CN114479902B - Device and method for preparing gasoline by catalytic hydrogenation of carbon dioxide - Google Patents

Device and method for preparing gasoline by catalytic hydrogenation of carbon dioxide Download PDF

Info

Publication number
CN114479902B
CN114479902B CN202011266069.0A CN202011266069A CN114479902B CN 114479902 B CN114479902 B CN 114479902B CN 202011266069 A CN202011266069 A CN 202011266069A CN 114479902 B CN114479902 B CN 114479902B
Authority
CN
China
Prior art keywords
gas
carbon dioxide
gasoline
tail gas
membrane separation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202011266069.0A
Other languages
Chinese (zh)
Other versions
CN114479902A (en
Inventor
葛庆杰
孙剑
位健
侯守福
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhuhai Fuyi Energy Technology Co ltd
Dalian Institute of Chemical Physics of CAS
Original Assignee
Zhuhai Fuyi Energy Technology Co ltd
Dalian Institute of Chemical Physics of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhuhai Fuyi Energy Technology Co ltd, Dalian Institute of Chemical Physics of CAS filed Critical Zhuhai Fuyi Energy Technology Co ltd
Priority to CN202011266069.0A priority Critical patent/CN114479902B/en
Publication of CN114479902A publication Critical patent/CN114479902A/en
Application granted granted Critical
Publication of CN114479902B publication Critical patent/CN114479902B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • 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
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • 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
    • C10G2/331—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 group VIII-metals
    • C10G2/332—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 group VIII-metals of the iron-group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/0278—Feeding reactive fluids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
    • B01J8/0449—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
    • C—CHEMISTRY; METALLURGY
    • 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
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • 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
    • C10G2/34—Apparatus, reactors
    • C10G2/341—Apparatus, reactors with stationary catalyst bed
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
    • F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
    • F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
    • C—CHEMISTRY; METALLURGY
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C—CHEMISTRY; METALLURGY
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline
    • C—CHEMISTRY; METALLURGY
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/26—Fuel gas

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Analytical Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The application discloses a device for preparing gasoline by catalytic hydrogenation of carbon dioxide, which comprises a pretreatment unit, a reaction unit, a product separation unit and a tail gas recycling unit; the pretreatment unit, the reaction unit, the product separation unit and the tail gas recycling unit are sequentially communicated. Also discloses a method for preparing gasoline by adopting the device for catalytic hydrogenation of carbon dioxide. The device for preparing gasoline by hydrogenating carbon dioxide is effectively combined with each system, the utilization rate of carbon dioxide resources can reach more than 80 percent, even more than 90 percent, almost no exhaust emission exists, and the environmental protection of the process is obviously improved. Meanwhile, the reaction system adopted by the invention ensures the stable operation of the whole system.

Description

Device and method for preparing gasoline by catalytic hydrogenation of carbon dioxide
Technical Field
The application relates to a device for preparing gasoline by catalytic hydrogenation of carbon dioxide, which belongs to the field of chemical technology for producing gasoline.
Background
The conversion of carbon dioxide to prepare liquid fuel and high-value chemicals has potential significance in the fields of energy and chemical industry in China, and is beneficial to emission reduction of carbon dioxide and effective utilization of carbon dioxide. In addition, the hydrogen produced by electrolysis of water with renewable energy sources (water energy, solar energy, wind energy and the like) can be converted into liquid fuel and high-value chemicals, and the energy storage problem which always plagues the renewable energy sources can be solved, so that the process of preparing the liquid fuel and the high-value chemicals by hydrogenating the carbon dioxide plays an important role in future energy systems. Among the products, gasoline is an important transportation fuel, is most widely applied worldwide, has the most perfect storage and transportation infrastructure, and can realize the application of preparing gasoline by hydrogenating carbon dioxide, thereby having extremely great promotion effect on the popularization and utilization of renewable energy.
But due to CO 2 Is chemically inert to CO 2 Hydroconversion to lower carbon compounds such as methane, methanol, etc. is relatively easy, but conversion to higher carbon compounds is very challenging and there is a need to develop more efficient catalyst systems. CO 2 The studies on hydrogenation of highly selective synthetic gasoline hydrocarbons can be divided into two categories: one is through the reaction of an oxygen-containing intermediate species such as methanol; the other is via a Fischer-Tropsch (FTS) like reaction. At present, most of research works mainly adopt FTS-like reaction paths, namely CO 2 CO is generated by Reverse Water Gas Shift (RWGS) reaction, and then the FTS reaction occurs after CO hydrogenation. In either way, the single pass yield of carbon dioxide is to be further improved; in addition, the research on the reaction device and the reactor in the process of preparing gasoline by hydrogenating carbon dioxide is less, and as the process is a rapid exothermic reaction, how to keep the uniform distribution of the reaction heat of the catalyst bed and timely remove the reaction heat is also an important problem to be solved in the process. CN110669543a patent relates to a device and method for directly preparing gasoline by hydrogenation of carbon dioxide. The apparatus and method employ indium oxide/molecular sieve (In 2 O 3 HZSM-5), a shell and tube type synthesis reactor with an external circulating heat exchange mechanism is adopted as the reactor, the outlet of the reactor is subjected to multistage cooling, a molecular sieve absorber is dehydrated, and after gas-liquid separation, a part of gas phase components in the reactor are recycled, and the part of gas phase components are used as a purge gas external discharge torch system. The characteristics of the device are suitable for In 2 O 3 The HZSM-5 catalyst has the characteristics of low conversion rate, high selectivity of gasoline products and low water content in the products. But for the iron-based/molecular sieve (Na-Fe 3 O 4 HZSM-5) multifunctionalThe composite catalyst is not suitable, for example, a molecular sieve absorber for dehydrating the mixed gas at the outlet of the reactor is not suitable for dehydrating the mixed gas containing non-trace moisture; meanwhile, a large amount of unreacted raw material gas components in the purge gas are directly discharged, so that the total conversion rate of the reaction is reduced. Thus, suitable iron-based/molecular sieves (na—fe 3 O 4 HZSM-5) a reaction apparatus system featuring a multifunctional composite catalyst molecular sieve is necessary.
Disclosure of Invention
For the current CO 2 The invention is mainly suitable for Na-Fe due to the characteristics of devices required by the reaction for preparing gasoline by hydrogenation 3 O 4 HZSM-5 catalyzed CO 2 The reaction device with the characteristics of the reaction process for preparing gasoline by hydrogenation achieves the characteristics of high gasoline yield, low energy consumption, economy, environmental protection and the like of a designed reaction device system.
According to one aspect of the present application, there is provided an apparatus for producing gasoline by catalytic hydrogenation of carbon dioxide, which is an effective combined use of each system, and comprises a pretreatment unit, a reaction unit, separation of reaction products, recycling of tail gas, and the like, wherein the pretreatment unit refers to pretreatment of feed gas CO 2 And H 2 Gas is made to meet the CO on the iron catalyst 2 And the reaction of hydrogen to gasoline requires gas and reaction conditions; the reaction unit refers to CO on an iron catalyst 2 The reaction unit of the invention comprises a reactor containing heat exchange components, wherein the catalyst in the reactor adopts multilayer dilution and filling, thus achieving even distribution of reaction heat and timely removal of excessive reaction heat when the system is in operation, and ensuring CO 2 The stable operation of the hydrogenation gasoline preparation reaction; the product separation unit adopts traditional pressure swing adsorption separation, and proper conditions are adopted to ensure the recovery of gasoline products; the tail gas recycling unit adopts a membrane separation system to separate hydrogen and CO 2 The tail gas of the reaction device can be recycled into the feed gas for secondary conversion and utilization according to the requirement of feed gas recycling, so that the conversion efficiency of the reaction device is further improved.
The device for preparing gasoline by catalytic hydrogenation of carbon dioxide comprises a pretreatment unit, a reaction unit, a product separation unit and a tail gas recycling unit;
the pretreatment unit, the reaction unit, the product separation unit and the tail gas recycling unit are sequentially communicated.
Optionally, the reaction unit is a reactor;
the reactor comprises a raw material gas distributor, a first-stage reaction zone and a second-stage reaction zone;
a catalyst I is placed in the first-stage reaction zone, and a catalyst II is placed in the second-stage reaction zone;
the raw material gas distributor is positioned in the first-stage reaction zone and is communicated with the first-stage reaction zone;
the second-stage reaction zone is positioned at the lower part of the first-stage reaction zone and is mutually communicated.
Optionally, the number of the raw material gas distributors is 1-100, preferably 1-50, and most preferably 1-10. If the reactor and the distributor are very different, more distributors can be installed, and in extreme cases, 100 or more distributors can be installed, and in the application process, the reactors can be correspondingly adjusted according to actual conditions.
Optionally, the raw material gas distributor comprises a shell I, wherein the shell I surrounds a columnar cavity;
the shell is provided with a plurality of air hole groups along the axial direction;
each air hole group comprises a plurality of air discharge holes arranged along the circumferential direction;
the distance between two adjacent air hole groups is set in a preset mode I from top to bottom along the axial direction;
the pore diameters of the exhaust pores in the two adjacent pore groups are also arranged in a preset mode II from top to bottom along the axial direction.
Optionally, the preset mode I is gradually increased; or alternatively, the process may be performed,
the preset mode I is gradually increased and then kept unchanged.
Optionally, the preset mode ii is gradually decreasing; or alternatively, the process may be performed,
the preset mode II is gradually reduced and then kept unchanged.
Optionally, the preset mode II is unchanged and then gradually reduced; or alternatively, the process may be performed,
the preset mode II is gradually reduced and then is reduced after being kept unchanged.
Optionally, the interval between two adjacent air hole groups is n, and the difference between the adjacent intervals is deltan;
wherein, delta n/n is more than or equal to 0 and less than or equal to 5;
alternatively, 0.ltoreq.Δn/n.ltoreq.3.
Alternatively, 0.2.ltoreq.Δn/n.ltoreq.1.
Alternatively, the gas outlet holes of each row are staggered up and down.
As a preferred embodiment, the first and second vent holes each have a pore size of 0.5mm and a pitch of 0.5cm; the aperture sizes of the third exhaust air hole and the fourth exhaust air hole are 0.4mm, the distance between the third exhaust air hole and the fourth exhaust air hole is 1.5cm, and the distance between the second row of the third exhaust air holes and the third exhaust air hole is 1cm; the method comprises the steps of carrying out a first treatment on the surface of the The aperture sizes of the fifth exhaust hole and the sixth exhaust hole are 0.3mm, the interval is 2cm, and the interval between the fourth row and the fifth exhaust hole is 2cm.
As a preferred embodiment, the first and second vent holes have a pore size of 0.7mm and 0.5mm, respectively, with a pitch of 0.7cm; the aperture sizes of the third exhaust air hole and the fourth exhaust air hole are 0.4mm, the distance between the third exhaust air hole and the fourth exhaust air hole is 1.5cm, and the distance between the second row of the third exhaust air holes and the third exhaust air hole is 1.0cm; the fourth vent holes had a pore size of 0.2mm and a pitch of 2.0cm.
Optionally, the 1 st vent is at a distance from the top end of the feed gas distributor that is greater than or equal to one eighth of the total length of the feed gas distributor.
Optionally, the 1 st vent is at a distance from the top end of the feed gas distributor that is greater than or equal to one half of the total length of the feed gas distributor.
In the application, the length, the inner diameter and the aperture of the gas outlet of the raw material gas distributor are not strictly limited, and in the actual use process, the corresponding matching selection is carried out according to the specification of the specifically selected reactor.
Optionally, the reactor further comprises a heat conducting device;
the inlet of the heat conduction device is connected with the first section reaction zone;
the outlet of the heat conduction device is connected with the second section reaction zone.
Optionally, the heat conduction device is a heat exchange system containing heat conduction oil. The heat transfer oil enters the reactor through the heat transfer oil inlet, flows out of the heat transfer oil pipe outlet of the reaction through the heat transfer oil pipe in the reactor and enters the heat exchange equipment of the heat transfer oil, and timely removes the reaction heat.
The reaction unit of the invention comprises a reactor containing heat exchange components, etc., wherein the catalyst in the reactor adopts multilayer dilution and filling (iron catalyst dilution and molecular sieve catalyst component non-dilution), and simultaneously adopts a reactor containing a raw material distributor and a heat conductor, thereby achieving the uniform distribution of reaction heat and timely removal of excessive reaction heat when the system is in operation, and ensuring CO 2 And (3) stably operating the reaction for preparing gasoline by hydrogenation.
The traditional fixed reactor is filled with catalyst, so that a catalyst bed is extremely easy to generate bed hot spots and generate bed temperature flying phenomenon. The normal catalyst reaction temperature is 320 ℃, but the hot spot temperature of the catalyst bed layer after the reaction appears, and the temperature rises to 500 quickly (within 2 hours) O Above C, the reaction can not be carried out, the catalyst structure is destroyed, and the reaction performance of the catalyst is seriously affected. By adopting the reactor designed by the invention, the bed temperature of the catalyst is basically controlled at about 320 ℃, the hot spot of the catalyst bed is not obvious and is not more than 350 ℃, and the reaction can be stably operated for nearly thousands of hours.
Optionally, the product separation unit comprises a pressure swing adsorption separation device. The product separation system comprises a secondary light component removal tower, and the main functions of the product separation system are to ensure the separation and purification of liquefied petroleum gas which is a main hydrocarbon byproduct, and increase the added value of the product and the economy of the process.
Optionally, the pressure swing adsorption separation device comprises a high pressure separation tank, a product separation tank, a light component removal tower I and a light component removal tower II;
the high-pressure separation tank, the product separation tank, the light component removal tower I and the light component removal tower II are sequentially communicated.
Optionally, a pressure reducing valve is connected among each of the high-pressure separation tank, the product separation tank, the light component removal tower I and the light component removal tower II.
Optionally, the high-pressure separation tank separates a gas part and a liquid part, and the liquid part separates light hydrocarbon gas, liquid oil and wastewater through the product separation tank; the liquid oil is separated by a light component removing tower I to obtain gasoline, and is separated by a light component removing tower II to obtain liquefied petroleum gas.
Optionally, a product conveying pump I is connected behind the light component removal tower I, and a product conveying pump II is connected behind the light component removal tower II.
Optionally, a heat exchanger and a cooler are arranged before the high-pressure separation tank.
Specifically, the product separation unit adopts traditional pressure swing adsorption separation, and the recovery of gasoline products is ensured by adopting proper conditions. Comprising the following steps: 001. heat exchanger and cooler 002, high pressure separating tank 003, pressure reducing valve I,004, pressure reducing valve II;005. in the system, the outlet gas flow of a reactor is subjected to cooling treatment through a heat exchanger and a cooler 001, cold gas (-30-10 ℃) enters a high-pressure separation tank 002 to obtain gas and liquid, wherein part of the gas enters a tail gas recycling system through the pressure reducing valve II 004, the liquid enters a product separation tank 005 through the pressure reducing valve I003, the pressure of the product separation tank is 0.5-2.5Mpa, and a small amount of separated light hydrocarbon gas enters a tail gas recycling system through the pressure reducing valve III 006; the separated liquid oil is decompressed by a decompression valve IV011 and is sent to a downstream light component removal tower I007 for further rectification and purification; the separated liquid water is continuously discharged; the gas of the top gas phase pipeline of the light component removal tower I007 enters the light component removal tower II008 through a pressure reducing valve V012, the bottom liquid phase outlet pipeline of the light component removal tower I007 is communicated with the inlet of a product conveying pump 009, and the outlet pipeline of the product conveying pump 009 is used for delivering qualified gasoline products; the gas of the top gas phase pipeline of the light component removal tower II008 enters the tail gas utilization system through a pressure reducing valve V013, the bottom liquid phase outlet pipeline is communicated with the inlet of the product conveying pump 010, and the qualified high-value byproduct liquefied petroleum gas is sent out from the outlet pipeline of the product conveying pump 010.
Optionally, the tail gas recycling unit comprises a membrane separation system;
the membrane separation system comprises a hydrogen permeable membrane separation system and/or a CO permeable membrane separation system 2 A membrane separation system.
The tail gas recycling unit adopts a membrane separator and a catalytic burner, and aims to ensure the full recycling of the carbon-containing tail gas, thereby enhancing the environmental protection performance of the process and improving the resource utilization rate of the process.
Optionally, the hydrogen permeable membrane separation system comprises a hydrogen permeable membrane separator and a catalytic combustor;
the catalytic burner is arranged at the rear of the hydrogen permeable membrane separator so as to catalyze and burn the gas separated from the hydrogen by the hydrogen permeable membrane separator to obtain carbon dioxide.
Optionally, a heat exchanger and a condenser are arranged behind the catalytic combustor, and a gas-liquid separator is arranged behind the heat exchanger and the condenser.
Optionally, the CO-permeable 2 The membrane separation system separates the tail gas into carbon dioxide and CO 2 And (3) separating tail gas by a membrane.
Optionally, the hydrogen permeable membrane separation system and CO permeable membrane 2 When the membrane separation systems coexist, the hydrogen permeable membrane separation system is arranged at the CO permeable position 2 After the membrane separation system.
Optionally, the hydrogen permeable membrane separation system is selected from one of an organic hydrogen permeable membrane separation system and a hydrogen permeable palladium membrane separation system.
Optionally, the hydrogen permeable membrane separation system is selected from one of a low temperature organic hydrogen permeable membrane separation system and a high Wen Touqing palladium membrane separation system.
In the application, the hydrogen permeation membrane separation system is adopted to separate the hydrogen from the tail gas, and CO permeation is adopted 2 Membrane separation system for separating CO from tail gas 2 . In a specific practical application scene, the corresponding hydrogen permeable membrane and CO permeable membrane can be selected according to practical conditions 2 And (3) a membrane assembly.
Optionally, the membrane separation system is preceded by a heat exchanger and a preheater.
Specifically, the tail gas recycling unit adopts a membraneA separation system for separating hydrogen and CO 2 The tail gas of the reaction device can be recycled into the feed gas for secondary conversion and utilization according to the requirement of feed gas recycling, so that the conversion efficiency of the reaction device is further improved. Comprising the following steps: A01. heat exchanger and preheater, a02, membrane separator, a03, catalytic burner, a04, heat exchanger and condenser, a05, gas-liquid separator, a06, flow regulating valve I, a07, flow regulating valve II, a08. In the system, tail gas flowing in from a product separation system enters a membrane separation system A02 through a heat exchanger and a preheater A01, and hydrogen on the permeation side of the membrane separation system A02 can be recycled into fresh raw gas through a flow regulating valve I A and a summarizing connector A08 according to the recycling requirement for secondary utilization of the raw gas. The membrane separation tail gas flows into a catalytic combustor A03, and the reducing gas low-carbon hydrocarbon and CO in the tail gas in the catalytic combustor are completely combusted to generate carbon dioxide and water, and the carbon dioxide and the CO in the tail gas are mixed with each other 2 After passing through the heat exchanger and the condenser A04, the liquid water enters the A05 gas-liquid separator, the separated liquid water is continuously discharged, and the gaseous carbon dioxide can be recycled into fresh feed gas through the flow regulating valve II A07 and the summarizing connector A08 according to the recycling requirement for secondary utilization of the feed gas.
Optionally, the pretreatment unit comprises a dryer, a deoxidizer and a heat exchanger;
the dryer, the deoxidizer and the heat exchanger are communicated in sequence.
Optionally, a compressor, a stop valve and a flowmeter are arranged between the deoxidizer and the heat exchanger in sequence.
Optionally, the pretreatment unit further comprises a gas pretreatment portion of the catalyst; comprises a dryer and a deoxidizer; the portion is connected to the summary connector via a shut-off valve.
The pretreatment unit has double functions, namely, the pretreatment unit reduces the catalyst; secondly, pretreatment of the raw materials. In a specific operation, this can be achieved by switching the gas.
Specifically, the pretreated gas (hydrogen or gas containing hydrogen) is subjected to the removal of trace water in the pretreated gas by a dryer 4, the removal of trace oxygen in the pretreated gas by a deoxidizer 6, and the pretreated gas is quantitatively fed into a reaction system 14 for the normal-pressure pretreatment of the catalyst after being preheated by a flowmeter 8, a stop valve 11, a summarizing connector 12 and a heat exchanger 13 in sequence; after the pretreatment of the catalyst is finished, the raw material gas is switched to start the reaction.
Specifically, pretreatment system refers to pretreatment of feed gas CO 2 And H 2 Gas is made to meet the CO on the iron catalyst 2 And the reaction of hydrogen to gasoline requires gas and reaction conditions; the system comprises: 1. the system comprises a raw material gas outlet, a pretreatment gas outlet, a dryer, a deoxidizer, a compressor, a flowmeter, a stop valve and a summarizing connector. In the system, before the reaction of the catalyst system, the reduction pretreatment is required, at this time, the pretreatment gas (hydrogen or gas containing hydrogen) flowing in from the pretreatment gas outlet 2 is subjected to the removal of trace water in the pretreatment gas by the dryer 4, the removal of trace oxygen in the pretreatment gas by the deoxidizer 6, and the pretreatment gas is quantitatively fed into the reaction system 14 to be subjected to the normal-pressure pretreatment of the catalyst after being preheated by the flowmeter 8, the stop valve 11, the summarizing connector 12 and the heat exchanger 13 in sequence; after the pretreatment of the catalyst is finished, switching the raw material gas to start the reaction: the raw material gas (gas containing raw materials such as hydrogen, carbon dioxide and the like) flowing in from the raw material gas outlet 1 is subjected to micro-water removal by the drier 3, micro-oxygen removal by the deoxidizer 5, and is preheated by the compressor 7, the stop valve 9, the flowmeter 10, the summarizing connector 12 and the heat exchanger 13 in sequence, and then quantitatively enters the high-pressure reaction system 14 to perform high-pressure reaction of the catalyst.
The device for directly preparing gasoline by hydrogenating carbon dioxide comprises a pretreatment unit, a reaction unit, reaction product separation, tail gas recycling and the like. Wherein, the liquid crystal display device comprises a liquid crystal display device,
the pretreatment unit refers to pretreatment of feed gas CO 2 And H 2 Gas is made to meet the CO on the iron catalyst 2 And the reaction of hydrogen to gasoline requires gas and reaction conditions; the system comprises a raw material gas purifying system (a dewatering pipe and a deoxidizing pipe), a compressor, a heat exchanger and a heater.
The reaction unit refers to CO on an iron catalyst 2 The reaction system of the invention comprises a reactor containing heat exchange components and the like, and the catalyst in the reactorThe adoption of multi-layer dilution filling achieves the uniform distribution of reaction heat and timely removal of excessive reaction heat when the system is in operation, and ensures the stable operation of the reaction for preparing gasoline by CO2 hydrogenation.
The product separation unit adopts traditional pressure swing adsorption separation, and proper conditions are adopted to ensure the recovery of gasoline products.
The tail gas recycling unit adopts a high-temperature hydrogen permeable membrane to separate hydrogen and CO 2 The tail gas of the reaction device can be recycled into the feed gas for secondary conversion and utilization according to the requirement of feed gas recycling, so that the conversion efficiency of the reaction device is further improved.
According to the second aspect of the application, the method for preparing the gasoline by catalytic hydrogenation of the carbon dioxide is provided, so that the utilization rate of carbon resources can be obviously improved, the utilization rate of the carbon dioxide resources can reach more than 80 percent, even more than 90 percent, almost no waste gas is discharged in the process, and the environmental protection performance of the process is obviously improved.
A method for preparing gasoline by catalytic hydrogenation of carbon dioxide, comprising the following steps:
(a) Will contain CO 2 And H 2 The raw material gas is treated by a pretreatment unit to obtain pretreated materials;
(b) Carrying out catalytic reaction on the pretreated material in a reaction unit to obtain a material flow I;
(c) Separating the material flow I in a product separation unit to separate tail gas and waste water and obtain liquefied petroleum gas and gasoline;
(d) Treating the tail gas by a tail gas recycling unit to obtain fresh raw gas;
the method for preparing gasoline adopts one of the devices.
Optionally, in step (a), H is present in the pretreated material 2 /CO 2 Volume ratio=0.5-8, temperature 230-460 ℃, pressure 1.0-6.0 MPa.
Optionally, in step (a), H is present in the pretreated material 2 /CO 2 Volume ratio=0.5-8, temperature 230-350 ℃, pressure 1.0-6.0 MPa.
Optionally, in step (b), the catalyst space velocity: 1000-10000 ml/(g.h), the reaction temperature is 250-450 ℃, and the pressure is 1.0-6.0 Mpa.
Alternatively, in step (b), the catalytic reaction is carried out in two stages. I.e. the catalyst is packed in two stages.
Optionally, the first stage reaction zone is packed with an iron-based catalyst. The first stage reaction zone is an inlet section, the process of synthesizing low-carbon olefin by CO through carbon dioxide hydrogenation occurs on the catalyst, and the total package reaction of the first stage is a strong exothermic reaction.
Optionally, the second stage reaction zone is packed with an acidic molecular sieve catalyst. The second stage reaction zone is an outlet section, the process of polymerizing, hydrogenating, isomerising and aromatizing the intermediate product low-carbon olefin to generate gasoline fraction hydrocarbon takes place on the catalyst of the second stage, and the total package reaction of the second stage is a mild exothermic reaction.
Alternatively, the iron-based catalyst is selected from Na-Fe 3 O 4 、K-Fe 3 O 4 、Na-Mn-Fe 3 O 4 At least one of them.
Optionally, the acidic molecular sieve is selected from at least one of HZSM-5, HZSM-22, HY, HSAPO-5.
Optionally, the silica-alumina ratio of the acidic molecular sieve is 15-500.
Optionally, the mass ratio of the iron-based catalyst to the molecular sieve catalyst is 1:3-3: 1.
in the application, the catalyst is filled in a plurality of sections, and the iron-based catalyst is filled in the raw gas inlet section and can be filled in one section and a plurality of sections according to actual conditions; the molecular sieve catalyst is filled in the outlet section of the raw material gas of the reactor and can be filled in one section or multiple sections according to actual conditions.
In this application, adopt raw materials distributor feeding, according to the root number (1-3) of reactor pipe diameter adjustment raw materials distributor, not only make the axial feeding of 1 bed sections of reactor catalyst distribute equally, make the radial feeding of 1 bed sections of catalyst distribute evenly simultaneously. Meanwhile, by combining the heat conduction system, the reaction heat of the reactor, particularly the reaction heat on the iron-based catalyst, can be removed uniformly in time, and the stable operation of the system is improved.
In particular, CO over an iron catalyst 2 The reaction unit of the invention comprises a reactor containing heat exchange components, wherein the catalyst in the reactor adopts multilayer dilution and filling (iron catalyst is diluted and molecular sieve catalyst components are not diluted), and simultaneously adopts a reactor containing a raw material distributor and a heat conductor, thereby achieving even distribution of reaction heat and timely removal of excessive reaction heat when the system is in operation, and ensuring CO 2 And (3) stably operating the reaction for preparing gasoline by hydrogenation. The raw material gas after being treated by the pretreatment unit enters a reactor through a raw material distributor and enters a catalyst 1 (Na-Fe) 3 O 4 ) And the gas containing gasoline products after the reaction flows out of the reaction gas and enters a product separation system. When the reaction is operated, a heat exchange system (the heat transfer oil enters the reactor through a heat transfer oil inlet and flows out of a heat transfer oil pipe line in the reactor from a heat transfer oil pipe outlet of the reaction to heat exchange equipment of the heat transfer oil) containing the heat transfer oil of the reaction device is started at the same time, and the reaction heat is timely removed. It is worth noting that the raw gas entering the distributor only flows out in the catalyst 1 bed, and enters the catalyst 2 bed after the reaction.
Optionally, in step (c), the pressure of the high-pressure separation tank is 1.0-5.0 Mpa; the pressure of the product separation tank is 0.5-2.5Mpa; the pressure of the light component removing tower I is 0.3-2.0MPa; the pressure of the light component removing tower II is 0.3-1.0MPa;
separating the material flow I in a high-pressure separating tank to obtain a gas part and a liquid part, wherein the gas part enters a tail gas recycling unit;
the liquid part is separated into light hydrocarbon gas, liquid oil and wastewater by a product separation tank, the light hydrocarbon gas enters a tail gas recycling unit, and the wastewater is discharged;
the liquid oil is separated by a light component removing tower I to obtain gasoline, and is separated by a light component removing tower II to obtain liquefied petroleum gas.
Optionally, in the step (d), the tail gas is separated by a hydrogen permeable membrane separation system to obtain hydrogen and hydrogen permeable membrane separation tail gas, the hydrogen permeable membrane separation tail gas is catalytically combusted to obtain carbon dioxide, and the hydrogen and the carbon dioxide are mixed and then are reused.
Optionally, in step (d)Tail gas is permeated by CO 2 The membrane separation system separates CO 2 And CO permeation 2 And (3) separating tail gas by a membrane.
Optionally, in step (d), CO permeation 2 The membrane separation tail gas is separated again by a hydrogen permeable membrane separation system to obtain hydrogen and hydrogen permeable membrane separation tail gas, and the hydrogen permeable membrane separation tail gas is catalytically combusted to obtain carbon dioxide, and the hydrogen and the carbon dioxide are mixed and then are reused.
The beneficial effects that this application can produce include:
1) The method realizes the efficient conversion of the carbon dioxide on the iron-based catalyst by direct hydrogenation to prepare gasoline, and the gasoline yield is obviously higher than that of the existing device for preparing gasoline by carbon dioxide hydrogenation. The reaction system adopts the reactor with the raw material distributor and the heat conductor, and the air outlets of the raw material distributor are distributed in the first bed section of the multi-section catalyst, so that the uniform distribution of the reaction heat not only in the catalyst bed is ensured, but also can be removed uniformly, and the stable reaction is ensured.
2) The carbon dioxide hydrogenation reaction device and the gasoline product separation and purification collection are integrated, so that the energy consumption of the reaction device and the separation device is reduced while the effective cyclic utilization of the reaction raw material gas is ensured, and the production cost of preparing gasoline from carbon dioxide is further reduced.
3) The tail gas recycling system adopts the membrane separator and the catalytic burner, so that the discharged waste gas can be greatly reduced, the carbon dioxide resource is fully utilized, and the influence of the discharged tail gas on the environment is greatly reduced.
4) The product separation system of the application not only produces qualified gasoline products, but also produces qualified high-value byproducts of liquefied petroleum gas, thereby improving the carbon resource utilization rate of the system.
5) The effective combined application of each system of the device for preparing gasoline by hydrogenating carbon dioxide can obviously improve the utilization rate of carbon resources in the process, the utilization rate of carbon dioxide resources can reach more than 80 percent, even more than 90 percent, almost no waste gas is discharged in the process, and the environmental protection property of the process is obviously improved. Meanwhile, the reaction system adopted by the invention ensures the stable operation of the whole system.
Drawings
FIG. 1 is a schematic diagram of a reaction apparatus for producing gasoline by catalytic hydrogenation of carbon dioxide.
FIG. 2 is a schematic diagram of a pretreatment system for preparing gasoline by catalytic hydrogenation.
FIG. 3 is a schematic diagram of a reaction system for producing gasoline by catalytic hydrogenation of carbon dioxide.
FIG. 4 is a schematic diagram of a feed gas distributor of a reaction system for producing gasoline by catalytic hydrogenation of carbon dioxide.
FIG. 5 is a schematic diagram of a separation system for producing gasoline products by catalytic hydrogenation of carbon dioxide.
Fig. 6 is a schematic diagram of recycling tail gas from the catalytic hydrogenation of carbon dioxide to gasoline.
Fig. 7 is a schematic diagram of recycling tail gas containing a carbon dioxide separation membrane from gasoline prepared by catalytic hydrogenation of carbon dioxide.
FIG. 8 is a schematic diagram of recycling tail gas from the catalytic hydrogenation of carbon dioxide to gasoline, which contains both a hydrogen permeable membrane and a carbon dioxide separation membrane.
In FIG. 2, 1. Raw gas outlet 2. Pretreated gas outlet 3. Dryer
4. Dryer 5, deoxidizer 6, deoxidizer
7. Compressor 8, flowmeter 9, stop valve
10. Flowmeter 11, stop valve 12, summary connector
13. Heat exchanger (preheater) 14 reaction system
In FIG. 5, 001. Heat exchanger and cooler 002. High pressure separator tank
003. Pressure reducing valve I004. Pressure reducing valve II
005. Product separation tank 006, pressure relief valve III
007. Light component removal tower I008 light component removal tower II
009. Product delivery Pump I010 product delivery Pump II
011. Pressure reducing valve IV 012 pressure reducing valve V
013. Pressure reducing valve VI
In FIG. 6, A01. Heat exchanger and preheater A02. Membrane separator
A03. Catalytic burner A04, heat exchanger and condenser
A05. Gas-liquid separator A06. Flow regulating valve I
A07. Flow regulating valve II A08 summarizing connector
In FIG. 7, B01. Heat exchanger and preheater B02. Membrane separator
B03. Flow regulating valve I B04 flow regulating valve II
B05. Summarizing connector
In FIG. 8, C01. Heat exchanger and preheater C02. Carbon dioxide Membrane separator
C03. Hydrogen permeable membrane separator C04 catalytic burner
C05. Heat exchanger and condenser C05 gas-liquid separator
C07. Flow regulating valve I C08 flow regulating valve II
C09. Summarizing connector c10 flow regulating valve III
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, both the starting materials and the catalysts in the examples of the present application were purchased commercially. Unless otherwise specified, the test methods all use conventional methods, and the instrument settings all use manufacturer recommended settings.
Wherein, the iron-based catalyst is Na-Fe 3 O 4 From the institute of chemical and physical of great company of academy of sciences of China.
HZSM-5 is purchased from a catalyst factory of Nankai university, and the silicon-aluminum ratio is 25-400.
The hydrogen permeable membrane separation system is from the institute of chemical and physical of China academy of sciences, and the main component of the hydrogen permeable membrane is a metal palladium hydrogen permeable membrane core component.
The carbon dioxide permeable membrane separation system is from the institute of chemical and physical of great company of China academy of sciences, and the main component of the carbon dioxide membrane separation system is a molecular sieve composite membrane separation system.
Reactant CO 2 The conversion and gasoline product yield of (c) are calculated as follows:
CO 2 single pass conversion (%) =co 2 Conversion mole number/CO 2 Number of moles of feed х% 100%
Gasoline product single pass yield (mg) Gasoline G catalyst -1 ·h -1 ) =volume space velocity of feedstock (ml·g catalyst) -1 ·h -1 ) CO in the x feedstock 2 Volume percent (%) x CO 2 Conversion (%) X gasoline product selectivity (%)/22400X gasoline molar mass (mg/mol)
CO 2 Cyclic utilization (%) =co 2 moles/CO for recycle conversion to hydrocarbon fuels 2 Molar number of recycle conversion х 100.100%
FIG. 1 is a device for directly preparing gasoline fraction hydrocarbon by hydrogenating carbon dioxide, which comprises a pretreatment system, a reaction product separation system and a tail gas recycling system; wherein, the liquid crystal display device comprises a liquid crystal display device,
the pretreatment system (fig. 2) includes: 1. the system comprises a raw material gas outlet, a pretreatment gas outlet, a dryer, a deoxidizer, a compressor, a flowmeter, a stop valve and a summarizing connector. In the system, before the reaction of the catalyst system, the reduction pretreatment is required, at this time, the pretreatment gas (hydrogen or gas containing hydrogen) flowing in from the pretreatment gas outlet 2 is subjected to the removal of trace water in the pretreatment gas by the dryer 4, the removal of trace oxygen in the pretreatment gas by the deoxidizer 6, and the pretreatment gas is quantitatively fed into the reaction system 14 to be subjected to the normal-pressure pretreatment of the catalyst after being preheated by the flowmeter 8, the stop valve 11, the summarizing connector 12 and the heat exchanger 13 in sequence; after the pretreatment of the catalyst is finished, switching the raw material gas to start the reaction: the raw material gas (gas containing raw materials such as hydrogen, carbon dioxide and the like) flowing in from the raw material gas outlet 1 is subjected to micro-water removal by the drier 3, micro-oxygen removal by the deoxidizer 5, and is preheated by the compressor 7, the stop valve 9, the flowmeter 10, the summarizing connector 12 and the heat exchanger 13 in sequence, and then quantitatively enters the high-pressure reaction system 14 to perform high-pressure reaction of the catalyst.
The reaction system (figure 3) comprises a reactor containing heat exchange components and the like, wherein the catalyst in the reactor adopts multi-layer dilution and filling (iron catalyst dilution and molecular sieve catalyst component non-dilution), and meanwhile, the reactor containing a raw material distributor (figure 4) and a heat conductor is adopted. In the system, raw gas treated by the pretreatment system enters a reactor through a raw material distributor and enters a catalyst 1 (Na-Fe 3 O 4 ) And the gas containing gasoline products after the reaction flows out of the reaction gas and enters a product separation system. When the reaction is operated, a heat exchange system (the heat transfer oil enters the reactor through a heat transfer oil inlet and flows out of a heat transfer oil pipe line in the reactor from a heat transfer oil pipe outlet of the reaction to heat exchange equipment of the heat transfer oil) containing the heat transfer oil of the reaction device is started at the same time, and the reaction heat is timely removed. It is worth noting that the raw gas entering the distributor only flows out in the catalyst 1 bed, and enters the catalyst 2 bed after the reaction.
The product separation system (fig. 5) includes: 001. heat exchanger and cooler 002, high pressure separating tank 003, pressure reducing valve I,004, pressure reducing valve II;005. in the system, the outlet gas flow of a reactor is subjected to cooling treatment through a heat exchanger and a cooler 001 and then enters a high-pressure separation tank 002 to obtain gas and liquid, wherein a gas part enters a tail gas recycling system through a pressure reducing valve II 004, the liquid enters a product separation tank 005 through the pressure reducing valve I003, the pressure of the product separation tank is 0.5-2.5Mpa, and a small amount of separated light hydrocarbon gas enters the tail gas recycling system through the pressure reducing valve III 006; the separated liquid oil is decompressed by a decompression valve IV011 and is sent to a downstream light component removal tower I007 for further rectification and purification; the separated liquid water is continuously discharged; the gas of the top gas phase pipeline of the light component removal tower I007 enters the light component removal tower II008 through a pressure reducing valve V012, the bottom liquid phase outlet pipeline of the light component removal tower I007 is communicated with the inlet of a product conveying pump 009, and the outlet pipeline of the product conveying pump 009 is used for delivering qualified gasoline products; the gas of the top gas phase pipeline of the light component removal tower II008 enters the tail gas utilization system through a pressure reducing valve V013, the bottom liquid phase outlet pipeline is communicated with the inlet of the product conveying pump 010, and the qualified high-value byproduct liquefied petroleum gas is sent out from the outlet pipeline of the product conveying pump 010.
The tail gas recycling system (fig. 6) comprises: A01. heat exchanger and preheater, a02, membrane separator, a03, catalytic burner, a04, heat exchanger and condenser, a05, gas-liquid separator, a06, flow regulating valve I, a07, flow regulating valve II, a08. In the system, tail gas flowing in from a product separation system enters a membrane separation system A02 through a heat exchanger and a preheater A01, and hydrogen on the permeation side of the membrane separation system A02 can be recycled into fresh raw gas through a flow regulating valve I A and a summarizing connector A08 according to the recycling requirement for secondary utilization of the raw gas. The membrane separation tail gas flows into a catalytic combustor A03, and the reducing gas low-carbon hydrocarbon and CO in the tail gas in the catalytic combustor are completely combusted to generate carbon dioxide and water, and the carbon dioxide and the CO in the tail gas are mixed with each other 2 After passing through the heat exchanger and the condenser A04, the liquid water enters the A05 gas-liquid separator, the separated liquid water is continuously discharged, and the gaseous carbon dioxide can be recycled into fresh feed gas through the flow regulating valve II A07 and the summarizing connector A08 according to the recycling requirement for secondary utilization of the feed gas.
Fig. 7 is a schematic diagram of recycling tail gas containing a carbon dioxide separation membrane from gasoline prepared by catalytic hydrogenation of carbon dioxide. In the schematic diagram, the tail gas flowing in from the product separation system enters the membrane separation system B02 through the heat exchanger and the preheater B01, and the carbon dioxide on the permeation side of the membrane separation system B02 can be recycled into fresh raw gas for secondary utilization through the flow regulating valve I B and the summarizing connector B05 according to the recycling requirement. The membrane separation tail gas can be recycled into fresh feed gas through a flow regulating valve II B03 and a summarizing connector B05 according to the recycling requirement for secondary utilization of the feed gas.
FIG. 8 is a schematic diagram of recycling tail gas from the catalytic hydrogenation of carbon dioxide to gasoline, which contains both a hydrogen permeable membrane and a carbon dioxide separation membrane. Comprising the following steps: C01. a heat exchanger and a preheater, C02. A carbon dioxide membrane separator, C03. A hydrogen permeable membrane separator; C04. in the system, tail gas flowing in from a product separation system enters a carbon dioxide membrane separation system C02 through a heat exchanger and a preheater C01, and carbon dioxide on the permeation side of the membrane separation system C02 can be recycled into fresh raw material gas for secondary utilization through a flow regulating valve II C08 and a summarizing connector C09 according to recycling requirements. The tail gas of the carbon dioxide membrane separation system enters a hydrogen permeable membrane separator C03, and hydrogen on the permeation side of the hydrogen permeable membrane separator C03 can be recycled into fresh feed gas through a flow regulating valve III C10 and a summarizing connector C09 according to the recycling requirement for secondary utilization of the feed gas. The tail gas of the hydrogen permeable membrane separator flows into a catalytic combustor C04, the reducing gas low-carbon hydrocarbon and CO in the tail gas in the catalytic combustor C04 are completely combusted to generate carbon dioxide and water, the carbon dioxide and the water enter a C06 gas-liquid separator after passing through a heat exchanger and a condenser C05, the separated liquid water is continuously discharged, and the gaseous carbon dioxide can be recycled into fresh raw gas for secondary utilization through a flow regulating valve I C and a summarizing connector C09 according to the recycling requirement.
The method for directly preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation specifically comprises the following operation steps:
the catalyst in the step (1) is subjected to reduction pretreatment; pretreatment gas (hydrogen 10% H) flowing in through the pretreatment gas outlet 2 2 /N 2 ) The catalyst is dehydrated at room temperature by a dryer 4, deoxidized at room temperature by a deoxidizer 6, preheated (230-350 ℃) by a flowmeter 8, a stop valve 11, a summarizing connector 12 and a heat exchanger 13, and quantitatively enters a reaction system 14 to perform the normal pressure 280-500 ℃ reduction pretreatment of the catalyst.
Step (2) introducing fresh raw material gas with the temperature of 10-50 ℃ and the pressure of 1.0-6.0 Mpa;
raw material gas (gas containing raw materials such as hydrogen, carbon dioxide and the like) with the temperature of 5-45 ℃ flows into a raw material gas outlet 1, is dehydrated at room temperature through a dryer 4, deoxidized at room temperature through a deoxidizer 6, and quantitatively enters a high-pressure reaction system 14 to perform high-pressure reaction of a catalyst after being preheated (230-350 ℃) sequentially through a compressor 7 (compression pressure is 1.0-6.0 MPa), a stop valve 9, a flowmeter 10, a summarizing connector 12 and a heat exchanger 13.
The high-temperature high-pressure reaction gas entering the reaction system in the step (3) reacts in the reactor designed by the invention to obtain reaction mixed gas, wherein the reaction temperature is 250-450 ℃, the pressure is 1.0-6.0 Mpa, and the general formula of the total reaction equation is as follows:
nCO 2 +(n～6n)H 2 ＝n 1 CO+n 2 CH 4 +(n 3 C 2 ～n 5 C 4 )+(n 6 C 5 ～n 12 C 11 )+n 13 H 2 O, the reaction catalyst is iron-based/molecular sieve (Na-Fe 3 O 4 HZSM-5) multifunctional composite catalyst;
cooling the outlet air flow of the reactor in the step (4) through a heat exchanger and a cooler 001 to obtain cooled and partially condensed low-temperature mixed gas/liquid, wherein the temperature of the low-temperature mixed gas/liquid is-30-10 ℃;
the low-temperature mixed gas/liquid in the step (5) is separated by a high-pressure separation tank 002 to obtain gas and liquid, and the pressure of the high-pressure separation tank 002 is 1.0-5.0 Mpa; wherein the gas part enters a tail gas recycling system after being depressurized by a depressurization valve II 004, and the temperature of the recycle gas is 15-60 ℃ and the pressure is 0.2-2.0MPa. The liquid enters a product separation tank 005 after passing through a pressure reducing valve I003, the pressure of the product separation tank is 0.5-2.5Mpa, and a small amount of separated light hydrocarbon gas enters a tail gas circulation system after passing through a pressure reducing valve III 006; the separated liquid oil is decompressed by a decompression valve IV011 and is sent to a downstream light component removal tower I007 for further rectification and purification, and the pressure of the light component removal tower I007 is 0.3-2.0MPa; the separated liquid water is continuously discharged; the gas of the top gas phase pipeline of the light component removal tower I007 enters the light component removal tower II008 through a pressure reducing valve V012, and the pressure of the light component removal tower II008 is 0.3-1.0MPa. The bottom liquid phase outlet pipeline of the light component removal tower I007 is communicated with the inlet of the product conveying pump 009, and the outlet pipeline of the product conveying pump 009 is used for delivering qualified gasoline products; the gas of the top gas phase pipeline of the light component removal tower II008 enters the tail gas utilization system through a pressure reducing valve V013, the bottom liquid phase outlet pipeline is communicated with the inlet of the product conveying pump 010, and the qualified high-value byproduct liquefied petroleum gas is sent out from the outlet pipeline of the product conveying pump 010.
Step (6) the tail gas flowing from the product separation system enters the heat exchanger and the preheater A01 (50-400℃)And the membrane separation system A02 (320-380 ℃), and hydrogen on the permeation side of the membrane separation system A02 can be recycled into fresh feed gas to carry out secondary utilization of the feed gas through a flow regulating valve I A and a summarizing connector A08 according to the recycling requirement. The tail gas of the membrane separation flows into a catalytic combustor A03 (room temperature-500 ℃), and the reducing gases of low-carbon hydrocarbon and CO in the tail gas in the catalytic combustor are completely combusted to generate carbon dioxide and water, and the carbon dioxide and the water are mixed with CO in the tail gas 2 After passing through the heat exchanger and the condenser A04, the liquid water enters the A05 gas-liquid separator, the separated liquid water is continuously discharged, and the gaseous carbon dioxide can be recycled into fresh feed gas through the flow regulating valve II A07 and the summarizing connector A08 according to the recycling requirement for secondary utilization of the feed gas.
Example 1
The raw material gas distributor is shown in fig. 4, a phi 12 stainless steel tube is adopted, each row of 8 holes is 6 rows of holes, each row is staggered up and down, and the specific aperture and the specific spacing are shown in fig. 4. In this example, 1 feed gas distributor was placed.
The method for directly preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation specifically comprises the following operation steps:
the catalyst in the step (1) is subjected to reduction pretreatment; pretreatment gas (10 vol% H) flowing in from the pretreatment gas outlet 2 2 /N 2 ) Dehydrating at room temperature by a dryer 4, deoxidizing at room temperature by a deoxidizer 6, preheating (260 ℃) by a flowmeter 8, a stop valve 11, a collecting connector 12 and a heat exchanger 13, and quantifying (3000 mL g) Cat -1 ·h -1 ) The reaction system 14 was charged with the catalyst subjected to a pretreatment for reduction at 350℃under normal pressure (0.1 MPa) for 6 hours.
Step (2), introducing fresh raw material gas;
the raw material gas outlet 1 is supplied with raw material gas (gas containing hydrogen, carbon dioxide, and nitrogen raw material, H) having a temperature of 50deg.C 2 /CO 2 Volume ratio=3), dehydrating at room temperature by a dryer 4, deoxidizing at room temperature by a deoxidizer 6, preheating (260 ℃) and quantifying (3000 mL g) by a compressor 7 (compression pressure is 3.5 MPa), a stop valve 9, a flowmeter 10, a summarizing connector 12 and a heat exchanger 13 in sequence Cat -1 ·h -1 ) And enters a high pressure reaction system 14 to perform high pressure reaction of the catalyst.
The high-temperature and high-pressure reaction gas entering the reaction system in the step (3) is reacted in the reactor designed by the invention to obtain the reaction mixture, the reaction temperature is 320 ℃, the pressure is 3.0Mpa, and the space velocity is 4000mL g of catalyst -1 ·h -1 。
The catalyst I is an iron-based catalyst and is Na-Fe 3 O 4 The dosage is 20g, the catalyst II is an acidic molecular sieve, the mass ratio of the iron-based catalyst to the acidic molecular sieve is 1/2, and the acidic molecular sieve is HZSM-5 (silicon-aluminum ratio is 200). The heat exchange medium in the heat exchange system adopts heat conduction oil.
Cooling the outlet air flow of the reactor in the step (4) through a heat exchanger and a cooler 001 to obtain cooled and partially condensed low-temperature mixed gas/liquid, wherein the temperature of the low-temperature mixed gas/liquid is 5 ℃;
step (5), separating the low-temperature mixed gas/liquid by a high-pressure separation tank 002 to obtain gas and liquid, wherein the pressure of the high-pressure separation tank 002 is 3.0Mpa; wherein the gas part enters a tail gas recycling system after being depressurized by a depressurization valve II 004, and the temperature of the recycle gas is 20 ℃ and the pressure is 0.5MPa. The liquid enters a product separation tank 005 after passing through a pressure reducing valve I003, the pressure of the product separation tank is 1.5Mpa, and a small amount of separated light hydrocarbon gas enters a tail gas circulation system after passing through a pressure reducing valve III 006; the separated liquid oil is decompressed through a decompression valve IV011, and is sent to a downstream light component removal tower I007 for further rectification and purification, and the pressure of the light component removal tower I007 is 0.5MPa; the separated liquid water is continuously discharged; the gas in the top gas phase pipeline of the light component removal column I007 enters the light component removal column II008 through a pressure reducing valve V012, and the pressure of the light component removal column II008 is 0.3MPa. The bottom liquid phase outlet pipeline of the light component removal tower I007 is communicated with the inlet of the product conveying pump 009, and the outlet pipeline of the product conveying pump 009 is used for delivering qualified gasoline products; the gas of the top gas phase pipeline of the light component removal tower II008 enters the tail gas utilization system through a pressure reducing valve V013, the bottom liquid phase outlet pipeline is communicated with the inlet of the product conveying pump 010, and the qualified high-value byproduct liquefied petroleum gas is sent out from the outlet pipeline of the product conveying pump 010.
The tail gas flowing from the product separation system in the step (6) enters a membrane separation system A02 (350 ℃) through a heat exchanger and a preheater A01 (350 ℃), A02 is a high Wen Touqing palladium membrane separation system, and hydrogen on the permeation side of the membrane separation system A02 can be recycled according to the recycling requirementFresh feed gas is recycled through a flow regulating valve I A and a summarizing connector A08 for secondary utilization of the feed gas. The tail gas of the membrane separation flows into a catalytic combustor A03 (300 ℃), and the reducing gas low-carbon hydrocarbon and CO in the tail gas in the catalytic combustor are completely combusted to generate carbon dioxide and water, and the carbon dioxide and the CO in the tail gas are mixed with each other 2 After passing through the heat exchanger and the condenser A04, the liquid water enters the A05 gas-liquid separator, the separated liquid water is continuously discharged, and the gaseous carbon dioxide can be recycled into fresh feed gas through the flow regulating valve II A07 and the summarizing connector A08 according to the recycling requirement for secondary utilization of the feed gas.
CO 2 Is 30% per pass conversion and the gasoline product per pass yield is 105mg Gasoline G catalyst -1 ·h -1 ，CO 2 The cyclic utilization rate of (2) is 85%.
Example 2
The same as in example 1 except that the tail gas recycling system was changed to a tail gas recycling system comprising a carbon dioxide separation membrane (FIG. 7). CO 2 The single pass conversion of (2) was 28%, and the single pass yield of the gasoline product was 95mg Gasoline G catalyst -1 ·h -1 ，CO 2 The cyclic utilization rate of (2) is 87%.
Example 3
The same as in example 1, except that the tail gas recycling system was changed to one comprising both a hydrogen permeable membrane (using a high Wen Touqing palladium membrane separation system) and a carbon dioxide separation membrane (FIG. 8). CO 2 The conversion of (2) was 31%, and the yield of the gasoline product was 106mg Gasoline G catalyst -1 ·h -1 ，CO 2 The cyclic utilization ratio of (2) is 91%.
Comparative example 1
The same procedure as in example 1 was followed except that the reaction system employed a conventional fixed bed reactor without a feed distributor and a heat transfer oil.
CO 2 The conversion of (2) was 50% and the single pass yield of the gasoline product was 30mg Gasoline G catalyst -1 ·h -1 ，CO 2 The cyclic utilization ratio of (2) is 30%.
The reaction heat in the reaction process causes the temperature of the catalyst bed layer of the reactor to rise rapidlyAt a temperature of above 500 ℃, CO 2 The conversion rate is rapidly increased, but the main products are converted into methane and CO, and the selectivity of gasoline products is rapidly reduced, so that the CO is calculated 2 The cyclic utilization rate of the catalyst is greatly reduced. In addition, the temperature of the catalyst bed layer is increased drastically, so that the active structure of the catalyst is destroyed, the reaction performance of the catalyst is further reduced, and the stability of the catalytic reaction is obviously reduced.
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.

Claims (19)

1. The device for preparing gasoline by catalytic hydrogenation of carbon dioxide is characterized by comprising a pretreatment unit, a reaction unit, a product separation unit and a tail gas recycling unit;
the pretreatment unit, the reaction unit, the product separation unit and the tail gas recycling unit are sequentially communicated;
the reaction unit is a reactor;
the reactor comprises a raw material gas distributor, a first-stage reaction zone and a second-stage reaction zone;
a catalyst I is placed in the first-stage reaction zone, and a catalyst II is placed in the second-stage reaction zone;
the raw material gas distributor is positioned in the first-stage reaction zone and is communicated with the first-stage reaction zone;
the second-stage reaction zone is positioned at the lower part of the first-stage reaction zone and is communicated with each other;
the number of the raw material gas distributors is 1-100;
the raw material gas distributor comprises a shell I, wherein the shell I surrounds a columnar cavity;
the shell is provided with a plurality of air hole groups along the axial direction;
each air hole group comprises a plurality of air discharge holes arranged along the circumferential direction;
the distance between two adjacent air hole groups is set in a preset mode I from top to bottom along the axial direction;
the pore diameters of the exhaust pores in two adjacent pore groups are also arranged in a preset mode II from top to bottom along the axial direction;
The preset mode I is gradually increased; or alternatively, the process may be performed,
the preset mode I is gradually increased and then kept unchanged;
the preset mode II is gradually reduced; or alternatively, the process may be performed,
the preset mode II is gradually reduced and then kept unchanged;
the distance between two adjacent air hole groups is n, and the difference between the adjacent air hole groups is delta n;
wherein, delta n/n is more than or equal to 0 and less than or equal to 5;
the air outlet holes of each row are staggered up and down.
2. The apparatus for producing gasoline by catalytic hydrogenation of carbon dioxide according to claim 1, wherein the reactor further comprises a heat conduction device;
the inlet of the heat conduction device is connected with the first section reaction zone;
the outlet of the heat conduction device is connected with the second section reaction zone.
3. The apparatus for producing gasoline by catalytic hydrogenation of carbon dioxide according to claim 1, wherein the product separation unit comprises a pressure swing adsorption separation apparatus.
4. The apparatus for preparing gasoline by catalytic hydrogenation of carbon dioxide according to claim 3, wherein the pressure swing adsorption separation device comprises a high pressure separation tank, a product separation tank, a light component removal tower I and a light component removal tower II;
the high-pressure separation tank, the product separation tank, the light component removal tower I and the light component removal tower II are sequentially communicated.
5. The device for preparing gasoline by catalytic hydrogenation of carbon dioxide according to claim 4, wherein a pressure reducing valve is connected among the high-pressure separating tank, the product separating tank, the light component removing tower I and the light component removing tower II.
6. The apparatus for preparing gasoline by catalytic hydrogenation of carbon dioxide according to claim 4, wherein the high-pressure separation tank separates a gas part and a liquid part, and the liquid part separates light hydrocarbon gas, liquid oil and wastewater through the product separation tank; the liquid oil is separated by a light component removing tower I to obtain gasoline, and is separated by a light component removing tower II to obtain liquefied petroleum gas.
7. The apparatus for preparing gasoline by catalytic hydrogenation of carbon dioxide according to claim 1, wherein the tail gas recycling unit comprises a membrane separation system;
the membrane separation system comprises a hydrogen permeable membrane separation system and/or a CO permeable membrane separation system 2 A membrane separation system.
8. The apparatus for preparing gasoline by catalytic hydrogenation of carbon dioxide according to claim 7, wherein the hydrogen permeable membrane separation system comprises a hydrogen permeable membrane separator and a catalytic burner;
the catalytic burner is arranged at the rear of the hydrogen permeable membrane separator so as to catalyze and burn the gas separated from the hydrogen by the hydrogen permeable membrane separator to obtain carbon dioxide.
9. The apparatus for producing gasoline by catalytic hydrogenation of carbon dioxide as claimed in claim 7, wherein the CO-permeable gas is a gas 2 The membrane separation system separates the tail gas into carbon dioxide and CO 2 And (3) separating tail gas by a membrane.
10. The apparatus for producing gasoline by catalytic hydrogenation of carbon dioxide as claimed in claim 7, wherein the hydrogen permeable membrane separation system and the CO permeable membrane are 2 When the membrane separation systems coexist, the hydrogen permeable membrane separation system is arranged at the CO permeable position 2 After the membrane separation system.
11. The apparatus for producing gasoline by catalytic hydrogenation of carbon dioxide according to claim 7, wherein the hydrogen permeable membrane separation system is selected from one of an organic hydrogen permeable membrane separation system and a hydrogen permeable palladium membrane separation system.
12. The apparatus for producing gasoline by catalytic hydrogenation of carbon dioxide according to claim 1, wherein the pretreatment unit comprises a dryer, a deoxidizer and a heat exchanger;
the dryer, the deoxidizer and the heat exchanger are communicated in sequence.
13. A method for preparing gasoline by catalytic hydrogenation of carbon dioxide, which is characterized by comprising the following steps:
(a) Will contain CO 2 And H 2 The raw material gas is treated by a pretreatment unit to obtain pretreated materials;
(b) Carrying out catalytic reaction on the pretreated material in a reaction unit to obtain a material flow I;
(c) Separating the material flow I in a product separation unit to separate tail gas and waste water and obtain liquefied petroleum gas and gasoline;
(d) Treating the tail gas by a tail gas recycling unit to obtain fresh raw gas;
the method for producing gasoline employs one of the apparatuses according to any one of claims 1 to 12.
14. The method for producing gasoline by catalytic hydrogenation of carbon dioxide according to claim 13, wherein in step (a), H is contained in the pretreated material 2 /CO 2 Volume ratio=0.5-8, temperature 230-460 ℃, pressure 1.0-6.0 MPa.
15. The method for producing gasoline by catalytic hydrogenation of carbon dioxide according to claim 13, wherein in step (b), the catalyst space velocity: 1000-10000 ml/(g.h), the reaction temperature is 250-450 ℃, and the pressure is 1.0-6.0 Mpa.
16. The method for producing gasoline by catalytic hydrogenation of carbon dioxide according to claim 13, wherein in step (c), the pressure of the high-pressure separation tank is 1.0 to 5.0Mpa; the pressure of the product separation tank is 0.5-2.5Mpa; the pressure of the light component removing tower I is 0.3-2.0MPa; the pressure of the light component removing tower II is 0.3-1.0MPa;
separating the material flow I in a high-pressure separating tank to obtain a gas part and a liquid part, wherein the gas part enters a tail gas recycling unit;
The liquid part is separated into light hydrocarbon gas, liquid oil and wastewater by a product separation tank, the light hydrocarbon gas enters a tail gas recycling unit, and the wastewater is discharged;
the liquid oil is separated by a light component removing tower I to obtain gasoline, and is separated by a light component removing tower II to obtain liquefied petroleum gas.
17. The method for producing gasoline by catalytic hydrogenation of carbon dioxide according to claim 13, wherein in the step (d), the tail gas is separated by a hydrogen permeable membrane separation system to obtain hydrogen and a hydrogen permeable membrane separation tail gas, the hydrogen permeable membrane separation tail gas is catalytically combusted to obtain carbon dioxide, and the hydrogen and the carbon dioxide are mixed and reused.
18. The method for producing gasoline by catalytic hydrogenation of carbon dioxide according to claim 13, wherein in step (d), the tail gas is CO-permeated 2 The membrane separation system separates CO 2 And CO permeation 2 And (3) separating tail gas by a membrane.
19. The method for producing gasoline by catalytic hydrogenation of carbon dioxide according to claim 18, wherein in step (d), CO is permeated 2 The membrane separation tail gas is separated again by a hydrogen permeable membrane separation system to obtain hydrogen and hydrogen permeable membrane separation tail gas, and the hydrogen permeable membrane separation tail gas is catalytically combusted to obtain carbon dioxide, and the hydrogen and the carbon dioxide are mixed and then are reused.
CN202011266069.0A 2020-11-13 2020-11-13 Device and method for preparing gasoline by catalytic hydrogenation of carbon dioxide Active CN114479902B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011266069.0A CN114479902B (en) 2020-11-13 2020-11-13 Device and method for preparing gasoline by catalytic hydrogenation of carbon dioxide

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011266069.0A CN114479902B (en) 2020-11-13 2020-11-13 Device and method for preparing gasoline by catalytic hydrogenation of carbon dioxide

Publications (2)

Publication Number Publication Date
CN114479902A CN114479902A (en) 2022-05-13
CN114479902B true CN114479902B (en) 2023-07-28

Family

ID=81489755

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011266069.0A Active CN114479902B (en) 2020-11-13 2020-11-13 Device and method for preparing gasoline by catalytic hydrogenation of carbon dioxide

Country Status (1)

Country Link
CN (1) CN114479902B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110669543A (en) * 2019-10-28 2020-01-10 东华工程科技股份有限公司 Device and method for directly preparing gasoline by carbon dioxide hydrogenation
CN111748366A (en) * 2020-07-13 2020-10-09 珠海市福沺能源科技有限公司 Device and method for directly preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation
CN213803649U (en) * 2020-11-13 2021-07-27 中国科学院大连化学物理研究所 Device for preparing gasoline by catalytic hydrogenation of carbon dioxide

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110669543A (en) * 2019-10-28 2020-01-10 东华工程科技股份有限公司 Device and method for directly preparing gasoline by carbon dioxide hydrogenation
CN111748366A (en) * 2020-07-13 2020-10-09 珠海市福沺能源科技有限公司 Device and method for directly preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation
CN213803649U (en) * 2020-11-13 2021-07-27 中国科学院大连化学物理研究所 Device for preparing gasoline by catalytic hydrogenation of carbon dioxide

Also Published As

Publication number Publication date
CN114479902A (en) 2022-05-13

Similar Documents

Publication Publication Date Title
Tijm et al. Methanol technology developments for the new millennium
JP6347995B2 (en) Method for simultaneous production of methanol and synthetic natural gas with coke oven gas and plant for achieving the method
CN100582066C (en) Process for producing ethylene by ethanol dehydration
CN108017487B (en) Two-stage reaction method for preparing aromatic hydrocarbon from oxygen-containing compound-containing raw material
CN101249949A (en) Technique for preparing hydrogen gas by hydrocarbons gases
CN110171804B (en) Hydrogen production and purification integrated device and use method
CN107162912B (en) Method for preparing methyl acetate by adopting sectional type adiabatic fixed bed reactor
CN213803649U (en) Device for preparing gasoline by catalytic hydrogenation of carbon dioxide
CN101115700B (en) Process for production of aromatic compound and process for production of hydrogenated aromatic compound
CN111320528A (en) Method and system for preparing ethanol by comprehensively utilizing steel mill tail gas
CN105779046A (en) Method for preparing LNG (Liquefied Natural Gas) by using Fischer-Tropsch synthesis tail gas as raw material
CN102656121A (en) Process for cleaning a process condensate
CN114524412A (en) Methanol and light hydrocarbon combined aromatization and hydrogen production system and method
CN114479902B (en) Device and method for preparing gasoline by catalytic hydrogenation of carbon dioxide
CN105130730A (en) Technological method for preparing light hydrocarbons through methanol by means of continuous regeneration moving beds and production system
CN111559949B (en) System and method for increasing yield of p-xylene by using carbon-rich natural gas
CN114874800A (en) Biomass-based organic liquid hydrogen storage system and method
CN102872772B (en) With the reaction unit that methyl alcohol and ethanol are raw material combined producing dimethyl ether and ethene
CN112295511B (en) Carbon-three liquid phase hydrogenation reactor and carbon-three hydrogenation reaction method
CN101870632A (en) Method for producing low-carbon olefin
CN108017485B (en) Process for preparing aromatic hydrocarbon and combustible gas from methanol
CN103992198A (en) Benzene production technology taking coke oven gas as raw material
CN214106876U (en) Feed gas distributor and reactor comprising same
CN102875298B (en) With the method that methyl alcohol and ethanol are raw material combined producing dimethyl ether and ethene
EP4289807A1 (en) Ethanol based intensified ethylene production

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right
TA01 Transfer of patent application right

Effective date of registration: 20230619

Address after: Room 801-8012, Hengqin International Business Center, No. 3000 Huandao East Road, Hengqin New District, Zhuhai City, Guangdong Province, 519031

Applicant after: Zhuhai Fuyi Energy Technology Co.,Ltd.

Applicant after: DALIAN INSTITUTE OF CHEMICAL PHYSICS, CHINESE ACADEMY OF SCIENCES

Address before: 116023 No. 457, Zhongshan Road, Liaoning, Dalian

Applicant before: DALIAN INSTITUTE OF CHEMICAL PHYSICS, CHINESE ACADEMY OF SCIENCES

GR01 Patent grant
GR01 Patent grant