, the output end of the digital display type gas supply busbar device 12 is connected with a helium bottle 13, a BOG feed gas removing helium device hand valve 14 is fixedly installed on the input end of the catalytic dehydrogenation reactor 1, the input end of the catalytic dehydrogenation reactor 1 is positioned at one side of the BOG feed gas removing helium device hand valve 14 and is fixedly provided with a BOG feed gas removing fuel gas pipe network hand valve 15, and a non-permeable gas removing BOG fuel gas hand valve, the cooler 2 is one of a water cooler or an air cooler, the heat exchanger 5 is one of a steam heater or an electric heater, the membrane separator is one of a single-stage membrane separation device, a secondary membrane separation device or a multi-stage membrane separation device, and the helium purifier comprises a pressure swing adsorption purifier and a cryogenic condensation purifier.
Example (b): according to the attached figure 1 of the specification, in use, when the BOG helium extraction device is put into use, the BOG raw material gas is closed to the fuel gas pipe network hand valve 15, the BOG raw material gas is opened to the helium extraction device hand valve 14, the membrane separator non-permeate gas is opened to the BOG fuel gas hand valve 16, the BOG purified helium system is put into use, when the BOG purified helium system is overhauled, the BOG raw material gas is opened to the fuel gas pipe network hand valve 15, the BOG raw material gas is closed to the helium extraction device hand valve 14, the membrane separator non-permeate gas is closed to the BOG fuel gas hand valve 16, and the BOG fuel gas pipe network can normally supply gas without influencing the use of subsequent users.
BOG raw material gas from an original BOG fuel gas pipe network is mixed with excessive air and then enters a catalytic dehydrogenation reactor 1, so that hydrogen in the BOG gas is completely combusted, at the moment, components in the gas comprise methane, helium, oxygen, water and nitrogen, the gas after the combustion reaction is cooled through a cooler 2 and enters a molecular sieve dryer 3 for dehydration, the dehydrated gas enters a raw material gas compressor 4 for compression, the compressed gas is heated through a heat exchanger 5 and then is sent to a membrane separator 6, a non-permeation gas outlet of the membrane separator 6 is merged into the original BOG fuel gas pipe network, permeation gas of the membrane separator 6 is crude helium, the crude helium is connected with an inlet of a vacuum pump 7, the pressure difference and the pressure ratio of the membrane separator 6 are increased through the vacuum pump 7, the separation coefficient of the gas is increased, and the crude helium after vacuum treatment enters a buffer tank 8 through the vacuum pump 7. An outlet of the buffer tank 8 is connected with a crude helium compressor 9, the crude helium compressor 9 compresses and sends crude helium to a helium purifier 10, if the amount of pure helium is small according to the processing capacity of the BOG feed gas, the helium purifier 10 is a pressure swing adsorption purifier, if the amount of pure helium is large, the helium purifier 10 is a cryogenic condensation purifier, the helium purifier 10 removes nitrogen, oxygen and methane in the crude helium, the desorption gas of the helium purifier 10 is mixed with the dehydrogenated BOG gas and separated again before being sent to the feed gas compressor 4, the recovery rate of the helium is increased, the purified gas purified by the helium purifier 10 is pressurized by a helium supercharger 11, and then is filled into a helium bottle 13 by a digital display type gas supply and confluence device 12.
As can be seen from the attached figure 1 of the specification, the process for extracting helium from BOG gas with high hydrogen content;
step 1: mixing BOG raw material gas with the pressure of 0.02MPaG from an original BOG fuel gas pipe network with air, and then, entering a catalytic dehydrogenation reactor 1 with the temperature of 200 ℃ for dehydrogenation to ensure that hydrogen in the BOG gas is completely combusted, wherein the components in the gas comprise methane, helium, oxygen, water and nitrogen at the moment;
step 2: cooling the dehydrogenated gas in the step one to be below 40 ℃ through a cooler 2, conveying the cooled gas into a molecular sieve dryer 3 for dehydration, wherein the molecular sieve dryer 3 adopts porous aluminosilicate crystals, the dew point of the dehydrated gas is reduced to be below-60 ℃, the dehydrated gas enters a raw material gas compressor 4 for compression, and the pressure of the compressed gas is 0.8 MPaG;
and step 3: conveying the gas compressed in the step 2 into a heat exchanger 5 with the temperature of 65 ℃ for heating;
and 4, step 4: and (3) conveying the gas heated in the step (3) to a membrane separator (6), merging the non-permeable gas of the membrane separator (6) into the original BOG fuel gas pipe network, conveying the non-permeable gas into a boiler for combustion, generating crude helium by the permeable gas of the membrane separator (6), wherein the content of the helium is 75% (v), conveying the crude helium into a vacuum pump (7), and increasing the pressure difference and pressure ratio of the membrane separator (6) and the separation coefficient of the gas by increasing the inlet pressure of the vacuum pump (7) to be-0.09 MPaG. The outlet pressure of the vacuum pump 7 is 0.05MPaG, and the crude helium is conveyed into a buffer tank 8 through the vacuum pump 7 for buffering;
and 5: conveying the crude helium buffered in the step 4 to a crude helium compressor 9, compressing the crude helium to 0.4MPaG by the crude helium compressor 9, and conveying the crude helium to a helium purifier 10 for purification, selecting the helium purifier 10 according to the processing capacity of BOG feed gas, wherein if the amount of pure helium is small, the helium purifier 10 selects a pressure swing adsorption purifier, if the amount of pure helium is large, the helium purifier 10 selects a cryogenic condensation purifier, and the helium purifier 10 removes nitrogen, oxygen and methane in the crude helium to enable the helium concentration to reach 99.999%;
step 6: and (3) mixing the decomposed gas generated in the purification process of the helium purifier 10 in the step (5) with the gas after dehydrogenation compression before the feed gas compressor 4, pressurizing the purified gas helium gas of the helium purifier 10 to 16.0MPaG through a helium supercharger 11, and filling a helium gas bottle 13 through a digital display type gas supply busbar device 12.
The technical solutions described above only represent the preferred technical solutions of the present invention, and some possible modifications to some parts of the technical solutions by those skilled in the art all represent the principles of the present invention, and fall within the protection scope of the present invention.
Claims (10)
1. A device for extracting helium from BOG gas with high hydrogen content comprises a catalytic dehydrogenation reactor (1), a cooler (2), a molecular sieve dryer (3), a feed gas compressor (4), a heat exchanger (5), a membrane separator (6), a vacuum pump (7), a buffer tank (8), a crude helium compressor (9), a helium purifier (10), a helium supercharger (11), a digital display type gas supply busbar device (12) and a helium bottle (13), and is characterized in that the output end of the catalytic dehydrogenation reactor (1) is connected with the input end of the cooler (2), the output end of the cooler (2) is connected with the input end of the molecular sieve dryer (3), the output end of the molecular sieve dryer (3) is connected with the input end of the feed gas compressor (4), and the output end of the feed gas compressor (4) is connected with the input end of the heat exchanger (5), the output end of the heat exchanger (5) is connected with the input end of a membrane separator (6), the gas permeation end of the membrane separator (6) is connected with a vacuum pump (7), the output end of the vacuum pump (7) is connected with the input end of a buffer tank (8), the output end of the buffer tank (8) is connected with the input end of a crude helium compressor (9), the output end of the crude helium compressor (9) is connected with the input end of a helium purifier (10), the output end of the analysis gas of the helium purifier (10) is connected with the input end of the raw material gas compressor (4), the purified gas output end of the helium purifier (10) is connected with the input end of a helium supercharger (11), the output end of the helium supercharger (11) is connected with the input end of a digital display type gas supply bus device (12), the output end of the digital display type gas supply bus device (12) is connected with a helium bottle (13).
2. The equipment for extracting the helium from the BOG gas with high hydrogen content according to claim 1, wherein a BOG raw material gas to helium extracting device hand valve (14) is fixedly installed at the input end of the catalytic dehydrogenation reactor (1), a BOG raw material gas to fuel gas pipe network hand valve (15) is fixedly installed at one side, located at one side of the BOG raw material gas to helium extracting device hand valve (14), of the input end of the catalytic dehydrogenation reactor (1), and a membrane separator non-permeable gas to BOG fuel gas hand valve (16) is fixedly installed at the non-permeable gas end of the membrane separator (6).
3. The apparatus for stripping BOG gas from helium with high hydrogen content as claimed in claim 1, wherein said cooler (2) is one of a water cooler or a wind cooler.
4. The apparatus for stripping BOG gas with high hydrogen content from helium according to claim 1, wherein the heat exchanger (5) is one of a steam heater or an electric heater.
5. The apparatus of claim 1, wherein the membrane separator is one of a single-stage membrane separation device, a two-stage membrane separation device, or a multi-stage membrane separation device.
6. The apparatus for extracting helium from BOG gas with high hydrogen content according to claim 1, wherein the helium purifier comprises a pressure swing adsorption purifier and a cryocondensation purifier.
7. A process for extracting helium from BOG gas with high hydrogen content is characterized by comprising the following steps:
step 1: mixing BOG raw material gas from an original BOG fuel gas pipe network with air, and then, entering a catalytic dehydrogenation reactor (1) with the temperature of 200 ℃ for dehydrogenation;
step 2: cooling the dehydrogenated gas in the step one to be below 40 ℃ through a cooler (2), conveying the cooled gas into a molecular sieve dryer (3) for dehydration, reducing the dew point of the dehydrated gas to be below-60 ℃, and compressing the dehydrated gas in a feed gas compressor (4), wherein the pressure of the compressed gas is 0.8 MPaG;
and step 3: conveying the gas compressed in the step 2 into a heat exchanger (5) with the temperature of 65 ℃ for heating;
and 4, step 4: conveying the gas heated in the step (3) to a membrane separator (6), feeding non-permeable gas of the membrane separator (6) into an original BOG fuel gas pipe network to be conveyed to a boiler for combustion, generating crude helium by the permeable gas of the membrane separator (6), conveying the crude helium into a vacuum pump (7), and conveying the crude helium into a buffer tank (8) for buffering through the vacuum pump (7);
and 5: conveying the crude helium buffered in the step 4 to a crude helium compressor (9), compressing the crude helium to 0.4MPaG by the crude helium compressor (9), and conveying the crude helium to a helium purifier (10) for purification;
step 6: and (3) mixing the analysis gas generated in the purification process of the helium purifier (10) in the step (5) with the gas after dehydrogenation compression before the raw material gas compressor (4), pressurizing the purified gas helium of the helium purifier (10) to 16.0MPaG through a helium supercharger (11), and filling a helium bottle (13) through a digital display type gas supply busbar device (12).
8. The process of claim 7, wherein the BOG feed gas pressure from the raw BOG fuel gas grid in step 1 is 0.02 MPaG.
9. The process for extracting helium from BOG gas with high hydrogen content as claimed in claim 7, wherein the molecular sieve dryer (3) in the step 2 adopts porous aluminosilicate crystals.
10. The process for extracting helium from a BOG gas with high hydrogen content as claimed in claim 7, wherein the inlet pressure of the vacuum pump (7) in the step 4 is-0.09 MPaG, and the outlet pressure of the vacuum pump (7) is 0.05 MPaG.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112880302A (en) * | 2021-01-26 | 2021-06-01 | 安徽中科皖能科技有限公司 | Method and equipment for liquefying natural gas and co-producing high-purity helium gas |
| CN112919437A (en) * | 2021-03-24 | 2021-06-08 | 北京中科富海低温科技有限公司 | Refining method and system for crude helium with high hydrogen content |
| CN113154798A (en) * | 2021-05-10 | 2021-07-23 | 大连理工大学 | Multi-target separation process for comprehensively utilizing liquefied tail gas of helium-rich natural gas |
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| CN112919437B (en) * | 2021-03-24 | 2022-08-19 | 北京中科富海低温科技有限公司 | Refining method and system for crude helium with high hydrogen content |
| CN113154798A (en) * | 2021-05-10 | 2021-07-23 | 大连理工大学 | Multi-target separation process for comprehensively utilizing liquefied tail gas of helium-rich natural gas |
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