CN115820305A - Device for removing acid gas in synthesis gas - Google Patents
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Abstract
The invention relates to a device for removing acid gas in synthesis gas, which comprises at least two reactors, wherein the gas outlet of one reactor is communicated with the gas inlet of the other reactor, the most upstream reactor is called a first-stage reactor and the most downstream reactor is called a last-stage reactor along the flow path of the synthesis gas, the gas inlet of the first-stage reactor is communicated with a synthesis gas storage tank for storing the synthesis gas, and the gas outlet of the last-stage reactor is communicated with a gas receiver. The reactors of the invention are provided with at least two reactors which are arranged in series, thereby ensuring that the synthesis gas fully reacts with water to fully remove the acid gas and having high removal rate.
Description
Technical Field
The invention relates to the technical field of synthesis gas purification in petrochemical industry, in particular to a device for removing acid gas in synthesis gas.
Background
The energy resources of China are rich, but the innate structure is unbalanced, and the characteristics of rich coal, poor oil and less gas are presented overall, so that the characteristic also determines that the coal is the main primary energy source for economic development of China. The utilization of coal is divided into civil coal and industrial coal, and the industrial coal mainly comprises coal-fired power generation and chemical coal. The coal chemical industry is an important component of carbonization industry, is a heavy chemical industry for producing six basic products of synthetic ammonia, hydrogen, methane, alcohol, oil and fuel gas, and is an important pillar for economic development of China. The most basic process of coal chemical industry is coal gasification, i.e. the conversion of coal into synthesis gas (CO + H) by incomplete combustion 2 ) The synthetic gas is the raw material for preparing synthetic liquid fuel and chemical products.
The synthesis gas produced by coal gasification is rich in acidic components such as carbon dioxide, hydrogen sulfide and the like, and particularly, the content of carbon dioxide in the synthesis gas after the hydrogen-carbon ratio is adjusted by CO transformation is higher. The acid gas in the synthesis gas needs to be removed, otherwise, the acid gas not only can lead to the effective component (CO + H) in the synthesis gas 2 ) The partial pressure is reduced, the volume of a reaction bed layer in the reactor is increased, the organic synthesis catalyst is poisoned and deactivated, or side reactions are generated, and the quality of the product is finally influenced.
At present, the removal of acid gas from synthesis gas mainly comprises a chemical solvent absorption method, a physical-chemical absorption method, a direct oxidation method, a pressure swing adsorption method and a membrane separation method, wherein the most common technology is a low-temperature methanol washing (Rectisol) technology. The technology takes methanol as an acid gas absorption liquid, and utilizes the physical characteristic that the methanol has great solubility to the acid gas at the low temperature of about minus 60 ℃ to selectively absorb and separate CO in the synthesis gas in a sectional manner 2 、H 2 S and various organic sulfur impurities. Although the low-temperature methanol washing (Rectisol) technology has the advantages of large absorption capacity, good selectivity, high purification degree and low operation cost, the process is a foreign patent technology, needs to be introduced from foreign countries and has high cost; the operation temperature is about-60 ℃, so that more heat exchange equipment is needed for effectively recovering energy and reducing energy consumption, and the process flow is complex; the pipeline of the equipment needs low-temperature steel material (3.5 Ni),at present, the processing technology is difficult to master at home, part of equipment needs to be manufactured abroad, the investment of fixed assets is high, and in addition, absorption liquid methanol adopted by the technology has toxicity, is difficult to operate and maintain, and has certain corrosivity on pipeline equipment.
Because part of the acid gas can be subjected to hydration reaction with water, the acid gas can also be removed by the method, the method for removing hydrogen sulfide from natural gas disclosed in the Chinese invention patent application with the patent number of CN201010274051.5 (the publication number of CN 101955828A) converts hydrogen sulfide gas in natural gas into solid hydrate under the conditions of the pressure of 2-10 MPa and the temperature of-15-25 ℃, and the hydrogen sulfide gas is separated from the natural gas and is removed. Mainly comprises the following devices: a. natural gas feed buffer tank (2), b. hydrogen sulfide hydrate tower (5), c. hydrogen sulfide hydrate forming tank (8), including the operating steps of: (1) standing and dehydrating; (2) synthesizing hydrogen sulfide hydrate; (3) forming hydrogen sulfide hydrate; (4) filtering and storing; (5) and outputting the desulfurized natural gas product.
However, only one hydrogen sulfide hydration tower is arranged in the patent, so that sufficient water in the natural gas can not be ensured to generate a hydration reaction, and the removal rate of the acid gas in the natural gas is low; in addition, the hydration reaction needs to be carried out at a lower temperature, which is exothermic, and there is no means for ensuring that the temperature in the hydration tower is lower.
Disclosure of Invention
The invention aims to solve the technical problem of providing a device for removing acid gas in synthesis gas with high removal rate of acid gas in synthesis gas aiming at the current situation of the prior art.
The technical scheme adopted by the invention for solving the technical problems is as follows: a device for removing acid gas in synthesis gas comprises a reactor, wherein the reactor is provided with a gas inlet for inflow of synthesis gas, an aqueous solution inlet for introduction of a water solution, a gas outlet for outflow of synthesis gas and a slurry outlet for outflow of slurry after reaction of synthesis gas and water;
the method is characterized in that: the reactor is provided with at least two adjacent reactors, wherein the gas outlet of one reactor is communicated with the gas inlet of the other reactor, the most upstream reactor is called a first-stage reactor, the most downstream reactor is called a last-stage reactor along the flow path of the synthesis gas, the gas inlet of the first-stage reactor is communicated with a synthesis gas storage tank for storing the synthesis gas, and the gas outlet of the last-stage reactor is communicated with a gas receiver.
The generation of hydrate belongs to an exothermic process, and the low temperature is favorable for forming a cage-shaped structure lattice by the combination of water molecules depending on hydrogen bonds, so that the growth of gas compounds can be promoted. But the special conditions of icing and the like exist when the hydration temperature is lower than the freezing point, the uncertainty exists, the energy consumption is high, the suitable temperature range of the hydration reaction is 273.15-278.85K, the optimal temperature is 273.85K, and in order to ensure that the temperature range exists in the reactor, the device for removing the acid gas in the synthesis gas also comprises a cooler, wherein the cooler is provided with a cooling medium discharge port and a cooling medium recovery port;
and each reactor is provided with a cooling medium inlet for cooling medium to enter and a cooling medium outlet for cooling medium to discharge, in two adjacent reactors, the cooling medium outlet on one reactor is communicated with the cooling medium inlet on the other reactor, the cooling medium discharge port is communicated with the cooling medium inlet on the last reactor, and the cooling medium outlet of the first reactor is communicated with the cooling medium recovery port on the cooler. As the hydration reaction is exothermic reaction, in the last-stage reactor, a large amount of hydrates can be quickly formed, so that the temperature rise amplitude in the last-stage reactor is maximum, and a cooling medium is firstly introduced into the last-stage reactor and then flows to the intermediate reactor and the first-stage reactor in sequence.
In order to ensure that the synthesis gas is cooled before entering the reactor, the temperature of the synthesis gas in the reactor is prevented from being influenced, and further the hydration reaction is influenced, the device for removing the acid gas in the synthesis gas further comprises a heat exchanger, a tube side inlet for the synthesis gas to enter and a tube side outlet for the synthesis gas to flow out are arranged on the heat exchanger, and the tube side outlet is communicated with a gas inlet on the first-stage reactor.
Preferably, a shell-side inlet of the heat exchanger is communicated with a cooling medium outlet of the primary reactor, and a shell-side outlet of the heat exchanger is communicated with a cooling medium recycling port on the cooler. The cooling medium cools the synthesis gas, and the cooling medium cools the synthesis gas, enters the cooler for refrigeration and then flows into the reactor, namely the cooling medium not only controls the temperature in the reactor at a lower temperature, but also can cool the synthesis gas.
The main factors influencing the generation rate of the crystalline hydrate are the strength of hydrogen bonds among water molecules, a surfactant is added into the aqueous solution, ions of the surfactant can enhance the hydrogen bond force among the water molecules, change the liquid microstructure (forming nano-scale micelles), reduce the gas-liquid interfacial tension, increase the solubility and diffusion coefficient of gas in a liquid phase, strengthen the gas-liquid contact on the nano-scale and molecular scale layers, promote the nucleation process of the hydrate, inhibit the coalescence of hydrate crystal grains and reduce the scale of the hydrate particles, so the device for removing the acid gas in the synthetic gas also comprises an aqueous solution preparation tank, a feed inlet for introducing sodium dodecyl sulfate, a water inlet for introducing industrial water and a solution outlet for allowing mixed solution of the sodium dodecyl sulfate and the water to flow out are arranged on the aqueous solution preparation tank, and the solution outlet is communicated with an aqueous solution inlet on each reactor.
The slurry discharged from the reactor is a solid-liquid two-phase mixture, solid-liquid separation is required, the separated solid is gas hydrate, the separated liquid is unreacted water and contains a large number of crystal nuclei of hydration crystals with small particle sizes, the crystal nuclei are important for accelerating the hydration reaction, so each reactor is correspondingly provided with a solid-liquid separation tank, the reactor is provided with a liquid recovery port and a gas recovery port, the solid-liquid separation tank is provided with a slurry inlet, a liquid outlet, a gas discharge port and a gas hydrate outlet, the slurry inlet is communicated with the slurry outlet on the corresponding reactor, the liquid outlet is used for discharging liquid water separated from the slurry, the liquid outlet is communicated with the liquid recovery port on the corresponding reactor, the gas discharge port is used for discharging unreacted synthesis gas in the slurry, and the gas discharge port is communicated with the gas recovery port on the corresponding reactor. The unreacted synthesis gas enters the corresponding reactor, the unreacted synthesis gas in the reactor enters a next-stage reactor together with the unreacted synthesis gas to continue reacting, and the separated liquid water enters and returns to the reactor to continue carrying out hydration reaction.
The separated gas hydrate needs to be further desorbed, materials are fully utilized, the device for desorbing the acid gas in the synthesis gas further comprises a desorption tower, a gas hydrate inlet for introducing the gas hydrate, a hot water inlet for introducing hot water, a liquid outlet for discharging the desorbed liquid and an exhaust port for discharging the desorbed gas are arranged on the desorption tower, and the gas hydrate inlet is communicated with a gas hydrate outlet on the reactor, so that the desorbed acid gas can be recycled. The decomposition method of the gas hydrate includes a chemical reagent method, a pressure reduction method, a hot water injection method, an electromagnetic heating method, a microwave heating method, and the like. The advantages and disadvantages of the comparative methods are shown in the following table.
Analysis of crystalline hydrate by desorption method
The method takes full consideration of various factors such as environmental protection, low investment, simple technology and the like, selects the hot water injection method as the excitation mode for hydrate decomposition, and designs the reaction condition of desorbing and decomposing the crystallized hydrate by the hot water injection method to be 20 ℃ and normal pressure.
The gas hydrate enters a desorption tower to be desorbed at normal temperature and normal pressure, the residual liquid of the desorbed gas is high-activity water which can accelerate the entry of the hydration reaction, and the residual liquid is recycled to the reactor to accelerate the hydration reaction. Therefore, the liquid outlet on the desorption tower is communicated with the aqueous solution inlet on at least one of the reactors.
In the scheme, the number of the desorption towers is consistent with that of the solid-liquid separation tanks, the desorption towers are arranged in a one-to-one correspondence manner, and a gas hydrate outlet on each solid-liquid separation tank is communicated with a gas hydrate inlet on the corresponding desorption tower;
in order to reduce the number of the desorption towers which is less than the number of the solid-liquid separation tanks, the gas hydrate outlets on at least two of the solid-liquid separation tanks which are positioned at the downstream are simultaneously communicated with the gas hydrate inlet on one desorption tower along the flow path of the synthesis gas. H 2 S will complete gas hydration in the first stage reactor, so the gas hydrate separated from the first stage hydration reactor contains H 2 S gas hydrate and CO 2 Gas hydrates, whereas the gas hydrates formed in the downstream reactor are mainly CO 2 Gas hydrate, so the gas hydrate discharged from the solid-liquid separation tank corresponding to the downstream reactor can be introduced into the same desorption tower.
The formation of gas hydrate is a gas-liquid-solid three-phase reaction, and the pressure of the gas has a great influence on the reaction. The hydrate is required to reach a critical pressure in the generation process to initiate the nucleation of the hydrate phase, so the device for removing the acid gas in the synthesis gas also comprises a gas compressor arranged between a gas inlet on the first-stage reactor and the synthesis gas storage device.
Compared with the prior art, the invention has the advantages that: the invention takes water as raw material to lead the water and CO in the synthesis gas 2 、H 2 S and other acidic gases are subjected to hydration reaction to generate ice-like crystal hydrate, the raw material safety is high, the defects of high cost, low reaction temperature and toxicity and corrosivity of absorption liquid of a low-temperature methanol washing technology are overcome, and the acidic gases in the synthesis gas are separated and removed with low investment, low operation cost, high yield and high environmental protection; in addition, the reactors are arranged in series, so that the synthesis gas can be fully reacted with water to fully remove the acid gas, and the removal rate is high.
Drawings
FIG. 1 is a schematic process flow diagram of an embodiment of the present invention.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
As shown in fig. 1, the apparatus for removing acid gas from synthesis gas comprises an aqueous solution preparation tank 1, a reactor, a gas compressor 3, a heat exchanger 4, a cooler 5, a solid-liquid separation tank 6, and a desorption tower 7.
The reactor is provided with a gas inlet 21 for inflow of synthesis gas, an aqueous solution inlet 22 for introduction of water solution, a gas outlet 23 for outflow of synthesis gas, and a slurry outlet 24 for outflow of slurry obtained by reaction of synthesis gas and water.
The reactors include at least two, adjacent two reactors, wherein the gas outlet 23 of one reactor is communicated with the gas inlet 21 of the other reactor, the most upstream reactor is called a first-stage reactor 2a, the most downstream reactor is called a last-stage reactor 2c, and the reactor between the first-stage reactor 2a and the last-stage reactor 2c is called an intermediate reactor 2b along the flow path of the synthesis gas, in this embodiment, the reactors include three, one first-stage reactor 2a, one intermediate reactor 2b, and one last-stage reactor 2c, and the gas and water in the first-stage reactor 2a are generally not completely reacted, so that the three reactors are designed, and in order to not complicate the post-treatment process, the pressure and temperature of the intermediate reactor 2b and the last-stage reactor 2c are the same as those of the first-stage reactor 2a, and the water and the acid gas are substantially completely reacted after the synthesis gas passes through the three reactors, and the acid gas in the synthesis gas is substantially removed. The reactor of this example employed a bubbling bed reactor.
The gas inlet 21 of the first reactor 2a is connected to a syngas storage tank (described in detail below) for storing syngas, and the gas outlet 23 of the last reactor 2c is connected to a gas receiver, which may be a storage tank for storing syngas or a pipeline for transporting syngas to a downstream device, and a first drying tank 20 is disposed therebetween.
The aqueous solution preparation tank 1 is provided with a feed inlet 11 for introducing sodium dodecyl sulfate, a water inlet 12 for entering industrial water and a solution outlet 13 for discharging a mixed solution of the sodium dodecyl sulfate and the industrial water, and the solution outlet 13 is communicated with an aqueous solution inlet 22 on each reactor.
The main factors influencing the generation rate of the crystalline hydrate are the strength of hydrogen bonds among water molecules, a surfactant is added into industrial water, ions of the surfactant can enhance the hydrogen bond force among the water molecules, a liquid microstructure is changed to form nano-scale micelles, the gas-liquid interfacial tension is reduced, the solubility and the diffusion coefficient of gas in a liquid phase are increased, the gas-liquid contact is enhanced on the level of the nano-scale and the molecular scale, the nucleation process of the hydrate is promoted, the coalescence of hydrate grains is inhibited, and the scale of hydrate grains is reduced.
In addition, the industrial water is adopted in the embodiment, and the pressure for generating the gas hydrate is smaller in the common industrial water compared with the pure water because the activity gamma of the industrial water is smaller than that of the gamma which contains almost no ions and the gas hydrate is generated more easily because the industrial water contains a trace amount of metal ions.
The generation of the hydrate belongs to an exothermic process, and the low temperature is favorable for forming a cage-shaped structure lattice by relying on hydrogen bond combination of water molecules, so that the growth of the gas compound can be promoted, but the hydration temperature is lower than the freezing point, so that special conditions such as icing exist, uncertainty exists, and the energy consumption is high, so that the suitable temperature range of the hydration reaction is 273.15K-278.85K, the optimal temperature is 273.85K, and in order to enable the temperature range in the reactor, the cold machine 5 is arranged, and the cold machine 5 is provided with a cooling medium discharge port 51 and a cooling medium recovery port 52.
Each reactor is provided with a cooling medium inlet 25 for cooling medium to enter and a cooling medium outlet 26 for cooling medium to discharge, in two adjacent reactors, the cooling medium outlet 26 on one reactor is communicated with the cooling medium inlet 25 on the other reactor, the cooling medium discharge port 51 is communicated with the cooling medium inlet 25 on the last reactor 2c, and the cooling medium outlet 26 of the first reactor 2a is communicated with the cooling medium recovery port 52 on the cooler 5.
Therefore, the synthesis gas is designed to flow from the first-stage reactor 2a to the last-stage reactor 2c, and the cooling medium flows from the last-stage reactor 2c to the first-stage reactor 2a, so as to balance the driving force of the hydration reaction in the three reactors and ensure the stable running of the hydration reaction in the three reactors; secondly, because the hydration reaction is an exothermic reaction, in the last reactor 2c, a large amount of hydrates can be quickly formed, so that the temperature rise amplitude in the last reactor 2c is the largest, and the cooling medium is firstly introduced into the last reactor 2c and then flows to the intermediate reactor 2b and the first reactor 2a in sequence.
The generation of crystalline hydrate at a gas-liquid interface is a coupling process of mass transfer and heat transfer, the increase of the gas-liquid contact area and the enhancement of mass transfer and heat transfer are main ways for improving the generation rate of the hydrate. Under the same temperature and pressure conditions, the gas-water ratio also has important influence on the formation of gas hydrate, and when the gas quantity is less and the water volume is large, the gas is favorable for generating hydrate, but the operation cost is increased; the gas quantity is large, the water volume is small, the reaction rate is low, and the gas is not favorable for generating hydrate. The selection of a low gas-liquid ratio is an important means for increasing the reaction rate, but the gas-liquid ratio is too low and the operating cost increases. In the industry, the gas-liquid ratio is based on the volume, the gas inlet modes are different, and the optimal gas-liquid ratio is different. The gas-liquid ratio (volume) ranges selected by the invention are as follows: 15-280, the optimal initial gas-liquid volume ratio is about 110, namely the volume ratio of the synthetic gas entering the primary reactor 2a to the aqueous solution is about 110.
Before entering the first-stage reactor 2a, the synthesis gas is compressed by a gas compressor 3, then subjected to heat exchange by a heat exchanger 4, and then enters the first-stage reactor 2a from a gas inlet 21 on the first-stage reactor 2 a.
The method is characterized in that the generation of the gas hydrate is a gas-liquid-solid three-phase reaction, the pressure of the gas has great influence on the reaction, the hydrate can initiate hydration phase nucleation only when reaching a critical pressure in the generation process, the suitable hydration reaction pressure is 1.5 MPa-6.0 MPa, and the optimal hydration reaction pressure is determined to be 3.5MPa, so that the synthesis gas is compressed by a gas compressor 3; in order to avoid the syngas affecting the temperature in the reactor and thus the progress of the hydration reaction, the syngas is cooled by means of a heat exchanger 4.
The heat exchanger 4 is provided with a tube side inlet 41 for synthetic gas to enter and a tube side outlet 42 for synthetic gas to flow out, the gas inlet port of the gas compressor 3 is communicated with a synthetic gas storage device for storing synthetic gas, the gas outlet port of the gas compressor 3 is communicated with the tube side inlet 41, and the tube side outlet 42 is communicated with the gas inlet 21 on the first-stage reactor 2 a.
The shell side inlet 43 of the heat exchanger 4 is communicated with the cooling medium outlet 26 of the primary reactor 2a, and the shell side outlet 44 of the heat exchanger 4 is communicated with the cooling medium recovery port 52 on the cold machine 5. Therefore, the heat exchanger 4 cools the synthesis gas by using the cooling medium of the cooler 5, the synthesis gas is cooled by the cooling medium, enters the cooler 5 for refrigeration and then flows into the reactor, and the cooling medium not only controls the temperature in the reactor at a lower temperature, but also can cool the synthesis gas.
The slurry discharged from the slurry outlet 24 of the reactor is a solid-liquid two-phase mixture, and needs to be subjected to solid-liquid separation, the separated solid is a gas hydrate, the separated liquid is unreacted water, and the unreacted water contains a large amount of crystal nuclei of hydration crystals with small particle sizes, which are important for accelerating the hydration reaction, so that each reactor is correspondingly provided with a solid-liquid separation tank 6, and after the unreacted water is separated out, the unreacted water flows back to the corresponding reactor to continue to participate in the hydration reaction.
The reactor is provided with a liquid recovery port 27 and a gas recovery port 28, the solid-liquid separation tank 6 is provided with a slurry inlet 61, a liquid outlet 62, a gas discharge port 63 and a gas hydrate outlet 64, the slurry inlet 61 is communicated with the slurry outlet 24 on the corresponding reactor, the liquid outlet 62 is used for flowing out liquid water separated from the slurry, and the liquid outlet 62 is communicated with the liquid recovery port 27 on the corresponding reactor.
The gas discharge port 63 is used for discharging the unreacted synthesis gas in the slurry, and the gas discharge port 63 is communicated with the gas recovery port 28 on the corresponding reactor, so that the unreacted synthesis gas enters the corresponding reactor and enters a next-stage reactor together with the unreacted synthesis gas in the reactor for continuous reaction.
The gas hydrate outlet 64 is used for the separated gas hydrate to flow out, and the separated gas hydrate is desorbed by the desorption tower 7, so that the materials are fully utilized.
The desorption tower 7 is provided with a gas hydrate inlet 71 for introducing gas hydrate, a hot water inlet 72 for introducing hot water, a liquid outlet 73 for discharging desorbed liquid and an exhaust port 74 for discharging desorbed gas, the gas hydrate inlet 71 is communicated with the gas hydrate outlet 64 on the reactor so as to allow the gas hydrate to enter the desorption tower 7, the gas hydrate enters the desorption tower 7 for desorption at normal temperature and normal pressure, the residual liquid after desorption of the gas is high-activity water which can accelerate the entry of hydration reaction and is circulated back to the hydration reactor for accelerating the hydration reaction. Therefore, the liquid outlet 73 on the desorption tower 7 is communicated with the aqueous solution inlet 22 on at least one of the reactors, in this embodiment, the liquid outlet 73 on the desorption tower 7 is communicated with the water inlet 12 of the aqueous solution preparation tank 1, so that the liquid outlet 73 on the desorption tower 7 is communicated with the aqueous solution inlets 22 on all the reactors.
A second drying tank 75 is provided downstream of the exhaust port 74 of the desorption tower 7 so that the desorbed acid gas can be recycled.
The number of the desorption towers 7 is less than that of the solid-liquid separation tanks 6, and the gas hydrate outlets 64 on at least two of the solid-liquid separation tanks 6 located downstream are simultaneously communicated with the gas hydrate inlet 71 on one desorption tower 7 along the flow path of the synthesis gas. In this embodiment, there are two desorbers 7, one desorber 7 for the first-stage reactor 2a, and one desorber 7 for the intermediate reactor 2b and the last-stage reactor 2c, because H 2 S in the first stage reactor 2a will first complete gas hydration, so the gas hydrate separated from the solid-liquid separation tank 5 corresponding to the first stage reactor 2a contains H 2 S gas hydrate and CO 2 Gas hydrates, whereas the gas hydrates formed in the intermediate reactor 2b and the final reactor 2c are mainly CO 2 Gas hydrates, so the gas hydrates discharged from the solid-liquid separation tanks 6 corresponding to the intermediate reactor 2b and the final reactor 2c can be introduced into the same desorption tower 7.
Of course, the number of the desorption towers 7 may be the same as the number of the solid-liquid separation tanks 6 and may be arranged in one-to-one correspondence, and the gas hydrate outlet 64 of each solid-liquid separation tank 6 is communicated with the gas hydrate inlet 71 of the corresponding desorption tower 7.
The working process of the device for removing acid gas in synthesis gas in the embodiment is as follows:
the cooler 5 works, the cooling medium is discharged from the cooling medium discharge port 51, then is sent into the final reactor 2c through the cooling medium inlet 25 of the final reactor 2c, then sequentially flows into the intermediate reactor 2b and the primary reactor 2a through the cooling medium outlet 26 of the final reactor 2c, finally flows out of the cooling medium outlet 26 of the primary reactor 2a, flows into the cooling medium recovery port 52 on the cooler 5 through the heat exchanger 4, a circulating closed loop is formed, and the temperature of each device is controlled to be about 273.85K.
Industrial water and sodium dodecyl sulfate are added into an aqueous solution preparation tank 1 to prepare an aqueous solution containing 300mg/L of sodium dodecyl sulfate, the aqueous solution is respectively sent into a first-stage reactor 2a, an intermediate reactor 2b and a last-stage reactor 2c through an aqueous solution inlet 22 on the reactors, and the temperature is reduced under the action of a cooling medium.
The synthesis gas after CO conversion and hydrogen-carbon ratio adjustment is pressurized to 3.5MPa by a gas compressor 3, enters a heat exchanger 4 and is cooled to 273.85K, then enters a primary reactor 2a from the lower part of the primary reactor 2a through a gas inlet 21, and is subjected to hydration reaction with an aqueous solution with the temperature of 273.85K in the reactor under the pressure of 3.5MPa to generate an ice-like gas hydrate crystal, and the generated gas hydrate crystal moves upwards along with bubbles and floats on the upper part of a liquid level and enters a solid-liquid separation tank 6 corresponding to the primary reactor 2a along with a part of liquid.
The liquid water separated from the solid-liquid separation tank 6 returns to the primary reactor 2a through the liquid recovery port 27 to continue the reaction; the gas hydrate separated from the solid-liquid separation tank 6 is sent into a corresponding desorption tower 7 for desorption; the gas escaping from the solid-liquid separation tank 6 returns to the primary reactor 2a through the gas recovery port 28, and enters the intermediate reactor 2b together with the unreacted synthesis gas in the primary reactor 2a to continue the hydration reaction.
The gas hydrate crystals generated in the intermediate reactor 2b float upwards to the liquid level, form solid-liquid slurry with part of the liquid, enter the solid-liquid separation tank 6 corresponding to the intermediate reactor 2b from the slurry outlet 24 for solid-liquid separation, and the separated liquid returns to the intermediate reactor 2b for continuous reaction; the separated solid is sent to a desorption tower 7 corresponding to the intermediate reactor 2b for desorption; the escaped gas is returned to the intermediate reactor 2b, and enters the final reactor 2c together with the unreacted synthesis gas in the intermediate reactor 2b to continue the hydration reaction.
The gas hydrate crystals generated in the last reactor 2c float upwards to the liquid level, form solid-liquid slurry with part of the liquid, enter a solid-liquid separation tank 6 corresponding to the last reactor 2c from a slurry outlet 24 for solid-liquid separation, and the separated liquid returns to the last reactor 2c for continuous reaction; the separated solid is sent to a corresponding desorption tower 7 for desorption; the escaped gas returns to the last reactor 2c, and enters the first drying tank 20 together with the unreacted synthesis gas in the last reactor 2c for drying and dehydration, and the obtained synthesis gas is the synthesis gas after the acid gas is removed.
The desorption process in the desorption tower 7 is as follows: the gas hydrate discharged from the solid-liquid separation tank 6 is sent to the corresponding desorption tower 7 and is scattered on the inclined plate in the desorption tower 7, and hot water introduced from the hot water inlet 72 at the upper part of the desorption tower 7 is sprayed on the inclined plate to raise the temperature of the hydrate on the inclined plate and desorb the gas hydrate at normal pressure and at 20 ℃.
The residual liquid water after the gas is desorbed is high-activity water, and flows out from the liquid outlet 73 to circularly enter the aqueous solution preparation tank 1 for recycling;
the desorbed gas mixture is discharged from an exhaust port 74 at the top of the desorption tower 7, enters a second drying tank 75 for dehydration, and the gas discharged from the exhaust port 74 of the desorption tower 7 corresponding to the first-stage reactor 2a is CO 2 And H 2 S mixed gas, after sulfur is recovered, CO can be comprehensively utilized 2 The gas discharged from the gas outlet 74 of the desorption tower 7 corresponding to the intermediate reactor 2b and the final reactor 2c is CO 2 The gas, CO which after sulphur recovery may be discharged from a stripper 7 corresponding to the primary reactor 2a 2 And (4) utilizing the components together.
The present embodiment is directed to carbon monoxide shift tuningCO in synthetic gas after hydrogen-carbon ratio 2 、H 2 The carbon monoxide in the synthesis gas produced by coal gasification is far higher than that of hydrogen, and is far different from the hydrogen-carbon ratio required by organic synthesis such as FT synthesis, and the hydrogen-carbon ratio needs to be adjusted by adopting CO conversion reaction. The following table shows that the hydrogen-carbon ratio of the synthesis gas obtained by gasification of a certain coal gasification technology is adjusted to 2 through CO shift reaction: synthesis gas composition after 1.
As can be seen from the above table, the acid gas in the syngas is composed of CO 2 、H 2 5363 and three gases of S, COS, wherein COS is an inorganic carbon compound similar to carbon disulfide and carbon dioxide in structure, and has active property and minimum content of only 0.0165mol% of the total amount of synthesis gas. Literature data indicate that COS is readily soluble in water, 54ml per 100ml of water at 20 ℃, and in addition, in the presence of water and steam, can react with COS and be slowly converted into CO 2 And H 2 And S. When the method is used for removing the acid gas by using the hydration reaction, part of COS in the synthesis gas can be dissolved in water, and part of COS can react with the water to be converted into CO 2 And H 2 S, the content of COS in the synthesis gas is very small, so the removal of the COS is not particularly considered when the acid gas is removed.
Claims (10)
1. A device for removing acid gas in synthesis gas comprises a reactor, wherein the reactor is provided with a gas inlet (21) for inflow of synthesis gas, a water solution inlet (22) for introducing water solution, a gas outlet (23) for outflow of synthesis gas and a slurry outlet (24) for outflow of slurry after reaction of synthesis gas and water;
the method is characterized in that: the reactor has at least two adjacent reactors, wherein the gas outlet (23) of one reactor is communicated with the gas inlet (21) of the other reactor, the most upstream reactor is called a first-stage reactor (2 a) and the most downstream reactor is called a last-stage reactor (2 c) along the flow path of the synthesis gas, the gas inlet (21) on the first-stage reactor (2 a) is communicated with a synthesis gas storage tank for storing the synthesis gas, and the gas outlet (23) on the last-stage reactor (2 c) is communicated with a gas receiver.
2. The apparatus for removing acid gases from synthesis gas according to claim 1, wherein: the device also comprises a cold machine (5), wherein the cold machine (5) is provided with a cooling medium discharge port (51) and a cooling medium recovery port (52);
each reactor is provided with a cooling medium inlet (25) for cooling medium to enter and a cooling medium outlet (26) for cooling medium to discharge, in two adjacent reactors, the cooling medium outlet (26) on one reactor is communicated with the cooling medium inlet (25) on the other reactor, the cooling medium discharge port (51) is communicated with the cooling medium inlet (25) on the last reactor (2 c), and the cooling medium outlet (26) of the first reactor (2 a) is communicated with the cooling medium recovery port (52) on the cooler (5).
3. The apparatus for removing acid gases in synthesis gas according to claim 2, wherein: the reactor also comprises a heat exchanger (4), wherein a tube side inlet (41) for the synthesis gas to enter and a tube side outlet (42) for the synthesis gas to flow out are arranged on the heat exchanger (4), and the tube side outlet (42) is communicated with a gas inlet (21) on the primary reactor (2 a).
4. The apparatus for removing acid gases in synthesis gas according to claim 3, wherein: the shell side inlet (43) of the heat exchanger (4) is communicated with the cooling medium outlet (26) of the primary reactor (2 a), and the shell side outlet (44) of the heat exchanger (4) is communicated with the cooling medium recovery port (52) on the cooler (5).
5. The apparatus for removing acid gases in synthesis gas according to any one of claims 1 to 4, wherein: the reactor is characterized by further comprising an aqueous solution preparation tank (1), wherein a feed inlet (11) for introducing the lauryl sodium sulfate, a water inlet (12) for water to enter and a solution outlet (13) for allowing a mixed solution of the lauryl sodium sulfate and water to flow out are formed in the aqueous solution preparation tank (1), and the solution outlet (13) is communicated with an aqueous solution inlet (22) on each reactor.
6. The apparatus for removing acid gases from synthesis gas according to any one of claims 1 to 4, wherein: each reactor is correspondingly provided with a solid-liquid separation tank (6), the reactor is provided with a liquid recovery port (27) and a gas recovery port (28), the solid-liquid separation tank (6) is provided with a slurry inlet (61), a liquid outlet (62), a gas discharge port (63) and a gas hydrate outlet (64), the slurry inlet (61) is communicated with the slurry outlet (24) on the corresponding reactor, the liquid outlet (62) is used for discharging liquid water separated from slurry, the liquid outlet (62) is communicated with the liquid recovery port (27) on the corresponding reactor, the gas discharge port (63) is used for discharging unreacted synthesis gas in the slurry, and the gas discharge port (63) is communicated with the gas recovery port (28) on the corresponding reactor.
7. The apparatus for removing acid gases from synthesis gas according to claim 6, wherein: the desorption tower (7) is provided with a gas hydrate inlet (71) for introducing gas hydrate, a hot water inlet (72) for introducing hot water, a liquid outlet (73) for discharging desorbed liquid and an exhaust port (74) for discharging desorbed gas, and the gas hydrate inlet (71) is communicated with a gas hydrate outlet (64) on the reactor.
8. The apparatus for removing acid gases in synthesis gas according to claim 7, wherein: a liquid outlet (73) on the desorption tower (7) is communicated with the aqueous solution inlet (22) on at least one reactor.
9. The apparatus for removing acid gases from synthesis gas according to claim 7, wherein: the number of the desorption towers (7) is consistent with that of the solid-liquid separation tanks (6) and the desorption towers are arranged in a one-to-one correspondence manner, and a gas hydrate outlet (64) on each solid-liquid separation tank (6) is communicated with a gas hydrate inlet (71) on the corresponding desorption tower (7); or the number of the desorption towers (7) is less than that of the solid-liquid separation tanks (6), and the gas hydrate outlets (64) on at least two of the solid-liquid separation tanks (6) positioned at the downstream are simultaneously communicated with the gas hydrate inlet (71) on one desorption tower (7) along the flow path of the synthesis gas.
10. The apparatus for removing acid gases from synthesis gas according to claim 7, wherein: also comprises a gas compressor (3) arranged between a gas inlet (21) on the primary reactor (2 a) and the synthesis gas storage.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211674072.5A CN115820305A (en) | 2022-12-26 | 2022-12-26 | Device for removing acid gas in synthesis gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211674072.5A CN115820305A (en) | 2022-12-26 | 2022-12-26 | Device for removing acid gas in synthesis gas |
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| Publication Number | Publication Date |
|---|---|
| CN115820305A true CN115820305A (en) | 2023-03-21 |
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|---|---|---|---|
| CN202211674072.5A Pending CN115820305A (en) | 2022-12-26 | 2022-12-26 | Device for removing acid gas in synthesis gas |
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| Country | Link |
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| CN (1) | CN115820305A (en) |
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- 2022-12-26 CN CN202211674072.5A patent/CN115820305A/en active Pending
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