CN108079910B - Reactor for controlling cracking hydrogenation by upstream differential speed and application thereof - Google Patents
Reactor for controlling cracking hydrogenation by upstream differential speed and application thereof Download PDFInfo
- Publication number
- CN108079910B CN108079910B CN201611041482.0A CN201611041482A CN108079910B CN 108079910 B CN108079910 B CN 108079910B CN 201611041482 A CN201611041482 A CN 201611041482A CN 108079910 B CN108079910 B CN 108079910B
- Authority
- CN
- China
- Prior art keywords
- reactor
- hydrogen
- side wall
- shell
- biomass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/0005—Catalytic processes under superatmospheric pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00026—Controlling or regulating the heat exchange system
- B01J2208/00035—Controlling or regulating the heat exchange system involving measured parameters
- B01J2208/00044—Temperature measurement
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00584—Controlling the density
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a reactor for controlling cracking hydrogenation by an upstream differential speed and application thereof, relating to the technical field of biological energy conversion. The invention provides an upflow differential speed controlled cracking hydrogenation reactor which comprises a closed shell; the conical bottom feeding hole is formed in the bottom of the shell; the conical discharge hole is formed in the top of the shell; the temperature control sensing device and the density measurement sensing device are arranged on the side wall of the shell in pairs; and the side wall hydrogen injection holes are formed in the side wall of the shell between the two pairs of the temperature control sensing devices and the density measurement sensing devices which are arranged in pairs in the flow direction of the cold hydrogen. The reactor of the invention can ensure that the use efficiency of the catalyst is improved and less coke is generated without specially using a coke-absorbing catalyst.
Description
Technical Field
The invention relates to the technical field of biological energy conversion, in particular to a reactor for controlling cracking hydrogenation by an upstream differential speed.
Background
Fossil non-renewable energy sources such as coal, crude oil, natural gas, and oil shale are gradually depleted with the rapid development of socioeconomic performance, and CO generated by their combustion2、SO2、NOxThe increasing environmental pollution caused by the pollutants causes that people have to seriously consider ways to obtain energy and methods for improving the environment. The biomass refers to all organic substances formed by photosynthesis of directly or indirectly available green plants, including plants, animals, microorganisms and excretion and metabolites thereof, and has the advantages of renewability, low pollution and wide distribution. Biomass is a renewable energy source, and has great potential and advantages in meeting energy demand, reducing environmental pollution and improving energy structure. In recent years, the conversion and utilization of biomass energy has been moving towards high efficiency and cleanliness, and biomass liquefactionTechnology is an important component thereof. At present, the biomass liquefaction technology mainly comprises two types of indirect liquefaction and direct liquefaction, wherein the direct liquefaction refers to that the biomass is directly liquefied into liquid from solid under the action of a solvent or a catalyst by adopting hydrolysis and supercritical liquefaction or introducing hydrogen, inert gas and the like under proper temperature and pressure. The biomass direct liquefaction technology mainly comprises pyrolysis liquefaction, catalytic liquefaction, pressurized hydrogenation liquefaction and the like, particularly the product obtained by the hydrogenation pressurization liquefaction has high yield and good quality, but the reaction condition of the high-pressure liquefaction is harsh, and the biomass direct liquefaction technology also comprises quite complicated procedures of drying, crushing, pulping, heating, pressurizing, reacting, separating and the like of solid materials, and does not have more advanced equipment to improve the current condition.
Therefore, chinese patent document CN105727845A discloses a dual solid-phase suspension bed reactor for heavy oil hydrocracking and its application, the prior art includes a shell, a conical bottom, a guide cylinder and a nozzle, the top of the shell is provided with a material outlet, the conical bottom is arranged at the bottom of the shell, the guide cylinder is coaxially arranged in the shell and has two open ends, the nozzle arranged at the bottom of the conical bottom has a loose gas outlet hole, a driving gas outlet and a liquid outlet, and the loose gas outlet hole is close to the bottom of the conical bottom, and the driving gas outlet and the liquid outlet are higher than the loose gas outlet hole. However, the reactor in the prior art only uses the coke-absorbing catalyst at the same time to play the roles of coke absorption and metal absorption, and is discharged together with liquid-phase materials in operation; and the high-activity hundred micron-sized coarse-particle catalyst always keeps high activity in the reaction and stays in the reactor for a long time to participate in the reaction, so that the generated coke is less and the service efficiency of the catalyst can be relatively improved.
Disclosure of Invention
Therefore, the technical problem to be solved by the present invention is to overcome the defects in the prior art that only coke absorption catalyst and high-activity hundred micron-sized coarse-particle catalyst are needed to generate a smaller amount of coke and the use efficiency of the catalyst is relatively improved, thereby providing an upflow differential speed controlled cracking hydrogenation reactor and applications thereof.
Therefore, the invention provides the following technical scheme:
an upflow differential controlled cracking hydrogenation reactor, comprising a closed shell;
the conical bottom feeding hole is formed in the bottom of the shell;
the conical discharge hole is formed in the top of the shell;
the temperature control sensing device and the density measurement sensing device are arranged on the side wall of the shell in pairs;
and the side wall hydrogen injection holes are formed in the side wall of the shell between the two pairs of the temperature control sensing devices and the density measurement sensing devices which are arranged in pairs in the flow direction of the cold hydrogen.
The height-diameter ratio of the reactor is 15:1-3: 1.
The operating pressure of the reactor is 13-25 MPa.
The number of the side wall hydrogen injection holes is 3-5.
The inventory of the solid catalyst in the reactor is controlled to be 5-30% of the total mass of the liquid.
The total gas velocity of the reactor is set to be 0.02-0.2 m/s.
The total gas velocity of the reactor is set to 0.05-0.08 m/s.
The operating temperature of the reactor is set to be 250 ℃ to 500 ℃, and the residence time in the reactor is 15 to 90 minutes.
Use of a reactor as described above.
The application of the reactor comprises the following specific steps:
(1) feeding a mixed gas-liquid-solid three-phase state of hydrogen, reaction liquid, biomass solid particles and catalyst particles from a conical bottom feeding hole;
(2) the solid content between the side wall hydrogen injection hole and the temperature control sensing device and the density measurement sensing device arranged above or below the side wall hydrogen injection hole is judged according to the temperature control sensing device and the density measurement sensing device, so that the flow of hydrogen entering the reactor and the amount of cold hydrogen injected into the side wall of the reactor are adjusted;
(3) the biomass is hydrolyzed, cracked and hydrogenated from bottom to top in the reactor, the biomass and solid particles with large specific gravity rise along with gas and light oil products, return to the bottom under the action of cold hydrogen on the upper part and participate in the reaction again, and the unconverted biomass and the solid catalyst are internally circulated and discharged in a balanced manner after the reaction is finished.
The technical scheme of the invention has the following advantages:
1. the reactor for controlling cracking hydrogenation by the upstream differential speed is simple and easy to process biomass, does not need excessive drying and dehydration, and can use water for high-pressure and high-temperature hydrolysis; and does not produce coke polycondensation under the action of hydrogen and catalyst.
2. When the reactor for controlling cracking hydrogenation by using the upstream differential speed is used in the pulping process, the mother liquor can adopt various liquid oil products, not only comprises processed pure biological product oil, but also can adopt liquid from coal and petroleum, and has wide sources.
3. The reactor for controlling cracking hydrogenation by the upstream differential speed can provide hydrogen transfer in time while hydrolyzing and cracking, thereby ensuring that coke polycondensation is not generated.
4. The reactor for cracking and hydrogenation controlled by the upflow differential speed can be used for cracking and hydrofining biomass, hydrogen is used as a speed-regulating medium to realize the speed supply of gas speed to various liquids, solids and catalysts, the difference of rising and staying in the reactor is realized by depending on the phase state and density difference of a mixture, and simultaneously, the gas quantity can be supplemented and adjusted by a hydrogen injection port on the outer wall of the reactor according to the density difference between layers in the reactor.
5. The reactor for controlling cracking hydrogenation by the upstream differential speed is large in height-diameter ratio, so that heavy materials which are not easy to hydrolyze and crack and solid catalysts can stay in the reactor for reaction as long as possible.
6. The reactor for controlling cracking hydrogenation by the upstream differential speed has high pressure and high hydrogen partial pressure, generally ensures the hydrogen partial pressure to be 12-22MPa, can better inhibit the generation of coke, and provides better hydrogenolysis and hydrogenation functions.
7. The reactor for controlling cracking and hydrogenation by the upstream differential speed provided by the invention is used for controlling different reaction depths and playing roles in hydrolysis, cracking, hydrogenation and stabilization, and each reaction condition can be adjusted according to requirements.
8. The reactor for controlling cracking and hydrogenation by the upstream differential speed can be divided into two, three, four or more reactors according to the number of the side wall hydrogen injection holes, the temperature control sensing devices and the density measurement sensing devices so as to facilitate the actual needs.
9. When the reactor for controlling cracking and hydrogenation by the upstream differential speed is used, the added catalyst is a catalyst with a plurality of micropores inside, the catalyst can coke on the surface of the catalyst along with coke, the volume of the catalyst is large, and the catalyst with large specific surface area can slightly run upwards due to the empty inside of the catalyst, so that the waste catalyst is brought out from the top.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic diagram of a preferred upflow differential controlled cracking hydrogenation reactor configuration of the present invention;
the drawings are numbered as follows: 1-a conical bottom feeding hole, 2-a temperature control sensing device, 3-a density measurement sensing device, 4-a side wall hydrogen injection hole, 5-a shell and 6-a top conical discharging hole.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; 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 in specific cases to those skilled in the art.
In addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
This example provides an upflow, differential velocity controlled cracking hydrogenation reactor, as shown in fig. 1, comprising a closed shell 5;
the conical bottom feed inlet 1 is arranged at the bottom of the shell 5;
the conical discharge hole 6 is arranged at the top of the shell 5;
the temperature control sensing device 2 and the density measurement sensing device 3 are arranged on the side wall of the shell 5 in pairs;
and the side wall hydrogen injection holes 4, wherein the side wall hydrogen injection holes 4 are arranged on the side wall of the shell between the temperature control sensing device 2 and the density measurement sensing device 3 which are arranged in pairs along the upward direction of the cold hydrogen flow.
The height-diameter ratio of the reactor is 15:1-3: 1.
The operating pressure of the reactor is 13-25 MPa.
The number of the side wall hydrogen injection holes is 3-5.
The amount of the solid catalyst in the reactor is controlled to be 5-30% of the total amount of the liquid.
The total gas velocity of the reactor is set to be 0.02-0.2 m/s.
The total gas velocity of the reactor is set to 0.05-0.08 m/s.
The operating temperature of the reactor is set to be 250 ℃ to 500 ℃, and the residence time in the reactor is 15 to 90 minutes.
Example 2.
The embodiment provides an upflow differential controlled cracking hydrogenation process, which uses the reactor described in the embodiment 1, the aspect ratio of the first reactor used in the embodiment is 15:1, and the specific steps are as follows:
(1) removing ash from corn straws with the granularity of 1-50 mu m to obtain straw particles, and mixing amorphous alumina (the particle size is 5-50 mu m) loaded with Mo oxide and Ni oxide, the straw particles and sulfur according to a mass ratio of 5: 100: 0.3, adding the mixture obtained by uniformly mixing the components into medium and low temperature coal tar to form slurry containing 10 wt% of biomass;
(2) injecting hydrogen at 60 ℃ and 13MPa into the slurry for the first time, wherein the volume ratio of the high-pressure hydrogen to the slurry is 50: 1, then raising the temperature of the slurry to 200 ℃, injecting hydrogen gas with the temperature of 200 ℃ and the pressure of 13MPa for the second time into the slurry, and controlling the volume ratio of the hydrogen gas injected for the two times to the slurry to be 800: 1, forming reaction raw materials to obtain a mixed gas-liquid-solid three-phase state;
(3) heating the mixed gas, liquid and solid three-phase state to 450 ℃, then sending the mixed gas, liquid and solid three-phase state into a reactor, carrying out hydrolysis, cracking and hydrogenation reactions under the conditions that the reaction pressure is 13MPa and the reaction temperature is 500 ℃, injecting cold hydrogen at 105 ℃ through 3 injection ports which are sequentially arranged on the side wall of the reactor along the height direction in the reaction process, controlling the total gas velocity in the reactor to be 0.02m/s and the inventory of the catalyst in the reactor to be 30 wt% of the mass of the liquid and the solid in the reactor, sending the material discharged from the reactor into a separation system for three-phase separation of gas, liquid and residue after reacting for 90min, and respectively obtaining biomass gas, bio-oil and residue; and (4) recycling the hydrogen in the system, and entering each hydrogen injection point in the step (3) together with fresh supplementary hydrogen.
Example 3
The embodiment provides an upflow differential controlled cracking hydrogenation process, which uses the reactor described in the embodiment 1, the aspect ratio of the first reactor used in the embodiment is 10:1, and the specific steps are as follows:
(1) dedusting the reed with the granularity of 20-1000 mu m to obtain reed particles, mixing amorphous alumina (the particle size of which is 100-150 mu m) loaded with W oxide and Ni oxide, the reed particles and sulfur in a mass ratio of iron oxide to reed particles and sulfur in a mass ratio of 2: 3: 100: 0.4 to obtain a mixture, and adding the mixture into vegetable oil to form slurry containing 30 wt% of biomass;
(2) and injecting hydrogen at 70 ℃ and 20MPa into the slurry for the first time until the volume ratio of the high-pressure hydrogen to the slurry is 100: 1, then heating the slurry to 250 ℃ in a heat exchanger, injecting hydrogen gas with the temperature of 250 ℃ and the pressure of 20MPa for the second time, and controlling the volume ratio of the hydrogen gas injected for the two times to the slurry to reach 900: 1, forming reaction raw materials to obtain a mixed gas-liquid-solid three-phase state;
(3) heating the mixed gas, liquid and solid three-phase state to 430 ℃, then sending the mixed gas, liquid and solid three-phase state into a reactor, carrying out hydrolysis, cracking and hydrogenation reactions under the conditions that the reaction pressure is 20MPa and the reaction temperature is 450 ℃, injecting cold hydrogen at 120 ℃ through 4 injection ports which are sequentially arranged on the side wall of the reactor along the height direction in the reaction process, controlling the total gas velocity in the reactor to be 0.06m/s and the inventory of the catalyst in the reactor to be 25 wt% of the mass of the liquid and the solid in the reactor, sending the material discharged from the reactor into a separation system for three-phase separation of gas, liquid and residue after reacting for 60min, and respectively obtaining biomass gas, bio-oil and residue; and (4) recycling the hydrogen in the system, and entering each hydrogen injection point in the step (3) together with fresh supplementary hydrogen.
Example 4
The embodiment provides an upflow differential controlled cracking hydrogenation process, which uses the reactor described in embodiment 1, wherein the aspect ratio of the first reactor used in the embodiment is 8:1, and the specific steps are as follows:
(1) deashing wheat straws with the granularity of 1500-2000 mu m to obtain straw particles, and mixing amorphous alumina (the particle size of which is 50-100 mu m) and ferric oxide loaded with Pd oxide and Ni oxide with the straw particles and sulfur in the step (1) according to the mass ratio of 2: 2: 100: 0.3 to obtain a mixture, and adding the mixture into the low-temperature animal oil to form slurry containing 25 wt% of biomass;
(2) and injecting hydrogen with the temperature of 100 ℃ and the pressure of 20MPa into the slurry for the first time until the volume ratio of the high-pressure hydrogen to the slurry is 150: 1, then heating the slurry to 300 ℃ in a heat exchanger, injecting hydrogen gas with the temperature of 300 ℃ and the pressure of 20MPa for the second time, and controlling the volume ratio of the hydrogen gas injected for the two times to the slurry to be 600: 1, forming reaction raw materials to obtain a mixed gas-liquid-solid three-phase state;
(3) heating the mixed gas-liquid-solid three-phase state to 440 ℃, then sending the mixed gas-liquid-solid three-phase state into a slurry bed reactor, carrying out hydrolysis, cracking and hydrogenation reactions under the conditions that the reaction pressure is 20MPa and the reaction temperature is 450 ℃, injecting cold hydrogen at 90 ℃ through 4 injection ports which are sequentially arranged on the side wall of the reactor along the height direction in the reaction process, controlling the total gas velocity in the reactor to be 0.08m/s and the inventory of the catalyst in the reactor to be 20 wt% of the mass of the liquid and the solid phases in the reactor, sending the material discharged from the slurry bed reactor into a separation system for three-phase separation of gas, liquid and residue after reacting for 40min, and respectively obtaining biomass gas, biological oil and residue; and (4) recycling the hydrogen in the system, and entering each hydrogen injection point in the step (3) together with fresh supplementary hydrogen.
Example 5
The embodiment provides an upflow differential controlled cracking hydrogenation process, which uses the reactor described in embodiment 1, wherein the aspect ratio of the first reactor used in the embodiment is 5:1, and the specific steps are as follows:
(1) removing dust from wood chips with the particle size of 4000-5000 microns to obtain wood chip particles, and mixing amorphous alumina loaded with Mo oxide and Co oxide (the particle size is 150-200 microns), the wood chip particles and sulfur according to the mass ratio of 3: 100: 0.2 to obtain a mixture, and adding the mixture into the low-temperature animal oil to form slurry containing 40 wt% of biomass;
(2) injecting hydrogen at 130 ℃ and 27MPa into the slurry for the first time, wherein the volume ratio of the high-pressure hydrogen to the slurry is 200: 1, then heating the slurry to 350 ℃ in a heat exchanger, injecting hydrogen gas with the temperature of 300 ℃ and the pressure of 27MPa for the second time, and controlling the volume ratio of the hydrogen gas injected for the two times to the slurry to be 1000: 1, forming reaction raw materials to obtain a mixed gas-liquid-solid three-phase state;
(3) heating the mixed gas-liquid-solid three-phase state to 380 ℃, then sending the mixed gas-liquid-solid three-phase state into a slurry bed reactor, carrying out hydrolysis, cracking and hydrogenation reactions under the conditions that the reaction pressure is 27MPa and the reaction temperature is 400 ℃, injecting cold hydrogen at 115 ℃ into 5 injection ports which are sequentially arranged along the height direction on the side wall of the reactor in the reaction process, controlling the total gas velocity in the reactor to be 0.1m/s and the inventory of the catalyst in the reactor to be 30 wt% of the mass of the liquid phase in the reactor, sending the material discharged from the slurry bed reactor into a separation system for three-phase separation of gas, liquid and residue after reacting for 50min, and respectively obtaining biomass gas, biological oil and residue; and (4) recycling the hydrogen in the system, and feeding the hydrogen into each hydrogen injection point in the step (3) together with fresh supplementary hydrogen.
Example 6
The embodiment provides an upflow differential controlled cracking hydrogenation process, which uses the reactor described in the embodiment 1, the aspect ratio of the first reactor used in the embodiment is 3:1, and the specific steps are as follows:
(1) removing ash from leaves with the particle size of 4000-: 2: 100: 0.25 to obtain a mixture, and adding the mixture into low-temperature vegetable oil to form slurry containing 20 wt% of biomass;
(2) injecting hydrogen at 135 ℃ and 25MPa into the slurry for the first time until the volume ratio of the high-pressure hydrogen to the slurry is 200: 1, then heating the slurry to 350 ℃ in a heat exchanger, injecting hydrogen gas with the temperature of 350 ℃ and the pressure of 25MPa for the second time, and controlling the volume ratio of the hydrogen gas injected for the two times to the slurry to be 650: 1, forming reaction raw materials to obtain a mixed gas-liquid-solid three-phase state;
(3) heating the mixed gas-liquid-solid three-phase state to 400 ℃, then sending the mixed gas-liquid-solid three-phase state into a slurry bed reactor, carrying out hydrolysis, cracking and hydrogenation reactions under the conditions that the reaction pressure is 25MPa and the reaction temperature is 450 ℃, injecting cold hydrogen at 100 ℃ through 5 injection ports which are sequentially arranged on the side wall of the reactor along the height direction in the reaction process, controlling the total gas velocity in the reactor to be 0.1m/s and the inventory of the catalyst in the reactor to be 25 wt% of the mass of the liquid phase in the reactor, after reacting for 15min, sending the material discharged from the slurry bed reactor into a separation system for gas-liquid-residue three-phase separation, and respectively obtaining biomass gas, bio-oil and residue; and (4) recycling the hydrogen in the system, and entering each hydrogen injection point in the step (3) together with fresh supplementary hydrogen.
Example 7
The embodiment provides an upflow differential speed controlled cracking hydrogenation process, which uses the reactor described in the embodiment 1, the aspect ratio of the first reactor used in the embodiment is 14:1, and the specific steps are as follows:
(1) amorphous alumina (with the grain diameter of 350-500 mu m) loaded with Mo oxide and Ni oxide, iron oxide, illegal cooking oil and sulfur in a mass ratio of 1: 1: 100: 0.1 to obtain a mixture, and preparing slurry of 50 wt% of biomass (illegal cooking oil);
(2) and injecting hydrogen with the temperature of 90 ℃ and the pressure of 20MPa into the slurry for the first time until the volume ratio of the high-pressure hydrogen to the slurry is 150: 1, heating the slurry to 300 ℃ in a heat exchanger, injecting hydrogen gas at 300 ℃ and 20MPa for the second time, and controlling the volume ratio of the hydrogen gas injected for the two times to the slurry to be 800: 1, forming reaction raw materials to obtain a mixed gas-liquid-solid three-phase state;
(3) heating the mixed gas-liquid-solid three-phase state to 430 ℃, then sending the mixed gas-liquid-solid three-phase state into a reactor, carrying out hydrolysis, cracking and hydrogenation reactions under the conditions that the reaction pressure is 20MPa and the reaction temperature is 500 ℃, injecting cold hydrogen at 120 ℃ through 5 injection ports which are sequentially arranged on the side wall of the reactor along the height direction in the reaction process, controlling the total gas velocity in the reactor to be 0.07m/s and the inventory of the catalyst in the reactor to be 30 wt% of the mass of the liquid phase in the reactor, sending the material discharged from the reactor into a separation system after reacting for 40min to carry out gas-liquid-residue three-phase separation, and respectively obtaining biomass gas, bio-oil and residue; and (4) recycling the hydrogen in the system, and entering each hydrogen injection point in the step (3) together with fresh supplementary hydrogen.
Comparative example 1
The biomass liquefaction process provided by the experimental example comprises the following steps:
(1) feeding the reed into a dryer for drying until the water content is 7 wt%, then crushing in a crusher until the granularity is 20-200 mu m, and then removing ash to obtain reed particles;
(2) amorphous alumina (with the grain diameter of 10-150 mu m) and ferric oxide loaded with Mo oxide and Ni oxide are mixed with the reed particles and sulfur in the step (1) according to the mass ratio of 1: 2: 100: 0.2 to obtain a mixture, and adding the mixture into low-temperature vegetable oil to form slurry containing 30 wt% of biomass;
(3) injecting hydrogen at 70 ℃ and 18MPa into the slurry for the first time, wherein the volume ratio of the high-pressure hydrogen to the slurry is 100: 1, then heating the slurry to 250 ℃ in a heat exchanger, injecting 230 ℃ and 18MPa hydrogen for the second time, and controlling the volume ratio of the hydrogen injected for the two times to the slurry to be 900: 1 to form a reaction raw material, heating the reaction raw material to 430 ℃, then sending the reaction raw material into a slurry bed reactor, carrying out hydrolysis, cracking and hydrogenation reactions under the conditions that the reaction pressure is 18MPa and the reaction temperature is 440 ℃, injecting cold hydrogen at 95 ℃ through 4 injection ports which are sequentially arranged on the side wall of the reactor along the height direction in the reaction process, controlling the total gas velocity in the reactor to be 0.06m/s and the storage amount of a catalyst in the reactor to be 30 wt% of the mass of a liquid phase in the reactor, sending a material discharged from the slurry bed reactor into a separation system for three-phase separation of gas, liquid and residue after reacting for 60min, and respectively obtaining biomass gas, biological oil and residue; and (4) recycling the hydrogen in the system, and entering each hydrogen injection point in the step (3) together with fresh supplementary hydrogen.
Comparative example 2
The liquefaction process of biomass provided by the experimental example comprises the following steps:
1) feeding the reed into a dryer for drying until the water content is 5 wt%, then crushing in a crusher until the granularity is 20-1000 mu m, and then removing ash to obtain reed particles;
(2) amorphous alumina (with the grain diameter of 10-150 mu m) and ferric oxide loaded with Mo oxide and Co oxide, the reed particles in the step (1) and sulfur in a mass ratio of 1: 1: 100: 0.2 to obtain a mixture, and adding the mixture into low-temperature vegetable oil to form slurry containing 30 wt% of biomass;
(3) injecting hydrogen at 70 ℃ and 18MPa into the slurry for the first time, wherein the volume ratio of the high-pressure hydrogen to the slurry is 100: 1, then heating the slurry to 250 ℃ in a heat exchanger, injecting hydrogen gas at 250 ℃ and 18MPa for the second time, and controlling the volume ratio of the hydrogen gas injected for the two times to the slurry to reach 900: 1 to form a reaction raw material, heating the reaction raw material to 380 ℃, then sending the reaction raw material into a slurry bed reactor, carrying out hydrolysis, cracking and hydrogenation reactions under the conditions that the reaction pressure is 18MPa and the reaction temperature is 400 ℃, injecting cold hydrogen at 90 ℃ through 4 injection ports which are sequentially arranged on the side wall of the reactor along the height direction in the reaction process, controlling the total gas velocity in the reactor to be 0.06m/s and the storage amount of a catalyst in the reactor to be 30 wt% of the mass of a liquid phase in the reactor, sending a material discharged from the slurry bed reactor into a separation system for three-phase separation of gas, liquid and residue after reacting for 60min, and respectively obtaining biomass gas, biological oil and residue; and (4) recycling the hydrogen in the system, and entering each hydrogen injection point in the step (3) together with fresh supplementary hydrogen.
Comparative example 3
The comparative example is biomass liquefaction (using the same raw materials as in example 3 of the present invention) according to the disclosure of the example of the double solid-phase suspension bed reactor for heavy oil hydrocracking and the application thereof in chinese patent document CN 105727845A.
Examples of the experiments
The results of evaluating the effects of the processes provided in examples 2 to 7 and comparative examples 1 to 2 of the present invention are shown in table 1.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. An upflow differential speed controlled cracking hydrogenation reactor is characterized in that,
comprises a closed shell;
the conical bottom feeding hole is formed in the bottom of the shell;
the conical discharge hole is formed in the top of the shell;
the temperature control sensing device and the density measurement sensing device are arranged on the side wall of the shell in pairs;
and the side wall hydrogen injection holes are formed in the side wall of the shell between the two pairs of the temperature control sensing devices and the density measurement sensing devices which are arranged in pairs in the flow direction of the cold hydrogen.
2. The reactor of claim 1, wherein the reactor height to diameter ratio is from 15:1 to 3: 1.
3. The reactor according to claim 2, characterized in that the operating pressure of the reactor is between 13 and 25 MPa.
4. The reactor of claim 3 wherein said sidewall hydrogen injection holes are 3-5.
5. The reactor of claim 4, wherein a reaction liquid and a solid catalyst are arranged in the reactor, and the inventory of the solid catalyst in the reactor is controlled to be 5-30% of the total amount of the liquid.
6. The reactor according to claim 5, wherein the total gas velocity of the reactor is set to 0.02 to 0.2 m/s.
7. The reactor according to claim 6, wherein the total gas velocity of the reactor is set to 0.05 to 0.08 m/s.
8. The reactor as claimed in claim 7, wherein the operating temperature of the reactor is set at 250 ℃ and 500 ℃ and the residence time in the reactor is 15 to 90 minutes.
9. Use of a reactor according to any of claims 1-8 for the hydrogenation of biomass.
10. The application of claim 9, comprising the following steps:
(1) feeding a mixed gas-liquid-solid three-phase state of hydrogen, reaction liquid, biomass solid particles and catalyst particles from a conical bottom feeding hole;
(2) the solid content between the side wall hydrogen injection hole and the temperature control sensing device and the density measurement sensing device arranged above or below the side wall hydrogen injection hole is judged according to the temperature control sensing device and the density measurement sensing device, so that the flow of hydrogen entering the reactor and the amount of cold hydrogen injected into the side wall of the reactor are adjusted;
(3) the biomass is hydrolyzed, cracked and hydrogenated from bottom to top in the reactor, the biomass and solid particles with large specific gravity rise along with gas and light oil products, return to the bottom under the action of cold hydrogen on the upper part and participate in the reaction again, and the hydrogen, biomass gas, bio-oil, unconverted biomass and solid catalyst are discharged from the conical discharge hole after the reaction is finished.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611041482.0A CN108079910B (en) | 2016-11-21 | 2016-11-21 | Reactor for controlling cracking hydrogenation by upstream differential speed and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611041482.0A CN108079910B (en) | 2016-11-21 | 2016-11-21 | Reactor for controlling cracking hydrogenation by upstream differential speed and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108079910A CN108079910A (en) | 2018-05-29 |
| CN108079910B true CN108079910B (en) | 2020-01-17 |
Family
ID=62170939
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611041482.0A Active CN108079910B (en) | 2016-11-21 | 2016-11-21 | Reactor for controlling cracking hydrogenation by upstream differential speed and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108079910B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL7000999A (en) * | 1969-01-28 | 1970-07-30 | ||
| US4690802A (en) * | 1985-12-31 | 1987-09-01 | Exxon Research And Engineering Company | Apparatus for controlling the temperature in catalyst regeneration |
| CN1077978A (en) * | 1993-01-28 | 1993-11-03 | 化学工业部北京化工研究院 | The improvement of petroleum hydrocarbon steam cracking method |
| CN101668833A (en) * | 2007-03-05 | 2010-03-10 | 荷兰能源建设基金中心 | By the equipment that generates product gas such as the fuel of biomass |
| CN101835876A (en) * | 2007-09-27 | 2010-09-15 | 新日铁工程技术株式会社 | Bubble column type hydrocarbon reactor and slurry level detection method |
| CN102277188A (en) * | 2011-07-25 | 2011-12-14 | 青岛福瑞斯生物能源科技开发有限公司 | Biomass thermal cracking liquefying fuel oil technology |
| CN102378748A (en) * | 2009-04-07 | 2012-03-14 | 瓦斯技术研究所 | Hydropyrolysis of biomass for producing high quality liquid fuels |
| CN103861532A (en) * | 2014-03-03 | 2014-06-18 | 北京旭荣工程设计有限公司 | Homogeneous three-phase reactor for jet aeration |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI124508B (en) * | 2009-02-27 | 2014-09-30 | Upm Kymmene Oyj | Method and apparatus for making fuel components from crude tall oil |
-
2016
- 2016-11-21 CN CN201611041482.0A patent/CN108079910B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL7000999A (en) * | 1969-01-28 | 1970-07-30 | ||
| US4690802A (en) * | 1985-12-31 | 1987-09-01 | Exxon Research And Engineering Company | Apparatus for controlling the temperature in catalyst regeneration |
| CN1077978A (en) * | 1993-01-28 | 1993-11-03 | 化学工业部北京化工研究院 | The improvement of petroleum hydrocarbon steam cracking method |
| CN101668833A (en) * | 2007-03-05 | 2010-03-10 | 荷兰能源建设基金中心 | By the equipment that generates product gas such as the fuel of biomass |
| CN101835876A (en) * | 2007-09-27 | 2010-09-15 | 新日铁工程技术株式会社 | Bubble column type hydrocarbon reactor and slurry level detection method |
| CN102378748A (en) * | 2009-04-07 | 2012-03-14 | 瓦斯技术研究所 | Hydropyrolysis of biomass for producing high quality liquid fuels |
| CN102277188A (en) * | 2011-07-25 | 2011-12-14 | 青岛福瑞斯生物能源科技开发有限公司 | Biomass thermal cracking liquefying fuel oil technology |
| CN103861532A (en) * | 2014-03-03 | 2014-06-18 | 北京旭荣工程设计有限公司 | Homogeneous three-phase reactor for jet aeration |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108079910A (en) | 2018-05-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2016176948A1 (en) | Multi-optimised slurry bed hydrogenation reactor, and design method therefor and use thereof | |
| CN110982552A (en) | Hydrogenation reactor, hydrogenation reaction device and catalytic hydrogenation process | |
| CN103415597A (en) | Systems and methods for gasifying a feedstock | |
| US20200181500A1 (en) | Use of cooling media in biomass conversion process | |
| CN103131468B (en) | Hydrofining and/or hydroisomerizing cracking system and process for low-temperature Fischer-Tropsch synthetic oil | |
| EP3352928B1 (en) | System and process for production of biofuel | |
| CN116601270A (en) | Fluidized bed reactor and associated hydropyrolysis process | |
| CN108277036B (en) | Multistage liquefaction process of biomass | |
| CN108219819B (en) | One-pot liquefaction process for coal and biomass | |
| CN108085048B (en) | One-pot liquefaction process of biomass | |
| RU2677911C1 (en) | Method of direct biomass liquefying | |
| CN108079910B (en) | Reactor for controlling cracking hydrogenation by upstream differential speed and application thereof | |
| US11198820B2 (en) | Conversion process for an organic material | |
| CN110408420B (en) | Organic matter conversion process | |
| CN108079911B (en) | Reaction system for controlling cracking hydrogenation by upstream differential speed and application thereof | |
| RU2674018C1 (en) | Method of manufacturing light oil by liquefying biomass | |
| CN108079909B (en) | Method for realizing control of difference of flow rates of materials of all phases in slurry bed reactor | |
| CN108085042B (en) | One-pot liquefaction process of biomass | |
| CN117616103A (en) | Method for subjecting biomass feedstock to hydropyrolysis | |
| WO2015023415A1 (en) | Integrated process for the production of renewable drop-in fuels | |
| CN108219818B (en) | One-pot liquefaction process of biomass | |
| CN112538367B (en) | Heavy oil cracking-gasification coupling reaction device | |
| CN109536197B (en) | Biomass liquefaction process | |
| CN108264919B (en) | Process for producing fuel oil and chemical raw materials by using biomass | |
| CN108264917B (en) | Hydrolysis hydrogenation process of biomass |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |