CN109913256A - Utilize the method and system of the biological oil and fat preparation fuel of high acid value - Google Patents
Utilize the method and system of the biological oil and fat preparation fuel of high acid value Download PDFInfo
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Abstract
The present invention provides a kind of method and system using the biological oil and fat preparation fuel of high acid value, is able to carry out thermal cracking deoxidation-catalytic pyrolysis deoxidation-catalytic hydrodeoxygenation --- triple deoxygenation steps, handles the biological grease of high acid value.It, can gradually deoxidation reduces acid value, preparation and the comparable clean fuel of fuel element obtained by crude oil refining or biological grease direct hydrogenation deoxidation by the biological glyceride stock of high acid value using method and system of the invention.
Description
Technical field
The invention belongs to energy regeneration technical fields, in particular to utilize the method for the biological oil and fat preparation fuel of high acid value
And system.
Background technique
For direct hydrogenation technology, WO2009/039347 is taught to bio-regeneration raw material (biorenewable
Feedstock the technology of diesel component is produced) with the progress of the two-step method of hydrogenation deoxidation and hydroisomerization.US2006/
0207166 teaches while the technology of hydrogenation deoxidation and hydroisomerization.One common defects of these technologies are catalyst
Stability it is poor, and the hydrogen of technique consumes high, and to equipment, there are etching problems, particularly with high oxygen-containing, the higher vegetable oil of acid value
It can be led to the problem of in the working process of animal tallow.
Particularly, direct hydrogenation technology is limited by free fatty acid content in raw material, until so far, the prior art
Document disclose only be up to 15% free fatty acid direct hydrogenation processing preparation HC fuel (Yanyong Liu et
al.,Chem.Lett.2009,38,552)。
There are also the technologies of other biological preparing biodiesel from lipid, such as US2006/0186020 in the prior art simultaneously
It discloses vegetable oil and crude oil is total to smelting method, wherein between content of vegetable oil 1-75%, but the method is not simple using plant
Object oil.And it is total to refining the problem is that the low temperature flow of the normal paraffin component generated in hydrogenation process is poor, it may
The low temperature service performance of final diesel product is influenced, and the desulfuration purification effect of petrifaction diesel may be influenced.
To sum up, for the prior art, although there are many prepare by Raw material processing of the biological grease of high acid value
The route and research achievement of fuel, but still remain low catalyst stability, corrosion of equipment, hydrogen and consume the problems such as high.
There are also the technologies of the biological preparing biodiesel from lipid of other utilization in the prior art simultaneously, such as
CN102492455A proposes the dual deoxy technology of catalytic pyrolysis deoxidation-catalytic hydrodeoxygenation.This technology is limited to feedstock oil
The continuous variation of component, once raw material components become weight, then the tower reactor of catalytic pyrolysis deoxidation tower needs higher temperature to guarantee one
Fixed overhead fraction yield, but the serious polymerization of tower reactor heavy oil can be caused simultaneously or the problem of coking.
Summary of the invention
A series of concept of reduced forms is introduced in Summary, this will in the detailed description section into
One step is described in detail.Summary of the invention is not meant to attempt to limit technical solution claimed
Key feature and essential features do not mean that the protection scope for attempting to determine technical solution claimed more.
Above-mentioned in order to overcome the problems, such as, the present invention provides a kind of method using the biological oil and fat preparation fuel of high acid value.
This method is preferably able to prepare the good biomass fuel for being suitable as diesel oil blending component, refines resulting combustion with crude oil
Expect that component is suitable.
Specifically, the present invention provides a kind of method using the biological oil and fat preparation fuel of high acid value, this method with
The biological grease of high acid value is raw material, which comprises
(a) in a heated condition, thermal cracking deoxygenation is carried out to the biological grease of the high acid value；
(b) product of step (a) is evaporated under reduced pressure, separation water outlet, high acid value fraction, low acid value fraction and recombination
Point；
(c) in the presence of catalytic pyrolysis dehydrogenation catalyst, in a heated condition, the high acid value that step (b) obtains is evaporated
Divide and carries out catalytic pyrolysis deoxygenation, separation water outlet and fixed gas；
(d) in a heated condition, in the presence of hydrogenation deoxidation catalyst, the product that obtains step (c), step (b)
The mixture of obtained low acid value fraction carries out catalytic hydrodeoxygenation with hydrogen and reacts.
According to practical application request, this method can also include: the product of (e) fractionating step (d), obtain gasoline component,
Diesel component and > 365 DEG C of heavy constituent；Heavy constituent wherein > 365 DEG C can be mixed with the high acid value fraction of step (b), as
A part of raw material for catalytic pyrolysis deoxygenation.
According to another aspect of the present invention, a kind of system using the biological oil and fat preparation fuel of high acid value is provided,
Include:
Pyrolysis reactor receives the biological grease of high acid value, makes the biological grease of the high acid value in heating condition
Lower progress thermal cracking deoxygenation；
Vacuum distillation tower is connected with the pyrolysis reactor, receives the product that thermal cracking deoxygenation obtains and goes forward side by side
Row vacuum distillation, separation water outlet, high acid value fraction, low acid value fraction and heavy constituent；
Catalytic pyrolysis deoxidation reactor is connected with the vacuum distillation tower, in the presence of catalytic pyrolysis dehydrogenation catalyst
Under, in a heated condition, catalytic pyrolysis deoxygenation is carried out to the high acid value fraction that vacuum distillation obtains, separation is discharged and does not coagulate
Gas；
Hydrofining reaction tower receives and carrys out the product of autocatalytic cleavage deoxidation reactor, from the low of vacuum distillation tower
Acid value fraction is simultaneously mixed, and in a heated condition with hydrogen, in the presence of hydrogenation deoxidation catalyst, it is de- to carry out catalytic hydrogenation
Oxygen reaction.
According to practical application request, which can also include atmospheric distillation tower, be connected with hydrofining reaction tower, use
In the product of fractionation hydrofining reaction tower.Further, which can also include preheater, with pyrolysis reactor phase
Even, for being preheated to the biological grease of high acid value for entering pyrolysis reactor.
Method and system of the invention use thermal cracking deoxidation-catalytic pyrolysis deoxidation-catalytic hydrodeoxygenation --- and it is triple de-
Oxygen step handles the preferably discarded biological grease of high acid value of the biological grease of high acid value.In addition, the heat in the present invention
Cracking deoxidation-catalytic pyrolysis deoxidation-catalytic hydrodeoxygenation can not only operate continuously, but also can be individually separated operation, i.e.,
Operating condition when according to practical application carries out continous way or intermittent operation respectively.In the present invention, additionally it is possible to comprehensively utilize
The waste residue and fixed gas of generation are heated, and keep entire production process more energy saving and environmentally friendly.
Detailed description of the invention
Following drawings of the invention is incorporated herein as part of the present invention for the purpose of understanding the present invention.Shown in the drawings of this hair
Bright embodiment and its description, principle used to explain the present invention.
Fig. 1 describes an embodiment of the system according to the present invention.
Primary clustering symbol description:
1. preheater
2. pyrolysis reactor
3. vacuum distillation tower
4. catalytic pyrolysis deoxidation reactor
5. hydrofining reaction tower
6. atmospheric distillation tower
Specific embodiment
In the following description, a large amount of concrete details are given so as to provide a more thorough understanding of the present invention.So
And it will be apparent to one skilled in the art that the present invention may not need one or more of these details and be able to
Implement.In other examples, some technical characteristics well known in the art are not described.
Pressure described herein is all gauge pressure.
The present invention relates to a kind of method using the biological oil and fat preparation fuel of high acid value, this method may include: that (a) exists
Under heating condition, thermal cracking deoxygenation is carried out to the biological grease of the high acid value；
(b) product of step (a) is evaporated under reduced pressure, separation water outlet, high acid value fraction, low acid value fraction and recombination
Point；
(c) in the presence of catalytic pyrolysis dehydrogenation catalyst, in a heated condition, the high acid value that step (b) obtains is evaporated
Divide and carries out catalytic pyrolysis deoxygenation, separation water outlet and fixed gas；
(d) in a heated condition, in the presence of hydrogenation deoxidation catalyst, the product for obtaining step (c), step (b)
The mixture of obtained low acid value fraction carries out catalytic hydrodeoxygenation with hydrogen and reacts.
The present invention uses thermal cracking deoxidation-catalytic pyrolysis deoxidation-triple deoxidization techniques of catalytic hydrodeoxygenation-.Using hot tearing
The technology that solution and vacuum distillation combine, is handled the biological grease of high acid value, this process can remove part in raw material
Oxygen element reduces acid value, the density and viscosity of raw material, and is divided into water, high acid value fraction and low acid value to evaporate biological grease
Divide and four parts of heavy constituent.One of the raw material that low acid value fraction can be reacted directly as catalytic hydrodeoxygenation, and high acid value
Fraction can further remove oxygen element therein by catalytic pyrolysis deoxygenation then its acid value is down to reduced levels (example
Such as < 50mgKOH/g).It is reacted finally by catalytic hydrodeoxygenation and removes remaining oxygen element.Due to thermal cracking deoxidation and catalysis
It does not need in the step of cracking deoxidation using hydrogen, and is stripped of most oxygen element, so in subsequent catalytic hydrogenation
In deoxygenation step, hydrogen gas consumption can be greatly lowered and add the more biological grease direct hydrogenation milder of operating condition of hydrogen.
In the thermal cracking deoxidation the step of, the reaction such as decarboxylation, degradation and isomerization is had occurred in partial fatty acid at high temperature,
Form alkane and alkene, ketone, water, CO2, CO, hydrogen, methane, ethane etc..To reduce acid value, density and viscosity,
Be conducive to the processing of grease next step.
In the catalytic pyrolysis deoxidation deacidification value the step of, remaining fatty acid passes through decarbonylation base or decarboxylation in high acid value fraction
Base removes part oxygen, generates CO2、CO、H2O and alkane, alkene.By this step acid value can be reduced to reduced levels (such as
<50mgKOH/g)。
In the catalytic hydrodeoxygenation the step of, the hydrogenated saturation of triglyceride plus hydrogen decarboxylation plus hydrogen decarbonylation base and add
N-alkane is generated after hydrogen deoxygenation.Hydrogenation deoxidation reaction, which can be removed further, does not have the oxygen-containing of removing to evaporate in aforementioned process
Point, while it is saturated the alkene generated in thermal cracking deoxidation-catalytic pyrolysis deoxidation process, obtain the high product of stability.
Fuel prepared by the present invention is commonly known as biomass fuel, it is intended that solid, the liquid for being made of or extracting biomass
Body or gas, and so-called biomass refers to the product of vivo or vivo metabolism.It is preferably implemented at one
In example, biodiesel of the invention is suitable with the component for refining resulting petroleum diesel via petrochemical material (such as crude oil), and two
Person has high degree of compatibility, can sufficiently reconcile, and reconciles resulting diesel oil with the comparable property of petroleum diesel and using model
It encloses.
A preferred embodiment according to the present invention, step (a), (b) and (d) can be operated continuously, and step (c) can be with
Continuous operation or intermittently operated.
The intermittently operated of a preferred embodiment according to the present invention, step (c) can be anti-using more distillation stills circulation
It answers.
The continuous operation of a preferred embodiment according to the present invention, step (c) can use continous way catalytic distillation
Reaction.
The present invention mainly by three thermal cracking deoxidation, catalytic pyrolysis deoxidation and catalytic hydrodeoxygenation steps based on, three steps
Rapid combination is very flexible, can not only operate continuously, but also can be individually separated operation.Specifically, hot tearing occurs to free
Oxygen reacts (step (a)) and is evaporated under reduced pressure first reaction section of (step (b)) and catalytic pyrolysis deoxygenation (step occurs
(c)) the third reaction section of second reaction zone section and generation catalytic hydrodeoxygenation reaction (step (d)) can be according to practical application
Operating condition, and carry out continous way or intermittent operation respectively.
In industry application, in the thermal cracking deoxidation and vacuum distillation step and third reaction section in the first reaction section
Catalytic hydrodeoxygenation step be both preferably continous way operation, its advantage is that stable reaction conditions, product stablize；And second is anti-
Answer the catalytic pyrolysis deoxygenation step in section that can operate using intermittent or continous way.As catalytic pyrolysis deoxygenation step can be used
More distillation still circulate operations can also be operated using continous way catalytic distillation.Preferably, catalytic pyrolysis deoxygenation step is using continuous
The operation of formula catalytic distillation.
A preferred embodiment according to the present invention, the biological grease of high acid value can be animality source, vegetalitas
Source, microbe-derived or mixture above-mentioned.The biological grease of high acid value can be the biological grease of discarded high acid value.It is high
The acid value of the biological grease of acid value can be with >=40% with >=80mgKOH/g or free fatty acid content.The free fatty acid
It is the fatty acid for the free state that biological grease generates.
Biological grease may include animality source, vegetalitas source, microbe-derived or mixture above-mentioned.Work
Industry is used or unedible biological grease can be utilized.Biological grease is rich in triglyceride and free fatty acid, rouge
Fat acid chain length is usually C12-C24, in the majority with C16 and C18.The example of biological grease illustrates but without limitation includes dish
Seed oil, soya-bean oil, palm oil, sunflower oil, cottonseed oil, curcas oil, olive oil, castor oil, microalgae oil, tallow, lard, Huang
Oil, poultry fat, fish oil, waste cooking oil.In one embodiment, it is preferred that vegetable fat is as raw material.
A preferred embodiment according to the present invention, the heating condition in step (a) can be 100 DEG C to 600 DEG C.
A preferred embodiment according to the present invention, the biological grease of high acid value in step (a) carry out hot tearing and free
The time of oxygen can be 1 to 60 minute.
A preferred embodiment according to the present invention, the product of step (a) may include alkene, alkane, ketone, fat
Acid, fatty alcohol, carbon monoxide, carbon dioxide, water.
A preferred embodiment according to the present invention, the acid value for the high acid value fraction that step (b) obtains can be in 80-
In the range of 120mgKOH/g, the acid value of low acid value fraction can be in the range of 10-50mgKOH/g.
A preferred embodiment according to the present invention, the product of step (b) may include water, high acid value fraction, low acid
It is worth fraction, heavy constituent, carbon dioxide, carbon monoxide.
A preferred embodiment according to the present invention, the heavy constituent of step (b) can be used as waste disposal or and raw material
Mix the raw material as step (a).
A preferred embodiment according to the present invention, step (b) can -0.05MPa to -0.3MPa pressure under into
Row.
The vacuum distillation of a preferred embodiment according to the present invention, step (b) can be in 100 DEG C to 500 DEG C temperature
It is carried out in range.
The catalytic pyrolysis dehydrogenation catalyst of a preferred embodiment according to the present invention, step (c) can be selected from oxidation
Or mixtures thereof aluminium, molecular sieve, silicon carbide.
A preferred embodiment according to the present invention, step (c) can carry out in 100 DEG C to 500 DEG C temperature ranges.
A preferred embodiment according to the present invention, step (d) can carry out in 200 DEG C to 400 DEG C temperature ranges,
Hydrogen partial pressure can be 1MPa to 6MPa, and volume space velocity can be 0.5h-1To 4.0h-1, hydrogen to oil volume ratio can be 200-
1200:1。
A preferred embodiment according to the present invention, method of the invention can also include: (e) fractionating step (d)
Product obtains gasoline component, diesel component and > 365 DEG C of heavy constituent.
A preferred embodiment according to the present invention, > 365 DEG C of heavy constituent can be with the high acid value fraction of step (b)
Mixing, a part as the raw material for catalytic pyrolysis deoxygenation.
A preferred embodiment according to the present invention, step (a) can also include carrying out to the biological grease of high acid value
The step of preheating.
A preferred embodiment according to the present invention, hydrogenation deoxidation catalyst are load type metal catalyst or metal sulphur
Compound.
A preferred embodiment according to the present invention, continous way catalytic distillation Reaction Separation are discharged and obtain after fixed gas
The fraction raw material that is used as catalytic hydrodeoxygenation in step (d) to react.
A preferred embodiment according to the present invention, acid value < 50mgKOH/g of the product of step (c).
The invention further relates to a kind of systems using the biological oil and fat preparation fuel of high acid value comprising: heat scission reaction
Device 2 receives the biological grease of high acid value, the biological grease of high acid value is made to be performed under heating conditions thermal cracking deoxygenation；
Vacuum distillation tower 3 is connected with pyrolysis reactor 2, receives the product that thermal cracking deoxygenation obtains and is evaporated under reduced pressure,
Separate water outlet, high acid value fraction, low acid value fraction and heavy constituent；Catalytic pyrolysis deoxidation reactor 4, with 3 phase of vacuum distillation tower
Even, in the presence of catalytic pyrolysis dehydrogenation catalyst, in a heated condition, the high acid value fraction from vacuum distillation tower is carried out
Catalytic pyrolysis deoxygenation, separation water outlet and fixed gas；Hydrofining reaction tower 5, and catalytic pyrolysis deoxidation reactor 4 and subtracts
It presses destilling tower 3 to be connected, receives the product for carrying out autocatalytic cleavage deoxidation reactor 4, the low acid value fraction from vacuum distillation tower 3 simultaneously
It is mixed, in a heated condition with hydrogen, in the presence of hydrogenation deoxidation catalyst, carries out catalytic hydrodeoxygenation reaction.
A preferred embodiment according to the present invention, catalytic pyrolysis deoxidation reactor 4 can using more distillation stills or
Catalytic distillation tower.It is highly preferred that catalytic pyrolysis deoxidation reactor 4 uses catalytic distillation tower, the high acid value from vacuum distillation tower 3
Fraction carries out the overhead fraction that catalytic pyrolysis deoxygenation obtains in catalytic distillation tower and tower reactor fraction all has reduced levels
Acid value (such as < 50mgKOH/g), meet requirement of the subsequent catalyst hydrodeoxygenation step to the acid value of charging.But in some feelings
Under condition, embodiments of the present invention can also replace catalytic distillation tower with more distillation stills.
A preferred embodiment according to the present invention, the heating condition in pyrolysis reactor 2 can be for 100 DEG C extremely
600 DEG C, residence time of the biological grease of high acid value in pyrolysis reactor 2 can be 1 to 60 minute.
A preferred embodiment according to the present invention, the product of pyrolysis reactor 2 may include alkene, alkane, ketone
Class, fatty acid, fatty alcohol, carbon monoxide, carbon dioxide, water.
A preferred embodiment according to the present invention, the acid value of the high acid value fraction that vacuum distillation tower 3 obtains can be
In the range of 80-120mgKOH/g, the acid value of low acid value fraction can be in the range of 10-50mgKOH/g.
A preferred embodiment according to the present invention, the product of vacuum distillation tower 3 may include water, high acid value fraction,
Low acid value fraction, heavy constituent, carbon dioxide, carbon monoxide；Preferably, heavy constituent can be used as waste disposal or mix with raw material
Raw material as pyrolysis reactor 2.
A preferred embodiment according to the present invention, pressure in vacuum distillation tower 3 can for -0.05MPa to -
0.3MPa, temperature can be 200 DEG C to 500 DEG C.
A preferred embodiment according to the present invention, catalytic pyrolysis dehydrogenation catalyst can selected from aluminium oxide, molecular sieve,
Or mixtures thereof silicon carbide.
The heating condition of a preferred embodiment according to the present invention, catalytic pyrolysis deoxidation reactor 4 can be at 100 DEG C
To 500 DEG C of temperature ranges.
A preferred embodiment according to the present invention, hydrogenation deoxidation catalyst can be load type metal catalyst or gold
Belong to sulfide.
A preferred embodiment according to the present invention, the heating condition in hydrofining reaction tower 5 can be for 200 DEG C extremely
400 DEG C, hydrogen partial pressure can be 1MPa to 6MPa, and volume space velocity can be 0.5h-1To 4.0h-1, hydrogen to oil volume ratio can be
200-1200:1。
A preferred embodiment according to the present invention, system can also include atmospheric distillation tower 6, anti-with hydrofinishing
It answers tower 5 to be connected, for being fractionated the product of hydrofining reaction tower 6, obtains gasoline component, diesel component and > 365 DEG C of recombination
Point.
A preferred embodiment according to the present invention, the height that > 365 DEG C of heavy constituent can be obtained with vacuum distillation tower 3
The mixing of acid value fraction, a part fed as catalytic pyrolysis deoxidation reactor 4.
A preferred embodiment according to the present invention, system can also include preheater 1, with pyrolysis reactor 2
It is connected, for being preheated to the biological grease of high acid value for entering pyrolysis reactor 2.
A preferred embodiment according to the present invention, acid value < 50mgKOH/ of the product of catalytic pyrolysis deoxidation reactor 4
g。
It is further detailed in conjunction with specific embodiment of the Fig. 1 to system of the invention.
After the biological grease injection preheater 1 of high acid value is gasified, it is anti-that thermal cracking deoxidation is carried out in heat scission reaction tower 2
It answers；Then, the product that heat scission reaction tower 2 obtains is sent into vacuum distillation tower 3 to be evaporated under reduced pressure, isolated product packet
Include water, high acid value fraction, low acid value fraction and heavy constituent；Isolated high acid value fraction will be evaporated under reduced pressure and inject catalytic pyrolysis
In deoxidation reactor 4, catalytic deoxidation reaction is carried out in catalytic pyrolysis deoxidation reactor 4；Then, vacuum distillation tower 3 will be come from
Low acid value fraction, the product that carrys out autocatalytic cleavage deoxidation reactor 4 mixed with hydrogen, configured with hydrogenation deoxidation catalyst
It is reacted in hydrofining reaction tower 5；Finally, the mixed fraction that hydrofining reaction tower 5 is obtained is sent into atmospheric distillation tower
6, fractionation obtains gasoline component, diesel component and > 365 DEG C of heavy constituent, and > 365 DEG C of heavy constituent can be evaporated under reduced pressure with coming from
The high acid value fraction of tower 3 mixes, a part fed as catalytic pyrolysis deoxidation reactor 4.
It is an advantage of the current invention that can be by biological oil by thermal cracking deoxidation and the dual deoxidation process of catalytic pyrolysis deoxidation
The acid value of rouge is reduced to the level that can operate, then carries out hydrogenation deoxidation reaction, and reaction condition is mild, and (hydrogen partial pressure is low, reaction temperature
It is low), catalyst stabilization degree is good, and hydrogen consumption is low, and can be with the etching problem of avoiding device.
Embodiment 1
Using palm sludge oil as the raw material of the method for the present invention.
The fundamental property and boiling range of palm sludge oil are as shown in table 1.Palm sludge oil is solid at room temperature, due to acid value
It is excessively high, it can not be processed and (be up to it has been observed that the prior art is only instructed using direct hydrogenation technology in the prior art
The direct hydrogenation process for producing HC fuel of 15% free fatty acid).However, it is possible to using the method for the present invention to palm sludge oil
It is processed.
The fundamental characteristics of table 1, palm sludge oil
After the injection preheater gasification of palm sludge oil, thermal cracking deoxygenation, hot tearing are carried out in heat scission reaction tower
Temperature control is solved between 100 DEG C to 600 DEG C, is passed through a certain amount of nitrogen as carrier gas, tower top pressure controls between 0-2MPa,
Oil product is in the residence time in reaction tower between 5-60 minutes.Then, decompression steaming is carried out to the product that thermal cracking deoxidation obtains
It evaporates, water, high acid value fraction (80-120mgKOH/g) and low acid value fraction (10-50mgKOH/g) is separated according to fraction temperature, tie
Fruit is as shown in table 2.
The product distribution being evaporated under reduced pressure after table 2, thermal cracking deoxygenation
Comparison sheet 1 and table 2, can be with water it is found that thermal cracking deoxidation by the method for the invention and vacuum distillation step
Form removes oxygen contained in feedstock oil, to reduce the removing of oxygen during subsequent processes, extends catalytic pyrolysis deoxidation and urges
The service life of agent and hydrogenation deoxidation catalyst.
It will be evaporated under reduced pressure in the tower reactor of isolated high acid value fraction injection catalytic distillation tower, be catalyzed after heating and gasifying
Catalytic pyrolysis deoxygenation is carried out in destilling tower, the bottom temperature of catalytic distillation tower controls between 100 DEG C to 600 DEG C, catalysis
Dehydrogenation catalyst and the control of feedstock oil ratio are cracked between 1-20 (weight ratio).The tower top of catalytic distillation tower and the fraction of tower reactor
Ratio is as shown in table 3.
Table 3, the distribution of catalytic pyrolysis deoxidation products
| Overhead fraction | Tower reactor fraction | Water | Fixed gas |
| 70% | 24.2% | 1.8% | 4% |
Then, will be evaporated under reduced pressure the overhead fraction and tower reactor fraction of isolated low acid value fraction and catalytic distillation tower with
Hydrogen mixing, is then reacted by the reaction tower configured with hydrogenation deoxidation catalyst.Vulcanized with load type metal or metal
Object is as hydrogenation deoxidation catalyst.Remaining reaction condition is as shown in table 4, and the component analysis of gained clean fuel is as shown in table 5.
Table 4, hydrodeoxygenation conditions
The component analysis of table 5, clean fuel
As shown in table 5, the fraction after the hot cracked deoxidation of oil of palm sludge and catalytic pyrolysis deoxidation carries out hydrogenation deoxidation again
After processing, obtained fraction acid value is reduced to 0.43mgKOH/g, far below the standard of the Biodiesel Standards (BD100) of China
Value.Method according to the present invention is strictly a kind of excellent diesel oil allotment component by the resulting clean fuel of palm sludge oil.
The present invention has been explained by the above embodiments, but it is to be understood that, above-described embodiment is only intended to
The purpose of citing and explanation, is not intended to limit the invention to the scope of the described embodiments.Furthermore those skilled in the art
It is understood that the present invention is not limited to the above embodiments, introduction according to the present invention can also be made more kinds of member
Variants and modifications, all fall within the scope of the claimed invention for these variants and modifications.Protection scope of the present invention by
The appended claims and its equivalent scope are defined.
Claims (40)
1. a kind of method using the biological oil and fat preparation fuel of high acid value, comprising:
(a) in a heated condition, thermal cracking deoxygenation is carried out to the biological grease of the high acid value；
(b) product of step (a) is evaporated under reduced pressure, separation water outlet, high acid value fraction, low acid value fraction and heavy constituent；
(c) in the presence of catalytic pyrolysis dehydrogenation catalyst, in a heated condition, the high acid value fraction that step (b) is obtained into
Row catalytic pyrolysis deoxygenation, separation water outlet and fixed gas；
(d) in a heated condition, in the presence of hydrogenation deoxidation catalyst, the product that obtains step (c), step (b) are obtained
Mixture and the hydrogen of low acid value fraction carry out catalytic hydrodeoxygenation and react.
2. the method as described in claim 1, wherein the step (a), (b) and (d) continuous operation, step (c) continuous operation
Or intermittently operated.
3. method according to claim 2, wherein the intermittently operated of step (c) uses more distillation still circular responses.
4. method according to claim 2, wherein the continuous operation of step (c) is reacted using continous way catalytic distillation.
5. the method as described in claim 1, wherein the biological grease of the high acid value be animality source, vegetalitas source,
Mixture microbe-derived or above-mentioned.
6. method as claimed in claim 5 the, wherein acid value >=80mgKOH/g or free rouge of the biological grease of the high acid value
Fat acid content >=40%.
7. the method as described in claim 1, wherein the heating condition in step (a) is 100 DEG C to 600 DEG C.
8. the method as described in claim 1, wherein the biological grease of the high acid value in step (a) carry out thermal cracking deoxidation when
Between be 1 to 60 minute.
9. the method as described in claim 1, wherein the product of step (a) includes alkene, alkane, ketone, fatty acid, fat
Alcohol, carbon monoxide, carbon dioxide, water.
10. the method as described in claim 1, the acid value for the high acid value fraction that wherein step (b) obtains is in 80-120mgKOH/g
In the range of, the acid value of low acid value fraction is in the range of 10-50mgKOH/g.
11. the method as described in claim 1, wherein the product of step (b) includes water, high acid value fraction, low acid value fraction, again
Component, carbon dioxide, carbon monoxide.
12. the method as described in claim 1, wherein the heavy constituent of step (b) can be used as waste disposal or mix with raw material
Raw material as step (a).
13. the method as described in claim 1, wherein step (b) carries out under the pressure of -0.05MPa to -0.3MPa.
14. the method as described in claim 1, wherein step (b) carries out in 100 DEG C to 500 DEG C temperature ranges.
15. the method as described in claim 1, wherein the catalytic pyrolysis dehydrogenation catalyst of step (c) is selected from aluminium oxide, molecule
Or mixtures thereof sieve, silicon carbide.
16. the method as described in claim 1, wherein step (c) carries out in 100 DEG C to 500 DEG C temperature ranges.
17. the method as described in claim 1, wherein the step (d) carries out in 200 DEG C to 400 DEG C temperature ranges, hydrogen
Partial pressure is 1MPa to 6MPa, volume space velocity 0.5h-1To 4.0h-1, hydrogen to oil volume ratio 200-1200:1.
18. the method as described in claim 1, further includes:
(e) product of fractionating step (d) obtains gasoline component, diesel component and > 365 DEG C of heavy constituent.
19. method as claimed in claim 18, wherein > 365 DEG C of heavy constituent is mixed with the high acid value fraction of step (b),
A part as the raw material for catalytic pyrolysis deoxygenation.
20. the method as described in claim 1, wherein step (a) further includes the step preheated to the biological grease of high acid value
Suddenly.
21. the method as described in claim 1, wherein the hydrogenation deoxidation catalyst is load type metal catalyst or metal sulphur
Compound.
22. method as claimed in claim 4, the fraction that wherein continous way catalytic distillation reacts is used as in step (d)
The raw material of catalytic hydrodeoxygenation reaction.
23. the method as described in claim 1, the acid value < 50mgKOH/g for the product that wherein step (c) obtains.
24. a kind of system using the biological oil and fat preparation fuel of high acid value comprising:
Pyrolysis reactor, receive the biological grease of high acid value, make the biological grease of the high acid value in a heated condition into
Row thermal cracking deoxygenation；
Vacuum distillation tower is connected with the pyrolysis reactor, receives the product that thermal cracking deoxygenation obtains and is subtracted
Pressure distillation, separation water outlet, high acid value fraction, low acid value fraction and heavy constituent；
Catalytic pyrolysis deoxidation reactor is connected with the vacuum distillation tower, in the presence of catalytic pyrolysis dehydrogenation catalyst,
Under heating condition, catalytic pyrolysis deoxygenation, separation water outlet and fixed gas are carried out to the high acid value fraction that vacuum distillation obtains；
Hydrofining reaction tower receives product, the low acid value from vacuum distillation tower for carrying out autocatalytic cleavage deoxidation reactor
Fraction is simultaneously mixed, and in a heated condition with hydrogen, in the presence of hydrogenation deoxidation catalyst, it is anti-to carry out catalytic hydrodeoxygenation
It answers.
25. system as claimed in claim 24, wherein the catalytic pyrolysis deoxidation reactor uses more distillation stills or catalysis
Destilling tower.
26. system as claimed in claim 24, wherein the biological grease of the high acid value is animality source, vegetalitas
Source, microbe-derived or mixture above-mentioned.
27. system as claimed in claim 24, wherein the heating condition in the pyrolysis reactor is 100 DEG C to 600 DEG C,
Residence time of the biological grease of high acid value in the pyrolysis reactor is 1 to 60 minute.
28. system as claimed in claim 24, wherein the product of the pyrolysis reactor includes alkene, alkane, ketone, rouge
Fat acid, fatty alcohol, carbon monoxide, carbon dioxide, water.
29. system as claimed in claim 24, wherein the acid value for the high acid value fraction that the vacuum distillation tower obtains is in 80-
In the range of 120mgKOH/g, the acid value of low acid value fraction is in the range of 10-50mgKOH/g.
30. system as claimed in claim 24, wherein the product of the vacuum distillation tower includes water, high acid value fraction, low acid
It is worth fraction, heavy constituent, carbon dioxide, carbon monoxide.
31. system as claimed in claim 24, wherein the obtained heavy constituent of the vacuum distillation tower as waste disposal or with
Raw material mixes the raw material as pyrolysis reactor.
32. system as claimed in claim 24, wherein the pressure in the vacuum distillation tower is -0.05MPa to -0.3MPa,
Temperature is 200 DEG C to 500 DEG C.
33. system as claimed in claim 24, wherein the catalytic pyrolysis dehydrogenation catalyst is selected from aluminium oxide, molecular sieve, carbon
Or mixtures thereof SiClx.
34. system as claimed in claim 24, wherein the heating condition of the catalytic pyrolysis deoxidation reactor be 100 DEG C extremely
500℃。
35. system as claimed in claim 24, wherein the hydrogenation deoxidation catalyst is load type metal catalyst or metal
Sulfide.
36. system as claimed in claim 24, wherein the heating condition in the hydrofining reaction tower is 200 DEG C to 400
DEG C, hydrogen partial pressure is 1MPa to 6MPa, volume space velocity 0.5h-1To 4.0h-1, hydrogen to oil volume ratio 200-1200:1.
37. system as claimed in claim 24, wherein the system also includes atmospheric distillation tower, it is anti-with the hydrofinishing
It answers tower to be connected, for being fractionated the product of the hydrofining reaction tower, obtains gasoline component, diesel component and > 365 DEG C of recombination
Point.
38. system as claimed in claim 37, wherein the height that > 365 DEG C of heavy constituent can be obtained with the vacuum distillation tower
The mixing of acid value fraction, a part as the charging of catalytic pyrolysis deoxidation reactor.
39. system as claimed in claim 24, wherein the system also includes preheater, with the pyrolysis reactor phase
Even, for being preheated to the biological grease of high acid value for entering the pyrolysis reactor.
40. system as claimed in claim 24, wherein acid value < 50mgKOH/ of the product of the catalytic pyrolysis deoxidation reactor
g。
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| CN201910104447.6A CN109913256B (en) | 2019-02-01 | 2019-02-01 | Method and system for preparing fuel by using high-acid-value biological grease |
| PCT/CN2020/073766 WO2020156421A1 (en) | 2019-02-01 | 2020-01-22 | Method and system for preparing fuel by using high acid value biological oil and fat |
| EP20749511.0A EP3919588A4 (en) | 2019-02-01 | 2020-01-22 | Method and system for preparing fuel by using high acid value biological oil and fat |
| US17/390,941 US12006484B2 (en) | 2019-02-01 | 2021-07-31 | Method and system for preparing fuel by using high acid value biological oil and fat |
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| WO2020156421A1 (en) * | 2019-02-01 | 2020-08-06 | 易高环保能源研究院有限公司 | Method and system for preparing fuel by using high acid value biological oil and fat |
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