KR102466732B1 - H2 and CO2 separation method with VPSA applied to increase hydrogen recovery rate - Google Patents

Abstract

The present invention relates to a method for simultaneous separation of hydrogen and carbon dioxide at the end of WGS during a syngasification process of petroleum coke for hydrogen production in which a gas containing carbon monoxide generated through the gasification of petroleum coke and a reaction gas containing steam is supplied to continuously and simultaneously separate synthesis gas converted to hydrogen by reacting with a high-temperature catalyst and/or a low-temperature catalyst, and there is an effect of being able to continuously separate the hydrogen and carbon dioxide at high concentrations in succession rather than a separate unit process.

Description

H2 and CO2 separation method with VPSA applied to increase hydrogen recovery rate { H2 and CO2 separation method with VPSA applied to increase hydrogen recovery rate }

The present invention relates to a method for separating H2 and CO2 using VPSA to increase the hydrogen recovery rate, and more particularly, the present invention supplies a gas containing carbon monoxide generated through gasification of petroleum coke and a reaction gas containing steam. It relates to a H2 and CO2 separation method applying VPSA for increasing the hydrogen recovery rate for continuously and simultaneously separating high concentration hydrogen and carbon dioxide from syngas converted into hydrogen by reacting with a high temperature catalyst and / or a low temperature catalyst.

The main energy sources in the 21st century are natural gas, electricity, and hydrogen along with ultra-clean fuel oil. Renewable energy source electricity and high value-added gasification/fueling of CO2 are emerging, and clean and easy-to-use gas/liquid fuel oil is used. Expansion is expected, and there is a great need to secure an inexpensive hydrogen energy source, but technology development and demonstration are required due to the lack of economic feasibility.

In particular, in terms of hydrogen production direction, gray hydrogen technology that uses by-product hydrogen generated during the reforming of fossil fuels such as heavy oil and natural gas or during steel mills or petrochemical processes as an energy source, low-grade coal, petroleum coke, and bio It is a blue hydrogen technology that produces hydrogen by producing syngas using mass and waste and reforming it, and a green hydrogen technology that produces hydrogen through electrolysis of water using renewable energy sources. can be classified normally.

Therefore, it is judged that it is necessary to develop blue hydrogen technology for hydrogen production required by the market before entering green hydrogen technology, which is not in the demonstration stage. In the short term, clean syngas plants are judged to be a key field in the overseas export plant market. In the case of Korea, the domestic synthesis gas market is large and the hydrogen market such as hydrogen cities and hydrogen fuel cell vehicles is expected to grow rapidly. It is judged to be an appropriate field for overseas exports and plant technology investment policies for national wealth creation.

The technology related to the plant for producing petroleum coke hydrogen of the present invention can be achieved through a number of fusion technologies.

Republic of Korea Patent Registration No. 10-2317351 discloses the discharge water inflow step in which the discharge water inlet and discharge unit is opened to introduce the discharge water containing fine particles into the case, and the filtered water discharge unit and the dehydration discharge unit are opened to facilitate the inflow. When the inflow of the discharged water is completed, the dehydration discharge unit is closed, the discharged water inlet and discharge unit continues to flow in the discharged water, and the filtered water discharge unit is opened to discharge the filtered discharged water. A filtration stop step in which the discharge water is discharged through the inflow and discharge portion, the filtered water discharge portion is closed, and the dehydration discharge portion is open. After all the discharge water is discharged in the filtration stop step, fine particles in the filter filtration portion are rotated through the filter filtration portion. A dehydration operation step in which only the dehydration discharge unit is opened for dehydration of the filter, and when the dehydration operation step is stopped, the fine particle detachment unit and the high-pressure spray nozzle unit move up and down to separate the fine particles located inside the filter filtration unit, filter filtration The part relates to a fine particle filtering device operated in a filter unit regeneration step that is operated in rotation and a fine particle discharge step that transports, stores, and discharges the fine particles desorbed in the filter unit regeneration step. In Korean Patent Registration No. 10-2316734, case 100; a plurality of channels 200 vertically formed inside the case; a catalyst permeation part 300 positioned between the channels and partially formed with a porous catalyst part; a reaction gas inlet 400 flowing into the side of the case; and at least two header portions 500 formed to allow fluid to move for heat exchange through the channels, wherein the plurality of channels have one or more annular shapes, and an annular portion 210 is formed around the central axis of the case, , The catalytic permeation portion is formed while being in contact with a plurality of channels formed of the annular portion, and the annular portion 210 has the reaction gas introduced between the upper and lower portions of the case at both ends of the outermost annular portion 211. Disclosed is a water gas shift isothermal catalytic reactor including a catalyst permeation unit, characterized in that a flow member 213 for inducing internal circulation and uniform dispersion and a channel member 214 having a circular cross section are formed. Republic of Korea Patent Registration No. 10-2316737 discloses a cylindrical reactor case, a central tube located at the center of the case and capable of moving fluid, a fluid supply unit connected to the upper part of the case to supply fluid to the inside, and the fluid supply unit. It is formed of a plurality of divided compartments for the catalytic reaction of the fluid supplied through, and one compartment is formed with an upper, middle, and lower end, so that only the upper and lower ends are open so that the fluid can move, and one side of the middle and bottom A first catalyst layer containing a catalyst, a first distribution unit included in the first catalyst layer and moving the fluid supplied through the fluid supply unit to the top of the first catalyst layer, and a first distribution unit included in the first catalyst layer A first confluence that moves the fluid distributed by the catalyst to join the central tube with the fluid in another compartment through the lower end after the catalytic reaction through the catalyst of the first catalyst layer, connected to the lower part of the case and connected to the center tube through the first confluence A water-gas conversion reactor comprising a fluid discharge unit for discharging to the outside moved to, a cooling water discharge unit for discharging cooling water located on one side of the fluid supply unit, and a cooling water supply unit for supplying cooling water located on one side of the fluid discharge unit. has been

Korean Patent Registration No. 10-2313690 discloses a synthesis gas converted into hydrogen by reacting with a high-temperature catalyst and/or a low-temperature catalyst by supplying a reaction gas including steam and a gas containing carbon monoxide generated through gasification of petroleum coke. It is a process using an iron chelate aqueous solution to make an iron chelate aqueous solution that can be directly recovered as sulfur (S) by removing high-concentration hydrogen sulfide (H2S) in the syngas by contacting the iron chelate and syngas in co-current. It relates to a high-concentration hydrogen sulfide removal device with low consumption of absorbent and increased contact efficiency during the petroleum coke syngasification process for hydrogen production using synthetic gas, which continuously removes hydrogen sulfide and discharges the hydrogen sulfide-removed syngas. A plurality of reaction tubes 100 in the form of a U-tube; Supply pipes 200 connected to the uppermost part of the reaction tube to supply an iron chelate aqueous solution; Pressurized injection nozzles 110 for injecting the iron chelate aqueous solution respectively formed into the inside of the uppermost part of the reaction tube connected to the supply tube; Discharge tubes 210 formed at the lowermost portions of the reaction tubes, through which the aqueous solution of iron chelate in which the hydrogen sulfide is collected is discharged; a water level control tank 300 for storing the iron chelate aqueous solution in which the hydrogen sulfide is collected, to which the plurality of discharge pipes are individually connected; The iron chelate aqueous solution containing the hydrogen sulfide from the water level control tank is reduced in pressure and brought into contact with oxygen or air.

A regeneration tank 400 for regenerating the iron chelate aqueous solution through fabric fluidization; a precipitation tank (500) which precipitates sulfur in the iron chelate aqueous solution supplied from the regeneration tank as elemental sulfur and separates it from the iron chelate aqueous solution; And a storage tank 600 for supplying and storing the iron chelate aqueous solution from the precipitation tank to the supply pipe, wherein the flow rate of the synthesis gas is rapidly lowered between the plurality of reaction tubes while reducing the consumption of the iron chelate aqueous solution. Disclosed is an apparatus for continuously removing high concentration hydrogen sulfide in petroleum coke syngas further comprising a right-angled triangle-shaped electrostatic spray reactor 700 to increase contact efficiency.

Korean Patent Registration No. 10-2313692 discloses a reaction tube 100 in the form of a U-tube formed so that synthesis gas is introduced, hydrogen sulfide is removed, and the synthesis gas from which the hydrogen sulfide is removed is discharged; a main reaction tube 200 in which an iron chelate aqueous solution formed at the front end of the reaction tube is sprayed to form a solvent curtain; a supply pipe 300 connected to the uppermost part of the main reaction tube and the reaction tube to supply the iron chelate aqueous solution; a plurality of first pressurized injection nozzles 210 for spraying the iron chelate aqueous solution formed into the main reaction tube connected to the supply tube; A plurality of discharge pipes 220 formed at the lowermost part of the main reaction pipe and discharging the iron chelate aqueous solution collecting the hydrogen sulfide; a water level control tank 400 for storing the iron chelate aqueous solution in which the hydrogen sulfide is collected, to which the plurality of discharge pipes are individually connected; a regeneration tank 400 for regenerating the iron chelate aqueous solution through bubble fluidization by reducing the pressure of the iron chelate aqueous solution collected from the water level control tank and bringing it into contact with oxygen or air; a precipitation tank (500) which precipitates sulfur in the iron chelate aqueous solution supplied from the regeneration tank as elemental sulfur and separates it from the iron chelate aqueous solution; and a storage tank 600 for supplying and storing the iron chelate aqueous solution from the precipitation tank to the supply pipe, wherein the first pressurized injection nozzle is based on the discharge pipe formation position in the longitudinal direction RL of the main reaction pipe. A plurality may be formed, and a plurality of nozzles are formed on the same cross section in the cross-sectional direction (RC) of the main reaction tube, and the first pressure injection nozzle is 180 degrees based on the upper cross-sectional line (RCU) on the same cross-section of the main reaction tube. It is formed at intervals of 10 degrees to 25 degrees in the area, and the first pressure injection nozzle is based on the upper section line (RCU) on the same section of the main reaction tube in the longitudinal direction (RL) of the main reaction tube.

The water level is adjusted in the water level control tank so that the lowermost part of the reaction tube formed while changing the formation angle, and the discharge tube is formed, the iron chelate aqueous solution collecting a predetermined amount of the hydrogen sulfide remains, and the water level is adjusted at the rear end of the main reaction tube. A plurality of second pressure injection nozzles 110 formed at predetermined positions in the vertical direction of the reaction tube formed in communication with each other, and an iron chelate aqueous solution collecting the hydrogen sulfide formed at the bottom of the reaction tube is discharged a reaction tube discharge pipe 120; Disclosed is a high-concentration hydrogen sulfide removal device using a solvent curtain film comprising a.

In Korean Patent Registration No. 10-2300741, during the petroleum coke syngasification process for hydrogen production, one or more welding objects of a roll-bent pipe or cap, a work table formed of a frame for welding the welding object, and one side of the upper surface of the work table A welding part for welding the object to be welded, a cap fixing part for fixing a cap to be welded, located on the other side of the upper surface of the work table, and a pipe fixing part for fixing a rolled pipe to be welded, located on the other side of the upper surface of the work table. , Roll bending welding device including an air cooling unit positioned between the cap fixing part and the pipe fixing part on the upper surface of the work table and blowing air to maintain a uniform temperature when the object to be welded is welded through the welding part. is starting

Korean Patent Registration No. 10-2351661 relates to a device for buffing a cam and a pipe during a petroleum coke syngasification process for hydrogen production, a buffing object that is a cap or a pipe, and a frame for performing the buffing operation of the buffing object. A work table formed of a work table, a fixing part installed on one side of the frame on the top surface of the work table and fixing the buffing object, an internal buffing part installed on the other side of the top surface of the work table and buffing the inside of the buffing object fixed to the fixing part, and another part on the top surface of the work table. Disclosed is a buffing apparatus including a second rail installed on one side, and an external buffing unit positioned on the second rail to buff the outside of a buffing object fixed to the fixing unit.

Korean Patent Registration No. 10-2292411 discloses a source gas supply unit 10 for supplying syngas produced in a petroleum coke gasification process; Water supply unit 20 for supplying supply water; a steam generator 100 stably producing superheated steam using the supply water supplied to the water supply unit 20; A high-temperature reactor 210 generating a first gas containing hydrogen under a first temperature condition using the raw material gas supplied from the supply unit 10 and steam produced from the steam generator 100 and discharging the same; A low-temperature reactor 220 for generating and discharging a second gas containing high concentration H2 under a second temperature condition using the intermediate product discharged from the high-temperature reactor 210 and the steam produced from the steam generator 100; and a hydrogen separator 400 separating hydrogen from the second gas, wherein the steam generator 100 includes a multi-stage steam production unit, and uses the second gas discharged from the low-temperature reactor 220 to Supply water supplied from the water supply unit 20 is preheated, and the preheated supply water is supplied to the first steam production unit 101 of the steam generator 100 to produce first steam, which is steam

A part of the mixed steam in the steam drum 110 is supplied to the second steam production unit 102 of the steam generator 100 to produce second steam, which is supplied to the steam drum 110. ), and a part of the mixed steam in the steam drum 110 is supplied to the third steam production unit 103 of the steam generator 100 to produce third steam to the high-temperature reactor 210 and the low-temperature A high-purity hydrogen production system characterized in that it stably produces superheated steam supplied to the reactor 220 is disclosed.

Republic of Korea Patent Registration No. 10-22922426 discloses a method for continuously separating hydrogen and carbon dioxide having a purity of 99% or more from syngas as a source invention of the present invention, wherein the syngas is supplied from the syngas through the supply pipe 100. A first step of passing through a first adsorption tower 110 or a second adsorption tower 120 filled with a plurality of first adsorbents capable of selectively adsorbing components other than hydrogen; A second step in which the hydrogen refined to high purity through the first adsorption tower or the second adsorption tower in the first step is captured in the hydrogen storage tank 140 through the hydrogen pipe 130; In the second step, the adsorption tower for washing the first adsorbent saturated with the first tail gas among the first adsorption tower or the second adsorption tower selectively stops the hydrogen production and the first adsorption tower of the first adsorption tower or the second adsorption tower. A third step of separating and cleaning the first tail gas from the adsorption tower by the first vacuum pump 160 formed on the tail gas pipe 150; a fourth step of discharging second tail gas from which moisture is removed while the first tail gas separated in the third step passes through a gas dryer 200 formed at a rear end of the first vacuum pump; The second tail gas that has passed through the gas dryer in the fourth step is filled with a second adsorbent capable of adsorbing carbon dioxide from the secondary tail gas through the second tail gas pipe 210 in a third adsorption tower ( 220) or the fifth step of passing through the fourth adsorption tower 230; a sixth step in which the second tail gas not adsorbed via the third adsorption tower or the fourth adsorption tower in the fifth step is circulated and supplied to the gas dryer through the circulation pipe 240; In the sixth step, the adsorption tower for washing the second adsorbent saturated with carbon dioxide among the third adsorption tower or the fourth adsorption tower selectively stops the circulation supply of the second tail gas to the gas dryer and the third adsorption tower. or a seventh step of separating and washing the carbon dioxide in the adsorption tower by the second vacuum pump 260 formed on the third tail gas pipe 250 of the fourth adsorption tower; and an eighth step in which the carbon dioxide separated in the seventh step is stored in the carbon dioxide storage tank 290 through the carbon dioxide pipe 280 at the rear end of the second vacuum pump. Adsorption pressure is 0.3 to 0.8 MPa, desorption pressure is -0.06 to 0.88 MPa, 0.001 to 0.07 MPa of the third and fourth adsorption towers, and desorption pressure is -0.07 to 0.06 MPa, hydrogen and carbon dioxide having a purity of 99% or more. A method for continuously separating is disclosed. However, there is a problem in that the hydrogen recovery rate is lowered during the adsorption process.

Korean Patent Publication No. 2009-0005508 discloses a pressure swing adsorption device comprising a plurality of adsorption towers connected to a raw material supply pipe, a hydrogen storage tank in which hydrogen purified in the adsorption tower is collected, and a valve that opens and closes a plurality of pipes connected to each adsorption tower. In the adsorption tower, activated carbon and zeolite 13X, zeolite 5A and carbon dioxide selective adsorbents other than zeolite 5A capable of removing carbon dioxide, methane and carbon monoxide contained in the hydrogen mixture supplied through the raw material supply pipe therein Adsorbent A technology is disclosed for a hydrogen purification method using a pressure swing adsorption device that is filled in a multi-layer structure and sequentially adsorbed on the adsorbent in the adsorption tower to minimize the carbon monoxide content in the discharged hydrogen, but syngas for increasing the hydrogen recovery rate A technique for a method for continuously and simultaneously separating hydrogen and carbon dioxide in a high concentration has not been disclosed.

Most of the conventional hydrogen purification processes are performed by applying the pressure swing adsorption method by the exhaust gas to the reforming reactor of methane using steam, and the conventional pressure swing adsorption (PSA) process is the use of the adsorbate for the adsorbent. As a method of separating mixed gas by using the difference in adsorption selectivity, the adsorption step of separating the weak adsorption component and the strong adsorption component is usually performed at high pressure, and the adsorbed component is desorbed by lowering the pressure of the adsorption tower. to regenerate the adsorbent.

In order to fully regenerate the adsorbent, it is cleaned at low pressure with high-purity weak adsorption components, and to pressurize with adsorption pressure, raw material gas or hydrogen product is used. It consists of a basic process such as an accumulating step. However, when only this process is applied, the recovery rate of not only hydrogen products but also mechanical energy for the adsorption device is lowered.

In addition, in the existing PSA process for separating hydrogen from syngas, hydrogen is separated and produced, and the remaining tail gas is discharged into the atmosphere or incinerated or recycled. Therefore, after gasifying petroleum coke in the technical field of the present invention, it is not appropriate to separate syngas, whose main components are hydrogen and carbon dioxide, through a water gas shift reaction by applying a one-step hydrogen PSA process. However, it is not appropriate in terms of process efficiency and operation.

In particular, the conventional hydrogen PSA process is being designed to include an adsorbent for removing moisture in one tower. Due to this, it is difficult to replace the entire adsorbent when it is necessary to replace the adsorbent for adsorbing moisture. In addition, as the volume of the adsorption tower increases, the amount of gas lost increases and the amount of washing also increases, so there is a limit to increasing the recovery rate.

It is necessary to install DRYER, a separate process to remove moisture when collecting CO2 from TAIL GAS of hydrogen PSA. Ultimately, both the hydrogen PSA process for purifying hydrogen and the Wuhan CO2 PSA for purifying CO2 need to have a DRYER function to remove moisture.

Therefore, research on a process method for producing syngas through gasification of petroleum coke and continuously separating the syngas obtained by converting carbon monoxide into hydrogen and carbon dioxide in high concentration to increase the hydrogen recovery rate. nothing is presented

Republic of Korea Patent Registration No. 10-2351661 Republic of Korea Patent Registration No. 10-2317351 Republic of Korea Patent Registration No. 10-2316734 Republic of Korea Patent Registration No. 10-2316737 Republic of Korea Patent Registration No. 10-2313690 Republic of Korea Patent Registration No. 10-2313692 Republic of Korea Patent Registration No. 10-2300741 Republic of Korea Patent Registration No. 10-2292411 Republic of Korea Patent Registration No. 10-2292426

The main object of the present invention to solve the above conventional problems is to supply a reaction gas containing gas and steam containing carbon monoxide generated through gasification of petroleum coke to react with a high-temperature catalyst and / or a low-temperature catalyst The purpose is to provide a simultaneous separation method for hydrogen and carbon dioxide at the end of WGS to increase the hydrogen recovery rate during the petroleum coke synthesis gasification process for hydrogen production that continuously and simultaneously separates high-concentration hydrogen and carbon dioxide from syngas converted into hydrogen. .

In addition, during the petroleum coke syngasification process for hydrogen production, which can produce syngas through gasification of petroleum coke and continuously separate syngas obtained by converting carbon monoxide into hydrogen and carbon dioxide in the produced syngas at a high concentration. It is an object of the present invention to provide a method for simultaneous separation of hydrogen and carbon dioxide after WGS to increase the hydrogen recovery rate.

Other objects, particular advantages and novel features of the present invention will become more apparent from the following detailed description and preferred embodiments taken in conjunction with the accompanying drawings.

The present invention for solving the above technical problem is a method for continuously separating hydrogen and carbon dioxide having a purity of 99% or more from syngas to increase the hydrogen recovery rate,

A first step in which the syngas is supplied to a gas dryer through the supply pipe 100 to absorb moisture; The syngas passing through the gas dryer is supplied through the supply pipe 100 to the first adsorption tower 110 or the second adsorption tower 110 filled with a plurality of first adsorbents capable of selectively adsorbing components other than hydrogen in the syngas. a second step through (120); A third step in which hydrogen purified to high purity through the first adsorption tower or the second adsorption tower in the second step is collected in the hydrogen storage tank 140 through the hydrogen pipe 130; In the second step, the adsorption tower for washing the first adsorbent saturated with the first tail gas among the first adsorption tower or the second adsorption tower selectively stops the hydrogen production and the first adsorption tower of the first adsorption tower or the second adsorption tower. A fourth step of separating the first tail gas from the adsorption tower by the first vacuum pump 160 formed on the tail gas pipe 150; After the hydrogen is collected in the hydrogen storage tank in the third step, the first tail gas is used to clean the first adsorption tower or the second adsorption tower or desorb moisture from the gas dryer by the first vacuum pump 160. 5th step to do; a sixth step of discharging the second tail gas while the first tail gas separated in the fifth step passes through the after cooler 300; The second tail gas that has passed through the aftercooler in the sixth step is supplied through a second tail gas pipe 210 through a third adsorption tower filled with a second adsorbent capable of adsorbing carbon dioxide from the secondary tail gas ( 220) or the seventh step of passing through the fourth adsorption tower 230; In the sixth step, the adsorption tower for cleaning the second adsorbent saturated with carbon dioxide among the third adsorption tower or the fourth adsorption tower is the second adsorption tower formed on the third tail gas pipe 250 of the third adsorption tower or the fourth adsorption tower. An eighth step of separating and washing the carbon dioxide in the adsorption tower by the vacuum pump 260; And a ninth step in which the carbon dioxide separated in the eighth step is stored in the carbon dioxide storage tank 290 through the carbon dioxide pipe 280 at the rear of the second vacuum pump; It may be a method for continuously separating 99% or more of hydrogen and carbon dioxide.

In addition, the pressurization of the gas dryer in the first step may be performed with the syngas.

In addition, the gas dryer of the first step includes activated alumina, molecular sieve, and activated carbon, and can remove moisture to a dew point of -70 ° C.

In addition, an adsorbent for adsorbing moisture may not be included in the first adsorption tower, the second adsorption tower, the third adsorption tower, and the fourth adsorption tower.

In addition, the synthesis gas may be a gas mixture of 40 ± 5 vol% of carbon monoxide, 30 ± 5 vol% of hydrogen, 10 ± 5 vol% of carbon dioxide and other components including moisture through gasification of petroleum coke.

In addition, the gas mixture may be 50 ± 5 vol% of hydrogen, 40 ± 5 vol% of carbon dioxide and other components including moisture through a water gas shift reaction.

In addition, an adsorption layer filled with an adsorbent capable of adsorbing carbon monoxide, carbon dioxide, moisture, nitrogen, hydrogen sulfide, COS, and methane may be selectively formed in the first adsorption tower and the second adsorption tower.

In addition, an adsorption layer filled with activated carbon and/or zeolite 13X for adsorbing carbon dioxide may be selectively formed in the third adsorption tower and the fourth adsorption tower.

In addition, the adsorption pressure of the first adsorption tower and the second adsorption tower may be 0.3 to 0.8 MPa.

In addition, the desorption pressure of the first adsorption tower and the second adsorption tower may be -0.06 to 0.88 MPa.

In addition, it may be 0.001 to 0.07 MPa of the third adsorption tower and the fourth adsorption tower.

In addition, the desorption pressure of the third adsorption tower and the fourth adsorption tower may be -0.07 to 0.06 MPa.

In addition, in the third step, a 4-way first valve connecting the first adsorption tower, the second adsorption tower, the supply pipe, and the first tail gas pipe to selectively stop the hydrogen production and clean the adsorption tower (170) may be formed.

In addition, in the seventh step, a 4-way connecting the third adsorption tower, the fourth adsorption tower, the second tail gas pipe, and the third tail gas pipe to selectively stop the carbon dioxide adsorption and clean the adsorption tower A second valve 270 may be formed.

In addition, the gas dryer may be filled layer by layer in the order of a first gravel layer, an activated alumina layer, a molecular sieve layer, an activated carbon layer, and a second gravel layer from the top.

In addition, the mass ratio of the activated alumina, the molecular sieve, and the activated carbon in the filling of the adsorbent in the gas dryer is 60 to 70 wt% of the molecular sieve, 20 to 30 wt% of the activated alumina, and 10 to 20 wt% of the activated carbon. It can be a % mass ratio.

In addition, the gas dryer of the first step may be a refrigeration type gas dryer capable of adsorbing moisture in the synthesis gas by lowering the temperature of the synthesis gas to +3 ° C.

In addition, blue silica gel may be further included to monitor the moisture adsorption state of the gas dryer.

In addition, blue silica gel may be further included to monitor carbon dioxide adsorption states of the third and fourth adsorption towers.

In addition, the second tail gas not adsorbed via the third adsorption tower or the fourth adsorption tower may be circulated and supplied to the gas dryer through a circulation pipe.

The simultaneous separation method of hydrogen and carbon dioxide at the end of WGS during the petroleum coke syngasification process for hydrogen production of the present invention has the effect of sequentially separating hydrogen and carbon dioxide at high concentrations, rather than a separate unit process.

In addition, by forcibly desorbing the tail gas from which hydrogen is first separated from the adsorbent using a vacuum pump to remove moisture, there is an effect of separating carbon dioxide at a high concentration.

In addition, since it is possible to operate without generating differential pressure in the hydrogen separation PSA adsorption tower, there is an effect that continuous operation is possible.

In addition, the present invention not only can increase the recovery rate through the separate installation of a gas dryer for removing moisture in the hydrogen PSA front process and process development, but also integrates each gas dryer function required for separating hydrogen and carbon dioxide in the prior art into one It works.

In addition, since it is a gas dryer configured separately in the process, there is an effect that the exchange of the adsorbent with a LIFE TIME of about 2 years can proceed easily.

1 is a conceptual diagram of a hydrogen separation process of an existing single process.
Figure 2 is a conceptual diagram according to the simultaneous separation method of hydrogen and carbon dioxide at the end of WGS during the petroleum coke syngasification process for hydrogen production to increase the hydrogen recovery rate of the present invention.
Figure 3 is a block diagram of a simultaneous separation method of hydrogen and carbon dioxide at the rear of WGS during the petroleum coke syngasification process for hydrogen production to increase the hydrogen recovery rate according to an embodiment of the present invention.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings. However, the accompanying drawings are only examples for easily explaining the content and scope of the technical idea of the present invention, and thereby the technical scope of the present invention is not limited or changed. In addition, it will be obvious to those skilled in the art that various modifications and changes are possible within the scope of the technical idea of the present invention based on these examples.

In addition, terms or words used in this specification and claims should not be construed as being limited to ordinary or dictionary meanings, and the inventor appropriately defines the concept of terms in order to explain his/her invention in the best way. It should be interpreted as meaning and concept consistent with the technical idea of the present invention based on the principle that it can be done. Therefore, since the embodiments described in this specification are only the most preferred embodiments of the present invention and do not represent all of the technical spirit of the present invention, there are various equivalents and modifications that can replace them at the time of this application. You need to understand that you can.

1 is a conceptual diagram of a hydrogen separation process of an existing single process.

When syngas for hydrogen separation is supplied, moisture and impurities can be adsorbed in one adsorption tower. After completion of hydrogen production, moisture and impurities can be desorbed using a vacuum pump.

After the hydrogen PSA process, the tail gas may contain moisture and impurities.

Therefore, a configuration of a gas dryer for separating moisture and impurities is required.

Figure 2 is a conceptual diagram according to the simultaneous separation method of hydrogen and carbon dioxide at the end of WGS during the petroleum coke syngasification process for hydrogen production to increase the hydrogen recovery rate of the present invention.

As a concept for solving the problems of the conventional single-step hydrogen separation process of FIG. 1, when syngas for hydrogen separation is supplied, it can be adsorbed in a gas dryer.

Impurities may be adsorbed in the syngas passing through the gas dryer in the adsorption tower.

After hydrogen production is completed, moisture can be desorbed using a vacuum pump.

Moisture in the gas dryer may be desorbed using the gas of the adsorption tower.

A vacuum pump suitable for performance and degree of vacuum must be used to desorb moisture from the gas dryer with the gas adsorbed in the adsorption tower.

Moisture can be removed by using alumina and molecular sieve with a dew point of -70℃.

The adsorption tower may be vacuum desorbed using a vacuum pump.

The adsorption tower may be cleaned using the cleaning gas, which is the impurity gas.

A gas dryer can be pressurized using the syngas and an adsorbent is filled in the tower to remove moisture in the existing adsorption tower, but the present invention installs a separate gas dryer in the process and operates the above process to reduce loss of hydrogen The hydrogen recovery rate can be increased.

As a method for continuously separating hydrogen and carbon dioxide with a purity of 99% or more from syngas to increase the hydrogen recovery rate,

A first step in which the syngas is supplied to a gas dryer through the supply pipe 100 to absorb moisture; The syngas passing through the gas dryer is supplied through the supply pipe 100 to the first adsorption tower 110 or the second adsorption tower 110 filled with a plurality of first adsorbents capable of selectively adsorbing components other than hydrogen in the syngas. a second step through (120); A third step in which hydrogen purified to high purity through the first adsorption tower or the second adsorption tower in the second step is collected in the hydrogen storage tank 140 through the hydrogen pipe 130; In the second step, the adsorption tower for washing the first adsorbent saturated with the first tail gas among the first adsorption tower or the second adsorption tower selectively stops the hydrogen production and the first adsorption tower of the first adsorption tower or the second adsorption tower. A fourth step of separating the first tail gas from the adsorption tower by the first vacuum pump 160 formed on the tail gas pipe 150; After the hydrogen is collected in the hydrogen storage tank in the third step, the first tail gas is used to clean the first adsorption tower or the second adsorption tower or desorb moisture from the gas dryer by the first vacuum pump 160. 5th step to do; a sixth step of discharging the second tail gas while the first tail gas separated in the fifth step passes through the after cooler 300; The second tail gas that has passed through the aftercooler in the sixth step is supplied through a second tail gas pipe 210 through a third adsorption tower filled with a second adsorbent capable of adsorbing carbon dioxide from the secondary tail gas ( 220) or the seventh step of passing through the fourth adsorption tower 230; In the sixth step, the adsorption tower for cleaning the second adsorbent saturated with carbon dioxide among the third adsorption tower or the fourth adsorption tower is the second adsorption tower formed on the third tail gas pipe 250 of the third adsorption tower or the fourth adsorption tower. An eighth step of separating and washing the carbon dioxide in the adsorption tower by the vacuum pump 260; And a ninth step in which the carbon dioxide separated in the eighth step is stored in the carbon dioxide storage tank 290 through the carbon dioxide pipe 280 at the rear of the second vacuum pump; It may be a method for continuously separating 99% or more of hydrogen and carbon dioxide.

Summarizing the second to fifth steps, two or more adsorption towers are provided, and in one adsorption tower, components other than hydrogen are adsorbed and removed to purify the syngas, and then converted to another adsorption tower, and components other than hydrogen are adsorbed. In the one adsorption tower in which components other than hydrogen have already been adsorbed and removed while purifying syngas by removing hydrogen, components other than hydrogen that have been adsorbed and removed may be desorbed and recovered by lowering the pressure in the adsorption tower.

In addition, the pressurization of the gas dryer in the first step may be performed with the syngas.

In addition, the gas dryer of the first step includes activated alumina, molecular sieve, and activated carbon, and can remove moisture to a dew point of -70 ° C.

In addition, an adsorbent for adsorbing moisture may not be included in the first adsorption tower, the second adsorption tower, the third adsorption tower, and the fourth adsorption tower.

In addition, the synthesis gas may be a gas mixture of 40 ± 5 vol% of carbon monoxide, 30 ± 5 vol% of hydrogen, 10 ± 5 vol% of carbon dioxide and other components including moisture through gasification of petroleum coke.

In addition, the gas mixture may be 50 ± 5 vol% of hydrogen, 40 ± 5 vol% of carbon dioxide and other components including moisture through a water gas shift reaction.

In addition, an adsorption layer filled with an adsorbent capable of adsorbing carbon monoxide, carbon dioxide, moisture, nitrogen, hydrogen sulfide, COS, and methane may be selectively formed in the first adsorption tower and the second adsorption tower.

In addition, an adsorption layer filled with activated carbon and/or zeolite 13X for adsorbing carbon dioxide may be selectively formed in the third adsorption tower and the fourth adsorption tower.

In addition, the adsorption pressure of the first adsorption tower and the second adsorption tower may be 0.3 to 0.8 MPa.

In addition, the desorption pressure of the first adsorption tower and the second adsorption tower may be -0.06 to 0.88 MPa.

In addition, it may be 0.001 to 0.07 MPa of the third adsorption tower and the fourth adsorption tower.

In addition, the desorption pressure of the third adsorption tower and the fourth adsorption tower may be -0.07 to 0.06 MPa.

In addition, in the third step, a 4-way first valve connecting the first adsorption tower, the second adsorption tower, the supply pipe, and the first tail gas pipe to selectively stop the hydrogen production and clean the adsorption tower (170) may be formed.

A method for continuously separating hydrogen and carbon dioxide having a purity of 99% or more from syngas to increase the hydrogen recovery rate includes a plurality of adsorption towers connected to a syngas supply pipe, a hydrogen storage tank in which hydrogen purified in the adsorption tower is collected, and A pressure swing adsorption device composed of valves that open and close a plurality of pipes connected to each adsorption tower may be configured.

The adsorption tower is not activated alumina or silica gel, activated carbon, zeolite 13X, zeolite 5A, or zeolite 5A capable of removing moisture, carbon dioxide, methane, and carbon monoxide contained in the hydrogen mixture gas supplied through the syngas supply pipe therein. The adsorbent of the carbon monoxide selective adsorbent is filled in a multi-layer structure, and the content of carbon monoxide in hydrogen discharged by being sequentially adsorbed on the adsorbent in the adsorption tower can be minimized.

In the adsorption tower, at least two or more adsorption towers may be arranged in parallel.

In the adsorbent filled in the adsorption tower, activated alumina or silica gel is filled in the lowermost layer, the activated carbon is filled in the upper portion, zeolite 13X is filled in the upper portion, zeolite 5A is filled in the upper portion, and zeolite is filled in the uppermost layer. Carbon monoxide selective adsorbents other than 5A may be sequentially packed.

The carbon monoxide selective adsorbent other than the zeolite 5A may be an alumina adsorbent impregnated with cuprous chloride (CuCl).

The alumina adsorbent impregnated with cuprous chloride may have a constant of Henry's law of carbon monoxide related to the adsorption equilibrium amount at room temperature that is 4 times higher than that of zeolite 5A.

Activated alumina, silica gel, or activated carbon in which a hydrogen mixture containing impurities such as moisture, carbon dioxide, methane, and carbon monoxide is stacked in the adsorption tower through a pressure adsorption shifter in which two or more adsorption towers in which a plurality of adsorbents are sequentially stacked are arranged in parallel , zeolite 13X, zeolite 5A, and carbon monoxide selective adsorbents excluding zeolite 5A in sequence (carbon monoxide content of less than 10ppm) can be purified with high purity hydrogen of 99% or more.

An aftercooler 300 may be formed at a rear end of the first vacuum pump to reduce the temperature of the introduced gas.

Hydrogen separated through the method for continuously separating hydrogen and carbon dioxide having a purity of 99% or more provides a recovery rate of 70% to 99% with a recovery rate of 80%, and carbon dioxide has a recovery rate of 70% to 99% with a recovery rate of 90%. can do. Preferably, a recovery rate of 75% to 95%, carbon dioxide may provide a recovery rate of 80% to 95%, and more preferably hydrogen may provide a recovery rate of 94% and carbon dioxide may provide a recovery rate of 96%.

The composition of the separated gas is 50 vol% to 60 vol% of hydrogen, 35 vol% to 45 vol% of carbon dioxide, 1 vol% to 2 vol% of nitrogen, 0.1 vol% to 1 vol% of carbon monoxide, 0.01 vol% to 0.1 vol% of methane, and water may be 0.1 vol% to 0.5 vol%.

In the PSA adsorbent regeneration step, in order to regenerate the adsorbent whose adsorption capacity has decreased due to the adsorption operation in the remaining PSA adsorption towers, the inside of the PSA adsorption tower is reduced from high pressure to normal pressure, and then the regeneration washing gas is passed through. As the cleaning gas for regeneration, hydrogen or carbon dioxide separated as in the conventional method may be used. In this way, by continuously operating a cycle composed of an unnecessary gas adsorption step and a PSA adsorbent regeneration step for a plurality of PSA adsorption towers, high-purity hydrogen and carbon dioxide can be continuously obtained while maintaining the adsorbent capacity for a long period of time.

Since the adsorption tower is filled with an adsorbent, the adsorption pressure, desorption pressure, or washing pressure may be adjusted according to the amount and type of the filler and the flow rate of the syngas.

In addition, it is obvious that coolers, heaters, and filters for temperature control may be selectively formed in the supply pipe, the first tail gas pipe, the second tail gas pipe, and the third tail gas pipe.

In addition, it is obvious that a ball valve, a check valve, and an orifice may be selectively formed in the supply pipe, the circulation pipe, the first tail gas pipe, the second tail gas pipe, and the third tail gas pipe.

In addition, it is obvious that supply valves, vacuum valves, recovery valves, and line valves may be formed in pipes before and after the first adsorption tower, the second adsorption tower, the third adsorption tower, and the fourth adsorption tower.

In addition, in the seventh step, a 4-way connecting the third adsorption tower, the fourth adsorption tower, the second tail gas pipe, and the third tail gas pipe to selectively stop the carbon dioxide adsorption and clean the adsorption tower A second valve 270 may be formed.

In addition, the gas dryer may be filled layer by layer in the order of a first gravel layer, an activated alumina layer, a molecular sieve layer, an activated carbon layer, and a second gravel layer from the top.

In addition, the mass ratio of the activated alumina, the molecular sieve, and the activated carbon in the filling of the adsorbent in the gas dryer is 60 to 70 wt% of the molecular sieve, 20 to 30 wt% of the activated alumina, and 10 to 20 wt% of the activated carbon. It can be a % mass ratio.

In addition, the gas dryer of the first step may be a refrigeration type gas dryer capable of adsorbing moisture in the synthesis gas by lowering the temperature of the synthesis gas to +3 ° C.

In addition, blue silica gel may be further included to monitor the moisture adsorption state of the gas dryer.

In addition, blue silica gel may be further included to monitor carbon dioxide adsorption states of the third and fourth adsorption towers.

In addition, the second tail gas not adsorbed via the third adsorption tower or the fourth adsorption tower may be circulated and supplied to the gas dryer through a circulation pipe.

As an example of the present invention, the supply pipe and the second tail gas pipe can additionally supply syngas, cleaning gas, and/or rinse gas, and are composed of pipes and valves for this purpose, and the lower end and/or upper end of the adsorption tower It may be formed singly or in plurality.

As an embodiment, the first adsorption tower or the second adsorption tower may include a syngas supply unit at the lower end and a cleaning gas supply unit at the upper end, and a rinsing gas supply unit at the lower end. The supply unit may be connected to the plurality of adsorption towers to supply syngas, cleaning gas, and/or rinsing gas according to processes performed in each adsorption tower.

An adsorbent used for adsorbing and removing carbon dioxide may be at least one selected from the group consisting of imogolite, activated carbon, and zeolite.

As an example of the present invention, the adsorbent may be appropriately selected according to the target product and the separation process of the target product, and the adsorbent has strong adsorption to the target product or the target product in order to selectively separate the target product. It may be non-adsorbent or have very weak adsorbability.

The first adsorption tower, the second adsorption tower, the third adsorption tower, and the fourth adsorption tower may increase the number of adsorption towers in order to increase the adsorption performance, and the tail gas of each adsorption tower may be recycled.

Preferably, the adsorption pressure of the first adsorption tower and the second adsorption tower may be 0.3 to 0.8 MPa, and the desorption pressure may be -0.06 to 0.88 MPa.

The adsorption pressure of the third adsorption tower and the fourth adsorption tower may be -0.2 to 4 MPa, and the desorption pressure may be -0.4 to 0.6 MPa.

Preferably, the third adsorption tower and the fourth adsorption tower are 0.001 to 0.07 MPa, and the desorption pressure may be -0.07 to 0.06 MPa.

In addition, the hydrogen PSA adsorption pressure of the first adsorption tower and the second adsorption tower may be 20 bar (gauge pressure) to -0.1 bar (gauge pressure), and preferably 10 bar (gauge pressure) to -0.3 bar (gauge pressure).

In addition, the carbon dioxide PSA adsorption pressure of the third adsorption tower and the fourth adsorption tower may be 2 bar (gauge pressure) to -0.1 bar (gauge pressure), more preferably 1 bar (gauge pressure) to -0.3 bar (gauge pressure). can

More preferably, the hydrogen PSA adsorption pressure may be 8 bar (gauge pressure) to -0.6 bar (gauge pressure), and the carbon dioxide PSA adsorption pressure may be 0.7 bar (gauge pressure) to -0.6 bar (gauge pressure).

When the pressure in the absorption tower is 2.0 MPa and the pressure in the regeneration tower is 7.4 MPa, the temperature in the absorption tower is about 50°C and the temperature in the regeneration tower is about 125°C. It is preferable to heat-exchange the absorbent liquid pressurized to 7.4 MPa or more with a high-pressure pump and the absorbent liquid returned by absorption or the like in the regeneration tower by means of a heat exchanger. The absorbent liquid pre-cooled by the heat exchanger and cooled to about 50° C. by the cooler is reduced in pressure from 7.4 MPa to 2.0 MPa by the pressure regulating valve.

At the end of the separated and stored hydrogen storage tank, hydrogen can be recycled to a hydrogen fermentation process or a fuel cell process.

In addition, the waste heat obtained in the fuel cell power generation process can be used to remove moisture from the gas dryer in the adsorption separation process or as heating heat for regeneration of the adsorbent for dehydration.

In this petroleum coke syngasification process, a device for generating hydrogen gas is provided. The device includes a reactor, the reactor including a catalyst and a membrane in fluid communication with the catalyst. The reactor also includes a heat exchanger integrated into the reactor.

The process plant may include a gasification unit that receives petroleum coke, oxygenates and hot steam or water and produces syngas. The gasification unit may be in interlock with a series of syngas coolers configured to remove heat and particulates and may be in fluid communication with a COS hydrolysis unit configured to convert carbonyl sulfide (COS) in syngas to hydrogen sulfide (H2S). can Syngas can be treated in a known syngas clean up section. The clean up section includes individual unit operations, specifically a high temperature shift (HTS) reactor, a low temperature shift (LTS) reactor, a H2S separation unit, a solvent regeneration (Claus/Scot process) unit, a CO2 recovery unit and a pressure swing adsorption (PSA) unit. =pressure swing adsorption) unit. The HTS reactor may contain a catalyst optimized for high temperature (about 300-400° C.) operation and the LTS reactor may contain a catalyst optimized for low temperature (about 200° C.) operation.

The thermodynamically defined water-gas shift reaction (CO+H2O⇔CO2+H2) converts carbon monoxide (CO) to CO2, but does not proceed to the endpoint in the presence of CO2, leaving about 1% CO in the synthesis gas. The synthesis gas is then cooled to about 50° C. and most of the steam present in the synthesis gas is condensed together with an aqueous acid gas such as but not limited to hydrogen chloride (HCl) and/or ammonia (NH3). H2S is usually then removed using a physical or chemical absorption process in an H2S separation unit. Any H2S removal process must use a solvent, which is regenerated in a solvent regeneration unit to produce elemental sulfur (S). The gas from the H2S separation unit enters the CO2 recovery unit, where the CO2 gas is removed using the same solvent used in the H2S separation unit. After CO2 recovery, the synthesis gas enters the PSA unit, where residual impurities are effectively removed and H2 gas with a purity of about 99.99% is produced. Residual fuel gas and H2 gas are also obtained from the PSA unit and can be used by the combined cycle power generation unit including the combustion turbine and heat recovery steam generator to produce electricity.

A WGS reactor may have a shell comprising a plurality of input channels and a plurality of output channels. The reactor is configured to receive synthesis gas in the first input channel. When syngas enters the reactor, it is at a temperature of about 250°C to 300°C.

A shift reactor catalyst is a component that converts CO to CO2. In one embodiment, the shift reactor catalyst includes iron (Fe) and iron chromium (Fe-Cr) alloys. In another embodiment, the shift reactor catalyst is a precious metal catalyst such as palladium (Pd), platinum (Pt), rhodium (Rh), platinum rhenium (Pt-Re), and the like with cerium oxide (CeO2) or aluminum oxide (Al2O3). It is supported on a ceramic with the same large surface area. In one embodiment, the catalyst is packed into a shell such that the heat exchanger is substantially enclosed within the catalyst.

As the syngas passes through the catalyst in the shell, an exothermic water-gas shift reaction (CO+H2O⇔CO2+H2) converts CO to CO2. The heat exchanger serves to remove excess heat from the exothermic shift reaction by actively cooling the catalyst. The catalyst, heat exchanger and membrane can integrate two unit operations, the HTS unit and the LTS unit, into one operation within the reactor.

The membrane is CO2 selective and allows continuous removal of the CO2 produced in the water-gas shift reactor and allows the equilibrium conversion of CO to CO2 to proceed to near complete CO removal (approximately 10 ppm CO in H2 product). Since the membrane is substantially encapsulated within the catalyst, the CO2 produced by the water-gas shift reaction is removed over the H2 stream. The membrane is also H2S selective, continuously removing H2S and thus easily achieving low levels (<100 ppb) of H2S in the H2 product. In addition, the membrane can be operated at high temperatures. For example, in one embodiment, the membrane can operate at high temperatures, i.e., about 250-500°C, with temperature rises of 50°C-250°C or more. Elevated operating temperature can reduce energy loss due to cooling and reheating. The integrated process can operate at temperatures of about 250°C to 500°C.

(Example)

An experiment was conducted to compare the hydrogen recovery rate of the existing process and the hydrogen and carbon dioxide separation process of the present invention.

Through the above experiment, it was confirmed that the recovery rate of the existing hydrogen recovery rate was improved by more than 14% compared to the existing process, and the recovery rate of carbon dioxide was confirmed to be improved by more than 6% compared to the existing process.

Although the present invention has been described in detail through representative examples above, those skilled in the art to which the present invention pertains can make various modifications to the above-described embodiments without departing from the scope of the present invention. will understand

Therefore, the scope of the present invention should not be limited to the described embodiments and should not be defined, and should be defined by not only the claims to be described later, but also those equivalent to these claims.

100: supply piping
110: first adsorption tower
120: second adsorption tower
130: hydrogen pipe
130a: first hydrogen pipe
130b: second hydrogen pipe
140: hydrogen storage tank
150: first tail gas pipe
160: first vacuum pump
170: 4way first valve
200: gas dryer
210: second tail gas pipe
220: third adsorption tower
230: 4th adsorption tower
240: circulation pipe
240a: first circulation pipe
240b: second circulation pipe
250: third tail gas pipe
260: second vacuum pump
270: 4way second valve
280: carbon dioxide pipe
281: compressor
290: carbon dioxide storage tank
300: aftercooler

Claims (20)

As a method for continuously separating hydrogen and carbon dioxide with a purity of 99% or more from syngas to increase the hydrogen recovery rate,
A first step in which the syngas is supplied to a gas dryer through the supply pipe 100 to absorb moisture;
The syngas passing through the gas dryer is supplied through the supply pipe 100 to the first adsorption tower 110 or the second adsorption tower 110 filled with a plurality of first adsorbents capable of selectively adsorbing components other than hydrogen in the syngas. a second step through (120);
A third step in which hydrogen purified to high purity through the first adsorption tower or the second adsorption tower in the second step is collected in the hydrogen storage tank 140 through the hydrogen pipe 130;
In the second step, the adsorption tower for cleaning the first adsorbent saturated with the first tail gas of the first adsorption tower or the second adsorption tower selectively stops the hydrogen collection and removes the first tail of the first adsorption tower or the second adsorption tower. A fourth step of separating the first tail gas from the adsorption tower by the first vacuum pump 160 formed on the gas pipe 150;
After the hydrogen is collected in the hydrogen storage tank in the third step, the first tail gas is used to clean the first adsorption tower or the second adsorption tower or desorb moisture from the gas dryer by the first vacuum pump 160. 5th step to do;
a sixth step of discharging the second tail gas while the first tail gas separated in the fifth step passes through the after cooler 300;
The second tail gas that has passed through the aftercooler in the sixth step is supplied through the second tail gas pipe 210 to the third adsorption tower 220 filled with a second adsorbent capable of adsorbing carbon dioxide from the second tail gas. ) or the seventh step of passing through the fourth adsorption tower 230;
In the sixth step, the adsorption tower for cleaning the second adsorbent saturated with carbon dioxide among the third adsorption tower or the fourth adsorption tower is the second adsorption tower formed on the third tail gas pipe 250 of the third adsorption tower or the fourth adsorption tower. An eighth step of separating and washing the carbon dioxide in the adsorption tower by the vacuum pump 260; and
A ninth step in which the carbon dioxide separated in the eighth step is stored in the carbon dioxide storage tank 290 through the carbon dioxide pipe 280 at the rear end of the second vacuum pump;
The pressurization of the gas dryer in the first step is a method for continuously separating hydrogen and carbon dioxide having a purity of 99% or more from the syngas to increase the hydrogen recovery rate performed with the syngas.
delete According to claim 1,
The gas dryer of the first step includes activated alumina, molecular sieve, and activated carbon, and continuously separates hydrogen and carbon dioxide having a purity of 99% or more from syngas to increase the hydrogen recovery rate by removing moisture to -70 ° C. way for.
According to claim 1,
The first adsorption tower, the second adsorption tower, the third adsorption tower, and the fourth adsorption tower do not contain an adsorbent for adsorbing moisture, and continuously separate hydrogen and carbon dioxide having a purity of 99% or more from syngas to increase the hydrogen recovery rate. way to do it.
According to claim 1,
The synthesis gas is a gas mixture of carbon monoxide 40 ± 5 vol%, hydrogen 30 ± 5 vol%, carbon dioxide 10 ± 5 vol% and other components including moisture through gasification of petroleum coke. In syngas to increase the recovery rate of hydrogen A method for continuously separating hydrogen and carbon dioxide with a purity of 99% or more.
According to claim 5,
50 ± 5 vol% of hydrogen, 40 ± 5 vol% of carbon dioxide and other components including water through the gas mixture through a water gas shift reaction. Hydrogen with a purity of 99% or more in syngas to increase the recovery rate of hydrogen and a method for continuously separating carbon dioxide.
According to claim 1,
In the first adsorption tower and the second adsorption tower, an adsorption layer filled with an adsorbent capable of adsorbing carbon monoxide, carbon dioxide, moisture, nitrogen, hydrogen sulfide, COS, and methane is selectively formed, and a purity of 99% or more in syngas to increase the hydrogen recovery rate Method for continuously separating hydrogen and carbon dioxide.
According to claim 1,
In the third adsorption tower and the fourth adsorption tower, an adsorption layer filled with activated carbon and/or zeolite 13X for adsorbing carbon dioxide is selectively formed to continuously separate hydrogen and carbon dioxide having a purity of 99% or more from syngas to increase the hydrogen recovery rate. way for.
According to claim 1,
The adsorption pressure of the first adsorption tower and the second adsorption tower is 0.3 to 0.8 MPa, a method for continuously separating hydrogen and carbon dioxide having a purity of 99% or more from syngas for increasing the hydrogen recovery rate.
According to claim 1,
The desorption pressure of the first adsorption tower and the second adsorption tower is -0.06 to 0.88 MPa A method for continuously separating hydrogen and carbon dioxide having a purity of 99% or more from syngas to increase the hydrogen recovery rate.
According to claim 1,
A method for continuously separating hydrogen and carbon dioxide having a purity of 99% or more from syngas for increasing the hydrogen recovery rate of 0.001 to 0.07 MPa of the third adsorption tower and the fourth adsorption tower.
According to claim 1,
The desorption pressure of the third adsorption tower and the fourth adsorption tower is -0.07 to 0.06 MPa A method for continuously separating hydrogen and carbon dioxide having a purity of 99% or more from syngas to increase the hydrogen recovery rate.
According to claim 1,
A 4-way first valve (170) connecting the first adsorption tower, the second adsorption tower, the supply pipe, and the first tail gas pipe to selectively stop the hydrogen production and clean the adsorption tower in the third step. ) A method for continuously separating hydrogen and carbon dioxide with a purity of 99% or more from syngas to increase the hydrogen recovery rate.
According to claim 1,
A 4-way second connecting the third adsorption tower, the fourth adsorption tower, the second tail gas pipe, and the third tail gas pipe to selectively stop the carbon dioxide adsorption and clean the adsorption tower in the seventh step. A method for continuously separating hydrogen and carbon dioxide having a purity of 99% or more from syngas for increasing the hydrogen recovery rate formed by the valve 270.
According to claim 3,
The gas dryer continuously releases hydrogen and carbon dioxide with a purity of 99% or more from the syngas to increase the hydrogen recovery rate filled layer by layer in the order of the first gravel layer, the activated alumina layer, the molecular sieve layer, the activated carbon layer, and the second gravel layer from the top. way to separate.
According to claim 15,
The mass ratio of the activated alumina, the molecular sieve, and the activated carbon in the filling of the adsorbent in the gas dryer is 60 to 70 wt% of the molecular sieve, 20 to 30 wt% of the activated alumina, and 10 to 20 wt% of the activated carbon. A method for continuously separating hydrogen and carbon dioxide having a purity of 99% or more from syngas to increase the phosphorus hydrogen recovery rate.
According to claim 1,
The gas dryer of the first stage is a refrigerant gas dryer capable of adsorbing moisture in the syngas by lowering the temperature of the syngas to +3 ° C. A method for continuously separating.
The method of claim 3 or 17,
A method for continuously separating hydrogen and carbon dioxide having a purity of 99% or more from a syngas for increasing the hydrogen recovery rate further comprising blue silica gel to monitor the moisture adsorption state of the gas dryer.
According to claim 1,
A method for continuously separating hydrogen and carbon dioxide having a purity of 99% or more from the syngas for increasing the hydrogen recovery rate further comprising blue silica gel to monitor the carbon dioxide adsorption state of the third adsorption tower and the fourth adsorption tower.
According to claim 1,
The second tail gas not adsorbed via the third adsorption tower or the fourth adsorption tower continuously converts hydrogen and carbon dioxide having a purity of 99% or more from syngas to increase the hydrogen recovery rate circulated and supplied to the gas dryer through a circulation pipe. way to separate.

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