CN102786986A - Refining technology of microalgae pyrolysis oil - Google Patents
Refining technology of microalgae pyrolysis oil Download PDFInfo
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- CN102786986A CN102786986A CN2012103082555A CN201210308255A CN102786986A CN 102786986 A CN102786986 A CN 102786986A CN 2012103082555 A CN2012103082555 A CN 2012103082555A CN 201210308255 A CN201210308255 A CN 201210308255A CN 102786986 A CN102786986 A CN 102786986A
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- 238000007670 refining Methods 0.000 title claims abstract description 23
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- 238000000034 method Methods 0.000 claims abstract description 51
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- 238000007233 catalytic pyrolysis Methods 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 14
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 229910017709 Ni Co Inorganic materials 0.000 claims abstract description 7
- 229910003267 Ni-Co Inorganic materials 0.000 claims abstract description 7
- 229910003262 Ni‐Co Inorganic materials 0.000 claims abstract description 7
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- 238000009835 boiling Methods 0.000 claims abstract description 6
- 239000012159 carrier gas Substances 0.000 claims abstract description 6
- 239000007791 liquid phase Substances 0.000 claims abstract description 6
- 230000008878 coupling Effects 0.000 claims abstract description 4
- 238000010168 coupling process Methods 0.000 claims abstract description 4
- 238000005859 coupling reaction Methods 0.000 claims abstract description 4
- 239000012075 bio-oil Substances 0.000 claims description 56
- 239000003921 oil Substances 0.000 claims description 56
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- 238000004904 shortening Methods 0.000 claims description 44
- 241000195493 Cryptophyta Species 0.000 claims description 35
- 239000002826 coolant Substances 0.000 claims description 16
- 238000004227 thermal cracking Methods 0.000 claims description 15
- 238000005336 cracking Methods 0.000 claims description 14
- 238000009827 uniform distribution Methods 0.000 claims description 10
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- 238000006555 catalytic reaction Methods 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 8
- 230000004941 influx Effects 0.000 claims description 8
- 238000003860 storage Methods 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- 241000206751 Chrysophyceae Species 0.000 claims description 6
- 241000192710 Microcystis aeruginosa Species 0.000 claims description 6
- 239000012071 phase Substances 0.000 claims description 6
- 230000008929 regeneration Effects 0.000 claims description 6
- 238000011069 regeneration method Methods 0.000 claims description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 5
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- 230000003197 catalytic effect Effects 0.000 claims description 5
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- 238000012423 maintenance Methods 0.000 claims description 5
- 238000010926 purge Methods 0.000 claims description 5
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- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 abstract description 2
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Abstract
The invention relates to a refining technology of microalgae pyrolysis oil. The refining technology comprises the steps of: carrying out fast catalytic pyrolysis on microalgae, coupling dehydration and operation of a catalytic hydrogenation refining unit, and mixing the microalgae with a catalyst MCM-41; taking N2 as carrier gas for feeding at 400-600 DEG C; carrying out fast pyrolysis to obtain crude liquid biological oil; condensing the clued liquid biological oil, carrying out centrifugal separation on a liquid phase, and obtaining pre-removed water biological oil after removing more than 80% of moisture and a few of low-boiling point components; carrying out catalytic hydrogenation on the pre-removed water biological oil for 10-90 minutes under the pressure of 1.5-10MPa at 150-350 DEG C to obtain hydrogenated biological oil; adding proper amount of anhydrous magnesium sulfate into the hydrogenated biological oil to remove water; and adding triethanolamine to adjust acid until the pH (Potential Of Hydrogen) is 6.5-7.0, and decompressing and filtering to remove solids so as to obtain refined biological oil. The technology disclosed by the invention is continuous in process, efficient and environment-friendly; the hydrogenation catalyst adopts Ni-Co/gamma-Al2O3 modified by Pd, and is recycled after being regenerated; the service life is long; the moisture content, the acid value, the viscosity, the heat value and the cetane number of the refined biological oil can reach fuel standard of direct utilization; and nitrogen and sulphur of which the contents are high in the oil produc are removed at the same time in a hydrodeoxygenation process.
Description
Technical field:
The present invention relates to a kind of process for refining of little algae thermal cracking oil, belong to biomass energy trans-utilization technical field.
Background technology:
The raising of exhausted day by day and people's environmental consciousness of petroleum resources has promoted countries in the world development and use biofuel to substitute the process of fossil oil greatly.Biofuel is as a kind of renewable energy source, and environmental pollution is little, can reduce the dependence to oil to its development research simultaneously, has sustainability, thereby receives the very big concern of various countries.
Bio-oil is that the mode through rapid heating makes the high molecular polymer of forming biomass be cracked into low molecular organic steam, and the method that adopts quenching condenses into it, and liquid obtains.Because this process does not reach thermodynamic(al)equilibrium, so the physicochemical property of bio oil are unstable usually.The oil product oxygen level of upgrading is high, causes its poor stability, calorific value is low, viscosity is big, and especially acid oxygenatedchemicals also can cause corrosion on Equipment, has influenced its widespread use to a certain extent, and therefore, the refining of bio oil is a problem demanding prompt solution.
In numerous biomass; Little algae has the photosynthetic efficiency height, living weight is big, growth cycle is short, adaptive capacity to environment is strong, be prone to cultivate, lipid content is high, efficient characteristics such as stabilizing carbon dioxide in the process of growth, is the good material for preparing biomass liquid fuel.Utilize little algae prepare liquid fuel all having very important significance aspect environmental protection and the power supply, Commercial Prospect is good.
Existing in the prior art several different methods is made with extra care to improve its quality bio-oil; Satisfy bio-oil act as a fuel oil request for utilization; The core of bio-oil purification techniques is the oxygen of removing wherein; Improve the H/C ratio, make it that sufficiently high combustion heat value arranged, and have suitable viscosity and pH value.
In the prior art, bio oil purified main method can reduce three types: shortening, catalytic pyrolysis and catalytic esterification.The refining biological oil calorific value that catalytic pyrolysis obtains is low, is difficult to reach the request for utilization as biofuel; Catalytic esterification requires bio oil (thick oil) to contain more alcoholic extract hydroxyl group or carboxyl, and the content of moisture is very big to the esterification yield influence in the bio oil (thick oil), and thoroughly dewatering is difficult to control; Shortening is a kind of purification techniques that application prospect is arranged.Yet in the prior art, shortening all carries out under high-temperature and high-pressure conditions, and is intermittent operation; In addition, biological water content in oil and tart are removed, and lack maturation in the prior art and process method efficiently.
Given this, set up a cover energy-conservation, continuously, bio oil process for refining efficiently, be the technical problem that the present invention solves.
Summary of the invention:
The objective of the invention is to overcome the shortcoming of prior art, the process for purification of a kind of little algae thermal cracking oil (thick oil) is provided, set up energy-conservation, continuous, efficient, the perfect bio oil process for refining of a cover.
In order to realize the foregoing invention purpose, the process for refining of a kind of little algae thermal cracking oil of the present invention, dewaters and the coupling of catalytic hydrofinishing unit operation is carried out at its little algae quick catalysis thermo-cracking, operates according to following steps:
The first step, little algae quick catalysis thermo-cracking: little algae is mixed with catalyzer MCM-41, under 400 ℃ ~ 600 ℃, with N
2Be the carrier gas charging, carry out fast pyrolysis and obtain the liquid crude bio oil;
In second step, oily water separation: the liquid crude bio oil that thermo-cracking is obtained is after condensation, and liquid phase is carried out spinning, 80% above moisture and a small amount of low boiling component are removed after, bio oil in advance must dewater;
In the 3rd step, shortening: hydrogenation catalyst is Ni-Co/ γ-Al
2O
3Or Ni-Co-Pd/ γ-Al
2O
3, consumption is the 3wt% ~ 40wt% of the bio oil weight that dewaters in advance, serves as to calculate benchmark with the catalytic hydrogenation catalyst gross weight; The content of Pd is 0.2wt% ~ 3wt%; With second the step gained the bio oil that dewaters in advance in 150 ℃ ~ 350 ℃, catalytic hydrogenation is 10 ~ 90 minutes under 1.5 ~ 10MPa pressure, the hydrogenation bio oil;
The 4th step; The hydrogenation bio oil dewaters and acid adjustment: by anhydrous magnesium sulfate: the hydrogenation bio oil is that the mass ratio of 1:3 ~ 1:8 adds anhydrous magnesium sulfate and dewaters; And to add the trolamine acid adjustment be 6.5 ~ 7.0 to pH, and decompress filter is removed solid and made refining biological oil.
The described little algae of technology of the present invention is chlorella, chrysophyceae or Microcystis aeruginosa.
The technical process of little algae catalytic pyrolysis is in the said the first step of technology of the present invention: nitrogen is written into the catalytic pyrolysis fluidized-bed reactor with the mixture of little algae and catalyzer MCM-41 by inlet; Cracked gas product is through condenser condenses, and non-condensable gases exports emptying through tail gas; Solid residue is discharged by discharge valve.
Preparatory dewatering process flow process was during technology of the present invention said second went on foot: the fast pyrolysis product liquid by condenser condenses obtains, carry out oily water separation through whizzer, and water-phase product is discharged by the water tap valve, and oil-phase product gets into storage tank.
The shortening of technology of the present invention in said the 3rd step carries out in pyrolysis oil shortening device, and this device comprises that main liquid flow inlet, auxiliary liq influx, gas inlet, gas distribution grid, shortening fluidized-bed reactor, separator, pneumatic outlet, liquid oil outlet, catalyzer add inlet, exhanst gas outlet, cyclonic separator, catalyst regenerator, catalyst cooler, coolant entrance, gas inlet, coolant outlet, pneumavalve, vacuum breaker, liquid distributing board.
Its catalytic hydrogenation process flow process is: hydrogenation catalyst is added inlet from catalyzer add, feed nitrogen purging gas circuit, the resistance to air loss of inspection units by the gas inlet; Feed hydrogen to the shortening fluidized-bed reactor, and make the gas uniform distribution through gas distribution grid, the maintenance hydrogen flowing quantity is 30ml/min ~ 90ml/min, and the pressure in the shortening fluidized-bed reactor is 1.5MPa ~ 10.0MPa, is heated to 150 ℃ ~ 350 ℃; Little algae thermal cracking oil that will obtain by catalytic pyrolysis fluidized-bed reactor in little algae catalytic pyrolysis technology; Being dewatered in advance to the injection of shortening fluidized-bed reactor from the main liquid flow inlet of pyrolysis oil shortening device and auxiliary liq influx respectively through fresh feed pump and preheater by the storage tank in the preparatory dewatering process, (water cut is 5%wt% ~ 20wt%) to bio oil; Keep the pyrolysis oil uniform distribution through liquid distributing board, keeping oily inlet amount simultaneously is 0.5～10.0ml/min; The hydrogenation after product is through separator separates, and tail gas is through the pneumatic outlet emptying, and liquid is discharged from the liquid oil outlet, and solid gets into catalyst regenerator and regenerates; In the catalyst regeneration process, air gets into catalyst regenerator by gas inlet, and in the catalyst cooler, refrigerant is got into by coolant entrance, is discharged by coolant outlet; Regenerated catalyst is after cyclonic separator separates, and part is returned the shortening fluidized-bed reactor through pneumavalve through vacuum breaker, and part is discharged, and constantly adds inlet from catalyzer again simultaneously and adds live catalyst; Regenerated flue gas is discharged by exhanst gas outlet.
The present invention compared with prior art, the major advantage that has is: 1, little algae quick catalysis thermo-cracking, dewater and catalytic hydrofinishing unit operation coupling is carried out, technological process is continuous, and is efficient, environmental protection; 2, hydrogenation catalyst adopts through the Ni-Co/ of Pd modification γ-Al
2O
3, recycle long service life after the regeneration; 3, the water cut of refining biological oil, acid number, viscosity, calorific value and cetane value all can reach the standard of fuel of direct utilization; 4, in the hydrogenation deoxidation process, removed higher nitrogen and the sulphur of content in the oil product simultaneously.
Description of drawings:
Fig. 1 is little algae catalytic pyrolysis and dewatering process synoptic diagram.
Fig. 2 is little algae pyrolysis oil shortening setting drawing.
Embodiment:
Below in conjunction with specific embodiment and accompanying drawing technology of the present invention is further elaborated.
Embodiment 1,
The first step, little algae quick catalysis thermo-cracking: chlorella is mixed by mass ratio 2:1 ~ 5:1 with catalyzer MCM-41, at 550 ℃, with N
2Be the carrier gas charging, carry out thermo-cracking and obtain the liquid crude bio oil.Originally operate in the catalytic pyrolysis fluidized-bed reactor and carry out; Technical process is as shown in Figure 1: nitrogen is written into catalytic pyrolysis fluidized-bed reactor 3 with the mixture of little algae and catalyzer MCM-41 by inlet 2; Cracked gas product is through condensing surface 5 condensations, and non-condensable gases exports 4 emptyings through tail gas; Solid residue is discharged by discharge valve 1.
The basic physical properties of chlorella pyrolysis oil is analyzed as shown in table 1:
The Physical Property Analysis of table 1 chlorella pyrolysis oil
Second the step, oily water separation: the liquid crude bio oil that the chlorella thermo-cracking obtains is after condensation, and liquid phase is carried out spinning, 80% above moisture and a small amount of low boiling component are removed after, make the bio oil that dewaters in advance.Technical process is as shown in Figure 1: the fast pyrolysis product liquid by condensing surface 5 condensations obtain, carry out oily water separation through whizzer 6, and water-phase product is discharged by water tap valve 7, and oil-phase product gets into storage tank 8.
In the 3rd step, shortening: in 150 ℃ ~ 350 ℃, catalytic hydrogenation is 10 ~ 90 minutes under 1.5 ~ 10MPa pressure with second bio oil that dewaters in advance that make of step, the hydrogenation bio oil, hydrogenation catalyst is Ni-Co/ γ-Al
2O
3Or Ni-Co-Pd/ γ-Al
2O
3, consumption is the 3wt% ~ 40wt% of the bio oil weight that dewaters in advance, serves as to calculate benchmark with the catalytic hydrogenation catalyst gross weight, the content of Pd is 0.2wt% ~ 3wt%.
Shortening carries out in pyrolysis oil shortening device; This device is as shown in Figure 2, comprises that main liquid flow inlet 11, auxiliary liq influx 12, gas inlet 13, gas distribution grid 14, shortening fluidized-bed reactor 15, separator 16, pneumatic outlet 17, liquid oil outlet 18, catalyzer add inlet 19, exhanst gas outlet 20, cyclonic separator 21, catalyst regenerator 22, catalyst cooler 23, coolant entrance 24, gas inlet 25, coolant outlet 26, pneumavalve 27, vacuum breaker 28, liquid distributing board 29.
Its technical process is: hydrogenation catalyst is added inlet 19 from catalyzer add, feed nitrogen purging gas circuit, the resistance to air loss of inspection units by gas inlet 13; Feed hydrogen to shortening fluidized-bed reactor 15; And make the gas uniform distribution through gas distribution grid 14; The maintenance hydrogen flowing quantity is 30ml/min ~ 90ml/min, and the pressure in the shortening fluidized-bed reactor 15 is 1.5MPa ~ 10.0MPa, is heated to 150 ℃ ~ 350 ℃; The chlorella thermal cracking oil that will obtain by catalytic pyrolysis fluidized-bed reactor 3 among Fig. 1; By storage tank among Fig. 18 through fresh feed pump 9 and preheater 10 respectively from Fig. 2 main liquid flow inlet 11 and auxiliary liq influx 12 inject the bio oil that dewaters in advance to shortening fluidized-bed reactor 15 (water cut be 5%wt% ~ 20wt%); Keep the pyrolysis oil uniform distribution through liquid distributing board 29, keeping oily inlet amount simultaneously is 0.5 ~ 10.0ml/min; The hydrogenation after product separates through separator 16, and tail gas is through pneumatic outlet 17 emptyings, and liquid is discharged from liquid oil outlet 18, and solid gets into catalyst regenerator 22 and regenerates; In the catalyst regeneration process, air gets into catalyst converter revivifier 22 by gas inlet 25, and in the catalyst cooler 23, refrigerant is got into by coolant entrance 24, is discharged by coolant outlet 26; Regenerated catalyst is after cyclonic separator 21 separates, and part is returned shortening fluidized-bed reactor 15 through pneumavalve 27 through vacuum breaker 28, and part is discharged, and constantly adds inlet 19 from catalyzer again simultaneously and adds live catalyst; Regenerated flue gas is discharged by exhanst gas outlet 20.
The 4th step; Dewater and acid adjustment: is that 7:1 adding anhydrous magnesium sulfate dewaters with the 3rd hydrogenation bio oil that obtain of step by the mass ratio of bio oil and anhydrous magnesium sulfate; The trolamine acid adjustment that adds a certain amount of (volume ratio is 10:1) is 6.5 ~ 7.0 to pH, and decompress filter is removed solid and made refining biological oil.
It is as shown in table 2 that each stage of present embodiment obtains the oily physical properties of liquid bio:
The physical properties of each stage oil of table 2 chlorella
Embodiment 2,
The first step, little algae quick catalysis thermo-cracking: chrysophyceae is mixed by mass ratio 2:1 ~ 5:1 with catalyzer MCM-41, with N
2Be the carrier gas charging, carry out fast pyrolysis, obtain the liquid crude bio oil.Originally operate in the catalytic pyrolysis fluidized-bed reactor and carry out, technical process is with embodiment 1.
Second the step, oily water separation: the liquid crude bio oil that the chrysophyceae thermo-cracking obtains is after condensation, and liquid phase is carried out spinning, 80% above moisture and a small amount of low boiling component are removed after, make the bio oil that dewaters in advance, technical process is with embodiment 1.
In the 3rd step, shortening: in 150 ℃ ~ 350 ℃, catalytic hydrogenation is 10 ~ 90 minutes under 1.5 ~ 10MPa pressure with second bio oil that dewaters in advance that make of step, the hydrogenation bio oil, hydrogenation catalyst is Ni-Co/ γ-Al
2O
3Or Ni-Co-Pd/ γ-Al
2O
3, consumption is the 3wt% ~ 40wt% of the bio oil weight that dewaters in advance, serves as to calculate benchmark with the catalytic hydrogenation catalyst gross weight, the content of Pd is 0.2wt% ~ 3wt%.
Shortening carries out in pyrolysis oil shortening device, and is as shown in Figure 2, and its technical process is: hydrogenation catalyst is added inlet 19 from catalyzer add, feed nitrogen purging gas circuit, the resistance to air loss of inspection units by gas inlet 13; Feed hydrogen to shortening fluidized-bed reactor 15; And make the gas uniform distribution through gas distribution grid 14; The maintenance hydrogen flowing quantity is 30ml/min ~ 90ml/min, and the pressure in the shortening fluidized-bed reactor 15 is 1.5MPa ~ 10.0MPa, is heated to 150 ℃～350 ℃; The chrysophyceae thermal cracking oil that will obtain by catalytic pyrolysis fluidized-bed reactor 3 among Fig. 1; By storage tank among Fig. 18 through fresh feed pump 9 and preheater 10 respectively from Fig. 2 main liquid flow inlet 11 and auxiliary liq influx 12 inject the bio oil that dewaters in advance to shortening fluidized-bed reactor 15 (water cut be 5%wt% ~ 20wt%); Keep the pyrolysis oil uniform distribution through liquid distributing board 29, keeping oily inlet amount simultaneously is 0.5 ~ 10.0ml/min; The hydrogenation after product separates through separator 16, and tail gas is through pneumatic outlet 17 emptyings, and liquid is discharged from liquid oil outlet 18, and solid gets into catalyst regenerator 22 and regenerates; In the catalyst regeneration process, air gets into catalyst regenerator 22 by gas inlet 25, and in the catalyst cooler 23, refrigerant is got into by coolant entrance 24, is discharged by coolant outlet 26; Regenerated catalyst is after cyclonic separator 21 separates, and part is returned shortening fluidized-bed reactor 15 through pneumavalve 27 through vacuum breaker 28, and part is discharged, and constantly adds inlet 19 from catalyzer again simultaneously and adds live catalyst; Regenerated flue gas is discharged by exhanst gas outlet 20.
The 4th step; Dewater and acid adjustment: is that 7:1 adding anhydrous magnesium sulfate dewaters with the 3rd hydrogenation bio oil that obtain of step by the mass ratio of bio oil and anhydrous magnesium sulfate; The trolamine acid adjustment that adds a certain amount of (volume ratio is 10:1) is 6.5 ~ 7.0 to pH, and decompress filter is removed solid and made refining biological oil.
It is as shown in table 3 that each stage of present embodiment obtains the oily physical properties of liquid bio:
The physical properties of each stage oil of table 3 chrysophyceae
Embodiment 3,
The first step, little algae quick catalysis thermo-cracking: Microcystis aeruginosa is mixed by mass ratio 2:1 ~ 5:1 with catalyzer MCM-41, with N
2Be the carrier gas charging, carry out fast pyrolysis, obtain the liquid crude bio oil.Originally operate in the catalytic pyrolysis fluidized-bed reactor and carry out, technical process is with embodiment 1.
Second the step, oily water separation: the liquid crude bio oil that the Microcystis aeruginosa thermo-cracking obtains is after condensation, and liquid phase is carried out spinning, 80% above moisture and a small amount of low boiling component are removed after, make the bio oil that dewaters in advance, technical process is with embodiment 1.
In the 3rd step, shortening: in 150 ℃ ~ 350 ℃, catalytic hydrogenation is 10 ~ 90 minutes under 1.5 ~ 10MPa pressure with second bio oil that dewaters in advance that make of step, the hydrogenation bio oil, hydrogenation catalyst is Ni-Co/ γ-Al
2O
3Or Ni-Co-Pd/ γ-Al
2O
3, consumption is the 3wt% ~ 40wt% of the bio oil weight that dewaters in advance, serves as to calculate benchmark with the catalytic hydrogenation catalyst gross weight, the content of Pd is 0.2wt% ~ 3wt%.
Shortening carries out in pyrolysis oil shortening device, and is as shown in Figure 2, and its technical process is: hydrogenation catalyst is added inlet 19 from catalyzer add, feed nitrogen purging gas circuit, the resistance to air loss of inspection units by gas inlet 13; Feed hydrogen to shortening fluidized-bed reactor 15; And make the gas uniform distribution through gas distribution grid 14; The maintenance hydrogen flowing quantity is 30ml/min ~ 90ml/min, and the pressure in the shortening fluidized-bed reactor 15 is 1.5MPa ~ 10.0MPa, is heated to 150 ℃ ~ 350 ℃; The Microcystis aeruginosa thermal cracking oil that will obtain by catalytic pyrolysis fluidized-bed reactor 3 among Fig. 1; By storage tank among Fig. 18 through fresh feed pump 9 and preheater 10 respectively from Fig. 2 main liquid flow inlet 11 and auxiliary liq influx 12 inject the bio oil that dewaters in advance to shortening fluidized-bed reactor 15 (water cut be 5%wt% ~ 20wt%); Keep the pyrolysis oil uniform distribution through liquid distributing board 29, keeping oily inlet amount simultaneously is 0.5 ~ 10.0ml/min; The hydrogenation after product separates through separator 16, and tail gas is through pneumatic outlet 17 emptyings, and liquid is discharged from liquid oil outlet 18, and solid gets into catalyst regenerator 22 and regenerates; In the catalyst regeneration process, air gets into catalyst converter revivifier 22 by inlet 25, and in the catalyst cooler 23, refrigerant is got into by coolant entrance 24, is discharged by coolant outlet 26; Regenerated catalyst is after cyclonic separator 21 separates, and part is returned shortening fluidized-bed reactor 15 through pneumavalve 27 through vacuum breaker 28, and part is discharged, and constantly adds inlet 19 from catalyzer again simultaneously and adds live catalyst; Regenerated flue gas is discharged by exhanst gas outlet 20.
The 4th step; Dewater and acid adjustment: is that 7:1 adding anhydrous magnesium sulfate dewaters with the 3rd hydrogenation bio oil that obtain of step by the mass ratio of bio oil and anhydrous magnesium sulfate; The trolamine acid adjustment that adds a certain amount of (volume ratio is 10:1) is 6.5 ~ 7.0 to pH, and decompress filter is removed solid and made refining biological oil.
It is as shown in table 4 that each stage of present embodiment obtains the oily physical properties of liquid bio:
The physical properties of each stage oil of table 4 Microcystis aeruginosa
Claims (6)
1. the process for refining of a little algae thermal cracking oil; It is characterized in that little algae quick catalysis thermo-cracking, dewater and catalytic hydrofinishing unit operation coupling is carried out; Operate according to following steps: the first step; Little algae quick catalysis thermo-cracking: little algae is mixed with catalyzer MCM-41, under 400 ℃ ~ 600 ℃, with N
2Be the carrier gas charging, carry out fast pyrolysis and obtain the liquid crude bio oil; In second step, oily water separation: the liquid crude bio oil that thermo-cracking is obtained is after condensation, and liquid phase is carried out spinning, 80% above moisture and a small amount of low boiling component are removed after, bio oil in advance must dewater; In the 3rd step, shortening: hydrogenation catalyst is Ni-Co/ γ-Al
2O
3Or Ni-Co-Pd/ γ-Al
2O
3, consumption is the 3wt% ~ 40wt% of the bio oil weight that dewaters in advance, serves as to calculate benchmark with the catalytic hydrogenation catalyst gross weight; The content of Pd is 0.2wt% ~ 3wt%; With second the step gained the bio oil that dewaters in advance in 150 ℃ ~ 350 ℃, catalytic hydrogenation is 10 ~ 90 minutes under 1.5 ~ 10MPa pressure, the hydrogenation bio oil; The 4th step; The hydrogenation bio oil dewaters and acid adjustment: by anhydrous magnesium sulfate: the hydrogenation bio oil is that the mass ratio of 1:3 ~ 1:8 adds anhydrous magnesium sulfate and dewaters; And to add the trolamine acid adjustment be 6.5 ~ 7.0 to pH, and decompress filter is removed solid and made refining biological oil.
2. the process for refining of a kind of little algae thermal cracking oil according to claim 1 is characterized in that described little algae is chlorella, chrysophyceae or Microcystis aeruginosa.
3. the process for refining of a kind of little algae thermal cracking oil according to claim 1; It is characterized in that the technical process of little algae catalytic pyrolysis is in the said the first step: nitrogen is written into the catalytic pyrolysis fluidized-bed reactor with the mixture of little algae and catalyzer MCM-41 by inlet; Cracked gas product is through condenser condenses, and non-condensable gases exports emptying through tail gas; Solid residue is discharged by discharge valve.
4. the process for refining of a kind of little algae thermal cracking oil according to claim 1; It is characterized in that in said second step that in advance the dewatering process flow process is: the fast pyrolysis product liquid that obtains by condenser condenses; Carry out oily water separation through whizzer; Water-phase product is discharged by the water tap valve, and oil-phase product gets into storage tank.
5. the process for refining of a kind of little algae thermal cracking oil according to claim 1; It is characterized in that the shortening in said the 3rd step carries out in pyrolysis oil shortening device, this device comprises that main liquid flow inlet, auxiliary liq influx, gas inlet, gas distribution grid, shortening fluidized-bed reactor, separator, pneumatic outlet, liquid oil outlet, catalyzer add inlet, exhanst gas outlet, cyclonic separator, catalyst regenerator, catalyst cooler, coolant entrance, gas inlet, coolant outlet, pneumavalve, vacuum breaker, liquid distributing board.
6. the process for refining of a kind of little algae thermal cracking oil according to claim 1; It is characterized in that said catalytic hydrogenation process flow process of the 3rd step is: hydrogenation catalyst is added inlet from catalyzer add; Feed nitrogen purging gas circuit, the resistance to air loss of inspection units by the gas inlet; Feed hydrogen to the shortening fluidized-bed reactor, and make the gas uniform distribution through gas distribution grid, the maintenance hydrogen flowing quantity is 30ml/min ~ 90ml/min, and the pressure in the shortening fluidized-bed reactor is 1.5MPa ~ 10.0MPa, is heated to 150 ℃ ~ 350 ℃; Little algae thermal cracking oil that will obtain by catalytic pyrolysis fluidized-bed reactor in little algae catalytic pyrolysis technology; Inject the bio oil that dewaters in advance from the main liquid flow inlet and the auxiliary liq influx of pyrolysis oil shortening device to the shortening fluidized-bed reactor by the storage tank in the preparatory dewatering process respectively through fresh feed pump and preheater; Water cut is 5%wt% ~ 20wt%; Keep the pyrolysis oil uniform distribution through liquid distributing board, keeping oily inlet amount simultaneously is 0.5 ~ 10.0ml/min; The hydrogenation after product is through separator separates, and tail gas is through the pneumatic outlet emptying, and liquid is discharged from the liquid oil outlet, and solid gets into catalyst regenerator and regenerates; In the catalyst regeneration process, air gets into catalyst regenerator by gas inlet, and in the catalyst cooler, refrigerant is got into by coolant entrance, is discharged by coolant outlet; Regenerated catalyst is after cyclonic separator separates, and part is returned the shortening fluidized-bed reactor through pneumavalve through vacuum breaker, and part is discharged, and constantly adds inlet from catalyzer again simultaneously and adds live catalyst; Regenerated flue gas is discharged by exhanst gas outlet.
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| CN105419848A (en) * | 2015-11-18 | 2016-03-23 | 江苏大学 | Method for preparing bio-oil through co-pyrolysis catalytic hydrogenation by means of algae and waste rubber |
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| CN105419848A (en) * | 2015-11-18 | 2016-03-23 | 江苏大学 | Method for preparing bio-oil through co-pyrolysis catalytic hydrogenation by means of algae and waste rubber |
| CN105647594A (en) * | 2016-01-07 | 2016-06-08 | 江苏大学 | Device and technique for preparing biological oil by microalgae hydrothermal liquefaction by using power plant extraction steam |
| CN105713715A (en) * | 2016-03-21 | 2016-06-29 | 江苏大学 | Method for preparing bio-oil online in layering and catalyzing mode through microalgae vacuum pyrolysis |
| CN106635114B (en) * | 2016-12-06 | 2018-09-18 | 青岛理工大学 | Device and method for realizing co-production of catalytic cracking oil gas by waste rubber powder in fluidized state |
| CN106635114A (en) * | 2016-12-06 | 2017-05-10 | 青岛理工大学 | Device and method for realizing co-production of catalytic cracking oil gas by waste rubber powder in fluidized state |
| WO2020016415A1 (en) * | 2018-07-20 | 2020-01-23 | Neste Oyj | Production of hydrocarbons from recycled or renewable organic material |
| US11427782B2 (en) | 2018-07-20 | 2022-08-30 | Neste Oyj | Purification of recycled and renewable organic material |
| US11499104B2 (en) | 2018-07-20 | 2022-11-15 | Neste Oyj | Purification of recycled and renewable organic material |
| US11624030B2 (en) | 2018-07-20 | 2023-04-11 | Neste Oyj | Production of hydrocarbons from recycled or renewable organic material |
| US11655422B2 (en) | 2018-07-20 | 2023-05-23 | Neste Oyj | Purification of recycled and renewable organic material |
| US11981869B2 (en) | 2018-07-20 | 2024-05-14 | Neste Oyj | Purification of recycled and renewable organic material |
| CN114053962A (en) * | 2021-11-08 | 2022-02-18 | 大连凯飞化学股份有限公司 | Fluidized bed reaction system and method for in-situ catalytic synthesis of thymol |
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