CN106190280B - A method of jet fuel is prepared with renewable raw materials - Google Patents
A method of jet fuel is prepared with renewable raw materials Download PDFInfo
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Abstract
A method of jet fuel is prepared with renewable raw materials, in hydrotreating reaction area, vegetable oil and/or animal fat, which are successively contacted with hydrogenation deoxidation catalyst and hydroisomerization catalyst, is reacted to obtain hydrotreating reaction product, in hydroisomerizing pour point depression reaction zone, gained hydrotreating reaction product and hydrogen are contacted with hydroisomerizing pour point depression catalyst together is reacted to obtain hydroisomerizing pour point depression reaction product, in hydrofining reaction area, gained hydroisomerizing pour point depression reaction product and hydrogen are contacted with Hydrobon catalyst together is reacted to obtain hydrofining reaction product, hydrofining reaction product is again through separating, jet fuel is obtained after fractionation.Using method provided by the invention, gained jet fuel yield is high, and freezing point is low.
Description
Technical field
Hydrofinishing is passed through using animal and plant fat the present invention relates to a kind of, the processes such as hydroisomerization prepare jet fuel
Method.
Background technique
As traditional fossil energy supply is becoming tight, the pressure of carbon dioxide discharge-reduction increasingly increases, and develops renewable, cleaning
Alternative energy source have become global common recognition.Since bioenergy has reproducibility, green, especially it is taken seriously in recent years,
It is considered as most one of the desirable route for solving global energy crisis.
As the demand of jet fuel is continuously increased, the technology of jet fuel is prepared increasingly by people from renewable raw materials
Attention.These renewable raw materials include but do not limit in this way, such as: vegetable oil (soybean oil, rapeseed oil, palm oil, leprosy
Tree oil, Chinese tallow), animal tallow (lard, butter, fish oil), acidification oil, various fatty acid and acidification oil etc..
Currently, research is more to be had, using vegetable oil and/or animal fat, fatty acid is prepared by ester exchange reaction
Methyl esters.Fatty acid methyl ester is a kind of clean renewable energy, is the substitute products of good petroleum diesel, is current using most
More biodiesel oil products.
Also there is the method by hydrotreating, vegetable oil and/or animal fat are prepared into the research of diesel component.Such as
US4992605A and US5705722A, which is disclosed with the method for hydrogen is added, prepares the diesel component of high cetane number, but this method
The diesel component of preparation is mainly made of n-alkane, and cold filter plugging point is higher, affects its scope of application.
CN101233212A discloses a kind of method of two-step method production diesel oil, and the first step generates positive structure by hydrogenation deoxidation
Alkane, second step reduce the cold filter plugging point of diesel oil by isomerization reaction.
In addition, US2009/0158637A1 discloses a kind of method for preparing jet fuel by renewable raw materials.This method
Vegetable oil and/or animal fat are first obtained into the n-alkane that carbon atom number is 8-24 by hydrogenation deoxidation, then by selection
Property cracking and isomerization reaction, then be fractionated the jet fuel met the requirements.However the yield of jet fuel is still in this method
It is so lower, also, this method, there is also generating portion alkene in cracking and isomerization process, the color etc. for influencing jet fuel is asked
Topic.
CN1382526A discloses a kind of preparation method of catalyst for hydrogenation de-waxing, and points out that the preparation method is prepared into
To catalyst can be used for the Hydrodewaxing process of content of wax lubricating oil, content of wax jet fuel, content of wax diesel oil.
Hydroisomerization process is taken as vegetable oil and/or animal fat prepares the important step of jet fuel to entire
The process for preparing jet fuel plays a crucial role, which determine the property for the jet fuel being prepared and yield,
But the technical problem that jet fuel yield is low or freezing point reduction amplitude is small exists in the prior art.
Summary of the invention
The purpose of the present invention is on the basis of existing technology, solve that jet fuel yield in the prior art is low, freezing point drop
The small problem of low amplitude.
The present invention provides a kind of methods for preparing jet fuel with renewable raw materials, comprising:
(1) in hydrotreating reaction area, at hydrotreating reaction conditions, vegetable oil and/or animal fat and hydrogen
Mixture, which is successively contacted with hydrogenation deoxidation catalyst and hydroisomerization catalyst, to be reacted, and hydrotreating reaction generation is obtained
Object, the hydrotreating reaction product are C8-C24Alkane, the sum of n-alkane and isoparaffin mass fraction are 100%,
Isoparaffin mass fraction is more than or equal to 15% simultaneously；
(2) in hydroisomerizing pour point depression reaction zone, under hydroisomerizing pour point depression reaction condition, hydrotreating obtained by step (1)
Reaction product and hydrogen are contacted with hydroisomerizing pour point depression catalyst together to be reacted, and is obtained the reaction of hydroisomerizing pour point depression and is generated
Object,
(3) in hydrofining reaction area, under the conditions of hydrofining reaction, the reaction of hydroisomerizing pour point depression obtained by step (2)
Product and hydrogen are contacted with Hydrobon catalyst together to be reacted, and hydrofining reaction product is obtained, then separated,
Jet fuel is obtained after fractionation.
The jet fuel being prepared using method of the invention is all made of saturated alkane, and property is stablized, full
Requirement of the foot as No. 3 jet fuels.
In method provided by the invention, the vegetable oil and/or animal fat are any to contain glyceride and free rouge
The raw material and vegetable oil and/or animal fat of fat acid pass through the fatty acid methyl ester or fatty-acid ethyl ester of ester exchange method preparation.
The glyceride includes triglycerides, diglyceride and monoglyceride.Including but not limited to, soybean oil, rapeseed oil, cottonseed
Oil, corn oil, rice bran oil, sunflower oil, peanut oil, castor oil, sesame oil, Fructus Zanthoxyli oil, tea oil, coconut oil, olive oil, Huang
Even one or more of wood oil, palm oil, tung oil, curcas oil, turpentine oil, Chinese tallow and algae oil.The vegetable and animals oils
Rouge further includes waste oil from restaurant.The vegetable oil and animal fat can be mixed with arbitrary proportion.In addition, according to the present invention
Vegetable and animals oils fat raw material also includes the fatty acid methyl ester or fatty-acid ethyl ester that animal and plant fat passes through ester exchange method preparation.
In hydrotreating reaction area, the hydrogenation deoxidation catalyst and hydroisomerization catalyst according to reactant flow direction into
Row successively layering filling, by volume and on the basis of the total amount of the catalyst, the content of hydrogenation deoxidation catalyst is 15%
~85%, preferably 30%~70%；The content of hydroisomerization catalyst is 15%~85%, preferably 30%~70%；Wherein, institute
Stating hydrogenation deoxidation catalyst is one or more of carriers contained selected from aluminium oxide and/or silica-alumina, with or without
The catalyst of one or more of fluorine, boron and phosphorus adjuvant component, the hydroisomerization catalyst are that one or more of be selected from contains
The catalyst of fluorine and/or molecular sieve.
According to the method provided by the invention, wherein the effect of the hydrogenation deoxidation catalyst is by the catalyst
In the presence of hydrogenation reaction, remove raw material in oxygenatedchemicals and alkene.Therefore, wherein the hydrogenation deoxidation catalyst can be with
Selected from one or more of the catalyst that this function arbitrarily may be implemented in the prior art.They can be commercially available commodity
Or it is prepared using any existing method.
It is preferred that the hydrogenation deoxidation catalyst contains the carrier selected from aluminium oxide and/or silica-alumina, it is selected from nickel
And/or the hydrogenation active metal component of cobalt, molybdenum and/or tungsten, with or without adjuvant components one or more of in fluorine, boron and phosphorus
And with or without organic additive, on the basis of catalyst, in terms of oxide, the content of nickel and/or cobalt is 1~5 weight %,
The content of molybdenum and/or tungsten is 12~35 weight %, and one or more of adjuvant components in fluorine, boron and phosphorus based on the element contain
Amount is 0~9 weight %, the molar ratio of the organic additive and the sum of hydrogenation active metal component in terms of oxide is 0~
2。
The organic additive is selected from the organic compound of one or more of oxygen-containing or organic compounds containing nitrogen, preferably
Oxygen-containing organic compound be selected from one or more of Organic Alcohol and organic acid；Preferred organic compounds containing nitrogen is selected from organic
One or more of amine.For example, oxygen-containing organic compound can enumerate ethylene glycol, glycerine, polyethylene glycol, (molecular weight is
200-1500), diethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1,2- cyclohexanediamine tetraacetic acid,
One or more of citric acid, tartaric acid, malic acid, organic compounds containing nitrogen can enumerate ethylenediamine, EDTA and its ammonium salt.
In one preferred embodiment of the invention, the hydrogenation deoxidation catalyst is the disclosed catalysis of CN85104438
Agent is γ-Al2O3Tungsten and nickel oxide and auxiliary agent fluorine are supported, on the basis of catalyst, consisting of: 1~5 weight of nickel oxide
%, 12~35 weight % of tungsten oxide are measured, fluorine is 1~9 weight %, and surplus is γ-Al2O3。
In one preferred embodiment of the invention, the hydrogenation deoxidation catalyst is one kind with silica-alumina
Composition for the catalyst of carrier, with or without auxiliary agent fluorine and/or phosphorus, after the catalyst roasting are as follows: 1~10 weight of nickel oxide
% is measured, the sum of molybdenum oxide and tungsten oxide are greater than 10 weight % to less than to be equal to 50 weight %, 0~10 weight % of auxiliary agent, surplus
For silica-alumina, wherein the molar ratio of tungsten oxide and molybdenum oxide is greater than 2.6 to 30.
The hydrogenation deoxidation catalyst contains selected from oxygen-containing or nitrogenous one or more of organic matter, described organic to add
The molar ratio for adding the sum of object and nickel, molybdenum and tungsten in terms of oxide is 0.03~2.
The oxygen-containing organic compound is selected from one or more of Organic Alcohol, organic acid, and organic compounds containing nitrogen is to have
The molar ratio of the sum of machine amine, the organic additive and nickel, molybdenum and tungsten in terms of oxide is 0.08~1.5.
CN1853780A disclose it is a kind of using silica-alumina as the fluorine-containing of carrier, phosphorus hydrogenation catalyst and its preparation,
Composition after catalyst roasting are as follows: 1~10 weight % of nickel oxide, the sum of molybdenum oxide and tungsten oxide are greater than 10 to 50 weight %,
Fluorine 1-10 weight %, 0.5~8 weight % of phosphorous oxide, surplus is silica-alumina.The catalyst is from including to silica-oxygen
Change the method preparation that alumina supporter introduces fluorine, phosphorus, molybdenum, nickel and tungsten, wherein the dosage of each component makes the composition after catalyst roasting
Are as follows: 1~10 weight % of nickel oxide, the sum of molybdenum oxide and tungsten oxide are greater than 10 to 50 weight %, 1~10 weight % of fluorine, phosphorous oxide
0.5~8 weight %, surplus are silica-alumina.
CN1853779A disclose it is a kind of using silica-alumina as the hydrogenation catalyst of containing fluorin of carrier and its preparation, should
Composition after catalyst roasting are as follows: 1~10 weight % of nickel oxide, the sum of molybdenum oxide and tungsten oxide are greater than 10 to 50 weight %, fluorine 1
~10 weight %, surplus are carrier.The preparation method of the catalyst include to silicaalumina carrier introduce fluorine, molybdenum, nickel and
Tungsten, wherein the dosage of each component make catalyst roast after composition are as follows: 1~10 weight % of nickel oxide, molybdenum oxide and tungsten oxide it
With greater than 10 to 50 weight %, 1~10 weight % of fluorine, surplus is carrier.
CN1853781A disclose it is a kind of using silica-alumina as the hydrogenation catalyst of containing phosphor of carrier and its preparation, should
Composition after catalyst roasting are as follows: 1~10 weight % of nickel oxide, the sum of molybdenum oxide and tungsten oxide are greater than 10 to 50 weight %, oxygen
Change 1~9 weight % of phosphorus, surplus is that the molar ratio of silica-alumina, wherein tungsten oxide and molybdenum oxide is greater than 2.6 to 30.This is urged
The preparation method of agent includes introducing phosphorus, molybdenum, nickel and tungsten to silicaalumina carrier, wherein the dosage of each component makes to be catalyzed
Composition after agent roasting are as follows: 1~10 weight % of nickel oxide, the sum of molybdenum oxide and tungsten oxide are greater than 10 to 50 weight %, phosphorous oxide 1
~9 weight %, surplus are silica-alumina, and the molar ratio of the tungsten oxide and molybdenum oxide is greater than 2.6 to 30.
CN1853781A discloses a kind of using aluminium oxide as the fluorine-containing of carrier, phosphorus hydrogenation catalyst and its preparation, the catalysis
Composition after agent roasting are as follows: 1~10 weight % of nickel oxide, the sum of molybdenum oxide and tungsten oxide are greater than 10 to 50 weight %, phosphorous oxide
0.5~8 weight %, 1~10 weight % of fluorine, surplus is aluminium oxide.The catalyst from include to alumina support introduce fluorine, phosphorus,
Prepared by the method for molybdenum, nickel and tungsten, wherein the dosage of each component makes the composition after catalyst roasting are as follows: 1~10 weight of nickel oxide
% is measured, the sum of molybdenum oxide and tungsten oxide are greater than 10 to 50 weight %, 1~10 weight % of fluorine, 0.5~8 weight % of phosphorous oxide, surplus
For aluminium oxide.
CN1872959A discloses a kind of using aluminium oxide as the hydrogenation catalyst of containing fluorin of carrier and its preparation, catalyst roasting
Composition after burning are as follows: 1~10 weight % of nickel oxide, the sum of molybdenum oxide and tungsten oxide are 10 to 50 weight %, 1~10 weight of fluorine
% is measured, remaining is aluminium oxide.The preparation method of the catalyst includes introducing fluorine, molybdenum, nickel and tungsten to alumina support, wherein each
The dosage of component makes the composition after catalyst roasting are as follows: 1~10 weight % of nickel oxide, the sum of molybdenum oxide and tungsten oxide are 10 to 50
Weight %, 1~10 weight % of fluorine, surplus is aluminium oxide.
CN1872960A discloses a kind of using aluminium oxide as the hydrogenation catalyst of containing phosphor of carrier and its preparation, catalyst roasting
Group after burning becomes nickel oxide 1-10 weight %, and the sum of molybdenum oxide and tungsten oxide are greater than 10 to 50 weight %, phosphorous oxide 1-9 weight
% is measured, surplus is aluminium oxide, wherein in terms of oxide, the molar ratio of tungsten and molybdenum is greater than 2.6 to 30.The catalyst from include to
Phosphorus, molybdenum, nickel and tungsten are introduced in alumina support, wherein the dosage of each component makes the composition after catalyst roasting are as follows: nickel oxide 1
~10 weight %, the sum of molybdenum oxide and tungsten oxide are greater than 10 to 50 weight %, and 1~9 weight % of phosphorous oxide, surplus is aluminium oxide,
Wherein, in terms of oxide, the molar ratio of tungsten and molybdenum is greater than 2.6 to 30.
The catalyst disclosed in CN1853780A, CN1853779A, CN1853781A, CN1872959A and CN1872960A
In, preferably also contain organic additive, wherein the organic matter rubs with the sum of hydrogenation active metal component in terms of oxide
You are than being 0.03~2 preferably 0.08~1.5.These catalyst can be used as the hydrogenation deoxidation catalyst and be used for the present invention.
It is on the books in above patent document about the more detailed preparation method of above-mentioned catalyst, here together using them as this
A part reference of summary of the invention.
According to the method provided by the invention, the effect of the hydroisomerization catalyst be by mild hydrogenation crack, it is different
Normal paraffin component in feedstock oil is converted to the low isoparaffin of the degree of branching by structureization reaction.Therefore, the hydroisomerizing catalysis
Agent can be selected from one or more of the catalyst that this function arbitrarily may be implemented in the prior art.They can be commercially available
Commodity or using any existing method prepare.
In one preferred embodiment of the invention, the carrier of the hydroisomerization catalyst is aluminium oxide and/or oxygen
SiClx-aluminium oxide, hydrogenation active metal component is selected from one or more of nickel, cobalt, molybdenum, tungsten, containing fluorine adjuvant component, and
With or without organic additive, on the basis of catalyst, the content of nickel and/or cobalt in terms of oxide is 1~5 weight %, molybdenum
And/or the content of tungsten is 12~35 weight %, the content of fluorine adjuvant component based on the element is 0.1~12 weight %, described to have
The molar ratio of machine additive and the sum of hydrogenation active metal component in terms of oxide is 0~2.
The hydroisomerization catalyst contains selected from oxygen-containing or nitrogenous one or more of organic matter, the organic matter
Molar ratio with the sum of hydrogenation active metal component in terms of oxide is 0.03-2.It is preferred that the oxygen-containing organic compound is selected from
One or more of Organic Alcohol, organic acid, organic compounds containing nitrogen are organic amine, the organic matter and adding in terms of oxide
The molar ratio of the sum of hydrogen activity metal component is 0.08-1.5.
In presently preferred embodiment, contain molecular sieve in the carrier of the hydroisomerization catalyst,
Remaining is aluminium oxide and/or silica-alumina, and hydrogenation active metal component is selected from one or more of nickel, cobalt, molybdenum, tungsten,
With or without adjuvant components one or more of in fluorine, boron and phosphorus, and with or without organic additive, using catalyst as base
Standard, the content of nickel and/or cobalt in terms of oxide are 1~5 weight %, and the content of molybdenum and/or tungsten is 12~35 weight %, with member
The content of one or more of adjuvant components in fluorine, boron and phosphorus of element meter is 0~9 weight %, the organic additive with
The molar ratio of the sum of the hydrogenation active metal component of oxide meter is 0~2.The molecular sieve is selected from zeolite or means of nonzeolitic point
The molecular sieve that one or more of son sieve, preferably bore dia are 0.6-0.8 nanometers, such as selected from L zeolite, y-type zeolite, X-type boiling
One or more of stone, Beta zeolite, modenite, ZSM-3, ZSM-4, ZSM-5, ZSM-18, ZSM-20, SAPO-5, into
One step is preferably Y type molecular sieve, is more highly preferred to the Y type molecular sieve through hydrothermal method super stabilizing.They can be commercially available commodity
Or it is prepared using any existing method.
The hydroisomerization catalyst contains selected from oxygen-containing or nitrogenous one or more of organic matter, the organic matter
Molar ratio with the sum of hydrogenation active metal component in terms of oxide is 0.03~2.The oxygen-containing organic compound, which is selected from, to be had
One or more of machine alcohol, organic acid, organic compounds containing nitrogen are organic amine, the organic matter and in terms of oxide plus hydrogen
The molar ratio of the sum of active metal component is 0.08~1.5.
For example, hydrotreating catalyst disclosed in CN1056514A, which hydrolyzed by alkyl aluminum or aluminum alkoxide
The load that high-temperature roasting obtains after a diaspore of the purity made of method greater than 65 weight %, the zeolite mixing exchanged with through cation
Body, fluorine auxiliary agent and nickel, tungsten active constituent are constituted, each component content (on the basis of catalyst, weight %) are as follows: and fluorine 0.5%~
5.0%, nickel oxide 2.5%~6.0%, tungsten oxide 10%~32%, remaining is carrier.
Hydrotreating catalyst disclosed in CN1872962A, the catalyst contain a kind of carrier containing molecular sieve, nickel, molybdenum and
Tungsten, the composition after roasting are as follows: 1~10 weight % of nickel oxide, the sum of molybdenum oxide and tungsten oxide are greater than 10 to less than are equal to 50 weights
% is measured, surplus is carrier.
Hydrocracking catalyst composition disclosed in CN1854261A, the composition is by a kind of acid sial, a effective amount of
At least one group VIII and the metal component and organic additive of at least one group VIB composition, organic matter therein are selected from
The molar ratio of oxygen-containing or nitrogenous one or more of organic matter, organic matter and group VIII metal component is 0.01-10.
Hydrocracking catalyst composition zeolite-containing disclosed in CN1854262A, the composition is by zeolite molecular sieve and oxygen
Change the metal component and organic additive group of the carrier loaded at least one group VIII of aluminium composite molding and at least one group VIB
At the organic matter is selected from oxygen-containing or nitrogenous one or more of organic matter, on the basis of the composition, zeolite molecules
Sieve content is 3~60 weight %, and the content of aluminium oxide is 10~80 weight %, and the content of group VIII metal is in terms of oxide
1~15 weight %, the content of vib metals are 5~40 weight %, and organic additive is 0.1~40 weight %.
These catalyst can be used as the hydroisomerization catalyst and be used for the present invention.About the more detailed of above-mentioned catalyst
Preparation method, it is on the books in above patent document, here together using they as the content of present invention a part quote.
Hydrogenation protecting catalyst is loaded, with volume in the top of the hydrogenation deoxidation catalyst in hydrotreating reaction area
It counts and on the basis of the hydrogenation deoxidation catalyst, the content of hydrogenation protecting catalyst is greater than 0 to less than to be equal to 80%, described
Hydrogenation protecting catalyst contains carrier, the hydrogenation active metal component selected from nickel and/or cobalt, molybdenum and/or tungsten, wherein described to add
The content of the hydrogenation active metal component of hydrogen guard catalyst is the content of the hydrogenation active metal component of hydrogenation deoxidation catalyst
10~30%.
Hydrotreating reaction condition are as follows: hydrogen partial pressure 1.0MPa~25MPa, preferably 3.0MPa~20MPa, reaction temperature are
150 DEG C~400 DEG C, preferably 180 DEG C~350 DEG C, volume space velocity 0.3h-1~8.0h-1, preferably 0.5h-1~5.0h-1, hydrogen oil volume
Than being 100~3000, preferably 200~1500.
It is 100% by the sum of n-alkane and isoparaffin mass fraction in the hydrogenation products in hydrotreating reaction area,
Wherein isoparaffin mass fraction is 15%-50%.The present invention, which uses, carries out either shallow isomerization in hydrotreating reaction area, mitigates
The reaction load of isomerization-visbreaking reaction zone, it is therefore prevented that n-alkane can reduce purpose in the overcracking of isomerization-visbreaking
Product yield is effectively increased while product freezing point.
In isomerization reaction, if the acidity of catalyst is strong, reaction can be made to carry out to cracking direction, lead to isomery
Change selectivity decline, purpose product yield is caused to decline.Due to generating water after the hydrogenated deoxidation of raw material, the presence of water is different to hydrogen is added
Acid centre on structure catalyst has certain adjustment effect.Pass through hydrogenation deoxidation catalyst and hydroisomerization catalyst
Grading loading, the water that hydrogenation deoxidation process generates can reduce the acid strength and sour density of hydroisomerization catalyst, make reaction to having
Conducive to the progress of isomerization reaction direction.
In hydroisomerizing pour point depression reaction zone of the invention, the hydroisomerizing pour point depression catalyst contain metal active ingredient and
Mesoporous molecular sieve, the metal active ingredient are selected from least one of nickel, platinum and palladium, in terms of simple substance, and total with catalyst
On the basis of weight, the content of the group VIII metal component is 0.01-10 weight %, and the medium-pore molecular is screened from ZSM-
5, one or more of ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-38, SAPO-11 and SAPO-41.With
Metal meter and on the basis of catalyst, the content of the group VIII metal is preferably 0.1-10 weight %, more preferably 0.1-5
Weight %.
The hydroisomerizing pour point depression reaction condition are as follows: hydrogen partial pressure 1.0MPa~20MPa, preferably 4.0MPa~18MPa, reaction
Temperature be 230 DEG C~400 DEG C, preferably 250 DEG C~380 DEG C, volume space velocity 0.3h-1~4.0h-1, preferably 0.5h-1~2.0h-1, hydrogen
Oil volume ratio is 100~3000, preferably 200~1000.
In hydrofining reaction area of the invention, the Hydrobon catalyst contains carrier and is supported on adding on carrier
Hydrogen activity ingredient, on the basis of the total amount of the Hydrobon catalyst, the content of the hydrogenation activity ingredient is 0.01~15
Weight %, the content of the carrier are 85~99.99 weight %, the hydrogenation activity ingredient be selected from noble metal or noble metal with
Mo, Co, Ni, W, V and Zn are any one or more of, and the noble metal is Pt and/or Pd.
The carrier is poriness silicon oxide-aluminium oxide, and in terms of poriness silicon oxide-aluminium oxide, the content of silica
For 1~40 weight %, for the content of alkali metal less than 1 weight %, BET specific surface area is 150~350 meters squared per grams, Kong Rongwei
0.15~1.5 cubic metre/gram, k value are 1~15, k=B/MSiO2, wherein k is the corresponding oxidation of unit mole oxygen SiClx introduction volume
Silicon-aluminium oxide B acid amount, B are the B acid amount of silica-alumina, MSiO2For silica mole point in silica-alumina
Number.
The hydrofining reaction condition are as follows: hydrogen partial pressure 1.0MPa~20MPa, preferably 4.0MPa~18MPa reaction temperature
It is 120 DEG C~380 DEG C, preferably 150 DEG C~350 DEG C, volume space velocity 0.3h-1~3.0h-1, preferably 0.5h-1~1.5h-1, hydrogen oil body
Product is than being 100~3000, preferably 200~1000.
The hydrofining reaction product, then separated, be fractionated after obtain jet fuel.Cut point can be obtained according to required
The standard of jet fuel determine, it is specifically known to those skilled in the art.
Advantages of the present invention:
The present invention can produce good jet fuel and good solvent naphtha with renewable raw materials, and jet fuel is received
Rate is higher, and freezing point is lower；Compared with prior art, in the case where obtaining same freezing point jet fuel, the present invention is obtained
The high income of jet fuel.
Specific embodiment
Below by embodiment, the invention will be further described, but not thereby limiting the invention.
In embodiment and comparative example:
1. catalyst used in hydrotreating reaction area:
The hydrogenation protecting catalyst is not particularly limited in the present invention, they can be commercially available commodity or use
Arbitrary prior art preparation.The preparation side of catalyst disclosed in CN1344781A, CN1966616A and CN101134173A
Method just can be used to prepare meet the present invention claims catalyst.Such as hydrogenation protecting catalyst described in CN1344781A embodiment 1
5.1 weight % of molybdenum oxide, 1.2 weight % of nickel oxide, surplus are heat resistant inorganic alumina support.
Hydrogenation deoxidation catalyst is prepared according to CN85104438A published method, consisting of: 3 weight % of nickel oxide, oxidation
25 weight % of tungsten, fluorine are weight 4%, and surplus is γ-Al2O3。
Hydroisomerization catalyst is catalyst C-4 disclosed in CN1854262A, consisting of: 3.1 weight % of nickel oxide, oxygen
Change 24.3 weight % of tungsten, 5 weight % of molybdenum oxide, 16.1 weight % of citric acid, surplus is carrier.Carrier is by aluminium oxide and ZSM-5
Molecular sieve, beta molecular sieve are constituted, wherein 40 weight % of alumina content, 30 weight %, beta molecular sieve 30 of ZSM-5 molecular sieve
Weight %.
2. catalyst used in hydroisomerizing pour point depression reaction zone:
Hydroisomerizing pour point depression catalyst is to be carried on according to prepared by the example 7 in CN1382526A by active component of platinum
Catalyst on SAPO-11 molecular sieve/alumina support, wherein the content of platinum is 1.0 weights on the basis of catalyst total amount
% is measured, remaining is carrier, and on the basis of carrier, the content of SAPO-11 molecular sieve is 58.4 weight %, aluminium oxide in the carrier
40.6 weight %.
3. the catalyst that hydrofining reaction area uses
Hydrobon catalyst is prepared according to the example 19 in CN1510112A, wherein the content of platinum is 0.12 weight
% is measured, the content of palladium metal is 0.23 weight %.
Feedstock oil is shown in Table 1.
1 raw material oil nature of table
| Project | Palm oil | Lard |
| Iodine number | 51.9 | 63.2 |
| Density (20 DEG C)/(g/cm3) | 0.9151 | 0.9232 |
| Fatty acid composition, weight % | ||
| C8 | / | / |
| C10 | / | / |
| C12 | / | / |
| C14 | 1.0 | 2 |
| C16 | 45.3 | 26 |
| C18 | 53.6 | 71.5 |
| C20 | 0.1 | 0.5 |
Embodiment 1
Feedstock oil uses palm oil, and property is shown in Table 1, wherein by volume, the total amount of hydrotreating reaction area catalyst
On the basis of, the dosage of hydrogenation protecting catalyst is 30%, and the dosage of hydrogenation deoxidation catalyst is 50%, hydroisomerization catalyst
Dosage is 20%.
Hydrogenation conditions are shown in Table 2, and product distribution and property are shown in Table 3.
Embodiment 2
Feedstock oil uses lard, and property is shown in Table 1, and reaction step is shown in Table respectively with embodiment 1, reaction condition and product distribution
2 with table 3.
Embodiment 3~5
Feedstock oil and reaction condition are the same as embodiment 1.
In embodiment 3 on the basis of hydrotreating reaction area catalyst total amount, the volume fraction of hydrogenation protecting catalyst is
15%, the volume fraction of hydrogenation deoxidation catalyst is 55%, and the volume fraction of hydroisomerization catalyst is 30%；
In embodiment 4 on the basis of hydrotreating reaction area catalyst total amount, the volume fraction of hydrogenation protecting catalyst is
40%, the volume fraction of hydrogenation deoxidation catalyst is 45%, and the volume fraction of hydroisomerization catalyst is 15%；
In embodiment 5 in hydrotreating reaction area, hydrogenation deoxidation catalyst is the preparation of CN1853781A example 2, nickel oxide
3.3 weight %, 23.5 weight % of tungsten oxide, 4.5 weight % of molybdenum oxide, 2.1 weight % of phosphorous oxide, remaining is alumina support.
Hydroisomerization catalyst uses the preparation of example 10 in CN1056514A, wherein 2.7 weight % of nickel oxide, 27.7 weight of tungsten oxide
%, 1.4 weight % of fluorine are measured, 7 weight % of Y molecular sieve content in carrier, remaining is aluminium oxide.With hydrotreating reaction area catalyst
Total amount is that the volume fraction of benchmark hydrogenation protecting catalyst is 30%, and the volume fraction of hydrogenation deoxidation catalyst is 50%, adds hydrogen
The volume fraction of heterogeneous catalyst is 20%.
Reaction condition and product distribution are shown in Table 2 and table 3 respectively.
Comparative example 1
Feedstock oil loads Hydrobon catalyst, discloses according to CN1085934A with embodiment 1, hydrotreating reaction area
Method preparation, consisting of: 1 weight % of magnesia, 4 weight % of nickel oxide, 29 weight % of tungsten oxide and remainder alumina.Add hydrogen
Isomerization-visbreaking catalyst and Hydrobon catalyst are the same as embodiment 1.
Reaction condition and product distribution are shown in Table 2 and table 3 respectively.
2 hydrogenation conditions of table
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 | |
| Hydrotreating zone | ||||||
| Hydrogen partial pressure/MPa | 6.0 | 12.0 | 6.0 | 6.0 | 6.0 | 6.0 |
| Reaction temperature/DEG C | 320 | 340 | 320 | 320 | 320 | 320 |
| Volume space velocity/h-1 | 1.0 | 0.8 | 1.0 | 1.0 | 1.0 | 1.0 |
| Hydrogen to oil volume ratio | 1000 | 1200 | 1000 | 1000 | 1000 | 1000 |
| Hydroisomerizing pour point depression area | ||||||
| Hydrogen partial pressure/MPa | 10.0 | 6.0 | 10.0 | 10.0 | 10.0 | 10.0 |
| Reaction temperature/DEG C | 330 | 320 | 330 | 330 | 330 | 340 |
| Volume space velocity/h-1 | 1.0 | 0.8 | 1.0 | 1.0 | 1.0 | 0.5 |
| Hydrogen to oil volume ratio | 600 | 800 | 600 | 600 | 600 | 600 |
| Hydrofinishing district | ||||||
| Hydrogen partial pressure/MPa | 10.0 | 6.0 | 10.0 | 10.0 | 10.0 | 10.0 |
| Reaction temperature/DEG C | 200 | 220 | 200 | 200 | 200 | 200 |
| Volume space velocity/h-1 | 1.0 | 1.2 | 1.0 | 1.0 | 1.0 | 1.0 |
| Hydrogen to oil volume ratio | 600 | 800 | 600 | 600 | 600 | 600 |
3 hydrotreating reaction area product property of table
4 product distribution of table and product property
From above-described embodiment in terms of comparative example, using method provided by the invention, either shallow is carried out in hydrotreating reaction area
Isomery, and the hydrotreating reaction area of comparative example only carries out hydrogenation deoxidation reaction, purpose product jet is fired in the embodiment of the present invention
The yield of material is apparently higher than the yield of jet fuel in comparative example, 20 percentage points high, while embodiment obtains jet fuel
Freezing point is relatively low.
Claims (25)
1. a kind of method for preparing jet fuel with renewable raw materials, comprising:
(1) in hydrotreating reaction area, at hydrotreating reaction conditions, the mixing of vegetable oil and/or animal fat and hydrogen
Object, which is successively contacted with hydrogenation deoxidation catalyst and hydroisomerization catalyst, to be reacted, and hydrotreating reaction product, institute are obtained
Stating hydrotreating reaction product is C8-C24Alkane, the sum of n-alkane and isoparaffin mass fraction are 100%, while different
Structure alkane mass fraction is more than or equal to 15%；
(2) in hydroisomerizing pour point depression reaction zone, under hydroisomerizing pour point depression reaction condition, hydrotreating reaction obtained by step (1)
Product and hydrogen are contacted with hydroisomerizing pour point depression catalyst together to be reacted, and hydroisomerizing pour point depression reaction product is obtained,
(3) in hydrofining reaction area, under the conditions of hydrofining reaction, the reaction of hydroisomerizing pour point depression obtained by step (2) is generated
Object and hydrogen are contacted with Hydrobon catalyst together to be reacted, and hydrofining reaction product is obtained, then after separation
To jet fuel.
2. according to the method for claim 1, which is characterized in that in hydrotreating reaction area, the hydrogenation deoxidation catalyst
It carries out successively layering according to the flow direction of reactant with hydroisomerization catalyst to load, by volume and with the total amount of the catalyst
On the basis of, the content of hydrogenation deoxidation catalyst is 15~85%, and the content of hydroisomerization catalyst is 15~85%, wherein described
Hydrogenation deoxidation catalyst is one or more of containing the carriers selected from aluminium oxide and/or silica-alumina, with or without fluorine,
The catalyst of one or more of boron and phosphorus adjuvant component, the hydroisomerization catalyst are one or more of selected from fluorine-containing
And/or the catalyst of molecular sieve.
3. method according to claim 1 or 2, which is characterized in that the hydrogenation deoxidation catalyst contains selected from aluminium oxide
And/or the carrier of silica-alumina, the hydrogenation active metal component selected from nickel and/or cobalt and molybdenum and/or tungsten, contain or not
Containing adjuvant components one or more of in fluorine, boron and phosphorus and with or without organic additive, on the basis of catalyst, with oxygen
The content of compound meter, nickel and/or cobalt is 1~5 weight %, and the content of molybdenum and/or tungsten is 12~35 weight %, choosing based on the element
The content of one or more of adjuvant components is 0~9 weight % from fluorine, boron and phosphorus, the organic additive in terms of oxide
The molar ratio of the sum of hydrogenation active metal component be 0~2.
4. according to the method for claim 1, which is characterized in that the hydrogenation deoxidation catalyst is by γ-Al2O3Support tungsten and
Nickel oxide and auxiliary agent fluorine, composition: 1~5 weight % of nickel oxide, 12~35 weight % of tungsten oxide, fluorine is 3~10 weight %, remaining
Amount is γ-Al2O3。
5. according to the method for claim 1, which is characterized in that the hydrogenation deoxidation catalyst is one kind with silica-oxygen
Change the catalyst that aluminium is carrier, the composition with or without auxiliary agent fluorine and/or phosphorus, after the catalyst roasting are as follows: nickel oxide 1~
10 weight %, the sum of molybdenum oxide and tungsten oxide are greater than 10 weight % to less than to be equal to 50 weight %, 0~10 weight % of auxiliary agent, surplus
For silica-alumina, wherein the molar ratio of tungsten oxide and molybdenum oxide is greater than 2.6 to less than equal to 30.
6. according to the method for claim 5, which is characterized in that the hydrogenation deoxidation catalyst contains selected from oxygen-containing or nitrogenous
One or more of organic matter, the molar ratio of the organic matter and the sum of nickel, molybdenum and tungsten in terms of oxide is 0.03~
2。
7. according to the method for claim 6, which is characterized in that the oxygen-bearing organic matter is in Organic Alcohol, organic acid
One or more, itrogenous organic substance are organic amine, and the molar ratio of the organic matter and the sum of nickel, molybdenum and tungsten in terms of oxide is
0.08~1.5.
8. method according to claim 1 or 2, which is characterized in that the carrier of the hydroisomerization catalyst is aluminium oxide
And/or silica-alumina, hydrogenation active metal component are selected from one or more of nickel, cobalt, molybdenum, tungsten, contain fluorine auxiliary agent group
Point, and with or without organic matter, on the basis of catalyst, the content of nickel and/or cobalt in terms of oxide is 1~5 weight %,
The content of molybdenum and/or tungsten is 12~35 weight %, and the content of fluorine adjuvant component based on the element is 0.1~12 weight %, described to have
The molar ratio of machine object and the sum of hydrogenation active metal component in terms of oxide is 0~2.
9. according to the method for claim 8, which is characterized in that the hydroisomerization catalyst contains selected from oxygen-containing or nitrogenous
One or more of organic matter, the organic matter and the molar ratio of the sum of hydrogenation active metal component in terms of oxide are
0.03~2.
10. according to the method for claim 9, which is characterized in that the oxygen-bearing organic matter is in Organic Alcohol, organic acid
One or more, itrogenous organic substance are organic amine, the organic matter and the sum of hydrogenation active metal component in terms of oxide
Molar ratio is 0.08~1.5.
11. method according to claim 1 or 2, which is characterized in that contain in the carrier of the hydroisomerization catalyst and divide
Son sieve, remaining be aluminium oxide and/or silica-alumina, hydrogenation active metal component be selected from one of nickel, cobalt, molybdenum, tungsten or
It is several, with or without adjuvant components one or more of in fluorine, boron and phosphorus, and with or without organic matter, be with catalyst
Benchmark, the content of nickel and/or cobalt in terms of oxide are 1~5 weight %, and the content of molybdenum and/or tungsten is 12~35 weight %, with member
The content of one or more of adjuvant components in fluorine, boron and phosphorus of element meter is 0~9 weight %, the organic matter with oxidation
The molar ratio of the sum of the hydrogenation active metal component of object meter is 0~2.
12. according to the method for claim 11, which is characterized in that the hydroisomerization catalyst contains selected from oxygen-containing or contain
The molar ratio of the sum of one or more of organic matter of nitrogen, the organic matter and the hydrogenation active metal component in terms of oxide
It is 0.03~2.
13. according to the method for claim 12, which is characterized in that the oxygen-bearing organic matter is in Organic Alcohol, organic acid
One or more, itrogenous organic substance is organic amine, the organic matter and the sum of hydrogenation active metal component in terms of oxide
Molar ratio be 0.08~1.5.
14. according to the method for claim 1, which is characterized in that the hydroisomerization catalyst is by alkyl aluminum or alkoxy
High-temperature roasting obtains after the molecular sieve mixing that a diaspore of the purity made of aluminum water solution greater than 65 weight % is exchanged with through cation
The carrier, fluorine auxiliary agent and the nickel that arrive, tungsten active component are constituted, on the basis of catalyst, composition are as follows: 0.5~5.0 weight % of fluorine, oxygen
Change 2.5~6.0 weight % of nickel, 10~32 weight % of tungsten oxide, surplus is carrier.
15. according to the method for claim 1, which is characterized in that the hydroisomerization catalyst is containing at least one point
The catalyst of carrier loaded nickel, molybdenum and tungsten that son sieves, the composition after roasting are as follows: 1~10 weight % of nickel oxide, molybdenum oxide and oxygen
Change the sum of tungsten to be greater than 10 weight to less than be equal to 50 weight %, surplus is carrier.
16. according to the method for claim 1, which is characterized in that hydrotreating reaction condition are as follows: hydrogen partial pressure 1.0MPa ~
25MPa, reaction temperature are 150 DEG C ~ 400 DEG C, 0.3 h of volume space velocity-1~8.0h-1, hydrogen to oil volume ratio is 100 ~ 3000.
17. according to the method for claim 1, which is characterized in that in the hydrotreating reaction product, isomeric alkane hydrocarbonaceous
Measuring score is 15%~50%.
18. according to the method for claim 1, which is characterized in that the hydroisomerizing pour point depression catalyst contains metal active
Ingredient and mesoporous molecular sieve, the metal active ingredient are selected from least one of nickel, platinum and palladium, in terms of simple substance, and to urge
On the basis of agent total weight, the content of the metal active ingredient is 0.01~10 weight %, the medium-pore molecular screened from
One of ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-38, SAPO-11 and SAPO-41 or several
Kind.
19. according to the method for claim 1, which is characterized in that hydroisomerizing pour point depression reaction condition are as follows: hydrogen partial pressure 1.0MPa
~ 20MPa, reaction temperature are 230 DEG C ~ 400 DEG C, 0.3 h of volume space velocity-1~4.0h-1, hydrogen to oil volume ratio is 100 ~ 3000.
20. according to the method for claim 1, which is characterized in that the Hydrobon catalyst contains carrier and is supported on
Hydrogenation activity ingredient on carrier, on the basis of the total amount of the Hydrobon catalyst, the content of the hydrogenation activity ingredient
For 0.01~15 weight %, the content of the carrier is 85~99.99 weight %, the hydrogenation activity ingredient be selected from noble metal or
Noble metal is any one or more of with Mo, Co, Ni, W, V and Zn, and the noble metal is Pt and/or Pd.
21. according to the method for claim 20, which is characterized in that the carrier is poriness silicon oxide-aluminium oxide, and with
The content of poriness silicon oxide-aluminium oxide meter, silica is 1~40 weight %, and the content of alkali metal compares table less than 1 weight %, BET
Area is 150~350 meters squared per grams, and 0.15~1.5 cubic metre/gram of Kong Rongwei, k value is 1~15, k=B/MSiO2, wherein k
The B acid amount of silica-alumina is corresponded to for unit mole oxygen SiClx introduction volume, B is the B acid amount of silica-alumina, MSiO2
For silica molar fraction in silica-alumina.
22. according to the method for claim 1, which is characterized in that the hydrofining reaction condition are as follows: hydrogen partial pressure 1.0MPa
~ 20MPa, reaction temperature are 120 DEG C ~ 380 DEG C, 0.3 h of volume space velocity-1~3.0h-1, hydrogen to oil volume ratio is 100 ~ 3000.
23. according to the method for claim 22, which is characterized in that in the hydrofining reaction condition: volume space velocity 0.5
h-1~1.5h-1。
24. method according to claim 1 or 2, which is characterized in that in hydrotreating reaction area, in the hydrogenation deoxidation
Hydrogenation protecting catalyst, by volume and on the basis of the hydrogenation deoxidation catalyst, hydrogenation protecting are loaded in the top of catalyst
The content of catalyst is greater than 0 to less than to be equal to 80%, the hydrogenation protecting catalyst contain carrier, selected from nickel and/or cobalt, with
And the hydrogenation active metal component of molybdenum and/or tungsten, wherein the content of the hydrogenation active metal component of the hydrogenation protecting catalyst
For the 10-30% of the content of the hydrogenation active metal component of hydrogenation deoxidation catalyst.
25. according to the method for claim 1, which is characterized in that the vegetable oil and/or animal fat be it is any containing
The raw material and vegetable oil and/or animal fat of glyceride and free fatty acid pass through the fatty acid methyl of ester exchange method preparation
Ester or fatty-acid ethyl ester.
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| US20110315598A1 (en) * | 2010-06-29 | 2011-12-29 | Chevron U.S.A. Inc | CATALYTIC PROCESSES AND SYSTEMS FOR BASE OIL PRODUCTION USING ZEOLITE SSZ-32x |
| CN102942958A (en) * | 2012-11-12 | 2013-02-27 | 大连理工大学 | Long chain paraffin hydrogenation heterogeneous condensation freezing point depressing method and catalyst thereof |
| CN103059900A (en) * | 2011-10-19 | 2013-04-24 | 中国石油化工股份有限公司 | Preparation method of jet fuel |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110315598A1 (en) * | 2010-06-29 | 2011-12-29 | Chevron U.S.A. Inc | CATALYTIC PROCESSES AND SYSTEMS FOR BASE OIL PRODUCTION USING ZEOLITE SSZ-32x |
| CN103059900A (en) * | 2011-10-19 | 2013-04-24 | 中国石油化工股份有限公司 | Preparation method of jet fuel |
| CN102942958A (en) * | 2012-11-12 | 2013-02-27 | 大连理工大学 | Long chain paraffin hydrogenation heterogeneous condensation freezing point depressing method and catalyst thereof |
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