CN117427570A - Methane preparation system and methane preparation method - Google Patents
Methane preparation system and methane preparation method Download PDFInfo
- Publication number
- CN117427570A CN117427570A CN202311322028.2A CN202311322028A CN117427570A CN 117427570 A CN117427570 A CN 117427570A CN 202311322028 A CN202311322028 A CN 202311322028A CN 117427570 A CN117427570 A CN 117427570A
- Authority
- CN
- China
- Prior art keywords
- gas
- synthesis
- methane
- tower
- equipment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0405—Apparatus
- C07C1/041—Reactors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/0242—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/0285—Heating or cooling the reactor
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/08—Production of synthetic natural gas
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/755—Nickel
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明提供一种甲烷制备系统及甲烷的制备方法。甲烷制备系统包括:第一热交换设备,其包括第一热量通道和第一介质通道;第一合成设备,第一合成设备内用于进行甲烷合成反应而得到第一塔后气;第二合成设备,用于接收升温后的合成气以及降温后的第一塔后气;第二热交换设备,其包括第二热量通道和第二介质通道;气液分离设备,以接收降温后的第二塔后气并进行气液分离而分离出水;增压设备,其设置于气液分离设备的下游,以接收分离水后的第二塔后气并进行增压而得到循环气;第三合成设备,以接收循环气并供循环气进行甲烷合成反应;降温及分离设备,以接收合成后的初步甲烷并对初步甲烷降温以及气液分离以得到甲烷产物。
The invention provides a methane preparation system and a methane preparation method. The methane preparation system includes: a first heat exchange device, which includes a first heat channel and a first medium channel; a first synthesis device, which is used to perform a methane synthesis reaction to obtain the first post-column gas; a second synthesis device Equipment, used to receive the heated synthesis gas and the cooled first tower post-gas; a second heat exchange equipment, which includes a second heat channel and a second medium channel; a gas-liquid separation equipment, to receive the cooled second gas The gas behind the tower is subjected to gas-liquid separation to separate water; a pressurizing device is provided downstream of the gas-liquid separation device to receive the second post-column gas after water separation and pressurize it to obtain circulating gas; a third synthesis device , to receive circulating gas and supply circulating gas for methane synthesis reaction; cooling and separation equipment to receive the synthesized preliminary methane, cool the preliminary methane and separate gas and liquid to obtain methane products.
Description
技术领域Technical field
本发明涉及甲烷制备技术领域,特别涉及一种甲烷制备系统及甲烷的制备方法。The present invention relates to the technical field of methane preparation, and in particular to a methane preparation system and a methane preparation method.
背景技术Background technique
目前甲烷的合成工艺主要包括带循环的绝热甲烷化合成甲烷工艺和不带循环的等温甲烷化合成甲烷工艺。At present, the synthesis process of methane mainly includes the adiabatic methanation synthesis process with circulation and the isothermal methanation synthesis process without circulation.
等温甲烷化合成甲烷工艺中,由于甲烷化反应速度快,反应热点温度将接近平衡温度,对于一氧化碳和二氧化碳含量较高的原料气,甲烷化热点温度将非常高,此时易发生析碳反应而造成甲烷化催化剂失效。虽然可以通过在原料气中直接加入大量蒸汽来稀释原料气中一氧化碳和二氧化碳浓度,实现控制甲烷化热点温度,但是由于需要直接加入大量蒸汽,能耗极高。对于一氧化碳和二氧化碳含量较低的原料气,由于等温反应移热,导致甲烷化热点温度不高,甲烷化反应速度随温度降低而降低,催化剂效率将降低。In the process of isothermal methanation to synthesize methane, due to the fast methanation reaction speed, the reaction hot spot temperature will be close to the equilibrium temperature. For feed gas with high carbon monoxide and carbon dioxide content, the methanation hot spot temperature will be very high. At this time, the carbon evolution reaction is prone to occur and Cause the methanation catalyst to fail. Although the concentration of carbon monoxide and carbon dioxide in the raw gas can be diluted by directly adding a large amount of steam to the raw gas to control the methanation hot spot temperature, the energy consumption is extremely high due to the need to directly add a large amount of steam. For feed gas with low carbon monoxide and carbon dioxide content, due to the heat transfer in the isothermal reaction, the methanation hot spot temperature is not high, the methanation reaction speed decreases as the temperature decreases, and the catalyst efficiency will decrease.
绝热甲烷化合成甲烷工艺中,将反应后的甲烷气体返回而稀释原料气中一氧化碳和二氧化碳浓度来控制甲烷化热点温度,由于绝热反应后温度较高,反应后气体中的一氧化碳和二氧化碳平衡浓度也较高。对于一氧化碳和二氧化碳含量较高的原料气,为了控制甲烷化热点温度,需要加大循环量且增加绝热甲烷化反应器数量,同时还要增加回收绝热甲烷化反应气高温热量的相关设施,造成投资较大,能耗也相对较高。In the process of adiabatic methanation to synthesize methane, the reacted methane gas is returned to dilute the concentration of carbon monoxide and carbon dioxide in the raw material gas to control the methanation hot spot temperature. Since the temperature after the adiabatic reaction is higher, the equilibrium concentration of carbon monoxide and carbon dioxide in the gas after the reaction is also higher. For feed gas with high carbon monoxide and carbon dioxide content, in order to control the temperature of methanation hot spots, it is necessary to increase the circulation volume and increase the number of adiabatic methanation reactors. At the same time, it is necessary to increase related facilities for recovering high-temperature heat of adiabatic methanation reaction gas, resulting in investment Larger, energy consumption is relatively high.
发明内容Contents of the invention
本发明的目的在于提供一种能耗较低的甲烷制备系统及甲烷的制备方法,以解决现有技术中的问题。The object of the present invention is to provide a methane preparation system and a methane preparation method with lower energy consumption, so as to solve the problems in the existing technology.
为解决上述技术问题,本发明提供一种甲烷制备系统,包括:In order to solve the above technical problems, the present invention provides a methane production system, including:
第一热交换设备,其包括相互独立并能够热交换的第一热量通道和第一介质通道;所述第一介质通道的入口用于接收外界的合成气,所述合成气中(H2-CO2)/(CO+CO2)的体积百分比大于3;The first heat exchange device includes a first heat channel and a first medium channel that are independent of each other and capable of heat exchange; the inlet of the first medium channel is used to receive external syngas, and the syngas contains (H 2 - The volume percentage of CO 2 )/(CO+CO 2 ) is greater than 3;
第一合成设备,其与所述第一介质通道的出口相连,以接收升温后的合成气;所述第一合成设备内用于进行甲烷合成反应而得到第一塔后气;所述第一合成设备的出口与所述第一热量通道的入口相通,以提供所述第一塔后气;A first synthesis device is connected to the outlet of the first medium channel to receive the heated synthesis gas; the first synthesis device is used to perform a methane synthesis reaction to obtain the first post-column gas; the first synthesis device The outlet of the synthesis equipment communicates with the inlet of the first heat channel to provide the gas after the first tower;
第二合成设备,其入口同时与所述第一介质通道的出口以及所述第一热量通道的出口相连,以用于接收升温后的合成气以及降温后的第一塔后气;所述第二合成设备内用于进行甲烷合成反应而得到第二塔后气;The inlet of the second synthesis device is connected to the outlet of the first medium channel and the outlet of the first heat channel at the same time, so as to receive the heated synthesis gas and the cooled first tower post-gas; The second synthesis equipment is used to carry out the methane synthesis reaction to obtain the gas after the second tower;
第二热交换设备,其包括相互独立并能够热交换的第二热量通道和第二介质通道;所述第二热量通道的入口与所述第二合成设备相连以接收所述第二塔后气;所述第二介质通道的出口与所述第一合成设备的进口相连通;The second heat exchange device includes a second heat channel and a second medium channel that are independent of each other and capable of heat exchange; the inlet of the second heat channel is connected to the second synthesis device to receive the gas after the second tower. ;The outlet of the second medium channel is connected with the inlet of the first synthesis device;
气液分离设备,其设置于所述第二热量通道的下游,以接收降温后的第二塔后气并进行气液分离而分离出水;Gas-liquid separation equipment, which is arranged downstream of the second heat channel to receive the cooled gas after the second tower and perform gas-liquid separation to separate water;
增压设备,其设置于所述气液分离设备的下游,以接收分离出水后的第二塔后气并进行增压而得到循环气,所述增压设备与所述第二介质通道的入口相通;A pressurizing device is provided downstream of the gas-liquid separation device to receive the post-gas from the second tower after water has been separated and pressurize it to obtain circulating gas. The pressurizing device is connected to the inlet of the second medium channel. communicate;
第三合成设备,其与所述第一合成设备并联设置并位于所述第二介质通道的下游,以接收所述循环气并供所述循环气进行甲烷合成反应;A third synthesis device, which is arranged in parallel with the first synthesis device and is located downstream of the second medium channel to receive the circulating gas and supply the circulating gas for methane synthesis reaction;
降温及分离设备,其设置于所述第三合成设备的下游以接收合成后的初步甲烷并对所述初步甲烷降温以及气液分离以得到甲烷产物。Cooling and separation equipment is provided downstream of the third synthesis equipment to receive the synthesized preliminary methane, cool the preliminary methane, and separate gas and liquid to obtain methane products.
在其中一实施方式中,所述第一介质通道与所述第一合成设备之间设有第一流量调节阀;和/或,In one embodiment, a first flow regulating valve is provided between the first medium channel and the first synthesis device; and/or,
所述第一介质通道与所述第二合成设备之间设有第二流量调节阀。A second flow regulating valve is provided between the first medium channel and the second synthesis device.
在其中一实施方式中,所述第一合成设备与所述第一热量通道之间还设有蒸汽过热器,所述蒸汽过热器包括加热管道,所述加热管道内部用于供蒸汽通过,所述蒸汽吸收所述第一塔后气的热量而形成过热蒸汽,所述加热管道的出口与所述第二合成设备的入口连通而向所述第二合成设备输入所述过热蒸汽。In one embodiment, a steam superheater is further provided between the first synthesis equipment and the first heat channel. The steam superheater includes a heating pipe, and the inside of the heating pipe is used for steam to pass through. The steam absorbs the heat of the gas after the first tower to form superheated steam. The outlet of the heating pipe is connected with the inlet of the second synthesis equipment to input the superheated steam to the second synthesis equipment.
在其中一实施方式中,所述第二合成设备与所述第二热交换设备之间还设有第一蒸汽发生器,所述第一蒸汽发生器包括用于供水流通的第一给水管道,所述第二塔后气用于向所述第一给水管道内的水提供热量以使水转化为蒸汽,所述第一给水管道的出口与所述蒸汽过热器的加热管道连通。In one embodiment, a first steam generator is further provided between the second synthesis device and the second heat exchange device, and the first steam generator includes a first water supply pipe for water supply circulation, The second post-column gas is used to provide heat to the water in the first water supply pipe to convert the water into steam. The outlet of the first water supply pipe is connected to the heating pipe of the steam superheater.
在其中一实施方式中,所述第二热交换设备与所述气液分离设备之间还设有第一冷却设备。In one embodiment, a first cooling device is further provided between the second heat exchange device and the gas-liquid separation device.
在其中一实施方式中,所述降温及分离设备包括第二蒸汽发生器和气液分离器;In one embodiment, the cooling and separation equipment includes a second steam generator and a gas-liquid separator;
所述第二蒸汽发生器包括用于供水流通的第二给水管道,所述初步甲烷用于向所述第二给水管道内的水提供热量以使水转化为蒸汽,所述气液分离器用于接收降温后的所述初步甲烷并进行气液分离而得到甲烷产物。The second steam generator includes a second water supply pipeline for water supply circulation, the preliminary methane is used to provide heat to the water in the second water supply pipeline to convert the water into steam, and the gas-liquid separator is used to The preliminary methane after cooling is received and gas-liquid separation is performed to obtain a methane product.
在其中一实施方式中,所述第二蒸汽发生器和气液分离器之间还设有第二冷却设备。In one embodiment, a second cooling device is provided between the second steam generator and the gas-liquid separator.
在其中一实施方式中,所述第一合成设备内填装有镍催化剂,所述第二合成设备内填装有镍催化剂,所述第三合成设备内填装有镍催化剂。In one embodiment, the first synthesis device is filled with a nickel catalyst, the second synthesis device is filled with a nickel catalyst, and the third synthesis device is filled with a nickel catalyst.
在其中一实施方式中,所述第一合成设备、所述第二合成设备以及所述第三合成设备均为轴径向型绝热合成反应器。In one embodiment, the first synthesis device, the second synthesis device and the third synthesis device are all axial-radial adiabatic synthesis reactors.
本发明还提供一种甲烷的制备方法,包括以下步骤:The invention also provides a method for preparing methane, which includes the following steps:
提供合成气,所述合成气中的(H2-CO2)/(CO+CO2)的体积百分比大于3;Providing synthesis gas, the volume percentage of (H 2 -CO 2 )/(CO + CO 2 ) in the synthesis gas is greater than 3;
所述合成气经热量交换升温后分别进入第一合成设备和第二合成设备内;The synthesis gas is heated up through heat exchange and then enters the first synthesis equipment and the second synthesis equipment respectively;
所述第一合成设备内进行甲烷合成反应而得到第一塔后气;A methane synthesis reaction is performed in the first synthesis equipment to obtain the first post-column gas;
所述第一塔后气与所述合成气经热量交换降温后进入所述第二合成设备内,所述第一塔后气和所述合成气在所述第二合成设备内共同进行甲烷合成反应而得到第二塔后气;The gas after the first tower and the synthesis gas enter the second synthesis equipment after being cooled by heat exchange. The gas after the first tower and the synthesis gas jointly perform methane synthesis in the second synthesis equipment. Reaction to obtain the second column back gas;
所述第二塔后气经降温冷却后进行气液分离而将所述第二塔后气中的水分离出去;The gas after the second tower is cooled and then subjected to gas-liquid separation to separate the water in the gas after the second tower;
分离水出后的第二塔后气经加压后形成循环气,所述循环气与所述第二塔后气进行热量交换升温后进入所述第一合成设备和第三合成设备内,所述第三合成设备内进行甲烷合成反应,而得到初步甲烷;The gas after the second tower after separated water is pressurized to form a circulating gas. The circulating gas exchanges heat with the gas after the second tower and is heated up before entering the first synthesis equipment and the third synthesis equipment. A methane synthesis reaction is carried out in the third synthesis device to obtain preliminary methane;
所述初步甲烷经降温以及气液分离后得到产物甲烷。After the preliminary methane is cooled and separated from gas and liquid, the product methane is obtained.
在其中一实施方式中,还包括以下步骤:In one of the embodiments, the following steps are also included:
调节所述合成气进入所述第一合成设备中的量,使所述第一合成设备中的所述合成气与所述循环气中总的碳氧化合物的摩尔百分比为3.0~5.0%;和/或,Adjust the amount of the synthesis gas entering the first synthesis device so that the molar percentage of the synthesis gas in the first synthesis device and the total carbon oxides in the circulating gas is 3.0 to 5.0%; and /or,
调节所述合成气进入所述第二合成设备中的量,使所述第二合成设备中的所述合成气与所述第二塔后气中总的碳氧化合物的摩尔百分比为3.0~10.0%。Adjust the amount of the synthesis gas entering the second synthesis equipment so that the molar percentage of the synthesis gas in the second synthesis equipment and the total carbon oxides in the gas after the second tower is 3.0 to 10.0 %.
在其中一实施方式中,在所述第二塔后气与所述循环气进行热量交换前,还包括以下步骤:In one of the embodiments, before heat exchange between the second column back gas and the circulating gas, the following steps are further included:
所述第二塔后气与水进行热量交换,释放热量使水转化为蒸汽,降温后的第二塔后气与所述循环气进行热量交换,所述蒸汽与所述第一塔后气进行热量交换。The gas after the second tower exchanges heat with water, releasing heat to convert the water into steam. The cooled gas after the second tower exchanges heat with the circulating gas, and the steam interacts with the gas after the first tower. heat exchange.
在其中一实施方式中,在所述第一塔后气与所述合成气进行热量交换前,还包括以下步骤:In one of the embodiments, before heat exchange between the first column back gas and the synthesis gas, the following steps are further included:
所述第一塔后气与上述蒸汽进行热量交换,释放热量使蒸汽转化为过热蒸汽,所述蒸汽为所述过热蒸汽进入所述第二合成设备内,降温后的第一塔后气与所述合成气进行热量交换。The gas after the first tower exchanges heat with the above-mentioned steam, releasing heat to convert the steam into superheated steam. The steam enters the second synthesis equipment as the superheated steam, and the cooled gas after the first tower and the above-mentioned steam are The synthesis gas exchanges heat.
在其中一实施方式中,所述合成气和所述循环气由所述第一合成设备的顶部进入,并自上而下经过镍基催化剂床层,在压力1~12MPa、温度250~500℃下,经催化反应得到所述第一塔后气;和/或,In one embodiment, the synthesis gas and the circulating gas enter from the top of the first synthesis equipment, and pass through the nickel-based catalyst bed from top to bottom, at a pressure of 1 to 12 MPa and a temperature of 250 to 500°C. Under, the first column post-gas is obtained through catalytic reaction; and/or,
所述合成气以及所述第一塔后气由所述第二合成设备的顶部进入,并自上而下经过镍基催化剂床层,在压力1~12MPa、温度250~550℃下,经催化反应得到所述第二塔后气;和/或,The synthesis gas and the gas after the first tower enter from the top of the second synthesis equipment, pass through the nickel-based catalyst bed from top to bottom, and are catalyzed at a pressure of 1 to 12 MPa and a temperature of 250 to 550°C. React to obtain the second column back gas; and/or,
所述循环气由所述第三合成设备的顶部进入,并自上而下经过镍基催化剂床层,在压力1~12MPa、温度250~300℃下,经催化反应得到所述初步甲烷。The circulating gas enters from the top of the third synthesis equipment, passes through the nickel-based catalyst bed from top to bottom, and undergoes a catalytic reaction to obtain the preliminary methane at a pressure of 1 to 12 MPa and a temperature of 250 to 300°C.
在其中一实施方式中,所述循环气进入所述第三合成设备的空速小于所述合成气以及所述第一塔后气进入所述第二合成设备的空速,所述循环气进入所述第三合成设备的空速小于所述合成气以及所述循环气进入所述第一合成设备的空速,所述合成气以及所述循环气进入所述第一合成设备的空速大于或等于所述合成气以及所述第一塔后气进入所述第二合成设备的空速。In one embodiment, the space velocity of the circulating gas entering the third synthesis device is smaller than the space velocity of the synthesis gas and the first tower post-gas entering the second synthesis device. The space speed of the third synthesis device is less than the space speed of the synthesis gas and the circulating gas entering the first synthesis device, and the space speed of the synthesis gas and the circulating gas entering the first synthesis device is greater than Or equal to the space velocity at which the synthesis gas and the gas after the first tower enter the second synthesis equipment.
由上述技术方案可知,本发明的优点和积极效果在于:It can be seen from the above technical solutions that the advantages and positive effects of the present invention are:
本发明中的第一合成设备、第二合成设备以及第三合成设备以串联以及并联的流程调配使合成气的反应平衡更彻底,并能够最大程度的获取单程甲烷转化率,且压缩功耗小,能量热回收较集中,降低了整个甲烷制备系统的能耗。The first synthesis equipment, the second synthesis equipment and the third synthesis equipment in the present invention are arranged in series and parallel processes to make the reaction balance of the synthesis gas more thorough, and to maximize the single-pass methane conversion rate, and to reduce the compression power consumption. , the energy heat recovery is more concentrated, which reduces the energy consumption of the entire methane preparation system.
本发明中的甲烷的制备方法的转化率高,循环比较小,甲烷化合成设备的温度灵活可控,产能调节范围大,系统热交换更合理,能耗较低,能量热回量高,收品蒸汽品次高。The methane preparation method in the present invention has high conversion rate, small cycle ratio, flexible and controllable temperature of methanation synthesis equipment, large production capacity adjustment range, more reasonable system heat exchange, low energy consumption, high energy heat recovery, and high energy recovery. The steam quality is high.
附图说明Description of the drawings
图1是本发明中液态二氧化碳的制备系统的示意图。Figure 1 is a schematic diagram of the liquid carbon dioxide preparation system in the present invention.
附图标记说明如下:The reference symbols are explained as follows:
1、第一热交换设备;2、第一合成设备;3、第二合成设备;4、第二热交换设备;5、气液分离设备;6、增压设备;7、第三合成设备;8、第一流量调节阀;9、蒸汽过热器;10、蒸汽调节阀;11、第二流量调节阀;12、第一蒸汽发生器;13、第一冷却设备;14、第二蒸汽发生器;15、气液分离器;16、第二冷却设备。1. First heat exchange equipment; 2. First synthesis equipment; 3. Second synthesis equipment; 4. Second heat exchange equipment; 5. Gas-liquid separation equipment; 6. Pressurization equipment; 7. Third synthesis equipment; 8. First flow regulating valve; 9. Steam superheater; 10. Steam regulating valve; 11. Second flow regulating valve; 12. First steam generator; 13. First cooling equipment; 14. Second steam generator ; 15. Gas-liquid separator; 16. Second cooling equipment.
具体实施方式Detailed ways
体现本发明特征与优点的典型实施方式将在以下的说明中详细叙述。应理解的是本发明能够在不同的实施方式上具有各种的变化,其皆不脱离本发明的范围,且其中的说明及图示在本质上是当作说明之用,而非用以限制本发明。Typical embodiments embodying the features and advantages of the present invention will be described in detail in the following description. It should be understood that the present invention can have various changes in different embodiments, without departing from the scope of the present invention, and the description and illustrations are essentially for illustration, not limitation. this invention.
为了进一步说明本发明的原理和结构,现结合附图对本发明的优选实施例进行详细说明。In order to further illustrate the principle and structure of the present invention, the preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.
需要说明的是,甲烷的合成反应方程式如下:It should be noted that the synthesis reaction equation of methane is as follows:
CO+3H2=CH4 CO2+4H2=CH4+2H2O。CO+3H 2 =CH 4 CO 2 +4H 2 =CH 4 +2H 2 O.
甲烷的合成反应为放热反应,低温可增加H2合成甲烷的概率。因此,温度越低,合成朝CH4方向移动的越多。The synthesis reaction of methane is an exothermic reaction, and low temperature can increase the probability of H 2 synthesizing methane. Therefore, the lower the temperature, the more the synthesis shifts towards CH4 .
本发明提供一种甲烷制备系统,其能够对包含氢气、一氧化碳和二氧化碳的合成气进行控温合成甲烷,能耗较低。The invention provides a methane preparation system, which can control the temperature of synthesis gas containing hydrogen, carbon monoxide and carbon dioxide to synthesize methane, and has low energy consumption.
图1示出了甲烷制备系统的示意图,参阅图1,甲烷制备系统包括第一热交换设备1、第一合成设备2、第二合成设备3、第二热交换设备4、气液分离设备5、增压设备6、第三合成设备7以及降温及分离设备。Figure 1 shows a schematic diagram of a methane production system. Referring to Figure 1, the methane production system includes a first heat exchange device 1, a first synthesis device 2, a second synthesis device 3, a second heat exchange device 4, and a gas-liquid separation device 5. , pressurizing equipment 6, third synthesis equipment 7 and cooling and separation equipment.
第一热交换设备1包括相互独立并能够热交换的第一热量通道和第一介质通道。第一介质通道的入口用于接收外界的合成气,即第一介质通道的入口用于与外界连通。The first heat exchange device 1 includes a first heat channel and a first medium channel that are independent of each other and capable of heat exchange. The inlet of the first medium channel is used to receive syngas from the outside, that is, the inlet of the first medium channel is used to communicate with the outside world.
其中,合成气的主要成分是氢气(H2)、一氧化碳(CO)和二氧化碳(CO2)。本申请中所采用的合成气中(H2-CO2)/(CO+CO2)的体积百分比大于3,即依据甲烷的合成反应,该合成气中氢气的含量使得在与一氧化碳和二氧化碳反应时是充足并富余的。Among them, the main components of syngas are hydrogen (H 2 ), carbon monoxide (CO) and carbon dioxide (CO 2 ). The volume percentage of (H 2 -CO 2 )/(CO + CO 2 ) in the synthesis gas used in this application is greater than 3, that is, according to the synthesis reaction of methane, the content of hydrogen in the synthesis gas is such that it reacts with carbon monoxide and carbon dioxide. Time is sufficient and abundant.
合成气在第一热交换设备1内进行热量交换,该合成气吸收热量而升温。The synthesis gas undergoes heat exchange in the first heat exchange device 1, and the synthesis gas absorbs heat to increase its temperature.
第一合成设备2与第一介质通道的出口相连,以接收升温后的合成气。第一合成设备2内用于进行甲烷合成反应而得到第一塔后气。其中,在第一合成设备2内,在循环气还未产生时,合成气进行甲烷合成反应。在循环气进入第一合成设备2后,合成气与循环气共同进行甲烷合成反应。The first synthesis device 2 is connected to the outlet of the first medium channel to receive the heated synthesis gas. The first synthesis equipment 2 is used to perform a methane synthesis reaction to obtain the first post-column gas. Among them, in the first synthesis device 2, before the circulating gas is generated, the synthesis gas undergoes a methane synthesis reaction. After the circulating gas enters the first synthesis device 2, the synthesis gas and the circulating gas jointly perform a methane synthesis reaction.
具体地,第一合成设备2为轴径向型绝热合成反应器。第一合成设备2内填装有镍催化剂。第一合成设备2采用外壳和内件分开设计,外壳承受外压,温度与进气温度一致,用材省。内件承担气体分布作用和催化剂反应热,但不承压。第一合成设备2整体结构安全可靠。Specifically, the first synthesis device 2 is an axial-radial type adiabatic synthesis reactor. The first synthesis device 2 is filled with a nickel catalyst. The first synthesis equipment 2 is designed with separate outer shell and internal parts. The outer shell can withstand external pressure and the temperature is consistent with the inlet air temperature, thus saving materials. The internal parts bear the role of gas distribution and catalyst reaction heat, but do not bear pressure. The overall structure of the first synthesis equipment 2 is safe and reliable.
第一合成设备2的出口与第一热量通道的入口相通,以输送第一塔后气。即在第一热交换设备1内,第一塔后气与合成气进行热量交换,第一塔后气释放热量而降温,合成气吸收热量而升温。The outlet of the first synthesis device 2 communicates with the inlet of the first heat channel to transport the gas after the first tower. That is, in the first heat exchange equipment 1, the gas after the first tower and the syngas exchange heat. The gas after the first tower releases heat and cools down, and the syngas absorbs heat and heats up.
进一步地,第一介质通道与第一合成设备2之间设有第一流量调节阀8。第一流量调节阀8的开度可调节,进而调节进入第一合成设备2内的合成气的量。通过调节进入第一合成设备2内的合成气的量,而调节第一合成设备2内合成气与循环气中总的碳氧化合物的体积百分比,进而调节甲烷合成的反应程度,从而能够控制第一合成设备2内的温升。Further, a first flow regulating valve 8 is provided between the first medium channel and the first synthesis device 2 . The opening of the first flow regulating valve 8 is adjustable, thereby adjusting the amount of synthesis gas entering the first synthesis device 2 . By adjusting the amount of synthesis gas entering the first synthesis device 2 and adjusting the volume percentage of the total carbon oxides in the synthesis gas and the circulating gas in the first synthesis device 2, the reaction degree of methane synthesis is adjusted, thereby controlling the third synthesis gas. A temperature rise within the synthesis equipment 2.
较佳地,第一合成设备2与第一热量通道之间还设有蒸汽过热器9。蒸汽过热器9包括加热管道,加热管道内用于供蒸汽通过,蒸汽吸收第一塔后气的热量而形成过热蒸汽。本实施例中,加热管道外设有筒体,筒体与加热管道之间具有供第一塔后气通过的空间,即第一塔后气在加热管道外通过,并向蒸汽提供热量。Preferably, a steam superheater 9 is also provided between the first synthesis equipment 2 and the first heat channel. The steam superheater 9 includes a heating pipe, and the heating pipe is used for steam to pass through, and the steam absorbs the heat of the gas after the first tower to form superheated steam. In this embodiment, a cylinder is provided outside the heating pipe, and there is a space between the cylinder and the heating pipe for the gas after the first tower to pass, that is, the gas after the first tower passes outside the heating pipe and provides heat to the steam.
加热管道的出口与第二合成设备3的入口连通而向第二合成设备3输入过热蒸汽。The outlet of the heating pipe communicates with the inlet of the second synthesis device 3 to input superheated steam into the second synthesis device 3 .
具体地,蒸汽过热器9与第二合成设备3之间还设有蒸汽调节阀10,即蒸汽调节阀10设置于加热管道与第二合成设备3之间,以调节进入第二合成设备3内的过热蒸汽的量。Specifically, a steam regulating valve 10 is disposed between the steam superheater 9 and the second synthesis equipment 3 , that is, the steam regulating valve 10 is disposed between the heating pipe and the second synthesis equipment 3 to regulate the flow into the second synthesis equipment 3 the amount of superheated steam.
第二合成设备3的入口同时与第一介质通道的出口以及第一热量通道的出口相连,以用于接收升温后的合成气以及降温后的第一塔后气。The inlet of the second synthesis device 3 is connected to the outlet of the first medium channel and the outlet of the first heat channel at the same time, for receiving the heated synthesis gas and the cooled first tower post-gas.
升温后的合成气以及降温后的第一塔后气在第二合成设备3内反应得到第二塔后气。The heated synthesis gas and the cooled first post-column gas react in the second synthesis device 3 to obtain the second post-column gas.
第二合成设备3内发生甲烷合成反应时,通过引入过热蒸汽,而控制甲烷合成反应的速度,避免反应过快。且过热蒸汽的进入还能降低整个第二合成设备3内的温升。When the methane synthesis reaction occurs in the second synthesis device 3, the speed of the methane synthesis reaction is controlled by introducing superheated steam to avoid the reaction being too fast. Moreover, the entry of superheated steam can also reduce the temperature rise within the entire second synthesis equipment 3 .
具体地,第二合成设备3为轴径向型绝热合成反应器。第二合成设备3内填装有镍催化剂。第二合成设备3采用外壳和内件分开设计,外壳承受外压,温度与进气温度一致,用材省。内件承担气体分布作用和催化剂反应热,但不承压。第二合成设备3整体结构安全可靠。Specifically, the second synthesis device 3 is an axial-radial type adiabatic synthesis reactor. The second synthesis device 3 is filled with a nickel catalyst. The second synthesis equipment 3 is designed with separate outer shell and internal parts. The outer shell can withstand external pressure, and the temperature is consistent with the inlet air temperature, thus saving materials. The internal parts bear the role of gas distribution and catalyst reaction heat, but do not bear pressure. The overall structure of the second synthesis equipment 3 is safe and reliable.
进一步地,第二合成设备3与第一介质通道之间设有第二流量调节阀11。第二流量调节阀11的开度可调节,进而调节进入第二合成设备3内的合成气的量。Further, a second flow regulating valve 11 is provided between the second synthesis device 3 and the first medium channel. The opening of the second flow regulating valve 11 is adjustable, thereby adjusting the amount of synthesis gas entering the second synthesis device 3 .
第二热交换设备4包括相互独立并能够热交换的第二热量通道和第二介质通道。第二热量通道的入口与第二合成设备3相连以接收第二塔后气,即第二塔后气释放热量而降温。第二介质通道的出口与第一合成设备2的进口相连通。The second heat exchange device 4 includes a second heat channel and a second medium channel that are independent of each other and capable of heat exchange. The inlet of the second heat channel is connected to the second synthesis device 3 to receive the gas after the second tower, that is, the gas after the second tower releases heat and is cooled. The outlet of the second medium channel is connected with the inlet of the first synthesis device 2 .
进一步地,第二合成设备3与第二热交换设备4之间还设有第一蒸汽发生器12。具体地,第一蒸汽发生器12与第二热量通道的入口相连。第一蒸汽发生器12包括用于供水流通的第一给水管道,第二塔后气用于向第一给水管道内的水提供热量以使水转化为蒸汽,第一给水管道的出口与蒸汽过热器9的加热管道连通。Furthermore, a first steam generator 12 is provided between the second synthesis device 3 and the second heat exchange device 4 . Specifically, the first steam generator 12 is connected with the inlet of the second heat channel. The first steam generator 12 includes a first water supply pipe for water supply circulation. The second tower back gas is used to provide heat to the water in the first water supply pipe to convert the water into steam. The outlet of the first water supply pipe is connected to the steam superheater. The heating pipe of device 9 is connected.
第一供水管道的入水口用于与外界连通。本实施例中,第一供水管道的水为锅炉水。The water inlet of the first water supply pipe is used to communicate with the outside world. In this embodiment, the water in the first water supply pipe is boiler water.
水进入第一供水管道后吸收热量转化为蒸汽,再进入蒸汽过热器9内转化为过热蒸汽进入第二合成设备3内。After water enters the first water supply pipe, it absorbs heat and is converted into steam, and then enters the steam superheater 9 and is converted into superheated steam and enters the second synthesis device 3 .
气液分离设备5设置于第二热量通道的下游,以接收降温后的第二塔后气并进行气液分离而分离出水。The gas-liquid separation equipment 5 is arranged downstream of the second heat channel to receive the cooled gas after the second tower and perform gas-liquid separation to separate water.
进一步地,第二热交换设备4与气液分离设备5之间还设有第一冷却设备13。第一冷却设备13用于进一步的冷却第二塔后气。本实施例中,第一冷却设备13可以为循环水冷却设备,也可以为脱盐水换热设备。Furthermore, a first cooling device 13 is provided between the second heat exchange device 4 and the gas-liquid separation device 5 . The first cooling device 13 is used to further cool the gas after the second tower. In this embodiment, the first cooling device 13 may be a circulating water cooling device or a desalted water heat exchange device.
具体地,第二塔后气经第一蒸发器、第二热交换设备4以及第一冷却设备13后的温度降至30~80℃。Specifically, the temperature of the gas after the second tower is reduced to 30-80°C after passing through the first evaporator, the second heat exchange device 4 and the first cooling device 13.
增压设备6设置于气液分离设备5的下游,以接收分离水后的第二塔后气并进行增压而得到循环气。本实施例中,增压设备6为循环机。The pressurizing device 6 is disposed downstream of the gas-liquid separation device 5 to receive the gas after the second tower after water separation and pressurize it to obtain circulating gas. In this embodiment, the boosting equipment 6 is a circulation machine.
增压设备6与第二介质通道的入口相通,即向第二热交换设备4的第二介质通道输送循环气。循环气在第二热交换设备4内与第二塔后气进行热量交换,循环气吸收热量而升温,第二塔后气释放热量而降温。The pressurizing device 6 communicates with the inlet of the second medium channel, that is, it delivers circulating gas to the second medium channel of the second heat exchange device 4 . The circulating gas exchanges heat with the gas after the second tower in the second heat exchange device 4. The circulating gas absorbs heat and increases its temperature, while the gas after the second tower releases heat and cools down.
第三合成设备7与第一合成设备2并联设置并位于第二介质通道的下游,以接收循环气并供循环气进行甲烷合成反应。The third synthesis device 7 is arranged in parallel with the first synthesis device 2 and is located downstream of the second medium channel to receive the circulating gas and supply the circulating gas for methane synthesis reaction.
具体地,第三合成设备7为轴径向型绝热合成反应器。第三合成设备7内填装有镍催化剂。第三合成设备7采用外壳和内件分开设计,外壳承受外压,温度与进气温度一致,用材省。内件承担气体分布作用和催化剂反应热,但不承压。第三合成设备7整体结构安全可靠。Specifically, the third synthesis device 7 is an axial-radial type adiabatic synthesis reactor. The third synthesis device 7 is filled with nickel catalyst. The third synthesis equipment 7 is designed with separate outer shell and internal parts. The outer shell can withstand external pressure, and the temperature is consistent with the inlet air temperature, thus saving materials. The internal parts bear the role of gas distribution and catalyst reaction heat, but do not bear pressure. The overall structure of the third synthesis device 7 is safe and reliable.
降温及分离设备设置于第三合成设备7的下游以接收合成后的初步甲烷并对初步甲烷降温以及气液分离以得到甲烷产物。The cooling and separation equipment is arranged downstream of the third synthesis equipment 7 to receive the synthesized preliminary methane, cool the preliminary methane, and separate gas and liquid to obtain methane products.
具体地,降温及分离设备包括第二蒸汽发生器14和气液分离器15。Specifically, the cooling and separation equipment includes a second steam generator 14 and a gas-liquid separator 15 .
第二蒸汽发生器14包括用于供水流通的第二给水管道,初步甲烷用于向第二给水管道内的水提供热量以使水转化为蒸汽,初步甲烷释放热量后温度降低。The second steam generator 14 includes a second water supply pipe for circulation of water supply. The preliminary methane is used to provide heat to the water in the second water supply pipe to convert the water into steam. After the preliminary methane releases heat, the temperature decreases.
具体地,第二蒸汽发生器14与第三合成设备7的出口相连,以接收初步甲烷。Specifically, the second steam generator 14 is connected to the outlet of the third synthesis device 7 to receive preliminary methane.
第二给水管道的出口输出低压饱和蒸汽,该低压饱和蒸汽可以保存并进行利用或销售。The outlet of the second water supply pipe outputs low-pressure saturated steam, which can be saved and utilized or sold.
气液分离器15用于分离出初步甲烷中的水。The gas-liquid separator 15 is used to separate water from preliminary methane.
进一步地,第二蒸汽发生器14和气液分离器15之间还设有第二冷却设备16。Further, a second cooling device 16 is provided between the second steam generator 14 and the gas-liquid separator 15 .
具体地,初步甲烷经第二蒸汽发生器14和第二冷却设备16的冷却后,温度降至30~50℃,然后再经气液分离器15的分离后,输出甲烷产物。Specifically, after the preliminary methane is cooled by the second steam generator 14 and the second cooling device 16, the temperature is lowered to 30-50°C, and then separated by the gas-liquid separator 15, the methane product is output.
本实施例的甲烷制备系统中,第一热交换热设备、第一合成设备2、第二合成设备3、第二热交换设备4、蒸汽过热器9、第一蒸汽发生器12、第一冷却设备13以及气液分离设备5形成一开式循环回路。In the methane production system of this embodiment, the first heat exchange heat equipment, the first synthesis equipment 2, the second synthesis equipment 3, the second heat exchange equipment 4, the steam superheater 9, the first steam generator 12, the first cooling The equipment 13 and the gas-liquid separation equipment 5 form an open circulation loop.
在上述开式循环回路中,第一合成设备2与第二合成设备3即以串联形式存在同时又以并联形式存在,其中,合成气分为两路分别进入第一合成设备2和第二合成设备3时,两者是并联关系,第一塔后气经降温后进入第二合成设备3时,两者是串联关系。In the above-mentioned open circulation loop, the first synthesis device 2 and the second synthesis device 3 exist both in series and in parallel. The synthesis gas is divided into two paths and enters the first synthesis device 2 and the second synthesis device respectively. When equipment 3 is used, the two are connected in parallel. When the gas after the first tower is cooled and then enters the second synthesis equipment 3, the two are connected in series.
第一合成设备2和第二合成设备3串联以及并联的搭配方式,合成气流量的分配以及过热蒸汽控制温升的设计,保证了适宜的反应温度,同时又实现了较高的转化率和稳定运行特性。The series and parallel combination of the first synthesis equipment 2 and the second synthesis equipment 3, the distribution of synthesis gas flow and the design of superheated steam control temperature rise ensure the appropriate reaction temperature and at the same time achieve a high conversion rate and stability. Operating characteristics.
在上述开式循环回路中,第一合成设备2为辅助反应器、第二合成设备3为主反应器。其中,第二合成设备3是整个甲烷制备系统的产量调节的设备,具体地,通过调节进入第二合成设备3内的过热蒸汽的量来调节整个制备系统的产能和循环比。因此,整个甲烷制备系统的产能控制调节范围大,适应能力强。In the above-mentioned open circulation loop, the first synthesis device 2 is an auxiliary reactor and the second synthesis device 3 is the main reactor. The second synthesis device 3 is a device for adjusting the output of the entire methane preparation system. Specifically, the production capacity and circulation ratio of the entire preparation system are adjusted by adjusting the amount of superheated steam entering the second synthesis device 3 . Therefore, the entire methane production system has a wide production capacity control and adjustment range and strong adaptability.
第三合成设备7与上述开式循环回路串联连接,接受循环气,因此,第三合成设备7内主要以深度净化反应为主,反应温度接近恒温,所产出的初步甲烷中几乎无碳氧化合物。The third synthesis equipment 7 is connected in series with the above-mentioned open circulation loop and receives circulating gas. Therefore, the third synthesis equipment 7 mainly conducts deep purification reactions. The reaction temperature is close to a constant temperature. There is almost no carbon and oxygen in the preliminary methane produced. compound.
合成气经过第一合成设备2以及第二合成设备3后碳氧化合物(CO+CO2)的含量得到较大的消耗,即所形成的第二塔后气中的碳氧化合物的含量较低。循环气经第三合成设备7后,碳氧化合物(CO+CO2)的含量得到深度净化,即所形成的初步甲烷中几乎无碳氧化合物。After the syngas passes through the first synthesis device 2 and the second synthesis device 3, the content of carbon oxides (CO+CO 2 ) is greatly consumed, that is, the content of carbon oxides in the gas after the second tower is relatively low. . After the circulating gas passes through the third synthesis device 7, the content of carbon oxides (CO+CO 2 ) is deeply purified, that is, there is almost no carbon oxides in the preliminary methane formed.
串联以及并联的流程调配使合成气的反应平衡更彻底,并能够最大程度的获取单程甲烷转化率,且压缩功耗小,能量热回收较集中,副产蒸汽品次更高、回收量高,较经济。The series and parallel process deployment makes the reaction balance of the syngas more thorough, and can maximize the single-pass methane conversion rate, with low compression power consumption, concentrated energy and heat recovery, higher quality and high recovery volume of by-product steam, More economical.
本发明还提供一种甲烷的制备方法,包括以下步骤:The invention also provides a method for preparing methane, which includes the following steps:
S1、提供合成气,合成气中的(H2-CO2)/(CO+CO2)的体积百分比大于3。S1. Provide synthesis gas. The volume percentage of (H 2 -CO 2 )/(CO + CO 2 ) in the synthesis gas is greater than 3.
该合成气可以自己通过生物质气化得到,也可以是外购得到。The synthesis gas can be obtained by biomass gasification yourself or purchased from outside.
通过合成气中氢气的量使该合成气在甲烷合成反应中处于富余状态,即在一氧化碳和二氧化碳与氢气反应时,按照理论计算,氢气的量能保证一氧化碳和二氧化碳完全反应生成甲烷。The amount of hydrogen in the synthesis gas makes the synthesis gas in a surplus state during the methane synthesis reaction. That is, when carbon monoxide and carbon dioxide react with hydrogen, according to theoretical calculations, the amount of hydrogen can ensure that carbon monoxide and carbon dioxide completely react to generate methane.
S2、合成气经热量交换升温后分别进入第一合成设备2和第二合成设备3内。S2. After the synthesis gas is heated up through heat exchange, it enters the first synthesis equipment 2 and the second synthesis equipment 3 respectively.
合成气分为两路分别进入第一合成设备2和第二合成设备3,此时,第一合成设备2和第二合成设备3可以理解为并联设置。The synthesis gas is divided into two paths and enters the first synthesis device 2 and the second synthesis device 3 respectively. At this time, the first synthesis device 2 and the second synthesis device 3 can be understood as being arranged in parallel.
较佳地,合成气进入第一合成设备2的量能够调节。调节合成气进入第一合成设备2中的量,使第一合成设备2中的合成气与循环气中总的碳氧化合物的摩尔百分比为3.0~5.0%。具体地,第一合成设备2和第一热交换设备1之间设有第一流量调节阀8,通过该第一流量调节阀8的调节实现进入第一合成设备2内的合成气的量。Preferably, the amount of syngas entering the first synthesis device 2 can be adjusted. The amount of syngas entering the first synthesis device 2 is adjusted so that the molar percentage of the total carbon oxides in the syngas in the first synthesis device 2 and the circulating gas is 3.0 to 5.0%. Specifically, a first flow control valve 8 is provided between the first synthesis device 2 and the first heat exchange device 1 , and the amount of synthesis gas entering the first synthesis device 2 is achieved by adjusting the first flow control valve 8 .
进一步地,还调节合成气进入第二合成设备3中的量,使第二合成设备3中的合成气与第二塔后气中总的碳氧化合物的摩尔百分比为3.0~10.0%。Furthermore, the amount of syngas entering the second synthesis device 3 is also adjusted so that the molar percentage of the total carbon oxides in the syngas in the second synthesis device 3 and in the gas after the second tower is 3.0 to 10.0%.
具体地,第二合成设备3和第一热交换设备1之间设有第二流量调节阀11,通过该第二流量调节阀11的调节实现进入第二合成设备3内的合成气的量。Specifically, a second flow regulating valve 11 is provided between the second synthesis device 3 and the first heat exchange device 1 , and the amount of synthesis gas entering the second synthesis device 3 is achieved by adjusting the second flow regulating valve 11 .
S3、第一合成设备2内进行甲烷合成反应而得到第一塔后气。S3. Carry out methane synthesis reaction in the first synthesis equipment 2 to obtain the first column post-gas.
具体地,合成气和后续所产生的循环气由第一合成设备2的顶部进入,并自上而下经过镍基催化剂床层,在压力1~12MPa、温度250~500℃下,经催化反应得到第一塔后气。Specifically, the synthesis gas and the subsequently generated circulating gas enter from the top of the first synthesis equipment 2, pass through the nickel-based catalyst bed from top to bottom, and undergo a catalytic reaction at a pressure of 1 to 12 MPa and a temperature of 250 to 500°C. After getting the first tower.
其中,在第一合成设备2内,75~85%的碳氧化物经催化转化生成甲烷。Among them, in the first synthesis device 2, 75 to 85% of the carbon oxides are catalytically converted to generate methane.
第一合成设备2内进行甲烷合成反应所产生的反应热一部分进入蒸汽过热器9内,而将热量释放给蒸汽,另一部分融入循环气中。Part of the reaction heat generated by the methane synthesis reaction in the first synthesis equipment 2 enters the steam superheater 9 and releases the heat to the steam, and the other part is integrated into the circulating gas.
S4、第一塔后气与合成气经热量交换降温后进入第二合成设备3内,第一塔后气和合成气在第二合成设备3内共同进行甲烷合成反应而得到第二塔后气。S4. The gas after the first tower and the synthesis gas enter the second synthesis device 3 after being cooled by heat exchange. The gas after the first tower and the synthesis gas jointly perform a methane synthesis reaction in the second synthesis device 3 to obtain the second gas after the tower. .
具体地,合成气以及第一塔后气由第二合成设备3的顶部进入,并自上而下经过镍基催化剂床层,在压力1~12MPa、温度250~550℃下,经催化反应得到第二塔后气。Specifically, the synthesis gas and the gas after the first tower enter from the top of the second synthesis equipment 3, and pass through the nickel-based catalyst bed from top to bottom, and undergo a catalytic reaction at a pressure of 1 to 12 MPa and a temperature of 250 to 550°C to obtain The second tower is behind the gas.
进一步地,在第一塔后气与合成气进行热量交换前,还包括以下步骤:Further, before the heat exchange between the gas after the first tower and the synthesis gas is carried out, the following steps are also included:
第一塔后气与蒸汽热量交换,释放热量使蒸汽转化为过热蒸汽,降温后的第一塔后气与合成气进行热量交换,过热蒸汽进入第二合成设备3内。The gas after the first tower exchanges heat with the steam, releasing heat to convert the steam into superheated steam. The cooled gas after the first tower exchanges heat with the synthesis gas, and the superheated steam enters the second synthesis equipment 3.
S5、第二塔后气经降温冷却后进行气液分离而将第二塔后气中的水分离出去。S5. After the gas after the second tower is cooled, gas-liquid separation is performed to separate the water in the gas after the second tower.
S6、分离水后的第二塔后气经加压后形成循环气,循环气与第二塔后气进行热量交换升温后进入第一合成设备2和第三合成设备7内,第三合成设备7内进行甲烷合成反应,而得到初步甲烷。S6. After water separation, the gas after the second tower is pressurized to form circulating gas. The circulating gas exchanges heat with the gas after the second tower and is heated up before entering the first synthesis equipment 2 and the third synthesis equipment 7. The third synthesis equipment The methane synthesis reaction is carried out within 7 days to obtain preliminary methane.
具体地,循环气和所述合成气由第三合成设备7的顶部进入,并自上而下经过镍基催化剂床层,在压力1~12MPa、温度250~300℃下,经催化反应得到初步甲烷。Specifically, the circulating gas and the synthesis gas enter from the top of the third synthesis equipment 7 and pass through the nickel-based catalyst bed from top to bottom. At a pressure of 1 to 12 MPa and a temperature of 250 to 300°C, a preliminary reaction is obtained through a catalytic reaction. Methane.
S7、初步甲烷经降温以及气液分离后得到产物甲烷。S7. After the preliminary methane is cooled and separated from gas and liquid, the product methane is obtained.
在上述制备方法中,控制循环气进入第三合成设备7的空速小于合成气以及第一塔后气进入第二合成设备3的空速,循环气进入第三合成设备7的空速小于合成气以及循环气进入第一合成设备2的空速,合成气以及循环气进入第一合成设备2的空速大于或等于合成气以及第一塔后气进入第二合成设备3的空速。In the above preparation method, the space velocity of the circulating gas entering the third synthesis device 7 is controlled to be smaller than the space velocity of the synthesis gas and the gas after the first tower entering the second synthesis device 3, and the space velocity of the circulating gas entering the third synthesis device 7 is smaller than the space velocity of the synthesis gas. The space velocity of the syngas and the circulating gas entering the first synthesis device 2 is greater than or equal to the space velocity of the syngas and the gas after the first tower entering the second synthesis device 3 .
其中,各合成设备的空速通过控制催化剂的装填量实现。具体地,通过控制催化剂装填量,引导气体以所需要的空速通过催化剂床层。Among them, the space velocity of each synthesis equipment is achieved by controlling the loading amount of the catalyst. Specifically, by controlling the catalyst loading amount, the gas is guided through the catalyst bed at the required space velocity.
上述甲烷的制备方法中,第一合成设备2以及第二合成设备3内的空速以及较大的通气量可有效的规避催化剂床层的局部热蓄积现象,利于降低催化反应热点温度,减缓甲烷催化剂在高氢、高碳分压下的局部区域内过度放热,使催化剂床层80~90%以上反应区域处于高温(350~550℃)、高转化率反应温区,因此,提高了催化剂的整体使用效率和使用年限。In the above methane preparation method, the space velocity and large ventilation volume in the first synthesis equipment 2 and the second synthesis equipment 3 can effectively avoid the local heat accumulation phenomenon in the catalyst bed, which is beneficial to reducing the hot spot temperature of the catalytic reaction and slowing down the methane production. The catalyst excessively releases heat in a local area under high hydrogen and high carbon partial pressure, causing more than 80 to 90% of the reaction area of the catalyst bed to be in a high temperature (350 to 550°C) and high conversion rate reaction temperature zone. Therefore, the catalyst improves overall efficiency and service life.
第三合成设备7内的空速较低,低空速、低碳分压使反应床层温度更均匀,使催化剂床层处于低温250~300℃、高转化深度反应温区,对提高合成回路单程转化率有利,达到甲烷气的深度净化要求。The space velocity in the third synthesis equipment 7 is low. The low space velocity and low carbon partial pressure make the reaction bed temperature more uniform, and the catalyst bed is in a low temperature 250-300°C, high conversion depth reaction temperature zone, which is beneficial to improving the single-pass synthesis loop. The conversion rate is favorable and meets the requirements for deep purification of methane gas.
第一合成设备2内,合成气以及循环气在高空速、适宜的碳氧化合物(CO+CO2)含量(3.0~5.0%)下反应,使得催化剂不出现局部超温。第二合成设备3内,合成气以及第一塔后气在较高空速,并外补过热蒸汽量,碳氧化合物(CO+CO2)含量(3.0-10%)下反应,并通过控制反应床层的温升和单程甲烷产量,使催化剂不出现局部超温。In the first synthesis device 2, the synthesis gas and the circulating gas react at high space velocity and appropriate carbon oxide (CO+CO 2 ) content (3.0-5.0%), so that the catalyst does not suffer from local overtemperature. In the second synthesis equipment 3, the synthesis gas and the gas after the first tower react at a relatively high space velocity, with external superheated steam, and a carbon oxide (CO+CO 2 ) content (3.0-10%), and the reaction is controlled by The temperature rise of the bed and the single-pass methane production prevent local overtemperature of the catalyst.
即,本申请中的甲烷的制备方法的转化率高,循环比较小,甲烷化合成设备温度灵活可控,产能调节范围大,系统热交换更合理,能耗较低,能量热回量高,收品蒸汽品次高。That is, the methane preparation method in this application has a high conversion rate, a small cycle ratio, flexible and controllable temperature of the methanation synthesis equipment, a large capacity adjustment range, more reasonable system heat exchange, low energy consumption, and high energy heat recovery. The quality of the received steam is high.
虽然已参照几个典型实施方式描述了本发明,但应当理解,所用的术语是说明和示例性、而非限制性的术语。由于本发明能够以多种形式具体实施而不脱离发明的精神或实质,所以应当理解,上述实施方式不限于任何前述的细节,而应在随附权利要求所限定的精神和范围内广泛地解释,因此落入权利要求或其等效范围内的全部变化和改型都应为随附权利要求所涵盖。While the present invention has been described with reference to several exemplary embodiments, it is to be understood that the terms used are illustrative and exemplary rather than limiting. Since the present invention can be embodied in various forms without departing from the spirit or essence of the invention, it should be understood that the above-described embodiments are not limited to any foregoing details, but are to be construed broadly within the spirit and scope defined by the appended claims. , therefore all changes and modifications falling within the scope of the claims or their equivalents shall be covered by the appended claims.
Claims (15)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311322028.2A CN117427570A (en) | 2023-10-12 | 2023-10-12 | Methane preparation system and methane preparation method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311322028.2A CN117427570A (en) | 2023-10-12 | 2023-10-12 | Methane preparation system and methane preparation method |
Publications (1)
Publication Number | Publication Date |
---|---|
CN117427570A true CN117427570A (en) | 2024-01-23 |
Family
ID=89550739
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202311322028.2A Pending CN117427570A (en) | 2023-10-12 | 2023-10-12 | Methane preparation system and methane preparation method |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN117427570A (en) |
-
2023
- 2023-10-12 CN CN202311322028.2A patent/CN117427570A/en active Pending
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4681701A (en) | Process for producing synthesis gas | |
CN105753646B (en) | A kind of energy-saving intersegmental high/low temperature gradient is divided to alcohol two sections of production alcohol method and devices | |
CN108463450A (en) | Methanol process | |
CN108463449A (en) | Methanol process | |
CN110550602B (en) | Controllable semi-isothermal conversion process for high-concentration carbon monoxide for oxo synthesis | |
WO2009052764A1 (en) | A composite reaction apparatus and the chemical production method using the same | |
CN106732201B (en) | Catalyst for Oxidative Coupling of Methane reactor | |
CN101580748B (en) | Method and device for producing natural gas from synthetic gas through methanation reaction | |
CN101480592A (en) | Fixed bed composite reaction equipment | |
CN101560406A (en) | Method and device for producing hydrocarbon by Fishcer-Tropsch reaction of synthesis gas | |
CN201211474Y (en) | Fixed bed composite reaction equipment | |
CN101659879B (en) | Chemical-electric poly-generation method and equipment | |
GB2546867A (en) | Methanol process | |
CN113772625A (en) | High-efficiency hydrogen production process by using methanol | |
CN117427570A (en) | Methane preparation system and methane preparation method | |
CN109054908B (en) | Isothermal transformation process matched with pulverized coal gasification | |
CN109071248A (en) | NH for extensive facility3Synthesis configuration | |
US11407702B2 (en) | Method for producing methanol in a reactor with bypass | |
CN201436064U (en) | A kind of by-product steam catalytic reaction equipment | |
CN214422541U (en) | Purge gas methanol synthesis system | |
CN101928206B (en) | Method for producing dimethyl ether by synthesis gas and equipment thereof | |
CN212451252U (en) | High-efficient methyl alcohol synthesis system | |
CN107974318A (en) | Compound tower-type methanation device and methanation process | |
CN207210294U (en) | A kind of process units of energy-saving acetic acid hydrogenation or ethyl acetate preparation of ethanol by hydrogenating | |
CN115916391A (en) | Multi-bed ammonia converter |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |