CN107216907B - Method and system for producing gasoline from biomass synthesis gas through dimethyl ether - Google Patents
Method and system for producing gasoline from biomass synthesis gas through dimethyl ether Download PDFInfo
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
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- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/334—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing molecular sieve catalysts
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
- C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/54—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed
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Abstract
The invention discloses a method and a system for producing gasoline by dimethyl ether from biomass synthesis gas. The method comprises the following steps: step (1), biomass synthesis gas and CO from step (3) 2 Mixing with unreacted biomass synthesis gas, and then entering a decarbonization device to remove CO 2 (ii) a Step (2) CO removal 2 The subsequent gas is subjected to one-step dimethyl ether synthesis reaction; and (3) introducing the gas after the reaction into a high-pressure water washing separation tower, and separating CO 2 And the unreacted biomass synthesis gas flows out through a gas phase outlet at the top of the tower and returns to the step (1), the aqueous solution at the bottom of the tower enters an analytical tower, and dimethyl ether and CO are evaporated out by decompression 2 (ii) a Step (4), dimethyl ether and CO 2 Mixing with the non-condensable gas returned in the step (5), and reacting in a second-stage reactor; and (5) condensing and separating the product after the reaction is finished to obtain a liquid-phase crude gasoline product, and returning the non-condensable gas to the step (4) through a gas-phase outlet at the top of the three-phase separator.
Description
Technical Field
The invention relates to the technical field of gasoline indirect synthesis by using synthesis gas, in particular to a method and a system for producing gasoline by using biomass synthesis gas through dimethyl ether.
Background
China is seriously lack of petroleum resources and depends on imports. Although the indirect liquefaction technology for synthesizing oil products by using coal-based synthesis gas as a gas source is relatively mature and is commercially produced, one of the negative effects of coal as a fossil fuel is serious environmental pollution and low energy efficiency. The biomass is the only renewable energy which can be directly converted into the liquid fuel, not only can the dependence on limited petroleum resources be eliminated, but also the emission of atmospheric pollutants and greenhouse gases can be greatly reduced, and the biomass fuel has important significance for the sustainable development of the economic society of China.
The methanol/dimethyl ether synthesis gasoline technology (commonly known as MTG technology) has been studied for over 40 years for synthesis gas. In the seventies of the 20 th century, the company Mobile in the united states successfully developed a technology for producing gasoline by converting methanol with ZSM-5 as a catalyst, and applied for a plurality of patents, such as: US3931349. The process adopts two-stage conversion, wherein the first stage is that methanol is dehydrated to prepare dimethyl ether, and then the generated mixture of dimethyl ether, methanol and water enters a two-stage reactor to generate products such as gasoline, liquefied gas and the like under the action of a molecular sieve catalyst. CN1923770A reports a process for preparing hydrocarbon products from methanol in shanxi coal chemical institute of chinese academy of sciences by one-step method. The process directly converts raw material methanol into a mixture of hydrocarbon products on a zeolite molecular sieve catalyst after the raw material methanol is gasified. The synthesis process based on methanol as an intermediate product has the advantages that the single-pass conversion rate of methanol synthesized by synthesis gas is not more than 15 percent due to thermodynamic limitation, so a large amount of unreacted synthesis gas needs to be returned to a methanol synthesis reactor with a large circulation ratio, and the equipment investment and the operation energy consumption of a compressor are greatly increased.
The technology for directly synthesizing gasoline by dimethyl ether follows the following reaction equations (1) - (2), and the intermediate product in the process is dimethyl ether without methanol. Such as: the patent CN101940934A develops a high-efficiency catalyst for preparing dimethyl ether by a synthesis gas one-step method; patent CN103788980A further researches and develops a process for synthesizing gasoline by one-step method of dimethyl ether from synthesis gas based on the catalyst. Compared with MTG using methanol as intermediate, the technology is used for synthesizing gas H 2 The requirement for the/CO molar ratio is reduced from 2. The thermodynamic limit of methanol is broken through by reaction equilibrium, and the conversion rate of CO per pass is obviously improved compared with that of MTG technology taking methanol as an intermediate.
Compared with coal-based synthesis gas, the synthesis gas prepared by pure oxygen gasification of biomass has the following characteristics: (1) H 2 a/CO of about 1; (2) Inert components of synthesis gas, e.g. CO 2 The content of (A) is higher; (3) the gas contains tar and other impurities. Such a combinationAfter the formed gas is purified, the formed gas can be directly synthesized into gasoline by dimethyl ether according to the stoichiometric ratio of the one-step dimethyl ether synthesis reaction (1) without conversion reaction modulation, the thermodynamic path design is more reasonable, the process route is more simplified, the equipment investment and the operation cost are saved, and the method has wide application and development prospects.
However, CO in Biomass syngas 2 High content (18-22 vol%), and CO associated with dimethyl ether production 2 The by-products allow the effective feed gas in the above reactions (1) and (2) to be greatly diluted. In patent CN103788980A, a large amount of CO 2 The unreacted synthesis gas enters a two-stage gasoline synthesis reactor along with the raw material dimethyl ether; in a three-phase separator, CO 2 And the unreacted synthesis gas and low-carbon hydrocarbons (mainly C1-C2 and a small amount of C3) generated by the gasoline synthesis reaction are separated together and enter the circulating gas, and the circulating gas is returned to the first section of dimethyl ether synthesizer for decarburization. Apparently, a large amount of CO 2 Not only greatly dilutes the reaction raw material gas, but also CO 2 The accumulation and circulation of (c) also greatly increases the power consumption of the compressor. Meanwhile, the circulation process of returning the two-section outlet to the first section is not beneficial to the independent operation and control optimization of each section of reactor, and is easy to cause the mutual influence and the adjustment lag of the two sections of reactors.
Accordingly, there is a need for improvements and developments in the art.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a method and a system for producing gasoline by using biomass synthesis gas through dimethyl ether, and aims to solve the problem of biomass synthesis gas H 2 Molar ratio of 1/CO 2 The content is higher, which causes the problems of low conversion rate of raw materials and large energy consumption.
The technical scheme of the invention is as follows:
a method for producing gasoline by biomass synthesis gas through dimethyl ether comprises the following steps:
step (1), compressing and boosting the biomass synthesis gas and the CO from the step (3) 2 Mixing with unreacted biomass synthesis gas, and then entering a decarbonization device to remove CO 2 ；
Step (2) removing CO 2 The gas enters a first-stage reactor to carry out a one-step dimethyl ether synthesis reaction;
and (3) introducing the gas after the reaction of the first-stage reactor into a high-pressure water washing separation tower, and separating CO 2 And (2) the unreacted biomass synthesis gas flows out from a gas phase outlet at the top of the high-pressure washing separation tower and returns to the step (1), the water solution at the bottom of the high-pressure washing separation tower enters an analytical tower, and dimethyl ether and CO are evaporated out by decompression 2 ；
Step (4), dimethyl ether and CO 2 Mixing with the non-condensable gas returned in the step (5), and reacting in a second-stage reactor;
and (5) feeding the product after the reaction of the second-stage reactor into a three-phase separator, condensing and separating to obtain a liquid-phase crude gasoline product, and returning the non-condensable gas to the step (4) through a gas-phase outlet at the top of the three-phase separator.
The method for producing the gasoline by the biomass synthesis gas through the dimethyl ether comprises the step (1), wherein the biomass synthesis gas is from biomass gasification, and H in the biomass synthesis gas 2 The molar ratio to CO is 0.7-1.3.
The method for producing the gasoline by the biomass synthesis gas through the dimethyl ether comprises the step (1), wherein in the step (1), the biomass synthesis gas is compressed and pressurized to 2.5-5.0MPa.
The method for producing gasoline by dimethyl ether from biomass synthesis gas comprises the step (1) of removing CO 2 First, CO in Biomass Synthesis gas 2 The volume concentration is 18-22%.
The method for producing gasoline by dimethyl ether from biomass synthesis gas comprises the step (1) of removing CO 2 After then, CO 2 The volume concentration is less than or equal to 5 percent.
The method for producing the gasoline by the biomass synthesis gas through the dimethyl ether comprises the following step (2), wherein in the step (2), the first-stage reactor is a tubular reactor, the pressure of the first-stage reactor is 2.5-5.0MPa, the temperature of the first-stage reactor is 210-280 ℃, and the gas volume space velocity is 500-3000h -1 。
The method for producing the gasoline by the biomass synthesis gas through the dimethyl ether comprises the following steps of (3), wherein in the step (3), the pressure of a high-pressure washing separation tower is 2.5-5.0MPa, and the temperature of the top of the high-pressure washing separation tower is 10-40 ℃; the pressure of the desorption tower is 1.0-2.5MPa, and the temperature of the bottom of the desorption tower is 190-240 ℃.
The method for producing the gasoline by the biomass synthesis gas through the dimethyl ether comprises the step (3), wherein the mass concentration of the dimethyl ether in the outlet gas at the top of the high-pressure water washing separation tower is less than or equal to 1%.
The method for producing the gasoline by the biomass synthesis gas through the dimethyl ether comprises the step (4), wherein the second-stage reactor is a fixed bed reactor, the temperature of the second-stage reactor is 320-490 ℃, the pressure of the second-stage reactor is 1.0-2.5MPa, and the gas volume space velocity is 800-2500h -1 。
The utility model provides a system for biomass synthesis gas produces petrol through dimethyl ether, wherein, including decarbonization device, one section reactor, high pressure washing knockout tower, analytic tower, two-stage process reactor and the three-phase separator who connects gradually, the gaseous phase export and the decarbonization device of high pressure washing knockout tower top are connected, and the gaseous phase export and the two-stage process reactor on three-phase separator top are connected.
Has the beneficial effects that: the invention aims at biomass synthesis gas CO 2 The characteristic of high content fully utilizes the pressure reduction process from the first section to the second section, and most of CO is simply and effectively separated from the outlet gas of the first section through a high-pressure water-washing separator and a desorption tower 2 And unreacted biomass synthesis gas, and the separated gas is mixed with fresh biomass synthesis gas for centralized decarburization, which is beneficial to CO 2 The concentrated capture and recovery of the reaction can also obviously improve the inlet H of the first-stage reactor 2 And the concentration of CO, thereby greatly improving the conversion rate of raw materials, saving the energy consumption of gas compression circulation and reducing the cost.
Drawings
Fig. 1 is a schematic structural diagram of a system for producing gasoline from biomass synthesis gas through dimethyl ether according to a preferred embodiment of the present invention.
Detailed Description
The invention provides a method and a system for producing gasoline by biomass synthesis gas through dimethyl ether, and the invention is further described in detail below in order to make the purpose, the technical scheme and the effect of the invention clearer and more clear. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
Referring to fig. 1, fig. 1 is a schematic structural diagram of a preferred embodiment of a system for producing gasoline from biomass synthesis gas through dimethyl ether according to the present invention, and as shown in the figure, the system includes a decarbonization device 1, a first-stage reactor 2, a high-pressure water washing separation tower 3, a desorption tower 4, a second-stage reactor 5, and a three-phase separator 6, which are connected in sequence, wherein a gas phase outlet at the top of the high-pressure water washing separation tower is connected to the decarbonization device 1, and a gas phase outlet at the top of the three-phase separator is connected to the second-stage reactor 5.
The invention aims at biomass synthesis gas CO 2 The characteristic of high content makes full use of the depressurization process from one section to two sections, and most of CO is simply and effectively separated from the outlet gas of the first section through a high-pressure water-washing separator and a desorption tower 2 And unreacted biomass synthesis gas, and the separated gas is mixed with fresh biomass synthesis gas for centralized decarburization, which is beneficial to CO 2 The concentrated capture and recovery of the reaction can also obviously improve the inlet H of the first-stage reactor 2 And the concentration of CO, thereby greatly improving the conversion rate of raw materials, saving the energy consumption of gas compression circulation and reducing the cost.
Referring to fig. 1, a preferred embodiment of the method for producing gasoline from biomass synthesis gas by dimethyl ether according to the present invention comprises:
step (1), compressing and boosting the biomass synthesis gas and the CO from the step (3) 2 Mixing with the unreacted biomass synthesis gas, and then entering a decarbonization device 1 to remove CO 2 。
In the step (1), purified biomass synthesis gas is introduced, the biomass synthesis gas is derived from biomass gasification, and H in the biomass synthesis gas 2 The molar ratio to CO is 0.7-1.3. The biomass synthesis gas is selected in the invention because of the H of the biomass synthesis gas 2 The molar ratio of the catalyst to CO is in accordance with the stoichiometric ratio H of the one-step method dimethyl ether reaction 2 CO =1, without modulation by shift reaction, the biomass synthesis gas is directly pressurized to 2.5-5.0MPa by a compressor and then mixed with CO returned from the step (3) 2 Mixing with unreacted synthesis gas, introducingDecarbonizing device for removing high-content CO in mixed gas 2 Removal of CO 2 And (4) collecting or recovering. Preferably, the decarbonization device can be used for treating CO by mature processes such as low-temperature methanol washing, hot potash process and the like 2 Is subjected to CO removal 2 While simultaneously desulfurizing and recovering CO 2 Can be stored in a centralized way.
CO removal 2 First, CO in Biomass syngas 2 18-22% volume concentration of CO 2 The content is high. Removal of CO 2 Then, CO in the mixed gas can be ensured 2 Volume concentration is less than or equal to 5 percent, H 2 The effective concentration of CO is greatly improved, and the reaction conversion is facilitated.
Specifically, before the step (1), the method further comprises: respectively loading one-step dimethyl ether composite catalyst (for catalyzing one-step dimethyl ether synthesis reaction) and modified ZSM-5 catalyst (for catalyzing gasoline synthesis reaction) into a first-stage reactor 2 and a second-stage reactor 5, and introducing H at normal pressure 2 And N 2 The mixed gas reduces the one-step dimethyl ether composite catalyst.
Step (2) removing CO 2 The gas enters a first-stage reactor 2 to carry out a one-step dimethyl ether synthesis reaction.
In the step (2), CO is removed 2 The gas enters a preheater through a flowmeter to be heated to 190-210 ℃, and then enters a first-stage reactor 2, the first-stage reactor is preferably a tubular reactor, the pressure of the first-stage reactor is 2.5-5.0MPa, the temperature of the first-stage reactor is 210-280 ℃, and the gas volume space velocity is 500-3000h -1 . Removal of CO 2 The gas after the reaction is subjected to dimethyl ether synthesis reaction on a catalyst (namely a substance obtained by reducing the dimethyl ether composite catalyst by the one-step method), the single-pass conversion rate of CO can reach 72-80%, and the product does not contain methanol.
The gas after the reaction of the first-stage reactor 2 in the step (3) enters a high-pressure water washing separation tower 3, and the separated CO 2 And the unreacted synthesis gas flows out through a gas phase outlet at the top of the high-pressure washing separation tower and returns to the step (1), the water solution at the bottom of the high-pressure washing separation tower enters an analytical tower 4, and dimethyl ether and CO are evaporated out by decompression 2 。
In the step (3), after the dimethyl ether synthesis reaction (as in the above reaction equation (1)) is performed in one step, the outlet gas of the first stage reactor contains a large amount of CO associated with dimethyl ether 2 The gas at the outlet of the first stage reactor is cooled to 20-40 ℃ after heat exchange, and then enters a high-pressure water-washing separation tower 3 for separation. Controlling the pressure at the top of the high-pressure washing separation tower to be 2.5-5.0MPa, and the temperature at the top of the high-pressure washing separation tower to be 10-40 ℃, and ensuring that the mass concentration of dimethyl ether in the outlet gas at the top of the high-pressure washing separation tower is less than or equal to 1%. Most of the CO not dissolved in water 2 And unreacted synthesis gas flows out through a gas phase outlet at the top of the high-pressure water washing separation tower, and the biomass synthesis gas contains methane, so that the outlet gas needs to be slightly relaxed, see a relaxed gas a in figure 1, and the heat value of the relaxed gas a is about 10-20MJ/Nm 3 And (3) the biomass gas can be independently stored and reused as fuel gas, and most of the fuel gas is pressurized by a compressor and circularly returned to the step (2) to be mixed with the fresh biomass synthesis gas, and the mixture enters a decarburization device for decarburization. Washing with water, washing with water at the bottom of the high-pressure water-washing separation tower, introducing into a desorption tower 4, decompressing, heating to evaporate dissolved dimethyl ether and part of CO 2 . Preferably, the pressure of the desorption tower is controlled to be 1.0-2.5MPa, the temperature of the bottom of the desorption tower is 190-240 ℃, the heat can be obtained by system recovery, and the water desorbed from the bottom of the desorption tower is cooled to normal temperature and can be returned to the high-pressure washing separation tower for recycling.
The invention aims at biomass synthesis gas CO 2 The characteristic of high content fully utilizes the pressure reduction process from the first section to the second section, and most of CO is simply and effectively separated from the outlet gas of the first section through a high-pressure water-washing separator and a desorption tower 2 And unreacted biomass synthesis gas, and the separated gas is mixed with fresh biomass synthesis gas for centralized decarburization, which is beneficial to CO 2 Can also obviously improve the inlet H of the first-stage reactor 2 And the concentration of CO.
Step (4), dimethyl ether and CO 2 Mixing with the non-condensable gas returned in the step (5), and reacting in a second-stage reactor 5;
in the step (4), the concentration of dimethyl ether in the gas phase outlet at the top of the desorption tower is shownIs remarkably improved and does not contain unreacted biomass synthesis gas, dimethyl ether and a small part of CO 2 And (3) mixing the gas with the non-condensable gas returned from the step (5), then entering a preheater to exchange heat with gas at a gas phase outlet of the gasoline synthesis reactor, and entering a secondary reactor 5 to react when the heat exchange temperature is 310-350 ℃. Preferably, the second-stage reactor is a fixed bed reactor, in order to avoid bed temperature runaway and catalyst life reduction caused by reaction heat release, the temperature of the second-stage reactor is controlled to be 320-490 ℃ by adjusting the circulation ratio, the pressure of the second-stage reactor is 1.0-2.5MPa, and the gas volume space velocity is 800-2500h -1 。
And (5) feeding the product after the reaction in the second-stage reactor 5 into a three-phase separator 6, condensing and separating to obtain a liquid-phase crude gasoline product, and returning the non-condensable gas to the step (4) through a gas-phase outlet at the top of the three-phase separator.
In the step (5), the product after the reaction in the second-stage reactor 5 is cooled to below 40 ℃ through heat exchange, then enters a three-phase separator 6, is condensed and separated to obtain a liquid-phase crude gasoline product, and part of the separated non-condensable gas is discharged as purge gas b (see figure 1) to maintain the balance of the system, wherein the purge gas b contains low-carbon hydrocarbon and has high heat value of 40-50MJ/Nm 3 It can be stored separately and reused as fuel gas. Most of the non-condensable gas is used as circulating gas, is compressed by a compressor and then returns to the step (5) to be mixed with gas phase outlet gas at the top of the desorption tower. The bottom of the three-phase separator 6 mainly separates water.
Compared with the prior art, the invention has the following obvious advantages:
1) Fully utilizes the biomass synthesis gas H 2 The mol ratio of/CO is in accordance with the stoichiometric ratio H of the one-step method for synthesizing dimethyl ether (see the reaction (1) above) 2 The process route for producing the gasoline by the synthesis gas through the dimethyl ether by the one-step method is designed, the synthesis gas does not need to be modulated by a shift reaction, and the process flow is simplified.
2) Aiming at biomass synthesis gas CO 2 The characteristic of high content makes full use of the pressure reduction process from one section to two sections, and the high-pressure water washing separator and the analysis tower are used for simply and effectively discharging from the first sectionSeparating most of CO from gas 2 And unreacted synthesis gas, and the separated gas is mixed with fresh biomass synthesis gas for centralized decarburization, which is beneficial to CO 2 The concentrated capture and recovery of the reaction can also obviously improve the inlet H of the first-stage reactor 2 And CO concentration.
3) The whole process design is beneficial to the effective components of the biomass synthesis gas, namely CO and H 2 The full conversion of the catalyst realizes the respective control and optimization of the two reactors, fully exerts the performance of each catalyst, improves the conversion per pass, greatly saves the energy consumption of gas compression circulation and reduces the equipment investment of a compression section.
4) The whole process has reasonable thermodynamic path, simple and flexible flow, low overall operation pressure, low system energy consumption and less equipment investment.
The present invention will be described in detail by examples.
Example 1
After the catalyst reduction in the first-stage reactor is finished, introducing biomass synthesis gas (H) 2 :CO:CO 2 :CH 4 0.385, 0.2 by volume) was compressed to 3.4MPa with a substantial amount of CO from step (3) 2 Mixing with unreacted biomass synthesis gas, and removing CO in a decarbonization device 2 . CO removal 2 The gas after the reaction is preheated to 210 ℃ and enters a first-stage reactor, the integral reaction pressure of the first-stage reactor is kept at 3.2MPa, the temperature of the first-stage reactor is controlled at 250 ℃, and the one-step dimethyl ether synthesis reaction is carried out. And (3) cooling the outlet gas after the reaction of the first-stage reactor to 40 ℃, isobarically feeding the outlet gas into a high-pressure washing separation tower, controlling the temperature of an outlet at the top of the high-pressure washing separation tower to be 25 ℃, and controlling the concentration of dimethyl ether in the gas at a gas phase outlet at the top of the high-pressure washing separation tower to be 0.04wt%. A small amount of the gas, most of the CO is discharged 2 And returning the unreacted biomass synthesis gas to the decarbonization device to be mixed with the fresh biomass synthesis gas. Reducing the pressure of the water solution at the bottom of the high-pressure water washing separation tower to 2.3MPa, feeding the water solution into an analytical tower, controlling the temperature at the bottom of the analytical tower to be 219 ℃, and evaporating dimethyl ether and a small amount of CO from the top of the analytical tower 2 . Preheating outlet gas of the desorption tower to 350 ℃, entering a two-stage reactor for reaction, and controlling the outlet temperature to be 467.7 ℃. Two-stage processAnd (3) cooling and heat exchanging outlet gas after the reactor reaction is finished to 40 ℃, then entering a three-phase separator for separation to obtain a liquid-phase product crude gasoline product, discharging a small amount of separated non-condensable gas, circulating most of the separated non-condensable gas to an inlet of the second-stage preheater, mixing the separated non-condensable gas with outlet gas at the top of the desorption tower, and diluting the feed gas to control the temperature rise of the second-stage reaction.
The reaction results show that the conversion per pass of CO reaches 72%, the total conversion of CO reaches 95.6%, and CO is treated by a high-pressure washing separation tower 2 Has a separation rate of 96%, i.e. CO at the outlet of the first stage reactor 2 Only 4% of the dimethyl ether is carried into the second-stage reactor along with the dimethyl ether. The dimethyl ether conversion rate of the two-stage reactor is 100 percent, and the crude gasoline product yield is 36 weight percent. Each standard square of the synthetic gas produces 0.142kg of crude gasoline.
Example 2
After the reduction of the first-stage catalyst is finished, biomass synthesis gas (H) is introduced 2 :CO:CO 2 :CH 4 0.375, volume ratio) compressed to 3.4MPa with the bulk of CO from step (3) 2 Mixing with unreacted biomass synthesis gas, and then entering a decarbonization device to remove CO 2 . And (3) preheating the decarbonized gas to 210 ℃, entering a first-stage reactor, keeping the overall reaction pressure of the system at 3.2MPa, controlling the first-stage reaction temperature at 250 ℃, and carrying out a one-step dimethyl ether synthesis reaction. And (3) after the temperature of the first-stage reaction outlet gas is reduced to 40 ℃, isobaric pressure enters a high-pressure washing separation tower, the temperature of the outlet of the top of the high-pressure washing separation tower is controlled to be 20.6 ℃, and the concentration of dimethyl ether in the outlet gas of the top of the high-pressure washing separation tower is 0.02wt%. A small amount of the gas, most of the CO is discharged 2 And mixing the unreacted biomass synthesis gas with the fresh synthesis gas before returning the unreacted biomass synthesis gas to the decarbonization device. Reducing the pressure of the water solution at the bottom of the high-pressure water washing separation tower to 2.3MPa, feeding the water solution into an analytical tower, controlling the temperature at the bottom of the analytical tower to be 219 ℃, and evaporating dimethyl ether and a small amount of CO from the top of the analytical tower 2 . Preheating the outlet gas to 350 ℃, then entering a secondary reactor for reaction, and controlling the outlet temperature to be about 466.8 ℃. The outlet gas of the two-stage reactor is cooled and heat-exchanged to 40 ℃ for separation to obtain a liquid-phase product crude gasoline product, a small amount of separated non-condensable gas is discharged, and most of the separated non-condensable gas is circulated to the inlet of the two-stage preheater and mixed with the outlet gas at the top of the desorption tower, and the raw gas is diluted to controlThe temperature of the second-stage reaction rises.
The reaction results show that the conversion per pass of CO reaches 79.3 percent, the total conversion of CO reaches 97.4 percent, and the CO is treated by a high-pressure washing separation tower 2 Has a separation rate of 95.5%, i.e. CO at the outlet of the first stage reactor 2 Only 4.5% of the dimethyl ether is carried into the second-stage reactor along with the dimethyl ether. The dimethyl ether conversion rate of the two-stage reactor is 100 percent, and the crude gasoline product yield is 36 weight percent. Each standard square of the synthetic gas produces 0.14kg of crude gasoline.
In summary, compared with the prior art, the method and the system for producing the gasoline by the biomass synthesis gas through the dimethyl ether have the following obvious advantages: 1) Fully utilizes the biomass synthesis gas H 2 The mol ratio of/CO is in accordance with the stoichiometric ratio H of the one-step method for synthesizing dimethyl ether reaction 2 The process for producing the gasoline by the synthesis gas through the one-step method of dimethyl ether is designed, and the synthesis gas does not need to be modulated through a shift reaction, so that the process flow is simplified. 2) Aiming at biomass synthesis gas CO 2 The characteristic of high content makes full use of the depressurization process from one section to two sections, and most of CO is simply and effectively separated from the outlet gas of the first section through a high-pressure water-washing separator and a desorption tower 2 And unreacted synthesis gas, and the separated gas is mixed with fresh biomass synthesis gas for centralized decarburization, which is beneficial to CO 2 The concentrated capture and recovery of the reaction can also obviously improve the inlet H of the first-stage reactor 2 And CO concentration. 3) The whole process design is beneficial to the effective components of the biomass synthesis gas, namely CO and H 2 The full conversion of the catalyst realizes the respective control and optimization of the two reactors, fully exerts the performance of each catalyst, improves the conversion per pass, greatly saves the energy consumption of gas compression circulation and reduces the equipment investment of a compression section. 4) The whole process has reasonable thermodynamic path, simple and flexible flow, low integral operation pressure, low system energy consumption and less equipment investment.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (7)
1. A method for producing gasoline by biomass synthesis gas through dimethyl ether is characterized by comprising the following steps:
step (1), compressing and boosting the biomass synthesis gas and the CO from the step (3) 2 Mixing with unreacted biomass synthesis gas, and then entering a decarbonization device to remove CO 2 ；
Step (2) removing CO 2 The gas enters a first-stage reactor to carry out a one-step dimethyl ether synthesis reaction;
and (3) introducing the gas after the reaction of the first-stage reactor into a high-pressure water washing separation tower, and separating CO 2 And (2) the unreacted biomass synthesis gas flows out from a gas phase outlet at the top of the high-pressure washing separation tower and returns to the step (1), the water solution at the bottom of the high-pressure washing separation tower enters an analytical tower, and dimethyl ether and CO are evaporated out by decompression 2 ；
Step (4), dimethyl ether and CO 2 Mixing with the non-condensable gas returned in the step (5), and reacting in a second-stage reactor;
step (5), the product after the reaction of the second-stage reactor enters a three-phase separator, a liquid-phase crude gasoline product is obtained after condensation and separation, and the non-condensable gas returns to the step (4) through a gas-phase outlet at the top of the three-phase separator;
in the step (1), CO is removed 2 After then, CO 2 The volume concentration is less than or equal to 5 percent;
in the step (3), the pressure of the high-pressure washing separation tower is 2.5-5.0MPa, and the temperature at the top of the high-pressure washing separation tower is 10-40 ℃; the pressure of the desorption tower is 1.0-2.5MPa, and the temperature of the bottom of the desorption tower is 190-240 ℃;
in the step (3), the mass concentration of dimethyl ether in the outlet gas at the top of the high-pressure water washing separation tower is less than or equal to 1 percent.
2. The method for producing gasoline from biomass synthesis gas through dimethyl ether according to claim 1, wherein in the step (1), the biomass synthesis gas is derived from biomass gasification, and H in the biomass synthesis gas 2 The molar ratio to CO is 0.7-1.3.
3. The method for producing gasoline from biomass synthesis gas through dimethyl ether according to claim 1, wherein in the step (1), the biomass synthesis gas is compressed and pressurized to 2.5-5.0MPa.
4. The method for producing gasoline from biomass synthesis gas through dimethyl ether according to claim 1, wherein in the step (1), CO is removed 2 First, CO in Biomass syngas 2 The volume concentration is 18-22%.
5. The method for producing gasoline by dimethyl ether from biomass synthesis gas according to claim 1, wherein in the step (2), the first-stage reactor is a tubular reactor, the pressure of the first-stage reactor is 2.5-5.0MPa, the temperature of the first-stage reactor is 210-280 ℃, and the gas volume space velocity is 500-3000h -1 。
6. The method for producing gasoline from biomass synthesis gas through dimethyl ether according to claim 1, wherein in the step (4), the second-stage reactor is a fixed bed reactor, the temperature of the second-stage reactor is 320-490 ℃, the pressure of the second-stage reactor is 1.0-2.5MPa, and the gas volume space velocity is 800-2500h -1 。
7. A system for producing gasoline by biomass synthesis gas through dimethyl ether is characterized by comprising a decarbonization device, a first-stage reactor, a high-pressure washing separation tower, an analytical tower, a second-stage reactor and a three-phase separator which are sequentially connected, wherein a gas phase outlet at the top of the high-pressure washing separation tower is connected with the decarbonization device, and a gas phase outlet at the top of the three-phase separator is connected with the second-stage reactor;
the first-stage reactor is a tubular reactor;
the second-stage reactor is a fixed bed reactor.
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