CN112175649A

CN112175649A - Coal and biomass multistage liquefaction system and process

Info

Publication number: CN112175649A
Application number: CN201910600384.3A
Authority: CN
Inventors: 张志炳; 李大鹏; 周政; 门存贵; 孟为民; 王宝荣; 杨高东; 罗华勋; 张锋; 李磊; 杨国强; 田洪舟; 曹宇
Original assignee: Nanjing Institute of Microinterface Technology Co Ltd
Current assignee: Nanjing Institute of Microinterface Technology Co Ltd
Priority date: 2019-07-04
Filing date: 2019-07-04
Publication date: 2021-01-05

Abstract

The invention relates to a coal and biomass multistage liquefaction system and a process, which comprises the following steps: a liquid phase feeding unit, a gas phase feeding unit, a micro-interface generator, at least two reactors and a separation tank. According to the invention, the gas is crushed to form micron-sized bubbles with micron scale, and the micron-sized bubbles and the biomass kerosene slurry are mixed to form gas-liquid emulsion, so that the phase interface area of gas-liquid two phases is increased, the effect of strengthening mass transfer in a lower preset range is achieved, and the reaction efficiency of the system is improved while the energy consumption is reduced; meanwhile, mass transfer is greatly enhanced, so that the gas-liquid ratio can be greatly reduced, and the energy consumption of subsequent gas cyclic compression is reduced while the gas material consumption is reduced; the method has the advantages of low process severity, high production safety, low ton product cost and strong market competitiveness.

Description

Coal and biomass multistage liquefaction system and process

Technical Field

The invention relates to the technical field of coal liquefaction, in particular to a coal and biomass multistage liquefaction system and process.

Background

At present, coal is used as a main energy source in China, the traditional coal utilization mode is combustion, but the problem of air pollution caused by coal combustion is increasingly serious; moreover, the coal quality of China is lowered year by year, so that the raw coal washing proportion is improved year by year, and the coal washing wastewater brings serious water pollution. The severe environmental problems have made the adjustment of energy structures one of the important tasks in energy development in our country. However, the storage condition of energy resources of China is poor oil and rich coal, a large amount of oil imports are needed to meet the production development requirement every year, if the energy structure of China is adjusted by reducing the utilization of coal resources, the energy resources with rich reserves are left, the importation amount of oil is also greatly increased, and the energy safety of China is certainly influenced.

The energy structure adjustment mode more suitable for the national conditions of China is to realize the clean and efficient utilization of coal resources. The kerosene refining technology is a technology developed recently for jointly processing coal and heavy oil, overcomes the harsh condition of direct coal liquefaction, and can also utilize the heavy oil at the same time, so that the technology becomes a research hotspot for clean utilization of coal. For example, chinese patent document CN102191072 discloses a coal liquefaction technology for kerosene co-refining, which first prepares coal particles and oil into a suspension, makes the suspension pass through two serially connected boiling beds with catalyst and hydrogen to perform liquefaction reaction, and then sends the obtained lighter components into a reactor for further hydrogenation reaction to finally obtain naphtha, kerosene and/or diesel oil, and heavy components. The reaction conditions in the two boiling beds are 325-420 ℃, 16-20 MPa, 350-450 ℃ and 16-20 MPa in sequence, and the temperature of the second boiling bed is always higher than that of the first boiling bed by more than 10 ℃; the reaction conditions of the reactor are 250-480 ℃ and 2-25 MPa.

However, this technique has two problems in common with most kerosene mixing processes of the prior art: low liquefaction efficiency and large hydrogen consumption.

The mechanism of coal hydrocracking is as follows:

in the first stage, coal is cracked to generate asphaltene and asphaltene, and gas, liquefied oil and macromolecular polycondensate are generated along with the asphaltene and the asphaltene.

In the second stage, under the condition of rich hydrogen, partial pre-asphaltene is hydrogenated to generate liquefied oil, and partial macromolecular polycondensate is hydrogenated and cracked again to generate liquefied oil with low molecular weight.

Since hydrogen cannot be sufficiently mixed with preasphaltene in the reaction process, the preasphaltene cannot be completely converted into liquefied oil, and thus, the efficiency of coal liquefaction is reduced.

Therefore, a large amount of hydrogen needs to be added in the reaction process to fully mix the hydrogen with the pre-asphaltene, so that the hydrogen consumption of the kerosene co-refining technology is high, and the running cost of the kerosene co-refining technology in the prior art is high due to the consumption of a large amount of hydrogen.

Disclosure of Invention

Therefore, the invention provides a coal and biomass multistage liquefaction system and a coal and biomass multistage liquefaction process, which are used for solving the problem of high system operation cost caused by insufficient mixing of hydrogen and reactants in the prior art.

In one aspect, the present invention provides a coal and biomass multi-stage liquefaction system comprising:

the liquid-phase feeding unit is used for storing and conveying biomass kerosene slurry;

a gas phase feed unit to store and deliver hydrogen;

the micro-interface generator is respectively connected with the liquid-phase feeding unit and the gas-phase feeding unit, converts pressure energy of gas and/or kinetic energy of liquid into bubble surface energy and transmits the bubble surface energy to hydrogen bubbles, so that the hydrogen is crushed into micron-sized bubbles with the diameters of more than or equal to 1 mu m and less than 1mm to improve the mass transfer area between the biomass kerosene slurry and the hydrogen, reduce the thickness of a liquid film and reduce the mass transfer resistance, and the biomass kerosene slurry and the micron-sized bubbles are mixed to form a gas-liquid emulsion after being crushed so as to enhance the reaction efficiency between the biomass kerosene slurry and the hydrogen within a preset operating condition range;

the reactor comprises at least two reactors, wherein each reactor is respectively connected with a corresponding micro-interface generator and is used for loading gas-liquid emulsion, providing a reaction space for biomass kerosene slurry and micron-sized bubbles in the gas-liquid emulsion and enabling the biomass kerosene slurry and the micron-sized bubbles to perform multi-stage reaction;

a separation tank connected to the reactor for separating the secondary hydrogenation product to form bio-oil.

Further, the liquid-phase feed unit comprises:

the liquid raw material tank is used for storing biomass kerosene slurry;

the feeding pump is connected with the liquid raw material tank and used for providing power for conveying the biomass kerosene slurry;

the liquid feeding preheater is connected with the feeding pump and used for preheating the biomass kerosene slurry conveyed by the feeding pump so as to enable the biomass kerosene slurry to reach a specified temperature, and a shunting pipeline is arranged at the outlet of the liquid feeding preheater and used for conveying the biomass kerosene slurry to the corresponding micro-interface generators respectively;

when the liquid-phase feeding unit is used for conveying the biomass kerosene slurry, the feeding pump starts to operate, the biomass kerosene slurry is pumped out of the liquid raw material tank and conveyed to the liquid feeding preheater, and the liquid feeding preheater heats the biomass kerosene slurry to a specified temperature and then conveys the biomass kerosene slurry to the micro-interface generator.

Further, the gas phase feed unit comprises:

a gas raw material buffer tank for storing hydrogen;

the compressor is connected with the gas raw material buffer tank and used for providing power for conveying hydrogen;

the gas feeding preheater is connected with the compressor and used for preheating the hydrogen conveyed by the compressor so as to enable the hydrogen to reach a specified temperature, and a shunting pipeline is arranged at the outlet of the gas feeding preheater and used for conveying the hydrogen to the corresponding micro-interface generators respectively;

when the gas-phase feeding unit is used for conveying hydrogen, the compressor starts to operate, the hydrogen is extracted from the gas raw material buffer tank and conveyed to the gas feeding preheater for preheating, and after preheating is completed, the gas feeding preheater conveys the hydrogen to the micro-interface generator so that the micro-interface generator can crush the hydrogen to a specified size.

Further, the reactor comprises:

the first-stage reactor is used for providing a reaction space for biomass kerosene slurry and micron-sized bubbles in the gas-liquid emulsion so as to carry out first-stage reaction on the biomass kerosene slurry and the micron-sized bubbles and generate a first-stage hydrogenation product;

the second-stage reactor is connected with the first-stage reactor in series, and an inlet at the lower end of the second-stage reactor is connected with the upper end of the first-stage reactor, so that a first-stage hydrogenation product and micron-sized bubbles are mixed through the micro-interface generator to form a first-stage gas-liquid emulsion, and a second-stage reaction is carried out in the second-stage reactor to generate a second-stage hydrogenation product;

further, the micro-interface generator includes:

the primary micro-interface generator is arranged at the bottom of the primary reactor and used for forming a gas-liquid emulsion and outputting the gas-liquid emulsion to the primary reactor, when the primary micro-interface generator runs, the liquid-phase feeding unit and the gas-phase feeding unit can respectively convey biomass kerosene slurry and hydrogen to the primary micro-interface generator, the primary micro-interface generator can break hydrogen bubbles to form micron-sized bubbles, the micron-sized bubbles and the biomass kerosene slurry are mixed to form the gas-liquid emulsion, and the gas-liquid emulsion is output to the primary reactor;

at least one second grade micro interface generator, it sets up second grade reactor bottom for form one-level gas-liquid emulsion and export one-level gas-liquid emulsion extremely in the second grade reactor, when second grade micro interface generator operation, first grade reactor and gaseous phase feed unit can carry one-level hydrogenation product and hydrogen to second grade micro interface generator respectively, and second grade micro interface generator can smash the hydrogen bubble and form the micron order bubble, mixes micron order bubble and one-level hydrogenation product and forms one-level hydrogenation product, and export one-level hydrogenation product extremely in the second grade reactor.

Furthermore, a waste outlet is formed in the side wall of the separation tank and used for conveying waste in the secondary hydrogenation product, a material outlet is formed in the bottom end of the separation tank and used for conveying bio-oil, after the reaction in the reactor is completed, the reactor conveys the reacted secondary hydrogenation product to the separation tank, the bio-oil in the secondary hydrogenation product is separated and then is settled to the bottom end of the separation tank and is output from the system through a liquid phase outlet, and the waste in the secondary hydrogenation product is output from the system through the waste outlet.

In another aspect, the present invention provides a multi-stage liquefaction process of coal and biomass, comprising:

step 1: adding a specified amount of biomass kerosene slurry into the liquid raw material tank before the system is operated, adding a specified amount of hydrogen into the gas raw material buffer tank, starting the system after the addition is finished, extracting the biomass kerosene slurry from the liquid raw material tank through a feed pump, extracting the hydrogen from the gas raw material buffer tank through a compressor, enabling the biomass kerosene slurry to flow through a liquid feed preheater, heating the biomass kerosene slurry to a specified temperature through the liquid feed preheater, enabling the hydrogen to flow through the gas feed preheater, and heating the hydrogen to the specified temperature through the gas feed preheater;

step 2: the biomass coal oil slurry is preheated and then split, the split biomass coal oil slurry is respectively conveyed to a micro-interface generator, hydrogen is preheated and then split, the split hydrogen is respectively conveyed to corresponding first-stage micro-interface generators, the first-stage micro-interface generators can control the proportion between the biomass coal oil slurry and the hydrogen received by the first-stage micro-interface generators, the hydrogen is smashed into micron-sized bubbles with the diameter being more than or equal to 1 mu m and less than 1mm, and after the smashing is finished, the micron-sized bubbles biomass coal oil slurry and the micron-sized bubbles are mixed by the first-stage micro-interface generators to form a gas-liquid emulsion;

and step 3: the first-stage micro-interface generator outputs the gas-liquid emulsion to the first-stage reactor after mixing is finished, the pressure and the temperature in the first-stage reactor are controlled, the gas-liquid emulsion flows in a specified direction, and the gas-liquid emulsion reacts in a preset pressure and temperature range to form a first-stage hydrogenation product;

and 4, step 4: after the reaction of the first-stage reactor is finished, conveying a first-stage hydrogenation product to a second-stage micro-interface generator, meanwhile, conveying preheated hydrogen to the corresponding second-stage micro-interface generator by a gas feeding preheater, controlling the proportion between the first-stage hydrogenation product and the hydrogen received by the second-stage micro-interface generator, crushing the hydrogen into micron-sized bubbles, and mixing the micron-sized bubbles and the first-stage hydrogenation product by each micro-interface generator to form a first-stage gas-liquid emulsion after the crushing is finished;

and 5: the second-stage micro-interface generator outputs the first-stage gas-liquid emulsion to the second-stage reactor after mixing is finished, the pressure and the temperature in the second-stage reactor are controlled, the first-stage gas-liquid emulsion flows in a specified direction, and a reaction is carried out to form a second-stage hydrogenation product;

step 6: after the reaction is finished, the secondary reactor conveys a secondary hydrogenation product to the separation tank, the secondary hydrogenation product is separated in the separation tank to form waste and bio-oil, the bio-oil is settled on the lower layer of the separation tank and is output from the system through the material outlet for subsequent treatment, and the waste is stopped on the upper layer of the separation tank and is output from the system through the waste outlet for subsequent treatment.

Further, the preparation method of the biomass kerosene slurry comprises the following steps:

collecting biomass with water content lower than 2wt%, crushing to medium particle size of 100-;

collecting coal with water content lower than 2wt%, pulverizing to median particle size of 50-100 μm, compression molding the pulverized coal under compression pressure of 5-15MPa, pulverizing the compression molded coal again to median particle size of 30-50 μm to obtain coal powder;

mixing the biomass powder, the coal powder, the catalyst and an oil product, grinding and pulping to obtain biomass kerosene slurry, wherein the biomass powder and the coal powder account for 60-70 wt% of the biomass kerosene slurry, the concentration of the biomass is 20-30 wt%, and the concentration of the coal powder is 30-45 wt%.

Further, the preset reaction pressure in the first-stage hydrogenation reaction is 1-15MPa, the preset reaction temperature is 280-350 ℃, the preset reaction pressure in the second-stage hydrogenation reaction is 1-15MPa, and the preset reaction temperature is 400-480 ℃.

Further, the preset reaction pressure in the first-stage hydrogenation reaction is 3-10MPa, the preset reaction temperature is 300-320 ℃, the preset reaction pressure in the second-stage hydrogenation reaction is 3-10MPa, and the preset reaction temperature is 420-460 ℃.

Compared with the prior art, the invention has the beneficial effects that the micron-scale bubbles are formed by crushing the gas, the micron-scale bubbles are mixed with the biomass kerosene slurry to form gas-liquid emulsion, so that the interfacial area of gas-liquid two phases is increased, the thickness of a liquid film is reduced, the mass transfer resistance is reduced, the effect of strengthening the mass transfer in a lower preset range is achieved, the pressure in the reaction process can be reduced by 10-80%, the energy consumption is reduced, and the reaction efficiency of the system is improved. In addition, the range of the preset operation conditions can be flexibly adjusted according to different raw material compositions or different product requirements, so that the full and effective reaction is further ensured, the reaction rate is further ensured, and the purpose of strengthening the reaction is achieved.

Furthermore, mass transfer is greatly enhanced, so that the gas-liquid ratio can be greatly reduced, and the energy consumption of subsequent gas cyclic compression is reduced while the gas material consumption is reduced; the method has the advantages of low process severity, high production safety, low ton product cost and strong market competitiveness.

In particular, the micron-sized bubbles do not coalesce in the process of collision with the movement of catalyst particles, so that the micron-sized bubbles can keep the original form. Therefore, the contact area of the gas phase and the liquid phase in the reactor is increased by geometric times, and the emulsification and mixing are more sufficient and stable, thereby achieving the effects of strengthening mass transfer and macroscopic reaction.

Furthermore, a feeding pump and a compressor are respectively arranged in the liquid-phase feeding unit and the gas-phase feeding unit, so that when the system operates, the feeding pump and the compressor can respectively provide power for transportation of biomass kerosene slurry and hydrogen, the biomass kerosene slurry and the hydrogen can be conveyed to a designated device at a designated speed, and the operating efficiency of the system is improved.

Particularly, the liquid-phase feeding unit and the gas-phase feeding unit are respectively provided with a liquid feeding preheater and a gas feeding preheater, when biomass kerosene slurry and hydrogen are conveyed, the liquid feeding preheater and the gas feeding preheater can respectively preheat the biomass kerosene slurry and the hydrogen, so that the reactor does not need to heat the biomass kerosene slurry and the hydrogen at high power when in operation, the resource consumption of the fixed bed is saved, and the energy consumption of the system is reduced.

Furthermore, the system is provided with at least one micro-interface generator, so that the system can enable biomass coal oil slurry and hydrogen to be fully mixed in different proportions by using a plurality of micro-interface generators, and the reaction efficiency of each substance in the gas-liquid emulsion can be obviously improved when the system reacts with a catalyst.

In particular, the method of the invention limits the temperature and pressure in the reactor, ensures that the gas-liquid emulsion in the reactor can react efficiently, controls the energy consumption of the system to be the lowest, and can further reduce the energy consumption of the system.

Drawings

Fig. 1 is a schematic structural diagram of a coal and biomass multi-stage liquefaction system according to the present invention.

Detailed Description

In order that the objects and advantages of the invention will be more clearly understood, the invention is further described below with reference to examples; it should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

Preferred embodiments of the present invention are described below with reference to the accompanying drawings. It should be understood by those skilled in the art that these embodiments are only for explaining the technical principle of the present invention, and do not limit the scope of the present invention.

It should be noted that in the description of the present invention, the terms of direction or positional relationship indicated by the terms "upper", "lower", "left", "right", "inner", "outer", etc. are based on the directions or positional relationships shown in the drawings, which are only for convenience of description, and do not indicate or imply that the device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention.

Furthermore, it should be noted that, in the description of the present invention, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.

Fig. 1 is a schematic structural diagram of a coal and biomass multi-stage liquefaction system according to an embodiment of the present invention, including a liquid feeding unit 1, a gas feeding unit 2, a Micro interface Generator 3 (MIG for short), a reactor 4, and a separation tank 5; the micro-interface generator 3 is respectively connected with the liquid feeding unit 1 and the gas feeding unit 2, and is used for receiving the biomass kerosene slurry conveyed by the liquid feeding unit 1 and the hydrogen conveyed by the gas feeding unit 2; the reactor 4 is connected with the micro-interface generator 3, and the output end of the micro-interface generator 3 is arranged in the reactor 4, so as to output the gas-liquid emulsion in the micro-interface generator 3 to the reactor; the separation tank 5 is connected with the reactor 4 and is used for receiving the secondary hydrogenation product output by the reactor 4 and separating the secondary hydrogenation product.

When the system is operated, the liquid feeding unit 1 is started, the biomass kerosene slurry stored in the liquid feeding unit is conveyed to the micro-interface generator 3, meanwhile, the gas feeding unit 2 is started, the hydrogen stored in the liquid feeding unit is conveyed to the micro-interface generator 3, the micro-interface generator 3 can break the hydrogen to a micron scale, micron-sized bubbles with the diameter being more than or equal to 1 micron and less than 1mm are formed, after the breaking is completed, the micro-interface generator 3 mixes the micron-sized bubbles with the biomass kerosene slurry to form a gas-liquid emulsion, the micro-interface generator 3 outputs the gas-liquid emulsion to the reactor 4 after the gas-liquid emulsion is mixed, and the gas-liquid emulsion is subjected to a first-stage reaction in the reactor by controlling the temperature, the air pressure and the airspeed of the gas-liquid emulsion in the reactor 4 to generate a first-stage hydrogenation product, at the moment, the micro-interface generator 3 breaks the hydrogen and mixes the hydrogen with the primary hydrogenation product to form a primary gas-liquid emulsion, a secondary reaction is carried out to generate a secondary hydrogenation product, the reactor 4 outputs the generated secondary hydrogenation product to the separation tank 5 after the reaction is finished, and the separation tank 5 separates the bio-oil from the waste material in the secondary hydrogenation product. It will be understood by those skilled in the art that the system of the present invention can also be used in other multiphase reactions, such as those using micro-mixing, micro-fluidization, ultra-micro fluidization, micro bubble fermentation, micro bubble bubbling, micro bubble mass transfer, micro bubble reaction, micro bubble absorption, micro bubble oxygenation, micro bubble contact, etc. by using micro-mixing, micro-fluidization, ultra-micro fluidization, micro bubble biochemical reactor, micro bubble biological reactor, etc. to form multiphase micro-mixed flow, multiphase micro-nano flow, multiphase emulsified flow, multi-phase micro-structured flow, micro-mixed flow of gas, liquid, solid, micro-nano flow, emulsified flow of gas, micro-bubble, micro bubble flow, micro bubble flow, micro bubble flow, micro, And micro-nano bubbling, micro-nano bubbling flow and the like are multiphase fluids formed by micron-sized particles or multiphase fluids (micro-interface fluids for short) formed by micro-nano-sized particles, so that the phase boundary mass transfer area between the gas phase and/or the liquid phase and/or the solid phase in the reaction process is effectively increased.

With continued reference to fig. 1, a liquid feed unit 1 according to an embodiment of the present invention includes: a liquid feedstock tank 11, a feed pump 12 and a liquid feed preheater 13; wherein the feed pump 12 is connected to the liquid material tank 11 for pumping out the biomass kerosene slurry in the liquid material tank 11; the liquid feeding preheater 13 is arranged at the output end of the feeding pump 12, the liquid feeding preheater 13 is connected with the micro-interface generator 3 and used for preheating the biomass kerosene slurry output by the feeding pump 12 and conveying the biomass kerosene slurry to the micro-interface generator 3 after preheating. When the liquid feed unit 1 is in operation, the feed pump 12 pumps the biomass kerosene slurry stored in the liquid material tank 11 and delivers it to the liquid feed preheater 13, and after the biomass kerosene slurry is preheated to a predetermined temperature by the liquid feed preheater 13, the biomass kerosene slurry is delivered to the micro-interface generator 3.

Specifically, the liquid material tank 11 is a tank body for storing the biomass coal oil slurry, and the liquid material tank 11 is connected to the feed pump 12 for delivering the biomass coal oil slurry to a specified position through the feed pump 12 when the system is in operation. It is understood that the liquid material tank 11 may be a metal oil tank or a nonmetal oil tank as long as the liquid material tank 11 can load a predetermined amount of biomass coal oil slurry.

Specifically, the feed pump 12 is a centrifugal pump, which is disposed at the outlet of the liquid feedstock tank 11 to provide power for the transportation of the biomass coal oil slurry. When the liquid feed unit 1 is in operation, the feed pump 12 starts to operate, and the biomass kerosene slurry in the liquid raw material tank 1 is pumped out and conveyed to the liquid feed preheating unit 13. It is understood that the type and power of the feed pump 12 are not particularly limited in this embodiment, as long as the feed pump 12 can deliver the biomass-kerosene slurry at a specified flow rate.

Specifically, the liquid feed preheater 13 is a preheater for preheating the biomass kerosene slurry, and a flow dividing pipe is disposed at an outlet of the liquid feed preheater 13 for respectively conveying the preheated biomass kerosene slurry to the interior of each micro-interface generator. When the feed pump 12 conveys the biomass kerosene slurry, the biomass kerosene slurry flows through the liquid feed preheater 13, the liquid feed preheater 13 preheats the biomass kerosene slurry and shunts the biomass kerosene slurry after reaching a specified temperature, and the biomass kerosene slurry is conveyed to the inside of each micro-interface generator respectively. It is understood that the kind of the preheater and the heating manner of the liquid feed preheater 13 are not particularly limited in this embodiment, as long as the liquid feed preheater 13 can preheat the biomass kerosene slurry to a specified temperature.

With continued reference to fig. 1, the gas feed unit 2 according to the embodiment of the present invention includes: a gas raw material buffer tank 21, a compressor 22, and a gas feed preheater 23; wherein, the compressor 22 is connected with the gas raw material buffer tank 21 and is used for pumping out the hydrogen in the gas raw material buffer tank 21; the gas feed preheater 23 is disposed at an output end of the compressor 22, and the gas feed preheater 23 is connected to the micro-interface generator 3, so as to preheat the hydrogen output by the compressor 22, and deliver the hydrogen to the micro-interface generator 3 after preheating. When the gas feed unit 2 is in operation, the compressor 22 extracts the hydrogen stored in the gas raw material buffer tank 21 and delivers the hydrogen to the gas feed preheater 23, and the gas feed preheater 23 delivers the hydrogen to the micro-interface generator 3 after preheating the hydrogen to a specified temperature.

Specifically, the gas material buffer tank 21 is a tank for storing hydrogen, and the gas material buffer tank 21 is connected to the compressor 22 for delivering hydrogen to a designated location through the compressor 22 when the system is in operation. It is to be understood that the present embodiment is not particularly limited as long as the gas raw material buffer tank 21 can load a prescribed amount of hydrogen gas.

Specifically, the compressor 22 is disposed at the outlet of the gas raw material buffer tank 21 to power the delivery of hydrogen gas. When the gas feed unit 2 is operated, the compressor 22 is operated to extract hydrogen gas from the gas raw material tank 2 and deliver the hydrogen gas to the gas feed preheating unit 23. It is to be understood that the power of the compressor 22 is not particularly limited in this embodiment, provided that the compressor 22 is capable of delivering hydrogen at a specified flow rate.

Specifically, the gas feed preheater 23 is a preheater for preheating hydrogen, and a flow dividing pipe is disposed at an outlet of the gas feed preheater 23 for respectively conveying the preheated hydrogen to the interior of each of the micro-interface generators. When the compressor 22 delivers hydrogen, the hydrogen flows through the gas feed preheater 23, and the gas feed preheater 23 preheats the hydrogen and splits the hydrogen after the hydrogen reaches a predetermined temperature, so as to deliver the hydrogen to the interior of each micro-interface generator. It is understood that the type of preheater and the heating method of the gas feed preheater 23 are not particularly limited in this embodiment, as long as the gas feed preheater 23 can preheat hydrogen to a predetermined temperature.

As shown in fig. 1, the micro-interface generator 3 of the present invention includes a first-stage micro-interface generator 31 and a second-stage micro-interface generator 32, the first-stage micro-interface generator 31 and the second-stage micro-interface generator 32 are respectively vertically disposed at the bottom of the designated reactor 4, the first-stage micro-interface generator 31 and the second-stage micro-interface generator 32 are parallel to each other, and an output port of each micro-interface generator 3 is disposed inside each reactor 4 to output the gas-liquid emulsion to the reactor 4. When the micro-interface generator 3 operates, the first-stage micro-interface generator 31 receives a specified amount of biomass kerosene slurry and hydrogen, the first-stage micro-interface generator 31 crushes the received hydrogen and crushes the hydrogen to a micron scale to form micron-sized bubbles after receiving the hydrogen, the micron-sized bubbles and the biomass kerosene slurry are mixed to form a gas-liquid emulsion after crushing, the gas-liquid emulsion is output to the reactor 4 for first-stage reaction after mixing, the second-stage micro-interface generator 32 receives the first-stage gas-liquid emulsion generated after reaction in the reactor 4 and the liquid feed preheater 13 to preheat the hydrogen, the second-stage micro-interface generator 32 crushes the received hydrogen and crushes the hydrogen to a micron scale to form micron-sized bubbles after receiving the hydrogen, and the micron-sized bubbles and the first-stage hydrogenation product are mixed to form a first-stage gas-liquid emulsion after crushing, and after the mixing is finished, outputting the first-stage gas-liquid emulsion to the reactor 4 for secondary reaction. It can be understood that the connection mode of the micro-interface generator 3 and the reactor 4 may be a pipeline connection, and the output end of the micro-interface generator 3 is arranged inside the reactor 4 or other connection modes, as long as the micro-interface generator 3 can output the gas-liquid emulsion to the reactor 4.

Specifically, the primary micro-interface generator 31 is a gas-liquid linkage micro-interface generator, is disposed at the bottom of the primary reactor 41, is connected to the liquid feed preheater 13 and the gas feed preheater 23, and is configured to crush hydrogen and output a gas-liquid emulsion formed by mixing micron-sized bubbles and biomass kerosene slurry into the reactor 4 for primary reaction. When the micro-interface generator 3 operates, the primary micro-interface generator 31 receives the biomass kerosene slurry and hydrogen gas in specified amounts, crushes the hydrogen gas bubbles to a micron scale by using the pressure energy of the gas and the kinetic energy of the liquid, vigorously mixes the micron-sized bubbles and the biomass kerosene slurry to form a gas-liquid emulsion after the crushing is completed, and outputs the gas-liquid emulsion to the reactor 4 after the mixing is completed.

Specifically, the secondary micro-interface generator 32 is a pneumatic micro-interface generator, which is disposed at the bottom of the secondary reactor 4, and is connected to the primary reactor 41 and the gas feed preheater 23, respectively, for breaking hydrogen and outputting a primary gas-liquid emulsion formed by mixing micron-sized bubbles and a primary hydrogenation product into the secondary reactor 42. When the micro-interface generator 3 operates, the second-stage micro-interface generator 31 receives the specified amounts of the first-stage hydrogenation product and hydrogen respectively, and uses the pressure of the gas to crush the hydrogen bubbles to the micrometer scale, after the crushing, the micrometer-scale bubbles and the first-stage hydrogenation product are violently mixed to form a first-stage gas-liquid emulsion, and after the mixing, the first-stage gas-liquid emulsion is output to the second-stage reactor 42.

As shown in fig. 1, the reactor 4 of the present invention includes a first-stage reactor 41 and a second-stage reactor 42, wherein the first-stage reactor 41 is connected to the first-stage micro-interface generator 31 for loading the gas-liquid emulsion and performing a first-stage reaction to generate a first-stage hydrogenation product, the second-stage reactor 42 is connected to the second-stage micro-interface generator 32, and the second-stage micro-interface generator is respectively connected to the first-stage reactor 41 and the gas-feed preheater 23 for loading the gas-liquid emulsion and performing a second-stage reaction to generate a second-stage hydrogenation product. When the reactor 4 operates, the first-stage micro-interface generator 31 outputs the gas-liquid emulsion to the inside of the first-stage reactor 41, the gas-liquid emulsion generates a first-stage reaction in the first-stage reactor 41 to generate a first-stage hydrogenation product, after the reaction is completed, the first-stage reactor 41 conveys the first-stage hydrogenation product to the second-stage micro-interface generator 32, and the second-stage micro-interface generator mixes the first-stage hydrogenation product with hydrogen to form a first-stage gas-liquid emulsion and conveys the first-stage gas-liquid emulsion to the second-stage reactor to perform a second-stage reaction to generate a second-stage hydrogenation product. It is understood that the size and material of each stage of the reactor 4 are not specifically limited in this embodiment, as long as the reactor can be loaded with a specified amount of gas-liquid emulsion and has a specified strength to withstand a preset reaction temperature and reaction pressure.

Referring to fig. 1, the separation tank 5 according to the embodiment of the present invention is a metal tank body, which is connected to the discharge port of the secondary reactor 42 for separating the secondary hydrogenation product output from the secondary reactor 42. 5 lateral walls of knockout drum are equipped with the waste material mouth for export the waste material, the bottom is equipped with the material mouth, is used for exporting biological oil. After the secondary reactor 42 outputs the reacted secondary hydrogenation product to the separation tank 5, the separation tank 5 separates the secondary hydrogenation product, and outputs the waste material through the waste material port and the bio-oil through the material port. It is understood that the size and material of the separation tank 5 are not particularly limited in this embodiment, as long as the separation tank 5 has a predetermined strength and can hold a predetermined volume of the secondary hydrogenation product.

The specific method and effect of the system of the present invention will be further described with reference to fig. 1.

A multi-stage coal and biomass liquefaction process comprising:

step 1: adding a specified amount of biomass kerosene slurry into the liquid raw material tank 11 before the system is operated, adding a specified amount of hydrogen into the gas raw material buffer tank 21, starting the system after the addition is finished, extracting the biomass kerosene slurry from the liquid raw material tank through the feed pump 12, extracting the hydrogen from the gas raw material buffer tank through the compressor 22, allowing the biomass kerosene slurry to flow through the liquid feed preheater 13, heating the biomass kerosene slurry to a specified temperature through the liquid feed preheater 13, allowing the hydrogen to flow through the gas feed preheater 23, and heating the hydrogen to a specified temperature through the gas feed preheater 23;

step 2: the biomass coal oil slurry is preheated and then split, the split biomass coal oil slurry is respectively conveyed to the micro-interface generators 3, hydrogen is preheated and then split, the split hydrogen is respectively conveyed to the corresponding primary micro-interface generators 31, the primary micro-interface generators 31 can control the proportion between the biomass coal oil slurry and the hydrogen, the hydrogen is smashed into micron-sized bubbles with the diameter being more than or equal to 1 mu m and less than 1mm, and after the smashing is finished, the micron-sized bubble biomass coal oil slurry and the micron-sized bubble biomass coal oil slurry are mixed by the primary micro-interface generators 31 to form a gas-liquid emulsion;

and step 3: the first-stage micro-interface generator 31 outputs the gas-liquid emulsion to the first-stage reactor 41 after mixing is completed, controls the pressure and the temperature in the first-stage reactor 41, enables the gas-liquid emulsion to flow in a specified direction, and reacts within a preset pressure and a preset temperature range to form a first-stage hydrogenation product;

and 4, step 4: after the reaction of the first-stage reactor 41 is finished, the first-stage hydrogenation product is conveyed to the second-stage micro-interface generator 32, meanwhile, the preheated hydrogen is conveyed to the corresponding second-stage micro-interface generator 32 by the gas feed preheater, the second-stage micro-interface generator 32 can control the proportion between the first-stage hydrogenation product and the hydrogen received by the second-stage micro-interface generator and smash the hydrogen into micron-scale bubbles, and after the smashing is finished, the micron-scale bubbles and the first-stage hydrogenation product are mixed by each micro-interface generator to form a first-stage gas-liquid emulsion;

and 5: the second-stage micro-interface generator 32 outputs the first-stage gas-liquid emulsion to the second-stage reactor 42 after mixing, and controls the pressure and temperature in the second-stage reactor 42 to make the first-stage gas-liquid emulsion flow in a specified direction and react to form a second-stage hydrogenation product;

step 6: after the reaction is completed, the secondary reactor 42 conveys the secondary hydrogenation product to the separation tank 5, the secondary hydrogenation product is separated in the separation tank 5 to form waste and bio-oil, the bio-oil is settled at the lower layer of the separation tank 5 and is output from the system through a material outlet for subsequent treatment, and the waste stays at the upper layer of the separation tank 5 and is output from the system through a waste outlet for subsequent treatment.

It can be understood that the range of the preset operation conditions can be flexibly adjusted according to different raw material compositions or different product requirements, so as to ensure the full and effective reaction, further ensure the reaction rate and achieve the purpose of strengthening the reaction. The coal is low-rank coal; the oil product is one or more of hogwash oil, kitchen waste grease, rancid oil, waste lubricating oil, waste engine oil, heavy oil, residual oil, wash oil, anthracene oil, coal tar, petroleum or biological oil prepared by the process.

Example one

The bio-oil is prepared using the above method, wherein:

the preparation method of the biomass kerosene slurry comprises the following steps: taking lignite, drying and dehydrating the lignite, crushing the lignite to obtain particles with the median particle size of 50 microns, and then sending the particles into a briquetting machine for extrusion forming at the forming pressure of 5MPa to obtain the lignite compressed material. And (3) feeding the lignite compressed material into a hammer crusher for crushing to obtain pulverized lignite with the particle size of 30 mu m. Adding the pulverized lignite, the vulcanized amorphous iron oxyhydroxide and the vulcanized amorphous aluminum oxide loaded with Mo oxide and Ni oxide into a mixture of liquid excrement and kitchen waste grease together to form biomass kerosene slurry.

Specifically, the pressure in the first-stage reactor 41 in the system is 3MPa, the temperature is 300 ℃, the reaction time is 30min, the pressure in the second-stage reactor 42 is 3MPa, the temperature is 420 ℃, and the reaction time is 40 min.

In this example, the conversion of biomass coal oil slurry was 97%, the yield of bio-oil was 79%, and the residue content was 0.9%. The content of C element in the biological oil is 91wt%, the content of H element is 6wt%, and the content of O element is 2 wt%.

Example two

The bio-oil is prepared using the above method, wherein:

the biomass is selected from straws, and the processing method comprises the following steps: taking wheat straws and corn straws, drying and dehydrating the wheat straws and the corn straws, crushing the wheat straws and the corn straws into particles with a median particle size of 100 mu m, and then sending the particles into a plodder to carry out extrusion forming under the forming pressure of 2MPa to obtain a straw compression material; and (3) feeding the straw compressed material into a hammer crusher, crushing to obtain straw crushed material with the median particle size of 30 mu m for later use.

The pulverized coal is lignite, and the treatment method comprises the following steps: taking lignite, drying and dehydrating the lignite, crushing the lignite to the median particle size of 100 microns, and then sending the lignite into a briquetting machine for extrusion forming at the forming pressure of 15MPa to obtain a lignite compressed material; and (3) feeding the lignite compressed material into a ball mill, and crushing to obtain pulverized lignite with the median particle size of 50 microns for later use.

The preparation method of the biomass kerosene slurry comprises the following steps: removing ash from the straw crushed materials and the brown coal crushed materials, mixing the straw crushed materials and the brown coal crushed materials with the biomass carbon loaded with iron oxide after vulcanization treatment to obtain a mixture, and adding the mixture into rancid oil to form biomass coal oil slurry; in the biomass kerosene slurry, the content of the straw is 30 wt%, and the content of the lignite is 40 wt%.

Specifically, the pressure in the first-stage reactor 41 in the system is 6MPa, the temperature is 310 ℃, the reaction time is 30min, the pressure in the second-stage reactor 42 is 7MPa, the temperature is 450 ℃, and the reaction time is 50 min.

In this example, the conversion of biomass coal oil slurry was 98%, the bio-oil yield was 82%, and the residue content was 0.6%. The content of C element in the biological oil is 90wt%, the content of H element is 9wt%, and the content of O element is 1.2 wt%.

EXAMPLE III

The bio-oil is prepared using the above method, wherein:

the biomass is reed, and the processing method comprises the following steps: taking the reed, drying and dehydrating the reed, and then sending the reed into a jet mill for crushing treatment to obtain a primary crushed material of the reed, wherein the particle size D50 is 300 mu m; feeding the crushed material of the reed into a briquetting machine or a plodder for extrusion molding, wherein the molding pressure is 5MPa, and obtaining a reed compressed material; and (3) feeding the compressed reed material into a jet mill, and performing secondary crushing to obtain secondary crushed reed material with the particle size D50 of 50 microns for later use.

The coal powder is selected from Shendong long flame coal, and the processing method comprises the following steps: drying and dehydrating the Shendong long flame coal, and then sending the dried and dehydrated Shendong long flame coal into a ball mill for crushing to obtain the primary crushed material of the Shendong long flame coal, wherein the particle size D50 is 80 mu m; sending the crushed material of the Shendong long flame coal into a briquetting machine or a plodder for extrusion molding, wherein the molding pressure is 12MPa, so as to obtain a Shendong long flame coal compressed material; and (3) feeding the Shendong long flame coal compressed material into a ball mill, and carrying out secondary crushing to obtain secondary crushed material of the Shendong long flame coal, wherein the particle size D50 is 40 mu m for later use.

The preparation method of the biomass kerosene slurry comprises the following steps: and (3) deashing the secondary crushed material of the reed powder and the coal, mixing the deashed secondary crushed material with the biomass charcoal loaded with the iron oxyhydroxide subjected to vulcanization treatment in the reactor to obtain a mixture, and adding the mixture into waste engine oil to form the biomass coal-oil slurry.

Specifically, the pressure in the first-stage reactor 41 in the system is 8MPa, the temperature is 320 ℃, the reaction time is 40min, the pressure in the second-stage reactor 42 is 9MPa, the temperature is 460 ℃, and the reaction time is 55 min.

In this example, the conversion of biomass coal oil slurry was 98%, the bio-oil yield was 85%, and the residue content was 0.4%. The content of C element in the biological oil is 85wt%, the content of H element is 13wt%, and the content of O element is 1.3 wt%.

Comparative example

A process for liquefaction of biomass comprising the steps of:

taking lignite, drying and dehydrating the lignite, crushing the lignite to 50 mu m of median particle size, and then sending the lignite into a briquetting machine or a plodder for extrusion molding at the molding pressure of 5MPa to obtain the lignite compression material. And (3) feeding the lignite compressed material into a hammer piece crusher, and crushing to obtain pulverized lignite with the particle size of 50 microns. Adding the pulverized lignite and the amorphous iron oxyhydroxide which is subjected to vulcanization treatment in the reactor into a mixture of liquid excrement and waste engine oil to form biomass kerosene slurry, introducing hydrogen into the biomass kerosene slurry to perform reaction, and controlling the reaction pressure to be 4MPa and the reaction temperature to be 430 ℃ to finally prepare the bio-oil.

In this comparative example, the conversion of biomass kerosene slurry was 57%, the yield of bio-oil was 23%, and the residue content was 9%. The content of C element in the biological oil is 75wt%, the content of H element is 11wt%, and the content of O element is 13 wt%.

In summary, compared with the comparative example, the conversion rate of the biomass and the coal and the yield of the bio-oil obtained by the process of the invention are both high, the residue amount is obviously reduced, and almost no coke is generated, so that the method of the invention can obviously improve the conversion rate of the biomass coal-oil slurry and the yield of the bio-oil and reduce the residue amount. In addition, the multistage liquefaction enables the hydrogenation reaction to be more sufficient, and the quality of the bio-oil is higher.

So far, the technical solutions of the present invention have been described in connection with the preferred embodiments shown in the drawings, but it is easily understood by those skilled in the art that the scope of the present invention is obviously not limited to these specific embodiments. Equivalent changes or substitutions of related technical features can be made by those skilled in the art without departing from the principle of the invention, and the technical scheme after the changes or substitutions can fall into the protection scope of the invention.

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention; various modifications and alterations to this invention will become apparent to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A coal and biomass multi-stage liquefaction system, comprising:

a gas phase feed unit to store and deliver hydrogen;

2. The coal and biomass multi-stage liquefaction system according to claim 1, characterized in that said liquid phase feed unit comprises:

the liquid raw material tank is used for storing biomass kerosene slurry;

3. The coal and biomass multi-stage liquefaction system according to claim 1, characterized in that said gaseous phase feed unit comprises:

a gas raw material buffer tank for storing hydrogen;

4. The coal and biomass multi-stage liquefaction system according to claim 1, characterized in that said reactor comprises:

and the secondary reactor is connected with the primary reactor in series, and an inlet at the lower end of the secondary reactor is connected with the upper end of the primary reactor, so that a primary hydrogenation product and micron-sized bubbles are mixed by the micro-interface generator to form a primary gas-liquid emulsion, and a secondary reaction is carried out in the secondary reactor to generate a secondary hydrogenation product.

5. The coal and biomass multi-stage liquefaction system according to claim 1 or 4, characterized in that said micro-interface generator comprises:

second grade micro interface generator, it sets up second grade reactor bottom for form one-level gas-liquid emulsion and export one-level gas-liquid emulsion extremely in the second grade reactor, when second grade micro interface generator operation, first grade reactor and gaseous phase feed unit can carry one-level hydrogenation product and hydrogen to second grade micro interface generator respectively, and second grade micro interface generator can smash the hydrogen bubble and form the micron order bubble, mixes micron order bubble and one-level hydrogenation product and forms one-level hydrogenation product, and export one-level hydrogenation product extremely in the second grade reactor.

6. The coal and biomass multi-stage liquefaction system according to claim 1, wherein the side wall of the separation tank is provided with a waste outlet for conveying waste materials in the secondary hydrogenation products, the bottom end of the separation tank is provided with a material outlet for conveying bio-oil, when the reaction in the reactor is completed, the reactor conveys the reacted secondary hydrogenation products to the separation tank, the bio-oil in the secondary hydrogenation products is separated and then is settled to the bottom end of the separation tank and is output from the system through the liquid phase outlet, and the waste materials in the secondary hydrogenation products are output from the system through the waste outlet.

7. A multi-stage coal and biomass liquefaction process, comprising:

8. The multi-stage coal and biomass liquefaction process according to claim 7, wherein the configuration method of the biomass coal oil slurry comprises the following steps:

9. The multi-stage coal and biomass liquefaction process as claimed in claim 7, wherein the preset reaction pressure in the first-stage hydrogenation reaction is 1-15MPa, the preset reaction temperature is 280-350 ℃, and the preset reaction pressure in the second-stage hydrogenation reaction is 1-15MPa, and the preset reaction temperature is 400-480 ℃.

10. The multi-stage liquefaction process of coal and biomass as claimed in claim 7, wherein the preset reaction pressure in the first-stage hydrogenation reaction is 3-10MPa, the preset reaction temperature is 300-320 ℃, and the preset reaction pressure in the second-stage hydrogenation reaction is 3-10MPa, the preset reaction temperature is 420-460 ℃.