CN218222370U - Device for improving conversion rate of methanol prepared from carbon dioxide - Google Patents
Device for improving conversion rate of methanol prepared from carbon dioxide Download PDFInfo
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- CN218222370U CN218222370U CN202220634350.3U CN202220634350U CN218222370U CN 218222370 U CN218222370 U CN 218222370U CN 202220634350 U CN202220634350 U CN 202220634350U CN 218222370 U CN218222370 U CN 218222370U
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Abstract
The utility model relates to an improve device of carbon dioxide system methanol conversion rate, including first reactor, the first gas heat exchanger of second reactor, first cooler, first separator, second gas heat exchanger, second cooler, second separator. The utility model discloses a two-stage reactor series flow, the steam of the different specifications of byproduct, first reactor export increases the cooling and divides the liquid device, reduce the mellow wine partial pressure and the water partial pressure of second reactor entry, be favorable to improving second reactor methanol conversion rate, add the stage branch liquid device with carbon dioxide and hydrogen step reaction, be favorable to the maximize to improve the conversion rate of whole device, gas separation with the reactor unreacted gets into the synthesis reactor recycle, it improves carbon dioxide total carbon conversion rate to be useful, introduce the second reactor with fresh synthesis gas through the bypass, when first reactor catalyst activity reduces in the reaction in terminal phase, move to the second reactor after will reacting, thereby guarantee the conversion rate and the output of whole device.
Description
Technical Field
The utility model relates to a chemical production technical field specifically indicates a device of improvement carbon dioxide system methanol conversion rate.
Background
Carbon dioxide is a common greenhouse gas, and in the industrial field of China, particularly industries depending on coal resources, a large amount of CO is available every year 2 And (4) generating.
In 9 months of 2020, china puts forward the aim and the vision that the carbon dioxide emission strives to reach the peak value 2030 years ago, strives for the aim and the vision of realizing carbon neutralization 2060 years ago, and relates to the perpetual development of Chinese nationality and the construction of human fate communities, which means that China more firmly follows the newly developed concept, constructs a newly developed pattern, promotes the transformation and the upgrade of industry, walks up the development path of green, low carbon and circulation, realizes high-quality development, and has very realistic and important significance for protecting the earth ecology and promoting the action of responding to climate change globally.
The concept of 'methanol economy' is proposed in 2005 by george, andrew and Euler of Nobel prize-winning chemists, and the methanol economy can be used as a solution for solving the problem of later energy in the oil and gas era. It is considered that hydrogen is produced from renewable energy sources, and carbon dioxide is recycled to synthesize methanol, which can be directly used as fuel, or synthesized into fuel or chemicals through processes of methanol-to-gasoline (MTG), methanol-to-aromatics (MTA), methanol-to-olefin (MTO), and methanol-to-propylene (MTP), and is a promising technology.
At present, a plurality of scientific research institutions and colleges in China collate CO 2 Catalyst for preparing methanol and CO 2 The research and development of the methanol preparation technology tend to be mature, and the technology plays a positive promoting role in national carbon peak reaching and carbon neutralization targets. Compared with the preparation of methanol from carbon monoxide, the preparation of methanol from carbon dioxide mainly depends on the use of a catalyst and the control of reaction temperature.
The existing catalyst preparation technology can meet the industrial requirement of preparing methanol from carbon dioxide. For example, patent application publication No. CN110975938A discloses a catalyst for preparing methanol by carbon dioxide hydrogenation and a preparation method thereof, wherein a skeleton-modified metal organic skeleton material MIL-101 (Cr) -NH is adopted 2 As a carrier, the shape selection selectivity of the pore channel structure of MIL-101 (Cr) is utilized to improve the selectivity of methanol; meanwhile, the MIL-101 (Cr) has high specific surface area to CO 2 Has high adsorption capacity and effectively improves CO 2 Catalytic selectivity of (3). Chinese patent with publication number CN110833843B discloses a catalyst for synthesizing methanol by carbon dioxide hydrogenation, which takes molybdenum disulfide as a main component of the catalyst for synthesizing methanol by carbon dioxide hydrogenation.
The patent application with publication number CN105622344A discloses a process for preparing methanol from carbon dioxide, which adopts a single-stage reactor and has a hydrogen-to-carbon ratio (H) 2 /CO 2 ) In the range of 2.0 to 3.0, adopting CO 2 Reverse water-steam transformation,Synthetic methanol reaction and gas recycling flow. Patent application publication No. CN113045383A, using a single stage reactor, hydrogen to carbon ratio (H) 2 +CO)/(CO+CO 2 ) Is 3.05 to 3.1, which introduces CO and therefore approaches the traditional methanol manufacturing process. The existing process for preparing methanol from carbon dioxide mostly adopts a first-stage reactor and a cooling separation process, so that the total carbon conversion rate is low, the energy consumption of a device is high, the content of methanol in a product is low, the load of subsequent rectification is large, and the comprehensive energy consumption is high.
Disclosure of Invention
The utility model aims to solve the technical problem that to prior art's current situation, provide a device of improvement carbon dioxide system methanol conversion rate that total carbon conversion is high, device total energy consumption is low.
The utility model provides a technical scheme that above-mentioned technical problem adopted does:
an apparatus for increasing conversion of carbon dioxide to methanol, comprising:
the first reactor is used for preparing methanol from carbon dioxide for reaction; the top of the first reactor is provided with an inlet for inputting raw material gas, and the bottom of the first reactor is provided with an outlet for outputting a first reaction product;
the second reactor is used for further reaction of methanol prepared from carbon dioxide; the top of the second reactor is provided with an inlet for inputting reaction raw materials, and the bottom of the second reactor is provided with an outlet for outputting a second reaction product;
the first gas-gas heat exchanger is connected to the outlet of the first reactor;
the first cooler is connected with the first outlet of the first gas-gas heat exchanger;
the first separator is connected with the downstream of the first cooler and is used for carrying out gas-liquid separation on the first reaction product output by the first reactor; the top outlet of the first separator is connected with the inlet of a first gas-gas heat exchanger, and the second outlet of the first gas-gas heat exchanger is connected with the inlet of a second reactor;
the second gas-gas heat exchanger is connected to the outlet of the second reactor;
the second cooler is connected with a third outlet of the second gas-gas heat exchanger; and
the second separator is connected with the downstream of the second cooler and is used for carrying out gas-liquid separation on a second reaction product output by the second reactor; and the top outlet of the second separator is connected with the inlet of a second gas-gas heat exchanger, and the fourth outlet of the second gas-gas heat exchanger is connected with the inlet of the first reactor.
Preferably, a feeding pipeline is connected to the inlet of the second gas-gas heat exchanger, the gas phase produced at the top of the second separator is input into the feeding pipeline as circulating gas through the first joint, and the fresh synthesis gas is input into the feeding pipeline through the second joint.
Preferably, a return line is connected between the second outlet of the first gas-gas heat exchanger and the inlet of the second reactor, a bypass line is connected between the feed line and the return line, and a valve for controlling the opening of the bypass line according to the temperature is arranged on the bypass line.
This can be seen from the following equation: the preparation of methanol from carbon dioxide is an exothermic reaction, the preparation of methanol from carbon dioxide consumes more hydrogen and generates more water than the traditional preparation of methanol from carbon monoxide, and one water is generated simultaneously when one part of methanol is generated.
CO 2 +3H 2 ≒CH 3 OH+H 2 O
CO+2H 2 ≒CH 3 OH
The utility model discloses directly introduce the second reactor entry with partial fresh gas, reduce the entry temperature of second reactor, improve carbon dioxide and hydrogen partial pressure, be favorable to improving second reactor entry driving force to further improve the interior methanol conversion rate of second reactor.
Preferably, the connection of the bypass line to the feed line is between the first junction and the second junction.
Preferably, the input of the fresh synthesis gas is provided with a first compressor, and the input of the recycle gas is provided with a second compressor.
Preferably, the top of the first reactor is connected with a # 1 steam drum, the bottom of the second reactor is connected with a # 2 steam drum, and the # 1 steam drum and the # 2 steam drum are communicated with each other and provided with a pipeline for inputting boiler water.
The utility model discloses in, set up gas heat exchanger in the middle of first reactor and the second reactor, utilize to export high-temperature gas to preheat second reactor entry gas to first reactor, utilize second reactor export high-temperature gas to preheat first reactor entry gas, the reaction heat has obtained rational utilization.
Compared with the prior art, the utility model has the advantages of: the utility model discloses a two-stage reactor series flow, the steam of the different specifications of by-product simultaneously, the utility model discloses export at first reactor and increase the cooling and divide the liquid device, reduce the mellow wine partial pressure and the water partial pressure of second reactor entry, be favorable to improving second reactor methanol conversion rate, the utility model discloses add stage branch liquid device with carbon dioxide and hydrogen step reaction, be favorable to the maximize to improve the conversion rate of whole device, the utility model discloses gas separation with the reactor unreacted gets into the synthesis reactor recycle, has the advantage of improving carbon dioxide total carbon conversion rate, the utility model discloses introduce the second reactor with fresh synthetic gas through the bypass, when first reactor catalyst activity reduces in the reaction later stage, move to the second reactor after will reacting to guarantee the conversion rate and the output of whole device.
Drawings
Fig. 1 is a process flow diagram of an embodiment of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments.
As shown in fig. 1, the apparatus for increasing the conversion rate of methanol from carbon dioxide in this embodiment includes:
a first reactor 1 for preparing methanol from carbon dioxide; the top of the first reactor 1 is provided with an inlet for inputting raw material gas, and the bottom is provided with an outlet for outputting a first reaction product;
the second reactor 2 is used for preparing methanol from carbon dioxide for reaction; the top of the second reactor 2 is provided with an inlet for inputting reaction raw materials, and the bottom is provided with an outlet for outputting a second reaction product;
a first gas-gas heat exchanger 10 connected to the outlet of the first reactor 1;
a first cooler 100 connected to a first outlet of the first gas-gas heat exchanger 10;
a first separator 01 connected to a downstream of the first cooler 100 for gas-liquid separation of the first reaction product output from the first reactor 1; the top outlet of the first separator 01 is connected with the inlet of a first gas-gas heat exchanger 10, and the second outlet of the first gas-gas heat exchanger 10 is connected with the inlet of the second reactor 2;
a second gas-gas heat exchanger 20 connected to the outlet of the second reactor 2;
the second cooler 200 is connected with a third outlet of the second gas-gas heat exchanger 20; and
a second separator 02 connected to a downstream of the second cooler 200 for gas-liquid separation of the second reaction product output from the second reactor 2; the top outlet of the second separator 02 is connected to the inlet of the second gas-gas heat exchanger 20, and the fourth outlet of the second gas-gas heat exchanger 20 is connected to the inlet of the first reactor 1.
In the above scheme, the inlet of the second gas-gas heat exchanger 20 is connected with a feeding line 201, the gas phase produced at the top of the second separator 02 is input into the feeding line 201 as a circulating gas through a first junction, and the fresh synthesis gas is input into the feeding line 201 through a second junction.
A return line 101 is connected between the second outlet of the first gas-gas heat exchanger 10 and the inlet of the second reactor 2, a bypass line 003 is connected between the feeding line 201 and the return line 101, and a valve 031 for controlling the opening degree according to the temperature is arranged on the bypass line 003. The junction of the bypass line 003 and the feed line 201 is between the first junction and the second junction. The input of the fresh synthesis gas is provided with a first compressor 04 and the input of the recycle gas is provided with a second compressor 05.
As can be seen from the following reaction scheme: the preparation of methanol from carbon dioxide is an exothermic reaction, the preparation of methanol from carbon dioxide consumes more hydrogen and generates more water than the traditional preparation of methanol from carbon monoxide, and one water is generated simultaneously when one part of methanol is generated.
CO 2 +3H 2 ≒CH 3 OH+H 2 O
CO+2H 2 ≒CH 3 OH
In this embodiment, a part of the fresh gas is directly introduced into the inlet of the second reactor 2, so as to reduce the inlet temperature of the second reactor 2, increase the partial pressure of carbon dioxide and hydrogen, and facilitate the improvement of the driving force of the inlet of the second reactor 2, thereby further improving the conversion rate of methanol in the second reactor 2.
In the embodiment, the top of the first reactor 1 is connected with a # 1 steam drum, the bottom of the second reactor 2 is connected with a # 2 steam drum, and the # 1 steam drum and the # 2 steam drum are communicated with each other and are provided with pipelines for inputting boiler water.
Taking a 20-ten-thousand-ton-scale process technology for preparing methanol from carbon dioxide as an example, the method for improving the conversion rate of preparing methanol from carbon dioxide in the embodiment comprises the following steps:
CO 2 and fresh synthesis gas-74100 Nm consisting of 3:1 of hydrogen 3 H, pressurized to 8MpaG, and mixed with the pressurized methanol plant recycle gas 444600Nm 3 After mixing, preheating to 240 ℃ through second gas heat exchange, entering a first-stage reactor, reacting in the presence of a catalyst, generating a methanol synthesis reaction and releasing heat:
CO 2 +3H 2 ≒CH 3 OH+H 2 O
the outlet temperature of the primary reactor is 280 ℃, and CH in the first reaction product 3 OH content 2.6% (moL), water content 2.3% (moL). The first reaction product is cooled to 90 ℃ in a first gas-gas heat exchanger, the liquid fraction is 7 wt%, the first reaction product is fed into a first separator, the first reaction product is separated into a gas phase and a liquid phase in the first separator, the liquid phase comprises 35% (moL) methanol and 63% (moL) water, the gas phase comprises mainly unreacted 11% (moL) carbon dioxide and 86% (moL) hydrogen, and CH in the gas phase is separated 3 The OH content is 1.8 percent (moL), the water content is 0.8 percent (moL), the gas phase at the outlet of the first separator is preheated by a first gas-gas heat exchanger, preheated to 220 ℃, enters a second reactor to continue to react, and a second reaction product is obtained; the outlet temperature of the second reactor is 250 ℃, and CH in the second reactant 3 OH content 3.2% (moL), water content 2.1% (moL), methanol concentration greater than the first reaction product;
the temperature of a reaction product at the outlet of the second reactor is 250 ℃, the reaction product enters a second gas-gas heat exchanger and a downstream cooler, a second reactant is cooled to 40 ℃ after the cooler, the reaction product enters a second separator, and the separated liquid phase contains 58 percent (moL) of methanol and 41 percent (moL) of water;
liquid phase products of the first-stage separator and the second-stage separator are mixed and then enter a downstream rectification system, the methanol content is 49% (moL), the per-pass conversion rate of carbon dioxide of the whole methanol synthesis system is 25%, and the total conversion rate of carbon dioxide is 90%;
in this example, after the second reactant was cooled and separated, the unreacted process gas was circulated into the synthesis system at a circulation ratio of 6, the methanol content in the recycle gas was 0.38% (moL), and a small amount of inert gas was discharged as purge gas.
In this example, the fresh synthesis gas is provided with a bypass line directly entering the inlet of the second reactor, the bypass line is provided with a valve for controlling the opening according to the temperature of the inlet of the second reactor, when the temperature of the inlet of the second reactor is 220 ℃, the valve is in a closed state, and in order to ensure that the temperature of the inlet of the second reactor is stabilized at 220 ℃, the valve flux is about 10 percent of the total amount of the fresh synthesis gas when the temperature is increased by 5 ℃ in operation.
In this embodiment, set up gas heat exchanger in the middle of first reactor and the second reactor, utilize to export high temperature gas to the first reactor and preheat second reactor entry gas, utilize second reactor export high temperature gas to preheat first reactor entry gas, first gas heat exchanger heat load ~38MW, second gas heat exchanger heat load ~22MW, the reaction heat has obtained rational utilization.
Claims (5)
1. The utility model provides an improve device of carbon dioxide system methanol conversion rate which characterized in that includes:
the first reactor is used for preparing methanol from carbon dioxide for reaction; the top of the first reactor is provided with an inlet for inputting raw material gas, and the bottom of the first reactor is provided with an outlet for outputting a first reaction product;
the second reactor is used for preparing methanol from carbon dioxide for reaction; the top of the second reactor is provided with an inlet for inputting reaction raw materials, and the bottom of the second reactor is provided with an outlet for outputting a second reaction product;
the first gas-gas heat exchanger is connected to the outlet of the first reactor;
the first cooler is connected with the first outlet of the first gas-gas heat exchanger;
the first separator is connected with the downstream of the first cooler and is used for carrying out gas-liquid separation on the reaction liquid output by the first reactor; the top outlet of the first separator is connected with the inlet of a first gas-gas heat exchanger, and the second outlet of the first gas-gas heat exchanger is connected with the inlet of a second reactor;
the second gas-gas heat exchanger is connected to the outlet of the second reactor;
the second cooler is connected with a third outlet of the second gas-gas heat exchanger; and
the second separator is connected with the downstream of the second cooler and is used for carrying out gas-liquid separation on the reaction liquid output by the second reactor; the top outlet of the second separator is connected with the inlet of a second gas-gas heat exchanger, and the fourth outlet of the second gas-gas heat exchanger is connected with the inlet of the first reactor;
and the inlet of the second gas-gas heat exchanger is connected with a feeding pipeline, the gas phase produced at the top of the second separator is used as circulating gas and is input into the feeding pipeline through a first joint, and the fresh synthesis gas is input into the feeding pipeline through a second joint.
2. The apparatus for increasing conversion rate of methanol from carbon dioxide according to claim 1, wherein: a return pipeline is connected between the second outlet of the first gas-gas heat exchanger and the inlet of the second reactor, a bypass line is connected between the feeding pipeline and the return pipeline, and a valve used for controlling the opening degree of the bypass line according to the temperature is arranged on the bypass line.
3. The apparatus for increasing conversion rate of methanol from carbon dioxide according to claim 2, wherein: the junction of the bypass line and the feed line is located between the first junction and the second junction.
4. The apparatus for increasing conversion rate of methanol from carbon dioxide according to claim 1, wherein: and a first compressor is arranged at the input part of the fresh synthesis gas, and a second compressor is arranged at the input part of the circulating gas.
5. The apparatus for increasing conversion rate of methanol from carbon dioxide according to any one of claims 1 to 4, wherein: the top of the first reactor is connected with a 1# steam drum, the bottom of the second reactor is connected with a 2# steam drum, and the 1# steam drum and the 2# steam drum are communicated with each other and are provided with pipelines for inputting boiler water.
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| CN202220634350.3U CN218222370U (en) | 2022-03-23 | 2022-03-23 | Device for improving conversion rate of methanol prepared from carbon dioxide |
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| CN202220634350.3U CN218222370U (en) | 2022-03-23 | 2022-03-23 | Device for improving conversion rate of methanol prepared from carbon dioxide |
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