TW406055B - Integrated steam methane reforming process for producing carbon monoxide and hydrogen - Google Patents

Abstract

The present invention is a process for producing an essentially pure carbon monoxide (CO) product and an essentially pure hydrogen product by reforming a hydrocarbon such as methane and steam in the presence of a reforming catalyst to produce a reformate product enriched in CO, carbon dioxide and hydrogen. The reformate is subjected to an integrated series of separation steps and carbon dioxide present in a portion of the waste effluent recovered from such series of separation steps is shifted to CO in an integrated sorption enhanced reaction (SER) process.

Description

4 i0605l Magic..u .. A7 B7 V. Description of the Invention (Amended in TT997) Cross-references are requested (Please read the notes on the back before filling this page) This application is April 1995 Part of the serial application of US Patent Application No. 08 / 419,317 filed on the 10th, the description of the case and the scope of the patent application are incorporated in this case and are deemed to be part of this application. Field of Invention of the Invention—Ί The present invention is a method for producing a substantially pure carbon monoxide (co) product and a substantially pure hydrogen product, which are produced by recombining hydrocarbons and steam in the presence of a recombination catalyst A reconstituted product rich in CO, digassed carbon and hydrogen. The IE group gas undergoes an integrated separation step 丨] *; column treatment, II. Exists in one's one: '!! The carbon dioxide and hydrogen of the exhaust effluent of the separation step sequence are extremely integrated adsorption enhancement reactions (SER) Force is converted to CO. BACKGROUND OF THE INVENTION The production of carbon monoxide is typically the catalytic recombination of a steamed hydrocarbon feed at high temperatures, and optionally, carbon dioxide. The reaction is carried out in a steam methane reformer (SMR), which comprises a furnace filled with a small tube filled with catalyst. The syngas leaving the recombiner follows the equilibrium established in the following reaction and contains carbon monoxide (CO) and hydrogen, carbon dioxide (C02), steam, and unconverted methane. CH4 + H20 <-> 3H2 + CO steam reorganization H2〇 + CO <-> H2 + C02 water gas conversion CH4 + C〇2 <-> 2H2 + 2C0 C〇2 reorganization 'human &; .. ::. ≫!, ^ Writer 栉 quasi (CIS'S) Λ4 specification (210X297 public super) Printed by A7 ^ υο055_Β7__ of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (2) The above reactions are usually 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. Typical SMR effluent composition (mol fraction) when the SMR reaction is performed using a feed mixture containing no CO2 and a 3: 1 water / methane molar ratio at 85 ° C and 25 atmospheres. Contains 75% H2, 13% CO, 8.5% CO2 and 5.5% CH4. The SMR effluent is subjected to a series of reactions and separation operations to recover a high-purity hydrogen product (99. 9 + mole%) or a high-purity CO product (99. 5 + mole%). Commercially produced carbon monoxide from SMR plants is typically used to produce isocyanates and polycarbonates via phosgene chemistry. In addition, some methods used to produce carbonyloxy alcohol require a 1: 1 hydrogen-to-carbon monoxide synthesis gas. Hydrogen and effluent steam formed as by-products of these SMR process stages may have fuel prices, 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. The CO2 concentration in the SMR feedstock can be further increased by recycling CO2 that is generated and separated from syngas or recovered from the furnace flue gas, or that extra CO2 is input from outside sources into the feed. SMR feedstocks with a high CO2 to methane ratio and reduced steam volume inhibit the water-gas conversion reaction from generating additional H2 from CO and under extreme reaction conditions will reverse the reaction and generate additional CO from H2. In -4- this paper size applies Chinese National Standard (CNS) Λ4 specification (210X297 mm) 83.3.10,000 ------------------- 1 --- order- ------ You '% (Please read the notes on the back before filling out this page) 5. Description of the invention (3) Some C02 in SMR raw materials will also react with methane to produce a symbiotic gas with a low H2 / CO ratio The amount of C0 produced in traditional SMR methods is limited by reaction thermodynamics, where the relatively low C0 conversion rate (~ 1 0-15%) makes it necessary to recover the required C0 product with considerable separation effort. It is known There are many prior art SMR methods for the production of syngas, which utilize multiple separation cycles to recover the required carbon monoxide product from a SMR reconstituted effluent typically containing a mixture of hydrogen, carbon monoxide, CO2 and methane. US Patent 3, 9 8 6, 8 4 9 reveals an SMR method for converting hydrogen and a source of methane, such as natural gas, into hydrogen products as described in Fig. 1. Methane and water are introduced into a conventional SMR reactor 2 via line 1, And react under recombination conditions to produce a hydrogen-rich recombination gas stream 3 Stream 3 is introduced into condenser 4 to produce steam and cooled reformed gas stream 6 at an intermediate temperature of 250-350 ° C. This cooled reformed gas is then directed to a water gas conversion reactor 7 (high temperature conversion reactor, Alone or in combination with a low-temperature conversion reactor) to convert a portion of C 0 in the recombined gas stream 6 to hydrogen by making C0 and H20 according to the reaction formula (CO + H20 <-> C02 + H2). Economy Printed by the Central Bureau of Standards, Shellfish Consumer Cooperative, the above-mentioned conversion reaction plays a key role in all methods when hydrogen is a required product, because the conversion should be performed before separating the recombination product mixture to produce substantially pure hydrogen. The reaction increases the concentration and amount of hydrogen in the reconstituted product mixture. By indirect heat exchange with the cooling water in the condenser 9, the conversion reactor effluent 8 is further cooled to near ambient temperature (25-50 ° C), at A considerable amount of water is passed from the recombined gas through the pipeline 83.3.! 0, 〇〇〇 (Please read the precautions on the back before filling this page) This paper size applies the Chinese National Standard (CNS) A4 specification ( (210X297 mm) A7 B7, printed by Shelley Consumer Cooperation, Central Bureau of Standards, Ministry of Economic Affairs 5. Description of the invention (4) 10 is condensed and removed. Finally, the stream il leaving the condenser is introduced into a hydrogen pressure increase / absorption unit. (H2-PSA) to produce pure hydrogen through stream 14 and an exhaust stream that can be used as fuel in a reformer 13 »US Patent 4, 1 7 1, 2 0 6 discloses an SMR method as described in Figure 2 for Water and a methane source such as natural gas are converted 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 a cooled recombined gas stream 26 and a condensate stream (not numbered) at an intermediate temperature of 25-30 ° C. The cooled reformed gas is then introduced into a water gas reforming reactor 27 to convert a portion of the CO in the reformed gas stream 26 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 reconstituted gas stream 31 leaving the condenser 29 is directed into a CO 2 air-addition, reduction (adsorption) (VSA) unit 32 where the reformed 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 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 2 » The Co2 VSA unit 32 and the H2-PSA unit 36 are integrated for maximum separation efficiency. A traditional SMR method is described in Figure 3, in which water and a methane source are introduced into a traditional SMR reactor 42-6 through line 41.-This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ) 83.3.10,000 — .1 II 'bound II book — gas (please read the notes on the back before filling out this page) Printed by the Shell Standard Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 406055 5. The invention description (5) React under recombination conditions to produce recombined gas stream 43. Stream 43 is directed into a CO2 absorber / stripper 44 containing a physical chemical solvent, which removes CO2 from the pre-cooled SMR effluent to provide stream 45 containing substantially pure CO2 And C02 depleted recombined gas stream 46, which is introduced into the thermal increase / decrease adsorption unit 47 to remove water and remaining CO2 and is discharged from the adsorption unit 47 via line 48. Water and C 0 2 depleted stream 49 are introduced into a cryogenic cold box 50 to produce a substantially pure hydrogen stream 51 'a substantially pure CO stream 53 and a waste containing unreacted methane that can be used as fuel in a reformer 42 Stream 52 »Another conventional SMR process is depicted in Figure 4 where water and a methane source are introduced into a traditional SMR reactor 62 via line 61 and reacted under recombination conditions to produce a recombined gas stream 6 3. Stream 63 is directed into a CO 2 absorber / stripper 44 containing a physicochemical solvent that removes CO 2 from the pre-cooled SMR effluent to provide a CO 2 enriched stream 6 5 which stream 6 5 may be compressed via compressor 66 and reintroduced into the SMR reactor 62 as line C02 feed via line 67. The C02 depleted reformed gas stream 68 leaves the TSA unit 69 via line 71 and is introduced into the cryogenic cold box 72 to produce a substantially pure hydrogen stream 73, a substantially pure CO stream 75, and can be used as fuel in the reformer 62. Waste stream 74 containing unreacted methane. U.S. Patent No. 4,9 1 5,7 1 1 discloses an SMR method as described in FIG. Water and a source of methane are introduced into a traditional SMR reactor 82 via line 81 and reacted under recombination conditions to produce reorganized paper. ^ 1 Applicable to China's national standards 2 丨 0 Father 297 mm) 83. 3.10,000 IIIIIII Order — IIII 1- ^ (Please read the note ^^ on the back before filling out this page) Printed by the Central Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperatives < ιϋβ055% _ V. Description of the invention (6) Gas flow 83. In addition, a C02 logistics can also be introduced into the reorganizer to increase C0 production. Stream 83 is directed into a 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 introduced into CO-VSA87 'where the reformed gas is separated to provide a substantially pure CO product stream 8 8 and an exhaust stream 8 9 that can be used as fuel in the reformer 8 2. Another SMR method is depicted in FIG. 6, where water and a source of A hospital 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 a condenser 94 to produce a condensate vapor 95 and a cooled reformed gas stream 96 at an intermediate temperature of 30 ° -1 20 ° 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. Stream 113 is introduced into condenser 114 to produce a cooled reformed gas stream 1 1 6 which is introduced into a water gas conversion reactor 117 to convert a portion of the water and reformed gas stream 116 to hydrogen. The hydrogen-rich recombined gas 127 is adapted to the Chinese national standard (CNS > Α4 (210 × 297 mm)) through the condenser 128 at this paper size. 83.3.10,000 (Please read the note on the back before filling this page)- Hold

、 1T Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, 406055 _ ^ _ V. Description of the Invention (7) The water 129 with water removed and depleted enters the H2-PSA unit 130 to provide fuel that can be used as fuel in the reformer 112 The waste stream 132 and the substantially pure hydrogen stream 1 3 1. A portion of the reformed gas can then flow into line 118 after valve 1 1 a 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 1 2 5 and then combined with pipeline 1 2 9 to enter Η 2-PSA 1 3 0 〇 Figure 8 depicts the production of substantially pure CO and substantially pure hydrogen. An SMR method. Water and a methane source are directed into a conventional SMR reactor 202 via line 201 and reacted under recombination conditions to produce a recombined gas stream 203. Stream 203 is directed into condenser 204 to produce a cooled reformed gas stream 206, which is introduced into a CO-VSA unit to provide a substantially pure CO stream 208 and a CO-depleted stream 209. The CO-depleted stream 209 is directed to a hydrogen-PSA unit 210. The process stream is further separated within the hydrogen-PSA unit 210 to provide a substantially pure hydrogen stream 2 1 2 and an exhaust gas stream 2 1 1 that can be used as fuel in the reformer 200 2. Those skilled in steam methane recombination techniques are working to find improved recombination methods in which the conversion of the required CO products and hydrogen products is maximized. Moreover, a method that promotes the reaction of co2 and hydrogen to form CO and water [reverse water gas conversion reaction] would be very desirable in the industry. Unfortunately, there is no known prior art SMR method integration that can directly exist in the program logistics-9- This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 83.3.10,000 II I Packing ~ order n ϋ 1 ^, (Please read the precautions on the back before filling this page) δα a 406055 'i \ 7 (Amended in November 1997) V. Description of the invention (8 CO2 and hydrogen are converted into CO and water. The backwater gas conversion The reaction is at temperature (please read the note ^ T on the back, and then fill out this page) at 800 ° C, which is thermodynamically unsuitable and the temperature typically needs to exceed 1000 ° C to obtain a moderate conversion of CO2 to CO. Therefore, this The 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 steps have not achieved commercial success because the product flow rate has not been maintained sufficiently fixed And compared with the undesired reaction products, unreacted raw materials, and rinses, the presence of the required product is too low. The industry is looking for ways to improve the SMR process to produce CO and hydrogen simultaneously. Ming Yan summarizes the method of wood hair 叨 α, called 齑, 祯, 祯, 祯, 纯粹, 祯, 纯粹, 纯粹 ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,-dielectric, hydrogen, (CO > The m group of ψ alkane and steam is used to produce a reconstituted fake that is rich in CO, two gasification carbon and hydrogen. The ® group gas is buried in a series of integrated separation steps and exists in Yilai meat The carbon dioxide and hydrogen of the exhaust effluent of these separation steps are converted to CO in an integrated adsorption enhanced reaction (SER) method. The method of the present application overcomes the problems related to the prior art methods, which are used to reconstitute methane and water When becoming carbon monoxide, it is typically encountered to produce a reformed gas containing excess C02 that has not been converted into the desired CO product, which must be separated from the reformed gas through an expensive separation cycle. Moreover, the method of the present application overcomes the problem of conversion with backwater gas The thermodynamic limitation of the reaction is that CO2 and hydrogen are converted into CO and water in this reaction. -10 .UK; 1; 榀 隼 (C, NS) 44 lattice (210X 297 male) Following Emei 'Zheng ^ ___ V. Description of the invention (9) (Amended in November 1997) The applicant's invention addresses these issues by first separating the SMR reformed gas to produce a substantially pure CO product and a CO depleted product, and subjecting the CO-depleted stream to another Separated to form a substantially pure hydrogen product and a hydrogen depleted stream. The carbon dioxide present in the nitrogen depleted stream reacts with hydrogen by using an adsorption enhancement reaction (SER) method, which allows the backwater gas to proceed at 250- It has a high CO2 to CO conversion rate at a mild temperature of 350 ° C and a pressure of 5-30 atmospheres. The produced CO-rich stream is recycled to recover the CO. Applicant's method integrates a SER method, which performs a series of cyclic steps in a plurality of reactors to convert CO 2 to CO and separates the converted gas product mixture into a concentrated CO stream. The reactor contains: • persimmon conversion catalyst fll, • admixture of water adsorbent, whose 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 CO. The water adsorbed is separated from the adsorbent by using a series of washing and decompression steps in accordance with a predetermined timing sequence. Therefore, the applicant's SER method performance integrated in the requested method A new cycle was developed to simultaneously achieve high conversion of CO2 to CO, produce a concentrated CO effluent stream, efficiently desorb water from the adsorbent, and prepare each reactor for the next process cycle. Applicant's general embodiment of a method for producing a CO product and a hydrogen product includes an initiation step which causes a feed containing methane and water to be present in the presence of a steam methane reforming catalyst over a temperature range from nl · · I Li I IT II n II nn TV * 'VT (Please read the notes on the back before filling out this page) -11-Printed by the Central Government Bureau of the Ministry of Economic Affairs and Consumer Cooperatives A7406055_B7_ V. Description of the Invention (10) The reaction is performed at 700 ° C to 1000 ° C and a 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 involves removing water from the reformed gas to form a water depleted reformed gas and separating the water depleted reformed gas into a CO product and a CO depleted stream. The third step of the process allows for The CO depleted stream is separated into a hydrogen product and a hydrogen depleted stream and the hydrogen depleted stream is compressed to form a pressurized hydrogen depleted stream. The fourth step of this general embodiment includes the hydrogen depleted stream Into a plurality of reactors, the reactors are operated in a predetermined timing sequence according to the following steps, and these steps are cyclically performed in each reactor: (1) a type containing a water adsorbent and a water gas conversion catalyst In the first reactor of the admixture, at the first pressure and at a temperature sufficient to convert carbon dioxide and hydrogen to carbon monoxide and adsorb water onto the adsorbent Under the reaction conditions, the pressurized hydrogen-depleted stream is reacted to form a CO-rich stream that is recycled to the second step of the water-depleted reformed gas stream; (2) by discharging a hydrogen-containing, carbon dioxide, A mixture of carbon monoxide and water to decompress the first reactor countercurrently to a second pressure; (3) at the second pressure to flush the first reactor countercurrently with a flushing fluid that is weakly adsorbing the adsorbent To order I- ^ from -12- _f-I 1 i I n from this adsorbent (please read the note on the back before filling this page) This paper size applies Chinese National Standard (CNS) A4 specifications ( 210X297 mm) 83.3.10,000 Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 406055 B7 V. Description of the invention (11) Water desorption and discharge of a mixture containing weakly adsorbed flushing fluid, unreacted raw materials, carbon monoxide and water (4) at the second pressure, flush the first reactor countercurrently with a CO-rich flushing fluid that does not contain hydrogen and carbon dioxide to desorb the weakly adsorbed flushing fluid, and discharge a weakly adsorbed flushing fluid containing the weakly adsorbed flushing fluid; A wash fluid, a mixture of carbon monoxide and water; and (5) pressurizing the first reactor countercurrently from the second pressure to the first reactor with the CO-rich flushing fluid before the first reactor begins another cycle A stress. Additional steps may also be performed under general specific embodiments. For example, a source of hydrogen or carbon dioxide can be introduced into the hydrogen depleted stream of the third step to control the hydrogen to carbon dioxide ratio present in the first reactor following step (1) of the fourth step. Alternatively, before the second step (0) and the second step (2), the first reactor may be flushed countercurrently at a first pressure by a weakly adsorbed flushing fluid, and a mixture containing unreacted raw materials, carbon monoxide and water Exhaust from the reactor >> The catalysts suitable for carrying out the steam methane reforming reaction according to the 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 the general examples, the SER cycle allows for a series of cycling steps in a plurality of reactors containing a conversion catalyst and an admixture of a water adsorbent. The admixture contains 5-95% by weight of sorbent and 95-5% by weight of catalyst. Suitable water sorbents include those selected from zeolite, alumina, or Chinese paper standard (CNS) A4 specifications applicable to this paper standard ( 210X297 mm) * If * ---------, installed ------ L ------ axe (please read the precautions on the back before filling this page) (11, 1997 Yue Xiu V. Description of the invention (12) (Please read the notes on the back before filling out this page) The group consisting of silicone. Suitable water gas conversion catalysts include those selected from iron-chromium high temperature conversion catalysts and copper / zinc oxide low temperature conversion catalysts. And copper / zinc oxide medium temperature conversion catalysts. It will become more apparent when reading the detailed description of the invention, by utilizing a novel series of reaction, adsorption and desorption steps to remove the The C02 of the PSA exhaust gas stream is converted to C0 and the greatly concentrated C0 is separated and collected at a feed pressure and a relatively fixed flow rate. The applicant's method overcomes the problems associated with previous techniques. The department that achieved this result The part is that the applicant unexpectedly used a kind of CO or CO-rich reaction product to flush the SER reactors and add the reactors to the reaction force before starting another SER cycle. Those skilled in the art will expect that at the beginning of the reaction step, rinsing and pressurizing the SER k reactor with a product that reverses the gas shift reaction will unbalance the balance The constant changes direction to form co2 and hydrogen; recitation: People have found that using product gas instead of C 0 2 or hydrogen or a male flushing fluid to flush these SER reactors provides a highly efficient method in which-a species rich in C 0 The stream can be collected at a feed pressure and a relatively constant flow rate. A brief description of the figure Figure 1 illustrates a steam formazan reorganization (SMR) method according to US Patent 3,986,849, where the SMR reactor regenerating gas is at A conversion reactor is further reacted and separated in a hydrogen pressure increase / decrease adsorption (A 2-PS A) unit to provide a high purity hydrogen product. Figure 2 illustrates an SMR in accordance with US Patent 4,1 7, 1,206 Fang-14- QG u. 3 ^ 406050 '·-, ^ _ V. Description of the invention (13) (Amended in November 1997) method, in which the reformed gas of the SMR reactor is further reacted in a conversion reactor and a CO 2 is used The integration of the -VSA and H2-PSA units is separated (please read the notes on the back before filling this page) to provide a substantially pure hydrogen stream. Figure 3 illustrates a prior art SMR method that uses a C02 absorber / stripper to remove C02 from the recombined gas stream, after which the recombined gas stream is directed to a thermal increase / decrease adsorption (TSA) unit to further remove the water therein. 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 gas stream containing perylene and CO, which can be used as a reformer Of fuel. Fig. 4 illustrates a modification method according to Fig. 3, in which a C02 absorber / stripper is used to remove the heavy radon gas stream before it is introduced into the TSA unit. ίΤ (绀 Gas inlet · Less removal of Xingshui and C02. The part of the separated C 0 2 is just shrunk and circulated into the SMR for further conversion into hydrogen and CO. Figure 5 illustrates an example. The previous technique SMR force method to produce substantially pure CO 'in which the SMRE group gas is condensed to remove water, and then the recombined gas is separated in a CO-VSA to provide a substantially pure CO product and a product that can be regenerated. The exhaust gas stream recycled as a reformer fuel. Fig. 6 illustrates an improved method according to Fig. 5 in which the exhaust gas stream collected from co-VS A is contacted with a selectively permeable polymer film to provide Exhaust gas stream used as recombiner fuel and a C 0 2 -rich stream 'Although the C 0 2 -containing stream is compressed, it is then reintroduced into the SMR reactor for progressive conversion to C 0 and hydrogen. Figure 7 illustrates a prior art Disc s MR method, in which s MR reaction -15- wood · ruler '+ .U'; 屮 丨 4, ϋΐ (CNS) Λ4 ^ grid (210/297 cm): Α7 Β7 (Amended in November 1997) V. Description of the invention (M (please read the notes on the back before filling this page) The reorganized gas is separated into A first stream and a second stream introduced into the conversion reactor, the second stream is introduced into the CO-VSA to produce a substantially pure CO product and a CO depleted stream, and the CO depleted stream reacts with the conversion The effluent from the reactor is combined and separated in an H2-PSA unit to provide a substantially pure hydrogen product. Figure 8 illustrates a prior art SMR method to produce CO and hydrogen 'where the recombination gas from the steam methane recombiner is in An integrated CO2-VSA and hydrogen PSA unit are separated to form a CO product stream, a hydrogen product stream, and an exhaust gas stream. Figure 9 illustrates the production of a substantially pure CO stream and a substantially pure CO stream in this case. A general specific embodiment of the SMR method of a hydrogen stream, which is 1 丨 1 1 丨 1 alkanes and water / [: · treatment of a tritium agent / 1: the following reaction forms: bismuth carbon, gasified carbon, and tritium. Ke take the feast. The SMRM is mad Sent to the • Separator to reduce the quality of pure CO products and CO-depleted streams. The CO-depleted streams are separated by W to separate-to form a pure hydrogen product and · Hydrogen-supply-depleted stream. By means of the Adsorption Enhancement Reaction (SER) method of Shanren Prefecture, some of the hydrogen-exhaust stream's CO2 reacts with hydrogen to produce an additional amount of co from the overall process. : 7,27,117 conversion reactor 42,62,82,92,112,202,202 steam methane reformer 4,9,24,29,84,94,119,114,128,204,404 condenser 301,302 SER reactor 331,360 pump 304,333,335 regulating container 66,103,125,411 compressor Detailed description: I will now discuss the issue of a purely pure CO product. 16-Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 ___B7 V. Description of the Invention (I5) and a substantially pure hydrogen product method Further details of this method provide many benefits over previous techniques. In particular, by reacting C 0 2 with hydrogen present in the hydrogen p s A exhaust gas stream to form CO through a reverse water gas reaction, the conversion of the larger reformer feed to the CO product can be achieved. If it is not the applicant's novel integration of its S E R cycle, the above treatment is economically unfeasible, as the reverse water gas reaction requires a temperature in excess of 1000 ° C to provide sufficient CO conversion. A general specific embodiment of the applicant's method is described in FIG. 9, which illustrates a method flow diagram describing a steam methane reformer 402 'condenser 404, SER reactors 301 and 302; multiple control valves; Manifolds A to E; pumps 331 and 360; separator 335; and regulating vessels 304 and 3 3 3 (optional). Referring to Fig. 9, a hydrocarbon feedstock such as methane or natural gas is desulfurized in a container (not shown) using a well-known adsorbent in the industry. The desulfurized hydrocarbon feedstock is mixed with steam to form a hybrid reformer feedstock, represented by stream 401. The raw material 401 is preheated in a preheater (not shown) and introduced into the SMR reformer 402. This recombiner is well known in the industry and is heated by burning a mixture of fuel and air (not shown). The reformer typically operates at 800. To a temperature of 1000 ° C and a pressure of 5 to 30 atmospheres and produce a reformed gas consisting of approximately 73% hydrogen, 13% (: 0, 9% (: 02 and 5% methane) on a dry basis. The reorganization The gas is sent to the condenser 404 via line 403, where the temperature of the gas is reduced and some of the water in the gas is condensed to remove and generate some steam. The water-depleted reformed gas 405 is introduced into an operation At 80 ° -120 -17- This paper size is in accordance with China National Standard (CNS) A4 (210X297 mm)-83.3.10,000 (锖 Please read the notes on the back before filling this page)-Binding · Order 40605 ^ > A7 B7 Consumption cooperation between employees of the Central Bureau of Standards of the Ministry of Economic Affairs Du Yinzhuang 5. Description of the invention (16) ° C traditional CO-VSA unit 406 to form a CO product logistics 407 and a CO depleted logistics 408 The purity of product stream 407 is at least 99.5%. The CO depleted stream 408 is introduced into a traditional H2-PSA unit 409 where the stream is divided into a hydrogen product stream 412 and a hydrogen depleted stream 410. The hydrogen product stream 412 The purity is at least 99.9%. The applicant's method provides a A good solution is to convert CO2 and hydrogen present in the hydrogen depleted stream into CO through an integrated SER process in a reverse water gas conversion reaction and produce a CO-rich recycle stream that can be recycled to CO-VSA for recovery Additional CO. The hydrogen depleted stream 4 1 0 is compressed to the first pressure in the compressor 4 1 1, and the pressurized hydrogen depleted stream 3 03 flows through line 303 and enters the regulating vessel 304 (optional). Where the fluid flows through line 305 into a heater (not shown) to form a heated, pressurized hydrogen depleted stream and is introduced into manifold A. The rest of FIG. 9 shows the SER method, where the The heated and pressurized hydrogen depleted stream is subjected to a reverse water gas conversion reaction in a cyclically operated multiple reactor to convert CO 2 and hydrogen in the process stream into a CO and water and recover a CO-rich stream, the CO-rich stream The stream is recycled to CO-VSA 406 via line 317 to recover CO. Although Figure 9 illustrates that line 317 and line 405 each enter CO-VSA 406 for the purposes discussed, those skilled in the art will To understanding The two individual streams may be combined into a single stream. Manifold A is in communication with branch line input pipes 311 and 321, and branch line input pipes 311 and 321 are connected to the input ends of reactors 301 and 302. Line-18----- ------ k pack-(Please read the notes on the back before filling in this page)

, tT ά. This paper size applies to China National Standard (CNS) Α4 specification (210 × 297 mm) 83.3.10,000 A7 B7 (Amended in November 1997), ·; Amendment 406㈣ ~ Charm 5. Invention Description (! 7 311 and 321 is connected to the inputs of reactors 301 and 302. Lines 311 and 321 are equipped with valves 31U and 321a, respectively. The opening of the appropriate valve allows the heated, pressurized hydrogen depleted stream to flow through manifold A to the selected start. It is then placed inside the reactor in the flow path. Therefore, by opening valve 311 a and closing valve 321 a, the stream can flow from manifold A into reactor 301 via line 311. The outputs of reactors 301 and 302 are respectively Connected to lines 340 and 350, which are each equipped with control valves 316a and 326a. Lines 340 and 350 are operatively connected to manifold E via lines 316 and 326, and from lines 316 and 326, a CO-rich stream from the reactor The 301 and 302 are discharged and can be directed into line 317 into the CO-VSA 406 for fuel or recirculation. Therefore, by opening the appropriate valve 3 1 6a or 326a, the CO-rich mixture is self-reacting in the reactor Inflow via lines 34o and 3 16 or lines 350 and 326 Pipe E enters line 317. Reactors 301 and 302 are operatively connected to lines 311 and 321, which communicate with lines 313 and 3 23, respectively. Lines 313 and 323 are equipped with control valves 3 1 3a and 3 2 3a, respectively, These lines communicate with the flow path of manifold B. Manifold B can communicate with the flow paths of reactors 301 and 302 via lines 3 13 and 323 when valves 3 1 3a or 323a are opened respectively. Manifold B is also connected to the lines The pump 360 of 362 communicates with the flow channel, and the fluid in the pipeline can be recirculated to the regulating vessel 304. Manifold C communicates with the reactors 3 0 1 and 30 2 via the lines 3 1 4 and 3 2 4 and the line 314 And 324 are equipped with valves 314a and 324a respectively. The regenerated effluent from reactors 30 1 and 302 flows into manifold C via lines 3 1 4 and 324 for separation 3 3 5 into a water-rich product stream 3 3 6 -19 This U :, ruler, Chuanxiong standard apple (CNS) Λ4 size (210X297 male) (Please read the precautions on the back before filling this page)

Imprint 406055 A7 B7, Shellfish Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs 5. Description of the Invention (18) and a stream 334 containing a weakly adsorbed flushing fluid, which can be introduced into a storage tank 333 (optional) for later use . Manifold D is connected to a pump 33 1 which receives various program fluids via lines 3 3 0 and 3 3 2. These process fluids are pressurized through line 330 or 332 and via pump 331. The pressurized fluid may pass through the manifold D, and the manifold D is in communication with the flow channels of the reactors 3 0 1 and 302 via the lines 3 1 5 and 3 2 5 respectively. The lines 315 and 325 are connected to the manifold D so that the flow from the manifold D into the reactors 3 01 and 30 2 can be controlled. Further, the weakly adsorbed flushing fluid can be delivered to the pump 3 3 1 through valve 3 3 2 a via line 3 3 2 or by inputting weakly adsorbed flushing fluid through line 330 to the SER cycle of the general embodiment shown in FIG. 9 The operation of will be interpreted in an arbitrarily selected cycle, as shown in Table 1. There are eight stages of ten minutes each. Although not limited to this, the SER method shown in Fig. 9 uses reactors 301 and 302, which operate in a loop in accordance with 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 method cycle. According to the general embodiment of FIG. 9, each of the reactors 301 and 302 undergoes four stages of reaction / adsorption. This step is called the adsorption step, the stage of the decompression step, the stage of the washing step I, the stage of the washing step 11, and the stage of the pressurizing step. As shown in Table 1, the steps taken at the beginning of each reactor 301 and 302 are -20- This paper size applies to China National Standard (CNS) A4 specification (210X297 cm) 83.3.! 0, 〇〇〇〇 ----------. > Install — (Please read the note on the back before filling this page)

.IT 4G60W g 5. Description of Invention (19) Both are carried out 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 sequence of steps: When performing the following steps, the first pressure range is from 2 to 50 atmospheres and the second pressure range is from 0.05 to 2 atmospheres.丨. — ———, I, installed — I i order ^ (Please read the notes on the back before filling this page) Printed by the Staff Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs-21-This paper size applies to Chinese national standards (CNS ) A4 specification (210X297) 嫠 83. 3.10,000 406055 V. Description of invention (20) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs -Ηε jI—lfnl skimming o-οε _1 ^ 銮 鬯 οε-ο < Ν㈣ 赵 銮 鬯 02- i 01-0itM 銮 薛 φ § ^ οουοϋουυουυυ os-oz, wake up after the silence M ^ ¥ α oouooouuoouu 0 /,-09 Il ^ i: crocodile ^^ U U00330U000U009-0S sfe oouououuouoo OS inch ¾¾ ---------- i— (Please read the precautions on the back before filling this page)

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A The paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 83. 3.10,000 Duanjia A, the consumer cooperation of employees of the Central Bureau of Standards of the Ministry of Economic Affairs A 7 _B7__ V. Description of the invention (21) (a) Adsorption Reaction--The heated and pressurized hydrogen-depleted stream (raw material) passes a reactor containing a conversion catalyst and an admixture of an adsorbent at a first predetermined pressure. The adsorbent has a preferential selectivity for water and is rich in one of them. The C 0 -containing stream is discharged from the reactor. Water is selectively adsorbed by the adsorbent, and a reaction material transfer zone (RMTZ) is formed in the reactor. When more raw materials pass through the reactor, the transfer zone faces the reaction. The outlet or discharge end of the device moves. The adsorbent at the leading edge of RMTZ is essentially free of adsorbed water, while the adsorbent at the trailing edge of RMTZ is in equilibrium with water according to local conditions. This adsorption reaction step continues until the 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 the reactor effluent end or disappeared. The CO-rich stream is discharged from the reactor (B) Decompression-By discharging a mixture containing unreacted raw materials, CO and water, the reactor is decompressed countercurrently to a second predetermined pressure. The decompression step continues until the reactor reaches a second predetermined pressure. (C Flushing I--The reactor was flushed countercurrently at a second pressure using a weakly-adsorbed flushing fluid to desorb water from the adsorbent, and a fluid containing the weakly-adsorbed flushing fluid, unreacted raw materials, part C0, and part The water mixture is discharged from the reactor. (D) Flushing II-The reactor is flushed countercurrently at a second pressure using a C 0 2 -free flushing fluid that is rich in C 0 and hydrogen to desorb the weak Adsorption rinse fluid, and a mixture containing the weakly adsorbed rinse fluid, CO and water is discharged from the reactor. (E) Pressurization-the reactor is enriched with -23- Paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 83. 3.10,000 (Please read the precautions on the back before filling out this page) 406055 A7 Printed by the Consumer Cooperatives of the Central Sample Bureau of the Ministry of Economic Affairs B7_ 五Invention description 22) The flushing fluid of CO is counter-pressurized from the second pressure to the first pressure. The positions of those valves in the above-mentioned operating cycle stages are also listed in Table 1. The indication " 0 " indicates that a specified valve is open. N C " represents that a designated valve is closed. The sequence of operations performed in a complete process cycle stage reactor 301 will be described in detail below in detail to enable continuous program operation It is fully understood. The sequence of the same steps according to Table 1 is performed in a slow sequence in the reactor 302. Once again, referring to the specific embodiment disclosed in FIG. 9 and the sequence stages and valve positions specified in Table 1, the reaction The reactor 301 has undergone four sequential stages of the adsorption reaction step. The raw materials stored in the storage tank 304 (optional) are introduced into the reactor 30 by opening the valves 31a and 316a and closing the valves 313a'314a and 315a. This allows the feedstock to flow through manifold A, line 311, and into reactor 301, which contains a required admixture of conversion catalyst and water-selective adsorbent. This adsorption reaction continues until the water 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 and then enters line 317 as previously described. The method carries out a stage of a decompression step, in which the reactor 301 discharges unreacted raw materials containing -24 by ------------ ¢ ------ ΤΓ ------ 4 (Please read the notes on the back before writing this page) This paper size applies to China National Standard (CNS) A4 specifications (2) 0X297 mm 83.3.10,000 Central Bureau of Standards, Ministry of Economic Affairs Printed by Shelley Consumer Cooperative 406055 A7 B7 V. Description of the invention (23) A mixture of material, C 0 and water was decompressed countercurrently to a second predetermined pressure. Valve 3 1 3 a is opened and valves 3 μ a and 3 1 4 a 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 the line 3 62 for use as fuel (not shown) or recycled into the conditioning vessel 304 as feedstock for subsequent process cycles. 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 valves 3 14a and 3 1 5 a and keeping valves 3 2 5 a and 3 3 2 a in the closed position, weakly adsorbed flushing fluid from an external source passes line 3 3 0 through pump 3 3 1 and at a second pressure The pump 3 3 1 is left to enter the outlet end of the reactor 301 via the manifold D, line 3 1 5 and line 340. A mixture containing a weakly adsorbed flushing fluid, unreacted feedstock 'C 0 and water is discharged from reactor 3 1 via 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, discharged for use outside the process, or separated in separator 335 to form a weakly adsorbed flushing stream and a water-rich stream 3 3 6. A portion of this weakly-adsorbed flushing fluid may be transported via line 334 into storage tank 333 for future use. By opening the valve 3 3 2 a upon request, this weakly adsorbed flushing fluid may be fed into the pump 3 3 1 via lines 3 3 2 and 3 3 0 for subsequent method cycle use. The reactor 301 then undergoes the stage of flushing step II, in which the reactor 301 is flushed countercurrently by a fluid that is free of hydrogen and CO 2 and rich in CO -25- I Yan- ^ 1 III, order H ϋ— ^ (please first Read the notes on the back and fill in this page) This paper size applies to Chinese national standards (CNS > Α4 size (2 丨 0X297 mm) 83. 3.10,000 406055 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (24) Washing. After opening valves 314a and 315a and keeping valves 325a and 332a in the closed position, a C0 rich flushing fluid from an external source passes pump 330 through line 330 and leaves pump 331 at a second pressure to pass through the manifold. Pipe D 'lines 315 and 340 enter the exit end of reactor 301. A mixture containing weakly adsorbed flushing fluid, water, and CO-rich flushing fluid is discharged from reactor 301 via line 311, line 314, and manifold C It is collected in a separator 3 3 5. The mixture may be used as fuel or discharged for use outside the method. The final step of the process cycle includes a single sequence of pressurized steps in which reactor 301 is A CO-rich flushing fluid (such as a branch stream from line 317) or a high-purity CO product stream 407 is counter-pressurized from a second pressure to a first pressure before starting another process cycle in the reactor. Specifically After opening valve 315a and keeping valves 311a, 313a, 3Ma, 325a and 332a in the closed position, the CO-rich flushing fluid passes through pump 3 3 1 via line 3 3 0 and leaves pump 3 3 1 at the second pressure to Via manifold D, line 3 15 and line 3 40 enter the outlet end of reactor 301. This step ends when reactor 301 reaches the first pressure. The method is performed according to the above steps listed in Table 1. Additional cycles. Although these sequential stages are described as equal in length, they are not necessary or necessary. The setting of time depends on the maximum allowable gas flow rate, the size of the valves and lines, and the nature of the adsorbent used. Interactive procedures may be Used to establish the duration of each cycle step. For example, other techniques well known in the industry, such as the analysis of reactor effluent composition, may be used to determine the end point of a particular step. -26- I--I--III ri装 -I (Please read the notes on the back before filling out this page) This paper size is in Chinese National Standard (CNS) A4 size (210X2M public holiday) 83. 3.! 0, 00 Associate Bureau employee consumer cooperatives printed Na 055 _ ^ _ V. Invention description (25) Several variations of the general specific embodiments may be implemented to meet the special needs of each plant. For example, in the adsorption reaction step and the Each reaction between the decompression steps may be performed at the first pressure with an additional countercurrent flushing step with a weakly adsorbed flushing fluid to discharge a mixture containing unreacted raw materials, CO and water, which can be used as raw materials via manifold B Pump 3 6 0 and line 3 2 2 are recycled into the SMR reactor. And a source of hydrogen or carbon dioxide (not shown) may be introduced into the hydrogen depleted stream 410 to control the ratio of hydrogen to C02 present in the first reactor of the SER process. Those skilled in the art will understand that unless an appropriate branch stream (not shown) can be discharged from stream 4 1 0 and recycled to the CO-VSA unit 406 before the reaction, methane may be applied in this case. Stacked during operation. This branch will typically be used as fuel for SMR 402. 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 reforming catalysts for reverse conversion reactions in reactors or SER cycles 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 conversion catalysts. 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 chemical -27- ---------- ^ ------ 1T ------ 4 (please read the precautions on the back before filling this page) This paper is in Chinese National Standard (CNS) A4 size (210X297). 83.3.10,000 Printed by Shellfish Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs 40605ο Α7 Β7 V. Description of the invention (26) It is neutral and cannot be used as an inverse Catalyst for 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. The following examples in the experimental section are provided to illustrate a method for CO production that the applicant has applied that integrates a conventional SMR method and a SER cycle to react CO 2 present in the off-gas stream of the separation unit via a backwater gas shift reaction Converted to C 0. The figures show the mass balance calculations for the selected method. The "HSC Chemistry for Windows" software package from Outokumpu Research Oy, Finland, was used to perform steam methane reformer effluent formation into -28- fk. I order IIII ^ (Please read the note on the back before filling this page) This The paper size is calculated according to the Chinese National Standard (CNS) A4 (210X297 mm) 83.3.10,000 Printed by the Consumers' Cooperative of the Central Government Standards Bureau of the Ministry of Economic Affairs 406055 A7 ____B7_ V. Description of the thermodynamic equilibrium of (27) points. 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 is operated at 850 ° C and 25 atmospheres; (0) The feed of the recombiner contains CH4 at 25 mol / min and H2 at 75 mol / min; (d) The CO-VSA process produces a substantially pure CO product at 85% -carbon oxide recovery ( (99.5%); (e) The H2-PSA method produces a substantially pure hydrogen product (99.9%) at 85% hydrogen recovery; (f) C 0 2 to C in the adsorption enhanced reactor method (SE RP) A conversion of 0 is 80% (that is, 80% of CO 2 fed to the reactor is discharged from the reactor as a CO product); Example 1 In a conventional CO production method, the exhaust gas is discharged from the reactor via the CO-SER method. Logistics production C 0 products Table 2 contains mass balance data described in Figure 8 and Figure 9 for some method plans for the production of carbon monoxide. This table provides the total moles of hydrogen and carbon monoxide products produced. ------ ------------ * Γ ------ Business (please read the notes on the back before filling this page) -29 -___ This paper size is applicable to Chinese national standards (CN S) A4 specification (210X297 mm) 83. 3.10,000 406055 at ___B7 V. Description of invention (28) Table 2 * Comparison of integrated SERP-SMR method plan for simultaneous production of CO and H2_ Comparison performance of H2 products Amount (Moore / minute) Net amount of C0 product (Moore / minute) Figure 8 SMR + CO-VSA + H2-PSA 57.7 10.3 Figure 9 SMR + CO-VSA + H2-PSA + SERP (handling 75% of H2 -PAS exhaust gas) 59.4 16.1 * SMR feed: 25 Mohr CH4 + 75 Mohr H20 (reference example). (Please read the note on the back before filling this page) The cooperative printed a baseline example method consisting of a steam methane reformer and a subsequent CO-VSA unit to separate carbon monoxide and a H2-PSA unit to separate hydrogen (Figure 8). The material can produce 57.7 mol / min hydrogen and 10.3 mol / min CO. The method applied by the applicant includes steam methane recombination, separation of carbon monoxide in a CO-VSA unit ', separation of hydrogen in a H2-PSA unit, and H2- PSA off-gas is split into a purge stream and a method stream (where the method stream represents 75% 112-? 5 into the exhaust gas stream) 'in a 8 £ 11 method to convert CO 2 and hydrogen of the H2-PSA exhaust gas stream to CO, and recycle the CO-rich stream from the SER process to the CO-VSA unit (application A specific embodiment of item 1 of the patent scope is illustrated in FIG. 9). This method achieves a C0 and 59.4 mo / min of 16.1 mo / min per reformer feed of 100 mo / min. Minutes of hydrogen. Therefore, the addition of the SER method to the conventional SMR method to treat H2-PSA exhaust gas at the same SMR feed rate resulted in a 56% increase in total CO production compared to the prior art method. The applicant's method also increased hydrogen productivity by approximately 3%. -30- The Chinese paper standard (CNS) A4 size (210X297 mm) 83. 3.10,000 Order 406055 ΑΊ Β7 V. Invention description (29) The invention has been described above. 'The invention is recognized The scope of an appropriate patent application is defined below. Order IIIII i III — I I- ^ (Please read the notes on the back before filling out this page) Employees' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, Yinju-31-This paper size applies to China National Standard (CNS) A4 (210X297) %) 83. 3.10,000

Claims (1)

(Amended in January 2000) Printed by the Employees' Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs (a) A raw material containing methane and water is present in the presence of a steam methane reforming catalyst selected from the group consisting of nickel-alumina, _ dimagnesium alumina and precious metal catalysts At a temperature ranging from 700t to 1000 ° C and a pressure ranging from 2 to 50 atmospheres, the reaction is performed to form a reformed gas containing hydrogen, carbon monoxide, carbon dioxide and unreacted raw materials; (b) removing water from the reformed gas To form a water depleted reformed gas and separate the water depleted reformed gas into a CO product and a CO depleted stream (c) separate the CO depleted stream into a hydrogen product and a hydrogen depleted stream and compress the hydrogen depleted stream To form a pressurized hydrogen depleted stream; (d) introducing the hydrogen depleted stream into a plurality of reactors that operate in a predetermined timing sequence according to the following steps, which are performed at each The reactors are all circulated: Π) a blending agent containing a water adsorbent and a water gas conversion catalyst under a first pressure ranging from 2 to 50 atmospheres In the first reactor, the pressurized hydrogen-depleted stream is reacted under reaction conditions sufficient to convert carbon dioxide and hydrogen to carbon monoxide and adsorb water on the adsorbent to form a recycled to step (b) CO-rich stream of water depleted reformed gas stream, wherein the water adsorbent is selected from the group consisting of zeolite, alumina, or silica gel, and the water gas conversion catalyst is rhenium iron-chromium high temperature conversion catalyst, copper / zinc oxide low temperature conversion Catalyst and -32-This paper size is applicable to Chinese national standard (CNS > A4tt ^ (210x297)) (Please read the note on the back before filling this page) ___ l · __: ------------- ^ -------- .. η——1 ---- .., 1 ----- C αc 4 8 888 ABCD (Amended in January 2000) Employees' Cooperatives, Central Standards Bureau, Ministry of Economic Affairs Print 6. The scope of the patent application for the copper / zinc gaseous medium temperature conversion catalyst group; (2) The first reactor is decompressed countercurrently by discharging a mixture containing hydrogen, carbon dioxide, carbon monoxide and water to Second boat force ranging from 0.05 to 2 atmospheres; (3) The second pressure flushes the first reactor countercurrently with a flushing fluid that is weakly adsorbed on the adsorbent to desorb water from the adsorbent and exhausts a weakly adsorbed flushing fluid, unreacted raw materials, carbon monoxide And water, wherein the weakly adsorbed flushing fluid is a group consisting of methane, ii, and carbon dioxide; (4) at the second pressure, a flushing fluid that is rich in C 0 without hydrogen and carbon dioxide Flush the first reactor counter-currently 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 cycle with The CO-rich flushing fluid counter-pressurizes the first reactor from the second pressure to the first pressure ΰ »2. The method according to item 1 of the patent application scope, further comprising: (e) introducing a Hydrogen or carbon dioxide is sourced into the hydrogen depleted stream of step (c) to control the ratio of hydrogen to carbon dioxide present in the first reactor according to step (d) (1). 3. As the method of applying for the first item in the scope of patent application, it further includes the following steps between step d (l) and step d (2) ··· At the first pressure with a weak _-33-This paper scale is universal China National Standard (CNS) AWjyg · (210X25) 7 mm) f— I ^^^ 1 ^^^ 1 111 t —HI— ^^^ 1 In -a, HM —SKI nn (Please read the precautions on the back first Fill out this page again) Apply for a patent A8 B8 C8 D8 (revised in January 2000) Adsorption flushing flow_Flush the first reactor, and discharge a mixture containing unreacted raw materials-carbon oxide and water. 4. The method of claim 1 in the scope of the patent application, wherein the catalyst and the sorbent blending agent comprise 5 to 5% by weight of an adsorbent and 95 to 5% by weight of a catalyst. 5. The method according to item 丨 of the patent application range, wherein the amount of water and methane contained in the raw material is a range of water to methane stoichiometric ratio ranging from L5 to 30 6 ----- 1 ---- pack- ------ Order ------- ^ 丨 4 (Please read the notes on the back before filling this page) Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs -34-This paper is a standard for China National Ladder Standard (CNS) A4 Specification (2 丨 〇 > < 297 mm)