TW406056B - Integrated steam methane reforming process for producing carbon monoxide - Google Patents

Abstract

A process for producing carbon monoxide (CO) by reforming methane and steam in the presence of a reforming catalyst to produce a reformate product enriched in CO, carbon dioxide (CO2) and hydrogen. CO2 in the reformate is shifted to CO in an integrated sorption enhanced reaction (SER) cycle which employs a series of cyclic steps to facilitate reaction of CO2 and hydrogen at high conversion and to produce a CO-enriched product obtained at reactor feed pressure and at essentially constant flow rate. A series of adsorbent regeneration steps including depressurization, purging and product pressurization are used to desorb water which is selectively adsorbed by the adsorbent during the shift reaction and to prepare the reactor for a subsequent process cycle.

Description

406056 A7 B7 V. Description of the invention (1) Cross-reference to related applications This application is part of a serial application of US Patent Application No. 08 / 419,317, filed on April 10, 1995. The description of the case and the patent application The scope is incorporated by reference into this case and is considered a part of this application. Technical Field of the Invention The present invention is a method for producing carbon monoxide (CO), which is to produce a recombinant product rich in carbon monoxide, carbon dioxide and hydrogen by recombining methane and steam in the presence of a recombination catalyst. The carbon dioxide (C02) in the concentrated reconstituted product is converted to CO in an integrated adsorption enhancement reaction (SER) cycle, which uses a series of cyclic steps to perform a reverse water gas conversion reaction to convert CO 2 Convert to CO, partially separate the reaction product mixture to recover a carbon monoxide-rich stream and prepare the SER reactors for subsequent SER process cycles. Background of the invention Printed by the Central Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, the production of carbon monoxide is typically a catalytic reforming of a steamed hydrocarbon feed ' and optionally, carbon dioxide, at high temperatures. The reaction is carried out in a steam methane reformer (SMR), which comprises a furnace filled in a small tube filled with catalyst. The syngas leaving the reformer contains carbon monoxide (CO) and hydrogen, carbon dioxide (co2) 'steam and unconverted methane in accordance with the equilibrium established in the following reactions. ch4 + h20 <-> 3H2 + CO steam reorganization 83. 3.10,000 (please read the note on the back ^^ before filling out this page) This paper size applies to China National Standard (CNS > A4 size (210X297 (Mm) Printed by the Consumer Cooperatives of the Central Procurement Bureau of the Ministry of Economic Affairs 406056 a? _B7__ V. Description of the invention (2) H2〇 + CO <-> H2 + C〇2 Water gas conversion CH4 + C〇2 <- -> 2H2 + 2C0 C〇2 Recombination The above reactions are usually carried out at high temperature (800-1000 ° C) and high pressure (5-30 atmospheres), where the reactants are contacted with a nickel-based catalyst These reactions are thermodynamically controlled. Therefore, the composition of the reconstituted effluent will depend on many variables including pressure, temperature, steam / methane mole ratio in the reactor feed, and carbon dioxide concentration in the reactor feed. When the SMR reaction A typical SMR effluent composition (mol fraction) containing 75% H2 when using a feed mixture containing no CO2 and a 3: 1 water / methane molar ratio at 850 ° C and 25 atmospheres, 13 % CO, 8.5% CO2 and 5.5% CH4. The SMR effluent undergoes a series of reaction And separation operations to recover high purity hydrogen products (99.9 + mole%) or high purity CO products (99.5% + mole%). Carbon monoxide produced by commercial SMR plants is typically used via phosgene Chemical production of isocyanates and polycarbonates. In addition, some methods for the production of carbonyloxy alcohols require a 1: 1 hydrogen-to-carbon monoxide synthesis gas. By-product hydrogen and effluent steam formed during these SMR process stages may be Fuel prices are high, but may not be considered as products. As is widely known in the industry, injecting CO2 into the reformer feedstock and reducing the steam-to-hydrocarbon ratio in the SMR feedstock can produce syngas with high carbon monoxide content. By C02 produced by recycling and separated from synthesis gas or recovered from furnace flue gas or additional C02 input from outside sources into the feedstock can further increase the concentration of C02 in the SMR feedstock. Has a high C02 to methane ratio and reduces steam volume SMR raw materials

I -4- This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297 mm) 813.10,000 I- 'ϋ I f 1 I nnn 11111 · ν (Please read the note on the back before filling this page) Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, 11 406056 A7, B7 V. Description of the invention (3) The water-to-gas conversion reaction generates additional h2 from C0 and under extreme reaction conditions, the reaction will be reversed and generated from H2 Extra C0. Some C02 in the SMR feedstock will also react with methane to produce a symbiotic gas with a low H2 / CO ratio. The amount of co produced in the traditional SMR method is limited by the thermodynamics of the reaction, where the relatively low CO conversion (~ 10-15%) makes recovery of the Co product necessary for considerable separation effort. Many prior art SMR processes are known for the production of syngas, which utilize multiple separation cycles to recover the desired carbon monoxide product from a SMR reconstituted effluent typically containing a mixture of hydrogen, carbon monoxide, CO2 and methane. U.S. Patent Nos. 3, 998, 8 and 9 disclose an SMR method as described in Fig. 1 for converting water and a source of methane such as natural gas into hydrogen products. Methane and water are directed into a conventional SMR reactor 2 via line 1 and reacted under recombination conditions to produce a hydrogen-rich recombined gas stream 3. Stream 3 is directed into condenser 4 to produce steam and cooled reformed gas stream 6 at an intermediate temperature of 250-350 ° C. The cooled reformed gas is then introduced into a water gas conversion reactor 7 (high temperature conversion reactor, alone or in combination with a low temperature conversion reactor) to make CO and H20 according to the reaction formula (CO + H2 0 <- -> Co2 + H2) converts part of the CO in the reformed gas stream 6 to hydrogen. When hydrogen is the desired product, the conversion reaction described above plays a key role in all methods, because the conversion reaction increases the hydrogen concentration in the recombinant product mixture before separating the recombinant product mixture to produce substantially pure hydrogen. And amount. By indirect with the cooling water in the condenser 9, the paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) 83.3.10,000 ---------- ^ ------ 、 11 ------ · ν (Please read the note on the back first and then fill out this page) Printed by the Shiyang Standard Bureau of the Ministry of Economic Affairs and printed by the Shellfish Consumer Cooperative 406056 A7 __B7 V. Description of the invention (4) Heat exchange, conversion reaction The reactor effluent 8 is further cooled to near ambient temperature (25-50 ° C.), where a considerable amount of water is condensed from the reformed gas via line 10 and removed. Finally, the stream 11 leaving the condenser is introduced into a hydrogen pressure increase / decrease adsorption unit (H2-PSA) to produce pure hydrogen via the stream 14 and an exhaust gas stream 13 which can be used as fuel in the reformer. U.S. Patent 4,171,206 discloses an SMR method as described in Figure 2 for converting water and a methane source such as natural gas to produce a high purity hydrogen product and a high purity CO 2 product simultaneously. Methane and water are introduced into a conventional SMR reactor 22 via a line 21 and are reacted under recombination conditions to produce a recombined gas stream 23. Stream 23 is introduced into condenser 24 to produce cooled recombined gas stream 26 and condensate stream (not numbered) at an intermediate temperature of 250-350 ° C. The cooled recombined gas is then introduced into water gas conversion reactor 27. Internally, a portion of the CO in the reformed gas stream 26 is converted to hydrogen. By indirect heat exchange with the cooling water in the condenser 29, the conversion reactor effluent 28 is further cooled to near ambient temperature (25-50 ° C), in which a considerable amount of water is condensed from the reformed gas And it is removed via line 30. Finally, the recombined gas stream 31 exiting the condenser 29 is directed into a CO 2 air addition / subtraction (VSA) unit 32 ′ where the recombined gas is separated to provide a substantially pure CO 2 product stream 35. The exhaust gas from the CO2 VSA unit 32 is directed into the H2-PSA unit 38 via line 34 and is separated to produce a substantially pure hydrogen stream 37 and an exhaust gas stream 36 that can be used as fuel in the reformer 22. The C02 VSA unit 32 and the H2-PSA unit 36 are integrated for maximum separation efficiency. -6- This paper size applies the Chinese Garden Standard (CNS) M specification (21〇 > < 297 mm) 83.3.10,000 ^ 1. II n I fi II 1 ^ I 11 I ^ (Please read the Matters needing attention to fill out this page again} Instruction 40605b a? _B7 of the Central Bureau of Standards of the Ministry of Economic Affairs of the Bayer Consumer Cooperative V. Description of the invention (5) A traditional SMR method is depicted in Figure 3, in which water and a source of methane are passed through the pipeline 41 It is introduced into a conventional SMR reactor 42 and reacts under recombination conditions to produce a recombined gas stream 43. The stream 43 is introduced into a CO2 absorber / stripper 44 containing a physical chemical solvent. In this solvent, CO 2 is removed from the pre-cooled SMR effluent to provide a stream 45 containing substantially pure CO 2 and a CO 2 depleted recombined gas stream 46, which is introduced into a thermal increase or decrease adsorption unit 47 to The water and remaining CO 2 are removed and discharged from the adsorption unit 47 via line 48. The water and CO 2 depleted stream 49 is directed into the cryogenic cold box 50 to produce a substantially pure hydrogen stream 51, a substantially pure C0 Logistics 53 and Available in Reorganizer 42 It is used as fuel to contain unreacted methane waste stream 52. Another conventional SMR method is depicted in Figure 4 where water and a methane source are directed via line 61 into a traditional SMR reactor 62 and under recombination conditions The reaction produces a reformed gas stream 63. Stream 63 is directed into a CO2 absorber / striker 44 containing a physicochemical solvent that removes CO2 from a pre-cooled SMR effluent to provide a CO2-rich The stream 65 may be compressed via the compressor 66 and reintroduced into the SMR reactor 62 as a C02 feed via line 67. The C02 depleted reformed gas stream 68 leaves the TSA unit 69 via line 71 and is It is introduced into the cryogenic cold box 72 to produce a substantially pure hydrogen stream 73, a substantially pure CO stream 75, and a waste stream 74 that can be used as fuel in the reformer 62 to contain unreacted methane.

U.S. Patent 4,915,711 discloses an SMR as described in FIG. 5. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) 83.3.10,000 II II —I—- I Order — — I 1 '" ( Please read the notes on the back before filling out this page) Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 406056 _ ^ _ V. Description of the Invention (6) Method. Water and a methane source are directed into a conventional SMR reactor 82 via line 81 and reacted under recombination conditions to produce a recombined gas stream 83. In addition, a C02 stream can also be introduced into the reformer to increase CO production. Stream 8 3 is directed into condenser 84 to produce a condensate vapor 85 and a cooled recombined gas stream 86 at an intermediate temperature 30 °-120 ° C. The cooled reformed gas is then directed into CO-VSA 87, where the reformed gas is separated to provide a substantially pure CO product stream 88 and an exhaust gas stream 89 that can be used as fuel in the reformer 82. Another SMR process is depicted in Figure 6 where water and a methane source are introduced into a conventional SMR reactor 92 via line 91 and reacted under recombination conditions to produce a recombined gas stream 93. Stream 93 is introduced into condenser 94 to produce a condensate vapor 95 and a cooled reformed gas stream 96 at an intermediate temperature of 30 ° to 120 ° C. The cooled recombined gas is then introduced into CO-VSA97, where the recombined gas is separated to provide a substantially pure CO2 product stream 98, and the CO-VSA exhaust stream is passed through line 99 into a traditional The polymer film 100 further processes the exhaust gas stream 99 and provides an exhaust gas stream 101 which is compressed via a compressor 103 and is introduced into the SMR reactor 92 as additional raw material via a line 104. Figure 7 illustrates another SMR process for producing substantially pure CO and substantially pure hydrogen. Water and a methane source are directed into a conventional SMR reactor 112 via line 111 and reacted under recombination conditions to produce a recombined gas stream 113. The logistics 113 is introduced into the condenser 114 to produce the cooled recombined gas stream 116, which is imported (please read the note on the back before filling this page). _ ， 1Τ h ·: This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) 83. 3.10,000 406056 A7 B7 V. Description of the invention (7) The water gas conversion reactor 1 1 7 is used to convert part of the water and reformed gas stream 116 to hydrogen. The hydrogen-rich reformed gas 127 passes through the condenser 128 to remove water and the water-depleted stream 129 enters the H2-PSA unit 130 to provide a waste stream 132 and a substantially pure hydrogen stream that can be used as fuel in the reformer 112. 131. A portion of the reformed gas can then flow into line 118 after valve 117a is opened. This reformed gas is introduced into condenser 119 to cool the gas and remove moisture before entering CO-VSA 122 via line 121, where the reformed gas is separated to provide a substantially pure CO stream 123 and a CO depleted stream 124, The latter can be optionally compressed by a compressor or blower 125 and then combined with pipeline 129 to enter 112-PSA 1 3 0 ° People familiar with steam methane recombination techniques are working to find improved recombination methods, which require C 0 products Conversions are maximized. Moreover, a method that promotes the reaction between C02 and hydrogen to form C0 and water [reverse water gas conversion reaction] would be very desirable in the industry. Unfortunately, there is no known prior art SMR method integration capable of converting CO 2 existing in SMR reformed gas logistics and printed hydrogen produced by the Central Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperatives into CO and water. This reverse water gas conversion reaction is thermodynamically unsuitable at a temperature of 800 ° C and the temperature typically needs to exceed 1000 ° C to obtain a moderate conversion of CO to CO. Therefore, this backwater gas conversion reaction has not been successfully integrated into the SMR process and used to produce CO. Moreover, the prior art methods of performing simultaneous reaction and adsorption treatment steps have not achieved commercial success because the product flow rate has not been maintained adequately and compared to undesired reaction products, unreacted raw materials, and rinses The presence of the required product is too low. The industry is looking for a method-9- 83.3.10,000 (Please read the notes on the back before filling out this page) Λ This paper size is applicable to China National Standard (CNS) Α4 size (210 × 297 mm) 406056 Central Bureau of Standards, Ministry of Economic Affairs Printed by Shelley Consumer Cooperative A7 ___B7____ V. Invention Description (8) Improve the general SMR method by increasing the overall method productivity or by increasing the CO Molar fraction of the product mixture that is introduced into the feed stream of the subsequent separation unit To produce CO. Summary of the Invention The present invention is a method for producing carbon monoxide (CO), which is a method for producing a recombination gas rich in carbon monoxide, carbon dioxide (CO2) and hydrogen by recombining methane and steam in the presence of a recombination catalyst. The CO 2 in the concentrated recombined gas is converted to CO in an integrated adsorption enhanced reaction (SER) cycle. The integrated adsorption enhanced reaction cycle uses a series of cyclic steps in a plurality of reactors to affect a conversion reaction. CO2 is converted to CO, a conversion reaction product mixture is separated to form a CO-rich product stream, and a SER reactor is prepared for subsequent SER process cycles. The method applied in this case overcomes the problems associated with previous techniques, which typically encountered when recombining methane and water to carbon monoxide produce a recombined gas that contains excess C02 that has not been converted to the desired CO product, which must be passed from the recombined gas through expensive The separation cycle is separated. Moreover, the method of the present application overcomes the thermodynamic limitations associated with backwater gas conversion reactions, in which CO2 and hydrogen are converted into CO and water. The applicant's invention solves these problems. The present invention converts the carbon dioxide present in the reactor reformed gas into additional CO before separating the required CO from the reactor reformed gas, thereby greatly reducing the costs associated with the separation cycle. This technical improvement is achieved by using a kind of suction 10- this paper is also applicable to China National Standard (CNS) A4 specification (210X297 mm) 83.3.10,000 I. I —I— nr-I II II Order — — III (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 406056 V. Description of the invention (9) With enhanced response (SER) cycle, which allows the backwater gas to be carried out at 25- With a mild temperature of 350 ° C and a pressure of 5-30 atmospheres, it has a high conversion of CO 2 to CO. Applicant's method integrates a SER process that performs a series of cyclic steps in a plurality of reactors to convert CO to CO and to separate the converted gas product mixture into a concentrated CO stream. Each reactor contains a conversion catalyst and a water-adsorbent admixture in which water is physically adsorbed from the reaction zone under the conversion reaction conditions and is selectively removed thereby changing the reaction equilibrium to form the desired C 0. Water absorbed by a series of flushing and decompressing steps is separated from the adsorbent according to a predetermined timing sequence. Therefore, the applicant's SER method, which is integrated with the applied method, represents a completely new cycle to simultaneously achieve high conversions from C02 to C0, produce a concentrated CO effluent stream, efficiently desorb water from the adsorbent, and Prepare each reactor for the next method cycle. Applicant's method integrates a SER cycle to provide a unique opportunity to react to CO 2 and hydrogen present in the SMR effluent to form additional CO before performing any procedural separation steps. Because the C0 product is present at high concentrations and most of the C02, which is typically removed during the separation step of a conventional SMR method, has been converted to the desired C0 product, the size of the separation unit is greatly reduced. The general embodiment of the applicant's method for the production of CO takes into account the use of a feedstock containing methane and water in the presence of a steam methane reforming catalyst at a temperature range from 700 ° C to 1000 ° C and a pressure range from 2 to 50 11-This paper size applies to China National Standards (CNS) A4 «^ (210X297 mm) 83.3.10,000 —. — — I— I Pack 11 n I n ^ 111 Is, (Please read the notes on the back before filling (In this page) 406G56 The Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, Co., Ltd. 5. Description of the invention (10) The reaction is carried out under pressure to form a reformed gas containing hydrogen, carbon monoxide, carbon dioxide and unreacted raw materials. The second step of the general embodiment considers removing water from the reformed gas to form a water-depleted reformed gas and heating the water-depleted reformed gas to a temperature ranging from 200 ° to 50 ° C. Water depleted heated reformed gas is formed. The third step of the general embodiment includes introducing the water-depleted heated reformed gas into a plurality of reactors. The reactors operate in a predetermined timing sequence according to the following steps. These steps are in each reactor. It is circulated: (1) Under the first pressure, in a first reactor containing a water adsorbent and a blender of a water gas conversion catalyst, in a reactor sufficient to convert carbon dioxide and hydrogen into carbon monoxide and adsorb water Under the reaction conditions on the agent, the water-depleted heated reformed gas is reacted and a CO-rich stream is discharged; (2) the first one is discharged by discharging a mixture containing unreacted raw materials, carbon monoxide and water The reactor is decompressed countercurrently to a second pressure; (3) at the second pressure, the first reactor is flushed countercurrently with a flushing fluid that weakly adsorbs the adsorbent, and water is desorbed from the adsorbent And discharge a mixture containing unreacted raw materials, carbon monoxide and water; (4) countercurrent with a flushing fluid that is free of hydrogen and carbon dioxide and rich in CO at the second pressure Flush the first reactor to desorb the weakly adsorbed flushing fluid and discharge a kind containing the weakly adsorbed flush -12- This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) 83.3.10,000 III fi 111 nnnn —.11 (Please read the note ^^ on the back before filling out this page) 406056 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (11) Washing fluid 'a mixture of carbon monoxide and water; and (5) Before the first reactor begins another method cycle, pressurize the first reactor countercurrently from the second pressure to the first pressure with the CO-rich flushing fluid. Additional steps may also be performed under general specific embodiments. For example, the CO-rich stream of step (1) can be separated using conventional techniques to form a CO-containing stream and a CO-depleted stream. The CO-depleted stream can be separated to form a hydrogen-rich exhaust gas stream and a hydrogen-depleted carbon dioxide-rich recycle stream, a portion of which can be recycled to the reformer. Or 'After step (1) and before step (2), the first reactor may be flushed countercurrently with a weakly adsorbed flushing fluid at a first pressure, and the unreacted raw material, carbon monoxide and water may be taken out of the reactor. Out of a mixture. This mixture can be recycled to the SER reactor as a feed. Finally, an additional source of carbon dioxide can be introduced into the water-depleted heated gas stream before performing steps (1) through (5). In another specific embodiment of the applicant's method for producing CO and hydrogen, it is considered to make a feedstock containing methane and water in the presence of a steam methane reforming catalyst in a temperature range from 7 0 ° C to 1 0 0 The reaction is carried out at 0 ° C and pressure ranging from 2 to 50 atmospheres to form a reformed gas containing hydrogen, carbon monoxide, carbon dioxide and unreacted raw materials. The second step of this another embodiment considers cooling the reformed gas to a temperature ranging from 200 ° to 500 ° C to form a cooled reformed gas and dividing the cooled reformed gas into a first stream And the second thing-13- This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 83.3.10,000 (Please read the precautions on the back before filling in this f).

, 1T y 406056 A7 B7 Printed by the Consumer Co-operation of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of Invention (12) Stream. The third step allows for contacting the first stream with a water gas conversion catalyst under reaction conditions sufficient to form a hydrogen-rich first stream. 'Cooling the hydrogen-rich first stream to form a cooled hydrogen-rich first stream. Stream, and the cooled hydrogen-rich first stream is separated to form a hydrogen product stream and a hydrogen depleted stream. The fourth step of this another embodiment considers removing water from the second stream to form a water depleted second stream, and heating the water depleted second stream to a range from 200 ° to 500 ° C Temperature to form a heated second stream of water depletion. The fifth step of the other specific embodiment includes introducing the water-depleted heated second stream into a plurality of reactors, which are operated in a predetermined timing sequence according to the following steps, which are performed in each reaction The reactors are all circulated: (1) at the first pressure, in the first reactor containing a water adsorbent and a blender of water gas conversion catalyst, in a reactor sufficient to convert carbon dioxide and hydrogen into carbon monoxide and adsorb water Under the reaction conditions on the adsorbent, the water-depleted heated second stream is reacted and a CO-rich stream is discharged; (2) by discharging a mixture containing unreacted raw materials, carbon monoxide, and water, The first reactor is decompressed countercurrently to a second pressure; (3) at the second pressure, the first reactor is flushed countercurrently with a flushing fluid that is weakly adsorbed to the adsorbent, and the first reactor is flushed from the adsorbent Water is desorbed, and a mixture containing unreacted raw materials' carbon monoxide and water is discharged; -14- ----------- pack-(please read the precautions on the back before filling this page) 1T Zhang scale is applicable to China National Standard (CNS) A4 specification (210X297 mm) 83. 3.10,000 406056 at B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (13) (4) Under this second pressure, Flush the first reactor countercurrently with a hydrogen- and carbon dioxide-free flushing fluid rich in CO to desorb the weakly-adsorbed flushing fluid, and discharge a mixture containing the weakly-adsorbed flushing fluid, carbon monoxide, and water; and ( 5) Before the first reactor starts another method cycle, the first reactor is counter-pressurized from the second pressure to the first pressure with the CO-rich flushing fluid. The sixth and final step of this another embodiment considers the CO-rich stream of the separation step (1) to form a CO-containing stream and a CO-depleted stream, compressing the CO-depleted stream, And before the cooled hydrogen-rich first stream of the third step is separated into a hydrogen product stream and a hydrogen-depleted stream, the compressed CO-depleted stream and the cooled hydrogen-rich first stream are separated Together. Additional steps may be performed under this another specific embodiment. For example, after step (1) and before step (2), the first reactor may be flushed countercurrently with a weakly adsorbed flushing fluid at a first pressure, and unreacted raw materials including carbon monoxide may be removed from the reactor. And water. Suitable catalysts for carrying out the steam methane reforming reaction according to this general and another embodiment include conventional steam methane reforming and pre-reforming catalysts, such as nickel-alumina, nickel-magnesium alumina, and precious metal catalysts. As stated in this general and another specific embodiment, the SER cycle allows for a series of cycling steps in a plurality of reactors that contain a conversion catalyst and a water-adsorbent admixture. The conversion catalyst -15- (Please read the precautions on the back before filling this page) A3, vs Γ This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 83.3.10,000

A7 B7 Imprint of the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the Invention (14) (Amended in November 1997) The admixture of the agent and the water adsorbent contains 5-95% by weight of the adsorbent and 95-5 % By weight of catalyst. Suitable water adsorbents include those selected from the group consisting of zeolite, alumina, or silicone. Suitable water gas conversion catalysts include those selected from the group consisting of iron-chromium high temperature conversion catalysts, copper / zinc oxide low temperature conversion catalysts and copper / zinc oxide medium temperature conversion catalysts. It will become clearer when reading the detailed description of the invention, by utilizing a novel series of reaction, adsorption and desorption steps to convert C02 present in the SMR reformed gas into C0 and at the feed pressure and relatively The separation and collection of greatly concentrated CO at a fixed flow rate, the applicant's method overcomes the problems associated with prior art methods. This result was achieved in part because the applicant unexpectedly flushed the SER reactors with a CO or CO-rich reaction product and pressurized the reactors to reaction pressure before commencing another SER cycle. Those skilled in the art will generally expect that flushing and pressurizing the SER reactor with a product that is a reverse water gas shift reaction before commencing the reaction step will poorly change the equilibrium constants to form CO 2 and hydrogen; the applicant It was found that using product gas instead of CO 2 or hydrogen or another flushing fluid to flush these SER reactors provided a highly efficient method in which a CO-rich stream could be fed at a feed pressure and a relatively constant flow rate Be collected. Brief Description of the Figures Figure 1 illustrates a steam methane reforming (SMR) process in accordance with US Patent 3,986,849, in which the SMR reactor reformed gas is utilized by utilizing a high temperature conversion (HTS) reactor and a hydrogen pressure increase adsorption (H2) -PSA) 单 -16- This paper uses Chinese National Standard (CNS) A4 specification (210X297 mm) -----_----- I Pack -------- Order one ^ ----- (Please read the Note- ^ item on the back before filling this page) A7 B7 40 $ 056 V. Description of Invention (15) (Amended in November 1997) The element was further reacted and separated to provide a high-purity hydrogen product. Figure 2 illustrates an SMR method according to U.S. Patent No. 4,171,206, in which the SMR reactor reformed gas is further reacted and separated by using the integration of a HTS reactor and a C02-VSA and H2-PSA unit to provide a A substantially pure carbon dioxide stream and a substantially pure hydrogen stream. Figure 3 illustrates a prior art SMR method that uses a C02 absorber / stripper to remove the C02 of the recombined gas stream, after which the recombined gas stream is introduced into a temperature swing adsorption (TS A) unit to further remove water and Carbon dioxide, followed by final separation in an ultra-cold cold box to produce a substantially pure hydrogen stream, a substantially pure CO stream, and an exhaust stream containing methane and CO, which can be used as fuel for a reformer . Figure 4 illustrates an improved method according to Figure 3, in which a CO2 absorber / stripper is used to remove the CO2 of the reformed gas stream before it is introduced into the TSA unit to further remove its water from the reformed gas. And Co2. A portion of the separated CO 2 is compressed and recycled into the SMR for further conversion to hydrogen and CO. Figure 5 illustrates a prior art SMR method to produce substantially pure CO, where the SMR reformed gas is condensed to remove water, after which the reformed gas is separated in a CO-VS A to provide a substantially pure CO product And an exhaust gas stream that can be recycled for use as a reformer fuel. FIG. 6 illustrates an improved method according to FIG. 5 in which the exhaust gas stream recovered from coys A is contacted with a selectively permeable polymeric film to provide an exhaust gas stream that can be recycled for use as a reformer fuel and a CO2-rich Logistics, the C02-rich logistics is compressed and re-imported into SMR anti-17- (CNS) A4 ^ m (210X297 ^ #) -----; ------- installation ------ order ------,-Line (Please read the notes on the back before filling out this page) Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

The Central Standards Bureau of the Ministry of Economic Affairs printed the reactors for further conversion into CO and hydrogen. Figure 7 illustrates a prior art SMR process in which the SMR reactor recombined gas is separated into a first stream and a second stream that are introduced into an HTS reactor, which is introduced into the CO-VSA to produce a substantially pure The CO product and a CO depleted stream are combined with the effluent of the HTS reactor and separated in an H2-PSA unit to provide a substantially pure hydrogen product. Fig. 8 illustrates a general specific embodiment of the SMR method for producing CO in this case, in which methane and water are reacted in the presence of a catalyst to form a reconstituted product comprising carbon dioxide, carbon monoxide and hydrogen. This method integrates an adsorption enhancement reaction (SER) cycle to further convert the carbon dioxide formed in the SMR reactor into additional carbon monoxide and remove water from the reaction mixture to further direct the equilibrium-controlled reaction to form CO. The SER cycle uses a series of cycling steps to separate the product mixture formed in the SER cycle and prepares the SER reactors for subsequent process cycles. FIG. 9 illustrates another specific embodiment of the SMR method applied to produce a substantially pure CO stream and a substantially pure hydrogen stream, in which methane and water are reacted in the presence of a catalyst to form carbon dioxide, carbon monoxide, and hydrogen. A reorganized product. The method integrates a high temperature conversion reactor to increase hydrogen production and an adsorption enhancement reaction (SER) cycle to further convert the carbon dioxide formed in the SMR reactor into additional carbon monoxide and remove water from the reaction mixture to further control the equilibrium controlled The reaction is directed to form CO. The SER cycle uses a series of cyclic steps to separate the product mixture formed in the SER cycle and prepare the -18-Ϊ4 nine-nine scales applicable to China National Standard (CNS) A4 specifications (210X297 mm > ϋ- ^ i— — 11 In II nI (Please read the notes on the back before filling this page) Thread 86. 11 · 3 years ...

Jj: A7 B7 (Amended in November 1997) 5. Description of the invention (π) These SER reactors are used for subsequent method cycles. Drawing number description 4,9,24,29,84,94,119,114,128,206,606,610,804 Condenser 7,27,117,802 Conversion reactor 66,103,125,808 Compressor 100,502 Membrane 42,62,82,92 , 112,204,604 Steam methane reformer 331, 360,731,760 Pump 208,212,612,616 Dryer, heater 210,333,614,733 Storage tank 301,302,601,602 SER reactor 317,335,717,735 Detailed description of the separator invention The applicant will now discuss its method of producing carbon monoxide (CO) Further details, this method provides a lot of benefits compared to previous techniques. In particular, the conversion of larger recombiner raw materials to CO products is achieved; a more concentrated reaction product is obtained, which can be obtained using only a traditional SMR method without using the applicant's SER cycle, details of which will be Discussed below, and the method of the present application can be operated under less severe conditions than prior art methods because the high conversion of CO 2 and hydrogen is obtained by removing a reaction product rather than by increasing the reactor temperature. A general specific embodiment of the Applicant's method is depicted in FIG. 8 and illustrates a method flow diagram describing a steam methane reformer 204, condenser 206, dryer 208, feed heater 212, SER reactor 301 And 302; many control valves; manifolds A to E; pumps 331 and 360; separators 317 and 3 3 5; and regulating vessels 210 and 33 3. Referring to Fig. 8, a hydrocarbon feedstock such as methane or natural gas is desulfurized in a container (not shown) using a well-known adsorbent. The desulfurized hydrocarbon feedstock is mixed with steam to form a hybrid recombiner represented by the logistics 203-19. This I standard is applicable to China National Standard (CNS) A4 specification (210X297 mm) -------- --- Installation -------- Order a r ----- line (please read the notes on the back before filling this page) Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 Central of the Ministry of Economic Affairs Printing of employees' cooperatives in the Bureau of Venezuela 5. V. Invention description (18) Raw materials. The raw material 203 is preheated in a preheater (not shown) and introduced into the SMR reformer 204. This reformer is well known in the industry and is heated by burning a mixture of fuel and air (not shown). The reformer is typically operated at a temperature of 800 ° to 1000 ° C and a pressure of 5 to 30 atmospheres and produces a dry weight of approximately 73% hydrogen '13% CO, 9% CO2 and 5 % Methane recombination gas. The reformed gas is sent to condenser 206 through line 205 where the temperature of the gas is reduced and some of the water in the gas is condensed and removed. The gas flows to dryer 208 via line 207, where the effluent stream is dried through a bed of water adsorbent. These dryer units are widely known in the industry and can be operated in thermal or pressure increase and decrease modes. The dry gas is sent to the conditioning vessel 210 (optional) via line 209, where the fluid is sent to the heater 212 via line 211 to form a water-depleted heated reformed gas stream and then sent to manifold A. Inside. The rest of FIG. 8 represents the SER process, in which the water-depleted heated reformed gas is subjected to a conversion reaction in a cyclically operated multiple reactor to convert CO 2 and hydrogen in the reformed gas into CO and water via a reverse water gas conversion reaction and Recovering a product rich in CO. Manifold A communicates with the branch line input pipes 3 1 1 and 3 2 1. Branch line input pipes 311 and 321 are connected to the input ends of reactors 301 and 302. Lines 3 1 1 and 3 2 1 are equipped with valves 3 1 1 a and 3 2 1 a, respectively. The opening of a suitable valve allows the compressed, water-depleted, heated recombined gas stream to pass through manifold A into a reactor that is selected to be placed in the flow path at the outset. Therefore, by opening the valve 3 1 1 a and closing the valve 32 1 a, the reformed gas can flow from the manifold A into the reactor 301 through the line 3 1 1. -20- (Please read the precautions on the reverse side before filling out this page).. Ιτ Λ This paper size applies to China Standard for Household Standards (CNS) A4 (210X297 mm) 83.3.10,000 406056 Staff of Central Standards Bureau, Ministry of Economic Affairs Printed by the Consumer Cooperative V. Description of the Invention (I9) The outputs of the reactors 301 and 302 are connected to the pipelines 340 and 350 respectively, and they are each equipped with control valves 316a and 326a. Lines 340 and 35.0 are operatively connected to manifold E via lines 3 1 6 and 3 2 6 and are discharged from reactors 301 and 302 via lines 316 and 326-a CO-rich stream that can be collected in separator 317 . The separator 317 can be composed of any conventional separation system including a CO-VSA unit or a conventional distillation system. This high purity CO product can be collected via line 318, and the residue can be collected via line 3! 9 for use as fuel or for recycling. Thus, by opening the appropriate valve 316a or 326a, the CO-rich mixture flows from the corresponding reactor into manifold E through lines 340 and 315 or lines 350 and 326 into the separator 317. Reactors 301 and 302 are operatively connected to lines 311 and 321, which communicate with the flow channels of lines 313 and 323, respectively. Lines 313 and 323 are equipped with control valves 313a and 323a, respectively, and these lines communicate with the manifold B flow path. The manifold B can communicate with the flow paths of the reactors 301 and 302 through the lines 313 and 323 when the valves 313a or 323a are opened respectively. Manifold B also communicates with the flow channel of pump 360 connected to line 362, which is combined with stream 207. Manifold C communicates with reactors 301 and 302 via flow lines of lines 314 and 324, which lines 3 1 4 and 3 2 4 are equipped with valves 3 1 4 a and 3 2 4 a, respectively. The regenerated effluent from reactors 301 and 302 flows into manifold C via lines 314 and 324 for separation by separator 335 into a water-rich product stream 336 and a stream 334 containing weakly adsorbed flushing fluid, which stream 334 can be directed to storage The slot 333 (optional) is for later use. -21-(Please read the notes on the back before filling out this page) --- Zeyan 4; This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 83.3.10,000 Central Bureau of Standards, Ministry of Economic Affairs Printed by Shelley Consumer Cooperative A7-406 & B6-5. Description of the Invention (20) The manifold D is connected to a pump 331, which receives various program fluids via lines 330 and 332. These process fluids are pressurized through line 330 or 332 and via pump 331. These pressurized fluids may pass through manifold D, which is in communication with reactors 301 and 302 flow channels via lines 315 and 325, respectively. The manner in which lines 3 1 5 and 3 2 5 are connected to manifold D allows the flow of fluid from manifold D into reactors 3 0 1 and 30 2 to be controlled. Moreover, the weakly adsorbed flushing fluid can be delivered to the pump 3 3 1 by opening the valve 3 3 2 a via line 3 3 2 or by inputting the weakly adsorbed flushing fluid through line 330. »SER of several embodiments shown in FIG. 8 The operation of the loop will be explained in an arbitrarily selected loop. The loop has eight stages of ten minutes each as shown in Table 1. Although not limited to this, the SER method shown in FIG. 8 uses the reactors 301 and 302, which operate in a loop according to a predetermined timing sequence. Other arrangements may use fewer or more reactors and connected manifolds and on-off valves, optionally with interrupted or discontinuous (using idling) operation of the pump. Other arrangements may use more than two reactors by proper sequencing of individual steps or stages of the process cycle. According to the general embodiment of FIG. 8, each of the reactors 301 and 302 performs a four-stage reaction / adsorption step, which is called a adsorption reaction step, a stage of a decompression step, and a step of washing the I step. Phase, phase of the rinse II step, and phase of the pressurization step. As shown in Table 1, the steps taken at the beginning of each of the reactors 301 and 302 were performed slowly to enable at least one of the two reactors to carry out the adsorption reaction step throughout the process cycle. The paper size of the present invention described in Figure 8-22 is applicable to the Chinese National Standard (CNS) A4 specification (2 丨 0X297 mm) 83.3.10, 〇〇〇 (Please read the precautions on the back before filling this page)- Installed.

.1T .V ----- 406056 A7 B7 V. Description of the Invention (21) The operation mainly includes the following sequence of steps: When performing the following steps, the first pressure range is from 2 to 50 atmospheres, and the second pressure range From 0. 5 to 2 atmospheres. --I-------- k pack-(Please read the precautions on the back before filling this page)

1.1T 'ν Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 23 This paper size applies to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) 83.3.10,000 A7406056_ £ 5. Description of the invention (22) Employees of the Central Bureau of Standards of the Ministry of Economic Affairs Consumption cooperative prints ooooououoouo π cloud U0003300U0U I cloud U300U3U0U0U li UUUUOUUOUOU ore is taken as εε #csfnjCNrn name l-HfnsI-tfo apostrophe οοοο οinch-οε ^ 赵 銮 盛 02 ^ 0 ^ 01¾¾ ^ ¾ 2-0 State ¾ ^ M ^ ¥ a υοουυουοουου 000 丨 0 Bu _M ^ uouuuoouooou 0S9 ilMts UOUUUOU0OO0U 09 · 0ς 0Mfe @ υοουυουουυου os-o Inch π_ Li this paper standard applies to the Chinese national standard (CN210) 297 A4 specifications . 3.10,000 -----------.— install— (Please read the precautions on the back before filling this page)

• IX Printed by AIX6G56 A7 _B7_ of the Consumer Cooperatives of the Central Government Bureau of the Ministry of Economic Affairs V. Invention Description (23) (a) Adsorption reaction-the water-depleted heated reformed gas (raw material) is passed at a pressure of ~~ predetermined pressure containing a conversion catalyst A reactor with an admixture of an adsorbent, which has a preferential selectivity to water, and one of the CO-rich streams is discharged from the reactor. Water is selectively adsorbed by the adsorbent, and a reaction material transfer zone (RMTZ) is formed in the reactor. The transfer zone moves toward the outlet or discharge end of the reactor as more raw materials pass through the reactor. The adsorbent at the leading edge of RMTZ is substantially free of adsorbed water, while the adsorbent at the trailing edge of R M T Z is balanced with water according to local conditions. This adsorption reaction step is continued until the adsorbent in the reactor is substantially saturated with water. In other words, the adsorption reaction step ends as soon as the adsorption RMTZ has reached or disappeared from the reactor effluent end. This CO-rich stream is discharged from the reactor. (b) Decompression-The reactor is depressurized counter-currently to a second predetermined pressure by discharging a mixture containing unreacted raw materials, CO and water. This decompression step continues until the reactor reaches a second predetermined pressure. (c) Flushing I--The reactor is flushed countercurrently at a second pressure using a weakly adsorbed flushing fluid to desorb water from the adsorbent, and a weakly adsorbed flushing fluid, unreacted raw materials, part C A mixture of 0 and part of the water is discharged from the reactor. (d) Flush II-the reactor is flushed countercurrently at a second pressure with a CO 2 -free flushing fluid rich in CO to desorb the weakly adsorbed flushing fluid, and a weakly adsorbed flushing fluid comprising the weakly adsorbed flushing fluid A mixture of fluid, CO and water is discharged from the reactor. (e) Pressurization--Before starting another cycle, the reactor was enriched with -25 --- i I n 11 [I order " ~ 1- ^ (Please read the notes on the back before filling (This page) This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 83. 3.10,000 406056 Printed by the Consumer Cooperatives of the Central Government Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (24) The flushing fluid from the second The pressure is pressurized countercurrent to the first pressure. The positions of those valves during the above-mentioned operating cycle stages are also listed in Table 1. The indication indicates that a specified valve is open and " C " indicates that a specified valve is closed. The sequence of operations performed in a complete process cycle stage reactor 301 will be described below in detail without omissions so that the operation of the continuous process can be fully understood. The same sequence of steps in Table 1 was followed in a slow sequence in reactor 302. Again, referring to the specific embodiment disclosed in FIG. 8 and the sequence stages and valve positions specified in Table 1, the reactor 301 has performed four sequence stages of the adsorption reaction step. The raw material stored in the storage tank 21 (optional) is introduced into the reactor 301 by opening the valves 311a and 316a and closing the valves 313a, 314a, and 315a, thereby allowing the raw material to flow through the manifold A, line 3 11 Instead, it enters reactor 301, which contains a required admixture of a conversion catalyst and a water-selective adsorbent. This adsorption reaction continues until the water substantially absorbed in the reactor 301 is saturated. Water is selectively adsorbed onto the adsorbent and a reaction material transfer zone (RMTZ) is formed inside the reactor 301, which transfer zone moves toward the discharge end of the reactor 301 as more raw materials pass through. When the MTZ reaches the outflow end of the reactor or disappears at a preset point, the adsorption reaction is complete. A CO-rich stream leaves the discharge end of reactor 301 via lines 340 and 316 and flows into manifold E for collection in separator 317. Alternatively, the mixture in the separator 317 can be traditionally increased by, for example, pressure increase or decrease adsorption, air increase or decrease adsorption, thermal increase or decrease adsorption, or distillation or condensation. -(Please read the note ^^ on the back before filling this page) • ^ This paper size applies to China National Standard (CNS) A4 (210X297 mm) 83.3.10,000 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 406056 g 5. Description of the invention (25) Technical separation to form a stream containing substantially pure CO that is discharged from the separator 317 via line 318 and the remaining components of the mixture are discharged via line 3 19. The method performs a stage of a decompression step in which the reactor 301 is decompressed countercurrently to a second predetermined pressure by discharging a mixture containing unreacted raw materials, CO, and water from an input of the reactor 301. Valve 313a is opened and valves 3 11a and 3 14a are closed to allow the mixture to enter manifold B through lines 311 and 313 and communicate with the pump 360 flow path. The mixture exits the discharge end of the pump 360 and passes through line 362 for use as fuel (not shown) or is recycled into line 207 for use as a raw material for subsequent process circulation. This decompression step continues until the reactor reaches a second predetermined pressure. The reactor 301 then undergoes the stage of the washing step I. The reactor 301 is flushed countercurrently with a weakly adsorbed flushing fluid at a second pressure. After opening the valves 314a and 315a and keeping the valves 325a and 332a in the closed position, the weakly adsorbed flushing fluid from an external source passes through the pump 3 3 1 via line 3 3 0 and leaves the pump 3 3 1 at the second pressure to pass through the manifold D , Lines 3 1 5 and 3 4 0 enter the outlet end of the reactor 301. A mixture containing a weakly adsorbed flushing fluid, unreacted feedstock 'CO, and water is discharged from reactor 301 via line 311, line 314, and manifold C and collected in separator 3 3 5. This mixture may be used as fuel, discharged for use outside the process, or separated in separator 335 to form a weakly adsorbed flushing stream and a water-rich stream 336. A portion of this weakly-adsorbed flushing fluid may be transported via line 334 into storage tank 333 for future use. Upon request, by opening the valve 3 3 2 a, the weakly adsorbed flushing fluid-27- (please read the precautions on the back before filling this page) -packing. The size of the paper is applicable to China National Standard (CNS) A4 specifications ( 210X297 mm) 83.3.10,000 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs ^ 06056 at ___B7__ V. Invention Description (26) May be input to pump 3 3 1 via pipelines 3 3 2 and 3 3 0 for subsequent The method is used cyclically. Reactor 301 then undergoes the stage of flush II step, in which reactor 301 is flushed countercurrently by a CO-rich fluid containing no hydrogen and co2. After opening valves 314a and 315a and keeping valves 325a and 332a in the closed position, a CO-rich flushing fluid from an external source passes pump 330 through line 330 and leaves pump 331 at a second pressure to pass through manifold D 'line 315 and Line 340 enters the outlet end of the reactor 301. A mixture comprising a weakly adsorbed flushing fluid, water, and a CO-rich flushing fluid is discharged from reactor 3 0 1 through line 3 1 1, line 3 1 4 and manifold C and collected in separator 3 3 5. This mixture may be used as fuel or discharged for use outside this method. The final step of the process cycle includes a single sequence of pressurization steps in which the reactor 301 is countercurrently flowed from the first to the first reactor cycle by a CO-rich flushing fluid or a high purity CO product stream 318 The two pressures are pressurized to the first pressure. In particular, after opening valve 315a and holding valves 311a, 313a, 314a, 325a, and 332a in the closed position, the CO-rich flushing fluid passes pump 330 through line 330 and leaves pump 331 at a second pressure to pass through the manifold D. Lines 315 and 340 enter the exit end of the reactor 301. This step ends when the reactor 301 reaches the first pressure. Following the above steps listed in Table 1, the method performs an additional cycle. Although these sequence stages are described as being of equal length, they are not necessary or necessary. The setting of time depends on the allowable maximum gas flow rate, the size of the valve and the pipeline, and the size of the valve. (Please read the precautions on the back before filling in this 萸 >). The paper size applies the Chinese National Standard (CNS) A4. Specifications (210X297 mm) 83.3.1, 〇〇〇 printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 406056 V. Description of invention (27) The nature of the adsorbent. Interactive procedures may be used to establish each cycle step For example, other techniques known in the industry, such as reactor effluent composition analysis, may be used to determine the end point of a particular step. Several variations of the general embodiment may be tested to meet the specific requirements of each plant. Yes, for example, the CO-rich stream of manifold E can be separated at separator 317 to form a stream 501 containing substantially pure CO stream 318 and a CO depleted stream. Stream 501 can be introduced into a traditional polymeric film 502 to form a hydrogen-rich exhaust gas stream 503 and a hydrogen-depleted carbon dioxide-rich recycle stream that can be recycled into the SMR reactor 204 5 0 4 _ Alternatively, each reaction may use a weak adsorption flushing fluid at the first pressure to perform an additional counter-current flushing step between the adsorption reaction step and the decompression step to discharge a mixture containing unreacted raw materials, CO and water. Recirculated as feed to these SER reactors via manifold B, pump 3 0 6 and line 3 6 2. Also, additional CO 2 may be added to the water depleted heated reformed gas stream 209 before the SER cycle is performed to balance Stoichiometry of C 0 2 and hydrogen in the conversion reaction. Another specific embodiment of the applicant's method is illustrated in FIG. 9, which illustrates a method flow diagram describing a steam methane reformer 604, a conversion reactor 802 , Hydrogen PSA unit 806, compressor 808, condenser 6 0 6, 6 10 and 8 0 4, dryer 6 12, feed heater 6 1 6 'SER reactor 6 0 1 and 6 0 2; many control valves ; Manifolds A to E; Pumps 731 and 760; Separator 717 and 735; and Regulating Vessel 614 and -29- (Please read the precautions on the back before filling out this page) This paper size applies Chinese National Standard (CNS) A4 Specifications (210X297 mm) 83.3 .10,000 A7 B7 Printed by the Shell Standard Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the Invention (28) 733. Referring to Figure 9, a hydrocarbon feedstock such as methane or natural gas is used in a container (not shown). Adsorbent desulfurization. The desulfurized hydrocarbon feedstock is mixed with steam to form a hybrid reformer feedstock represented by stream 603. The feedstock 603 is preheated in a preheater (not shown) and is introduced into the SMR reformer 604 within. This reformer is well known in the industry and is heated by burning a mixture of fuel and air (not shown). The reformer typically operates at a temperature of 800 ° to 100 ° C and a pressure of 5 to 30 atmospheres and produces a dry weight of approximately 73% hydrogen, 13% CO, 9% C. Recombination gas consisting of 2 and 5% methane. The reformed gas is sent to condenser 606 via line 605 where the temperature of the gas is reduced to 200 ° to 500 ° C. This gas is split into a first stream flowing through line 801 and a second stream flowing through condenser 6 10. The cooled recombined gas flows through a conversion reactor 802 through a line 801 where CO and water are converted into hydrogen. The hydrogen-rich stream 803 leaving the conversion reactor is cooled in a condenser 804 to 30 ° to 120 ° C, in which a large amount of water is removed by condensation. The water depleted hydrogen-rich stream 805 is sent to a hydrogen PSA 806 to produce a high purity hydrogen stream 807 and a waste stream. This second stream entering the condenser 610 is cooled to ambient temperature, and water is removed by condensation. The gas flows through line 611 to dryer 612, where the effluent is dried through a bed of water adsorbent. These dryer units are widely known in the industry and can be operated in thermal or pressure increase and decrease modes. This substantially dry gas is conveyed into the conditioning vessel 6 14 via line 6 13, where the fluid is conveyed through line 615 into heater 616 to form a water depleted heated reformed gas stream and is introduced into manifold A. The rest of Figure 9 shows the SER method, of which -30- (please read the note on the back ^ before filling this page) -pack- * 11- This paper size applies to China National Standard (CNS) A4 (210X297 mm) 83. 3.10,000 406056 A7 B7 Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (29) Water-exhausted heated recombined gas will be subjected to a conversion reaction in a plurality of reactors operating in circulation to recombine The CO 2 and hydrogen in it are converted into CO and water through a reverse water gas conversion reaction and a CO-rich product is recovered. The manifold A is in communication with the branch line input pipes 711 and 721, and the branch line input pipes 711 and 721 are connected to the input ends of the reactors 601 and 602. Lines 711 and 721 are equipped with valves 711a and 721a, respectively. The opening of a suitable valve allows the compressed, water-depleted, heated recombined gas stream to pass through manifold A into a reactor that is selected to be placed in the flow path at the outset. Therefore, by opening the valve 71a and closing the valve 721a, the recombined gas can flow from the manifold A to the reactor 6 01 through the line 7 1 1. The outputs of the reactors 6 0 and 6 0 2 are connected to lines 7 4 0 and 750, respectively, which are each equipped with control valves 716a and 726a »Lines 740 and 750 are operatively connected to manifold E via lines 716 and 726 The CO-rich stream is discharged from reactors 601 and 602 via lines 716 and 726 and can be collected in separator 717. The separator 717 can be composed of any conventional separation system including a CO-VSA unit or a conventional distillation system. The high purity CO product can be collected via line 718, and the CO depleted stream 7 19 is compressed at compressor or blower 808 and combined with line 805 is introduced into hydrogen PSA 806. Therefore, by opening the appropriate valve 716a or 7 2 6 a, the C 0 rich mixture flows from the corresponding reactor into manifold E through lines 7 4 0 and 716 or lines 750 and 726 into the separator 717 Inside. Reactors 601 and 602 are operatively connected to lines 711 and 721, which communicate with the flow channels of lines 7 1 3 and 7 2 3, respectively. .Pipelines 7 1 3 and 7 2 3 are installed separately -31-—.1 —— Order IIIIIIII ^ (Please read the note ^^ on the back before filling this page) This paper size applies to China National Standard (CNS) A4 specifications ( 210X297 mm) 83.3.10,000 Printed by the Central Procurement Bureau of the Ministry of Economic Affairs, Consumer Cooperatives, printed 406056 b; V. Description of the invention (30) There are control valves 713a and 723a, these lines communicate with the manifold b channel. The manifold B can communicate with the flow channels of the reactors 601 and 602 through the lines 7 and 723 when the valves 7 1 a or 7 2 3 a are opened respectively. Manifold b also communicates with the flow channel of pump 7 60 connected to line 7 6 2, which line 7 6 2 is combined with stream 6 1 1. Manifold C communicates with reactors 601 and 602 via lines 714 and 724, which are equipped with valves 714a and 724a, respectively. The regenerated effluent from reactors 601 and 602 flows into manifold C via lines 714 and 724 for separation by separator 735 into a water-rich product stream 736 and a stream 734 containing weakly adsorbed flushing fluid, which stream 734 can be Into the storage tank 7 3 3 for later use. Manifold D is connected to a pump 731, which receives various program fluids via lines 730 and 732. These process fluids are pressurized via line 7 30 or 7 3 2 and via pump 731. The pressurized fluid may pass through manifold D, which is in communication with reactors 601 and 602 flow channels via lines 715 and 725, respectively. Lines 7 15 and 7 2 5 are equipped with valves 7 15a and 725a, respectively, so that the flow from manifold D into reactors 601 and 602 can be controlled. Moreover, the weakly adsorbed flushing fluid can be operated to open the valve 7 3 2 a via line 732 or by inputting the weakly adsorbed flushing fluid via line 730 to the operation of the SER cycle of several embodiments shown in FIG. 9. It will be interpreted in an arbitrarily selected cycle with eight cycles of ten minutes each as shown in Table 2. Although not limited to this, the SER method shown in FIG. 9 uses reactors 601 and 602, which operate in a cycle in accordance with a predetermined timing sequence -32- _ 83.3.10,000 This paper size applies the Chinese National Standard (CNS) A4 specification (hOXW7 (Mm) 1 — — — — — 装 — — ^ Order (please read the notes on the back before filling this page) A7 B7 V. Description of the invention (31). Other arrangements may use fewer or more reactors and associated gas manifolds and on-off valves, optionally with interrupted or discontinuous (using idling) operation of the pump. Other arrangements may use more than two reactors by appropriate sequencing of individual steps or stages of the process cycle. — II Order I — ^ (Please read the notes on the back before filling out this page) Printed by the Consumers' Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs -33-83. 3.10,000 This paper size applies the Chinese National Standard (CNS) A4 specification ( (210X297 mm) A7406056 B7 clearly states that the printing of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs printed 3303000303033 s < ΙΙ_υυοου3ουου3υυ? I_UU00U3UU03UU Sil ουοοοοοουυυυυυ__οοουυ 0υ 0υουου

Zhenyi U033U00U00UUUU 'mMM ¥ a υουυυυυυυοοουυ mmm uooouuouuuooouu Proof 30300U0U0UU0UU Predicate U03UU30UUUUU0UU (please read the notes on the back first and then fill out this page) Packing. 09-05 〇οο, ε义 密 义 02-06 _ 吕 06-000? 11¾¾ 08 · 0Α Μ < ^ s: 0S9 i OSS Md < Zhen 4 This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 83. 3.10 10,000, the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, 406056 a? _B7 __ V. Description of the Invention (33) According to another specific embodiment of FIG. 9, each of the reactors 601 and 602 performs a four-stage reaction / The adsorption step is called the adsorption reaction step, the stage of the decompression step, the stage of the washing step I, the stage of the washing step II, and the stage of the pressurizing step. As shown in Table 2, each of the reactors 601 and 602 is started The steps taken at this time are performed slowly so that at least one of the two reactors can carry out the adsorption reaction step throughout the process cycle. The operation of the present invention described in FIG. 9 mainly includes the following steps Column: When the following steps are performed, the first pressure range is from 2 to 50 atmospheres, and the second pressure range is from 0.05 to 2 atmospheres. (A) Adsorption reaction-the water-depleted heated reformed gas (raw material) A predetermined pressure is passed through a reactor containing a conversion catalyst and an admixture of an adsorbent, the adsorbent has a preferential selectivity to water, and a CO-rich stream is discharged from the reactor. The water is selectively selected by the adsorbent. Ground adsorption, and a reaction material transfer zone (RMTZ) is formed in the reactor. As more raw materials pass through the reactor, the transfer zone moves toward the outlet or discharge end of the reactor. The adsorbent at the leading edge of the RMTZ is substantially free of The adsorbed water and the adsorbent at the rear edge of the R M TZ reach equilibrium with water according to local conditions. The adsorption reaction step continues until the adsorbent in the reactor is substantially saturated with water. In other words, once RMTZ is adsorbed The adsorption reaction step ends when the effluent end of the reactor has been reached or disappeared. The CO-rich stream is discharged from the reactor. (B) Decompression-By discharging the unreacted raw material, C A mixture of O and water The reactor is decompressed countercurrently to a second predetermined pressure. The decompression step continues until the reactor reaches a second predetermined pressure. -35----------- 装 ---- --Order ------ ^ (Please read the notes on the back before filling out this page) This paper size applies to China National Standard (CNS) A4 (210X297mm) 83.3.10,000 406056 Central Ministry of Economic Affairs Printed by the Consumer Cooperative of the Bureau of the People's Republic of China. 5. Description of the invention (34) (C) Flushing I-The reactor is flushed countercurrently with a weak adsorption flushing fluid at a second pressure to desorb water from the adsorbent, and a A mixture containing the weakly adsorbed flushing fluid, unreacted raw materials, part of CO and part of water is discharged from the reactor. (d) Flushing 11-the reactor is flushed countercurrently at a second pressure with a flushing fluid rich in C0 that does not contain CO 2 and hydrogen to desorb the weakly adsorbed flushing fluid, and a weakly adsorbed flushing fluid containing the weakly adsorbed flushing fluid, A mixture of CO and water is discharged from the reactor. (e) Pressurization-the reactor is pressurized countercurrently from the second pressure to the first pressure with a CO-rich flushing fluid before starting another cycle. The positions of those valves in the above-mentioned operating cycle stages are also listed in Table 2. The indication n 〇 __ shows that a specified valve is open and " C " indicates that a specified valve is closed. The sequence of operations performed in a complete process cycle stage reactor 601 will be described below in detail without omissions so that the operation of the continuous process can be fully understood. The same sequence of steps according to Table 2 was performed in reactor 602 in a slow sequence. Once again, referring to the specific embodiment disclosed in FIG. 9 and the sequence stages and valve positions specified in Table 2, the reactor 601 has performed four sequence stages of the adsorption reaction step. The raw material stored in the storage tank 614 is preheated by the heater 616, and then is introduced into the reactor 601 by opening the valves 71a and 716a and closing the valves 713a, 714a, and 715a, thereby allowing the raw material to flow through the manifold A, Line 7 1 1 enters reactor 6 0 1, which contains a required admixture of a conversion catalyst and a water-selective adsorbent. The adsorption reaction continues until the reactor 60 1 is substantially adsorbed with water plus -36 ------------- (please read the precautions on the back before filling this page) Γ The scale of this paper is applicable to China Standard (CNS) A4 specification (210 × 297 mm) 83.3.10,000 40605 ^ A7 B7 Printed by the Consumers' Cooperatives of the China Standards Bureau of the Ministry of Economic Affairs 5. The invention description (35) is saturated. Water is selectively adsorbed onto the adsorbent and a reaction material transfer zone (RMTZ) is formed inside the reactor 301, which transfer zone moves toward the discharge end of the reactor 601 as more raw materials pass through. When the MTZ reaches the outflow end of the reactor or disappears at a preset point, the adsorption reaction is complete. A CO-rich stream leaves the discharge end of reactor 601 via lines 740 and 716 and flows into manifold E for collection within separator 717. Alternatively, the mixture in the separator 7 1 7 can be separated by conventional techniques such as pressure increase or decrease adsorption, air increase or decrease adsorption, heat increase or decrease adsorption, or distillation or condensation to form a stream, which is contained via line 718. The substantially pure CO discharged from the separator 717 and the remaining components of the mixture are discharged via the line 7 1 9. The method performs a stage of a decompression step in which the reactor 601 is decompressed countercurrently to a second predetermined pressure by discharging a mixture containing unreacted raw materials, CO, and water from an input of the reactor 601. Valve 713a is opened and valves 711a and 714a are closed to allow the mixture to enter manifold B through lines 711 and 713 and communicate with the flow path of pump 760. The mixture exits the discharge end of the pump 76 and passes through line 762 for use as fuel (not shown) or is recycled into line 611 as a raw material for subsequent process circulation. This decompression step continues until the reactor reaches a second predetermined pressure. The reactor 601 then undergoes the stage of the flushing step I. The reactor 601 is flushed countercurrently with a weakly adsorbed flushing fluid at a second pressure. After opening the valves 7Ma and 7l5a and keeping the valves 725a and 732a in the closed position, the weakly adsorbed flushing fluid from an external source passes the pump 7 3 1 through line 7 3 0 and -37-II n. 装 装 IIII IIIIII —- ^ (Please read the notes on the back before filling this page) This paper size applies to Chinese national standards (CNS > A4 size (210X297 mm) 83.3.10,000 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 __4〇6Q56 _B7__ 5 Explanation of the invention (36) Leaving the pump 73 at the second pressure to enter the outlet end of the reactor 601 via the manifold D, the line 715 and the line 740. A weakly adsorbed flushing fluid, unreacted raw material 'C 0 and water The mixture is discharged from reactor 601 via line 711, line 714, and manifold C and collected in separator 7 3 5. This mixture may be used as fuel, discharged for use outside of this method, or in separator 735 Separated to form a weakly adsorbed flushing fluid stream and a water-rich stream 7 3 6. A portion of the weakly adsorbed flushing fluid may be transported via line 734 into storage tank 733 for future use By opening the valve 732a upon request, the weakly adsorbed flushing fluid may be fed into the pump 7 31 via lines 7 3 2 and 7 3 0 for subsequent method recycling. The reactor 601 then undergoes the stage of the flushing II step, at Wherein reactor 601 is flushed countercurrently by a CO-rich fluid that does not contain hydrogen and CO 2. After opening valves 714a and 715a and keeping valves 725a and 732a in the closed position, a CO-rich flushing fluid from an external source passes through the line 730 passes through pump 731 and exits pump 731 at a second pressure to enter the outlet end of reactor 601 via manifold D, line 715, and line 740. A mixture comprising a weakly adsorbed flushing fluid, water, and a flushing fluid rich in CO. It is discharged from reactor 601 via line 711, line 714, and manifold C and collected in separator 7 35. The mixture may be used as fuel or discharged for use outside the process. The final step of the process cycle includes a A single sequence of pressurization steps in which reactor 601 is flushed with a CO-rich flushing fluid or a high purity CO product stream 718 before the reactor begins another method cycle -38- Paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 83.3.10,000 ---------- installation ----- 1T ------ 4 (Please read the Note for refilling this page) Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, A7406056_b7__ V. Description of the invention (37) Pressurize from the second pressure to the first pressure countercurrently. In particular, after valve 715a is opened and valves 7 " a, 713a, 7 14a, 725a, and 732a are in the closed position, the CO-rich flushing fluid passes pump 731 via line 730 and leaves pump 731 at a second pressure to Enter the outlet end of the reactor 601 via manifold D, line 715 and line 740. This step ends when the reactor 601 reaches the first pressure. Following the above steps listed in Table 2, the method performs an additional cycle. Although these sequence stages are described as being of equal length, they are not necessary or necessary. The time setting depends on the maximum allowable gas flow rate, the size of the valves and lines, and the nature of the sorbent used. Interactive procedures may be used to establish a period of cyclic steps. For example, other techniques well known in the industry, such as the analysis of the composition of reactor effluents, may be used to determine the end point of a particular step. Alternatively, each reaction may use a weak adsorption flushing fluid at the first pressure to perform an additional countercurrent flushing step between the adsorption reaction step and the decompression step to discharge a mixture containing unreacted raw materials, CO and water. Recycled as feed to these SER reactors via manifold B, pump 760 and line 762. Suitable steam methane reforming catalysts include traditional steam methane reforming and pre-reforming catalysts such as nickel-alumina, nickel-magnesium alumina And precious metal catalysts. Suitable water gas conversion catalysts for reverse conversion reactions in the reactor or SER cycle include traditional conversion catalysts such as iron-chromium high temperature conversion catalysts, copper-zinc oxide low temperature conversion catalysts, and copper / zinc oxide medium temperature -39-nk devices. I order I (Please read the notes on the back before filling this page) This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 83. 3.10,000 Printed by the Consumer Cooperatives of the Central Sample Bureau of the Ministry of Economic Affairs 406056 A7 _B7_ V. Description of the invention (38) Conversion catalyst. A water adsorbent suitable for an integrated SER process reactor must be active under the reaction conditions, which means that the adsorbent must retain its capacity and selectivity for the more adsorbable product. Secondly, the adsorbent must be chemically neutral and cannot be used as a catalyst for the reverse water gas conversion reaction. The term weakly adsorbed fluid is a fluid that can replace the product adsorbed by the adsorbent during the operation phase of the method, and the fluid can be desorbed by the less adsorbed product, allowing subsequent process cycles to be performed in each reactor. Those skilled in the art can easily select a weakly adsorbed fluid or a mixture thereof suitable for the claimed invention. The general and another specific embodiments of the present invention can be operated using conventional hardware equipment. For example, a suitable reactor includes any vessel capable of withstanding the reaction conditions under which a particular equilibrium control method is implemented, such as a shell and tube reactor. Moreover, the separators enumerated in the method can be easily selected by those skilled in the art in consideration of, for example, the particular mixture to be separated, the volume of the separated fluid, and the like. The following examples are provided to further illustrate the method for applicants for producing CO. These examples are illustrative and are not intended to be used to limit the scope of patent application in this case. In the experimental part, the following examples are provided to illustrate a method for producing CO applied by the applicant, which integrates a conventional SMR method and a SER cycle to pass CO 2 present in the SMR reformed gas through backwater gas -40- This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 83. 3.10,000 nn nn I n I f — nnn ^ 111111 (Please read the notes on the back before filling this page) 406C56 at B7 Economy Printed by the Consumers' Cooperative of the Ministry of Standards and Standards of the People's Republic of China 5. Description of Invention (39) The conversion reaction is converted to C0. Figures 1 to 7 describe the mass balance calculations for the selected method. The "HSC Chemistry for Windows" software package from Finland Outokumpu Research Oy was used to calculate the thermodynamic equilibrium of the composition of the effluent from the steam methane reformer. All other calculations are common knowledge for those skilled in the chemical engineering industry. The following assumptions were used in these calculations: (a) the composition of the recombined product depends on the equilibrium conversion of the recombiner product at a constant temperature and pressure; (b) the steam methane recombiner operates at 850 ° C and 25 atmospheres (C) the feed to the reformer contains 25 mol / min CH4 and 75 mol / min H2O; (d) when considering input C02 (Figure 5, Figure 8), an additional 60 mol Hrs / hour of the CO2 feed stream is added to the reformer or adsorption enhancement reactor; (e) The CO-VSA process produces substantially pure CO products (99.5%) at 85% —carbon oxide recovery; (f ) The H2-PSA method produces a substantially pure hydrogen product at 95% hydrogen recovery (99.9%); (g) the conversion of CO2 to CO in the adsorption enhanced reactor method is 80% (i.e. 80% of the CO2 fed to the reactor is discharged from the reactor as CO products); (h) The membrane separator in Figure 6 and Figure 8 emits 30% of the feed hydrogen and 67% of the carbon dioxide feed , And 97% of the input carbon monoxide and methane, -41-(Please read the note ^^ on the back before filling out this page) -Packing · -5 This paper size applies to China National Naked Standard (CNS) A4 specifications ( 210X297 mm) 83.3.10,000 A7 B7

4Q6Q5B V. Description of the invention (40) where the emission parameter is defined as the ratio of the amount of a specific component in the recombined gas (or high pressure) stream leaving the membrane unit to the amount of the component in the membrane unit feed stream; and (i ) The carbon monoxide conversion in these conversion reactors is 80%. Example 1 Integration of the CO-SER method with the CO production method Table 3 contains mass balance data for some of the method plans for carbon monoxide production described in Figures 5, 6, and 8. The table provides the total number of moles of carbon monoxide produced, the number of moles of carbon monoxide produced per mole of new methane fed to the SMR reactor (CO / CH4), and the total number of all ingredients fed to the SMR reactor. Total Moire number (which is proportional to the number of tubes and heat of the reformer). Table 3 * Comparative performance of the integrated SERP-SMR method book for the production of CO -42- The paper size applies the Chinese National Standard (CNS) Α4 specification (210 × 297 mm) (Please read the precautions on the back before filling this page) -Equipped with the cooperation of employees of the Central Bureau of Standards of the Ministry of Economic Affairs, the net amount of CO products printed by Moore (Moore) Total amount fed to SMR (Moore) (CO / CH4) Figure 5 SMR + CO-VSA 10.3 100.0 0.41 Figure 5 SMR + CO-VSA with input C02 as SMR »31.9 160.0 1.28 Figure 6 SMR + CO-VSA with CO2 / CH4 from CO-VSA recycling as SMR ^ 20.0 153.3 0.80 Figure 8 SMR + SERP + CO -VSA 15.7 100.0 0.63 Figure 8 SMR + SERP + CO-VSA with input C02 as SERP feed 46.2 100.0 1.85 _8 SMR + SERP + CO-VSA with CO-VS A exhaust gas recirculation C02 / CH4 when For SMR feed 22.8 Plant 154.4 0.91 * SMR feed: 25 Mohr CH4 + 75 Moore η2〇 (benchmark example) 83. 3.10,000 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 406056 Α7 Β7 V. Description of the invention (41) A reference example system consisting of a steam methane reformer and a subsequent CO-VSA unit to separate carbon monoxide (Figure 5) The data show that the reformer feed per 100 mol / min can produce CO of 10.3 mol / min, and the CO / CH4 ratio is 0.41. Applicant's method consists of steam restructuring, adsorption enhancement reaction of CO2 and H2 into CO, and carbon monoxide separation of a CO-VSA unit (a specific example of the first item in the scope of the patent application is illustrated in Figure 8), It achieves 15.7 mol / min of CO per 100 mol / min of recombiner feed, and the CO / CH4 ratio is 0.63 ^ Therefore, adding the SER cycle to the SMR process produces a feed at the same SMR feed Unexpected results of an increase of 5 2% CO production compared to previous techniques.

Those familiar with steam methane reforming will understand that adding carbon dioxide to the feed of a steam methane reformer can increase CO production. Data from a benchmark system consisting of a steam methane reformer with an additional input of C02 feed and a subsequent CO-VSA unit to separate carbon monoxide (Figure 5) shows that the reformer feed (100 Moore / minute of methane / steam mixture plus 60 mole / minute of carbon dioxide) can produce 31.9 Moore / minute of CO, and the CO / CH4 ratio is 1.28. Applicant's new method consists of steam methane recombination, a dry recombination gas stream plus a pure carbon dioxide admixture feed, which undergoes an absorption enhancement reaction to convert C 0 2 and Η 2 into CO and a CO-VSA unit. It is composed of carbon monoxide separation (a specific embodiment of item 5 of the patent application is illustrated in Figure 8), which reaches 46.2 moles / minute of carbon monoxide per 100 moles / minute of reformer feed, and CO The / CH4 ratio is 1.85. Therefore, the SER follows -43-this paper size applies to the Chinese National Standard (CNS) Α4 specification (210 × 297 mm) 83. 3.10,000 ----- ρ ------- install-(Please read first Note the item on the back, please fill in this page), π 4, printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shelley Consumer Cooperative A7406056_B7_V. Description of the invention (42) Ring added to the existing SMR method at 62% of the previous technology method This results in a substantial 45% increase in CO production compared to previous techniques. In other words, for a total reformer feed rate (methane + steam + carbon dioxide), using the method applied by the applicant can increase CO production by 132%. At the same reformer feed rate, the applicant's method produced 4.48 times more CO than the baseline example consisting of a steam methane reformer and a subsequent CO-VSA unit separating carbon monoxide (Figure 5). If the incoming carbon dioxide is not available, those familiar with steam methane reforming will understand the ability to recover a carbon dioxide-rich stream from the separation system. This stream can be recycled to the feed of the steam methane reformer to increase the CO productivity of the process. It consists of a steam methane reformer with an additional CO2-rich recycle stream feed and a subsequent CO-VSA unit to separate carbon monoxide and form the CO2-rich recycle stream from the CO-depleted stream (Figure 6) The system data show that every 153.3 mol / min of reformer feed (100 mol / min of methane / steam mixture plus 53.3 mol / min of CO2-rich stream) can produce 20.0 mol / min of CO, And the CO / CH4 ratio is 0.80. Applicant's method consists of a steam methane reformer with an additional feed of a CO 2 -rich recycle stream, and a SER cycle to convert CO 2 and H 2 in the dried reformed gas to CO and then a CO-VSA The unit separates carbon monoxide and from the CO depleted stream to form the C 0 2 -enriched recycle stream (a specific example of item 4 in the patent application scope is illustrated in Figure 8), which reaches The feed of the reformer can produce 22.8 mol / min of carbon monoxide, and (: 0 / (: 114 -44-I i 111I ^ (Please read the note on the back before filling this page). The paper size applies to Chinese national standards (CNS) A4 specification (210X297 mm) 83.3.10,000 Employees' Cooperative Cooperative A7 B7 of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (43) The ratio is 0.9 1. Therefore, the SER cycle is added to the existing SMR method At a 65% prior art process feed rate, a significant 14% increase in C0 production results over the prior art process. In other words, for a total reformer feed rate (methane + steam + CO2-rich recycle stream) , With the method applied by the applicant, the production of C 0 can be increased by 75%. At a rate of only 54% higher than the reformer feed rate, the method applied by the applicant produces C0 that is produced by a steam methane reformer and a subsequent CO- The VSA unit separated carbon monoxide (Figure 5) and produced a baseline example of 2.21 times more C0. Example 2 Integration of the CO-SER method and 1 ^ 2_ production method Table 4 contains hydrogen production (Figure 1) and a smaller amount of total Mass balance data for some method plans for product carbon monoxide (Figures 7 and 9). This table provides the total moles of hydrogen and carbon monoxide products produced. Table 4 * is an integrated SERP for the simultaneous production of C0 and H2 Comparison of SMR method plan_ Comparison of performance H2 product net (Moore) CO product net (Moore) Figure 1 smr + h2-psa 66.0 0 Figure 7 SMR + H2-PSA + CO-VSA 65.2 1.03 Figure 9 SMR + H2-PSA + SERP + CO-VSA 65.0 "1.56 * SMR feed: 25 Mohr CH4 + 75 Mohr H2〇 (base example). A steam reformer and a subsequent H2-PSA unit Min -45-This paper size applies Chinese National Standard (CNS) A4 ^ (21 × 297mm) 83.3.10,000 (Please read the back first Note to fill out this page) - installed.

.1T 406056 Printed by the Consumer Cooperatives of the Central Sample Bureau of the Ministry of Economic Affairs. 5. Description of the invention (44) The standard case method composed of hydrogen (Figure 1) shows that it can produce 66.0 per 100 mol / min of reformer feed. Mohr / min H2. Those familiar with steam methane recombination will understand the ability to take a portion of the recombined gas (known as a branch stream), cool it to ambient temperature, and then separate the carbon monoxide through a suitable separator to obtain a small amount of co-product carbon monoxide * and then come from The CO-depleted exhaust gas of the separator can be recycled to the H2-PSA unit to partially recover the remaining hydrogen. Figure 7 illustrates a specific embodiment of this method. When 10% of the stream leaving condenser 114 is passed through the CO-VSA process as a branch stream (via line 118), every 100 mol / min of reformer feed can produce 1.03 mol / min of CO2 and the hydrogen product stream Reduced to 65.2 Moores / minute (1.2% lower than the baseline example). The method applied by the applicant includes steam methane recombination, separation of the recombined gas into two streams (one of which is a branch stream), removal of water from the branch stream to form a dried recombined gas stream, and an adsorption enhancement reaction The method reacts the stream to convert CO 2 and hydrogen to CO, recovers carbon monoxide from the stream in a CO-VSA unit, and finally recycles the exhaust gas from the CO-VSA unit to the plutonium 2-PSA unit to partially recover the remaining hydrogen ( A specific example of the 12th scope of the patent application is illustrated in Figure 9). This method achieves the performance of the reformer feed per 100 mol / min (assuming that the branch stream is composed of 10% of the reformed gas stream leaving the condenser 606). It produced 1.56 mol / min of carbon monoxide and 65.0 mol / min of hydrogen (1.5% lower than the reference example). Therefore, the addition of the SER method to the existing method at the same tributary flow rate yielded a 51% increase in CO production and a slight decrease in hydrogen productivity (< 2%) over the prior art method. -46- (Please read the notes on the back before filling in this page)-* This paper size is applicable to China National Standard (CNS) A4 ^ (210X297 mm) 83.3.10,000 406056 Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs System A7 B7 V. Description of the invention (45) The present invention has been described above, and the scope of the present invention that is considered to be appropriate for patent application is defined as follows. -47- 1 II — 订 — II n I ^ (Please read the Note: Please fill in this page again.) 83. 3.10,000 This paper size applies the Chinese National Standard (CNS) A4 specification (2! 0X297 mm)

Claims (1)

Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A8 4 (^ 4--1¾ (as amended in January) Trrj / U 1. A method for producing carbon monoxide, comprising the following steps: (a) Making methane and The raw material for water is in the presence of a steam methane reforming catalyst composed of a group of nickel-gasified aluminum, lock-MMJh aluminum and precious metal catalysts, at a temperature range from 700t to 1000 ° C and a pressure range from 2 to 50 atmospheres React to form a reformed gas containing hydrogen, carbon monoxide, carbon dioxide, and unreacted feedstock; (b) remove water from the reformed gas to form a water-depleted reformed gas and heat the water-depleted reformed gas to a temperature range From 200 ° to 500 ° C to form water-depleted heated reformed gas; (c) introducing the water-depleted heated reformed gas into a plurality of reactors, which are operated in a predetermined timing sequence according to the following steps, the These steps are circulated in each reactor: (1) the first one containing a water adsorbent and a water gas conversion catalyst at a first pressure ranging from 2 to 50 atmospheres; In a reactor, under reaction conditions sufficient to convert carbon dioxide and hydrogen to carbon monoxide and adsorb water on the adsorbent, the water-depleted heated reformed gas is reacted and a CO-rich stream is discharged, wherein the water adsorbent It is selected from the group consisting of zeolite, alumina, or silica gel, and the water gas conversion catalyst is a group selected from the group consisting of iron-chromium high-temperature conversion catalyst, copper / zinc argon low-temperature conversion catalyst, and copper / zinc gas middle-range conversion · catalyst; (2) Decompress the first reactor countercurrently to a second pressure ranging from 0.05 to 2 atmospheres by discharging a mixture containing unreacted raw materials, carbon monoxide and water; __- 48 -__ 本^ Zhang scale is applicable to China National Standards (CNS) A4 specification (210X297 mm) ~ '(Please read the notes on the back before filling this page) * 1T Printed by A8 B8406056_Stc, Application by the Central Standards Bureau of the Ministry of Economic Affairs Patent scope (3) at the second pressure, flush the first reactor countercurrently with a flushing fluid that weakly adsorbs the adsorbent, and desorb water from the adsorbent A mixture containing unreacted raw materials, carbon monoxide and water is discharged, wherein the weakly adsorbed flushing fluid is a group consisting of methane, tritium, gas, and carbon dioxide; (4) at the second pressure, a A flushing fluid containing hydrogen and carbon dioxide and rich in CO flushes the first reactor countercurrently to desorb the weakly adsorbed flushing fluid and discharge a mixture containing the weakly adsorbed flushing fluid, carbon monoxide and water; and (5) in the Before the first reactor begins another method cycle, the first reactor is counter-pressurized from the second pressure to the first pressure with the CO-rich flushing fluid. 2. The method according to item 1 of the patent application scope, further comprising: (d) separating step c (l) by pressure increase or decrease, air increase / decrease adsorption, thermal increase / decrease adsorption, distillation or condensation The CO-rich stream forms a CO-containing stream and a CO-depleted stream. 3. The method of claim 1 in the scope of patent application, further comprising the following steps between steps c (l) and c (2): flushing the first countercurrently with a weakly adsorbed flushing fluid at the first pressure Reactor, and a mixture containing unreacted raw materials, carbon monoxide, and water was discharged. 4. If the method of applying for the second item of the patent scope, which further includes the following steps ___- 49: __ This paper size adopts China National Standards (CNS) A4 specifications (210X297 male thin) (January 2000 (Revision) IIII! II _ 'Ill IIII (Please read the precautions on the back before filling out this page) 406056 A8 B8 C8 D8 (Amended in January 2000) Patent application scope Step (d) CO exhausted logistics by pressure Increase or decrease adsorption, increase vacuum adsorption, increase or decrease thermal adsorption, distillation or condensation to separate to form—a hydrogen-rich exhaust gas stream and a hydrogen-depleted carbon dioxide-rich recycle stream, and recycle at least a portion of the The recycle stream is used as the feed for step (a). 5. The method of claim 1, further comprising: (d) introducing a source of carbon dioxide into the water-depleted heated reformed gas stream before performing step (c). 6. The method according to item 1 of the patent application range, wherein the admixture of the catalyst and the adsorbent comprises 5 to 95% by weight of an adsorbent and 95 to 5% by weight of a catalyst. 7. The method according to item 1 of the patent application range, wherein the amount of water and methane contained in the raw material is a stoichiometric ratio of water to methane ranging from 1.5 to 30. I ------ Strategy-- (Please read the notes on the back before filling out this page) Order printed by the Central Consumers' Bureau of the Ministry of Economic Affairs, Consumer Cooperatives 8.—A method for producing carbon monoxide, which includes the following steps: ( a) Make a raw material containing methane and water in the presence of a core steam methane reforming catalyst formed from a group of tungsten-aluminum argon, town-bell alumina and precious metal catalysts, in a temperature range from 70CTC to 1000 ° C and pressure ranging from 2 to 50 atmospheres to perform a reaction to form a reformed gas containing hydrogen, carbon monoxide, carbon dioxide, and unreacted raw materials; W (CNS) A4 ^ (21〇x'297; i *) 406056 8 8 8 8 ABCD (Amended in January 2000) Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 6. Patent application scope (b) Cool the recombined gas to a temperature ranging from 200 ° to 500 ° C. Forming a cooled recombined gas, and dividing the cooled recombined gas into a first stream and a first stream; (c) bringing the first stream into contact with a reaction stream under conditions sufficient to form a hydrogen-rich first stream; Water gas conversion catalyst to cool the hydrogen-rich first stream To form a cooled hydrogen-rich first stream, and separate the cooled hydrogen-rich first stream to form a hydrogen product stream and a hydrogen depleted stream; (d) remove water from the second stream to form water The depleted second stream, and the water depleted second stream is heated to a temperature ranging from 200 ° to 500 ° C to form a water depleted heated second stream; (e) introducing the water depleted heated second stream into a plurality of Within the reactor, the reactors are operated in a predetermined timing sequence according to the following steps, which are cyclically performed in each reactor: (1) a first in the range of 2 to 50 atmospheres Boat power, in a first reactor containing a water adsorbent and a blender of water gas conversion catalyst, under reaction conditions sufficient to convert carbon dioxide and hydrogen to carbon monoxide and adsorb water to the adsorbent, The water-depleted heated second stream reacts and discharges a CO-rich stream, where the water adsorbent is rhenium, zeolite, alumina, or silicone, and the water gas conversion catalyst is selected from the group consisting of iron-chromium high flux Catalyst group consisting of catalyst 1, copper / zinc gaseous low-temperature conversion catalyst, and copper / zinc gaseous Φ temperature ^ conversion catalyst; (2) By discharging an unreacted raw material, carbon monoxide and water _ _-51- This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) ^^^ 1 n ^ — I Bn— * nl m 1 T. i.-'(Please read the note ^ on the back before filling in this (Page) 6 5 side 8 S 8 8 ABCD (revised in January 2000) The Central Standards Bureau of the Ministry of Economic Affairs printed a patent-pending mixture for the consumer cooperative, and decompressed the first reactor countercurrently to the range of 0.05. A second pressure to 2 atmospheres; (3) at the second pressure, flushing the first reactor countercurrently with a pair of flushing fluids weakly adsorbing the adsorbent to desorb water from the adsorbent, and A mixture containing unreacted raw materials, carbon monoxide, and water is discharged, wherein the weakly adsorbed flushing fluid is a group composed of methane, gas, nitrogen, and carbon dioxide; (4) at the second pressure, a non- The CO-rich flushing fluid containing hydrogen and carbon dioxide flushes the countercurrently The first reactor to desorb the weakly adsorbed flushing fluid and discharge a mixture containing the weakly adsorbed flushing fluid, carbon monoxide, and water; and (5) before the first reactor begins another method cycle, use the rich The CO-containing flushing fluid counter-pressurizes the first reactor from the second pressure to the first pressure; and (f) separates the CO-rich stream from step e (l) to form a CO-containing stream and a CO depleted stream, the CO depleted stream is compressed, and the compressed CO depleted stream is separated before the cooled hydrogen-rich first stream of step c is separated into a hydrogen product stream and a hydrogen depleted stream. Combined with this cooled hydrogen-rich first stream. 9. The method according to item 8 of the patent application, further comprising the following steps between steps e (l) and e (2): flushing the first countercurrently with a weakly adsorbed flushing fluid at a first pressure Reactor, and a mixture containing unreacted raw materials, carbon monoxide and water is discharged. Good paper size applies to China National Standards (CNS > A4 size (210X297mm) n '1 ^ 1 nmnnn »I nnnn an T 5,-** (Please read the note on the back ^ > before filling out this page ) 406 056 8 8 88 ABCD (Amended in January 2000) 6. Application for patent scope 10. The method as in item 8 of the patent scope, wherein the admixture of catalyst and adsorbent contains 5 to 95% by weight of adsorbent And 95 to 5% by weight of the catalyst. 1 1. The method of claim 8 in the patent scope, wherein the amount of water and methane contained in the feedstock is a stoichiometric ratio of water to methane ranging from i 5 to 彳 3. HI -1 ^^^ 1 HI I 1—-I nn — ^ nn mt I—-I-s -LI (Please read the note on the back before filling this page) -53-This paper size applies to China National Standard (CNS) A4 (210X297 mm)