Apparatus and method for co-production of aviation fuel and chemical feedstocks from waste biomass in an anti-coking stable operation

Abstract

The application discloses a device for producing aviation fuel and co-producing chemical raw materials from waste biomass in a stable anti-coking operation mode, which comprises a low-energy-consumption second-level biomass drying coupling pyrolysis and biomass crude oil conversion unit, a biomass crude oil suspended bed deoxygenation and upgrading conversion low-oxygen bio-oil unit and a low-oxygen bio-oil molecular fixed bed reconstruction and conversion hydrocarbon aviation fuel unit; a flash reaction thermal starting mechanism capable of realizing stepwise temperature rise coking inhibition and online switching coking removal is arranged to quickly cross the coking reaction time point and shift the coking position, so that the coking risk space-time decoupling and long-period stable operation of the device for producing aviation fuel and co-producing chemical raw materials from waste biomass are realized. The whole process adopts a coupling hydrogen and heat self-sustaining operation mode, so that the drying heat and upgrading hydrogen are self-supplied, and the problem of high external cost is solved. The application further provides a method for producing aviation fuel and co-producing chemical raw materials from waste biomass in a stable anti-coking operation mode.

Description

TECHNICAL FIELD

[0001] The present application relates to the emerging field of zero-carbon biomass fuels, and specifically relates to a device and method for producing aviation fuel and co-producing chemical raw materials from waste biomass with anti-coking and stable operation. BACKGROUND

[0002] Greenhouse gas emissions from the aviation industry account for about 13% of all transportation industry sources of carbon dioxide emissions. In addition, by 2050, aviation emissions are expected to grow to about 1.8 billion tons of carbon dioxide per year, almost twice that of 2019. Therefore, in order to achieve the goal of net zero carbon emissions by 2050, about 8.2 billion tons of carbon dioxide need to be reduced, which poses a huge challenge to the aviation industry. Compared with other industries, the aviation industry has limited options and paths for emission reduction, and the difficulty of emission reduction is great, and is one of the "difficult-to-reduce" fields. Sustainable aviation fuel has the characteristics of high calorific value and zero emissions, and the use of sustainable aviation fuel does not require large-scale modification of existing infrastructure, aircraft engines and operation management systems, thereby significantly reducing the cost of emission reduction. Therefore, it brings new possibilities and prospects for emission reduction in the aviation industry.

[0003] Currently, the main raw materials for sustainable aviation fuel are kitchen waste oil, algae and lipid raw materials, but they still cannot meet the demand for raw materials for the preparation of sustainable aviation fuel. Waste biomass such as straw and sawdust not only serves as a medium for storing solar energy, but also follows the principle of "not competing with people for food and land", and has zero carbon properties. It is expected to be used as a complementary raw material to replace petroleum in the production of sustainable aviation fuel and help carbon emission reduction in the aviation industry. Therefore, it is urgent to use waste biomass as raw material to produce biomass aviation fuel as a complementary oil product.

[0004] However, the technology of producing high-value fuels from waste biomass still faces many challenges in the stable operation of bio-oil hydro-upgrading units and the service life of catalysts. Bio-oil is an unstable oil product because of its high oxygen content and large amount of low-boiling volatile substances. During high-temperature heating, a series of polymerization or polycondensation reactions occur, resulting in coking components that block the reactor bed. Studies have found that the ebullated bed hydrogenation process has good bio-oil deoxygenation performance and can achieve high oil hydrogenation conversion levels. However, bio-oil has poor hydrogen solubility, making it difficult to disperse and react quickly in the reactor, leading to equipment and pipeline coking and blocking problems that affect the long-term stable operation of the unit. Therefore, there is an urgent need for a feed supply method that helps to suppress reactor inlet coking and avoid reactor inlet coking that causes bed plugging in the unit. On the other hand, during the hydrogenation deoxygenation process in the reactor, bio-oil will experience strong heat release, and the temperature of the unit is prone to runaway, causing sintering, structure collapse, and deactivation of the metal active components of the catalyst. This reduces the service life of the catalyst, increases the cost of catalyst preparation and unit operation, and can cause serious safety risks.

[0005] Chinese invention patent CN116286067A discloses a long-term stable operation method and device for producing gasoline and diesel from biomass. Although this method uses a series of deoxygenation and upgrading devices to overcome catalyst coking and deactivation caused by single-stage reactions and the risk of "temperature runaway" in the unit, it produces gasoline and diesel, which does not meet the standard requirements of biomass aviation fuel and does not meet the technical requirements of directly producing biomass aviation fuel. At the same time, the dry heat energy consumption and the large amount of hydrogen source required for the hydrogenation upgrading process are supplied externally, increasing the economic cost of operation; due to the high temperature at the reactor inlet, the biomass oil entering the reactor will cause coking loss; the use of ebullated bed catalysts increases the investment and operating cost of the catalyst addition and removal system.

[0006] Chinese invention patent CN102732304A discloses a naphtha hydrogenation reactor and hydrogenation reaction method for extending the operation cycle. Although a preheating reactor, a decoking tank, and a heating furnace are added at the feed end to economically and effectively extend the hydrogenation operation cycle, this method has the disadvantage of using a hydrogenation reactor that includes a pre-hydrogenation reactor and a main hydrogenation reactor. After the reaction, the two reactors' dirt accumulators and decoking tanks need to be cleaned and returned, which ultimately increases the number of start-up and shutdown operations, prolongs maintenance time, and increases operating costs, and still cannot guarantee the long-term stable operation of the equipment.

[0007] US patent US10876056B2 discloses a process and device for hydrogenation of heavy oil using a suspension bed, a part of the oil is mixed with the catalyst to form a mixed oil, and the mixed oil is subjected to first and second shearing in turn to achieve high dispersion and mixing of the catalyst and the raw oil. However, this method is mainly based on hydrogenation pyrolysis, which is not suitable for the process requirements of biomass pyrolysis oil hydrogenation and deoxidation, and it is difficult to meet the characteristics of biomass pyrolysis oil such as easy coking, high oxygen content, high polarity and difficulty in mixing with hydrocarbons. The cold wall and discharge port in the suspension bed reactor will cause equipment alternating stress fatigue due to frequent cooling and high pressure, reducing the service life of the device.

[0008] Chinese invention patent CN112442404A uses different types of biomass raw materials to prepare pyrolysis solids and liquids after independent drying, mixing and pyrolysis in different zones. This invention needs to dry different biomasses in different zones with hot air, which has high labor cost, large floor area, long time period, high energy consumption, and the economic benefit of biomass semicoke is much lower than that of biomass aviation fuel.

[0009] In summary, although many methods and devices for biomass drying-pyrolysis, bio-oil hydrogenation and deoxidation, pyrolysis coupled with hydrogenation and upgrading to produce bio-oil, and hydrogenation and upgrading coupled with isomerization to produce biomass fuel have been developed, but there is no method and device that can completely solve the reactor coking and plugging, low cost, high efficiency and long period stable operation of biomass aviation fuel production.

[0010] Therefore, in view of the technical problems in the simple or complex processing process of existing biomass production of biomass aviation fuel, it is urgent to develop a long-period stable operation method and device for producing biomass aviation fuel, to heat at a super-high rate, shorten the coking reaction time node, transfer and decouple the coking risk in the reactor, reduce the cost of decoking; at the same time, reduce the energy loss of catalyst heat source, prolong the service life of catalyst, break through the technical barriers of biomass aviation fuel production, and realize industrialized large-scale application. SUMMARY

[0011] The purpose of the present application is to solve the problems of high cost, difficulty in effective long-term stable operation and inability to meet the demand of biomass aviation fuel in the prior art of biomass fuel production, provide an equipment and method for producing aviation fuel and co-producing chemical raw materials from waste biomass, which not only can obtain high-quality biomass aviation fuel, but also has the advantages of low energy consumption, anti-coking and long-period stable operation.

[0012] To achieve the above purpose, the present application adopts the following technical solutions.

[0013] The application provides a device for producing aviation fuel and co-producing chemical raw materials by waste biomass in an anti-coking stable operation mode, which comprises a second-level biomass drying and coupling pyrolysis and biomass oil conversion unit, a biomass oil suspension bed deoxygenation and upgrading low-oxygen bio-oil conversion unit and a low-oxygen bio-oil molecular fixed bed reconstruction and conversion hydrocarbon aviation fuel unit.

[0014] The second-level biomass drying and coupling pyrolysis and biomass oil conversion unit is used for second-level drying and coupling heat treatment of biomass, obtaining biomass oil, pyrolysis gas and pyrolysis carbon; and the pyrolysis gas is converted into green hydrogen as a hydrogen source, and the biomass oil and the hydrogen source are both used as reaction raw materials and input into the biomass oil suspension bed deoxygenation and upgrading low-oxygen bio-oil conversion unit.

[0015] The biomass oil suspension bed deoxygenation and upgrading low-oxygen bio-oil conversion unit is used for quickly crossing a coking reaction time point, shifting a coking position and realizing space-time decoupling of coking risk; then low-oxygen bio-oil is obtained through biomass oil deoxygenation and upgrading reaction, gas-liquid separation, flash evaporation and oil-water separation, hydrogen obtained through gas-liquid separation is purified and used as a hydrogen source, heavy oil obtained through flash evaporation is used as circulating slurry, and organic solution obtained through oil-water separation is reformed to prepare green hydrogen as a hydrogen source.

[0016] The low-oxygen bio-oil molecular fixed bed reconstruction and conversion hydrocarbon aviation fuel unit is used for hydrogenation reconstruction reaction of low-oxygen bio-oil components, oil-water separation and fractionation to obtain biomass aviation fuel components and biomass naphtha chemical raw materials, organic solution obtained through oil-water separation is reformed to prepare green hydrogen as a hydrogen source, and co-produced distillate biomass naphtha obtained through fractionation is used as a hydrogen donor of the biomass oil suspension bed deoxygenation and upgrading low-oxygen bio-oil conversion unit.

[0017] The second-level biomass drying and coupling pyrolysis and biomass oil conversion unit comprises a second-level dryer, a second-level pyrolysis reactor, a cyclone separator, a combustion furnace, a cooling tower and a water-gas shift reactor; the second-level dryer and the second-level pyrolysis reactor are connected, dried biomass is sent into the second-level pyrolysis reactor for coupling heat treatment reaction to obtain pyrolysis oil gas and pyrolysis carbon; the pyrolysis oil gas and the pyrolysis carbon are separated through the cyclone separator, the separated pyrolysis carbon is returned to the combustion furnace to provide heat for the second-level dryer or / and the second-level pyrolysis reactor; the separated pyrolysis oil gas is discharged after the cooling tower, the pyrolysis gas enters the water-gas shift reactor, and then green hydrogen is prepared through a first hydrogen purification device connected with the water-gas shift reactor; and the cooled pyrolysis oil is collected through a biomass oil collecting device.

[0018] The biomass crude oil suspension bed deoxygenation upgrading low-oxygen bio-oil unit includes a biomass crude oil mixing tank, a flash reaction thermal starting mechanism, a suspension bed deoxygenation upgrading reactor and a separator assembly. The biomass crude oil mixing tank mixes biomass crude oil, circulating slurry and hydrogen donor, and then inputs the mixture into the flash reaction thermal starting mechanism after being premixed with a hydrogen source. The flash reaction thermal starting mechanism rapidly preheats the mixture to 200-400 DEG C, transfers the coking risk to the flash reaction thermal starting mechanism, and realizes space-time decoupling. The preheated mixture is subjected to deoxygenation upgrading reaction in the suspension bed deoxygenation upgrading reactor. The reaction product is subjected to oil-water separation and flash evaporation by the separator assembly, and low-oxygen bio-oil is obtained.

[0019] The flash reaction thermal starting mechanism includes a flash reaction thermal starting furnace group and a high-temperature supplementary furnace. The flash reaction thermal starting furnace group includes two or more flash reaction thermal starting furnaces for preheating the mixture to 150-300 DEG C. The two or more flash reaction thermal starting furnaces can simultaneously preheat the biomass crude oil and switch off the coking by parallel structure operation, realizing the dual functions of coking inhibition and coking removal. The high-temperature supplementary furnace is used to continue preheating the mixture from the flash reaction thermal starting furnace group to 200-400 DEG C. The flash reaction thermal starting furnace, the high-temperature supplementary furnace and the suspension bed deoxygenation upgrading reactor constitute a gradient heating, which can make the raw material reaction more thorough, and improve the reaction efficiency and the reaction degree. In a preferred implementation mode, the flash reaction thermal starting furnace group includes two flash reaction thermal starting furnaces. When one group is switched off for coking removal, the other group is used to preheat the mixture, so that the coking risk is transferred without shutdown. The flash reaction thermal starting furnace includes a furnace body, a heating pipe arranged in the furnace body and an electromagnetic induction coil wound on the heating pipe. The heating pipe is designed in a Z-shaped structure, which can further increase the heat exchange area and improve the exchange efficiency. The electromagnetic induction coil has a heating rate of 30-50 DEG C / s and a residence time of 3-5 s, so as to realize efficient conveying of the material. The electromagnetic induction coil can effectively improve the heating rate, so as to cross the coking reaction temperature point, avoid the increase of the carbon deposition amount in the pipe caused by slow heating, provide high-quality feedstock and realize efficient conveying of the material. The high-temperature supplementary furnace uses a conventional heating furnace, which can fully utilize the energy and improve the local hydrogen concentration and catalyst concentration.

[0020] The catalyst for the deoxygenation and upgrading reaction is also added into the biomass crude oil mixing tank; the amount of catalyst is controlled by controlling the circulating state of the catalyst in the operating zone of the suspended bed deoxygenation and upgrading reactor. The coarse catalyst participates in the circulation in the reactor, the fine catalyst participates in the circulation outside the reactor, and the powder catalyst is separated and discharged; the discharged catalyst is supplemented through the biomass crude oil mixing tank; the particle size of the coarse catalyst is 70-100% of the particle size of the initial catalyst; the fine catalyst is 30-70% (not including the end value) of the particle size of the initial catalyst; the powder catalyst is 0-30% (not including the end value 0) of the particle size of the initial catalyst. The initial catalyst is the newly added catalyst that does not participate in the reaction, and the particle size of the initial catalyst ranges from 10 to 200 microns.

[0021] The inside of the suspended bed deoxygenation and upgrading reactor is sequentially provided with a raw material inlet, a reaction bed layer and a reactant outlet from bottom to top; a three-phase cyclone separator is further arranged above the reaction bed layer. The three-phase cyclone separator is additionally provided with an annular gap structure, and the specific structure can be referred to CN113816460A. The annular gap structure is used for overflow drainage, and the outlet pressure difference caused by the self-overflow iterative separation is used for recovering the bio-oil dispersed at the outlet, so as to solve the problem of low separation efficiency caused by the large amount of circulating flow and short circuit flow in the cyclone. A waste catalyst replacement port is arranged at the horizontal end of the three-phase cyclone separator, which is used for replacing the catalyst and reducing the loss of heat source energy consumption when the deactivated catalyst is replaced, and slowing down the equipment maintenance and loss caused by frequent switching of high and low pressure and alternating stress fatigue.

[0022] The separator assembly includes a hot high-pressure separator, a cold high-pressure separator, a flash tank and a cold low-pressure separator; the products obtained by the deoxygenation and upgrading reaction are first subjected to gas and liquid phase separation by the hot high-pressure separator (at this time, the temperature and pressure of the entering products are relatively high, so it is called a hot high-pressure separator); the separated gas is cooled by a first cooler, then further separated by the cold high-pressure separator (although the temperature of the products is reduced at this time, the gas pressure is still relatively high, so it is called a cold high-pressure separator here), and then purified by a first hydrogen purification device to serve as a hydrogen source; based on the different boiling points, the separated liquid is separated into light oil and heavy oil by the flash tank, and the heavy oil is transported to the biomass crude oil mixing tank as a circulating slurry; the light oil obtained by the flash tank is mixed with the liquid phase separated by the cold high-pressure separator after being cooled by a second cooler, and then subjected to oil and water phase separation by a cold low-pressure separator (at this time, the product pressure needs to be controlled at 1-2.5 MPa), and the obtained oil phase is the low-oxygen bio-oil, and the obtained water phase is the organic solution, which is sent to an organic solution reforming hydrogen production reactor, and the hydrogen produced is purified by a second hydrogen purification device to obtain green hydrogen. The purpose of the flash tank is to separate the light oil and the heavy oil, and the working temperature is 175-350℃, and the pressure is 1-1.7 MPa; in addition, the catalyst is discharged from the flash tank pipeline as an oil residue.

[0023] In the preferred implementation, the obtained low-oxygen bio-oil part (5-10%) is transported to the biomass crude oil mixing tank as the circulating slurry, and 90-95% is transported to the low-oxygen bio-oil molecular fixed-bed reconfiguration conversion hydrocarbon aviation fuel unit. The part as the circulating slurry is used to coat the biomass crude oil, preventing the reaction coking during the pipeline transportation process and at the suspended bed feed port.

[0024] In addition, in order to realize the supplement of the catalyst for the deoxygenation upgrading reaction, the catalyst is also added to the biomass crude oil mixing tank. In order to improve the effect of the catalyst, the amount of the circulating slurry can also be controlled to control the catalyst in the suspended state at the operating domain of the suspended bed deoxygenation upgrading reactor.

[0025] The low-oxygen bio-oil molecular fixed-bed reconfiguration conversion hydrocarbon aviation fuel unit described above is used for hydrogenation reconfiguration reaction of the low-oxygen bio-oil to obtain a standard biomass aviation fuel component. The low-oxygen bio-oil molecular fixed-bed reconfiguration conversion hydrocarbon aviation fuel unit includes a fixed-bed molecular reconfiguration reactor, a circulating separator, a liquid phase separator, and a fractionation unit; the fixed-bed molecular reconfiguration reactor performs hydrogenation reconfiguration reaction on the low-oxygen bio-oil component under the action of the hydrogen source of the first hydrogen purification device, the hydrogen separated by the circulating separator is purified by the first hydrogen purification device and then enters the circulating hydrogen compressor, and the liquid phase separated enters the liquid phase separator to separate the oil phase and the water phase; the oil phase enters the fractionation unit to fractionate C8-C 16 The hydrocarbon biomass aviation fuel is obtained, and co-produced distillates are obtained; the water phase is an organic solution, which is sent to an organic solution reforming hydrogen production reactor, and the prepared hydrogen is purified by a second hydrogen purification device to obtain green hydrogen.

[0026] The fixed-bed molecular reconfiguration reactor is internally provided with a micro-nano bubble generating device at the top, which is used for sufficient mixing of the green hydrogen and the low-oxygen bio-oil, and improves the hydrogen dissolving capacity and mass and heat transfer of the biomass pyrolysis oil. The structure of the micro-nano bubble generating device is described in CN111298670A.

[0027] The application also provides a biomass aviation fuel production method, which uses the above-mentioned anti-coking stable operation waste biomass aviation fuel co-production chemical raw material equipment and is performed according to the following steps:

[0028] S1: drying and coupling heat treatment of waste biomass by the second biomass drying and coupling pyrolysis and quality conversion biomass crude oil unit to obtain pyrolysis oil gas and pyrolysis carbon; the pyrolysis oil gas and pyrolysis carbon are separated by a cyclone separator; the pyrolysis oil gas is cooled to produce pyrolysis gas, and then green hydrogen is prepared by a water-gas shift reaction as a hydrogen source; the pyrolysis oil gas is cooled to obtain biomass crude oil at the same time; the pyrolysis carbon is combusted to provide heat for the biomass drying and coupling heat treatment;

[0029] S2 converts the biomass crude oil into low-oxygen bio-oil by a biomass crude oil suspension bed deoxygenation upgrading low-oxygen bio-oil unit; the biomass crude oil, hydrogen donor, and circulating slurry are premixed and mixed with a hydrogen source in a pipeline, and then quickly enter a reaction state through a flash reaction hot start mechanism, and the biomass crude oil is deoxygenated and upgraded to obtain low-oxygen bio-oil; the heavy oil separated during the reaction is used as the circulating slurry, the hydrogen gas separated is purified and used as the hydrogen source, and the organic solution separated is reformed to prepare green hydrogen as the hydrogen source;

[0030] S3 obtains a biomass aviation fuel component by a hydrogenation reconstruction reaction of the low-oxygen bio-oil component through a low-oxygen bio-oil molecular fixed bed reconstruction hydrocarbon aviation fuel unit; the organic solution separated during the reaction is reformed to prepare green hydrogen as the hydrogen source, and the cogeneration distillate obtained by fractional distillation is used as the hydrogen donor.

[0031] In the above step S1, the biomass second-level drying is performed under the conditions of 5-20 seconds, room temperature-85°C, and cyclone dewatering; the temperature of the second-level coupling heat treatment (i.e., second-level pyrolysis) is 400-700°C, and the heating rate is between 1000K / s-10000K / s. The generated biomass crude oil has a water content of less than 30% and an oxygen content of 30-50%; the pyrolysis carbon is completely combusted to meet the energy requirements of the second-level drying and the second-level pyrolysis, of which 30-50% is supplied to the second-level dryer, and 50-70% is supplied to the second-level pyrolysis reactor.

[0032] In the above step S2, the premixed material is pressurized and then mixed with a hydrogen source in a pipeline, which helps the mixed material quickly pass through the flash reaction hot start furnace group and the high-temperature supplementary furnace, enter the suspension bed deoxygenation upgrading reactor, and quickly enter a reaction state to obtain a gas-liquid-solid three-phase reaction raw material. The hydrogen source used in this step also needs to be used after being compressed by a circulating hydrogen gas compressor. The deoxygenation upgrading reaction temperature of the biomass pyrolysis oil is 200°C-400°C, the reaction pressure is 8-15MPa, the volume space velocity is 0.6-2.0h -1 , the hydrogen to oil ratio is 400:1-1500:1, the residence time is 1-4h, and the oxygen content of the obtained product is 0.2-1%.

[0033] The catalyst used in the deoxygenation upgrading reaction is a hard type fine particle with a diameter of 10-200 microns (preferably 70-150 microns), for example, a silicon-based or aluminum-based carrier, and the macroscopic shape includes a tooth ball, a column, and a particle, and the active metal loaded on the particle is a transition metal element from group IIIB to group IIB in the periodic table of elements, or an alloy formed by combining any two or more of the transition metal elements. The loading amount of the catalyst fine particle accounts for 20-85% of the volume of the suspended bed hydrogenation reactor. The coarse catalyst (70-100% of the initial catalyst particle size) is circulated in the reactor, and the larger diameter catalyst in the suspended bed reactor is driven upward by the gas-liquid mixture under the cooperation of the cyclone and the ring gap member with a guiding function, forming an internal circulation of the catalyst, which can realize the complete fluidization of the catalyst in the bed, improve the desulfurization rate, and reduce the amount of catalyst impurities in the biomass pyrolysis oil; the fine catalyst (30-70% of the initial catalyst particle size) is circulated outside the reactor, and the slightly smaller diameter catalyst is discharged from the reactor into the pipeline along with the low-oxygen bio-oil, reducing catalyst loss; the powder catalyst (0-30% of the initial catalyst particle size) is discharged, and the discharged catalyst is supplemented through a biomass crude oil mixing tank, and the supplementing amount is consistent with the discharging amount; the amount of circulating slurry can be controlled to control the catalyst in the suspended bed deoxygenation upgrading reactor to be in a suspended state at the operating domain, thereby regulating the amount of catalyst inside and outside the reactor. Avoid the damage of high temperature and high pressure alternating stress fatigue and creep interaction, prolong the running period of the device.

[0034] In the above step S3, the hydrogenation reconstruction reaction temperature of the low-oxygen bio-oil is 150-450℃, the pressure is 5-20MPa, the reaction volume space velocity is 0.25-4.0h -1 -1, the hydrogen to oil ratio is 400:1-1500:1, and the residence time is 1-4h; the final boiling point after reconstruction is 200-300℃, the main product biomass aviation fuel accounts for 50-60% of the total liquid yield, and is C8-C 16 long chain alkanes, which meet the biomass aviation fuel standard of ASTMD7566 or GB 6537-2018. The co-produced distillate is a biomass naphtha, and the components with a boiling point higher than that of the biomass aviation fuel participate in the cycle as a hydrogen donor.

[0035] Compared with the prior art, the device and method for producing aviation fuel and co-producing chemical raw materials from waste biomass provided by the application have the following beneficial effects:

[0036] 1) The full-process coupling hydrogen and heat self-sustaining operation mode is constructed, the drying heat required in the conversion process and the upgrading hydrogen are self-supplied, and the problem of high operation cost of conventional bio-oil conversion is solved

[0037] The product pyrolysis carbon in the biomass crude oil unit is used as an energy and heat supply material by coupling biomass drying with pyrolysis, green hydrogen produced by gas water shift and organic solution reforming is used for deoxygenation and upgrading and reconstruction reaction, the "running closed cycle" heat source utilization and self-supply hydrogen mode are realized, and the problems of high drying cost and high hydrogen use cost in the conventional process from waste biomass to oil products are solved.

[0038] 2) The flash reaction thermal starting mechanism with stepwise temperature rise and online switching of coke removal is arranged, the coking risk is decoupled in space and time, and the problem of continuous and stable operation of the device is solved

[0039] The flash reaction thermal starting mechanism is arranged for the bio-oil reaction, the coking risk point of the bio-oil in the reactor is transferred to outside the reactor, the space decoupling of the reaction core area and the coking risk area is realized, the flash reaction thermal starting mechanism has the stepwise temperature rise feature, the coking temperature point can be quickly crossed to enter the reaction temperature, the time decoupling of the bio-oil heating process and the coking process is realized, the flash reaction thermal starting mechanism has the switching coke removal capacity, the device can be continuously operated without stopping for coke removal, and the time decoupling of the continuous operation process and the coke removal and maintenance process is realized, and the problem of continuous and stable operation of the device is solved by the coking risk space-time decoupling design.

[0040] 3) The present application realizes the catalyst cyclone internal circulation, prolongs the catalyst life, solves the problems of high temperature, high pressure and alternating stress fatigue and creep of the equipment, and guarantees the long-period operation of the device

[0041] The three-phase cyclone separator and the self-overflow ring gap part are internally arranged in the suspended bed deoxygenation upgrading reactor, the catalyst cyclone internal circulation is realized, the catalyst life is prolonged, the heat source energy consumption caused by catalyst replacement is reduced, the bed pressure drop loss caused by valve jamming, wear and internal leakage is reduced, the maintenance time is prolonged, the internal ring gap solves the problem of low separation efficiency in the cyclone, resource recovery is improved, and the long-period operation of the device is guaranteed. BRIEF DESCRIPTION OF DRAWINGS

[0042] Figure 1 The flowchart of the device for producing aviation fuel and co-producing chemical raw materials from waste biomass is provided for the embodiments of the present application;

[0043] Figure 2 The structure diagram of the flash reaction thermal starting furnace group is shown;

[0044] Figure 3 The structure diagram of the suspended bed deoxygenation upgrading reactor is shown;

[0045] Figure 4 The device operation condition and product yield change trend in three months in embodiment 1 are shown;

[0046] Figure 5To implement the 3-month device operation and product yield change trend in Example 2;

[0047] Parts, positions and numbers in the figure:

[0048] 1. A unit for coupling biomass drying and pyrolysis to convert biomass crude oil, 11. A secondary dryer, 12. A secondary pyrolysis reactor, 13. A cyclone separator, 14. A combustion furnace, 15. A cooling tower, 16. A water-gas shift reactor, 17. A first hydrogen purification device, 18. A biomass crude oil collection device, 19. A circulating hydrogen compressor, 110. A hydrogen donor storage, 111. A heat exchanger;

[0049] 2. A unit for biomass crude oil suspended bed deoxygenation and upgrading to convert low-oxygen bio-oil, 21. A biomass crude oil mixing tank, 21-1. A circulating pump, 22. A flash reaction hot start furnace group, 22-1. A raw material mixing pipeline, 22-2. A water vapor passage, 22-3. Flash reaction hot start furnace A, 22-4. Flash reaction hot start furnace B, 22-5. An electromagnetic induction coil, 22-6. A mixed material outlet, 23. A high-temperature supplementary furnace, 24. A suspended bed deoxygenation and upgrading reactor, 24-1. A raw material inlet, 24-2. A reaction bed, 24-3. A reaction product outlet, 24-4. A three-phase cyclone separator, 24-5. An annular structure, 24-6. A waste catalyst replacement port, 25. A hot high-pressure separator, 26. A cold high-pressure separator, 27. A flash tank, 28. A cold low-pressure separator, 29. An organic solution reforming hydrogen production reactor, 210. A water vapor generator, 211. A first cooler, 212. A second cooler;

[0050] 3. A unit for low-oxygen bio-oil molecular fixed bed reconstruction to convert hydrocarbon aviation fuel, 31. A fixed bed molecular reconstruction reactor, 32. A circulating separator, 33. A liquid phase separator, 34. A fractionation unit, 35. A second hydrogen purification device, 36. A first heater, 37. A second heater. DETAILED DESCRIPTION

[0051] The technical solutions of the embodiments of the present application will be described clearly and completely in combination with the drawings. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor belong to the present application.

[0052] Example 1

[0053] This embodiment provides a device for producing aviation fuel and co-producing chemical raw materials from waste biomass with anti-coking stable operation, such as Figure 1As shown, it includes a second-level biomass drying coupled with pyrolysis and fractional conversion to biomass crude oil unit 1, a biomass crude oil suspension bed deoxygenation and upgrading conversion to low-oxygen bio-oil unit 2, and a low-oxygen bio-oil molecular fixed bed reconstruction and conversion to hydrocarbon aviation fuel unit 3. In the second-level biomass drying coupled with pyrolysis and fractional conversion to biomass crude oil unit 1, biomass is dried at room temperature or low temperature, and then pyrolyzed at low temperature to convert it into biomass crude oil, pyrolysis gas, and pyrolysis char. All pyrolysis char is burned for heating, and the pyrolysis gas is purified by water-gas shift reaction to produce green hydrogen, which is then introduced into the biomass crude oil suspension bed deoxygenation and upgrading conversion to low-oxygen bio-oil unit 2. A flash reaction hot start mechanism is set up to transfer the risk of coking at the reactor inlet. A three-phase cyclone separator is installed in the suspension bed deoxygenation and upgrading reactor to achieve a long catalyst lifespan and low-energy consumption cycle. Finally, in the low-oxygen bio-oil molecular fixed bed reconstruction and conversion to hydrocarbon aviation fuel unit 3, C8-C is fractionated to produce C8-C. 16 Hydrocarbon biomass aviation fuel, combined with biomass naphtha as a hydrogen donor, and the process of producing hydrogen through organic solution reforming to participate in long-cycle operation.

[0054] (1) Second-level biomass drying coupled with pyrolysis fractional conversion of biomass into crude oil unit

[0055] like Figure 1 As shown, the second-level biomass drying coupled with pyrolysis and fractional conversion biomass crude oil unit 1 is used to perform second-level drying and coupled heat treatment on biomass to obtain biomass crude oil, pyrolysis gas and pyrolysis char; and convert the pyrolysis gas into green hydrogen as a hydrogen source; both biomass crude oil and hydrogen source are used as reaction raw materials to be input into the biomass crude oil suspension bed deoxygenation and upgrading conversion low-oxygen bio-oil unit 2.

[0056] The second-level biomass drying coupled pyrolysis fractional conversion biomass crude oil unit 1 includes a second-level dryer 11, a second-level pyrolysis reactor 12, a cyclone separator 13, a combustion furnace 14, a cooling tower 15, a water-gas shift reactor 16, a first hydrogen purification device 17, and a biomass crude oil collector 18.

[0057] The second-level dryer 11 and the second-level pyrolysis reactor 12 are connected, and the second-level pyrolysis reactor 12 is connected to the cyclone separator 13. The solid outlet of the cyclone separator 13 is connected to the inlet of the combustion furnace 14, and the outlet of the combustion furnace 14 is connected to both the second-level dryer 11 and the second-level pyrolysis reactor 12. The separated pyrolysis char serves as a heat source in the combustion furnace 14 to power the second-level dryer 11 and the second-level pyrolysis reactor 12.

[0058] The gas outlet of the cyclone separator 13 is connected with a cooling tower 15, and the gas outlet of the cooling tower 15 is connected with a water-gas shift reactor 16 and a biomass crude oil collector 18. Further, the outlet pipeline of the cooling tower 15 is also connected with a heat exchanger 111 returning to the cooling tower. The separated pyrolysis gas is discharged from the cooling tower, and then enters the water-gas shift reactor. In the water-gas shift reactor 16, the CO2 in the pyrolysis gas is purified by the water-gas shift reaction to obtain H2, and the obtained green hydrogen is purified by the first hydrogen purification device 17 and then supplied to the biomass crude oil suspension bed deoxygenation and upgrading conversion low-oxygen bio-oil unit 2 and the low-oxygen bio-oil molecular fixed bed reconstruction conversion hydrocarbon aviation fuel unit 3.

[0059] The above-mentioned second pyrolysis reactor 12 uses a down-flow fluidized bed reactor, and the specific structure can be referred to CN116286067A. The above-mentioned first hydrogen purification device uses a PSA hydrogen purification device.

[0060] (2) Biomass crude oil suspension bed deoxygenation and upgrading conversion low-oxygen bio-oil unit

[0061] The biomass crude oil suspension bed deoxygenation and upgrading conversion low-oxygen bio-oil unit 2 is used to make the reaction raw material quickly enter the reaction state to realize the space-time decoupling, and then to obtain low-oxygen bio-oil (the oxygen content is less than 1%) through deoxygenation and upgrading reaction, gas-liquid separation, flashing, and oil-water separation. The hydrogen obtained by the gas-liquid separation is purified and used as a hydrogen source; the heavy oil obtained by the flashing is used as a circulating slurry; and the organic solution obtained by the oil-water separation is reformed to prepare green hydrogen as a hydrogen source.

[0062] In a specific implementation manner, as shown in Figure 1 The biomass crude oil suspension bed deoxygenation and upgrading conversion low-oxygen bio-oil unit 2 includes a biomass crude oil mixing tank 21, a flash reaction thermal starting mechanism, a suspension bed deoxygenation and upgrading reactor 24, and a separator assembly.

[0063] The biomass crude oil mixing tank 21 mixes the biomass crude oil, the circulating slurry, the hydrogen donor, and the catalyst used for the deoxygenation and upgrading reaction, and then inputs the mixture into the flash reaction thermal starting mechanism after being mixed with the hydrogen source and the water vapor through a circulating pump 21-1. The hydrogen source is provided by a circulating hydrogen compressor 19 connected with the first hydrogen purification device 17. The water vapor is provided by a water vapor generator 210 and is mainly used for coke cleaning.

[0064] The flash reaction thermal starting mechanism quickly preheats the mixed material. The flash reaction thermal starting mechanism includes a flash reaction thermal starting furnace group 22 and a high-temperature supplementary furnace 23 connected in series. As shown in Figure 2As shown in the figure, the flash reaction hot start furnace group includes two groups of flash reaction hot start furnaces, flash reaction hot start furnace A 22-3 and flash reaction hot start furnace B 22-4, the inlets of the flash reaction hot start furnace A 22-3 and the flash reaction hot start furnace B 22-4 are connected with the raw material mixing pipeline 22-1 and the water vapor passage 22-2 connected with the water vapor generator 210, and valves are arranged on each connecting pipeline; the raw material mixing pipeline is connected with the circulating hydrogen compressor through a pipeline; the outlets of the flash reaction hot start furnace A 22-3 and the flash reaction hot start furnace B 22-4 are connected with the mixed material outlet 22-6, and valves are arranged on the connecting pipelines. The flash reaction hot start furnace A 22-3 and the flash reaction hot start furnace B 22-4 are the same in structure, and each includes a furnace body, a heating pipe arranged in the furnace body, and an electromagnetic induction coil wound on the heating pipe; the heating pipe is a thick circular pipe in a Z shape, which is beneficial to increase the heat exchange area and improve the exchange efficiency, and 6-9 groups of electromagnetic induction coils are sleeved on the pipe; through the heating of the electromagnetic induction coil, the heating rate can be improved, the coking reaction temperature point can be crossed, the increase of the carbon deposition amount in the pipe caused by slow heating can be avoided, high-quality feed can be provided, and efficient material conveying can be realized. The high-temperature supplementary furnace is used to continue preheating the mixed material from the flash reaction hot start furnace group. The high-temperature supplementary furnace 23 uses a basic heating furnace. The outlet of the high-temperature supplementary furnace 23 is connected with the inlet of the suspended bed deoxygenation upgrading reactor 24.

[0065] As shown in the figure, Figure 3 The inside of the suspended bed deoxygenation upgrading reactor 24 is sequentially provided with a raw material inlet 24-1, a reaction bed layer 24-2 and a reaction material outlet 24-3 from bottom to top. A three-phase cyclone separator 24-4 is further arranged above the reaction bed layer 24-2. The specific structure of the three-phase cyclone separator 24-4 can be referred to CN113816460A. The annular gap structure 24-5 added on the three-phase separator solves the problem of low separation efficiency caused by too much circulating flow and short circuit flow in the cyclone. A waste catalyst replacement port 24-6 is arranged at the horizontal end of the three-phase cyclone separator, which is used for replacing the catalyst, reducing the heat source energy consumption lost due to the replacement of the deactivated catalyst, and slowing down the equipment maintenance and loss caused by frequent switching between high and low pressures and alternating stress fatigue. The catalyst used in the suspended bed deoxygenation upgrading reactor is a 50 μm fine particle, and the active metal loaded thereon is nickel and molybdenum. The loading amount of the catalyst particles accounts for 35% of the volume of the suspended bed deoxygenation upgrading reactor. The catalyst in the suspended bed deoxygenation upgrading reactor 24 is controlled to be in a suspended state at the operating domain by controlling the amount of circulating slurry. The hydrogen oil ratio of the deoxygenation upgrading reaction is controlled by controlling the amount of hydrogen source.

[0066] The separator assembly includes a hot high-pressure separator 25, a cold high-pressure separator 26, a flash tank 27 and a cold low-pressure separator 28. The product obtained by the deoxygenation upgrading reaction is first subjected to gas-liquid separation by the hot high-pressure separator 25; the separated gas is further separated into hydrogen by the first cooler 211 and the cold high-pressure separator 26, and purified by the first hydrogen purification device 17; the separated liquid phase is separated into light oil and heavy oil by the flash tank, and the heavy oil is circulated back to the biomass crude oil mixing tank 21 as a circulating slurry through the bed flow; the light oil obtained by the flash tank 27 is mixed with the liquid phase separated by the cold high-pressure separator 26 through the second cooler 212, and subjected to oil-water separation by the cold low-pressure separator 28, and the obtained oil phase is the low-oxygen bio-oil, and the obtained water phase is the organic solution, and the organic solution reforming hydrogen production reactor is connected to the lower end of the cold low-pressure separator 28, and the hydrogen produced by the organic solution reforming hydrogen production reactor is purified by the second hydrogen purification device to obtain green hydrogen.

[0067] In one implementation, part of the obtained low-oxygen bio-oil is transported to the biomass crude oil mixing tank 21 as a circulating slurry through a pipeline, and part is transported to the low-oxygen bio-oil molecular fixed bed reconstruction conversion hydrocarbon aviation fuel unit 3 through a pipeline, and a valve is arranged on each pipeline.

[0068] The above-mentioned organic solution reforming hydrogen production reactor adopts a conventional device disclosed in the art, and the specific structure is described in (CN 213231513U).

[0069] (3) Low-oxygen bio-oil molecular fixed bed reconstruction conversion hydrocarbon aviation fuel unit

[0070] The low-oxygen bio-oil molecular fixed bed reconstruction conversion hydrocarbon aviation fuel unit 3 is used for hydrogenation reconstruction reaction, oil-water separation and fractionation of the low-oxygen bio-oil to obtain a biomass aviation fuel component, the waste liquid obtained by oil-water separation is subjected to reforming to produce green hydrogen as a hydrogen source, and the co-produced distillate obtained by fractionation is used as a hydrogen donor.

[0071] The low-oxygen bio-oil molecular fixed bed reconstruction conversion hydrocarbon aviation fuel unit 3 includes a fixed bed molecular reconstruction reactor 31, a circulating separator 32, a liquid phase separator 33 and a fractionation unit 34.

[0072] The low-oxygen bio-oil is heated by the heater 36 and then input into the fixed bed molecular reconstruction reactor 31, and then the hydrogenation reconstruction reaction of the low-oxygen bio-oil is carried out under the action of the hydrogen source of the first hydrogen purification device 17.

[0073] The product obtained by the fixed bed molecular reconstruction reactor 31 is subjected to the circulating separator 32, the separated hydrogen is purified by the first hydrogen purification device 17, and the separated liquid phase is subjected to oil-water separation by the liquid phase separator 33; the oil phase is subjected to fractionation by the fractionation unit 34 to obtain C8-C 16The biomass aviation fuel of the hydrocarbon is obtained, and a co-produced distillate naphtha is obtained; the water phase is a waste liquid, which is sent to an organic solution reforming hydrogen production reactor, and the obtained hydrogen is purified by a second hydrogen purification device 35 to obtain green hydrogen.

[0074] The fixed bed molecular restructuring reactor 31 uses a fixed bed reactor, and the specific structure is described in CN 118755495A. Moreover, a micro-nano bubble generator is arranged in the top of the fixed bed molecular restructuring reactor 31, which is used for sufficient mixing of green hydrogen and low-oxygen bio-oil, and improves the hydrogen dissolving capacity and mass transfer and heat transfer of the oil product. The structure of the micro-nano bubble generator is described in CN 111298670A. The catalyst used in the fixed bed molecular restructuring reactor 31 is aluminum oxide, and the active metals loaded thereon are nickel, molybdenum and zirconium. The specific surface area of the catalyst is 180 m 2 / g.

[0075] The second hydrogen purification device 25 has the same structure as the first hydrogen purification device 17.

[0076] In this embodiment, the equipment for producing aviation fuel and co-producing chemical raw materials from waste biomass by using the above anti-coking stable operation is used to prepare biomass aviation fuel according to the following steps:

[0077] S1: The biomass is dried and coupled with heat treatment by the biomass crude oil unit 1 for biomass drying and coupled pyrolysis and fractionation to obtain pyrolysis oil gas and pyrolysis carbon; the pyrolysis oil gas and pyrolysis carbon are separated by a cyclone separator; the pyrolysis oil gas is cooled to produce pyrolysis gas, which is then subjected to a water-gas shift reaction to produce green hydrogen as a hydrogen source; the pyrolysis oil gas is cooled to obtain biomass crude oil; and the pyrolysis carbon is combusted to provide heat for the biomass drying and coupled heat treatment.

[0078] The example uses waste straw as biomass, which is added from the top of the second drying device 11 and dried. The drying time is 8 seconds, and the drying temperature is 85°C. The moisture content of the biomass is reduced from 35% to 8%. The dried biomass is discharged from the bottom of the second drying device 11, enters the second pyrolysis reactor 12 through the top of the second pyrolysis reactor 12, and is heated to 600°C to undergo rapid pyrolysis. The pyrolysis process uses a heating rate of 1000K / s and a pyrolysis oil gas cooling rate of 500K / s. The pyrolysis carbon and pyrolysis oil gas generated by pyrolysis are separated by a cyclone separator. The separated pyrolysis carbon directly enters the combustion furnace. A small part (about 30%) of the hot gas stream generated in the combustion furnace 14 enters the second drying device 1, and most (about 70%) enters the second pyrolysis reactor 12. The pyrolysis oil gas (high-temperature oil gas) generated by pyrolysis is cooled to 60°C in the cooling tower 5 to obtain biomass crude oil. A part of the biomass crude oil is further cooled to 30°C in the heat exchanger 6 and then returned to the high-temperature oil gas in the cyclone separator 3. Another part of the cooled biomass crude oil enters the biomass crude oil collection device 9. The properties of the biomass crude oil are shown in Tables 1 and 2. The pyrolysis gas discharged from the cooling tower is subjected to a water-gas shift reaction in the water-gas shift reactor 7 to produce green hydrogen. The green hydrogen is purified in the first hydrogen purification device and then enters the suspended bed deoxygenation and upgrading reactor 24 and the fixed bed molecular restructuring reactor 31.

[0079] S2 converts the biomass crude oil into low-oxygen bio-oil in the biomass crude oil suspended bed deoxygenation and upgrading conversion low-oxygen bio-oil unit 2. The biomass crude oil, hydrogen donor, and circulating slurry are premixed and mixed with hydrogen in the pipeline, and then rapidly enter the reaction state through the flash reaction hot start mechanism. The biomass crude oil is deoxygenated and upgraded to obtain low-oxygen bio-oil. The heavy oil separated during the reaction is used as circulating slurry, the hydrogen gas separated is used as hydrogen source after purification, and the organic solution separated is used as hydrogen source after reforming to produce green hydrogen.

[0080] The biomass crude oil, hydrogen donor, and circulating slurry are mixed in the biomass crude oil mixing tank 12. The mixture is pressurized by the circulating pump 21-1 and mixed with hydrogen from the circulating hydrogen compressor 19 in the pipeline, and then rapidly heated to 200°C in the flash reaction hot start furnace A 22-3, and then preheated to 300°C in the high-temperature supplementary furnace 23, and then enters the suspended bed deoxygenation and upgrading reactor 24. The mixture and spherical catalyst are rapidly heated, mixed, and diluted in the suspended bed deoxygenation and upgrading reactor 24 under the high-speed disturbance to undergo deoxygenation and upgrading reaction. The amount of circulating slurry is controlled to control the suspension state of the deoxygenation and upgrading catalyst, and to meet the operating domain of the suspended bed reactor. The amount of circulating hydrogen is controlled to control the hydrogen to oil ratio of the deoxygenation and upgrading reaction. In this example, the catalyst is a fine particle spherical catalyst loaded with active metal nickel, and the hydrogen to oil volume ratio is 400:1. The reaction volume space velocity of this example is 0.6h -1, the reaction pressure is 13.0 MPa, and the reaction temperature is 300 DEG C. The low-oxygen bio-oil product after the deoxygenation upgrading reaction passes through a hot high-pressure separator 25, the gas phase passes through a first cooler 211 and enters a cold high-pressure separator 26, the generated cold high-pressure hydrogen gas is recovered into a first hydrogen purification device 17; the low-oxygen bio-oil liquid phase passes into a flash tank 27 (working temperature 300 DEG C, pressure 1.25 MPa), the flash tank 27 separates light oil, heavy oil and waste catalyst, the heavy oil is recycled as a circulating slurry and is circulated back to the biomass crude oil mixing tank 12 through the bed layer; another outlet is connected to a second cooler 212 and a cold low-pressure separator 28 (the pressure is controlled at 2 MPa), the cold low-pressure separator 28 is connected with an organic solution reforming hydrogen production reactor 29 at the lower end, and the low-oxygen bio-oil separated out is directly input into the low-oxygen bio-oil molecular fixed-bed reconfiguration conversion hydrocarbon aviation fuel unit 3.

[0081] S3, the low-oxygen bio-oil is subjected to a hydrogen reconfiguration reaction through the low-oxygen bio-oil molecular fixed-bed reconfiguration conversion hydrocarbon aviation fuel unit 3, and a biomass aviation fuel component is obtained; the waste liquid separated out in the reaction process is subjected to reforming to prepare green hydrogen as a hydrogen source, and the cogeneration distillate obtained by fractionation is used as a hydrogen donor.

[0082] In this embodiment, the hydrogen to oil ratio for the reconfiguration reaction is 800:1. The hydrogen reconfiguration catalyst in this embodiment is a tooth ball type aluminum oxide catalyst, the reaction volume space velocity of this embodiment is 0.8 h -1 , the reaction pressure is 15.0 MPa, and the reaction temperature is 300 DEG C. The oxygen in the low-oxygen bio-oil is removed to 0.1%, and the sulfur content is less than 10 ppm.

[0083] The biomass aviation fuel preparation process in this embodiment can realize stable operation for 3 months, and the deoxygenated reconfigured biomass aviation fuel product still reaches the sustainable aviation fuel standard for 3 months. The energy consumption of the whole process is reduced by 40%, and the total yield of the biomass aviation fuel is increased to 85%, Figure 4 The product yield trend in 3 months can be seen from the figure, and the equipment for producing aviation fuel and cogeneration chemical raw materials from waste biomass provided by the application can realize long-period stable operation, and even after cleaning the coking, the operation of the equipment is not affected.

[0084] Table 1 Properties of straw crude oil and low-oxygen straw oil generated by deoxygenation upgrading reaction

[0085]

[0086] Table 2 GCMS result analysis of straw crude oil and low-oxygen straw oil

[0087]

[0088] Table 3 Analysis of straw aviation fuel results

[0089]

[0090] Table 1 and Table 2 give the component and performance analysis results of the biomass crude oil and the low-oxygen bio-oil generated by the deoxygenation and upgrading reaction. As can be seen from the tables, the quality of the bio-oil product is significantly improved, the yield of alcohol, lipid, ketone, aldehyde and other substances is significantly reduced, and the total amount of alkane and aromatic hydrocarbon is significantly improved, which is helpful to the occurrence of subsequent reconstruction reaction.

[0091] Table 3 gives the analysis results of the partial composition of the reconstructed bio-mass aviation fuel. The main product bio-mass aviation fuel accounts for 50-60% of the total liquid yield, contains C8-C 16 alkane, and the aromatic hydrocarbon accounts for 47.68-49.73%, which meets the standard of bio-mass aviation fuel of ASTM D7566 or GB 6537-2018.

[0092] Example 2

[0093] In this embodiment, compared with Example 1, no flash reaction hot start furnace group 22 is set, and only one high-temperature supplementary furnace is provided, and the other operating conditions and process are the same as those of Example 1. Table 4 is the property comparison of the low-oxygen bio-oil in Example 2 and Example 1, and Table 5 is the GCMS result analysis of the low-oxygen bio-oil in Example 2 and Example 1, Figure 5 Table 6 is the yield change comparison of the bio-mass aviation fuel in Example 2 and Example 1.

[0094] Table 4 Comparison of properties of low-oxygen bio-oil in Example 2 and Example 1

[0095]

[0096] Table 5 GCMS result analysis of low-oxygen bio-oil in Example 2 and Example 1

[0097]

[0098] After three months of continuous operation, the low-oxygen bio-oil obtained in this embodiment was compared with that of Example 1, as shown in Tables 4 and 5. Compared with Example 1, the process of Example 2 lacks the flash reaction hot start furnace group to transfer the coking raw material, so that there is tar carbon deposition in the suspended bed deoxygenation upgrading reactor and the pipeline, which needs to be shut down for decoking, shortening the operation period of the device; because the mixture is not gradient heated, the mixture is not fully reacted, and the reaction efficiency and degree are lower than those of Example 1. As shown in Tables 4 and 5, the bio-oil product obtained without setting the flash reaction hot start furnace group has a significant decrease in quality compared with Example 1, the bio-oil heat value decreases from 45 MJ / kg to 35 MJ / kg, the oxygen content increases from 0.1 wt.% to 20.4 wt.%, the yield of substances such as alcohols, lipids, ketones, and aldehydes increases, the total amount of alkanes and aromatic hydrocarbons decreases from 74.34% to 54.36%, the bio-oil quality is poor, and it is difficult to carry out subsequent reconstruction reactions. Figure 5 It can be seen that the device cannot be operated stably for a long period, and needs to be shut down for maintenance for 10-20 days due to coking.

[0099] Example 3

[0100] In this embodiment, compared with Example 1, the annular gap structure with a guiding function is not set in the suspended bed deoxygenation upgrading reactor, and the catalyst cannot realize internal circulation. The other operating conditions and process flow are the same as those of Example 1. The catalyst discharged from the suspended bed deoxygenation upgrading reactor 24 is severely deactivated, the catalyst consumption increases, the material cost and valve maintenance cost increase by 20%, which is not conducive to engineering amplification, and the operation period decreases from 3 months to 2 months. This is due to the fact that the catalyst does not participate in the cyclone internal circulation, the catalyst life is shortened, the heat source energy consumption increases due to catalyst replacement, the equipment needs to withstand the interactive damage failure mode of alternating stress fatigue and creep under high temperature and high pressure, the bed pressure drop loss caused by valve jamming, wear and internal leakage leads to the extension of maintenance time, and the high-quality conversion of the biomass aviation fuel product cannot be realized.

[0101] Example 4

[0102] In this embodiment, compared with Example 1, the fixed bed molecular reconstruction reactor 31 does not use circulating green hydrogen, and the other operating conditions and process flow are the same as those of Example 1. Table 6 shows the comparison of various parameters of the biomass aviation fuel of Example 4 and Example 1.

[0103] Table 6 Comparison of various parameters of the biomass aviation fuel of Example 4 and Example 1

[0104]

[0105] The comparison of the biomass aviation fuel obtained in this example with that of Example 1 is shown in Table 6. Compared with Example 1, the low-oxygen bio-oil in Example 4 enters the fixed-bed molecular restructuring reactor without circulating green hydrogen for deep hydrogenation. Since the restructuring reaction is highly exothermic, the fixed-bed molecular restructuring reactor may have a situation where the heat release rate of the exothermic reaction is greater than the heat transfer rate during production, resulting in device temperature runaway, severe temperature rise, and causing the structure of the active components of the catalyst to collapse and sinter to be deactivated. As shown in Table 6, the freezing point of the biomass aviation fuel obtained in Example 4 is higher than that of Example 1, which may be because the fixed-bed molecular restructuring reactor has unstable device temperature, and the active sintering of the catalyst causes carbon deposition and blocks the active sites of the catalyst, resulting in slow reaction, poor restructuring effect, reduced product yield, and difficulty in achieving long-term stable operation. The operation period is shortened from 3 months in Example 1 to 2 months.

[0106] Example 5

[0107] In this example, compared with Example 1, the second-level biomass drying coupled with pyrolysis and fractionation conversion of biomass crude oil unit 1, the biomass crude oil suspension bed deoxygenation and upgrading conversion of low-oxygen bio-oil unit 2, and the low-oxygen bio-oil molecular fixed-bed restructuring conversion of hydrocarbon aviation fuel unit 3 are independently operated. The waste hydrogen and organic sewage produced by the deoxygenation and upgrading system are directly discharged, resulting in a significant increase in the supply of external hydrogen sources (hydrogen and hydrogen-donating agents) and an increase of 23% in the energy consumption of the whole process compared with Example 1.

[0108] The processing cost of the waste biomass aviation fuel product in this example is about 6000 yuan / ton of oil product. The second-level biomass drying coupled with pyrolysis and fractionation conversion of biomass crude oil unit 1 uses external drying heat energy supply at a cost of 600 yuan / ton of oil product. The biomass crude oil suspension bed deoxygenation and upgrading conversion of low-oxygen bio-oil unit 2 and the low-oxygen bio-oil molecular fixed-bed restructuring conversion of hydrocarbon aviation fuel unit 3 are independently operated, and the external hydrogen supply cost is 1500 yuan / ton of oil product. Compared with Example 1, the whole process cost increases by 35%, mainly due to the external supply of drying heat energy and hydrogen sources.

[0109] In summary, the application provides a device and method for co-production of aviation fuel and chemical raw materials from waste biomass with anti-coking stable operation. The biomass is dried and pyrolyzed at 100℃ or below to produce green hydrogen and biomass crude oil with low energy consumption. The pyrolysis oil and gas are reformed to purify hydrogen, which is used for deoxygenation, upgrading and reconstruction. The biomass crude oil, circulating slurry and hydrogen source are preheated in the flash reaction hot start furnace group. The operation mode of stepwise temperature rise and online decoking can transfer the coking risk from the reactor inlet to the flash reaction hot start furnace group, realize the spatial decoupling of coking risk, and solve the hidden danger caused by device blockage. The catalyst with large diameter in the suspended bed deoxygenation and upgrading reactor realizes internal circulation under the cooperation of cyclone and ring gap component with guiding function, solves the problems of high temperature, high pressure and alternating stress fatigue and creep, prolongs the service life of the catalyst, and ensures the long-period operation of the device. The fixed bed reconstruction reactor for aviation fuel production realizes long-period stable operation of the device. The hydrogen produced in the process is purified and sent to the circulating hydrogen compressor for recycling, so that the device can realize 30% reduction in energy consumption, 35% reduction in product processing cost, 85% increase in total yield of biomass aviation fuel, and 3-month continuous stable operation. The biomass aviation fuel product meets the bio-based aviation coal component standard of ASTM7566 or GB6537-2018, the carbon footprint analysis emission is less than 28.2g CO2 / GJ, and the sustainable fuel standard of the European Union is met.

[0110] Those skilled in the art will appreciate that the embodiments described herein are presented for the purpose of aiding the reader in understanding the principles of the application, and should be understood as not limiting the scope of protection of the application to such specific statements and embodiments. Those skilled in the art can make various other specific modifications and combinations according to the technical inspiration disclosed in the application without departing from the essence of the application, and these modifications and combinations are still within the scope of protection of the application.

Claims

1. A device for producing aviation fuel and co-producing chemical raw materials from waste biomass with anti-coking and stable operation, characterized in that, include: The second-level biomass drying coupled pyrolysis fractional conversion of biomass crude oil unit (1), biomass crude oil suspension bed deoxygenation and upgrading conversion of low-oxygen bio-oil unit (2), and low-oxygen bio-oil molecule fixed bed reconstruction conversion of hydrocarbon aviation fuel unit (3). The second-level biomass drying coupled pyrolysis fractional conversion biomass crude oil unit (1) is used to obtain biomass crude oil, pyrolysis gas and pyrolysis char; and reforms the pyrolysis gas into green hydrogen as a hydrogen source, and both biomass crude oil and hydrogen source are used as reaction raw materials to be input into the biomass crude oil suspension bed deoxygenation and upgrading conversion low-oxygen bio-oil unit (2). The biomass crude oil suspension bed deoxygenation and upgrading conversion low-oxygen bio-oil unit (2) is used to quickly cross the coking reaction time point, transfer the coking location, and achieve spatiotemporal decoupling of coking risk; then, through biomass crude oil deoxygenation and upgrading reaction, gas-liquid separation, flash evaporation, and oil-water separation, low-oxygen bio-oil is obtained, and the hydrogen obtained from gas-liquid separation is purified and used as a hydrogen source; the heavy oil obtained from flash evaporation is used as circulating slurry; the organic solution obtained from oil-water separation is reformed to prepare green hydrogen as a hydrogen source; the biomass crude oil suspension bed deoxygenation and upgrading conversion low-oxygen bio-oil unit (2) includes a biomass crude oil mixing tank (21), a flash reaction hot start mechanism, a suspension bed deoxygenation and upgrading reactor (24), and a separator assembly; the biomass crude oil mixing tank (21) mixes biomass crude oil, circulating slurry, and hydrogen supply agent, and then premixes it with the hydrogen source before inputting it into the flash reaction hot start mechanism, transferring the coking risk to the flash reaction hot start mechanism, and achieving spatiotemporal decoupling; the preheated mixture is deoxygenated in the suspension bed deoxygenation and upgrading reactor (24). The reaction product is separated into oil and water and flash evaporated by a separator assembly to obtain low-oxygen bio-oil; the flash reaction thermal start-up mechanism includes a flash reaction thermal start-up furnace group (22) and a high-temperature supplementary furnace (23); the flash reaction thermal start-up furnace group includes two or more flash reaction thermal start-up furnaces, which are used to preheat the mixture to 150-300℃. The two or more flash reaction thermal start-up furnaces can simultaneously perform biomass crude oil preheating and switching decoking through parallel operation, realizing the dual functions of inhibiting coking and decoking; the high-temperature supplementary furnace is used to continue preheating the mixture from the flash reaction thermal start-up furnace group to 200-400℃, and the energy is fully utilized through two-stage preheating; the interior of the suspended bed deoxygenation and upgrading reactor (24) consists of a raw material inlet (24-1), a reaction bed (24-2), and a reactant outlet (24-3) from bottom to top; a three-phase cyclone separator (24-4) and an annular gap (24-5) are also provided above the reaction bed (24-2). The low-oxygen bio-oil molecule fixed bed reconstruction and conversion hydrocarbon aviation fuel unit (3) is used to perform hydrogenation reconstruction reaction, oil-water separation and fractionation on low-oxygen bio-oil components to obtain biomass aviation fuel components and biomass naphtha chemical raw materials. The organic solution obtained from oil-water separation is reformed to prepare green hydrogen as a hydrogen source. The co-product distillate biomass naphtha obtained from fractionation is used as a hydrogen supply agent for the low-oxygen bio-oil unit (2) of biomass crude oil suspension bed deoxygenation and upgrading conversion.

2. The equipment for producing aviation fuel and co-producing chemical raw materials from waste biomass with anti-coking and stable operation according to claim 1, characterized in that, The second-level biomass drying coupled pyrolysis fractional conversion biomass crude oil unit (1) includes a second-level dryer (11), a second-level pyrolysis reactor (12), a cyclone separator (13), a combustion furnace (14), a cooling tower (15), and a water-gas shift reactor (16). The second-level dryer (11) and the second-level pyrolysis reactor (12) are connected. The dried biomass is sent to the second-level pyrolysis reactor for coupled heat treatment to obtain pyrolysis oil and gas and pyrolysis char. The pyrolysis oil and gas and pyrolysis char are separated by the cyclone separator. The separated pyrolysis char is returned to the combustion furnace, which in turn provides heat for the second-level dryer and / or the second-level pyrolysis reactor. The pyrolysis gas discharged after passing through the cooling tower enters the water-gas shift reactor and is then processed by the first hydrogen purification device (17) connected to the water-gas shift reactor to prepare green hydrogen. The cooled pyrolysis oil is the bio-crude oil, which is collected by the biomass crude oil collection device (18).

3. The equipment for producing aviation fuel and co-producing chemical raw materials from waste biomass with anti-coking and stable operation according to claim 1, characterized in that, The biomass crude oil mixing tank (21) also includes a catalyst for the deoxygenation and upgrading reaction; the amount of catalyst is controlled by controlling the circulation state of the catalyst in the operating area of ​​the suspended bed deoxygenation and upgrading reactor (24); the crude catalyst participates in the internal circulation of the reactor, the fine catalyst participates in the external circulation of the reactor, and the powdered catalyst is separated and discharged; the discharged catalyst is replenished through the biomass crude oil mixing tank (21); the particle size of the crude catalyst is 70-100% of the initial catalyst particle size; the particle size of the fine catalyst is 30-70% of the initial catalyst particle size, excluding the end values ​​at both ends; the particle size of the powdered catalyst is 0-30% of the initial catalyst particle size, excluding the end value of 0.

4. The equipment for producing aviation fuel and co-producing chemical raw materials from waste biomass with anti-coking and stable operation according to claim 1, characterized in that, The separator components in the biomass crude oil suspension bed deoxygenation and upgrading conversion low-oxygen bio-oil unit (2) include a hot high-pressure separator (25), a cold high-pressure separator (26), a flash tank (27), and a cold low-pressure separator (28). The products obtained from the deoxygenation and upgrading reaction are first separated into gas and liquid phases by the hot high-pressure separator (25). The separated gas phase is further separated into hydrogen by the cold high-pressure separator (26) and purified by the first hydrogen purification unit (17) as a hydrogen source. Based on the different boiling points, The separated liquid phase is separated into light oil and heavy oil by a flash tank. The heavy oil is used as a circulating slurry and transported to the biomass crude oil mixing tank (21). The light oil obtained by flash evaporation in the flash tank (27) is mixed with the liquid phase separated by the cold high-pressure separator (26) and separated into oil and water phases by the cold low-pressure separator (28). The resulting oil phase is low-oxygen bio-oil, and the resulting water phase is organic solution. It is sent to the organic solution reforming hydrogen production reactor. The hydrogen produced is purified by the second hydrogen purification unit to obtain green hydrogen.

5. The equipment for producing aviation fuel and co-producing chemical raw materials from waste biomass with anti-coking and stable operation according to claim 1 or 4, characterized in that, The low-oxygen bio-oil molecule fixed-bed reconstruction and conversion hydrocarbon aviation fuel unit (3) includes a fixed-bed molecular reconstruction reactor (31), a circulating separator (32), a liquid phase separator (33), and a fractionation unit (34). Under the action of the hydrogen source of the first hydrogen purification device (17), the fixed-bed molecular reconstruction reactor (31) performs a hydrogenation reconstruction reaction on the low-oxygen bio-oil components. The hydrogen gas separated by the circulating separator (32) is purified by the first hydrogen purification device. The separated liquid phase enters the liquid phase separator (33) to separate the oil phase and the water phase. The oil phase enters the fractionation unit to fractionate C8-C. 16 Hydrocarbon biomass aviation fuel is produced and co-produced distillates are obtained; the aqueous phase is an organic solution, which is sent to an organic solution reforming hydrogen production reactor, and the hydrogen produced is purified by a second hydrogen purification unit (35) to obtain green hydrogen.

6. A method for producing aviation fuel and co-producing chemical feedstock from waste biomass with anti-coking and stable operation, characterized in that, The equipment for producing aviation fuel and co-producing chemical feedstock from waste biomass, which is designed to resist coking and operate stably according to any one of claims 1 to 5, shall be carried out according to the following steps: S1 uses a second-level biomass drying coupled with pyrolysis fractional conversion biomass crude oil unit (1) to dry and coupled heat treat waste biomass to obtain pyrolysis oil gas and pyrolysis char; the pyrolysis oil gas and pyrolysis char are separated by a cyclone separator; the pyrolysis gas generated by cooling the pyrolysis oil gas is then used to prepare green hydrogen as a hydrogen source through a water-gas shift reaction, and the pyrolysis oil gas is cooled to obtain biomass crude oil; the heat released by the combustion of pyrolysis char provides heat for biomass drying and coupled heat treatment; S2 converts biomass crude oil into low-oxygen bio-oil through a biomass crude oil suspension bed deoxygenation and upgrading unit (2); biomass crude oil, hydrogen supply agent, and circulating slurry are premixed and mixed with hydrogen source in the pipeline, and then rapidly enter the reaction state through a flash reaction thermal start mechanism. Biomass crude oil is deoxygenated and upgraded to obtain low-oxygen bio-oil; the heavy oil separated during the reaction is used as circulating slurry, the separated hydrogen is purified and used as hydrogen source, and the separated organic solvent is reformed to prepare green hydrogen as hydrogen source; S3 uses a low-oxygen bio-oil molecule fixed bed reconstruction and conversion hydrocarbon aviation fuel unit (3) to carry out hydrogenation reconstruction reaction of low-oxygen bio-oil components to obtain biomass aviation fuel components; the organic solution separated during the reaction is reformed to prepare green hydrogen as a hydrogen source, and the co-product distillate obtained by fractionation is used as a hydrogen supply agent.

7. The method for producing aviation fuel and co-producing chemical raw materials from waste biomass with anti-coking and stable operation according to claim 6, characterized in that, The deoxygenation and upgrading reaction of biomass crude oil takes place at temperatures of 200℃-400℃, reaction pressures of 8-15MPa, and volume hourly space velocities of 0.6-2.0 h⁻¹. -1 With a hydrogen-to-oil ratio of 400:1-1500:1 and a residence time of 1-4 hours, the oxygen content of the resulting product is 0.2-1%. The hydrogenation and remodeling reaction of low-oxygen bio-oil is carried out at a temperature of 150-450℃, a pressure of 5-20 MPa, and a volume hourly space velocity of 0.25-4.0 h⁻¹. -1 The hydrogen-to-oil ratio is 400:1-1500:1, the residence time is 1-4 h, the final boiling point after molecular reconstruction is 200-300℃, the main product is biomass aviation fuel, accounting for 50-60% of the total yield of biomass crude oil, and the co-product is biomass naphtha chemical feedstock.

Images