CN108079909A - A kind of method of each phase materials flow velocity otherness control in achievable paste state bed reactor - Google Patents
A kind of method of each phase materials flow velocity otherness control in achievable paste state bed reactor Download PDFInfo
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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Abstract
The method that the present invention discloses each phase materials flow velocity otherness control in a kind of achievable paste state bed reactor, is related to bioenergy transformation technology field.The present invention controls sensing device and density measure sensing device and the temperature being arranged in pairs in two Dui flowed to along cold hydrogen to control and between sensing device and density measure sensing device side wall is set to note hydrogen holes by being arranged in pairs temperature on the side wall of paste state bed reactor, is controlled so as to fulfill each phase materials flow velocity otherness.The method of the present invention need not can guarantee while the service efficiency for improving catalyst exclusively with char catalyst is inhaled and generate less amount of coke.
Description
Technical field
The present invention relates to bioenergy transformation technology fields, and in particular to can be achieved to each phase materials in paste state bed reactor
Flow velocity otherness control technology.
Background technology
The fossils non-renewable energy such as coal, crude oil, natural gas, oil shale is increasingly withered with the fast development of social economy
Exhaust and they burn after the CO that generates2、SO2、NOxThe environmental pollution of getting worse caused by grade pollutants, this causes people
Class has to think better of the approach for obtaining the energy and the method for improving environment.Biomass refers to that all are directly or indirectly available
Green plants photosynthesis formed organic substance, including plant, animal, microorganism and its excretion and metabolin, it has
Recyclability, low stain, widely distributed property.Biomass is a kind of regenerative resource, is meeting energy demand, is reducing environment
Pollution all possesses huge potentiality and advantage in terms of improving energy resource structure.In recent years, conversion and utilization to biomass energy
Advance always towards efficient, clean direction, biomass liquefying technology is important component therein.Biomass liquefying at present
Technology mainly has two class of indirect liquefaction and direct liquefaction, and wherein direct liquefaction refers under the action of solvent or catalyst, uses
Hydrolysis, supercritical liquefaction are passed through hydrogen, inert gas etc., by biomass directly from solid liquid under appropriate temperature, pressure
It is melted into liquid.Biomass Direct liquefaction technology mainly has pyrolysis liquefaction, catalytic liquefaction, pressurization hydrogenation liquefaction etc., especially with hydrogenation
Pressurized liquefied product yield is high, and quality is good, and still, the severe reaction conditions of high-pressure liquefaction additionally include solid material and do
The sufficiently complex processes such as dry, crushing, slurrying, heating, pressurization, reaction, separation, also without more advanced equipment to improve mesh
Preceding situation.
For this purpose, Chinese patent literature CN105727845A discloses a kind of double solid suspension beds for hydrocracking heavy oil
Reactor and its application, the prior art include housing, conical bottom, guide shell and nozzle, and case top is equipped with material outlet, cone
Shape bottom is located at housing bottom, and guide shell is co-axially located in housing and both ends open, nozzle are arranged on the nozzle of conical bottom bottom
With loosening gas outlet opening, the outlet of driving gas and liquid outlet, and gas outlet opening is loosened close to conical bottom bottom, driving gas exports
The loosening gas outlet opening is higher by with liquid outlet.However the reactor of the prior art is only at the same time using the burnt catalysis of suction
Agent is discharged with playing the role of inhaling burnt, suction metal with liquid phase material in operation；And hundred micron orders of high activity are thick
Beaded catalyst remains high activity in the reaction, and prolonged stay participates in reacting in the reactor, could cause generation
Amount of coke is less and can relatively improve the service efficiency of catalyst.
The content of the invention
Therefore, the technical problem to be solved in the present invention is of the prior art in need use is overcome to inhale char catalyst
With hundred micron order coarse granule catalyst of high activity the amount of coke of generation could be caused less and improve the use of catalyst relatively
The defects of efficiency, so as to provide a kind of method that can be achieved to each phase materials flow velocity otherness control in paste state bed reactor.
For this purpose, the present invention provides following technical solution：
A kind of method of each phase materials flow velocity otherness control in achievable paste state bed reactor, by slurry reactor
Temperature control sensing device and density measure sensing device are arranged in pairs on the side wall of device and in two couple flowed to along cold hydrogen
Between the temperature control sensing device and density measure sensing device that are arranged in pairs side wall is set to note hydrogen holes, so as to fulfill each
Phase materials flow velocity otherness controls.
The side wall note hydrogen holes is 3-5.
The ratio of height to diameter of the reactor is 15:1-3:1；The operating pressure of the reactor is 13-25MPa.
The specific surface area of the catalyst is 70~300m2/g；The bulk density of catalyst is 0.4~1.5；Catalyst is put down
Equal aperture is 1~100nm.
Storage control of the solid catalyst in reactor is in the 5-30% of liquid gross mass；
The total gas velocity of reactor is set to 0.02-0.2m/s.
The operation temperature of the reactor is set to 250-500 DEG C, and the residence time is 15-90 minutes in reactor.
The reactor is 2, is respectively first reactor and second reactor.
The paste state bed reactor further includes the housing of closing；
Conical bottom feed inlet is located at the bottom of the housing；
Conical discharge port is located at the top of the housing.
It is as follows：
(1) hydrogen, reaction liquid, biomass solid particle, the gas-liquid mixture of catalyst granules is made to consolidate three-phase from taper
Bottom throat-fed；
(2) temperature control sensing device set above or below hydrogen holes is noted according to the side wall and density measure senses
Device both judges the solid content between note hydrogen holes, enters the flow and sidewall of reactor of reactor so as to adjust hydrogen
Inject the amount of cold hydrogen；
(3) biomass bottom in the reactor hydrolyze from bottom to top, cracking, hydrogenation, heavy biomass and solid
Body particle rises with gas and light-end products, and bottom is returned under the action of the cold hydrogen on top, participates in reaction, reaction knot again
The inside of unconverted biomass and solid catalyst Xun Huan and balance discharge after beam.
After the temperature controls sensing device and density measure sensing device to measure catalyst and biomass concentration, lead to
It crosses the hydrogen flowing quantity for changing reactor bottom and sidewall of reactor respectively injects the amount of cold hydrogen, to realize the concentration of catalyst
Control is the 5~30% of liquid stereoplasm amount..
Technical solution of the present invention has the following advantages that：
1. the method processing life of each phase materials flow velocity otherness control in achievable paste state bed reactor provided by the invention
Preprocessing substance is simple and practicable, and excessive drying and dehydrating is not required, and can utilize water into horizontal high voltage, pyrohydrolysis；And in hydrogen
Under the action of catalyst, coke polycondensation will not be generated.
2. the method for each phase materials flow velocity otherness control is added in achievable paste state bed reactor provided by the invention
Catalyst have all microporous catalyst for inside, catalyst can be as coke be in its surface coking, and volume is grown up, due to urging
It is empty inside agent, the catalyst of bigger serface can lighten and run up, and useless catalyst is brought out from top.
3. the method for each phase materials flow velocity otherness control is in slurrying in achievable paste state bed reactor provided by the invention
Process not only includes the pure biological product oil after processing in use, plurality of liquid oil product may be employed in mother liquor, can also be used to from
The liquid of coal, oil, source are very extensive.
4. the method for each phase materials flow velocity otherness control can be in achievable paste state bed reactor provided by the invention
While hydrolysis, cracking, hydrogen migration is timely provided, so that it is guaranteed that not generating coke polycondensation.
5. the method for each phase materials flow velocity otherness control can be used in achievable paste state bed reactor provided by the invention
Biomass is cracked and hydrofinishing, the medium of speed governing is served as with hydrogen, realize gas velocity to various liquid, solid,
The speed supply of catalyst, and the difference that rises, stop is realized by the phase of mixture, density variation in reactor, simultaneously
Can the hydrogen injection mouth supplement adjustment tolerance of reactor outer wall be passed through according to the density contrast of each interlayer in reactor.
6. the method ratio of height to diameter of each phase materials flow velocity otherness control in achievable paste state bed reactor provided by the invention
Greatly so that the heavy material and solid catalyst of bad hydrolysis and cracking being stopped in reactor for length can carry out instead as far as possible
It should.
7. pressure in the method for each phase materials flow velocity otherness control in achievable paste state bed reactor provided by the invention
Height, hydrogen partial pressure are high, generally assure that hydrogen partial pressure in 12-22MPa, can preferably inhibit the generation of coke, and provide more preferable
Hydrogenolysis and hydrogenating function.
8. the method for each phase materials flow velocity otherness control uses in achievable paste state bed reactor provided by the invention
It controls different reaction depths and plays the role of hydrolysis, cracking, hydrogenation, stabilization, each reaction condition can be adjusted as needed
It is whole.
9. the method for each phase materials flow velocity otherness control can root in achievable paste state bed reactor provided by the invention
According to side wall note hydrogen holes, temperature control sensing device and density measure sensing device quantity split into two, three, four or
More reactors are to facilitate actual needs.
Description of the drawings
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution of the prior art
Embodiment or attached drawing needed to be used in the description of the prior art are briefly described, it should be apparent that, in describing below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, can also be obtained according to these attached drawings other attached drawings.
Fig. 1 is the structure of reactor schematic diagram of currently preferred upper differential control cracking and hydrogenation；
Attached drawing mark is as follows：1- conical bottom feed inlets, 2- temperature control sensing device, 3- density measure sensing devices, 4-
Side wall notes hydrogen holes, 5- housings, 6- top tapered discharge ports.
Specific embodiment
Technical scheme is clearly and completely described below in conjunction with attached drawing, it is clear that described implementation
Example is part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill
Personnel's all other embodiments obtained without making creative work, belong to the scope of protection of the invention.
Embodiment 1
The present embodiment provides a kind of reactors of upper differential control cracking and hydrogenation, as can be achieved in paste state bed reactor
Reactor used in the method for each phase materials flow velocity otherness control, as shown in Figure 1, the reactor includes the housing of closing
5；
Conical bottom feed inlet 1 is located at the bottom of the housing 5；
Conical discharge port 6 is located at the top of the housing 5；
Temperature controls sensing device 2 and density measure sensing device 3, is arranged in pairs in the side wall of the housing 5；
And side wall note hydrogen holes 4 and side wall note hydrogen holes 4, the side wall note hydrogen holes 4 are located at along two couple in cold hydrogen flow direction
On the side wall of housing between the temperature control sensing device 2 and density measure sensing device 3 that are arranged in pairs.
The reactor ratio of height to diameter is 15:1-3:1.
The operating pressure of the reactor is 13-25MPa.
The side wall note hydrogen holes is 3-5.
Storage control of the solid catalyst in reactor is in the 5-30% of total amount of liquid.
The total gas velocity of reactor is set to 0.02-0.2m/s.
The total gas velocity of reactor is set to 0.05-0.08m/s.
The operation temperature of the reactor is set to 250-500 DEG C, and the residence time is 15-90 minutes in reactor.
Embodiment 2.
The present embodiment provides the methods of each phase materials flow velocity otherness control in achievable paste state bed reactor, use implementation
Reactor described in example 1, the ratio of height to diameter of first reactor used in the present embodiment are 15:1, it is as follows：
(1) by granularity to obtain stalk particle after 1~50 μm of maize straw ash disposal, Mo oxides and Ni aoxidize load
(its grain size is 5 μm -50 μm to the unformed aluminium oxide of object, specific surface area 150m2/g；The bulk density of catalyst is 0.8；It urges
The average pore size of agent is 5nm) it is 5 in mass ratio with the stalk particle and sulphur：100：0.3 ratio is uniformly mixed so as to obtain mixed
It closes object and adds in into middle coalite tar the slurries for forming the 10wt% containing biomass；
(2) injected for the first time into the slurries 60 DEG C, the volume ratio of hydrogen to high pressure hydrogen and the slurries of 13MPa be
50：1, the slurries that then heat up are to 200 DEG C, then 200 DEG C, the hydrogen of 13MPa of second of injection, and this is controlled to inject twice thereto
Hydrogen and the volume ratios of slurries reach 800：1, to form reaction raw materials, obtains gas-liquid mixture and consolidates three-phase；
(3) gas-liquid mixture is consolidated after three-phase is warming up to 450 DEG C again and is sent into reactor, be 13MPa, instead in reaction pressure
Temperature is answered as hydrolysis, cracking and hydrogenation reaction occur under conditions of 500 DEG C, and by sidewall of reactor in this reaction process
3 inlets being set gradually along short transverse inject 105 DEG C of cold hydrogen, control total gas velocity in reactor as 0.02m/s
And storage of the catalyst in reactor is liquid, the 30wt% of solid phase quality in reactor, it, will be from reaction after 90min is reacted
The material of device discharge is sent into piece-rate system and carries out air-liquid, residue three phase separation, respectively obtains biomass gas, bio oil and residual
Slag；Hydrogen in system recycles, and enters step each note hydrogen point of (2) together with fresh hydrogen make-up.
Embodiment 3
The present embodiment provides the methods of each phase materials flow velocity otherness control in achievable paste state bed reactor, use implementation
Reactor described in example 1, the ratio of height to diameter of first reactor used in the present embodiment are 10:1, it is as follows：
(1) load there are into W oxides and Ni oxides by granularity to obtain reed particle after 20~1000 μm of reed ash disposal
Unformed aluminium oxide (its grain size be 100 μm -150 μm, specific surface area 200m2/g；The bulk density of catalyst is 0.7；It urges
The average pore size of agent is 30nm) with the reed particle and sulphur be in mass ratio iron oxide with reed particle and sulphur by matter
Amount is than being 2：3：100：0.4 ratio is uniformly mixed so as to obtain mixture, adds the mixture into vegetable oil and is formed containing biomass
The slurries of 30wt%；
(2) injected for the first time into the slurries 70 DEG C, the volume ratio of hydrogen to high pressure hydrogen and the slurries of 20MPa be
100：1, the slurries are then warming up to 250 DEG C, then 250 DEG C, the hydrogen of 20MPa of second of injection thereto in heat exchanger,
And the volume ratio of hydrogen that this injects twice and slurries is controlled to reach 900：1, to form reaction raw materials, obtains gas-liquid mixture and consolidates three-phase
State；
(3) gas-liquid mixture is consolidated after three-phase is warming up to 430 DEG C again and is sent into reactor, be 20MPa, instead in reaction pressure
Temperature is answered as hydrolysis, cracking and hydrogenation reaction occur under conditions of 450 DEG C, and by sidewall of reactor in this reaction process
4 inlets being set gradually along short transverse inject 120 DEG C of cold hydrogen, control total gas velocity in reactor as 0.06m/s
And storage of the catalyst in reactor is liquid, the 25wt% of solid phase quality in reactor, it, will be from reaction after 60min is reacted
The material of device discharge is sent into piece-rate system and carries out air-liquid, residue three phase separation, respectively obtains biomass gas, bio oil and residual
Slag；Hydrogen in system recycles, and enters step each note hydrogen point of (2) together with fresh hydrogen make-up.
Embodiment 4
The present embodiment provides the methods of each phase materials flow velocity otherness control in achievable paste state bed reactor, use implementation
Reactor described in example 1, the ratio of height to diameter of first reactor used in the present embodiment are 8:1, it is as follows：
(1) by granularity be after 1500~2000 μm of wheat stalk ash disposal stalk particle, by load have Pd oxides and
(its grain size is 50 μm -100 μm to the unformed aluminium oxide of Ni oxides, specific surface area 70m2/g；The bulk density of catalyst is
1.4；The average pore size of catalyst is 50nm) and the stalk particle and sulphur of iron oxide and step (1) be 2 in mass ratio：2：
100：0.3 ratio is uniformly mixed so as to obtain mixture, adds the mixture into low temperature animal oil and forms the 25wt%'s containing biomass
Slurries；
(2) injected for the first time into the slurries 100 DEG C, the volume ratio of hydrogen to high pressure hydrogen and the slurries of 20MPa be
150：1, the slurries are then warming up to 300 DEG C, then 300 DEG C, the hydrogen of 20MPa of second of injection thereto in heat exchanger,
And the volume ratio of hydrogen that this injects twice and slurries is controlled to reach 600：1, to form reaction raw materials, obtains gas-liquid mixture and consolidates three-phase
State；
(3) gas-liquid mixture is consolidated after three-phase is warming up to 440 DEG C again and is sent into paste state bed reactor, be in reaction pressure
Under conditions of being 450 DEG C hydrolysis, cracking and hydrogenation reaction occur for 20MPa, reaction temperature, and pass through reaction in this reaction process
4 inlets being set gradually along short transverse on device side wall inject 90 DEG C of cold hydrogen, control total gas velocity in reactor to be
The storage of 0.08m/s and catalyst in reactor is liquid, the 20wt% of solid phase quality in reactor, will after 40min is reacted
The material discharged from paste state bed reactor is sent into piece-rate system and carries out air-liquid, residue three phase separation, respectively obtains biogas
Body, bio oil and residue；Hydrogen in system recycles, and enters step each note of (2) together with fresh hydrogen make-up
Hydrogen point.
Embodiment 5
The present embodiment provides the methods of each phase materials flow velocity otherness control in achievable paste state bed reactor, use implementation
Reactor described in example 1, the ratio of height to diameter of first reactor used in the present embodiment are 5:1, it is as follows：
(1) load there are into Mo oxides and Co oxygen by granularity to obtain wood pellet after 4000~5000 μm of sawdust ash disposal
(its grain size is 150 μm -200 μm to the unformed aluminium oxide of compound, specific surface area 210m2/g；The bulk density of catalyst is
0.5；The average pore size of catalyst is 3nm) it is 3 in mass ratio with wood pellet and sulphur：100：0.2 ratio is uniformly mixed so as to obtain mixed
Object is closed, adds the mixture into low temperature animal oil and forms the slurries of the 40wt% containing biomass；
(2) injected for the first time into the slurries 130 DEG C, the volume ratio of hydrogen to high pressure hydrogen and the slurries of 27MPa be
200：1, the slurries are then warming up to 350 DEG C, then 300 DEG C, the hydrogen of 27MPa of second of injection thereto in heat exchanger,
And the volume ratio of hydrogen that this injects twice and slurries is controlled to reach 1000：1, to form reaction raw materials, obtains gas-liquid mixture and consolidates three-phase
State；
(3) gas-liquid mixture is consolidated after three-phase is warming up to 380 DEG C again and is sent into paste state bed reactor, be in reaction pressure
Under conditions of being 400 DEG C hydrolysis, cracking and hydrogenation reaction occur for 27MPa, reaction temperature, and pass through reaction in this reaction process
5 inlets being set gradually along short transverse on device side wall inject 115 DEG C of cold hydrogen, according to temperature control sensing device and
The solid content that density measure sensing device is measured between the two and note hydrogen holes is 5%, by reducing conical bottom into the air-flow of hydrogen
0.08m/s is measured, storage of the catalyst in reactor to be further promoted to the 30wt% of liquid phase quality in reactor, is treated
After reacting 50min, the material discharged from paste state bed reactor is sent into piece-rate system and carries out air-liquid, residue three phase separation, respectively
Obtain biomass gas, bio oil and residue；Hydrogen in system recycles, and is entered step together with fresh hydrogen make-up
(2) each note hydrogen point.
Embodiment 6
The present embodiment provides the methods of each phase materials flow velocity otherness control in achievable paste state bed reactor, use implementation
Reactor described in example 1, the ratio of height to diameter of first reactor used in the present embodiment are 3:1, it is as follows：
(1) by granularity to obtain leaf particle after 4000-5000 μm of leaf ash disposal, W oxides and Co aoxidize load
(its grain size is 250 μm -350 μm to the unformed aluminium oxide of object, specific surface area 80m2/g；The bulk density of catalyst is 0.9；
The average pore size of catalyst is 20nm) and the wood pellet and sulphur of iron oxide and step (1) be 1 in mass ratio：2：100：
0.25 ratio is uniformly mixed so as to obtain mixture, adds the mixture into microtherm oil and forms the slurry of the 20wt% containing biomass
Liquid；
(2) injected for the first time into the slurries 135 DEG C, the volume ratio of hydrogen to high pressure hydrogen and the slurries of 25MPa be
200：1, the slurries are then warming up to 350 DEG C, then 350 DEG C, the hydrogen of 25MPa of second of injection thereto in heat exchanger,
And the volume ratio of hydrogen that this injects twice and slurries is controlled to reach 650：1, to form reaction raw materials, obtains gas-liquid mixture and consolidates three-phase
State；
(3) gas-liquid mixture is consolidated after three-phase is warming up to 400 DEG C again and is sent into paste state bed reactor, be in reaction pressure
Under conditions of being 450 DEG C hydrolysis, cracking and hydrogenation reaction occur for 25MPa, reaction temperature, and pass through reaction in this reaction process
5 inlets being set gradually along short transverse on device side wall inject 100 DEG C of cold hydrogen, control total gas velocity in reactor to be
The storage of 0.1m/s and catalyst in reactor is the 25wt% of liquid phase quality in reactor, will be from slurry after 15min is reacted
The material of state bed reactor discharge is sent into piece-rate system and carries out air-liquid, residue three phase separation, respectively obtains biomass gas, life
Object oil and residue；Hydrogen in system recycles, and enters step each note hydrogen point of (2) together with fresh hydrogen make-up.
Embodiment 7
The present embodiment provides the methods of each phase materials flow velocity otherness control in achievable paste state bed reactor, use implementation
Reactor described in example 1, the ratio of height to diameter of first reactor used in the present embodiment are 14:1, it is as follows：
(1) will load have the unformed aluminium oxide of Mo oxides and Ni oxides (its grain size be 350 μm -500 μm, ratio
Surface area is 180m2/g；The bulk density of catalyst is 0.9；The average pore size of catalyst is 40nm) and iron oxide and gutter oil
And sulphur is 1 in mass ratio：1：100：0.1 ratio is uniformly mixed so as to obtain mixture, prepares the slurry of biomass (gutter oil) 50wt%
Liquid；
(2) injected for the first time into the slurries 90 DEG C, the volume ratio of hydrogen to high pressure hydrogen and the slurries of 20MPa be
150：1, the slurries are then warming up to 300 DEG C, then 300 DEG C, the hydrogen of 20MPa of second of injection thereto in heat exchanger,
And the volume ratio of hydrogen that this injects twice and slurries is controlled to reach 800：1, to form reaction raw materials, obtains gas-liquid mixture and consolidates three-phase
State；
(3) gas-liquid mixture is consolidated after three-phase is warming up to 430 DEG C again and is sent into reactor, be 20MPa, instead in reaction pressure
Temperature is answered as hydrolysis, cracking and hydrogenation reaction occur under conditions of 500 DEG C, and by sidewall of reactor in this reaction process
5 inlets being set gradually along short transverse inject 120 DEG C of cold hydrogen, control total gas velocity in reactor as 0.07m/s
And storage of the catalyst in reactor is the 30wt% of liquid phase quality in reactor, after 40min is reacted, will be arranged from reactor
The material gone out is sent into piece-rate system and carries out air-liquid, residue three phase separation, respectively obtains biomass gas, bio oil and residue；System
Hydrogen in system recycles, and enters step each note hydrogen point of (2) together with fresh hydrogen make-up.
Comparative example 1
The biomass liquefying process that this experimental example provides includes the following steps：
(1) it is 7wt% by being dried in reed feeding drying machine to water content, granularity is then crushed in pulverizer as 20
~200 μm, then reed particle is obtained after ash disposal；
(2) load there are into the unformed aluminium oxide of Mo oxides and Ni oxides (its grain size is 10 μm -150 μm) and oxygen
It is 1 in mass ratio to change the reed particle of iron and step (1) and sulphur：2：100：0.2 ratio is uniformly mixed so as to obtain mixture, this is mixed
It closes object and adds in into microtherm oil the slurries for forming the 30wt% containing biomass；
(3) injected for the first time into the slurries 70 DEG C, the volume ratio of hydrogen to high pressure hydrogen and the slurries of 18MPa be
100：1, the slurries are then warming up to 250 DEG C, then 230 DEG C, the hydrogen of 18MPa of second of injection thereto in heat exchanger,
And the volume ratio of hydrogen that this injects twice and slurries is controlled to reach 900：1 to form reaction raw materials, then by the reaction raw materials liter
Into feeding paste state bed reactor after 430 DEG C under conditions of reaction pressure is 18MPa, reaction temperature is 440 DEG C water occurs for temperature
Solution, cracking and hydrogenation reaction, and pass through 4 notes set gradually along short transverse in sidewall of reactor in this reaction process
Entrance injects 95 DEG C of cold hydrogen, controls that total gas velocity in reactor is 0.06m/s and storage of the catalyst in reactor is anti-
Answer the 30wt% of liquid phase quality in device, after 60min is reacted, by the material discharged from paste state bed reactor be sent into piece-rate system into
Row air-liquid, residue three phase separation, respectively obtain biomass gas, bio oil and residue；Hydrogen in system recycles, with
Fresh hydrogen make-up enters step each note hydrogen point of (3) together.
Comparative example 2
The liquefaction process for the biomass that this experimental example provides includes the following steps：
1) it is 5wt% by being dried in reed feeding drying machine to water content, granularity is then crushed in pulverizer as 20
~1000 μm, then reed particle is obtained after ash disposal；
(2) load there are into the unformed aluminium oxide of Mo oxides and Co oxides (its grain size is 10 μm -150 μm) and oxygen
It is 1 in mass ratio to change the reed particle of iron and step (1) and sulphur：1：100：0.2 ratio is uniformly mixed so as to obtain mixture, this is mixed
It closes object and adds in into microtherm oil the slurries for forming the 30wt% containing biomass；
(3) injected for the first time into the slurries 70 DEG C, the volume ratio of hydrogen to high pressure hydrogen and the slurries of 18MPa be
100：1, the slurries are then warming up to 250 DEG C, then 250 DEG C, the hydrogen of 18MPa of second of injection thereto in heat exchanger,
And the volume ratio of hydrogen that this injects twice and slurries is controlled to reach 900：1 to form reaction raw materials, then by the reaction raw materials liter
Into feeding paste state bed reactor after 380 DEG C under conditions of reaction pressure is 18MPa, reaction temperature is 400 DEG C water occurs for temperature
Solution, cracking and hydrogenation reaction, and pass through 4 notes set gradually along short transverse in sidewall of reactor in this reaction process
Entrance injects 90 DEG C of cold hydrogen, controls that total gas velocity in reactor is 0.06m/s and storage of the catalyst in reactor is anti-
Answer the 30wt% of liquid phase quality in device, after 60min is reacted, by the material discharged from paste state bed reactor be sent into piece-rate system into
Row air-liquid, residue three phase separation, respectively obtain biomass gas, bio oil and residue；Hydrogen in system recycles, with
Fresh hydrogen make-up enters step each note hydrogen point of (3) together.
Comparative example 3
This comparative example is hanged according to a kind of double solid phases for hydrocracking heavy oil of Chinese patent literature CN105727845A
Embodiment disclosure of that in floating bed reactor and its application is carried out biomass liquefying and (is implemented using raw material and the present invention
Example 3 is identical).
Experimental example
The effect for providing the above embodiment of the present invention 2~7 and comparative example 1~3 technique is evaluated, as a result respectively such as
Shown in table 1.
Obviously, the above embodiments are merely examples for clarifying the description, and is not intended to limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And the obvious variation thus extended out or
Among changing still in the protection domain of the invention.
Claims (11)
1. a kind of method of each phase materials flow velocity otherness control in achievable paste state bed reactor, which is characterized in that by
Temperature control sensing device and density measure sensing device are arranged in pairs on the side wall of paste state bed reactor and along cold hydrogen stream
Between temperature control sensing device and density measure sensing device that upward two couple is arranged in pairs side wall is set to note hydrogen holes,
It is controlled so as to fulfill each phase materials flow velocity otherness.
2. according to the method described in claim 1, it is characterized in that, side wall note hydrogen holes is 3-5.
3. according to the method described in claim 2, it is characterized in that, the ratio of height to diameter of the reactor is 15:1-3:1；It is described anti-
The operating pressure for answering device is 13-25MPa.
4. according to the method described in claim 3, it is characterized in that, the specific surface area of the catalyst is 70~300m2/g；It urges
The bulk density of agent is 0.4~1.5；The average pore size of catalyst is 1~100nm.
5. according to the method described in claim 4, it is characterized in that, storage of the solid catalyst in reactor is controlled in liquid
The 5-30% of gross mass.
6. according to the method described in claim 5, it is characterized in that, the total gas velocity of the reactor is set to 0.02-0.2m/s.
7. according to the method described in claim 6, it is characterized in that, the operation temperature of the reactor is set to 250-500 DEG C, instead
It is 15-90 minutes to answer the residence time in device.
It is respectively first reactor and the 8. the method according to the description of claim 7 is characterized in that the reactor is 2
Two reactors.
9. according to the method described in claim 8, it is characterized in that, the paste state bed reactor further includes the housing of closing；
Conical bottom feed inlet is located at the bottom of the housing；
Conical discharge port is located at the top of the housing.
10. it according to the method described in claim 9, it is characterized in that, is as follows：
(1) make hydrogen, reaction liquid, biomass solid particle, the gas-liquid mixture of catalyst granules consolidate three-phase from conical bottom into
Material mouth is fed；
(2) temperature control sensing device set above or below hydrogen holes and density measure sensing device are noted according to the side wall
Both judge the solid content between note hydrogen holes, so as to adjust hydrogen enter the flow of reactor and sidewall of reactor injection
The amount of cold hydrogen；(3) biomass bottom in the reactor hydrolyze from bottom to top, cracking, hydrogenation, heavy biomass and solid
Body particle rises with gas and light-end products, and bottom is returned under the action of the cold hydrogen on top, participates in reaction, reaction knot again
The inside of unconverted biomass and solid catalyst Xun Huan and balance discharge after beam.
11. according to the method described in claim 10, it is characterized in that, when temperature control sensing device and density measure pass
After induction device measures catalyst and biomass concentration, by the hydrogen flowing quantity and sidewall of reactor that change reactor bottom
The amount of cold hydrogen is respectively injected, the concentration of catalyst is controlled to realize as 5~30%.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4982027A (en) * | 1986-01-24 | 1991-01-01 | Rheinische Braunkohlenwerke Ag | Process for the reprocessing of carbon containing wastes |
| US20080072478A1 (en) * | 2006-09-22 | 2008-03-27 | Barry Cooper | Liquefaction Process |
| CN101353583A (en) * | 2008-09-19 | 2009-01-28 | 肖进彬 | Biomass processing method |
| US20090082606A1 (en) * | 2007-09-20 | 2009-03-26 | Marker Terry L | Production of Diesel Fuel from Biorenewable Feedstocks |
| CN102051194A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Method for preparing liquid fuel from biomass through hydrogen-donor solvent |
| CN102127462A (en) * | 2010-01-12 | 2011-07-20 | Ifp新能源公司 | Direct biomass hydroliquefaction process comprising two ebullated bed hydroconversion steps |
| 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 |
| CN104194949A (en) * | 2014-08-01 | 2014-12-10 | 四川省阳明能源科技有限公司 | Preparation method of bio-diesel |
| CN104560093A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing fuel oil from biomass |
-
2016
- 2016-11-21 CN CN201611041474.6A patent/CN108079909B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4982027A (en) * | 1986-01-24 | 1991-01-01 | Rheinische Braunkohlenwerke Ag | Process for the reprocessing of carbon containing wastes |
| US20080072478A1 (en) * | 2006-09-22 | 2008-03-27 | Barry Cooper | Liquefaction Process |
| US20090082606A1 (en) * | 2007-09-20 | 2009-03-26 | Marker Terry L | Production of Diesel Fuel from Biorenewable Feedstocks |
| CN101353583A (en) * | 2008-09-19 | 2009-01-28 | 肖进彬 | Biomass processing method |
| CN102051194A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Method for preparing liquid fuel from biomass through hydrogen-donor solvent |
| CN102127462A (en) * | 2010-01-12 | 2011-07-20 | Ifp新能源公司 | Direct biomass hydroliquefaction process comprising two ebullated bed hydroconversion steps |
| CN104560093A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing fuel oil from biomass |
| 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 |
| CN104194949A (en) * | 2014-08-01 | 2014-12-10 | 四川省阳明能源科技有限公司 | Preparation method of bio-diesel |
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