CN107974265A - A kind of method by waste grease production aviation fuel component - Google Patents
A kind of method by waste grease production aviation fuel component Download PDFInfo
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- CN107974265A CN107974265A CN201610941393.5A CN201610941393A CN107974265A CN 107974265 A CN107974265 A CN 107974265A CN 201610941393 A CN201610941393 A CN 201610941393A CN 107974265 A CN107974265 A CN 107974265A
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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
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
- C10G3/46—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof in combination with chromium, molybdenum, tungsten metals or compounds thereof
-
- 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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/001—Refining fats or fatty oils by a combination of two or more of the means hereafter
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/12—Refining fats or fatty oils by distillation
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
- C11C3/10—Ester interchange
-
- 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
- C10G2300/1003—Waste materials
-
- 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
- C10G2300/1003—Waste materials
- C10G2300/1007—Used oils
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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- Oil, Petroleum & Natural Gas (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a kind of method by waste grease production aviation fuel component, including：Waste grease esterification unit, hydrotreating reaction unit, hydroconversion reactions unit and separation fractionation unit, the present invention is reacted with methanol first using waste grease as raw material, displace glycerine and remove the chlorine in raw material, metal and the acid number for reducing raw material, then the aviation fuel component for meeting product requirement is produced, it can be achieved that waste grease resource efficiently uses by hydrogenation deoxidation and selective cracking reaction.
Description
Technical field
The invention belongs to a kind of production method of bio-fuel, is that one kind produces aviation by waste grease more specifically
The method and system of fuel element.
Background technology
As traditional fossil energy supply is becoming tight, the pressure of carbon dioxide discharge-reduction increasingly increases, and development is renewable, cleaning
Alternative energy source become the whole world common recognition.
Liquid fuel, such as gasoline, diesel oil and aviation fuel, are the main sources of CO2 emission in air.These
Liquid is mostly from oil, natural gas and coal.Relative to fossil fuel, the fuel from biomass absorbs dioxy in growth course
Change carbon, compared with fossil fuel, can effectively reduce the discharge capacity of carbon dioxide.Therefore bio-fuel is considered as transportation
Reduce most one of desirable route of CO2 emission.
In the raw material of bio-fuel is prepared, animal and plant fat is main a kind of raw material.But in development bio-fuel
When must comply with do not striven with people grain, do not striven with grain ground principle.Therefore it is development biology combustion beneficial to inedible, waste grease
The inevitable choice of material.
Waste grease refers to that natural oil (vegetable oil and animal tallow) is being processed and produced during edible consumption, mistake
The leftover bits and pieces produced, residential households, hotel, meal are removed during the fatty wastes of edible value, including oil seed production edible oil
Drink industry and the food enterprises use frying excess oil, the food waste oil produced in edible oil, meat production and by-product in processing
Animal tallow, also have more than edible oil of shelf-life etc..Conservative estimation, the waste grease of the annual output of China is more than 10,000,000
Ton.
Waste grease is mishandling will to become serious pollution sources, contaminated land, water body and air.Waste grease once when
Make animal feed additive or for producing Betengent product, but found that this use will continue its harm to the mankind later,
Harmless treatment can only be carried out with pollutant, but intractability is big, it is costly.
It is ester exchange method by the traditional handicraft that grease is converted into liquid fuel, carrying out ester exchange using methanol and grease can
Grease is converted into fatty acid methyl ester and glycerine, product is usually fatty acid methyl ester (also referred to as first generation biodiesel).
Ester exchange method mainly includes：Acid catalysis, base catalysis, enzymatic and supercritical technology etc..But the reaction that acid, base catalysis carry out
To the more demanding of raw material, it is impossible to directly handle waste grease, supercritical technology can directly handle waste grease.
But when using waste grease production biodiesel, the acid number of biodiesel tends not to meet target level of product quality
Requirement, the new revision national standard that such as American-European standard and China will issue has product acid number the requirement of higher, that is, is not more than
0.5mgKOH/g.Also need to be further processed to reduce product acid number, add investment and the operating cost of device.
Moreover, the low temperature flow of fatty acid methyl ester difference limits its use under colder environmental condition, while carbon-carbon double bond is deposited
Reducing the stability of fatty acid methyl ester.Due to the presence of oxygen atom in fatty acid methyl ester, can cause in combustion more
The discharge of high NOx.Fatty acid methyl ester needs to be used in mixed way with traditional diesel oil in use, its mixed proportion is generally not
More than 10%.
It is method of hydrotreating by another method that grease is converted into liquid fuel, grease is converted into by carbon by hydrogenation deoxidation
Hydrogen fuel, compared with first generation biodiesel, without oxygen element, Cetane number is up to 70~100, has preferable storage to stabilize
Property, and can be reconciled with traditional petroleum based diesel with arbitrary proportion.In addition, aircraft industry is in face of carbon dioxide discharge-reduction and carbon tax
Dual-pressure, places high hopes the aviation fuel from biomass, it is believed that bio-fuel realizes carbon dioxide discharge-reduction target
Unique selection.
However, waste grease species is more, source is complicated, channel disperses, impurity forms and content is unstable, it is impossible to directly into
The processing of row fixed bed hydrogenation.As free fatty acid content scope is very wide in waste grease, from 1% to 80% more than, free-fat
The excessive requirement that can increase equipment corrosion protection of acid content；Also contain diversified impurity in waste grease, including in grease
Colloid, soaps, hetero atom organic matter of generation etc. are aoxidized in intrinsic phosphatide and collection process；It is particularly chloride
The presence of compound, endangers bigger, and inorganic acid will can be produced during follow-up hydrogenation, aggravates equipment corrosion, induces safe thing
Therefore.Therefore need to reduce the acid number of raw material, colloid, metal ion and the chlorine for removing raw material etc. by certain methods before hydrogenation
Impurity, extends the service life of catalyst to reduce the burn into of equipment, and improves the continuity of production.As CN101583694 is public
That opens has in the method for biological source mixture production hydrocarbon-fraction, it is desirable to raw material is pre-processed before hydrogenation deoxidation, in advance
Processing method includes absorption, spent ion exchange resin or the processing of faintly acid detergent.Diesel oil model is prepared disclosed in CN101233212
In the method for enclosing hydrocarbon, then limit alkali or alkaline earth metal in raw material and be less than 10mg/kg.
CN102504866 discloses a kind of method that kitchen waste oil prepares biodiesel.This method is using the method washed
Kitchen waste oil is pre-processed, to remove the metal in raw material.Then pretreated raw material is subjected to hydrodemetallization, taken off
Colloid and part deoxygenation；Again with carrying out secondary hydrogenation after mineral oil, finally by being hydrocracked or isomerization reaction
To improve product property.Kitchen waste oil is pre-processed by the method for washing, metal that can only be in partial removal raw material is right
The acid number of chlorine and raw material in raw material does not improve.
The content of the invention
It is a kind of by waste grease production aviation fuel component the purpose of the present invention is overcoming the deficiencies of the prior art and provide
Method.
Method provided by the invention comprises the following steps：
(1) waste grease esterification unit, waste grease and methanol carry out alcoholysis reaction after mixing, boosting and heat,
Crude glycerine and thick methyl esters are obtained, thick methyl esters obtains smart methyl esters through flash distillation；
(2) hydrotreating reaction unit, including hydrotreating fixed bed reactors, set at least two catalyst beds,
Smart methyl esters in the presence of hydrogen, is at least divided into two stocks and does not introduce hydrotreating fixed bed reactors obtained by step (1)
At least two catalyst beds in, contacted with hydrotreating catalyst, carry out deoxygenation under hydroprocessing conditions, obtain
Hydrotreating product；The hydrotreating catalyst include with the carrier of composite alumina and load on this carrier plus
Hydrogen activity component, the hydrogenation active component is at least one to be selected from VIII group and at least one metal component selected from group vib,
The alumina support is preparation process is included through steam treatment the step of；
(3) hydroconversion reactions unit, by hydrotreating product obtained by step (2) in the presence of hydrogen, with
Hydrogenation conversion catalyst contacts, and the making choice property cracking reaction under the conditions of hydro-conversion, obtains hydro-conversion product；
(4) fractionation unit is separated, step (3) is obtained into hydro-conversion generation oil after separation and fractionation, obtains kerosene group
Point and diesel component.
Present disclosure is further described below：
(1) waste grease esterification unit
Waste grease and methanol carry out alcoholysis reaction after mixing, boosting and heat, and obtain crude glycerine and thick methyl esters；It is thick sweet
Oil is by refinement treatment production glycerol product；Thick methyl esters obtains smart methyl esters and heavy grease through flash distillation.After esterification reaction of organic acid,
Glyceryl in grease is converted into glycerine by methanol, and the impurity enriched of raw material is in heavy grease, so as to displace glycerine and take off
Except the chlorine in raw material, metal and the acid number for reducing raw material.
The operating condition of waste grease esterification unit is：The temperature that with methanol alcoholysis reaction occurs for waste grease is 180
~320 DEG C, preferably 220~300 DEG C, more preferred 240~280 DEG C；Reaction pressure is 4~10MPa, preferably 5~8MPa；Methanol
Mass ratio with grease is 0.2~1:1, preferably 0.3~0.7:1；Reaction time is 30~120min, preferably 60~90min.
By method provided by the invention, the mixed material after alcoholysis reaction enters rectifying column, is extracted using the method for rectifying
Packed tower, plate column, preferred filler tower may be selected in methanol, rectifying column.
In the present invention, in waste grease esterification unit, thick methyl esters glycerol subsidence separator and thick methyl esters is set to flash
Container, the mixed material after alcoholysis reaction enter thick methyl esters glycerol subsidence separator, separator continuous operation, behaviour after separating methanol
It is as condition：Temperature of charge is maintained at 40~80 DEG C, preferably 50~70 DEG C；Residence time preferred 0.5h~3h, preferably 1~2h；
After the completion of sedimentation, thick methyl esters exits into thick methyl esters flash chamber from separator top, and crude glycerine leaves from separator lower part, can
Carry out further refinement treatment；Thick methyl esters obtains smart methyl esters after flash distillation process, and thick methyl esters flash chamber is flash tank or sudden strain of a muscle
Steam tower.
By method provided by the invention, the purpose of thick methyl esters flash distillation is to realize the separation of methyl esters and heavy grease, obtains essence
Methyl esters.Thick methyl esters flash chamber is flash tank or flash column, and the operating condition of flash column is：220~350 DEG C of temperature, preferably 260
~320 DEG C；2~0.3kPa of pressure, preferably 1.5~0.5kPa.
For fatty acid methyl ester more than 95%, sulfur content is not more than 1 no more than 10 μ g/g, Cl contents in the smart methyl esters of gained
The sum of μ g/g, various metal ion contents are not more than 2 μ g/g.
In method provided by the invention, the waste grease is produced not in animal and plant fat processing and edible consumption
The fatty wastes preferably eaten again.Including aliphatic acid, the acidification oil etc. produced during oil seed production edible oil；Residential households,
Hotel, catering industry and the food enterprises use all kinds of meal such as the frying excess oil, food waste oil, hogwash fat produced in edible oil
Drink waste oil；The animal tallow of by-product, also has more than edible oil of shelf-life etc. in meat production and processing.
During oil hydrogenation, the glyceryl in grease can be hydrogenated generation propane, need to increase if propane is recycled
The investment of oil (gas) filling device.It and glycerine is important industrial chemicals, both can directly use, biology, chemical process system can also be passed through
Standby other chemical products.Methanol is as a kind of industrial chemicals, it is derived from a wealth of sources, and price is cheap compared with glycerine.With low price
The outbid glycerine of value of methanol replacement can improve the value of waste grease, reduce the production cost of bio-fuel；And pass through
Ester exchange reaction, can also realize the pretreatment of waste grease, meet the needs of follow-up hydrogenation technique.
(2) hydrotreating reaction unit
Hydrotreating reaction unit includes at least one hydrotreating fixed bed reactors, it sets at least two catalyst
Bed, in the presence of hydrogen, being at least divided into two stocks, not introduce hydrotreating fixed bed anti-for smart methyl esters obtained by step (1)
In at least two catalyst beds for answering device, contacted with hydrotreating catalyst, carry out deoxygenation under hydroprocessing conditions,
Obtain hydrotreating product.
The reaction condition of the hydrotreating reaction unit is：200~400 DEG C of reaction temperature, hydrogen dividing potential drop 1.0~
10.0MPa, 0.5~10.0h of volume space velocity during liquid-1, 500~1500Nm of hydrogen to oil volume ratio3/m3.Mixed material is in reaction condition
The reaction such as hydrogenation deoxidation, alkene saturation and hydrodesulfurization is carried out under the action of lower and catalyst, is reacted for strong exothermal reaction.
In one preferred embodiment of the invention, liquid phase material is partly recirculated at hydrogenation in hydrotreating product
Reaction member entrance is managed, the mass ratio of liquid phase material of the smart methyl esters with circulating is 1:1~1:2.
The method provided according to the present invention, the hydrotreating catalyst as carrier and are supported on the carrier using aluminium oxide
On hydrogenation active component, the hydrogenation active component is at least one to be selected from VIII group and at least one gold selected from group vib
Belong to component.The alumina support includes through steam treatment step in preparation process.Preferably, the carrying alumina
Body does not include calcination steps in preparation process.Substantial amounts of water can be generated during the hydrogenation deoxidation of raw material, vapor is deposited
The stability of catalyst can be being influenced, is especially being had an impact to catalyst carrier.The method provided according to the present invention, what is used urges
The carrier of agent passes through steam treatment, and without roasting, can obvious stable carrier property, so as to avoid hydrotreating
Influence of the water of reaction process generation to hydrotreating catalyst.
The method provided according to the present invention, the hydrotreating catalyst preparation process include：
(1) by hydrated alumina mixed-forming, drying；
(2) steam treatment is carried out, obtains carrier；
(3) step (2) resulting vehicle is immersed in the prepared aqueous solution containing hydrogenation active component, then through drying,
Hydrotreating catalyst is obtained after roasting.
The hydrated alumina is boehmite.The drying condition of step (1) is：80~200 DEG C of temperature, the time 1~
24 it is small when.
The condition of step (2) steam treatment step includes：450~750 DEG C of temperature, when the time 4~8 is small, vapor stream
Measure for 0.5~5.0 standard cubic meter/kilogram carrier it is small when.
Step (3) immersion condition is：20~100 DEG C of temperature, when the time 1~24 is small.
The condition of roasting is in step (3)：400~650 DEG C of temperature, when the time 2~6 is small.
In hydrotreating catalyst, preferably described group VIII metal component is cobalt and/or nickel, and the metal component of group vib is
Molybdenum and/or tungsten, are counted by oxide and on the basis of catalyst, and the content of the group VIII metal component is 1~10 weight %, institute
The content for stating group vib metal component is 10~45 weight %.
The aqueous solution containing hydrogenation active component, as the compound water solution of cobalt, molybdenum, nickel and tungsten can be according to a conventional method
Prepare.Cobalt, molybdenum, the compound of nickel and tungsten are respectively selected from the one or more in their soluble compound.The wherein change of molybdenum
The preferred ammonium molybdate of compound, the preferred ammonium tungstate of compound of tungsten, ammonium metatungstate, ethyl ammonium metatungstate, one kind in metatungstic acid nickel or
It is several.The compound of nickel and cobalt is respectively preferably nickel nitrate, cobalt nitrate, nickel chloride, cobalt chloride, basic nickel carbonate, basic carbonate
One or more in cobalt.
Hydrotreating catalyst before use, is vulcanized by conventional vulcanization process, oxidation state metal is converted into
Sulphided state metal.Hydrogenation active metals become sulphided state from oxidation state, are conducive to improve the activity and stability of catalyst.Grease
In be substantially free of sulphur, therefore in hydroprocessing processes, in order to maintain the sulphided state of catalyst, it is necessary to ensure that the sulphur in charging contains
Amount.Contain vulcanizing agent in the charging of the hydrotreating reaction unit, the 100-5000mg/kg in terms of elementary sulfur, the vulcanization
Agent is selected from H2S、CS2, dimethyl disulfide, Dimethyl sulfide, the one or more in n-butyl sulfide and thiophene.
The method provided according to the present invention, the reactor of hydrotreating reaction unit are fixed bed reactors, catalyst bed
Layer is at least divided into 2 catalyst beds, introduces smart methyl ester feedstocks in catalyst bed interlayer, catalyst is adjusted by subregion charging
Bed temperature, stablizes hydrotreating reaction and carries out, and the temperature rise of catalyst bed is controlled in appropriate scope.Catalyst
Filling ratio and fresh feed fractionation ratio are determined according to the control of temperature rise and the thermal discharge of reaction.The present invention can be reduced effectively
The ratio of recycle stock and raw material, although total circulation object amount is significantly less than circulated material quantity of the prior art, for every
For a catalyst bed, recycle ratio is not small, can effectively reduce the temperature rise of catalyst bed, but also can reduce fresh
The preheating temperature of raw material.
In one of which embodiment of the present invention, two catalyst beds are set in hydrotreating fixed bed reactors,
On the basis of the entirety of loading catalyst, the Catalyst packing volume ratio of first catalyst bed is 30~50%, second
The Catalyst packing volume ratio of a catalyst bed is 50~70%.Smart methyl ester feedstocks are divided into two strands, whole with smart methyl ester feedstocks
On the basis of body, the part by weight of first burst of charging is 30~50%, and is fed from reactor head entrance, the weight of second burst of charging
Amount ratio is 50~70%, from first catalyst bed and second catalyst bed interlayer charging.
In one of which embodiment of the present invention, three catalyst beds are set in hydrotreating fixed bed reactors,
On the basis of the entirety of loading catalyst, the Catalyst packing volume ratio of first catalyst bed is 20~50%, second
The Catalyst packing volume ratio of a catalyst bed is 20~50%, the Catalyst packing volume ratio of the 3rd catalyst bed
Example is 30~60%.Smart methyl ester feedstocks are divided into three strands, and on the basis of smart methyl ester feedstocks entirety, the part by weight of first burst of charging is
20~50%, and fed from reactor head entrance, the part by weight of second burst of charging is 20~50%, from first catalyst
Bed and second catalyst bed interlayer charging, the part by weight of three feeding streams is 30~60%, from second catalyst bed
Layer and the 3rd catalyst bed interlayer are fed.
In one of which embodiment of the present invention, four catalyst beds are set in hydrotreating fixed bed reactors,
On the basis of the entirety of loading catalyst, the Catalyst packing volume ratio of first catalyst bed is 20~50%, second
The Catalyst packing volume ratio of a catalyst bed is 20~50%, the Catalyst packing volume ratio of second catalyst bed
Example is 20~50%, and the Catalyst packing volume ratio of the 4th catalyst bed is 30~60%.Smart methyl ester feedstocks are divided into four
Stock, on the basis of smart methyl ester feedstocks entirety, first burst charging part by weight be 20~50%, and from reactor head entrance into
Material, the part by weight of second burst of charging is 20~50%, is fed from first catalyst bed and second catalyst bed interlayer,
The part by weight of three feeding streams is 20~50%, from second catalyst bed and the 3rd catalyst bed interlayer charging；The
The part by weight of four bursts of chargings is 30~60%, from the 3rd catalyst bed and the 4th catalyst bed interlayer charging.
It is C to mainly generate carbon number after smart methyl ester hydrogenation processing8-C24Alkane, water, CO, CO2And CH4Deng.In gas-phase product
Contain substantial amounts of hydrogen and CO, CO2、H2S、CH4Deng impurity, CO conversion, PAS pressure-variable adsorptions or steam reformation etc. can be used
Method carries out purification Posterior circle and uses.The C of generation8-C24Alkane dehydration after enter hydroconversion reactions unit.
(3) hydroconversion reactions unit
Hydrotreating product obtained by step (2) in the presence of hydrogen, is contacted with hydrogenation conversion catalyst,
Making choice property cracking reaction under the conditions of hydro-conversion, obtains hydro-conversion product.C during the reaction8-C24Alkane lead to
Selective cracking and isomerization are crossed, obtains including C9-C16The blending ingredients of isoparaffin, in this unit, effectively improve production
The cryogenic property of product simultaneously have adjusted product fraction distribution.
It is in the reaction condition of hydroconversion reactions unit：200~500 DEG C of reaction temperature, is preferably 300~380 DEG C；Hydrogen
1.0~10.0Mpa of partial pressure, is preferably 3.0~8.0MPa；0.1~5.0h of volume space velocity during liquid-1, it is preferably 0.5~3.0h-1；
300~1200Nm of hydrogen to oil volume ratio3/m3, it is preferably 400~800:1.
The hydrogenation conversion catalyst contain the molecular sieve with one-dimensional central hole structure, heat-resistant inorganic oxide matrix and
Hydrogenation metal component.
On the basis of hydrogenation conversion catalyst total amount, the content of the one-dimensional mesoporous molecular sieve is 20~80 heavy %, oxidation
The content of aluminium is 15~75 heavy %, and in terms of oxide, the content of hydrogenation metal is the sum of 0.2~5 heavy %, above-mentioned each component content
For 100%.It is preferred that one or more of the hydrogenation metal component in cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, molybdenum and tungsten.
The one-dimensional medium-pore molecular is screened from ZSM-22, Nu-10, Thete-1, ISI-1, ZSM-23, SAPO-11, SAPO-31, SAPO-
One or more in 41.
The metal active constituent of the hydrogenation conversion catalyst is reduction-state, needs to be gone back catalyst before use
Used after original, which is routine techniques.
Currently preferred hydrogenation conversion catalyst has suitable acid and hydrogenation activity, can realize that selectivity is split
Change, obtain C in high yield9-C16Isoparaffin, while meet the aviation fuel products standard such as freezing point, boiling range, viscosity.
Due to having hydrocracking reaction in whole reaction process, substantial amounts of reaction heat can be produced, if crossing to control
The temperature rise of reactor is made, more secondary crackings can be triggered to react, cause target product yield to reduce.There is provided according to the present invention
Method, the reactor of hydroconversion reactions unit is preferably fixed bed reactors, and catalyst bed is urged for 2 or more than 2
Agent bed, catalyst bed interlayer can be controlled bed temperature by way of injecting cold hydrogen.
(4) product is fractionated
Step (3) is obtained into hydro-conversion generation oil after separation and fractionation, obtains kerosene component and diesel component.
Compared with prior art, it is rotten to efficiently solve metal deposit in waste grease hydrogenation process, chlorion by the present invention
The problem of erosion, hydrogenation reaction heat are concentrated；Adaptability to raw material is strong, all waste glyceride stock can be used for bio-aviation fuel
Production；The methanol of low value can be converted into and be worth higher glycerol product, realized efficiently using for waste grease resource, carry
The high economic benefit of technique.Prepared aviation fuel not sulfur-bearing, nitrogen, oxygen and aromatic hydrocarbons, are a kind of clean fuels；Realize useless
Serialization, the industrialized production of grease are abandoned, there is realistic meaning.
Brief description of the drawings
Fig. 1 is the flow diagram of waste grease esterification unit provided by the invention
Fig. 2 is the flow diagram of hydrotreating reaction unit provided by the invention
Fig. 3 is the flow diagram of hydroconversion reactions unit provided by the invention
Embodiment
The invention will be further described below in conjunction with the accompanying drawings, but not thereby limiting the invention.
Fig. 1 is the flow diagram of waste grease esterification unit provided by the invention, as shown in Figure 1, waste grease 1,
Fresh methanol 2 and the methanol 5 of circulation react after mixing, boosting and heat into alcoholysis reaction device 100；It is mixed after alcoholysis reaction
Compound material 3 enters rectifying column 20, and the methanol 5 separated recycles；Methyl esters and glycerine are mainly contained in remaining mixed material 4,
Into thick methyl esters glycerol subsidence separator 30, thick methyl esters 7 exits into thick methyl esters flash chamber 40 from 30 top of separator, thick sweet
Oil 6 leaves from 30 lower part of separator, goes further refinement treatment.Thick methyl esters 7 obtains in thick methyl esters flash chamber 40 through flash distillation
Smart methyl esters 8 and heavy grease 9, fuel can be used as instead of heavy oil by flashing remaining heavy grease 9.Smart methyl esters 8 enters at hydrogenation
Manage reaction member.
Fig. 2 is the flow diagram of hydrotreating reaction unit provided by the invention, as shown in Fig. 2, coming from waste grease
The smart methyl esters 21 of esterification unit divides for three strands, and the liquid phase material 30 circulated in first gang of 21A and hydrotreating product mixes,
Supplement vulcanizing agent, then enter after heating after mix with new hydrogen 22, recycle hydrogen 26 load hydrotreating catalyst fixed bed it is anti-
Answering in device 200, second gang of charging 21B is fed between first catalyst bed 200A and second catalyst bed 200B, the
Three feeding streams 21C is fed between second catalyst bed 200B and the 3rd catalyst bed 200C.Material 23 after reaction
Enter high pressure vapour liquid separator 50 after heat exchange cools down, product is divided into gaseous phase materials 25, water 24 and liquid hydrocarbon 27, gas phase
Material 25 enters air processing unit 60 and removes CO, CO2、CH4Deng being used as 26 Returning reactor entrance of recycle hydrogen after impurity.Generation
Water 24 discharged from separator bottom, liquid hydrocarbon 27 further removes water and H into stripper 702The impurity such as S, 28 row of gas
Go out stripper 70, liquid material 29 is partly into hydroconversion reactions unit, and another part is as recycle stock 30 and hydrogenation
Handle the raw material mixing of reaction member.
Fig. 3 is the flow diagram of hydroconversion reactions unit provided by the invention, as shown in figure 3, coming from hydrotreating
Liquid material 31 and new hydrogen 32, the recycle hydrogen 33 of reaction member enter the fixation that hydrogenation conversion catalyst is housed through heating after mixing
Bed reactor 300.Material 34 after reaction enters high pressure vapour liquid separator 80 after heat exchange cools down, and gained vapor-phase material 33 is made
Used for recycle hydrogen, gained liquid phase material 35 is separated into fractionating column 90, obtains liquefied gas 36, naphtha 37, kerosene group
Divide 38 and diesel component 39.
The following examples will be further described method provided by the invention, but therefore not limit this
Invention.
In following embodiments, freezing point, flash-point and the total acid number of kerosene component be respectively according to GB/T2430, GB/T261 and
The method of GB/T12574 measures.The mass yield of kerosene component refers to that the quality for the kerosene component being prepared accounts for abandoned oil
The percentage of the quality of fat raw material oil.
Prepare the preparation of 1 hydrotreating catalyst of embodiment
500 grams of boehmites (being derived from Chang Ling catalyst plant production) are weighed, are extruded into the milli of circumscribed circle diameter 1.6 with banded extruder
The cloverleaf pattern bar of rice, when 120 DEG C of dryings 6 are small.Wherein 300 grams are taken, with one-step method method for steam treatment, is steamed in air and water
The volume ratio 1 of gas:0.6, when gas flow is 1.0 standard cubic meters/kilogram small, when processing 6 is small under the conditions of 600 DEG C of temperature, system
Obtain carrier S.
100 grams of carrier Ss are weighed, with the aqueous solution containing 53.4 grams of 5.8 grams of ammonium paramolybdate, 29.7 grams of nickel nitrate and ammonium metatungstate
When 86 milliliters of dippings 2 are small, when 120 DEG C of dryings 3 are small, when 450 DEG C of roastings 4 are small, hydrotreating catalyst C is obtained.In catalyst
MoO3, NiO and WO3Weight content be respectively 2.8%, 4.4% and 25.7%.
Prepare the preparation of 1 hydrotreating catalyst of comparative example
500 grams of boehmites (being derived from Chang Ling catalyst plant production) are weighed, are extruded into the milli of circumscribed circle diameter 1.6 with banded extruder
The cloverleaf pattern bar of rice, when 120 DEG C of dryings 6 are small, when then 600 DEG C of roastings 4 are small in atmosphere, is made carrier DS.
100 grams of carrier DS are weighed, with containing the water-soluble of 53.4 grams of 5.8 grams of ammonium paramolybdate, 29.7 grams of nickel nitrate and ammonium metatungstate
When 86 milliliters of dippings 2 of liquid are small, when 120 DEG C of dryings 3 are small, when 450 DEG C of roastings 4 are small, hydrotreating catalyst DC is obtained.In catalyst
MoO3, NiO and WO3Weight content be respectively 2.6%, 4.5% and 25.8%.
Prepare the preparation of 2 hydrogenation conversion catalyst of embodiment
Method according to embodiment in CN102205250A 1 prepares catalyst, and by a kind of ZSM-22 molecular sieves, (Chang Ling is catalyzed
Agent factory provides, silica alumina ratio 56) it is uniformly mixed with boehmite P1-1, sesbania powder, addition aqueous solution of nitric acid, abundant kneading, so
The cloverleaf pattern bar of 1.3 millimeters of diameter is extruded on banded extruder afterwards, at 120 DEG C it is dry 4 it is small when, then in atmosphere 600 DEG C
Roast 2 it is small when, obtain carrier.Carrier is used and contains Pt (NH3)4Cl2Solution carry out saturation dipping, it is then dry at 110 DEG C
4 it is small when, in air atmosphere 400 DEG C roasting 3 it is small when.Then gained catalyst is reduced, reduction temperature is 350 DEG C, also
When former time 4 is small, Hydrogen Vapor Pressure 0.1MPa.Catalyst after reduction is hydrogenation conversion catalyst, ZSM-22 contents in catalyst
50.2 weight %, 49.0 weight %, Pt content of alumina content, 0.8 weight %.
Embodiment 1
(1) waste grease esterification unit
The use of the waste grease from catering trade is raw material, its quality index is as follows：Density 0.91gcm-3, acid number
78mgKOH/g oil, S35 μ g/g, 29 μ g/g of chlorine, 0.12 weight % of mechanical admixture, 11 μ g/g of metal ion content, saponifiable matter
92.7 weight % of content, the miscellaneous 6.3 weight % of glue, 0.9 weight % of moisture.Methanol and above-mentioned raw materials are pressed 0.3:0.7 ratio is mixed
After conjunction, heating and pressurization, temperature are increased to 260 DEG C, and pressure rise to 6.5MPa, then into reactor, the residence time 1 is small
When, cool down after leaving reactor and decompression enters the methanol rectifying tower that theoretical cam curve is 30,125 DEG C of bottom temperature of control, tower
Push up the conditions such as 67 DEG C of temperature, tower reactor pressure 0.03MPa, tower top pressure 0.005MPa, reflux ratio 1 and carry out separating methanol.Separate
The methanol water content arrived is 0.05%, is recycled.The kettle liquid of methanol rectifying tower is carried out into thick methyl esters glycerol subsidence separator
Split-phase is settled, when stop 1 is small, the glycerine extraction of lower floor goes to refine, and the thick methyl esters on upper strata enters thick methyl esters flash column, the absolute pressure of tower
For 0.7kPa, isolated essence methyl esters and mink cell focus.Fatty acid methyl ester 97% in smart methyl esters, acid number 1.7mgKOH/g oil,
Kinematic viscosity (40 DEG C) 4.2mm2/ s, 4 μ g/g, Cl content of sulfur content, 1 μ g/g, metal ion content is (with Na+Meter) 0.7 μ g/g.
(2) hydrotreating reaction unit
For hydrotreating catalyst to prepare catalyst prepared by embodiment 1, catalyst is divided to two sections of fillings, first catalytic stage
Admission space percentage be 45%, the admission space percentage of second segment is 55%.From waste grease esterification unit
Smart methyl esters is divided into 2 bursts of chargings, and the percentage by weight of first burst of charging is 45%, liquid phase material, H with circulation2Mixed, and
The sulfur-containing compound of 1000 μ g/g of sulfur content is added, is fed from reactor head entrance；Second burst charging part by weight be
55%, fed from two catalyst bed interlayers.The thinner ratio of every section of catalyst zone is 4：1, total essence methyl esters and the liquid phase thing of circulation
The ratio between material is 1:1.8.The reaction condition of hydrotreating is：Pressure 5.0MPa, 320 DEG C of mean temperature, volume space velocity 1.0h-1, hydrogen
The volume ratio of gas and reaction raw materials is 1000:1.
(3) hydroconversion reactions unit
The mixture of liquid phase stream and hydrogen obtained by hydrotreating reaction unit is contacted with hydrogenation conversion catalyst.Hydrogenation
The catalyst that reforming catalyst is prepared for preparation embodiment 2.Hydroprocessing condition includes：Pressure is 5.0MPa, mean temperature is
330 DEG C, volume space velocity 1.0h-1, hydrogen to oil volume ratio 500:1.
(4) product separative element
Product after hydroconversion reactions unit is fractionated to obtain 150-280 DEG C of kerosene component, gained kerosene component
Property is as shown in table 1.
Embodiment 2
(1) waste grease esterification unit
Using after fried food remaining waste grease be raw material, its quality index is as follows：Density 0.91g
cm-3, acid number 5mgKOH/g oil, 13 μ g/g of sulphur, 7.8 μ g/g of chlorine, 0.22 weight % of mechanical admixture, 5.9 μ g/g of metal ion content,
95.3 weight % of saponifiable content, the miscellaneous 3.9 weight % of glue, 0.7 weight % of moisture.Methanol and above-mentioned raw materials are pressed 0.4:0.6
Ratio mixing after, heating and pressurization, temperature are increased to 280 DEG C, pressure rise to 8MPa, then into reactor, stop
When time 1.5 is small, cools down after leaving reactor and decompression enters the methanol rectifying tower that theoretical cam curve is 26.Control bottom temperature
110 DEG C, 65 DEG C of tower top temperature, tower reactor pressure 0.015MPa, tower top pressure 0.002MPa, the condition such as reflux ratio 1.3 carry out methanol
Separation.Isolated methanol water content is 0.046%, is recycled.The kettle liquid of methanol rectifying tower is sunk into thick methyl esters glycerine
Drop separator carries out sedimentation split-phase, and when stop 1.5 is small, the glycerine extraction of lower floor goes to refine, and the thick methyl esters on upper strata enters thick methyl esters
Flash column, the absolute pressure of tower is 0.5kPa, isolated essence methyl esters and mink cell focus.Fatty acid methyl ester in wherein smart methyl esters
98%, acid number 0.6mgKOH/g oil, kinematic viscosity (40 DEG C) 4.0mm2/ s, 1 μ g/g, Cl contents of sulfur content are without metal ion contains
Amount is (with Na+Meter) 0.4 μ g/g.
(2) hydrotreating reaction unit
Hydrotreating catalyst is prepares catalyst prepared by embodiment 1, and three sections of catalyst point loads, first catalytic stage
Admission space percentage be 30%, the admission space percentage of second segment is 35%, and the 3rd section of admission space percentage is
35%.Smart methyl esters from waste grease esterification unit is divided into 3 bursts of chargings, and the percentage by weight of first burst of charging is 30%,
Liquid phase material, H with circulation2Mixed, and add the sulfur-containing compound of 1000 μ g/g of sulfur content, from reactor head entrance
Charging；The percentage by weight of second burst of charging is 35%, from first catalyst bed and second catalyst bed interlayer charging；
The percentage by weight of three feeding streams is 35%, from second catalyst bed and the 3rd catalyst bed interlayer charging.Every section
The thinner ratio of catalyst zone is 6：1, always the ratio between essence methyl esters and the liquid phase material of circulation are 1:1.8.
The reaction condition of hydrotreating is：Pressure 5.0MPa, 330 DEG C of mean temperature, volume space velocity 2.0h-1, hydrogen with it is anti-
The volume ratio for answering raw material is 1000:1.
(3) hydroconversion reactions unit
The mixture of the liquid phase material of hydrotreating reaction unit and hydrogen is contacted with hydrogenation conversion catalyst.Hydrogenation turns
Change catalyst to prepare catalyst prepared by embodiment 2.Hydroprocessing condition includes：Pressure is 5.0MPa, mean temperature 340
DEG C, volume space velocity 1.5h-1, hydrogen to oil volume ratio 500:1.
(4) product separative element
The product of hydroconversion reactions unit is fractionated to obtain 150-280 DEG C of kerosene component, the property of gained kerosene component
Matter is as shown in table 1.
Embodiment 3
(1) waste grease esterification
Soybean acidified oil using the acidified generation of oil foot and soap stock produced from soybean oil refinement is raw material, its matter
Figureofmerit is as follows：Density 0.90gcm-3, acid number 139mgKOH/g oil, 7 μ g/g of sulphur, 1.4 μ g/g of chlorine, 0.37 weight of mechanical admixture
Measure %, 255.6 μ g/g of metal ion content, 93.7 weight % of saponifiable content, the miscellaneous 5.1 weight % of glue, 1.1 weight of moisture
Measure %.Methanol and above-mentioned raw materials are pressed 0.27:After 0.73 ratio mixing, heating and pressurization, temperature are increased to 250 DEG C, pressure
6MPa is increased to, then into reactor, when the residence time 1 is small, cools down after leaving reactor and decompression enters theoretical tray
Number is 32 methanol rectifying tower.Control 105 DEG C of bottom temperature, 67 DEG C of tower top temperature, tower reactor pressure 0.010MPa, tower top pressure
The conditions such as 0.001MPa, reflux ratio 0.9 carry out separating methanol.Isolated methanol water content is 0.066%, is recycled.
The kettle liquid of methanol rectifying tower carries out sedimentation split-phase into thick methyl esters glycerol subsidence separator, and when stop 1.0 is small, the glycerine of lower floor is taken out
Go out to refine, the thick methyl esters on upper strata enters thick methyl esters flash column, and the absolute pressure of tower is 0.8kPa, isolated essence methyl esters and heavy
Oil.Fatty acid methyl ester 99% in wherein smart methyl esters, acid number 1.9mgKOH/g oil, kinematic viscosity (40 DEG C) 4.1mm2/ s, sulphur
Content and Cl contents are without metal ion content is (with Na+Meter) 3.8 μ g/g.
(2) hydrotreating reaction unit
Hydrotreating catalyst is prepares catalyst prepared by embodiment 1, and four sections of catalyst point loads, first catalytic stage
Admission space percentage be 20%, the admission space percentage of second segment is 20%, and the 3rd section of admission space percentage is
30%, the 4th section of admission space percentage is 30%.Smart methyl esters from waste grease esterification unit is divided into 4 bursts of chargings,
The percentage by weight of first burst of charging is 20%, liquid phase material, H with circulation2Mixed, and add 1000 μ g/g of sulfur content
Sulfur-containing compound, from reactor head entrance feed；The percentage by weight of second burst of charging is 20%, from first catalyst
Bed and second catalyst bed interlayer charging；The percentage by weight of three feeding streams is 30%, from second catalyst bed
Fed with the 3rd catalyst bed interlayer；The percentage by weight of 4th burst of charging is 30%, from the 3rd catalyst bed and the
Four catalyst bed interlayer chargings.The thinner ratio of every section of catalyst zone is 5：1, the ratio between total essence methyl esters and liquid phase material of circulation are
1:1。
The reaction condition of hydrotreating is：Pressure 5.0MPa, 320 DEG C of mean temperature, volume space velocity 1.0h-1, hydrogen with it is anti-
The volume ratio for answering raw material is 1000:1.
(3) hydroconversion reactions unit
The liquid phase material of hydrotreating reaction unit and hydrogen mixture are contacted with hydrogenation conversion catalyst.Hydro-conversion
The catalyst that catalyst is prepared for preparation embodiment 2.Hydroprocessing condition includes：Pressure is 5.0MPa, mean temperature 330
DEG C, volume space velocity 1.0h-1, hydrogen to oil volume ratio 500:1.
(4) product separative element
Product after aforementioned hydrogenation conversion reaction unit is fractionated to obtain 150-280 DEG C of kerosene component, gained kerosene group
The property divided is as shown in table 1.
Embodiment 4
(1) waste grease esterification unit
The use of the acidification oil produced from palm oil refining is raw material, its quality index is as follows：Density 0.89gcm-3、
Acid number 151mgKOH/g oil, 12 μ g/g of sulphur, 23.4 μ g/g of chlorine, 0.41 weight % of mechanical admixture, 107.3 μ g/ of metal ion content
G, 94.1 weight % of saponifiable content, the miscellaneous 4.4 weight % of glue, 1.4 weight % of moisture.Methanol and above-mentioned raw materials are pressed 0.5:
After 0.5 ratio mixing, heating and pressurization, temperature are increased to 270 DEG C, and pressure rise to 7MPa, then into reactor, stops
When staying the time 1 small, cool down after leaving reactor and decompression enters the methanol rectifying tower that theoretical cam curve is 36.Control bottom temperature
125 DEG C, 69 DEG C of tower top temperature, tower reactor pressure 0.022MPa, tower top pressure 0.0015MPa, the condition such as reflux ratio 1.1 carry out methanol
Separation.Isolated methanol water content is 0.035%, is recycled.The kettle liquid of methanol rectifying tower is sunk into thick methyl esters glycerine
Drop separator carries out sedimentation split-phase, and when stop 1.0 is small, the glycerine extraction of lower floor goes to refine, and the thick methyl esters on upper strata enters thick methyl esters
Flash column, the absolute pressure of tower is 0.6kPa, isolated essence methyl esters and mink cell focus.Fatty acid methyl ester in wherein smart methyl esters
97.5%, acid number 1.4mgKOH/g oil, kinematic viscosity (40 DEG C) 4.0mm2/ s, sulfur content and Cl contents are without metal ion content
(with Na+Meter) 2.3 μ g/g.
(2) hydrotreating reaction unit
Hydrotreating catalyst is prepares catalyst prepared by embodiment 1, and four sections of catalyst point loads, first catalytic stage
Admission space percentage be 20%, the admission space percentage of second segment is 20%, and the 3rd section of admission space percentage is
30%, the 4th section of admission space percentage is 30%.Smart methyl esters from waste grease esterification unit is divided into 4 bursts of chargings,
The percentage by weight of first burst of charging is 20%, liquid phase material, H with circulation2Mixed, and add 1000 μ g/g of sulfur content
Sulfur-containing compound, from reactor head entrance feed；The percentage by weight of second burst of charging is 20%, from first catalyst
Bed and second catalyst bed interlayer charging；The percentage by weight of three feeding streams is 30%, from second catalyst bed
Fed with the 3rd catalyst bed interlayer；The percentage by weight of 4th burst of charging is 30%, from the 3rd catalyst bed and the
Four catalyst bed interlayer chargings.The thinner ratio of every section of catalyst zone is 5：1, the ratio between total essence methyl esters and liquid phase material of circulation are
1:1.The reaction condition of hydrotreating is：Pressure 5.0MPa, 320 DEG C of mean temperature, volume space velocity 1.0h-1, hydrogen is with reacting former
The volume ratio of material is 1000:1.
(3) hydroconversion reactions unit
The mixture of the liquid phase material of hydrotreating reaction unit and hydrogen is contacted with hydrogenation conversion catalyst.Hydrogenation turns
Change catalyst to prepare catalyst prepared by embodiment 2.Hydroprocessing condition includes：Pressure is 5.0MPa, mean temperature 330
DEG C, volume space velocity 1.0h-1, hydrogen to oil volume ratio 500:1.
(4) product separative element
Product after aforementioned hydrogenation conversion reaction unit is fractionated to obtain 150-280 DEG C of kerosene component, gained kerosene group
The property divided is as shown in table 1.
The some properties of 1 jet fuel of table
The kerosene component that method using the present invention is prepared it can be seen from the result of table 1 meets ASTM D7566
In come from ester and aliphatic acid synthesis paraffin coal oil standard, aviation fuel component can be used as.
1 hydrotreating catalyst stability of comparative example compares
By the smart methyl esters obtained by 1 waste grease esterification unit of embodiment, the liquid phase material with circulating, H2Mixed,
And the sulfur-containing compound of 1000 μ g/g of sulfur content is added in the feed, contacted with hydrotreating catalyst；Smart methyl esters and circulation
The ratio between liquid phase material is 1:3, hydrotreating catalyst prepares embodiment 1 and makes to prepare the catalyst C of the preparation of embodiment 1 and contrast
Standby catalyst DC.The reaction condition of hydrotreating is：Pressure 5.0MPa, 320 DEG C of mean temperature, volume space velocity 2.0h-1, hydrogen
Volume ratio with reaction raw materials is 1000:1.Hydrogenation deoxidation activity data after steady running for a period of time is shown in Table 2.
Hydrogenation deoxidation activity refers to the oxygen content * 100% of (oxygen contents of oxygen content-liquid hydro-carbon products of raw material)/raw material
The opposite hydrogenation deoxidation activity of 2 hydrotreating catalyst of the table difference duration of runs
It can be seen that the method provided according to the present invention from the data of table 2, the carrier warp of the hydrotreating catalyst used
Cross steam treatment, and without roasting, can obvious stable carrier property, avoid the water of hydrotreating reaction process generation
Influence to hydrotreating catalyst.
Claims (22)
1. a kind of method by waste grease production aviation fuel component, comprises the following steps：
(1) waste grease esterification unit, waste grease and methanol carry out alcoholysis reaction after mixing, boosting and heat, and obtain
Crude glycerine and thick methyl esters, thick methyl esters obtain smart methyl esters through flash distillation；
(2) hydrotreating reaction unit, including hydrotreating fixed bed reactors, set at least two catalyst beds, step
(1) the smart methyl esters of gained in the presence of hydrogen, is at least divided into two stocks and does not introduce hydrotreating fixed bed reactors extremely
In few two catalyst beds, contacted with hydrotreating catalyst, carry out deoxygenation under hydroprocessing conditions, be hydrogenated with
Handle product；The hydrotreating catalyst includes the hydrogenation activity group of the carrier and load of aluminium oxide on this carrier
Point, the hydrogenation active component is at least one to be selected from VIII group and at least one metal component selected from group vib, the oxygen
Change alumina supporter preparation process is included through steam treatment the step of；
(3) hydroconversion reactions unit, with hydrogenation by hydrotreating product obtained by step (2) in the presence of hydrogen
Reforming catalyst contacts, and the making choice property cracking reaction under the conditions of hydro-conversion, obtains hydro-conversion product；
(4) separate fractionation unit, by step (3) obtain hydro-conversion generation oil after separation and fractionation, obtain kerosene component and
Diesel component.
2. in accordance with the method for claim 1, it is characterised in that the waste grease is animal and plant fat processing and eats
The fatty wastes that should not be eaten again produced in consumption.
3. in accordance with the method for claim 1, it is characterised in that the operating condition of waste grease esterification unit is：It is discarded
The temperature that with methanol alcoholysis reaction occurs for grease is 180~320 DEG C, and preferably 220~300 DEG C, reaction pressure is 4~10MPa, excellent
Select 5~8MPa, the mass ratio of methanol and grease is 0.2~1:1, preferably 0.3~0.7:1；Reaction time is 30~120min, excellent
Select 60~90min.
4. in accordance with the method for claim 1, it is characterised in that in the waste grease esterification unit of step (1), alcoholysis
Mixed material after reaction enters rectifying column, extracts methanol using the method for rectifying, rectifying column is packed tower or plate column.
5. according to the method described in claim 1 or 4, it is characterised in that in the waste grease esterification unit of step (1),
Thick methyl esters glycerol subsidence separator and thick methyl esters flash chamber be set, the mixed material after alcoholysis reaction separate enter after methanol it is thick
Methyl esters glycerol subsidence separator, separator continuous operation, operating condition are：Temperature of charge is maintained at 40~80 DEG C, preferably 50~
70℃；Residence time preferred 0.5h~3h, preferably 1~2h；After the completion of sedimentation, thick methyl esters exits into thick first from separator top
Ester flash chamber, crude glycerine leave from separator lower part；Thick methyl esters obtains smart methyl esters after flash distillation process, and thick methyl esters flash distillation is held
Device is flash tank or flash column.
6. in accordance with the method for claim 5, it is characterised in that thick methyl esters flash chamber is flash tank or flash column, is flashed
The operating condition of tower is：220~350 DEG C of temperature, 2~0.3kPa of pressure.
7. according to the method described in claim 1 or 5, it is characterised in that fatty acid methyl ester exceedes in the essence methyl esters
95%, sulfur content is not more than 10 μ g/g, and chlorinity is not more than 2 μ g/g no more than the sum of 1 μ g/g, various metal ion contents.
8. in accordance with the method for claim 1, it is characterised in that the reaction condition of the hydrotreating reaction unit is：
200~400 DEG C, 1.0~10.0MPa of hydrogen dividing potential drop of reaction temperature, 0.5~10.0h of volume space velocity during liquid-1, hydrogen to oil volume ratio 500~
1500Nm3/m3。
9. in accordance with the method for claim 1, it is characterised in that liquid phase material, which is partly recirculated to, in hydrotreating product adds
Hydrogen handles reaction member entrance, and the mass ratio of liquid phase material of the smart methyl esters with circulating is 1:1~1:2.
10. in accordance with the method for claim 1, it is characterised in that two catalysis are set in hydrotreating fixed bed reactors
Agent bed, on the basis of the entirety of loading catalyst, the Catalyst packing volume ratio of first catalyst bed for 30~
50%, the Catalyst packing volume ratio of second catalyst bed is 50~70%.Smart methyl ester feedstocks are divided into two strands, with smart first
On the basis of ester raw material entirety, first burst charging part by weight be 30~50%, from reactor head entrance feed, second strand into
The part by weight of material is 50~70%, from first catalyst bed and second catalyst bed interlayer charging.
11. in accordance with the method for claim 1, it is characterised in that three catalysis are set in hydrotreating fixed bed reactors
Agent bed, on the basis of the entirety of loading catalyst, the Catalyst packing volume ratio of first catalyst bed for 20~
50%, the Catalyst packing volume ratio of second catalyst bed is 20~50%, the catalyst of the 3rd catalyst bed
Admission space ratio is 30~60%.Smart methyl ester feedstocks are divided into three strands, on the basis of smart methyl ester feedstocks entirety, first burst charging
Part by weight is 20~50%, is fed from reactor head entrance, and the part by weight of second burst of charging is 20~50%, from first
A catalyst bed and second catalyst bed interlayer charging, the part by weight of three feeding streams is 30~60%, from second
Catalyst bed and the 3rd catalyst bed interlayer charging.
12. in accordance with the method for claim 1, it is characterised in that four catalysis are set in hydrotreating fixed bed reactors
Agent bed, on the basis of the entirety of loading catalyst, the Catalyst packing volume ratio of first catalyst bed for 20~
50%, the Catalyst packing volume ratio of second catalyst bed is 20~50%, the catalyst of second catalyst bed
Admission space ratio is 20~50%, and the Catalyst packing volume ratio of the 4th catalyst bed is 30~60%.Smart methyl esters
Raw material is divided into four strands, and on the basis of smart methyl ester feedstocks entirety, the part by weight of first burst of charging is 20~50%, and from reactor
Top entry is fed, and the part by weight of second burst of charging is 20~50%, from first catalyst bed and second catalyst
Fed between bed, the part by weight of three feeding streams is 20~50%, from second catalyst bed and the 3rd catalyst bed
Interlayer is fed；The part by weight of 4th burst of charging is 30~60%, from the 3rd catalyst bed and the 4th catalyst bed
Between feed.
13. in accordance with the method for claim 1, it is characterised in that the hydrotreating catalyst preparation process includes：
(1) by hydrated alumina mixed-forming, drying；
(2) steam treatment is carried out, obtains carrier；
(3) step (2) resulting vehicle is immersed in the prepared aqueous solution containing hydrogenation active component, then through drying, roasting
After obtain hydrotreating catalyst.
14. in accordance with the method for claim 13, it is characterised in that the hydrated alumina is boehmite.
15. according to the method described in claim 1 or 13, it is characterised in that the condition of steam treatment step includes：Temperature
450~750 DEG C, when the time 4~8 is small, when vapor flow is that 0.5~5.0 standard cubic meter/kilogram carrier is small.
16. in accordance with the method for claim 13, it is characterised in that the condition of roasting is in step (3)：Temperature 400~650
DEG C, when the time 2~6 is small.
17. according to the method described in claim 1 or 13, it is characterised in that the hydrogenation activity group of the hydrotreating catalyst
In point, group VIII metal component is cobalt and/or nickel, and the metal component of group vib is molybdenum and/or tungsten, in terms of oxide and with catalysis
On the basis of agent, the content of the group VIII metal component is 1~10 weight %, the content of the group vib metal component for 10~
45 weight %.
18. in accordance with the method for claim 1, it is characterised in that be in the reaction condition of hydroconversion reactions unit：Reaction
200~500 DEG C, 1.0~10.0Mpa of hydrogen dividing potential drop of temperature, 0.5~5.0h of volume space velocity during liquid-1, hydrogen to oil volume ratio 300~
1200Nm3/m3。
19. in accordance with the method for claim 1, it is characterised in that the hydrogenation conversion catalyst contains with one-dimensional
Molecular sieve, heat-resistant inorganic oxide matrix and the hydrogenation metal component of pore structure.
20. in accordance with the method for claim 18, it is characterised in that on the basis of hydrogenation conversion catalyst total amount, described one
The content for tieing up mesoporous molecular sieve is 20~80 heavy %, and the content of aluminium oxide is 15~75 heavy %, in terms of oxide, hydrogenation metal group
The content divided is that the sum of 0.2~5 heavy %, above-mentioned each component content is 100%.
21. according to the method described in claim 19 or 20, it is characterised in that the hydrogenation metal component be selected from cobalt, nickel, ruthenium,
One or more in rhodium, palladium, osmium, iridium, platinum, molybdenum and tungsten.
22. according to the method described in claim 19 or 20, it is characterised in that the one-dimensional medium-pore molecular screened from ZSM-22,
One or more in Nu-10, Thete-1, ISI-1, ZSM-23, SAPO-11, SAPO-31, SAPO-41.
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