CN213803649U - Device for preparing gasoline by catalytic hydrogenation of carbon dioxide - Google Patents
Device for preparing gasoline by catalytic hydrogenation of carbon dioxide Download PDFInfo
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- CN213803649U CN213803649U CN202022633275.2U CN202022633275U CN213803649U CN 213803649 U CN213803649 U CN 213803649U CN 202022633275 U CN202022633275 U CN 202022633275U CN 213803649 U CN213803649 U CN 213803649U
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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 communicated in sequence. Also discloses a method for preparing gasoline by catalytic hydrogenation of carbon dioxide by adopting the device. The device for preparing gasoline by carbon dioxide hydrogenation is effectively combined and applied to each system, the utilization rate of carbon dioxide resources can reach more than 80 percent, even more than 90 percent, almost no waste gas is discharged, and the environmental protection property of the process is obviously improved. And simultaneously, the utility model discloses a reaction system, whole system's steady operation has been guaranteed.
Description
Technical Field
The application relates to a device for preparing gasoline by catalytic hydrogenation of carbon dioxide, belonging to the field of chemical processes for producing gasoline.
Background
The method for preparing the liquid fuel and the high-value chemical products by converting the carbon dioxide has potential significance in the fields of energy and chemical industry in China, is beneficial to emission reduction of the carbon dioxide, and is beneficial to effective utilization of the carbon dioxide as a resource. In addition, hydrogen produced by electrolyzing water by using renewable energy sources (water energy, solar energy, wind energy and the like) and carbon dioxide can be converted into liquid fuel and high-value chemicals, and the problem of energy storage which always troubles the renewable energy sources can be solved, so that the process of producing the liquid fuel and the high-value chemicals by hydrogenating the carbon dioxide plays an important role in a future energy system. Among many products, gasoline is an important transportation fuel, is most widely applied worldwide, has the most perfect storage and transportation infrastructure, and has a great promoting effect on the popularization and utilization of renewable energy sources undoubtedly if the application of gasoline prepared by carbon dioxide hydrogenation can be realized.
But due to CO2Is chemically inert to CO2The conversion of lower carbon compounds such as methane, methanol, etc. by hydrogenation is relatively easy, but the conversion to higher carbon containing compounds is very challenging, and there is a need to develop more efficient catalyst systems. CO22The research on the hydrogenation high-selectivity synthesis of gasoline hydrocarbon compounds can be divided into two categories: one is through the reaction of oxygen-containing intermediate species such as methanol; the other is via a Fischer-Tropsch synthesis (FTS) like reaction. Currently, most of the research work mainly employs FTS-like reaction pathways, i.e., CO2CO is generated through a Reverse Water Gas Shift (RWGS) reaction, and then the FTS reaction is generated after the CO is hydrogenated. In any way, the single-pass yield of the carbon dioxide needs to be further improved; in addition, the research on the reaction device and reactor in the process of preparing gasoline by carbon dioxide hydrogenation is less, because the process is a processThe rapid exothermic reaction, how to keep the uniform distribution of the reaction heat of the catalyst bed and the timely removal of the reaction heat are important problems to be solved when the process is applied. The prior art relates to a device and a method for directly preparing gasoline by carbon dioxide hydrogenation. The device and the method adopt indium oxide/molecular sieve (In)2O3The reactor adopts a tubular synthesis reactor with an external circulating heat exchange mechanism, the outlet of the reactor is cooled in multiple stages, a molecular sieve adsorber is used for dehydration, gas-liquid separation is carried out, gas phase components in the gas phase components are partially recycled, and the gas phase components are partially used as purge gas and discharged out of a torch system. The device has characteristics suitable for In2O3The reaction for preparing gasoline by catalyzing carbon dioxide with HZSM-5 has the characteristics of low conversion rate, high gasoline product selectivity and low water content in the product. But has high conversion rate for catalyzing carbon dioxide hydrogenation to prepare gasoline, high gasoline product selectivity and high water content of product iron-based/molecular sieve (Na-Fe)3O4/HZSM-5) multifunctional composite catalyst is not suitable, for example, a molecular sieve adsorber 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, and the total conversion rate of the reaction is also reduced. Therefore, development of suitable iron-based/molecular sieves (Na-Fe)3O4The reaction device system with the characteristics of the/HZSM-5) multifunctional composite catalyst molecular sieve is necessary.
SUMMERY OF THE UTILITY MODEL
Aiming at the current CO2The device characteristics required by the reaction of hydrogenation gasoline production, the utility model is mainly suitable for Na-Fe3O4HZSM-5 catalyzed CO2The reaction device has the characteristics of the reaction process for preparing gasoline by hydrogenation, and simultaneously, the designed reaction device system has the characteristics of high gasoline yield, low device energy consumption, economy, environmental protection and the like.
According to one aspect of the application, the device for preparing the gasoline by catalytic hydrogenation of the carbon dioxide is effectively combined and applied to various systems and comprises a pretreatment unit, a reaction unit, reaction product separation, tail gas recycling and the like, wherein the pretreatment unit is used for pretreating feed gas CO2And H2Gas to satisfy CO on iron catalyst2The reaction with hydrogen to gasoline meets the requirements of gas and reaction conditions; the reaction unit refers to the CO reaction carried out on an iron catalyst2Conversion system petrol go on, the utility model discloses a reaction unit is including the reactor that contains heat transfer part etc, and the catalyst adopts the multilayer to dilute to load in the reactor, and the evenly distributed of reaction heat and too much reaction heat ground in time desorption have reached when the system operation, have guaranteed CO2The hydrogenation gasoline reaction is stably operated; the product separation unit adopts the traditional pressure swing adsorption separation and adopts proper conditions to ensure the recovery of gasoline products; the tail gas recycling unit adopts a membrane separation system, so that the separated hydrogen and CO are contained2The tail gas can be circularly fed into the raw material gas for secondary conversion and utilization according to the requirement of the circulation of the raw material gas, so that the conversion efficiency of the reaction device is further improved.
A 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 communicated in sequence.
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 feed 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 the first-stage reaction zone.
Optionally, the number of the raw material gas distributors is 1-100, the optimization is 1-50, and the optimal number is 1-10. If the difference between the reactor and the distributor is large, more distributors can be arranged, and in extreme cases, 100 distributors or more can be arranged, and the corresponding adjustment can be carried out according to actual conditions in the application process.
Optionally, the feed gas distributor comprises a shell I, and the shell I encloses 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 every two adjacent air hole groups is arranged along the axial direction according to a preset mode I from top to bottom;
and the aperture of the exhaust vent in the adjacent two vent groups is also arranged from top to bottom along the axial direction according to a preset mode II.
Optionally, the preset mode i is gradually increased; alternatively, the first and second electrodes may be,
the preset mode I is gradually increased and then is kept unchanged.
Optionally, the preset mode ii is gradually decreased; alternatively, the first and second electrodes may be,
and the preset mode II is gradually reduced and then is kept unchanged.
Optionally, the preset mode II is unchanged and then gradually reduced; alternatively, the first and second electrodes may be,
and the preset mode II is that the preset mode II is gradually reduced and then is reduced after the preset mode II is kept unchanged.
Optionally, the distance between two adjacent air hole groups is n, and the difference between the adjacent distances is Δ n;
wherein, delta n/n is more than or equal to 0 and less than or equal to 5;
alternatively, 0 ≦ Δ n/n ≦ 3.
Alternatively, 0.2 ≦ Δ n/n ≦ 1.
Alternatively, the outlet holes of each row are staggered up and down.
In a preferred embodiment, the aperture size of each of the first and second exhaust holes is 0.5mm, and the distance between the first and second exhaust holes is 0.5 cm; the aperture sizes of the third and fourth air outlet holes are both 0.4mm, the distance is 1.5cm, and the distance between the second and third air outlet holes is 1 cm; (ii) a The aperture sizes of the fifth and sixth air outlet holes are both 0.3mm, the distance is 2cm, and the distance between the fourth and fifth air outlet holes is 2 cm.
In a preferred embodiment, the first and second discharge holes have a hole diameter of 0.7mm and 0.5mm, respectively, and a pitch of 0.7 cm; the aperture sizes of the third and fourth air outlet holes are both 0.4mm, the distance is 1.5cm, and the distance between the second and third air outlet holes is 1.0 cm; the aperture size of the fourth exhaust holes is 0.2mm, and the distance is 2.0 cm.
Optionally, the distance between the 1 st discharge hole and the top end of the feed gas distributor is more than or equal to one eighth of the total length of the feed gas distributor.
Optionally, the distance between the 1 st discharge hole and the top end of the feed gas distributor is greater than or equal to one half of the total length of the feed gas distributor.
In this application, do not strictly limit to the length of feed gas distributor, internal diameter to and the aperture of venthole, in the in-service use process, according to the specification of the reactor of specific selection carry out corresponding matching selection can.
Optionally, the reactor further comprises a heat conducting means;
the inlet of the heat conducting device is connected with the first-stage reaction zone;
and the outlet of the heat conduction device is connected with the second-stage reaction zone.
Optionally, the heat transfer device is a heat exchange system containing heat transfer oil. The heat conducting oil enters the reactor through the heat conducting oil inlet, flows out from the outlet of the heat conducting oil pipe of the reaction through the heat conducting oil pipe line in the reactor, enters the heat exchange equipment of the heat conducting oil, and removes the reaction heat in time.
The utility model discloses a reaction unit is including the reactor etc. that contain heat transfer part, and the catalyst adopts the multilayer to dilute to load in the reactor (iron catalyst dilutes, molecular sieve catalyst component does not dilute), has adopted the reactor that contains raw material distributor, heat conductor simultaneously, and the evenly distributed of reaction heat and too much reaction heat ground in time desorption when reaching the system operation have guaranteed CO2The hydrogenation gasoline reaction is stable in operation.
Catalyst is filled in a traditional fixed reactor, and bed hot spots and bed temperature runaway phenomena are easy to occur on a catalyst bed. The normal catalyst reaction temperature is 320 ℃, but the hot spot temperature appears on the catalyst bed layer after the reaction, and the temperature is rapidly increased to more than 500 ℃ (within 2 hours), so that the reaction can not be carried out, the catalyst structure is damaged, and the reaction performance of the catalyst is seriously influenced. By adopting the reactor designed by the utility model, the bed temperature of the catalyst is basically controlled to be about 320 ℃, the hot point of the catalyst bed is not obvious and is not more than 350 ℃, and the reaction can be stably operated for nearly thousand 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 primary function of the product separation system is to ensure the separation and purification of the main hydrocarbon byproduct liquefied petroleum gas, and increase the added value of the products and the economical efficiency 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 communicated in sequence.
Optionally, a pressure reducing valve is connected between each of the high-pressure separation tank, the product separation tank, the light component removal column I and the light component removal column 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 in front of the high-pressure separation tank.
Specifically, the product separation unit adopts the traditional pressure swing adsorption separation and adopts proper conditions to ensure the recovery of gasoline products. The method comprises the following steps: 001. a heat exchanger and a cooler, 002, a high-pressure separation tank, 003, a pressure reducing valve I, 004 and a pressure reducing valve II; 005. in the system, after the gas at the outlet of a reactor flows through a heat exchanger and a cooler 001 for cooling treatment, cold gas (minus 30-10 ℃) enters a high-pressure separation tank 002 to obtain gas and liquid, wherein the gas part enters a tail gas recycling system after passing through a pressure reducing valve II 004, 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 circulating system after passing through the pressure reducing valve 006 III; reducing the pressure of the separated liquid oil by a pressure reducing valve IV011, and sending the liquid oil to a downstream lightness-removing tower I007 for further rectification and purification; the separated liquid water is discharged continuously; gas in a gas phase pipeline at the top of the light component removal tower I007 enters a light component removal tower II008 through a pressure reducing valve V012, a liquid phase outlet pipeline at the bottom of the light component removal tower I007 is communicated with an inlet of a product delivery pump 009, and an outlet pipeline of the product delivery pump 009 delivers qualified gasoline products; the gas in the top gas phase pipeline of the light component removal tower II008 enters the tail gas utilization system through the pressure reducing valve V013, the bottom liquid phase outlet pipeline is communicated with the inlet of the product delivery pump 010, and the qualified high-value byproduct liquefied petroleum gas is delivered out of the outlet pipeline of the product delivery pump 010.
Specifically, a heat exchanger and a cooler are connected with a high-pressure separation tank, one end of the high-pressure separation tank discharges tail gas through a pressure reducing valve, and the other end of the high-pressure separation tank is connected with a product separation tank through the pressure reducing valve; one end of the product separation tank discharges tail gas through a pressure reducing valve, the other end of the product separation tank discharges waste water, and the other end of the product separation tank is connected with a light component removal tower I through the pressure reducing valve; one end of the light component removal tower I is used for conveying gasoline out through a product conveying pump I, and the other end of the light component removal tower I is connected with a light component removal tower II through a pressure reducing valve; one end of the light component removal tower II is conveyed with liquefied petroleum gas through a product conveying pump II, and the other end of the light component removal tower II is discharged with waste gas through a pressure reducing valve.
Optionally, the off-gas recycle unit comprises a membrane separation system;
the membrane separation system comprises a hydrogen permeable membrane separation system and/or a CO permeable membrane separation system2A membrane separation system.
The tail gas recycling unit adopts a membrane separator and a catalytic burner, and aims to ensure the complete recycling of the carbon-containing tail gas, enhance the environmental protection performance of the process and improve 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 combustor is arranged behind the hydrogen permeable membrane separator, so that the gas separated from the hydrogen permeable membrane separator is catalytically combusted 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 permeation2The membrane separation system separates the tail gas into carbon dioxide and CO2And (4) separating tail gas by using a membrane.
Optionally, the hydrogen permeable membrane separation system and CO permeable2When the membrane separation system exists simultaneously, the hydrogen permeable membrane separation system is arranged for permeating CO2After 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-temperature hydrogen permeable palladium membrane separation system.
In the application, a hydrogen permeable membrane separation system is adopted to separate the tail gas into hydrogen, and CO is permeated2Membrane separation system for separating CO from tail gas2. In a specific practical application scene, the corresponding hydrogen permeable membrane and CO permeable membrane can be selected according to the practical situation2A membrane module.
Optionally, the membrane separation system is preceded by a heat exchanger and a preheater.
Specifically, the tail gas recycling unit adopts a membrane separation system, so that the separated hydrogen and CO are contained2The tail gas can be circularly fed into the raw material gas for secondary conversion and utilization according to the requirement of the circulation of the raw material gas, so that the conversion efficiency of the reaction device is further improved. The method comprises the following steps: A01. the system comprises a heat exchanger, a preheater, an A02 membrane separator, an A03 catalytic combustor, an A04 heat exchanger, a condenser, an A05 gas-liquid separator, an A06 flow regulating valve I, an A07 flow regulating valve II and an A08 summarizing connector. 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 circulated into fresh gas through a flow regulating valve I A06 and a summarizing connector A08 according to circulation requirementsAnd carrying out secondary utilization on the raw material gas. The tail gas from membrane separation flows into a catalytic combustor A03, the reducing gases of low carbon hydrocarbon and CO in the tail gas from the catalytic combustor are completely combusted to generate carbon dioxide and water, and the carbon dioxide and the CO in the tail gas2After passing through a heat exchanger and a condenser A04, the liquid water enters an A05 gas-liquid separator, the separated liquid water is continuously discharged, and the gas carbon dioxide can be circularly fed into fresh feed gas for secondary utilization of the feed gas through a flow regulating valve II A07 and a gathering connector A08 according to the circulation requirement.
Specifically, the heat exchanger and the preheater are connected with a hydrogen permeable membrane separator; one end of the catalytic combustor is connected with a heat exchanger and a condenser, the heat exchanger and the condenser are connected with a gas-liquid separator, one end of the gas-liquid separator discharges waste water, the other end of the gas-liquid separator obtains carbon dioxide, and the hydrogen and the carbon dioxide respectively pass through a flow regulating valve and a gathering connector to obtain fresh feed gas.
Specifically, the heat exchanger and the preheater are connected with a carbon dioxide permeable membrane separator; one end of the reactor is separated to obtain carbon dioxide, the other end of the reactor is separated to obtain hydrogen, carbon monoxide and low carbon hydrocarbon, and the carbon dioxide and the hydrogen respectively pass through a flow regulating valve and a gathering connector to obtain fresh feed gas.
Specifically, the heat exchanger and the preheater are connected with a carbon dioxide permeable membrane separator, one end of the heat exchanger is used for separating carbon dioxide, and the other end of the heat exchanger is connected with a hydrogen permeable membrane separator; one end of the hydrogen permeable membrane separator is used for separating hydrogen, the other end of the hydrogen permeable membrane separator is connected with the catalytic combustor, a heat exchanger and a condenser are connected behind the catalytic combustor, a gas-liquid separator is connected behind the heat exchanger and the condenser, waste water is discharged from one end of the gas-liquid separator, and carbon dioxide is obtained from the other end of the gas-liquid separator; the carbon dioxide separated by the carbon dioxide permeable membrane separator, the hydrogen separated by the hydrogen permeable membrane separator and the carbon dioxide separated by the gas-liquid separator are respectively treated by a flow regulating valve and a collecting connector to obtain fresh raw material gas.
Optionally, the pretreatment unit comprises a dryer, a deoxygenator, and a heat exchanger;
the dryer, the deoxygenator and the heat exchanger are communicated in sequence.
Optionally, a compressor, a stop valve and a flow meter are sequentially arranged between the deoxygenator and the heat exchanger.
Optionally, the pretreatment unit further comprises a gas pretreatment portion of a catalyst; comprises a dryer and a deoxygenator; this part is connected to the summing connector via a shut-off valve.
The pretreatment unit has double functions, namely, reduction treatment on the catalyst; secondly, the raw materials are pretreated. In a specific operation, the operation can be realized by switching gas.
Specifically, the pretreatment gas (hydrogen or gas containing hydrogen) is subjected to trace water removal of the pretreatment gas by a dryer 4 and trace oxygen removal of the pretreatment gas by a deoxygenator 6, and is preheated by a flowmeter 8, a stop valve 11, a summary connector 12 and a heat exchanger 13 in sequence and then quantitatively enters a reaction system 14 for normal-pressure pretreatment of the catalyst; and after the pretreatment of the catalyst is finished, switching the raw material gas to start reaction.
Specifically, the pretreatment system refers to pretreatment of feed gas CO2And H2Gas to satisfy CO on iron catalyst2The reaction with hydrogen to gasoline meets the requirements of 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, a flow meter, a stop valve and a collecting connector, wherein the raw material gas outlet is 2, the pretreatment gas outlet is 3, the dryer is 4, the deoxidizer is 5, the deoxidizer is 6, the compressor is 7, the flow meter is 8, the stop valve is 9, the flow meter is 10, the stop valve is 11, and the collecting connector is 12. In the system, before the catalyst system reacts, reduction pretreatment needs to be carried out, at the moment, pretreatment gas (hydrogen or gas containing hydrogen) flowing from a pretreatment gas outlet 2 is subjected to trace water removal of the pretreatment gas through a dryer 4 and trace oxygen removal of the pretreatment gas through a deoxygenator 6, and is preheated through a flow meter 8, a stop valve 11, a summary connector 12 and a heat exchanger 13 in sequence and then quantitatively enters a reaction system 14 for normal-pressure pretreatment of the catalyst; after the pretreatment of the catalyst is finished, switching raw material gases to start reaction: the raw gas (gas containing raw materials such as hydrogen, carbon dioxide and the like) flowing into the raw gas outlet 1 is subjected to micro-water removal of the raw gas through the dryer 3 and micro-oxygen removal of the raw gas through the deoxygenator 5, and then is preheated through the compressor 7, the stop valve 9, the flowmeter 10, the collecting connector 12 and the heat exchanger 13 in sequence and then quantitatively enters the high-pressure reaction system 14 for catalytic reactionHigh pressure reaction of the reactants.
Specifically, a raw material gas outlet is connected with a dryer, the dryer is connected with a deoxygenator, and a compressor, a stop valve and a flowmeter are sequentially connected behind the deoxygenator.
Specifically, the pretreatment gas outlet is connected with a dryer, the dryer is connected with a deoxygenator, and a flowmeter and a stop valve are sequentially connected behind the deoxygenator.
Specifically, the raw gas and the pretreatment gas finally pass through a gathering connector, and a heat exchanger (preheater) is connected behind the gathering connector and leads to the reaction system.
The device for directly preparing gasoline by carbon dioxide hydrogenation comprises a pretreatment unit, a reaction unit, reaction product separation, tail gas recycling and the like. Wherein the content of the first and second substances,
the pretreatment unit is used for pretreating feed gas CO2And H2Gas to satisfy CO on iron catalyst2The reaction with hydrogen to gasoline meets the requirements of gas and reaction conditions; the system comprises a raw material gas purification system (a dehydration pipe and a deoxidation pipe), a compressor, a heat exchanger and a heater.
The reaction unit refers to the CO reaction carried out on an iron catalyst2The conversion system petrol goes on, the utility model discloses a reaction system adopts the multilayer to dilute to load including the reactor that contains heat transfer part etc. catalyst in the reactor, and the steady operation of CO2 hydrogenation system petrol reaction has been guaranteed to the timely desorption of the evenly distributed of reaction heat and too much reaction heat ground when having reached the system operation.
The product separation unit adopts the traditional pressure swing adsorption separation and adopts proper conditions to ensure the recovery of gasoline products.
The tail gas recycling unit adopts a high-temperature hydrogen permeation membrane to separate hydrogen and CO2The tail gas can be circularly fed into the raw material gas for secondary conversion and utilization according to the requirement of the circulation of the raw material gas, so that the conversion efficiency of the reaction device is further improved.
The method for preparing the gasoline by carrying out the carbon dioxide catalytic hydrogenation by adopting the device comprises the following steps:
(a) will contain CO2And H2The raw material gas is pretreated by a pretreatment unitProcessing to obtain a pretreated material;
(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 to 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.
In step (b), the catalytic reaction is carried out in two stages. I.e. the catalyst is filled in two stages. The first stage reaction zone was packed with an iron-based catalyst. The first stage reaction zone is the inlet section, the process of synthesizing low carbon olefin by CO through carbon dioxide hydrogenation takes place on the catalyst, and the total reaction in the first stage is a strong exothermic reaction.
The second stage reaction zone is filled with an acidic molecular sieve catalyst. The second section of reaction zone is an outlet section, the process of producing gasoline fraction hydrocarbon by the polymerization, hydrogenation, isomerization and aromatization of intermediate products of low-carbon olefin occurs on the catalyst, and the total reaction of the section is a mild exothermic reaction.
In the application, the catalyst is filled in a plurality of sections, and the iron-based catalyst is filled in the feed gas inlet section, and can be filled in one section or a plurality of sections according to the actual situation; the molecular sieve catalyst is filled in the raw material gas outlet section of the reactor and can be filled in one section or multiple sections according to actual conditions.
In the application, the raw material distributor is adopted for feeding, and the number (1-3) of the raw material distributor is adjusted according to the tube diameter of the reactor, so that the axial feeding distribution of the 1 bed section of the catalyst in the reactor is balanced, and the radial feeding distribution of the 1 bed section of the catalyst is uniform. Meanwhile, the reaction heat of the reactor, especially the reaction heat on the iron-based catalyst can be timely and uniformly removed by combining a heat conduction system, and the stable operation of the system is improved.
In particular, CO is carried out on iron catalysts2The conversion of gasoline, the reaction unit of the utility model comprises a reactor containing a heat exchange part, a catalyst in the reactorAdopts multilayer dilution filling (iron catalyst dilution, molecular sieve catalyst component dilution-free), and adopts a reactor containing a raw material distributor and a heat conductor, so as to achieve uniform distribution of reaction heat and timely removal of excessive reaction heat during system operation, thereby ensuring CO2The hydrogenation gasoline reaction is stable in operation. The raw material gas treated by the pretreatment unit enters a reactor through a raw material distributor and enters a catalyst 1 (Na-Fe)3O4) Then the gas flows into a catalyst 2(HZSM-5) bed layer, and the reacted gas containing the gasoline product flows out of the reaction gas and enters a product separation system. When the reaction is operated, a heat exchange system containing heat conducting oil of the reaction device is started (the heat conducting oil enters the reactor through a heat conducting oil inlet and flows out from a heat conducting oil outlet of the reaction to enter heat exchange equipment of the heat conducting oil through a heat conducting oil pipeline in the reactor) at the same time, and reaction heat is removed in time. It is worth noting that the raw gas entering the distributor is only distributed and flows out in the catalyst 1 bed layer, and enters the catalyst 2 bed layer after reaction.
In the step (c), the pressure of the high-pressure separation tank is 1.0-5.0 Mpa; the pressure of the product separation tank is 0.5-2.5 Mpa; the pressure of the light component removing tower I is 0.3-2.0 MPa; the pressure of the light component removal tower II is 0.3-1.0 MPa;
separating the material flow I in a high-pressure separation tank to obtain a gas part and a liquid part, and enabling the gas part to enter a tail gas recycling unit;
the liquid part is separated into light hydrocarbon gas, liquid oil and wastewater through a product separating 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.
In the step (d), the tail gas is separated by a hydrogen permeable membrane separation system to obtain hydrogen and the tail gas separated by the hydrogen permeable membrane, the tail gas separated by the hydrogen permeable membrane is catalytically combusted to obtain carbon dioxide, and the hydrogen and the carbon dioxide are mixed for secondary utilization.
In step (d), the tail gas is passed through CO2Separating by a membrane separation system to obtain CO2And CO permeation2And (4) separating tail gas by using a membrane.
In step (d), CO is permeated2The tail gas after membrane separation passes through a hydrogen permeable membrane againThe separation system separates hydrogen and hydrogen permeable membrane separation tail gas, the hydrogen permeable membrane separation tail gas is catalyzed and combusted to obtain carbon dioxide, and the hydrogen and the carbon dioxide are mixed and then are recycled.
The beneficial effects that this application can produce include:
1) the application realizes that the gasoline is prepared by directly hydrogenating and efficiently converting the carbon dioxide on the iron-based catalyst, and the gasoline yield is obviously higher than that of the conventional device for preparing the gasoline by hydrogenating the carbon dioxide. The reaction system adopts the reactor containing the raw material distributor and the heat conductor at the same time, and the gas outlets of the raw material distributor are distributed at the first bed layer section of the multi-section catalyst, so that the reaction heat is uniformly distributed on the catalyst bed layer and can be uniformly removed, and the stable reaction is ensured.
2) The application provides a carbon dioxide hydrogenation reaction unit and the collection of petrol product separation and purification are integrative, when guaranteeing the effective cyclic utilization of reaction feed gas, have reduced reaction unit and separator's energy consumption, and then have reduced the manufacturing cost of carbon dioxide system petrol.
3) The tail gas cyclic utilization system of this application has adopted membrane separator and catalytic combustor, can reduce outer exhaust waste gas by a wide margin, not only make full use of the carbon dioxide resource, reduced the influence of emission tail gas to the environment simultaneously by a wide margin.
4) The product separation system can produce qualified gasoline products, and meanwhile, by-product qualified high-value by-product liquefied petroleum gas, so that the utilization rate of carbon resources of the system is improved.
5) The application effectively combines the application of each system of carbon dioxide hydrogenation system petrol device, can make the carbon resource utilization ratio of this process obviously improve, and the utilization ratio of carbon dioxide resource can reach more than 80%, more than 90% even, and this process almost has no exhaust emission, has obviously improved the feature of environmental protection of process. And simultaneously, the utility model discloses a reaction system, whole system's steady operation has been guaranteed.
Drawings
FIG. 1 is a schematic diagram of a reaction device system for preparing gasoline by catalytic hydrogenation of carbon dioxide.
FIG. 2 is a schematic diagram of a pretreatment system for producing 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 view 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 gasoline products from catalytic hydrogenation of carbon dioxide.
FIG. 6 is a schematic diagram of recycling of tail gas from gasoline production by catalytic hydrogenation of carbon dioxide.
FIG. 7 is a schematic diagram of recycling of tail gas containing carbon dioxide separation membranes in gasoline production by catalytic hydrogenation of carbon dioxide.
FIG. 8 is a schematic view of recycling tail gas containing a hydrogen permeable membrane and a carbon dioxide separation membrane in the preparation of gasoline by catalytic hydrogenation of carbon dioxide.
In figure 2, 1, raw material gas outlet 2, pretreated gas outlet 3 and dryer
4. Dryer 5, deoxygenator 6, deoxygenator
7. Compressor 8, flowmeter 9, stop valve
10. Flowmeter 11, stop valve 12, collecting connector
13. Heat exchanger (preheater) 14 reaction system
In FIG. 5, 001, heat exchanger and cooler 002, high pressure knockout drum
003. Pressure reducing valve I004 pressure reducing valve II
005. Product separation tank 006 pressure reducing valve III
007. Light component removing tower I008, light component removing 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 control valve I
A07. Flow control valve II A08 summary connector
In FIG. 7, B01. Heat exchanger and preheater B02. Membrane separator
B03. Flow control valve I B04. flow control valve II
B05. Collecting 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 control valve I C08. flow control valve II
C09. Connector C10. flow control valve III
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials and catalysts in the examples of the present application were all purchased commercially. If not stated, the test method adopts the conventional method, and the instrument setting adopts the setting recommended by the manufacturer.
Wherein the iron-based catalyst is Na-Fe3O4From the institute of chemico-physical research, university of Chinese academy of sciences.
HZSM-5 was purchased from catalyst factories of southern Kai university with a silica-alumina ratio of 25-400.
The hydrogen permeable membrane separation system is from the institute of chemical and physical research of the university of Chinese academy of sciences, and the main component of the hydrogen permeable membrane is a core component of the metal palladium hydrogen permeable membrane.
The carbon dioxide permeable membrane separation system is from the institute of chemical and physical, which is the institute of academy of sciences of China, and the main component of the carbon dioxide permeable membrane separation system is a molecular sieve composite membrane separation system.
Reactant CO2Conversion and gasoline product yield ofThe calculation formula is as follows:
CO2per pass conversion (%) ═ CO2Conversion of moles/CO2Feed mole number х 100%
One-way yield (mg) of gasoline productGasoline (gasoline)G catalyst-1·h-1) Space velocity (mL. g catalyst) of raw material volume-1·h-1) X CO in raw material2Percent volume (%). times.CO2Conversion (%). times gasoline product selectivity (%)/22400. times.gasoline molar mass (mg/mol)
CO2Cyclic utilization ratio (%) of CO2moles/CO recycled for conversion to hydrocarbon fuels2Molar conversion of the cycle х 100%
FIG. 1 is a schematic diagram of a device for directly preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation, which comprises a pretreatment system, a reaction product separation system and a tail gas recycling system; wherein the content of the first and second substances,
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, a flow meter, a stop valve and a collecting connector, wherein the raw material gas outlet is 2, the pretreatment gas outlet is 3, the dryer is 4, the deoxidizer is 5, the deoxidizer is 6, the compressor is 7, the flow meter is 8, the stop valve is 9, the flow meter is 10, the stop valve is 11, and the collecting connector is 12. In the system, before the catalyst system reacts, reduction pretreatment needs to be carried out, at the moment, pretreatment gas (hydrogen or gas containing hydrogen) flowing from a pretreatment gas outlet 2 is subjected to trace water removal of the pretreatment gas through a dryer 4 and trace oxygen removal of the pretreatment gas through a deoxygenator 6, and is preheated through a flow meter 8, a stop valve 11, a summary connector 12 and a heat exchanger 13 in sequence and then quantitatively enters a reaction system 14 for normal-pressure pretreatment of the catalyst; after the pretreatment of the catalyst is finished, switching raw material gases to start 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 of the raw material gas by the dryer 3 and micro-oxygen removal of the raw material gas by the deoxygenator 5, and then is preheated by the compressor 7, the stop valve 9, the flowmeter 10, the collecting connector 12 and the heat exchanger 13 in sequence and then quantitatively enters the high-pressure reaction system 14 for high-pressure reaction of the catalyst.
The reaction system (figure 3) comprises a reactor containing heat exchange components and the like, and the catalyst in the reactor adopts a plurality of layers of thin filmsThe reactor is filled with diluted iron catalyst and undiluted molecular sieve catalyst component, and has material distributor (figure 4) and heat conducting device. In the system, raw material gas treated by a pretreatment system enters a reactor through a raw material distributor and enters a catalyst 1 (Na-Fe)3O4) Then the gas flows into a catalyst 2(HZSM-5) bed layer, and the reacted gas containing the gasoline product flows out of the reaction gas and enters a product separation system. When the reaction is operated, a heat exchange system containing heat conducting oil of the reaction device is started (the heat conducting oil enters the reactor through a heat conducting oil inlet and flows out from a heat conducting oil outlet of the reaction to enter heat exchange equipment of the heat conducting oil through a heat conducting oil pipeline in the reactor) at the same time, and reaction heat is removed in time. It is worth noting that the raw gas entering the distributor is only distributed and flows out in the catalyst 1 bed layer, and enters the catalyst 2 bed layer after reaction.
As shown in fig. 4, which is a schematic diagram of the raw material distributor, a phi 12 stainless steel tube is adopted, 6 discharge air hole groups are axially arranged, 8 holes are arranged in each row, the holes in each row are staggered up and down, and the distance from the first discharge air hole group to the top end of the raw material gas distributor is three-fourths of the total length of the raw material gas distributor. The aperture of the first row and the second row of exhaust holes is 0.5mm, the aperture of the third row and the fourth row of exhaust holes is 0.4mm, the aperture of the fifth row and the sixth row of exhaust holes is 0.3mm, the distance from the first exhaust hole group to each exhaust hole group of the sixth exhaust hole group is 0.5cm, 1cm, 1.5cm, 2cm and 2cm in sequence, and the distance from the sixth exhaust hole group to the bottom end is 0.7 cm.
As shown in fig. 3, which is a schematic view of a reactor for preparing gasoline by carbon dioxide hydrogenation, a tubular shell is divided into a first-stage reaction zone, a second-stage reaction zone and an outlet-stage zone from top to bottom, wherein a catalyst 1 is placed in the first-stage reaction zone, and a catalyst 2 is placed in the second-stage reaction zone; the heat conducting oil inlet is connected with the upper part of the first-stage reaction area, and the heat conducting oil outlet is connected with the bottom of the reactor; the feed gas distributor is positioned at the upper part of the first-stage reaction zone and is communicated with the first-stage reaction zone.
The product separation system (fig. 5) includes: 001. a heat exchanger and a cooler, 002, a high-pressure separation tank, 003, a pressure reducing valve I, 004 and a pressure reducing valve II; 005. in the system, gas at the outlet of a reactor flows through a heat exchanger and a cooler 001 to be cooled and then enters a high-pressure separation tank 002 to obtain gas and liquid, wherein the gas part enters a tail gas recycling system after passing through a pressure reducing valve II 004, 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 gas enters a tail gas circulating system after passing through the pressure reducing valve III 006; reducing the pressure of the separated liquid oil by a pressure reducing valve IV011, and sending the liquid oil to a downstream lightness-removing tower I007 for further rectification and purification; the separated liquid water is discharged continuously; gas in a gas phase pipeline at the top of the light component removal tower I007 enters a light component removal tower II008 through a pressure reducing valve V012, a liquid phase outlet pipeline at the bottom of the light component removal tower I007 is communicated with an inlet of a product delivery pump 009, and an outlet pipeline of the product delivery pump 009 delivers qualified gasoline products; the gas in the top gas phase pipeline of the light component removal tower II008 enters the tail gas utilization system through the pressure reducing valve V013, the bottom liquid phase outlet pipeline is communicated with the inlet of the product delivery pump 010, and the qualified high-value byproduct liquefied petroleum gas is delivered out of the outlet pipeline of the product delivery pump 010.
The tail gas recycling system (figure 6) comprises: A01. the system comprises a heat exchanger, a preheater, an A02 membrane separator, an A03 catalytic combustor, an A04 heat exchanger, a condenser, an A05 gas-liquid separator, an A06 flow regulating valve I, an A07 flow regulating valve II and an A08 summarizing connector. 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 feed gas through a flow regulating valve I A06 and a summarizing connector A08 according to the recycling requirement to carry out secondary utilization of the feed gas. The tail gas from membrane separation flows into a catalytic combustor A03, the reducing gases of low carbon hydrocarbon and CO in the tail gas from the catalytic combustor are completely combusted to generate carbon dioxide and water, and the carbon dioxide and the CO in the tail gas2After passing through a heat exchanger and a condenser A04, the liquid water enters an A05 gas-liquid separator, the separated liquid water is continuously discharged, and the gas carbon dioxide can be circularly fed into fresh feed gas for secondary utilization of the feed gas through a flow regulating valve II A07 and a gathering connector A08 according to the circulation requirement.
FIG. 7 is a schematic diagram of recycling of tail gas containing carbon dioxide separation membranes in gasoline production by catalytic hydrogenation of carbon dioxide. In the schematic diagram, tail gas flowing in from a product separation system enters a membrane separation system B02 through a heat exchanger and a preheater B01, and carbon dioxide on the permeation side of the membrane separation system B02 can be recycled into fresh feed gas through a flow regulating valve I B04 and a summarizing connector B05 according to the recycling requirement to carry out secondary utilization of the feed gas. The membrane separation tail gas can be circularly fed into fresh raw gas through a flow regulating valve II B03 and a gathering connector B05 according to the circulation requirement to carry out the secondary utilization of the raw gas.
FIG. 8 is a schematic view of recycling tail gas containing a hydrogen permeable membrane and a carbon dioxide separation membrane in the preparation of gasoline by catalytic hydrogenation of carbon dioxide. The method comprises the following steps: C01. a heat exchanger and a preheater, a carbon dioxide membrane separator, a C03 hydrogen permeable membrane separator; C04. the system comprises a catalytic combustor, a heat exchanger and a condenser, a gas-liquid separator, a flow regulating valve I, a flow regulating valve II, a summarizing connector and a flow regulating valve III, wherein the tail gas flowing in from a product separation system enters a carbon dioxide membrane separation system C02 through the heat exchanger and a preheater C01, and the carbon dioxide at the permeation side of the membrane separation system C02 can be recycled into fresh raw gas through the flow regulating valve II C08 and the summarizing connector C09 according to the recycling requirement to carry out the secondary utilization of the raw gas. The tail gas of the carbon dioxide membrane separation system enters a hydrogen permeable membrane separator C03, and the hydrogen at the permeation side of the hydrogen permeable membrane separator C03 can be recycled into fresh feed gas for secondary utilization of the feed gas through a flow regulating valve III C10 and a gathering connector C09 according to the recycling requirement. The tail gas of the hydrogen permeable membrane separator flows into a catalytic combustor C04, reducing gases, namely low-carbon hydrocarbon and CO in the tail gas of the catalytic combustor C04 are completely combusted to generate carbon dioxide and water, the carbon dioxide and the water pass through a heat exchanger and a condenser C05 and then enter a C06 gas-liquid separator, the separated liquid water is continuously discharged outside, and the gas carbon dioxide can be recycled into fresh raw material gas through a flow regulating valve I C07 and a collecting connector C09 according to the recycling requirement to carry out the secondary utilization of the raw material gas.
The method for directly preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation specifically comprises the following operation steps:
the catalyst is subjected to reduction pretreatment in the step (1)C, processing; the pre-treatment gas (hydrogen 10% H) flowing in from the pre-treatment gas outlet 22/N2) Dehydrating at room temperature by a drier 4, deoxidizing at room temperature by a deoxidizer 6, preheating by a flowmeter 8, a stop valve 11, a collecting connector 12 and a heat exchanger 13 (230-.
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 the raw material gas outlet 1, is dehydrated at room temperature through a dryer 4, is deoxidized at room temperature through a deoxidizer 6, sequentially passes through a compressor 7 (the compression pressure is 1.0-6.0 MPa), a stop valve 9, a flowmeter 10, a gathering connector 12 and a heat exchanger 13, is preheated (230-.
Step (3) gets into reaction system's high temperature high pressure reaction gas is in the utility model discloses a react in the reactor, obtain reaction gas mixture, reaction temperature is 250 ~ 450 ℃, and pressure is 1.0 ~ 6.0Mpa, and total reaction equation general formula is:
nCO2+(n～6n)H2＝n1CO+n2CH4+(n3C2～n5C4)+(n6C5～n12C11)+n13H2o, reaction catalyst is iron-based/molecular sieve (Na-Fe)3O4/HZSM-5) multifunctional composite catalyst;
cooling the outlet gas of the reactor in the step (4) through a heat exchanger and a cooler 001 to obtain a cooled and partially condensed low-temperature mixed gas/liquid, wherein the temperature of the low-temperature mixed gas/liquid is-30-10 ℃;
separating the low-temperature mixed gas/liquid in a high-pressure separation tank 002 to obtain gas and liquid, wherein 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 decompressed by a decompression valve II 004, the temperature of the circulating gas is 15-60 ℃, and the pressure is 0.2-2.0 MPa. 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; reducing the pressure of the separated liquid oil by a pressure reducing valve IV011, and sending the liquid oil to a downstream lightness-removing tower I007 for further rectification and purification, wherein the pressure of the lightness-removing tower I007 is 0.3-2.0 MPa; the separated liquid water is discharged continuously; the gas in 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 0.3-1.0 MPa. A liquid phase outlet pipeline at the bottom of the light component removal tower I007 is communicated with an inlet of a product delivery pump 009, and an outlet pipeline of the product delivery pump 009 delivers qualified gasoline products; the gas in the top gas phase pipeline of the light component removal tower II008 enters the tail gas utilization system through the pressure reducing valve V013, the bottom liquid phase outlet pipeline is communicated with the inlet of the product delivery pump 010, and the qualified high-value byproduct liquefied petroleum gas is delivered out of the outlet pipeline of the product delivery pump 010.
And (3) the tail gas flowing in from the product separation system in the step (6) enters a membrane separation system A02(320-380 ℃) through a heat exchanger and a preheater A01(50-400 ℃), and the hydrogen on the permeation side of the membrane separation system A02 can be recycled into fresh raw material gas for secondary utilization of the raw material gas through a flow regulating valve I A06 and a summarizing connector A08 according to the recycling requirement. The tail gas from membrane separation flows into a catalytic combustor A03 (room temperature-500 ℃), the reducing gases of low-carbon hydrocarbon and CO in the tail gas from the catalytic combustor are completely combusted to generate carbon dioxide and water, and the carbon dioxide and the CO in the tail gas2After passing through a heat exchanger and a condenser A04, the liquid water enters an A05 gas-liquid separator, the separated liquid water is continuously discharged, and the gas carbon dioxide can be circularly fed into fresh feed gas for secondary utilization of the feed gas through a flow regulating valve II A07 and a gathering connector A08 according to the circulation requirement.
Example 1
The raw material gas distributor adopts a raw material gas distributor shown in figure 4, a phi 12 stainless steel pipe is adopted, 8 holes in each row have 6 rows of holes, each row is staggered up and down, and the specific hole diameter and the specific space are shown in figure 4. In this example, 1 raw material gas distributor was placed.
The method for directly preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation specifically comprises the following operation steps:
carrying out reduction pretreatment on the catalyst in the step (1); pretreatment gas (10 vol% H) flowing into the pretreatment gas outlet 22/N2) Dehydrating at room temperature with a drier 4, deoxidizing with a deoxygenator 6 at room temperatureThe mixture was preheated (260 ℃) by a flowmeter 8, a stop valve 11, a collective connector 12 and a heat exchanger 13 in this order and then quantified (3000 mL. g)Cat -1·h-1) Enters a reaction system 14 for carrying out reduction pretreatment of the catalyst for 6 hours at the normal pressure (0.1MPa) and the temperature of 350 ℃.
Introducing fresh raw material gas in the step (2);
the raw material gas (H, gas containing hydrogen, carbon dioxide and nitrogen) with a temperature of 50 deg.C flows into the raw material gas outlet 12/CO2Volume ratio of 3) was dehydrated in a desiccator 4 at room temperature, deoxygenated in a deoxygenator 6 at room temperature, preheated (260 ℃) in sequence in a compressor 7 (compression pressure of 3.5MPa), a stop valve 9, a flowmeter 10, a collective connector 12, and a heat exchanger 13, and then quantified (3000mL g)Cat -1·h-1) Enters the high-pressure reaction system 14 to perform high-pressure reaction of the catalyst.
The high-temperature high-pressure reaction gas entering the reaction system in the step (3) reacts in the reactor designed by the utility model to obtain reaction mixed gas, the reaction temperature is 320 ℃, the pressure is 3.0Mpa, and the space velocity is 4000 mL. g catalyst-1·h-1。
Catalyst I is an iron-based catalyst and selects Na-Fe3O4The 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 (the silicon-aluminum ratio is 200). The heat exchange medium in the heat exchange system adopts heat conduction oil.
Cooling the outlet gas flow of the reactor in the step (4) through a heat exchanger and a cooler 001 to obtain a cooled and partially condensed low-temperature mixed gas/liquid, wherein the temperature of the low-temperature mixed gas/liquid is 5 ℃;
separating the low-temperature mixed gas/liquid in a high-pressure separation tank 002 to obtain gas and liquid, wherein the pressure of the high-pressure separation tank 002 is 3.0 Mpa; wherein the gas part enters a tail gas recycling system after being decompressed by a decompression valve II 004, the temperature of the circulating gas is 20 ℃, and the pressure is 0.5 MPa. 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 circulating system after passing through a pressure reducing valve III 006; reducing the pressure of the separated liquid oil by a pressure reducing valve IV011, and sending the liquid oil to a downstream lightness-removing tower I007 for further rectification and purification, wherein the pressure of the lightness-removing tower I007 is 0.5 MPa; the separated liquid water is discharged continuously; and gas in a gas phase pipeline at the top 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 MPa. A liquid phase outlet pipeline at the bottom of the light component removal tower I007 is communicated with an inlet of a product delivery pump 009, and an outlet pipeline of the product delivery pump 009 delivers qualified gasoline products; the gas in the top gas phase pipeline of the light component removal tower II008 enters the tail gas utilization system through the pressure reducing valve V013, the bottom liquid phase outlet pipeline is communicated with the inlet of the product delivery pump 010, and the qualified high-value byproduct liquefied petroleum gas is delivered out of the outlet pipeline of the product delivery pump 010.
And (3) tail gas flowing in 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-temperature hydrogen-permeable palladium membrane separation system, and hydrogen on the permeation side of the membrane separation system A02 can be recycled into fresh raw material gas through a flow regulating valve I A06 and a gathering connector A08 according to recycling requirements to carry out secondary utilization on the raw material gas. The tail gas from membrane separation flows into a catalytic combustor A03(300 ℃), the reducing gases of low-carbon hydrocarbon and CO in the tail gas from the catalytic combustor are completely combusted to generate carbon dioxide and water, and the carbon dioxide and the CO in the tail gas2After passing through a heat exchanger and a condenser A04, the liquid water enters an A05 gas-liquid separator, the separated liquid water is continuously discharged, and the gas carbon dioxide can be circularly fed into fresh feed gas for secondary utilization of the feed gas through a flow regulating valve II A07 and a gathering connector A08 according to the circulation requirement.
CO2The one-way conversion rate of the gasoline is 30 percent, and the one-way yield of the gasoline product is 105mgGasoline (gasoline)G catalyst-1·h-1，CO2The recycling rate of (a) was 85%.
Example 2
The same as 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). CO22The one-way conversion rate of the gasoline is 28 percent, and the one-way yield of the gasoline product is 95mgGasoline (gasoline)G catalyst-1·h-1，CO2The cycle utilization of (a) was 87%.
Example 3
Same as example 1 except that the tail gas was recycledThe utilization system is changed into a system which simultaneously contains a hydrogen permeable membrane (a high-temperature hydrogen permeable palladium membrane separation system) and a carbon dioxide separation membrane tail gas recycling system (figure 8). CO22The conversion rate of (A) was 31% and the gasoline product yield was 106mgGasoline (gasoline)G catalyst-1·h-1，CO2The cycle utilization of (a) was 91%.
Comparative example 1
The same as example 1, except that the reaction system used a conventional fixed bed reactor without the raw material distributor and the heat transfer oil.
CO2The conversion rate is 50 percent, and the once-through yield of the gasoline product is 30mgGasoline (gasoline)G catalyst-1·h-1，CO2The cyclic utilization of (a) is 30%.
The reaction heat in the reaction process causes the temperature of the catalyst bed layer of the reactor to be rapidly raised to over 500 ℃, and CO2The conversion rate is rapidly increased, but the main products are converted into methane and CO, the selectivity of the gasoline product is rapidly reduced, and the CO is calculated and calculated2The cyclic utilization rate is greatly reduced. In addition, the temperature of the catalyst bed layer is increased violently, 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.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. The device for preparing the gasoline by catalytic hydrogenation of the 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 communicated in sequence.
2. The device for preparing gasoline by catalytic hydrogenation of carbon dioxide according to claim 1, wherein 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 feed 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 the first-stage reaction zone.
3. The device for preparing gasoline by catalytic hydrogenation of carbon dioxide according to claim 2, wherein the feed gas distributor comprises a shell I, and the shell I encloses 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 every two adjacent air hole groups is arranged along the axial direction according to a preset mode I from top to bottom;
the aperture of the exhaust vent in two adjacent vent groups is also arranged from top to bottom along the axial direction according to a preset mode II;
the preset mode I is gradually increased; alternatively, the first and second electrodes may be,
the preset mode I is gradually increased and then is kept unchanged;
the preset mode II is gradually reduced; alternatively, the first and second electrodes may be,
and the preset mode II is gradually reduced and then is kept unchanged.
4. The apparatus for producing gasoline by catalytic hydrogenation of carbon dioxide according to claim 2, wherein the reactor further comprises a heat transfer device;
the inlet of the heat conducting device is connected with the first-stage reaction zone;
and the outlet of the heat conduction device is connected with the second-stage reaction zone.
5. 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;
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 communicated in sequence.
6. The apparatus for producing gasoline by catalytic hydrogenation of carbon dioxide according to claim 5, wherein pressure reducing valves are connected between the high-pressure separation tank, the product separation tank, the light component removal column I and the light component removal column II.
7. The device 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 system2A membrane separation system.
8. The apparatus for producing 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 combustor;
the catalytic combustor is arranged behind the hydrogen permeable membrane separator, so that the gas separated from the hydrogen permeable membrane separator is catalytically combusted to obtain carbon dioxide.
9. The apparatus for producing gasoline by catalytic hydrogenation of carbon dioxide according to claim 7, wherein the hydrogen permeable membrane separation system and the CO permeable membrane separation system2When the membrane separation system exists simultaneously, the hydrogen permeable membrane separation system is arranged for permeating CO2After the membrane separation system.
10. The apparatus for preparing gasoline by catalytic hydrogenation of carbon dioxide according to claim 1, wherein the pretreatment unit comprises a dryer, a deoxygenator and a heat exchanger;
the dryer, the deoxygenator and the heat exchanger are communicated in sequence.
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| CN202022633275.2U CN213803649U (en) | 2020-11-13 | 2020-11-13 | Device for preparing gasoline by catalytic hydrogenation of carbon dioxide |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114479902A (en) * | 2020-11-13 | 2022-05-13 | 中国科学院大连化学物理研究所 | Device and method for preparing gasoline by catalytic hydrogenation of carbon dioxide |
| CN114671730A (en) * | 2022-03-07 | 2022-06-28 | 中石化广州工程有限公司 | Method for preparing alpha-olefin by carbon dioxide hydrogenation |
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2020
- 2020-11-13 CN CN202022633275.2U patent/CN213803649U/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114479902A (en) * | 2020-11-13 | 2022-05-13 | 中国科学院大连化学物理研究所 | Device and method for preparing gasoline by catalytic hydrogenation of carbon dioxide |
| CN114479902B (en) * | 2020-11-13 | 2023-07-28 | 珠海市福沺能源科技有限公司 | Device and method for preparing gasoline by catalytic hydrogenation of carbon dioxide |
| CN114671730A (en) * | 2022-03-07 | 2022-06-28 | 中石化广州工程有限公司 | Method for preparing alpha-olefin by carbon dioxide hydrogenation |
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