CN107200722A - A kind of preparation method of aviation fuel production raw material and aviation fuel - Google Patents

A kind of preparation method of aviation fuel production raw material and aviation fuel Download PDF

Info

Publication number
CN107200722A
CN107200722A CN201610157216.8A CN201610157216A CN107200722A CN 107200722 A CN107200722 A CN 107200722A CN 201610157216 A CN201610157216 A CN 201610157216A CN 107200722 A CN107200722 A CN 107200722A
Authority
CN
China
Prior art keywords
reaction
acid catalyst
aviation fuel
acid
alcohol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201610157216.8A
Other languages
Chinese (zh)
Other versions
CN107200722B (en
Inventor
郭勇
王艳芹
丁大千
李春锐
夏启能
刘晓晖
张永光
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Original Assignee
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Research Institute of Petroleum Processing, China Petroleum and Chemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to CN201610157216.8A priority Critical patent/CN107200722B/en
Publication of CN107200722A publication Critical patent/CN107200722A/en
Application granted granted Critical
Publication of CN107200722B publication Critical patent/CN107200722B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
    • C07D307/48—Furfural
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/22—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by reduction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C59/185—Saturated compounds having only one carboxyl group and containing keto groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
    • C07C69/716—Esters of keto-carboxylic acids or aldehydo-carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C9/00—Aliphatic saturated hydrocarbons
    • C07C9/14—Aliphatic saturated hydrocarbons with five to fifteen carbon atoms
    • C07C9/15—Straight-chain hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C9/00—Aliphatic saturated hydrocarbons
    • C07C9/14—Aliphatic saturated hydrocarbons with five to fifteen carbon atoms
    • C07C9/16—Branched-chain hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C9/00—Aliphatic saturated hydrocarbons
    • C07C9/22—Aliphatic saturated hydrocarbons with more than fifteen carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/16—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
    • C07D307/48—Furfural
    • C07D307/50—Preparation from natural products
    • 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
    • C10G3/47—Catalytic treatment characterised by the catalyst used containing platinum group 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Field is converted the present invention relates to biomass catalyzing, the preparation method of a kind of aviation fuel production raw material and aviation fuel is disclosed.Wherein, preparing the method for aviation fuel production raw material includes：In the presence of the water-soluble inorganic salt that alcohol, acid catalyst, reaction medium and selectivity are used, sugar source is carried out molecule inner dewatering reaction, obtain being dissolved with the organic phase of R Furnan products and levulic acid esters compound, the alcohol is C1‑6Monohydric alcohol, reaction medium is the mixture of water and non-alcohols organic solvent.In addition, the method disclosed by the invention for preparing aviation fuel includes：The organic phase for being dissolved with R Furnan products and levulic acid esters compound is prepared according to the method described above；The organic phase is subjected to aldol reaction；The product after aldol reaction is taken to carry out deoxidation hydrogenation reaction.By above-mentioned technical proposal, the present invention can prepare aviation fuel based on upright connect of protist, be advantageously implemented sustainable development.

Description

A kind of preparation method of aviation fuel production raw material and aviation fuel
Technical field
The present invention relates to biomass catalyzing convert field, in particular it relates to one kind prepare aviation fuel production raw material and The preparation method of aviation fuel.
Background technology
With the growth of World Economics, fossil fuel resource, especially oil become worsening shortages, and bring more Come more serious environment and social concern.Therefore, prepare synthetic fuel from the biomass energy that can be regenerated and become more meticulous The correlative study of product turns into one of focus that domestic and international scientific worker pays close attention to.The biological aviation synthesized from renewable biomass Fuel, structure is similar to traditional aviation fuel, it is not necessary to change oil burning installation and engine system, and more environmental protection and economy, Help to realize Green Sustainable and the carbon cycle of aircraft industry.
At present, the bio-aviation fuel production technology route of more maturation has the hydro-conversion and biology of natural plant grease The Fischer-Tropsch Synthesis of matter, You Duojia oil companies carrying out the research and development of the process units of this type.But natural plants The source that grease limits raw material causes the cost of fuel to raise, and the Fischer-Tropsch Synthesis of biomass needs to first pass through the oxygen of gas phase one Change the conversion of carbon and hydrogen, it is higher to the cost requirement of process units.Biomass compound is carried out to extensive in pure liquid phase Reaction require expedited the emergence of important synthetic method another kind of in recent years, the i.e. carbon of biomass platform small molecule in the liquid phase Chain propagation reaction, using the biomass platform chemicals for containing furan nucleus as part material, is alkylated instead by acid catalyzed Should or base catalysis aldol condensation, produce long-chain the unsaturated alkane compound containing furan nucleus, be hydrogenated with eventually through deoxidation Obtain saturation long chain alkane fuel (such as CN103450940A, CN104119943A, CN103805224A and CN 102850157A Deng).However, such method requirement uses the compound for containing aldehyde radical or ketone group as another condensation raw material, such as formaldehyde, second Aldehyde, butyraldehyde, acetone, acetylacetone,2,4-pentanedione, 4-methyl-2 pentanone etc., and these raw materials typically can not be produced directly from protist matter And must be converted via fossil feedstock, so as to limit the application of such method and the further reduction of cost.
CN104650947A discloses a kind of using 5 hydroxymethyl furfural and levulinate or from a series of structure phases Like functional group's identical compound, through NaOH base catalyzed condensations produce oxygen-containing long chain alkane compound and hydrogenation deoxidation technique and Method.However, it is not directed to by protist matter directly while preparing these sugared platform chemicals.
The content of the invention
The purpose of the present invention is to overcome that directly aviation fuel can not be prepared not from protist matter in the prior art There is provided a kind of method for preparing aviation fuel production raw material based on protist matter and directly preparing aviation fuel for foot.
It was found by the inventors of the present invention that by using alcohol and two phase reaction medium, directly can be converted from protist matter R- Furnan products (such as furfural and 5 hydroxymethyl furfural) and levulic acid or levulinate are obtained, so as to realize raw material Pure protist matter sourceization.Therefore, to achieve these goals, aviation fuel production use is prepared the invention provides one kind The method of raw material, this method includes：The presence of the water-soluble inorganic salt used in alcohol, acid catalyst, reaction medium and selectivity Under, sugar source is carried out molecule inner dewatering reaction, obtain being dissolved with the organic phase of compound shown in Formulas I and Formula II,
Wherein, the alcohol is C1-6Monohydric alcohol, the reaction medium is the mixture of water and non-alcohols organic solvent；R1 For-H ,-CH2OH、-CH2OCH3、-CH2OCH2CH3、-CH2OC3H7、-CH2OC4H9、-CH2OC5H11Or-CH2OC6H13；R2For-H or C1-6Alkyl.
In addition, present invention also offers a kind of method for preparing aviation fuel, this method comprises the following steps：
A, the organic phase for being dissolved with compound shown in Formulas I and Formula II is prepared according to the method described above；
B, the organic phase progress aldol reaction that compound shown in Formulas I and Formula II will be dissolved with；
C, take the product after aldol reaction carry out deoxidation hydrogenation reaction.
By above-mentioned technical proposal, the present invention can prepare aviation fuel based on upright connect of protist, and can not draw Enter other ketone or aldehyde, therefore, method of the invention is more beneficial for realizing sustainable development, is worthy of popularization.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points and any value of disclosed scope are not limited to the accurate scope or value herein, these scopes or Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more New number range, these number ranges should be considered as specific open herein.
In the present invention, in the case where not making opposite explanation, the term " aviation fuel " used refers to containing long alkane Hydrocarbon is as the fuel of primary combustion composition, and " long chain alkane " refers to the chain alkane that carbon number (is particularly 9-20) more than 9.
The method that what the present invention was provided prepare aviation fuel production raw material includes：Alcohol, acid catalyst, reaction medium and In the presence of the water-soluble inorganic salt that selectivity is used, sugar source is carried out molecule inner dewatering reaction, obtain being dissolved with Formulas I and Formula II The organic phase of shown compound,
Wherein, the alcohol is C1-6Monohydric alcohol, the reaction medium is the mixture of water and non-alcohols organic solvent；R1 For-H ,-CH2OH、-CH2OCH3、-CH2OCH2CH3、-CH2OC3H7(such as-CH2O(CH2)2CH3Or-CH2OCH(CH3)2)、- CH2OC4H9(such as-CH2O(CH2)3CH3Or-CH2OCH2CH(CH3)2)、-CH2OC5H11(such as-CH2O(CH2)4CH3) or-CH2OC6H13 (such as-CH2O(CH2)4CH3)；R2For-H or C1-6Alkyl.Wherein, C1-6Alkyl be preferably-CH3、-CH2CH3、-C3H7(as- (CH2)2CH3Or-CH (CH3)2)、-C4H9(such as-(CH2)3CH3Or-CH2CH(CH3)2)、-C5H11(such as-(CH2)4CH3) or-C6H13 (such as-(CH2)5CH3)。
According to the present invention, the weight ratio preferably 1 of the sugar source and alcohol:0.1-2 (such as 1:0.1、1:0.5、1:0.8、1: 0.9、1:1、1:1.5、1:Arbitrary value between 2 or aforementioned value), more preferably 1:0.17-1.The alcohol can be at 25 DEG C The lower alcohol of solubility >=0.01g/100g water in water, preferably methanol, ethanol, propyl alcohol, isopropanol, butanol, isobutanol With the one or more in 1- amylalcohols.
According to the present invention, the weight ratio preferably 1 of the sugar source and reaction medium:2-100 (such as 1:2、1:5、1:10、1: 15、1:17、1:20、1:25、1:30、1:40、1:50、1:60、1:70、1:80、1:90、1:Appointing between 100 or aforementioned value Meaning value).
According to the present invention, the weight ratio of water and non-alcohols organic solvent is preferably 1:0.5-2 (such as 1:0.5、1:0.8、1: 0.9、1:1、1:1.2、1:1.3、1:1.4、1:1.5、1:1.6、1:1.8、1:Arbitrary value between 2 or aforementioned value), more preferably For 1:1-1.5.The non-alcohols organic solvent can be the conventional organic solvent of various not hydroxyls, such as C1-C20 (and polarity Less than methanol) organic solvent, preferably tetrahydrofuran, 4-methyl-2 pentanone, acetone, dioxane, 2- methyl tetrahydrochysene furans Mutter, the one or more in toluene, dimethylbenzene, aliphatic hydrocarbon, petroleum ether, dichloromethane and chloroform, more preferably toluene, two At least one of toluene and aliphatic hydrocarbon.The aliphatic hydrocarbon can be C6-C20 aliphatic hydrocarbon, such as hexamethylene, normal octane, positive ten Dioxane etc..
According to the present invention, the water-soluble inorganic salt is that selectivity is used, and main function is to promote water to have with non-alcohols Machine demixing of solvents (is layered) between the non-alcohols organic solvent and water that itself can particularly be dissolved each other with water.To the water-soluble nothing The consumption of machine salt is not required particularly, it is preferable that the sugar source and the weight of water-soluble inorganic salt ratio are 1:0.01-1.It is described Water-soluble inorganic salt can be the various inorganic salts (dissolvings at 25 DEG C in water that water can be made to be layered with non-alcohols organic solvent Degree preferably >=1g/100g water), preferably one kind or many in the nitrate of the chloride of metal, the sulfate of metal and metal Plant (one or more in such as sodium chloride, potassium chloride, sodium sulphate, potassium sulfate, sodium nitrate and potassium nitrate).
According to the present invention, the weight ratio preferably 1 of the sugar source and acid catalyst:0.01-1 (such as 1:0.01、1:0.05、 1:0.1、1:0.2、1:0.3、1:0.4、1:0.5、1:Arbitrary value between 1 or aforementioned value).The acid catalyst can be selected from Inorganic acid, solid acid catalyst, molecular sieve catalyst, metallic catalyst, metal oxide, metal sulfide or complex catalysis Agent, for example, the acid catalyst can be selected from immobilized phosphoric acid, phosphorus tungsten/phosphato-molybdic heteropolyacid, Si-Al zeolite molecular sieve, phosphorus aluminium point Son sieve, sulfonate resin, chloride, phosphate and sulfate containing Nb, Zr, Fe, Al, Zn, Mo, Cu, W, Sn contain transition gold The fluoroform sulphonate of category or rare earth metal such as Zr, La, Mo, Yb, In, carbon material, phosphoric acid, sulfuric acid, hydrochloric acid and nitric acid In one or more.
A preferred embodiment of the invention, the acid catalyst is that solid acid catalyst I and/or solid acid are urged Agent II.
The solid acid catalyst I has impalpable structure and chemical formula is Alx1Siy1O(3x1+4y1)/2, wherein, y1 and x1 It is each independently positive integer and y1:X1=0.25-200:1, it is preferable that y1:X1=40-60:1.
Preferably, the acid amount of the solid acid catalyst I is in more than 0.3mmol/g, more preferably 0.4-0.6mmol/g It is (any between such as 0.4mmol/g, 0.45mmol/g, 0.5mmol/g, 0.55mmol/g, 0.6mmol/g or aforementioned value Value).
Preferably, the specific surface area of the solid acid catalyst I is in 750m2/ more than g, more preferably 770-850m2/ g is (such as 770m2/g、780m2/g、790m2/g、800m2/g、810m2/g、820m2/g、830m2/g、840m2/g、850m2/ g or foregoing numbers Arbitrary value between value).
Preferably, the average pore size of the solid acid catalyst I is in the range of 2.3-3.5nm, more preferably 2.8-3nm (arbitrary value between 2.8nm, 2.85nm, 2.9nm, 2.95nm, 3nm or aforementioned value).
Wherein, the acid amount passes through NH3- TPD is measured；Specific surface area passes through N2Adsorption-desorption method is measured；Average pore size passes through BJH (Barrett-Joyner-Halenda) model method is measured.
Preferably, Pyridine adsorption IR spectra (Py-FTIR) shows the L acid acid amounts and B acid acid of the solid acid catalyst I Ratio between amount is 0.05-50：1 (such as 0.05:1、0.1:1、0.5:1、1:1、5:1、10:1、15:1、20:1、25:1、30: 1、35:1、40:1、45:1、50:Arbitrary value between 1 or aforementioned value), preferably 0.1-5：1.Wherein, L acid acid amount and B acid The computational methods of acid amount are referred to document (Catal.Commun., 2008,9,1959-1965).Py-FTIR results can be adopted Measured and obtained under 100 DEG C (or 200 DEG C or 400 DEG C) with the type infrared spectrometers of U.S. Nicolet Model 710.Concrete operations Step can be：50mg catalyst dries under infrared lamp, be ground to it is powdered after transfer them in pelleting press, after tabletting To circular thin slice, thin slice is put into sample cell afterwards；Sample cell is evacuated to high vacuum state, sample sheet pretreatment 2 is small When, remove the moisture and other impurity of sample adsorption；Sample is cooled to room temperature (25 DEG C) afterwards, and recorded after now pretreatment The infrared spectrum of sample then leads to pyridine steam at ambient temperature as background, until sample adsorption saturation (infrared spectrogram Think adsorption saturation when no longer changing)；Sample is gradually heating to 100 DEG C (or 200 DEG C or 400 DEG C), and protected at such a temperature Hold 1 hour, record the infrared spectrogram of now sample.
Preferably, NH3- TPD analyses also show absworption peak faces of the solid acid catalyst I in the range of 100-200 DEG C Product accounts for the 15-50% of the broad peak gross area in the range of 100-700 DEG C, the absorption peak area in the range of 200-400 DEG C and accounts for 100-700 The 30-70% of the broad peak gross area, the absorption peak area in the range of 400-700 DEG C account for 100-700 DEG C of scope inner width in the range of DEG C The 5-40% of the peak gross area.It is highly preferred that NH3The solid acid catalyst I is in the range of 100-200 DEG C for-TPD analysis displays Absorb peak area account for the broad peak gross area in the range of 100-700 DEG C 20-40% (such as 20%, 25%, 28%, 30%, 32%, 35%th, the arbitrary value between 40% or aforementioned value), the absorption peak area in the range of 200-400 DEG C account for 100-700 DEG C of scope The 40-60% (arbitrary value between such as 40%, 45%, 50%, 55%, 60% or aforementioned value) of the interior broad peak gross area, Absorption peak area in the range of 400-700 DEG C account for the broad peak gross area in the range of 100-700 DEG C 10-30% (such as 10%, 15%, 18%th, the arbitrary value between 20%, 22%, 25%, 28%, 30% or aforementioned value).Wherein, the solid acid catalyst I exists Absorption peak area in the range of 100-200 DEG C, 200-400 DEG C and 400-700 DEG C accounts for the broad peak gross area in the range of 100-700 DEG C Percentage reflects in the solid acid catalyst I content of " weak acid, middle strong acid and strong acid " respectively.
NH3- TPD concrete operation step can be：Catalyst sample is placed in U-shaped quartz ampoule, in 45mL/min N2 With 10 DEG C of min under atmosphere-1Heating rate rise to 500 DEG C from room temperature, and pre-process 1 hour at this temperature；Pretreatment knot Shu Hou, cools the temperature to 50 DEG C and keeps constant, be passed through N2/NH3=9:1 gas is adsorbed in advance, keeps inhaling at this temperature Attached 45min, after absorption terminates, temperature is risen into 90 DEG C makes the NH of catalyst surface physical absorption3Desorption is clean, opens bridge electric current and walks Baseline, after baseline is walked surely, with 10 DEG C of min-1Heating rate rise to 500 DEG C from 90 DEG C, by TCD detectors at 110 DEG C Lower synchronous acquisition NH3The signal of desorption.
The solid acid catalyst I that the present invention is used converts glucose into the yield of 5 hydroxymethyl furfural for 15-60% (such as 15%th, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 52%, 55%, 56%, 57%, 58%, 59%, 60% or Arbitrary value between aforementioned value), wherein, mole/glucose of yield=5 hydroxymethyl furfural of 5 hydroxymethyl furfural Mole × 100%.The solid acid catalyst I that the present invention is used by the yield that xylose is furfural be 25-75% (such as 25%th, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 62%, 65%, 68%, 70%, 71%, 72%, 73%, 74%th, the arbitrary value between 75% or aforementioned value), wherein, the mole of mole/xylose of yield=furfural of furfural × 100%.The test condition of above-mentioned yield includes：It is 7 toward 10ml volume ratios:3 hexone and the saturation of potassium chloride 0.5g glucose or xylose are added in the mixed liquor of the aqueous solution, 0.1g solid acid catalyst I is added, is filled with nitrogen, is heated to 160 DEG C, reaction system is cooled to 25 DEG C by reaction after 3 hours, isolates solid acid catalyst I, and by the efficient liquid of obtained liquid phase Phase chromatogram is analyzed, and calculates the yield of 5 hydroxymethyl furfural or furfural.
The preparation method for the solid acid catalyst I that the present invention is used includes：By silicon source and silicon source in the presence of hydrolytic reagent Dry glue is made, dry glue is carried out aging, the material after aging is washed and is calcined successively, wherein, the silicon source and silicon source Mol ratio be 0.25-200:1 (is preferably 40-60:1), the silicon source is in terms of element silicon, and source of aluminium is in terms of aluminium element.
In solid acid catalyst I preparation method, methods described avoids using template that (or aging is without template Carried out in system), the present invention results in amorphous solid acid catalyst I of the invention using template by avoiding, and its Higher yield is resulted in when preparing Furnan products for catalysis.
In solid acid catalyst I preparation method, the preparation method of the dry glue can be carried out according to conventional mode, example Such as, preparing the method for dry glue can include：By silicon source, silicon source, hydrolytic reagent and water mix, by obtained mixture stirring bar Incubated and dried successively under part.It can also be ground after drying, to obtain particle diameter smaller (such as 1-2mm) dry glue powder It is standby.Wherein it is possible to first mix silicon source, silicon source and water, add after hydrolytic reagent is mixed and incubated.The temperature of incubation can be with For 20-50 DEG C.The time of incubation can be 10-20h.
In solid acid catalyst I preparation method, the consumption and species of the hydrolytic reagent are had no particular limits.It is preferred that In the case of, the weight ratio of the hydrolytic reagent and silicon source is 0.1-0.4：1.The hydrolytic reagent can be various (20 DEG C soluble in water Solubility >=10g/100g water in Shi Shui) acidic materials or alkaline matter.Preferably, the hydrolytic reagent is inorganic acid And/or organic acid (C1-C10) or inorganic base and/or organic base (C1-C10), more preferably HCl, H2SO4、HNO3、CH3COOH At least one of at least one of with oxalic acid, or NaOH, KOH, triethylamine, ethylenediamine and tetramethylethylenediamine.
In solid acid catalyst I preparation method, the silicon source various can be used to prepare to be commonly used in the art The silicon-containing material (or the material of silicon can be provided) of sieve and silica-sesquioxide, for example, estersil (C1-C10, such as tetraethyl orthosilicate), oxidation At least one of silicon (can be provided in the form of Ludox or white carbon), silicate (such as sodium metasilicate).Preferably, the silicon Source is at least one of tetraethyl orthosilicate, Ludox, waterglass and white carbon, more preferably tetraethyl orthosilicate.
In solid acid catalyst I preparation method, source of aluminium various can be used to prepare to be commonly used in the art The aluminium-containing substance (or the material of aluminium can be provided) of sieve and silica-sesquioxide, for example, inorganic aluminate (such as aluminum sulfate, alchlor, vulcanization Aluminium), organic aluminium salt (C1-C10, such as aluminium isopropoxide), at least one of aluminium hydroxide and aluminum oxide.Preferably, source of aluminium For at least one of aluminium isopropoxide, boehmite, alchlor and aluminum sulfate, more preferably aluminium isopropoxide.
In solid acid catalyst I preparation method, aging condenses dry glue for (standing a period of time at a certain temperature) Process.The condition of the aging can be the conventional selection of this area.Preferably, the temperature of aging is 100-300 DEG C, aging Time be 50-100h.It is roasted to the process that (at high temperature) make silicon and aluminium be converted into oxide form.The condition of the roasting It can be the conventional selection of this area.Preferably, the temperature of roasting is 300-800 DEG C (be preferably 450-550 DEG C), roasting when Between be 3-100h.
In solid acid catalyst I preparation method, according to most preferred embodiment, the hydrolytic reagent is triethylamine, institute The mol ratio for stating silicon source and silicon source is 40-60:1, the silicon source is tetraethyl orthosilicate, and source of aluminium is aluminium isopropoxide, roasting Temperature is 450-550 DEG C.Solid acid catalyst I catalytic efficiency is higher according to made from the preferred embodiment.Preferably, institute The chemical formula for stating solid acid catalyst I is Al2Si100O203, acid amount is 0.4mmol/g, and specific surface area is 770m2/ g, average pore size For 2.8nm, the weight ratio of weak acid, middle strong acid and strong acid is 3:4:Ratio between 3, L acid acid amounts and B acid acid amounts is 5:1, by wood The yield that sugar is converted into furfural is 73.2%, and the yield for converting glucose into 5 hydroxymethyl furfural is 58.6%.
In solid acid catalyst I preparation method, mode of washing etc. is not required particularly, as long as can be by aging Hydrolytic reagent in material afterwards removes and makes it in neutrality.It can be water to wash the reagent used, and the mode of washing is this Known to art personnel, it will not be repeated here.
The solid acid catalyst II has impalpable structure and chemical formula is Ax2Py2O(4x2+5y2)/2, wherein, A represents IVB Race's metallic element and/or IVA races metallic element, y2 and x2 are each independently positive integer and y2:X2=0.5-4:1, it is preferable that y2:X2=1.5-3:1.
Preferably, the acid of the solid acid catalyst II is measured in more than 0.1mmol/g, more preferably 0.4-1mmol/g (such as 0.4mmol/g、0.45mmol/g、0.5mmol/g、0.55mmol/g、0.6mmol/g、0.65mmol/g、0.7mmol/g、 Between 0.75mmol/g, 0.8mmol/g, 0.85mmol/g, 0.9mmol/g, 0.95mmol/g, 1mmol/g or aforementioned value Arbitrary value).
Preferably, the specific surface area of the solid acid catalyst II is in 55m2/ more than g, more preferably in 80m2/ more than g, most Preferably 90-300m2/ g (such as 90m2/g、100m2/g、110m2/g、115m2/g、120m2/g、125m2/g、130m2/g、140m2/ g、150m2/g、160m2/g、170m2/g、180m2/g、190m2/g、200m2/g、210m2/g、220m2/g、230m2/g、240m2/ g、250m2/g、260m2/g、270m2/g、280m2/g、285m2/g、290m2/g、295m2/g、300m2Between/g or aforementioned value Arbitrary value).
Preferably, the average pore size of the solid acid catalyst II 2.3-10nm (2.3nm, 2.5nm, 3nm, 3.5nm, 4nm、4.5nm、5nm、5.5nm、6nm、6.5nm、7nm、7.5nm、8nm、8.5nm、9nm、9.5nm、9.6nm、9.7nm、 Arbitrary value between 9.8nm, 9.9nm, 10nm or aforementioned value) in the range of, more preferably 2.8-3nm.
Wherein, the acid amount passes through ammonia temperature programmed desorption analytic approach (NH3- TPD) measure；Specific surface area passes through N2Inhale Desorption method is measured；Average pore size is measured by BJH (Barrett-Joyner-Halenda) model method.
Preferably, Pyridine adsorption IR spectra (Py-FTIR) shows the L acid acid amounts and B acid of the solid acid catalyst II Ratio between acid amount is 0.08-50：1 (such as 0.08:1、0.1:1、0.5:1、1:1、1.5:1、2:1、2.5:1、3:1、3.5:1、 4:1、4.5:1、5:1、10:1、15:1、20:1、25:1、30:1、35:1、40:1、45:1、50:Appointing between 1 or aforementioned value Meaning value), preferably 0.1-4.5：1.Wherein, the computational methods of L acid acid amount and B acid acid amounts are referred to document (Catal.Commun.,2008,9,1959-1965).Py-FTIR results can be red using the U.S.'s 710 types of Nicolet Model External spectrum instrument is measured under 100 DEG C (or 200 DEG C or 400 DEG C) and obtained.Concrete operation step is as previously described.
Preferably, NH3- TPD analyses also show absworption peak faces of the solid acid catalyst II in the range of 100-200 DEG C Product accounts for the 4-20% of the broad peak gross area in the range of 100-600 DEG C, the absorption peak area in the range of 200-400 DEG C and accounts for 100-600 The 35-55% of the broad peak gross area, the absorption peak area in the range of 400-600 DEG C account for 100-600 DEG C of scope inner width in the range of DEG C The 35-55% of the peak gross area.It is highly preferred that NH3The solid acid catalyst II is in the range of 100-200 DEG C for-TPD analysis displays Absorption peak area account for the broad peak gross area in the range of 100-600 DEG C 10-15% (such as 10%, 10.5%, 11%, 12%, 13%th, the arbitrary value between 14%, 15% or aforementioned value), the absorption peak area in the range of 200-400 DEG C account for 100-600 In the range of DEG C the broad peak gross area 40-50% (40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%th, the arbitrary value between 50% or aforementioned value), the absorption peak area in the range of 400-600 DEG C account for 100-600 DEG C of scope The 40-50% (40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50% of the interior broad peak gross area Or the arbitrary value between aforementioned value).Wherein, the solid acid catalyst II is in 100-200 DEG C, 200-400 DEG C and 400-600 The percentage that absorption peak area in the range of DEG C accounts for the broad peak gross area in the range of 100-600 DEG C reflects the solid acid catalysis respectively The content of " weak acid, middle strong acid and strong acid " in agent II.NH3- TPD concrete operation step is as previously described.
The yield that the solid acid catalyst II that the present invention is used converts glucose into 5 hydroxymethyl furfural is 10-55% It is (any between such as 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 52%, 55% or aforementioned value Value), wherein, mole × 100% of mole/glucose of yield=5 hydroxymethyl furfural of 5 hydroxymethyl furfural.This hair The bright solid acid catalyst II used by the yield that xylose is furfural be 25-75% (such as 25%, 30%, 35%, 40%, 45%th, 50%, 55%, 60%, 62%, 65%, 68%, 70%, 71%, 72%, 73%, 74%, 75% or aforementioned value it Between arbitrary value), wherein, mole × 100% of mole/xylose of yield=furfural of furfural.The test of above-mentioned yield Condition includes：It is 7 toward 10ml volume ratios:Added in the mixed liquor of 3 hexone and the saturated aqueous solution of potassium chloride 0.5g glucose or xylose, add 0.1g solid acid catalyst II, are filled with nitrogen, are heated to 160 DEG C, will be anti-after reacting 3 hours Answer system to be cooled to 25 DEG C, isolate solid acid catalyst II, and obtained liquid phase is analyzed with high performance liquid chromatography, count Calculate the yield of 5 hydroxymethyl furfural or furfural.
The preparation method for the solid acid catalyst II that the present invention is used includes：In the presence of the solvent, by metal ion source Mixed with phosphorus source, gained solid phase is dried and is calcined, wherein, the metallic element in metal ion source includes Group IVB metal Element and/or IVA races metallic element；The mol ratio of the metal ion source and phosphorus source is 0.5-4:1 (is preferably 1.5-3:1), The metal ion source is with elemental metal, and phosphorus source is in terms of P elements.
In solid acid catalyst II preparation method, the metal ion source can for it is commonly used in the art can The material of quadrivalent metallic ion is provided, for example, the various salt or oxychlorination things form of Group IVB metal and/or IVA races metal.It is excellent Selection of land, the metal ion source is nitrate, chloride, oxychlorination things and the sulfate of Group IVB metal and/or IVA races metal At least one of.Wherein, Group IVB metal is preferably at least one of titanium, zirconium and hafnium.IVA races metal be preferably germanium and/or Tin.It is highly preferred that the metal ion source is zirconium nitrate and/or zirconium oxychloride.
In solid acid catalyst II preparation method, phosphorus source various be able to can carry to be commonly used in the art The material of phosphorus supply, for example, organic phosphate and/or inorganic phosphate.Preferably, phosphorus source is ammonium phosphate, diammonium hydrogen phosphate At least one of with ammonium dihydrogen phosphate.
In solid acid catalyst II preparation method, the mixing can be conventional hybrid mode, as long as can make Metal ion source fully contacts to form white opacity thing with phosphorus source.For example, can be by metal ion source and phosphorus source point Mixing Tian Jiazhi not be realized in solvent, the solution in metal ion source can also be mixed with the solution containing phosphorus source.It is preferred that Ground, the mode of the mixing is：In the solution that solution containing phosphorus source is added dropwise to metal ion source, it is 1- to control rate of addition 10mL/min, continues to react 0.5-10h after being added dropwise to complete.Wherein, to metal ion source solution and the solution containing phosphorus source Concentration do not require particularly, can be respectively in more than the 0.1mol/L concentration of saturated solution (upper limit be) and more than 0.1mol/L (upper limit is the concentration of saturated solution).
Similarly, the condition to mixing is not required particularly, for example, the temperature of mixing can be 5-50 DEG C, mixing Time can be 0.5-20h (if using the hybrid mode being added dropwise, the time represents to continue the time of reaction after being added dropwise to complete). Those skilled in the art can be selected the time of mixing, such as the formation degree by observing white opacity thing.
The solvent can be with the common various solvents in this area, such as water.
It is described to be roasted to (at high temperature) and metal and phosphorus is converted into oxidation in solid acid catalyst II preparation method The process of thing form.The condition of the roasting can be the conventional selection of this area.Preferably, the temperature of roasting is 300-800 DEG C (be preferably 380-450 DEG C), the time of roasting is 3-100h.
In solid acid catalyst II preparation method, according to most preferred embodiment, the metal ion source is nitre The mol ratio of sour zirconium and/or zirconium oxychloride, the metal ion source and phosphorus source is 1.5-3:1, the temperature of roasting is 380-450 ℃.Solid acid catalyst II catalytic efficiency is higher according to made from the preferred embodiment.Preferably, the solid acid catalysis Agent II chemical formula is ZrP2O7, acid amount is 0.6mmol/g, and specific surface area is 110.4m2/ g, average pore size is 2.9nm, weak acid, The weight ratio of middle strong acid and strong acid is 1:4.3:Ratio between 4.7, L acid acid amounts and B acid acid amounts is 3.8:1, by xylose It is 51.6% for the yield of furfural, the yield for converting glucose into 5 hydroxymethyl furfural is 52%.
In solid acid catalyst II preparation method, before drying, solid phase can be washed, so that it is in neutrality. It can be water to wash the reagent used, and the mode of washing is well known to those skilled in the art, will not be repeated here.
According to the present invention, the condition of molecule inner dewatering reaction can include：Temperature is 70-210 DEG C, preferably 120-150 ℃.The condition of molecule inner dewatering reaction can also include：Time is 1-100h, preferably 1-25h.
According to the present invention, the sugar source can be for monosaccharide and disaccharide, polysaccharide and containing at least one of sugared biomass.Institute It can be glucose, fructose, lyxose and xylose etc. to state monose；The disaccharide can be sucrose, cellobiose, lactose etc.；Institute It can be synanthrin, xylan, starch, cellulose and hemicellulose etc. to state polysaccharide.The biomass can give up for various biomass Expect (such as stalk, seed hulls).Preferably, the sugar source is glucose, sucrose, fructose, cellobiose, synanthrin, lactose, lysol One in sugar, xylose, xylan, cellulose, hemicellulose, starch, corncob, bagasse, stalk, seed hulls and wood materials Plant or a variety of, more preferably at least one of mixture of corncob, stalk, bagasse and glucose and xylose.
A preferred embodiment of the invention, the sugar source is corncob, bagasse, stalk, seed hulls and wood During one or more in material, sugar source produces solid residue after molecule inner dewatering reaction, and methods described also includes：Make The solid residue of generation is converted into porous carbon material.
Wherein, solid residue is allow to be converted into porous carbon material for high-temperature process, for example, locating at 200-500 DEG C Manage 3-8h.The carbon material of acquisition can be used for preparing the solid acid catalyst that can be used in step a and/or preparing can be used for step Catalyst in c, so as to realize recycling for material.
The method that what the present invention was provided prepare aviation fuel comprises the following steps：
A, the method for preparing aviation fuel production raw material according to above-mentioned prepare and are dissolved with compound shown in Formulas I and Formula II Organic phase；
B, the organic phase progress aldol reaction that compound shown in Formulas I and Formula II will be dissolved with；
C, take the product after aldol reaction carry out deoxidation hydrogenation reaction.
The aldol reaction can be carried out in the way of this area is conventional, according to the side of being preferable to carry out of the present invention Formula, the mode of the aldol reaction is：Under 20-120 DEG C (preferably 60-80 DEG C), it will be dissolved with shown in Formulas I and Formula II and change The organic phase of compound is mixed with alkaline solution.Solute in the alkaline solution can be sodium hydroxide, potassium hydroxide, hydroxide At least one of ammonium, sodium carbonate and potassium carbonate.The content of solute in the alkaline solution can be 0.5-2.5mol/L.This Art personnel can be selected the time that organic phase is mixed with alkaline solution, for example, can be 1-50h (preferably 3- 12h)。
According to the present invention, methods described also includes the alkaline matter neutralized in the product after aldol reaction, and/or returned Receive the organic phase in the product after aldol reaction.Wherein, the mode of neutralization can be by product and inorganic acid (such as sulfuric acid, At least one of hydrochloric acid and nitric acid) contact, and/or, by product and (high pressure) CO2Gas is contacted, and is tieed up at 50-100 DEG C Hold 10-100h.In order to ensure being smoothed out for deoxidation hydrogenation reaction, the above-mentioned neutralization operation of progress, neutralized step are generally required Treat that the material of deoxidation hydrogenation is separated out with precipitation form afterwards, deoxidation hydrogenation reaction is can be used to through separation of solid and liquid.The mode of recovery can Think：After collecting organic phase after product AUTOMATIC ZONING.The organic phase of collection can be organic molten as non-alcohols using in return to step a Agent, so as to realize recycling for material.The sequencing for neutralizing and reclaiming is not required particularly, those skilled in the art It can be selected according to whether operation is convenient.
The deoxidation hydrogenation reaction can be carried out in the way of this area is conventional, according to the side of being preferable to carry out of the present invention Formula, the mode of the deoxidation hydrogenation reaction is：In 140-260 DEG C (more preferably 200-250 DEG C) and 1-8MPa (more preferably 5- Under conditions of 8MPa), the product (or the solid phase obtained after neutralizing) of aldol reaction is mixed with deoxidation hydrogenation catalyst.Hydroxyl The time that the product of aldehyde condensation reaction is mixed with deoxidation hydrogenation catalyst can be 5-50h, preferably 10-15h.
According to another preferred embodiment of the present invention, the mode of the deoxidation hydrogenation reaction is：Aldol condensation is anti- The product answered is mixed with deoxidation hydrogenation catalyst, respectively in 80-220 DEG C (more preferably 150-200 DEG C) and 1-8MPa (more preferably 5- Pre-deoxidation hydrogenation (time can be 10-50h, preferably 15-20h) is carried out under conditions of 8MPa) and (more excellent at 140-260 DEG C Select 200-250 DEG C) and 1-8MPa (more preferably 5-8MPa) under conditions of carry out deoxidation hydrogenation (time can be 10-50h, preferably 10-15h), wherein, pre-deoxidation hydrogenation needed for temperature than deoxidation be hydrogenated with needed for low 40-100 DEG C (the more preferably 50-70 of temperature ℃)。
In above-mentioned preferred embodiment, the deoxidation hydrogenation catalyst can be the conventional deoxidation hydrogenation catalyst in this area Agent, such as metal-solids acid multifunction catalyst, such as Pd/NbOPO4Catalyst, can be made by infusion process, i.e. in reduction In the presence of agent (such as sodium borohydride and/or potassium borohydride), solid acid catalyst (above-mentioned solid acid catalyst II) is impregnated in In the maceration extract of soluble compound (such as ammino palladium of dichloro four) containing active component, so that precious metal simple substance palladium is reduced in solid Body acid catalyst surface, so as to obtain Pd/NbOPO4Catalyst.
In the present invention, the product obtained after deoxidation hydrogenation reaction can be used as aviation fuel or aviation fuel component, Application method is well known to those skilled in the art, and will not be repeated here.
The present invention will be described in detail by way of examples below.In following examples, the concentration of the concentrated sulfuric acid is 98 weights Measure %.
Preparation example 1
This preparation example is used for illustrating preparing R- Furnan products and levulic acid esters by different protist matter raw materials The method of compound.
50g toluene, 45g water and 5g isopropanols are added in 200ml batch reactor, the 1g concentrated sulfuric acids is added and is used as acid Catalyst, adding 5g protist matter raw material, (wherein soluble starch is purchased from Shanghai Ling Feng chemical reagent Co., Ltd, and article No. is 303902129, cellulose is purchased from Fluka companies；Other are taken from Yunnan) as substrate, 24h is reacted at 180 DEG C (soluble Starch reacts 6h at 150 DEG C), take toluene mutually to carry out efficient liquid phase chromatographic analysis, obtain R- Furnan products (including chaff Aldehyde, 5 hydroxymethyl furfural and 5- isopropoxy methylene furfurals) and levulic acid esters Compound (levulic acid isopropyl ester,) yield (R- Furnan products (or the acetyl in=product Propionic acid ester compound) weight/raw material weight × 100%) as shown in table 1 below.
Efficient liquid phase chromatographic analysis condition is：Raw material and product analysis are carried out on the type HPLC of Agilent 1200, chromatogram Post is XDB-C18 chromatographic columns (4.5 μm, 250mm, Eclipse USA), and chromatographic column constant temperature is at 35 DEG C.The analysis of sugar is used Agilent G1362A types differential refraction detectors (RID), mobile phase is pure water, and flow velocity is 1.0mLmin-1.Furfural, 5- hydroxyls The analysis of methyl furfural (HMF), 5- isopropoxy methylene furfurals and levulic acid isopropyl ester uses Agilent G1314B types UV-detector (VWD), mobile phase is the mixed liquor of methanol and pure water, and volume ratio is 20:80, flow velocity is 0.6mLmin-1。
As can be seen that soluble starch and the resulting R- Furnan products (formula I) of hay conversion and second after analysis The ratio of the yield of acyl propionic acid ester compound (formula II) is close to 1:1, being suitable for carrying out C10-C11 condensation, (main reaction formula is I+formula of formula, II → C10/11+H2O, single Aldol condensations)；R- Furnan products and levulinic that corncob and stover are obtained The ratio of the yield of acid esters compound is close to 2:1, be suitable for carry out C15-C17 condensation (main reaction formula be 2 × formula, I+formula II →C15/16/17+2H2O, a levulic acid esters compound (formula II) can be condensed with two Furnan products (formula I), Double Aldol condensations).
The reaction equation of single Aldol condensation is：
Or,
The reaction equation of double aldol condensation is：
Preparation example 2
This preparation example is used for the method for illustrating to prepare R- Furnan products and levulic acid esters compound by different sugar.
50g toluene, 45g water and 5g isopropanols are added in 200ml batch reactor, the 1g concentrated sulfuric acids is added and is used as acid Catalyst, the monose (disaccharides is 0.015mol) that addition total amount is 0.03mol reacts 2-6h at 150 DEG C, takes first as substrate Benzene mutually carries out efficient liquid phase chromatographic analysis (condition is with preparation example 1), obtains R- Furnan products (including furfural, 5- methylols Furfural and 5- isopropoxy methylene furfural) and levulic acid esters compound yield (the R- furfural class chemical combination in=product Mole × 100% of mole/raw material of thing (or levulic acid esters compound)) it is as shown in table 1 below.
Preparation example 3
This preparation example is used for illustrating preparing R- Furnan products and levulic acid esters compound by different acid catalysts Method.
5g toluene, 4.5g water and 0.5g isopropanols are added in 50ml batch reactor, 0.001mol acid is added and urges Agent (H3PW12O40Purchased from traditional Chinese medicines；H-beta molecular sieves are purchased from Catalyst Factory, Nankai Univ, and article No. is 20130016；A15 sulfonic acid Resin is purchased from lark prestige, and article No. is 20140117；Al2(SO4)3Purchased from traditional Chinese medicines, Yb (TOf)3Purchased from lark prestige), adding total amount is (mol ratio is 1 to 0.003mol mixed sugar:The mixture of 1 glucose and xylose) as substrate, 6h is reacted at 150 DEG C, Take toluene mutually to carry out efficient liquid phase chromatographic analysis (condition is with preparation example 1), obtain R- Furnan products (including furfural, 5- hydroxyls Methyl furfural and 5- isopropoxy methylene furfural) and levulic acid esters compound yield (the R- furfural classes in=product Mole × 100% of mole/raw material of compound (or levulic acid esters compound)) it is as shown in table 1 below.
Wherein, solid acid catalyst I preparation method is as follows：
Silicon source (tetraethyl orthosilicate) and silicon source (aluminium isopropoxide) are weighed in (silica alumina ratio is 50 in pp bottles:1), magnetic agitation 1 Hour, obtain solution A.By hydrolytic reagent triethylamine, (the weight ratio with silicon source is 0.2 again：1) added with deionized water in solution A, Stirring 40 minutes.Then bottle cap is opened, resulting material, is finally put into by open stirring 12h in the oil bath pan of constant temperature (35 DEG C) It is dried overnight in baking oven；Fine powder is ground to, dry glue is obtained.Take dry glue to be placed in in foraminate tetrafluoro container, then container is put In in crystallizing kettle, bottom adds a small amount of water, screws kettle cover, is put into aging 72 hours in 160 DEG C of constant temperature ovens.Then take out and take out It is placed in after filter, washing to neutrality, filtration cakes torrefaction (100 DEG C, 12h) in Muffle furnace and is calcined 5h at 500 DEG C, obtains solid acid catalysis Agent I (Al2Si100O203, amorphous, acid amount is 0.4mmol/g, and specific surface area is 770m2/ g, average pore size is 2.8nm).Solid Acid catalyst I is through NH3- TPD, which determines display, has weak acid, middle strong acid and strong acid, wherein based on weak acid and middle strong acid, Shao Liangqiang (the weight ratio of weak acid, middle strong acid and strong acid is 3 to acid:4:3).Solid acid catalyst I shows described through the Py-FTIR results determined Solid acid catalyst I is based on L acid, and with a small amount of B acid, (ratio between L acid acid amounts and B acid acid amounts is 5：1).
It is 7 that 10ml volume ratios are added in batch reactor:3 hexone and the saturated aqueous solution of potassium chloride Mixed liquor, then add 0.5g glucose, be separately added into 0.1g solid acid catalysts I made from above-mentioned steps, be filled with nitrogen, 160 DEG C are heated to, reaction system is cooled to room temperature (25 DEG C) after 3 hours, centrifuges out catalyst by constant temperature stirring, reaction. Reaction solution is analyzed with high performance liquid chromatograph, calculates the yield (58.6%) of 5 hydroxymethyl furfural.Glucose is replaced with Xylose, calculates the yield (73.2%) of furfural.The condition of efficient liquid phase chromatographic analysis is as follows herein：
Reaction solution using the types of Agilent 1200 HPLC analyze, chromatographic column be XDB-C18 chromatographic columns (4.5 μm, 250mm, Eclipse USA), chromatographic column constant temperature is at 35 DEG C.Liquid chromatogram assembles an Agilent G1329A type automatic sampler, is used for Increase the repeatability of sample introduction.The HMF and chaff of reaction generation are detected using Agilent G1314B types UV-detectors (VWD) Aldehyde product, ultraviolet wavelength is 254nm, and mobile phase is the mixed liquor of methanol and pure water, and volume ratio is 20:80, flow velocity is 0.6mL min-1.Using the type HPLC chromatograms of Agilent 1200 configuration Agilent G1362A types differential refraction detectors (RID) and Bio- Rad Aminex HPX-87H sugar post come detect reaction after remaining xylose and glucose, chromatographic column constant temperature is in 80 DEG C, mobile phase For pure water, flow velocity is 0.8mLmin-1。
Solid acid catalyst II preparation method is as follows：
Solution a is obtained by metal ion source (zirconyl chloride) is soluble in water (using the concentration of metal ion as 1mol/L)； Solution b is obtained by phosphorus source (ammonium dihydrogen phosphate) is soluble in water (concentration counted using P elements is 1mol/L)；At 25 DEG C, by solution B, which is slowly added dropwise to solution a, (controls rate of addition to be 3mL/min, phosphorus gold is than being 2:1) in, there is white opacity thing, completion of dropping Continue to stir 1h afterwards, be placed in after then carrying out suction filtration, washing to neutrality, filtration cakes torrefaction (100 DEG C, 12h) in Muffle furnace at 400 DEG C Lower roasting 4h, obtains solid acid catalyst II (ZrP2O7, amorphous, acid amount is 0.6mmol/g, and specific surface area is 110.4m2/ g, Average pore size is 2.9nm).Obtained solid acid catalyst II is through NH3- TPD, which determines display, has weak acid, middle strong acid and strong acid, Wherein based on middle strong acid and strong acid, (the weight ratio of weak acid, middle strong acid and strong acid is 1 to a small amount of weak acid:4.3:4.7).Solid acid Catalyst II shows the solid acid catalyst II based on L acid through the Py-FTIR results determined, with a small amount of B acid (L acid acid Ratio between amount and B acid acid amounts is 3.8：1).Gold is used as using niobium oxalate (being purchased from Dongfang Tantalum Industry Co., Ltd., Ningxia Hui autonomy Region) Category ion gun simultaneously can obtain NbOPO according to above identical method4(similarly hereinafter).
5 hydroxymethyl furfural is prepared according to solid acid catalyst II catalysis is determined with solid acid catalyst I identical modes Yield is 52% and the yield of furfural is 51.6%.
In the above-mentioned method for preparing solid acid catalyst I and solid acid catalyst II, X-ray diffraction (XRD) spectrogram exists It is measured on Siemens D5005 type x-ray diffractometers, using Cu target K α (λ=0.154056nm) source, test voltage is 40kV, test electric current is 40mA, and 10-80 ° of scanning range, 6 °/min of sweep speed judges that gained catalyst is according to XRD spectra No is impalpable structure；Element constitutes (chemical formula) and obtained by Energy Dispersive X-ray detector (EDX) sign；Acid amount passes through Ammonia temperature programmed desorption analytic approach (NH3- TPD) measure, concrete operation step is as follows：Catalyst sample is placed in U-shaped quartz In pipe, in 45mL/min N2With 10 DEG C of min under atmosphere-1Heating rate rise to 500 DEG C from room temperature, it is and pre- at this temperature Processing 1 hour.After pretreatment terminates, cool the temperature to 50 DEG C and keep constant, be passed through N2/NH3=9:1 gas carries out pre-suction It is attached, absorption 45min is kept at this temperature, and after absorption terminates, temperature is risen into 90 DEG C makes the NH of catalyst surface physical absorption3 Desorption is clean, opens bridge electric current and walks baseline, after baseline is walked surely, with 10 DEG C of min-1Heating rate rise to 500 DEG C from 90 DEG C, lead to Cross TCD detectors (110 DEG C) synchronous acquisition NH3The signal of desorption；Specific surface area and average pore size are in Micromeritics companies Determined on ASAP2405 static state n2 absorption apparatus, sample is pre-processed under 180 DEG C of vacuum condition first, after having pre-processed, in liquid Analyzed at nitrogen temperature (77K), with nitrogen as adsorbate, the pore structure and specific surface area of catalyst are determined, using BJH methods Calculate the average pore size of catalyst.
Preparation example 4
This preparation example is used for illustrating to prepare at different temperatures R- Furnan products and levulic acid esters compound Method.
5g toluene, 4.5g water and 0.5g isopropanols are added in 50ml batch reactor, the 0.1g concentrated sulfuric acids is added and makees For acid catalyst, using the mixed sugar that total amount is 0.003mol, (mol ratio is 1:The mixture of 1 glucose and xylose) conduct Substrate, reacts 6h at different temperature, takes toluene mutually to carry out efficient liquid phase chromatographic analysis (condition is with preparation example 1), obtains R- Furnan products (including furfural, 5 hydroxymethyl furfural and 5- isopropoxy methylene furfural) and levulic acid esters compound Yield (mole of mole/raw material of the R- Furnan products (or levulic acid esters compound) in=product × 100%) it is as shown in table 1 below.
As can be seen that mixed sugar converts resulting R- furfural classes at a temperature of between 140-150 DEG C after analysis The ratio of compound and the yield of levulic acid esters compound is close to 1:1, it is suitable for carrying out C10-C11 condensation；130-135℃ At a temperature of between obtained Furnan products and the yield of levulic acid esters compound ratio close to 2:1, it is suitable for Carry out C15-C17 condensation.When temperature is higher than 160 DEG C, the yield of levulic acid esters compound is higher.
Preparation example 5
This preparation example is used for illustrating to prepare at different temperatures R- Furnan products and levulic acid esters compound Method.
Using the 0.1g concentrated sulfuric acids as acid catalyst, using 0.5g corncob as substrate, in 50ml reactor 5g toluene, 4g water and 1g isopropanols are added, 24h is reacted at different temperature, takes toluene mutually to carry out efficient liquid phase chromatographic analysis, Obtain R- Furnan products (including furfural, 5 hydroxymethyl furfural and 5- isopropoxy methylene furfural) and levulic acid esters Yield (the weight of weight/raw material of the R- Furnan products (or levulic acid esters compound) in=product of compound × 100%) as shown in table 1 below.
Preparation example 6
This preparation example is used for illustrating to prepare R- Furnan products and levulic acid esters chemical combination under the differential responses time The method of thing.
Using the 0.1g concentrated sulfuric acids as acid catalyst, using the mixed sugar that total amount is 0.003mol, (mol ratio is 1:1 Portugal The mixture of grape sugar and xylose) as substrate, 5g toluene, 4.5g water and 0.5g isopropyls are added in 50ml batch reactor Alcohol, certain time is reacted at 150 DEG C, is taken toluene mutually to carry out efficient liquid phase chromatographic analysis (condition is with preparation example 1), is obtained R- chaffs Aldehyde compound (including furfural, 5 hydroxymethyl furfural and 5- isopropoxy methylene furfural) and levulic acid esters compound Yield (mole of mole/raw material of the R- Furnan products (or levulic acid esters compound) in=product × 100%) it is as shown in table 1 below.
As can be seen that mixed sugar reacts the Furnan products and acetyl obtained by 4h conversions at 150 DEG C after analysis The ratio of the yield of propionic acid ester compound is close to 2:1, it is suitable for carrying out C15-C17 condensation；The furfural class that 6h conversions are obtained The ratio of the yield of compound and levulic acid esters compound is close to 1:1, it is suitable for carrying out C10-C11 condensation.
Preparation example 7
This preparation example is used for the side for illustrating to prepare R- Furnan products and levulic acid esters compound using different alcohol Method.
Using the 0.1g concentrated sulfuric acids as acid catalyst, using the mixed sugar that total amount is 0.003mol, (mol ratio is 1:1 Portugal The mixture of grape sugar and xylose) as substrate, 5g toluene, 4.5g water and 0.5g are added in 50ml batch reactor Alcohol, 6h is reacted at 150 DEG C, takes toluene mutually to carry out efficient liquid phase chromatographic analysis (condition is with preparation example 1), obtains R- furfural classes The yield of compound (including furfural, 5 hydroxymethyl furfural and 5- isopropoxy methylene furfural) and levulic acid esters compound (mole × 100% of mole/raw material of the R- Furnan products (or levulic acid esters compound) in=product) It is as shown in table 1 below.
Table 1
Preparation example 8
This preparation example is used for illustrating to prepare R- Furnan products and levulic acid esters under different time by different sugar The method of compound.
Using the 0.1g concentrated sulfuric acids as acid catalyst, bottom is used as 0.003mol glucose (or fructose) using total amount Thing, 5g toluene, 4g water and 1g isopropanols are added in 50ml batch reactor, certain time is reacted at 150 DEG C, takes first Benzene mutually carries out efficient liquid phase chromatographic analysis (condition is with preparation example 1), obtains R- Furnan products (including furfural, 5- methylols Furfural and 5- isopropoxy methylene furfural) and levulic acid esters compound yield (the R- furfural class chemical combination in=product Mole × 100% of mole/raw material of thing (or levulic acid esters compound)) it is as shown in table 2 below.
Table 2
Embodiment 1
The present embodiment is used for illustrating the preparation method of aviation fuel.
(1) aldol condensation：Take in preparation example 1 by corncob be obtained after raw material reacts containing R- Furnan products and The common 102g of toluene solution (the condensation raw material for including about 2.5g) of levulic acid esters compound, the K with 25ml 1mol/L2CO3 Solution is uniformly mixed, the heating stirring at 60 DEG C, and stirring 3h after-condensations feed stock conversion is 55.6%；Stir 6h after-condensation raw materials Conversion ratio is 89.7%；Stirring 12h after-condensation raw materials are converted completely, and R- Furnan products and levulic acid are not present in toluene Ester type compound (calculates conversion ratio=((or second of R- Furnan products in the toluene before reaction by efficient liquid phase chromatographic analysis Acyl propionic acid ester compound) weight-reacted toluene in R- Furnan products (or levulic acid esters compound) Weight)/reaction before toluene in R- Furnan products (or levulic acid esters compound) weight × 100%, analyze bar Part is referring to preparation example 1, similarly hereinafter).
(2) condensation product is separated：The aqueous phase for taking 25ml steps (1) to obtain, is put into 50ml batch reactor, continuously It is passed through 3MPa CO2Gas, is heated to 70 DEG C and stirs 12h, and 2.13g contractings are obtained after separation of solid and liquid and drying (12h at 100 DEG C) Product is closed, above condensation product is dissolved using 4-methyl-2 pentanone as solvent to be followed by by makings coupled HPLC (GC-MS (Agilent 7890A-5975C), HP-5 chromatographic columns, 50-200 DEG C of temperature programming, 270 DEG C of fid detector temperature, carrier gas He,
Similarly hereinafter) analyze and determine structural formula.
Condensation product C10, C11 dissolve in more than 60 DEG C of hot water, and C15, C17 are water insoluble, therefore use>More than 60 DEG C Hot water repeatedly wash weighted solid mixture, by the filtrate after washing concentrate and add with water can be layered it is organic molten Agent such as 4-methyl-2 pentanone is simultaneously extracted, and pure C10/C11 can be obtained through GC-MS analyses；After washing after remaining solid drying Weigh, C10, C11 for having dissolved weight can be calculated with Subtraction method；Remaining solid is used1H NMR and high resolution mass spectrum analysis are Pure C15 or C17.Two kinds of products can carry out quantitative analysis as standard specimen.Calculated through dissolving post-decrementing, in above-mentioned condensation product The C15-C17 long-chain carboxylic acids of C10-C11 long-chain carboxylic acids (molecular weight is 194-224) and 90.8 weight % containing 9.2 weight % (molecular weight is 272-332).
(3) deoxidation is hydrogenated with：The condensation product of gained in 1g steps (2) is added in 50ml batch reactors, 20g is added Hexamethylene is solvent, adds 0.1g Pd/NbOPO4(Pd weight accounts for the 5% of total catalyst weight, preparation method to catalyst For：By NbOPO4It is impregnated in the ammino palladium solution of dichloro four, stirring 1h is well mixed it, ultrasonic 30min, then will be freshly prepd Sodium borohydride solution (concentration is 5 weight %) is added dropwise, and reduction palladium is in NbOPO4Surface, then suction filtration, washing, drying, under Deoxidation hydrogenation is carried out together), and hydrogenation hydrogen pressure is 6MPa, and terminating reaction after 12h is reacted at 220 DEG C.Reacted solution is through GC-MS As can be seen that all oxygen containing long chain alkanes are completely converted into C9-C17 saturated alkane, (total content in the solution is for analysis 7.2 weight %, assay method is：Concentration is calculated in GC-MS by C9, C10, C11 to all saturated alkane standard samples of C17 After curve, quantitative analysis is carried out to reaction mixture and is drawn after being summed to all C9-C17 hydro carbons concentration in solution, under Together), its structural formula is as follows：
It is computed, corncob changes into the yield (weight of weight/corncob of=obtained long chain alkane of long chain alkane × 100%) be 15.4%.
Embodiment 2
The present embodiment is used for illustrating the preparation method of aviation fuel.
Aviation fuel is prepared in the way of embodiment 1, unlike, the step of (3) deoxidation is hydrogenated with is as follows：
The condensation product of gained in step (2) is taken, is removed with 80 DEG C of hot washes after C10 and C11, takes 0.5g C15- C17 long-chain carboxylic acids are added in 50ml batch reactors, add 10g hexamethylenes as solvent, 0.3g business 5%Ru/C (is purchased from Beijing lark prestige reagent, article No. is R0076) as catalyst, hydrogenation hydrogen pressure is 6MPa, at 160 DEG C after pre-hydrotreating reaction 16h Terminating reaction.Reacted solution is analyzed through GC-MS, and it is the mixed of structure several compounds as follows to draw pre- hydrogenation products Compound：
The further deoxidation hydrogenation of above-mentioned product：Above-mentioned product is introduced into 50ml batch reactors and adds 0.1g's Pd/NbOPO4Catalyst carries out deoxidation hydrogenation, and hydrogenation hydrogen pressure is 6MPa, and terminating reaction after 12h is reacted at 220 DEG C.After reaction It can be drawn through GC-MS tests, all raw materials are converted into C15-C17 saturated alkane, total content is 3.9 weight %, its structure Formula is as follows：
It is computed, the yield that corncob changes into long chain alkane is 11.4%.
Embodiment 3
The present embodiment is used for illustrating the preparation method of aviation fuel.
(1) aldol condensation：Take in preparation example 2 by 1:1 equimolar mixed sugar contains R- chaffs for what is obtained after raw material reaction 6h Aldehyde compound and the common 102g of toluene solution of levulic acid esters compound (including about 2g condensations raw material), with 25ml's 1mol/L Na2CO3Solution is uniformly mixed, the heating stirring at 60 DEG C, and stirring 3h after-condensations feed stock conversion is 82.5%；Stir Mix 6h after-condensation raw materials to convert completely, R- Furnan products and levulic acid esters compound are not present in toluene.
(2) condensation product is separated：The aqueous phase for taking 25ml steps (1) to obtain, is put into 50ml batch reactor, continuously It is passed through 3MPa CO2Gas, is heated to 70 DEG C and stirs 12h, and 1.69g contractings are obtained after separation of solid and liquid and drying (12h at 100 DEG C) Product is closed, above condensation product is dissolved using 4-methyl-2 pentanone as solvent to be followed by being analyzed by makings coupled HPLC, learns production Thing is C10-C11 long-chain carboxylic acids (molecular weight is 194-224).
(3) deoxidation is hydrogenated with：The C10-C11 long-chain carboxylic acids obtained in 1g steps (2) are added in 50ml batch reactors, 10g hexamethylenes are added as solvent, 0.3g business 5%Ru/C (being purchased from Beijing lark prestige reagent, article No. is R0076) is as catalysis Agent, hydrogen pressure is 6MPa, the terminating reaction after pre-hydrotreating reaction 16h at 160 DEG C.Reacted solution is analyzed through GC-MS, is drawn pre- Hydrogenation products are the mixtures of structure several compounds as follows：
Wherein C10 contents are that 96.1 weight %, C11 contents are 3.9 weight %.
The cyclohexane solution containing 10 weight % substrates after 11g is hydrogenated with advance is added in 50ml batch reactors, plus Enter 0.1g 5%Pt/NbOPO4Catalyst carries out deoxidation hydrogenation, and hydrogenation hydrogen pressure is 5MPa, is terminated after 220 DEG C of reaction 12h anti- Should.Reacted solution is analyzed through GC-MS, and the saturated alkane that all oxygen containing long chain alkanes are completely converted into C9-C11 (always contains Measure as 7.42 weight %), consisting of the mixture of structure several compounds as follows：
It is computed, 1:The mixed sugar of 1 equimolar glucose and xylose changes into the yield (=obtained long-chain of long chain alkane The weight of weight/mixed sugar of alkane × 100%) is 20.9%.
Embodiment 4
The present embodiment is used for illustrating the preparation method of aviation fuel.
(1) aldol condensation：Take in preparation example 7 by glucose be raw material react 3h after obtain contain R- Furnan products With the common 10.5g of two parts of toluene solution of levulic acid esters compound (including about 0.5g condensations raw material), with 5ml 1mol/L's K2CO3Solution is uniformly mixed, and is converted completely after heating stirring 12h at 80 DEG C.
(2) condensation product is separated：The aqueous phase for taking 5ml steps (1) to obtain, is put into 50ml batch reactor, continuously It is passed through 3MPa CO2Gas, is heated to 70 DEG C and stirs 12h, and 0.35g contractings are obtained after separation of solid and liquid and drying (12h at 100 DEG C) Product is closed, above condensation product is dissolved using 4-methyl-2 pentanone as solvent to be followed by being analyzed by makings coupled HPLC, and product is The mixture of two kinds of long-chain carboxylic acids, the first be molecular weight be 224 C11 carboxylic acids, second be molecular weight be 332 C17 carboxylics Acid, both respectively account for 57.6 weight % and 42.4 weight %.
(3) deoxidation is hydrogenated with：The condensation product of gained in 1g steps (2) is added in 50ml batch reactors, is added 0.1g Pd/NbOPO4Deoxidation is hydrogenated with after catalyst, and hydrogenation hydrogen pressure is 6MPa, and terminating reaction after 12h is reacted at 220 DEG C.Instead Hydrogen pressure drop is 4.9MPa after should stopping.Reacted solution is analyzed through GC-MS, and all oxygen containing long chain alkanes are completely converted into C10, C11, C16 and C17 saturated alkane (total content is 7.11 weight %), structure is as follows：
It is computed, glucose changes into the yield (weight of weight/glucose of=obtained long chain alkane of long chain alkane × 100%) be 22.6%.
Embodiment 5
The present embodiment is used for illustrating the preparation method of aviation fuel.
Method according to embodiment 4 prepares aviation fuel, unlike, the step of (3) deoxidation is hydrogenated with is as follows：
The mixture of C11 and C17 long-chain carboxylic acids obtained by being added in 50ml batch reactors in 1g steps (2), 10g hexamethylenes are added as solvent, 0.3g business 5%Rd/C (being purchased from Beijing lark prestige reagent, article No. is P1490) is as catalysis Agent, hydrogen pressure is 6MPa, the terminating reaction after pre-hydrotreating reaction 16h at 160 DEG C.Reacted solution is analyzed through GC-MS, is drawn pre- Hydrogenation products are the mixtures for several compounds that structure is as follows：
The further deoxidation hydrogenation of above-mentioned product：The solution of above-mentioned product is introduced into 50ml batch reactors and added 0.1g Pd/NbOPO4Catalyst carries out deoxidation hydrogenation, and hydrogenation hydrogen pressure is 6MPa, and terminating reaction after 12h is reacted at 220 DEG C. It can show that all raw materials are converted into C10, C11, C16 and C17 saturated alkane solution, total content through GC-MS tests after reaction For 6.79 weight %, its structural formula is as follows：
It is computed, the yield that glucose changes into long chain alkane is 24.7%.
Embodiment 6
Method according to embodiment 4 prepares aviation fuel, unlike, using in preparation example 3 use solid acid catalyst I Solution warp after the obtained toluene solution containing R- Furnan products and levulic acid esters compound, deoxidation hydrogenation reaction GC-MS is analyzed, and all oxygen containing long chain alkanes are completely converted into C10, C11, C16 and C17 saturated alkane, and (total content is 4.22 Weight %), structure is as follows：
It is computed, glucose changes into the yield (weight of weight/glucose of=obtained long chain alkane of long chain alkane × 100%) be 21.3%.
Embodiment 7
Method according to embodiment 4 prepares aviation fuel, unlike, using in preparation example 3 use solid acid catalyst Solution after toluene solution containing R- Furnan products and levulic acid esters compound made from II, deoxidation hydrogenation reaction Analyzed through GC-MS, all oxygen containing long chain alkanes are completely converted into C10, C11, C16 and C17 saturated alkane, and (total content is 3.65 weight %), structure is as follows：
It is computed, glucose changes into the yield (weight of weight/glucose of=obtained long chain alkane of long chain alkane × 100%) be 17.3%.
Comparative example 1
Aviation fuel is prepared in the way of preparation example 1 and embodiment 1, unlike, the consumption of toluene is 55g and not made With isopropanol, R- Furnan products (including furfural, 5 hydroxymethyl furfural and 5- isopropoxy methylene furfural) and second are obtained The yield of acyl propionic acid ester compound is respectively 15.9% and 1.5%.
Solution after deoxidation hydrogenation reaction is through GC-MS analyses as can be seen that all oxygen containing long chain alkanes are completely converted into C15-C17 saturated alkane (total content is 0.32 weight %), its structural formula is as follows：
It is computed, corncob changes into the yield (weight of weight/mixed sugar of=obtained long chain alkane of long chain alkane × 100%) be 3.2%.
Comparative example 2
Aviation fuel is prepared in the way of preparation example 1 and embodiment 1, unlike, the consumption of toluene is 95g and not made With water, R- Furnan products (including furfural, 5 hydroxymethyl furfural and 5- isopropoxy methylene furfural) and levulinic are obtained The yield of acid esters compound is respectively 3.92% and 2.06%.
Solution after deoxidation hydrogenation reaction is through GC-MS analyses as can be seen that all oxygen containing long chain alkanes are completely converted into C9-C17 saturated alkane (total content is 5.31 weight %), its structural formula is as follows：
It is computed, corncob changes into the yield (weight of weight/mixed sugar of=obtained long chain alkane of long chain alkane × 100%) be 5.31%.
From above-described embodiment as can be seen that the present invention, which can be directly based upon protist matter, prepares aviation fuel, and can be with Other ketone or aldehyde are not introduced.Comparing embodiment 1 and comparative example 1-2 can be seen that only while using alcohol and reaction medium (water With the mixture of non-alcohols organic solvent) it can expeditiously prepare aviation fuel.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should equally be considered as content disclosed in this invention.

Claims (10)

1. a kind of method for preparing aviation fuel production raw material, it is characterised in that this method includes：In alcohol, acid catalyst, anti- Answer in the presence of the water-soluble inorganic salt that medium and selectivity are used, sugar source is carried out molecule inner dewatering reaction, be dissolved with The organic phase of compound shown in Formulas I and Formula II,
Wherein, the alcohol is C1-6Monohydric alcohol, the reaction medium is the mixture of water and non-alcohols organic solvent；R1For-H ,- CH2OH、-CH2OCH3、-CH2OCH2CH3、-CH2OC3H7、-CH2OC4H9、-CH2OC5H11Or-CH2OC6H13；R2For-H or C1-6's Alkyl, C1-6Alkyl be preferably-CH3、-CH2CH3、-C3H7、-C4H9、-C5H11Or-C6H13。
2. according to the method described in claim 1, wherein, the weight ratio of the sugar source and alcohol is 1:0.1-2；
And/or, the weight ratio of the sugar source and acid catalyst is 1:0.01-1；
And/or, the weight ratio of the sugar source and reaction medium is 1:2-100；
And/or, the weight ratio of water and non-alcohols organic solvent is 1:0.5-2；
And/or, the weight ratio of the sugar source and water-soluble inorganic salt is 1:0.01-1.
3. method according to claim 1 or 2, wherein, the alcohol is methanol, ethanol, propyl alcohol, isopropanol, butanol, isobutyl One or more in alcohol and 1- amylalcohols；
And/or, the non-alcohols organic solvent is tetrahydrofuran, 4-methyl-2 pentanone, acetone, dioxane, 2- methyl tetrahydrochysenes One or more in furans, toluene, dimethylbenzene, aliphatic hydrocarbon, petroleum ether, dichloromethane and chloroform；
And/or, the water-soluble inorganic salt is the chloride of metal, the sulfate of metal and one kind in the nitrate of metal or It is a variety of；
And/or, the acid catalyst is solid acid catalyst I and/or solid acid catalyst II, the solid acid catalyst I tools There is impalpable structure and chemical formula is Alx1Siy1O(3x1+4y1)/2, wherein, y1 and x1 is each independently positive integer and y1:X1= 0.25-200:1；The solid acid catalyst II has impalpable structure and chemical formula is Ax2Py2O(4x2+5y2)/2, wherein, A is represented Group IVB metallic element and/or IVA races metallic element, y2 and x2 are each independently positive integer and y2:X2=0.5-4:1.
4. according to the method described in claim 1, wherein, the condition of molecule inner dewatering reaction includes：Temperature be 70-210 DEG C, when Between be 1-100h；Preferably, the condition of molecule inner dewatering reaction includes：Temperature is 120-150 DEG C, the time is 1-25h.
5. the method according to any one in claim 1-4, wherein, the sugar source is glucose, sucrose, fructose, fibre Tie up disaccharides, synanthrin, lactose, lyxose, xylose, xylan, cellulose, hemicellulose, starch, corncob, bagasse, stalk, One or more in seed hulls and wood materials.
6. according to the method described in claim 1, wherein, the sugar source is corncob, bagasse, stalk, seed hulls and wooden During one or more in material, sugar source produces solid residue after molecule inner dewatering reaction, and methods described also includes：Make production Raw solid residue is converted into porous carbon material.
7. a kind of method for preparing aviation fuel, it is characterised in that this method comprises the following steps：
A, according to described in any one in claim 1-6 method prepare be dissolved with the organic of compound shown in Formulas I and Formula II Phase；
B, the organic phase progress aldol reaction that compound shown in Formulas I and Formula II will be dissolved with；
C, take the product after aldol reaction carry out deoxidation hydrogenation reaction.
8. method according to claim 7, wherein, the mode of the aldol reaction is：, will be molten at 20-120 DEG C The organic phase that solution has compound shown in Formulas I and Formula II is mixed with alkaline solution.
9. method according to claim 8, wherein, methods described also includes neutralizing in the product after aldol reaction The organic phase in product after alkaline matter, and/or recovery aldol reaction.
10. method according to claim 7, wherein, the mode of the deoxidation hydrogenation reaction is：In 140-260 DEG C and 1- Under conditions of 8MPa, the product of aldol reaction is mixed with deoxidation hydrogenation catalyst；Or,
The mode of the deoxidation hydrogenation reaction is：The product of aldol reaction is mixed with deoxidation hydrogenation catalyst, existed respectively Pre-deoxidation hydrogenation is carried out under conditions of 80-220 DEG C and 1-8MPa and deoxidation is carried out under conditions of 140-260 DEG C and 1-8MPa Hydrogenation, wherein, the temperature needed for the temperature needed for pre-deoxidation hydrogenation is hydrogenated with than deoxidation is low 40-100 DEG C.
CN201610157216.8A 2016-03-18 2016-03-18 Raw material for aviation fuel production and preparation method of aviation fuel Active CN107200722B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610157216.8A CN107200722B (en) 2016-03-18 2016-03-18 Raw material for aviation fuel production and preparation method of aviation fuel

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610157216.8A CN107200722B (en) 2016-03-18 2016-03-18 Raw material for aviation fuel production and preparation method of aviation fuel

Publications (2)

Publication Number Publication Date
CN107200722A true CN107200722A (en) 2017-09-26
CN107200722B CN107200722B (en) 2020-07-28

Family

ID=59904567

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610157216.8A Active CN107200722B (en) 2016-03-18 2016-03-18 Raw material for aviation fuel production and preparation method of aviation fuel

Country Status (1)

Country Link
CN (1) CN107200722B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108997275A (en) * 2018-06-20 2018-12-14 昆明理工大学 A method of primary product distribution in control fructose-ethanol synthesis system
CN111215073A (en) * 2018-11-23 2020-06-02 中国石油化工股份有限公司 Nickel-silicon composite oxide, preparation method thereof, catalyst containing oxide and application thereof
CN111470927A (en) * 2020-04-15 2020-07-31 华东师范大学 Method for preparing high-melting-point wax from furfural

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102260229A (en) * 2010-05-28 2011-11-30 中国科学院大连化学物理研究所 Method for preparing 5-hydroxymethylfurfural and 5-alkoxymethylfurfural
CN103467418A (en) * 2012-06-07 2013-12-25 中国科学院大连化学物理研究所 Method for preparing furan derivatives by catalytic conversion of fructose-based biomass
CN104650947A (en) * 2015-02-06 2015-05-27 中国科学院广州能源研究所 Method of preparing long chain alkane for jet fuel by virtue of sugar platform compound

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102260229A (en) * 2010-05-28 2011-11-30 中国科学院大连化学物理研究所 Method for preparing 5-hydroxymethylfurfural and 5-alkoxymethylfurfural
CN103467418A (en) * 2012-06-07 2013-12-25 中国科学院大连化学物理研究所 Method for preparing furan derivatives by catalytic conversion of fructose-based biomass
CN104650947A (en) * 2015-02-06 2015-05-27 中国科学院广州能源研究所 Method of preparing long chain alkane for jet fuel by virtue of sugar platform compound

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108997275A (en) * 2018-06-20 2018-12-14 昆明理工大学 A method of primary product distribution in control fructose-ethanol synthesis system
CN111215073A (en) * 2018-11-23 2020-06-02 中国石油化工股份有限公司 Nickel-silicon composite oxide, preparation method thereof, catalyst containing oxide and application thereof
CN111215073B (en) * 2018-11-23 2024-03-12 中国石油化工股份有限公司 Nickel-silicon composite oxide, preparation method thereof, catalyst containing nickel-silicon composite oxide and application of nickel-silicon composite oxide
CN111470927A (en) * 2020-04-15 2020-07-31 华东师范大学 Method for preparing high-melting-point wax from furfural
CN111470927B (en) * 2020-04-15 2022-12-30 华东师范大学 Method for preparing high-melting-point wax from furfural

Also Published As

Publication number Publication date
CN107200722B (en) 2020-07-28

Similar Documents

Publication Publication Date Title
Khanday et al. Biodiesel byproduct glycerol upgrading to glycerol carbonate over lithium–oil palm ash zeolite
Wang et al. Conversion of fructose into furfural or 5-hydroxymethylfurfural over HY zeolites selectively in γ-butyrolactone
CN105283463B (en) It is single oxidation or the method for polyoxy chemoattractant molecule by lignocellulosic biomass conversion
CN104711007A (en) Preparation method of aviation kerosene or diesel oil scope liquid alkane
Kusema et al. Hydrolytic hydrogenation of hemicellulose over metal modified mesoporous catalyst
CN105473227B (en) For converting the sugars into lactic acid and the method for 2- hydroxyls -3-butenoic acid or its ester in the presence of metal-silicate material and metal ion
CN104016371B (en) The in-situ synthetic method of cupric mordenite
CN104232140A (en) Method for synthesizing high-density aviation fuel by using cyclopentanone as raw material
CN107200722A (en) A kind of preparation method of aviation fuel production raw material and aviation fuel
CN103030516B (en) Purification method of coking xylene
CN108499607A (en) A kind of Preparation method and use of Quito aqueous acid medium alkali bifunctional MOFs pore catalyst
CN106861754B (en) A kind of modified Pd/C is directly catalyzed the method that carbohydrate prepares 2,5- dimethyl furan
CN107952486A (en) A kind of compound acidic solid catalyst PVP-HNTs@UiO-66-SO3H and preparation method thereof
CN103990473A (en) Sulfate radical composite oxide solid acid catalyst, its preparation method, and method for catalyzing conversion of xylan to furfural through using it
CN105728042A (en) Catalyst for producing levulinate through furfural and preparation method and application of catalyst
ZHENG et al. Catalytic conversion of cellulose and starch to furfural over zeolites
CN105622419A (en) Method for preparing from glycolic acid ester from carbohydrate
CN108727180A (en) A kind of method of surface amination Sn-Beta molecular sieve catalytics carbohydrate lactic acid producing
CN103626810A (en) Method for catalyzing glucose by using magnetic solid acid to produce methyl glucoside
CN110002934A (en) A method of low-carbon alkene is prepared by oleic acid
CN107199043B (en) Solid acid catalyst, preparation method and application thereof, and method for preparing furfural compound
CN110314696B (en) Composite catalyst, preparation method thereof and preparation method of ethylene
CN107199028A (en) Solid acid catalyst and its preparation method and application and the method for preparing Furnan products
CN102816054B (en) Environment-friendly method for preparing adipic acid by catalytic oxidation
Zhang et al. Production of furans from pulp sheet over sulfated solid acid catalysts

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant