CN105622326B - A kind of method that low-carbon alkene is prepared by sucrose - Google Patents

A kind of method that low-carbon alkene is prepared by sucrose Download PDF

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CN105622326B
CN105622326B CN201410590013.9A CN201410590013A CN105622326B CN 105622326 B CN105622326 B CN 105622326B CN 201410590013 A CN201410590013 A CN 201410590013A CN 105622326 B CN105622326 B CN 105622326B
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acid
catalyst
solvent
dehydration
carbon
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CN105622326A (en
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张兆斌
王国清
李蔚
周丛
杜志国
张永刚
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • 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
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

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Abstract

The invention discloses a kind of method that low-carbon alkene is prepared by sucrose, this method includes：In the presence of the first solvent and dehydration catalyst, dehydration will be carried out from six-carbon monosaccharide is mixed made from sucrose, then in the presence of condensation catalyst, the dehydration reaction product of acquisition is subjected to self-condensation reaction, again in the presence of the 3rd solvent and hydrogenation catalyst, the self-condensation reaction product of acquisition is subjected to hydrogenation reaction；Finally the hydrogenation reaction product of acquisition is cracked.The method provided by the invention that low-carbon alkene is prepared by sucrose can be using sucrose as raw material, efficient obtained low-carbon alkene, the gross production rate of pyrolysis furnace low-carbon alkene can also be effectively improved simultaneously, also effectively reduced while improving the utilization rate and value to natural resources in the production of low-carbon alkene to the demand of petroleum.

Description

A kind of method that low-carbon alkene is prepared by sucrose
Technical field
The present invention relates to the preparation field of low-carbon alkene, in particular it relates to a kind of method that low-carbon alkene is prepared by sucrose.
Background technology
Low-carbon alkene typically refers to the general name of the unsaturated hydrocarbon of carbon four and carbon below four, mainly including ethene, Propylene, isobutene, butadiene etc. have the Organic Chemicals of high economic value.With China's expanding economy, these are organic The demand of industrial chemicals increases year by year.Although the production scale of low-carbon alkene is also increasing year by year, can not also meet increasingly The demand of growth.
For a long time, China prepares low-carbon alkene product with naphtha, large-scale with petroleum chemical enterprise's process units scale Change, the disposal ability that China singly covers oil refining apparatus alreadys exceed 10,000,000 tons/year, and the ethene of matched ethylene unit is given birth to Production capacity power has also reached 80~1,200,000 tons/year.But with the increasingly reduction of fossil resources, the petrochemical industry based on crude oil Production cost improves year by year.Therefore, there is an urgent need to develop a kind of new raw material and method that prepare low-carbon alkene.
The content of the invention
In order to solve the problems, such as the nervous and lasting cost increase of the raw materials requirement of existing petroleum base low-carbon alkene production, The present invention proposes a kind of method that low-carbon alkene is prepared by sucrose.This method can be efficient to be made using sucrose as raw material Low-carbon alkene, while the gross production rate of pyrolysis furnace low-carbon alkene can also be effectively improved, it is right in the production of low-carbon alkene effectively to reduce The demand of petroleum.
The present inventor is after research it was unexpectedly observed that by the mixing six-carbon monosaccharide obtained from sucrose in ionic liquid The 5 hydroxymethyl furfural (5-hydroxymethylfurfural, HMF) for carrying out obtaining after dehydration in body can be in catalyst In the presence of occur self-condensation reaction generation 5,5 '-dihydroxymethyl chaff accidental cause (5,5 '-di (hydroxymethyl) furoin, DHMF C10-C12 saturated straight chain alkane can be obtained by), then to 5,5 '-dihydroxymethyl chaff accidental cause carrying out hydrogenation reaction, finally right C10-C12 saturated straight chain alkane, which carries out steam cracking, can obtain low-carbon alkene.This method can be expeditiously by from sucrose The mixing six-carbon monosaccharide of middle acquisition is converted into low-carbon alkene, can also improve the gross production rate of pyrolysis furnace low-carbon alkene, effectively reduces The production of low-carbon alkene is to the demand of petroleum, so as to complete the present invention.
The invention provides a kind of method that low-carbon alkene is prepared by sucrose, this method comprises the following steps：
(1) in the presence of the first solvent and dehydration catalyst, will be dehydrated from six-carbon monosaccharide is mixed made from sucrose Reaction；
(2) in the presence of condensation catalyst, the dehydration reaction product that step (1) is obtained carries out self-condensation reaction；
(3) in the presence of the 3rd solvent and hydrogenation catalyst, the self-condensation reaction product that step (2) obtains is added Hydrogen reacts；
(4) hydrogenation reaction product that step (3) obtains is cracked.
The method provided by the invention that low-carbon alkene is prepared by sucrose can be using sucrose as raw material, efficient obtained low-carbon Alkene, while the gross production rate of pyrolysis furnace low-carbon alkene can also be effectively improved, improve the utilization rate to natural resources and utilization Also effectively reduced while value in the production of low-carbon alkene to the demand of petroleum.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is 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 present invention provides a kind of method that low-carbon alkene is prepared by sucrose, and this method comprises the following steps：
(1) in the presence of the first solvent and dehydration catalyst, will be dehydrated from six-carbon monosaccharide is mixed made from sucrose Reaction；
(2) in the presence of condensation catalyst, the dehydration reaction product that step (1) is obtained carries out self-condensation reaction；
(3) in the presence of the 3rd solvent and hydrogenation catalyst, the self-condensation reaction product that step (2) obtains is added Hydrogen reacts；
(4) hydrogenation reaction product that step (3) obtains is cracked.
According to the present invention, in step (1), the sucrose can be made using sugarcane or beet as raw material.Sucrose has can be again Natural disposition and it is widely distributed the characteristics of, the carbon list of mixing six being made up of the glucose and fructose of equivalent can be produced after being degraded Sugar.
In step (1), the operation of mixing six-carbon monosaccharide is prepared from sucrose to be included：By sucrose in degraded solvent and degraded Degraded under the conditions of catalyst is existing.Then the catabolite of acquisition can be obtained to six carbon of mixing after desolventizing is handled The crystallization of monose.Wherein, the degraded solvent can be selected from least one of water, methanol, ethanol, ether and acetone.It is described Degradation catalyst can be the complex of metallic copper.In the complex of the metallic copper, part can be selected from group At least one of propylhomoserin, imidazoles, alanine, monoethanolamine, Pehanorm and 2- ethyl -5- methylimidazoles.The degraded The dosage of catalyst can be the 5-70 mass %, preferably 10-60 mass % of sucrose.The operating condition of the degraded includes temperature It can be 25-120 DEG C, preferably 50-110 DEG C, the time can be 30-240min, preferably 45-150min.
In step (1), first solvent can be ionic liquid.The ionic liquid can be selected from 1- alkyl -3- first At least one of base imidazoles chlorine, 1- alkyl -3- methylimidazoles carboxylic acid and 1- alkyl -3- methylimidazolidinyl phosphates.It is preferred that Ground, the ionic liquid are selected from 1- butyl -3- methylimidazoles chlorine, 1- pi-allyl -3- methylimidazoles chlorine, 1- pi-allyl -3- methyl At least one of imidazole formic acid, 1- ethyl-3-methylimidazoles methyl orthophosphoric acid and 1- ethyl-3-methylimidazole acetic acid.
In step (1), the dehydration catalyst can be in inorganic acid, organic acid and metal halide at least one Kind.The inorganic acid can be selected from least one of sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid.The organic acid can be selected from acetic acid, At least one of propionic acid, benzoic acid, benzene sulfonic acid, ethanedioic acid, maleic acid, phthalic acid and terephthalic acid (TPA).The metal Halide can be selected from least one of chromium, aluminium, sodium, iron, copper, vanadium, molybdenum, platinum, ruthenium and the chloride of rhodium or bromide.It is preferred that Ground, the dehydration catalyst be selected from sulfuric acid, hydrochloric acid, acetic acid, benzoic acid, benzene sulfonic acid, chromium dichloride, chromium trichloride, alchlor, In sodium chloride, ferric trichloride, copper chloride, vanadium chloride, molybdenum chloride, platinous chloride, platinum tetrachloride, ruthenic chloride and radium chloride at least It is a kind of.The usage amount of the dehydration catalyst can be the 0.01-10 moles of %, preferably 1-8 moles of % of the six-carbon monosaccharide.
In step (1), it can be 50-200 DEG C that the condition of the dehydration, which includes temperature, preferably 70-180 DEG C, the time It can be 0.5-10 hours, preferably 2-6 hours.The dehydration can be carried out under agitation.The dehydration knot Shu Hou, you can dehydration reaction product 5 hydroxymethyl furfural is obtained in the mixture obtained after dehydration.It is anti-from the dehydration Should after the mode of 5 hydroxymethyl furfural is obtained in obtained mixture can include：Water is added into the mixture after dehydration And organic solvent, and it is sufficiently mixed the mixture after dehydration, water and organic solvent, then stand and make aqueous phase and organic solvent It is separated, 5 hydroxymethyl furfural is obtained after then concentrating organic solvent phase.The organic solvent can be selected from dichloromethane, tetrachloro Change at least one of carbon, chloroform, petroleum ether, ether and hexamethylene.
According to the present invention, in step (2), the condensation catalyst can be organic nitrogen heterocycle carbine.Preferably, the contracting Close catalyst and be selected from 1,3,4- tri-tert -1,2,4- triazole -5- Cabbeens, 1,3,4- triphenyl -1,2,4- triazoles -5- cards At least one of guest and the naphthyl -1,2,4- triazole -5- Cabbeens of 1,3,4- tri-.The usage amount of the condensation catalyst can be 0.01-10 moles of % of the dehydration reaction product (5 hydroxymethyl furfural), preferably 1-5 moles of %.
In step (2), the self-condensation reaction can be carried out under conditions of presence or absence of the second solvent.Described Two solvents can be selected from least one of tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide (DMSO) and ionic liquid.It is described Ionic liquid and above-mentioned identical.
In step (2), it can be 30-200 DEG C that the condition of the self-condensation reaction, which includes temperature, preferably 50-120 DEG C, when Between can be 0.1-10 hours, preferably 0.5-5 hours.After the self-condensation reaction terminates, you can obtained after self-condensation reaction Mixture in be derived from condensation reaction products 5,5 '-dihydroxymethyl chaff accidental cause.The mixing obtained after the self-condensation reaction The mode of 5,5 '-dihydroxymethyl chaff accidental cause is obtained in thing to be included：The second solvent is first steamed into (if any), Ran Houyong Hexamethylene washs obtained solid, can obtain 5 after drying, 5 '-dihydroxymethyl chaff accidental cause.
According to the present invention, in step (3), the active component of the hydrogenation catalyst can be Metal Palladium and/or platinum.It is described The carrier of hydrogenation catalyst can be inorganic acid and/or inorganic acid salt, acid organic salt, activated carbon and heteropoly acid and/or miscellaneous At least one of multi-acid salt.The inorganic acid can be selected from least one of sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid.The nothing Machine hydrochlorate can be phosphoric acid tantalum and/or niobium phosphate.The acid organic salt can be selected from [bmim]3PW12O40、[MIMPS]3PW12O40、[PyPS]3PW12O40[TEAPS]3PW12O40At least one of.The heteropoly acid can be H3PW12O40.It is described Heteropolyacid salt can be selected from CsH2PW12O40、NaH2PW12O40、LiH2PW12O40And KH2PW12O40At least one of.Preferably, The hydrogenation catalyst is selected from phosphoric acid and the mixture and/or phosphoric acid tantalum and the mixture of platinum carbon of palladium carbon.Specifically, the hydrogenation Catalyst can be selected from Pd/CH3PO4、Pt/CsH2PW12O40、Pt/Cs2.5H0.5PW12O40And Pt/CTaOPO4At least one of. The dosage of the hydrogenation catalyst can be for self-condensation reaction product (the 5,5 '-dihydroxymethyl with gauge with active component Chaff accidental cause) 0.01-10% moles of %, preferably 0.1-5 moles of %.
In step (3), it can be 0.1-30MPa, preferably 1-10MPa that the condition of the hydrogenation reaction, which includes pressure, temperature It can be 25-350 DEG C, preferably 50-300 DEG C, the time can be 0.5-10 hours, preferably 1-5 hours.Preferably, institute is being carried out Before stating hydrogenation reaction, the air in inert gas replacement reaction vessel is used.The inert gas can be nitrogen and/or zero Race's gas.The hydrogenation reaction can be carried out under agitation.
In step (3), the 3rd solvent can be selected from least one of hydro carbons, alcohols and water.The varsol At least one of ether, petroleum ether, dichloromethane, chloroform, heptane, hexane, pentamethylene and hexamethylene can be selected from.Institute At least one of glycerine, ethanol and methanol can be selected from by stating alcohols solvent.After the hydrogenation reaction terminates, you can anti-from hydrogenation C10-C12 saturated straight chain alkane is obtained in the mixture that should be obtained afterwards.Obtained in the mixture obtained after the hydrogenation reaction Obtaining the mode of C10-C12 saturated straight chain alkane can include：The mixture obtained after hydrogenated reaction is filtered, filters out hydrogenation Catalyst simultaneously reclaims, and then removes the 3rd solvent.
According to the present invention, in step (4), the cracking can be steam cracking.The steam cracking can split in steam Carried out in solution stove.Preferably, the condition of the steam cracking is carried out in the steam cracking furnace can include steam cracking furnace Coil outlet temperature be 710-890 DEG C, preferably 780-860 DEG C, step (3) obtain hydrogenation reaction product and water vapour matter Amount is than being 1：(0.3-1), preferably 1：(0.4-0.8).
In step (4), low-carbon alkene can be obtained from pyrolysis product.Low-carbon alkene is obtained from the pyrolysis product Mode can be operating method commonly used in the art.The mode that low-carbon alkene is obtained from pyrolysis product for example can be according to Flow including following operation order separates to pyrolysis product：Pyrolysis product isolates cracking by oil scrubber and water scrubber Fuel oil and drippolene simultaneously remove the acidic materials in cracking gas, after compression, hydrogen and methane are isolated with domethanizing column, Ethene and propylene are isolated with dethanizer, ethene and propylene are isolated with depropanizing tower, four groups of carbon is isolated with debutanizing tower Point, isolated each component is passed through into the isolated corresponding low-carbon alkene of rectifying column respectively.
Below will the present invention will be described in detail by specific embodiment.
In following examples and comparative example：
In step (1), the computational methods of the yield of mixing six-carbon monosaccharide (total monosaccharide) are as follows：
In step (1), the computational methods of HMF yield are as follows：
In step (2), the computational methods of DHMF yield are as follows：
The computational methods of the yield of the saturated straight chain alkane for the C10-C12 that step (3) obtains are as follows：
In step (4), the computational methods of the yield of each pyrolysis product are as follows：
Embodiment 1
(1) suitable quantity of water is added into the stirred tank equipped with sucrose, is completely dissolved sucrose, then adds and accounts for into stirred tank The N of the mass % of sucrose 10 three-fold coordination, N- bis- (2- ethyl -5- methyl-imidazoles -4- methylene) monoethanolamine copper is (public purchased from Sigma Department), in 90 DEG C of stirring reactions 6 hours, obtain the solution containing mixing six-carbon monosaccharide.The solution for mixing six-carbon monosaccharide is carried out dense Contracting, crystallization, filter and mixing six-carbon monosaccharide is obtained after drying, the yield for measuring mixing six-carbon monosaccharide (total monosaccharide) is 91.7%.
Using 1- butyl -3- methylimidazoles chlorine (as solvent), mass fraction be 98% the concentrated sulfuric acid (as catalyst) and (content of sulfuric acid is six carbon lists of mixing wherein in the concentrated sulfuric acid in the mixing six-carbon monosaccharide addition stirred tank obtained by the above method 0.5 mole of % of sugar), then under agitation, reacted 3 hours at 80 DEG C；Obtained material is taken out, adds water and dichloro The methane and material, water and dichloromethane that make to obtain are sufficiently mixed, then stand and make aqueous phase and organic solvent phase (dichloromethane phase) Separation, 5 hydroxymethyl furfural (HMF) is obtained after concentrating organic solvent phase, methanol is added into aqueous phase, separate out unreacted sugar. It is computed, HMF yield is 91%.
(2) using tetrahydrofuran (as solvent), 1,3,4- tri-tert -1,2,4- triazole -5- Cabbeens (as catalysis Agent) and step (1) obtain HMF add stirred tank in (the wherein use of 1,3,4- tri-terts -1,2,4- triazoles -5- Cabbeens Measure 1.0 moles of % for HMF), then under agitation, reacted 1 hour at 80 DEG C；Obtained material is taken out, by tetrahydrochysene Furans washs the solid obtained with hexamethylene again after being evaporated off, then obtains 5,5 '-dihydroxymethyl chaff accidental cause (DHMF) after drying.Through Calculate, DHMF yield is 89%.
(3) using methanol (as solvent), Pd/C H3PO4The DHMF that (as catalyst) and step (2) obtain adds pressure (wherein Pd/C H in kettle3PO43.2 moles of % using the dosage that Pd is counted as DHMF), then replace the sky in autoclave pressure with argon gas Gas, then hydrogen is filled with into autoclave pressure, the pressure in autoclave pressure is reached 3.45MPa, then under agitation, at 200 DEG C Lower reaction 6 hours；Obtained material is taken out, catalyst is removed by filtration and the C10- of acquisition oily after solvent is distilled off C12 saturated straight chain paraffins mixture.The C10-C12 of the oily obtained through chromatogram and mass spectral analysis saturated straight chain alkane mixes The content of C10 alkane, the content of C11 alkane, the content of C12 alkane, the content of total alkane are shown in Table 1 in compound.
(4) the saturated straight chain paraffins mixture for the C10-C12 for obtaining vapor and step (3) is 1 according to mass ratio： 0.5 ratio is injected in small-sized cracking analogue means (being purchased from Sinopec Beijing Research Institute of Chemical Industry) Row steam cracking reaction, maintenance reaction 40 minutes at being 790 DEG C in the coil outlet temperature of small-sized cracking analogue means.Pass through color Low-carbon alkene composition in the gas-phase product that spectrum detection reaction obtains, and calculate the yield of each pyrolysis product.Each pyrolysis product Yield is shown in Table 2.
Embodiment 2
In addition to following operating condition, other are and embodiment 1 is identical.
In step (1), the first solvent is changed into 1- pi-allyl -3- methylimidazole chlorine, dehydration catalyst changes chromium dichloride into, Reaction temperature is changed to 100 DEG C.
In step (2), 1,3,4- triphenyls -1,2, the nitrogen of 4- tri- are changed into without using the second solvent, while by condensation catalyst Azoles -5- Cabbeens, reaction temperature are changed to 60 DEG C.
HMF yield, DHMF yield, the content of C10 alkane, C11 alkane in C10-C12 saturated straight chain paraffins mixture The content of hydrocarbon, the content of C12 alkane, the content of total alkane are shown in Table 1.
The composition of the low-carbon alkene finally obtained and the yield of each pyrolysis product are shown in Table 2.
Embodiment 3
In addition to following operating condition, other are and embodiment 1 is identical.
In step (1), the first solvent is changed into 1- pi-allyl -3- methylimidazole formic acid, dehydration catalyst changes tri-chlorination into Chromium, reaction temperature are changed to 120 DEG C.
In step (2), 1,3,4- triphenyls -1,2, the nitrogen of 4- tri- are changed into without using the second solvent, while by condensation catalyst Azoles -5- Cabbeens, reaction temperature are changed to 60 DEG C.
In step (3), hydrogenation catalyst is changed into Pt/CsH2PW12O40, reaction temperature is changed to 250 DEG C, the pressure in autoclave pressure Power is changed to 3.20MPa.
In step (4), the mass ratio of the saturated straight chain paraffins mixture for the C10-C12 that vapor and step (3) are obtained It is changed to 1：0.6, the coil outlet temperature of small-sized cracking analogue means is changed to 820 DEG C.
HMF yield, DHMF yield, the content of C10 alkane, C11 alkane in C10-C12 saturated straight chain paraffins mixture The content of hydrocarbon, the content of C12 alkane, the content of total alkane are shown in Table 1.
The composition of the low-carbon alkene finally obtained and the yield of each pyrolysis product are shown in Table 2.
Embodiment 4
In addition to following operating condition, other are and embodiment 1 is identical.
In step (1), the first solvent is changed into 1- ethyl-3-methylimidazole methyl orthophosphoric acids, dehydration catalyst changes trichlorine into Change aluminium, reaction temperature is changed to 180 DEG C.
In step (2), the second solvent is changed into 1- ethyl-3-methylimidazole acetic acid, condensation catalyst changes 1,3,4- tri- into Naphthyl -1,2,4- triazole -5- Cabbeens, reaction temperature are changed to 100 DEG C.
In step (3), hydrogenation catalyst is changed into Pt/CsH2PW12O40, reaction temperature is changed to 300 DEG C, the pressure in autoclave pressure Power is changed to 5.00MPa.
In step (4), the mass ratio of the saturated straight chain paraffins mixture for the C10-C12 that vapor and step (3) are obtained It is changed to 1：0.6, the coil outlet temperature of small-sized cracking analogue means is changed to 820 DEG C.
HMF yield, DHMF yield, the content of C10 alkane, C11 alkane in C10-C12 saturated straight chain paraffins mixture The content of hydrocarbon, the content of C12 alkane, the content of total alkane are shown in Table 1.
The composition of the low-carbon alkene finally obtained and the yield of each pyrolysis product are shown in Table 2.
Embodiment 5
In addition to following operating condition, other are and embodiment 1 is identical.
In step (2), the second solvent is changed into 1- ethyl-3-methylimidazole acetic acid, condensation catalyst changes 1,3,4- tri- into Naphthyl -1,2,4- triazole -5- Cabbeens, reaction temperature are changed to 100 DEG C.
In step (3), hydrogenation catalyst is changed into Pt/C TaOPO4, the 3rd solvent changes water into, and reaction temperature is changed to 300 DEG C, the pressure in autoclave pressure is changed to 3.45MPa.
In step (4), the mass ratio of the saturated straight chain paraffins mixture for the C10-C12 that vapor and step (3) are obtained It is changed to 1：0.7, the coil outlet temperature of small-sized cracking analogue means is changed to 850 DEG C.
HMF yield, DHMF yield, the content of C10 alkane, C11 alkane in C10-C12 saturated straight chain paraffins mixture The content of hydrocarbon, the content of C12 alkane, the content of total alkane are shown in Table 1.
The composition of the low-carbon alkene finally obtained and the yield of each pyrolysis product are shown in Table 2.
Embodiment 6
In addition to following operating condition, other are and embodiment 1 is identical.
In step (2), 1,3,4- triphenyls -1,2, the nitrogen of 4- tri- are changed into without using the second solvent, while by condensation catalyst Azoles -5- Cabbeens, reaction temperature are changed to 60 DEG C.
In step (3), hydrogenation catalyst is changed into Pt/C TaOPO4, the 3rd solvent changes water into, and reaction temperature is changed to 300 DEG C, the pressure in autoclave pressure is changed to 3.45MPa.
In step (4), the mass ratio of the saturated straight chain paraffins mixture for the C10-C12 that vapor and step (3) are obtained It is changed to 1：0.7, the coil outlet temperature of small-sized cracking analogue means is changed to 850 DEG C.
HMF yield, DHMF yield, the content of C10 alkane, C11 alkane in C10-C12 saturated straight chain paraffins mixture The content of hydrocarbon, the content of C12 alkane, the content of total alkane are shown in Table 1.
The composition of the low-carbon alkene finally obtained and the yield of each pyrolysis product are shown in Table 2.
Comparative example 1
Naphtha with physical property shown in table 3 is anti-according to the operating method progress steam cracking of the step of embodiment 1 (4) Should.
The composition of the low-carbon alkene finally obtained and the yield of each pyrolysis product are shown in Table 2.
Table 1
HMF yields DHMF yields C10 yields C11 yields C12 yields Total alkane yield
Embodiment 1 91% 89% 18.6% 37.6% 32.2% 88.4%
Embodiment 2 88% 99% 18.6% 37.6% 32.2% 88.4%
Embodiment 3 89% 99% - 24.3% 67.6% 91.9%
Embodiment 4 90% 91% 4.3% 36.8% 38.6% 79.7%
Embodiment 5 91% 91% 27.0% 22.9% 45.6% 95.5%
Embodiment 6 91% 99% 27.0% 22.9% 45.6% 95.5%
In table 2, low-carbon alkene total recovery refers to the total recovery of ethene, propylene, butylene and butadiene.
Table 2
Hydrogen yield Yield of ethene Propene yield Butylene yield Butadiene yield Low-carbon alkene total recovery
Embodiment 1 0.40% 33.65% 18.25% 6.52% 5.03% 63.45%
Embodiment 2 0.40% 33.65% 18.25% 6.52% 5.03% 63.45%
Embodiment 3 0.61% 38.91% 18.55% 5.16% 5.84% 68.46%
Embodiment 4 0.61% 38.91% 18.55% 5.16% 5.84% 68.46%
Embodiment 5 0.71% 42.82% 16.95% 3.47% 5.83% 69.07%
Embodiment 6 0.71% 42.82% 16.95% 3.47% 5.83% 69.07%
Comparative example 1 0.83% 29.30% 16.38% 4.84% 4.60% 55.12%
In table 3, the content of each component is weight/mass percentage composition in naphtha, and unit is " quality % ".
Table 3
N-alkane Isoparaffin Cycloalkane Alkene Aromatic hydrocarbons Hydrocarbon more than C12 Other impurities
37.83 35.23 16.16 0.10 10.33 0.32 0.03
As it can be seen from table 1 using it is provided by the invention by sucrose prepare low-carbon alkene method can with it is efficient from Mixing six-carbon monosaccharide is made in sucrose, while the efficient six-carbon monosaccharide that will mix changes into HMF, by the efficient conversions of HMF Into DHMF, and further, by carrying out hydrogenation reaction, acquisition C10-C12 that can be in high yield saturated straight chain to DHMF Alkane.
From table 2 it can be seen that compared with comparative example 1, the method provided by the invention that low-carbon alkene is prepared by sucrose is used Higher low-carbon alkene total recovery can be obtained.Meanwhile there is the ethene and fourth two of essential industry application value in embodiment 1-6 The yield of alkene is significantly higher than comparative example 1.

Claims (44)

  1. A kind of 1. method that low-carbon alkene is prepared by sucrose, it is characterised in that this method comprises the following steps：
    (1) in the presence of the first solvent and dehydration catalyst, dehydration will be carried out from six-carbon monosaccharide is mixed made from sucrose；
    (2) in the presence of condensation catalyst, the dehydration reaction product that step (1) is obtained carries out self-condensation reaction, the contracting Conjunction catalyst is organic N-heterocyclic carbine；
    (3) in the presence of the 3rd solvent and hydrogenation catalyst, the self-condensation reaction product that step (2) obtains be hydrogenated with instead Should；
    (4) hydrogenation reaction product that step (3) obtains is cracked, the hydrogenation reaction product is that C10-C12 saturation is straight Alkane.
  2. 2. according to the method for claim 1, wherein, in step (1), the operation of mixing six-carbon monosaccharide is prepared from sucrose to be included Sucrose is degraded under the conditions of existing for degraded solvent and degradation catalyst.
  3. 3. according to the method for claim 2, wherein, the degraded solvent is in water, methanol, ethanol, ether and acetone At least one.
  4. 4. according to the method for claim 2, wherein, the degradation catalyst is the complex of metallic copper.
  5. 5. according to the method for claim 4, wherein, in the complex of the metallic copper, part be selected from histidine, At least one of imidazoles, alanine, monoethanolamine, Pehanorm and 2- ethyl -5- methylimidazoles.
  6. 6. according to the method for claim 2, wherein, it is 25-120 DEG C that the operating condition of the degraded, which includes temperature, the time For 30-240min.
  7. 7. according to the method for claim 6, wherein, it is 50-110 DEG C that the operating condition of the degraded, which includes temperature, the time For 45-150min.
  8. 8. according to the method described in any one in claim 1-7, wherein, in step (1), first solvent is ionic liquid Body.
  9. 9. according to the method for claim 8, wherein, the ionic liquid is selected from 1- alkyl -3- methylimidazoles chlorine, 1- alkane At least one of base -3- methylimidazoles carboxylic acid and 1- alkyl -3- methylimidazolidinyl phosphates.
  10. 10. according to the method for claim 8, wherein, the ionic liquid is selected from 1- butyl -3- methylimidazoles chlorine, 1- alkene Propyl group -3- methylimidazoles chlorine, 1- pi-allyl -3- methylimidazoles formic acid, 1- ethyl-3-methylimidazoles methyl orthophosphoric acid and 1- ethyls - At least one of 3- N-Methylimidazoleacetics.
  11. 11. according to the method described in any one in claim 1-7, wherein, in step (1), the dehydration catalyst is selected from At least one of inorganic acid, organic acid and metal halide.
  12. 12. according to the method for claim 11, wherein, the dehydration catalyst be selected from sulfuric acid, hydrochloric acid, acetic acid, benzoic acid, Benzene sulfonic acid, chromium dichloride, chromium trichloride, alchlor, sodium chloride, ferric trichloride, copper chloride, vanadium chloride, molybdenum chloride, dichloride At least one of platinum, platinum tetrachloride, ruthenic chloride and radium chloride.
  13. 13. according to the method for claim 11, wherein, in step (1), the usage amount of the dehydration catalyst is described six 0.01-10 moles of % of carbon monose.
  14. 14. according to the method for claim 12, wherein, in step (1), the usage amount of the dehydration catalyst is described six 0.01-10 moles of % of carbon monose.
  15. 15. the method according to claim 13 or 14, wherein, the usage amount of the dehydration catalyst is the six-carbon monosaccharide 1-8 moles of %.
  16. 16. according to the method described in any one in claim 1-7, wherein, in step (1), the condition of the dehydration It it is 50-200 DEG C including temperature, the time is 0.5-10 hours.
  17. 17. according to the method for claim 16, wherein, the condition of the dehydration includes 70-180 DEG C of temperature, time For 2-6 hours.
  18. 18. according to the method described in any one in claim 1-7, wherein, in step (2), the condensation catalyst is selected from 1,3,4- tri-tert -1,2,4- triazole -5- Cabbeens, 1,3,4- triphenyl -1,2,4- triazole -5- Cabbeens and 1,3,4- tri- At least one of naphthyl -1,2,4- triazole -5- Cabbeens.
  19. 19. according to the method for claim 18, wherein, in step (2), the usage amount of the condensation catalyst is described de- 0.01-10 moles of % of water reaction product.
  20. 20. according to the method for claim 19, wherein, the usage amount of the condensation catalyst is the dehydration reaction product 1-5 moles of %.
  21. 21. according to the method described in any one in claim 1-7, wherein, in step (2), the self-condensation reaction is being deposited Or in the absence of carrying out under conditions of the second solvent.
  22. 22. the method according to claim 11, wherein, when the self-condensation reaction enters under conditions of it the second solvent be present During row, second solvent in tetrahydrofuran, DMF, dimethyl sulfoxide (DMSO) and ionic liquid at least one Kind.
  23. 23. according to the method described in any one in claim 1-7, wherein, in step (2), the bar of the self-condensation reaction It is 30-200 DEG C that part, which includes temperature, and the time is 0.1-10 hours.
  24. 24. according to the method for claim 23, wherein, it is 50-120 DEG C that the condition of the self-condensation reaction, which includes temperature, Time is 0.5-5 hours.
  25. 25. according to the method described in any one in claim 1-7, wherein, in step (3), the work of the hydrogenation catalyst Property component is Metal Palladium and/or platinum.
  26. 26. according to the method for claim 25, wherein, the carrier of the hydrogenation catalyst is inorganic acid and/or inorganic acid Salt, acid organic salt, activated carbon and at least one of heteropoly acid and/or heteropolyacid salt.
  27. 27. according to the method for claim 26, wherein, the inorganic acid in sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid extremely Few one kind.
  28. 28. according to the method for claim 26, wherein, the inorganic acid salt is phosphoric acid tantalum and/or niobium phosphate.
  29. 29. according to the method for claim 26, wherein, the acid organic salt is selected from [bmim]3PW12O40、[MIMPS]3PW12O40、[PyPS]3PW12O40[TEAPS]3PW12O40At least one of.
  30. 30. according to the method for claim 26, wherein, the heteropoly acid is H3PW12O40。
  31. 31. according to the method for claim 26, wherein, the heteropolyacid salt is selected from CsH2PW12O40、NaH2PW12O40、 LiH2PW12O40And KH2PW12O40At least one of.
  32. 32. according to the method described in any one in claim 26-31, wherein, the hydrogenation catalyst is selected from phosphoric acid and palladium The mixture and/or phosphoric acid tantalum and the mixture of platinum carbon of carbon.
  33. 33. according to the method for claim 26, wherein, the hydrogenation catalyst is selected from Pd/CH3PO4、Pt/CsH2PW12O40、 Pt/Cs2.5H0.5PW12O40With Pt/C TaOPO4At least one of.
  34. 34. according to the method described in any one in claim 26-31, wherein, in step (3), the hydrogenation catalyst Dosage is calculated as 0.01-10 moles of % of the self-condensation reaction product with the dosage of active component.
  35. 35. according to the method for claim 34, wherein, the dosage of the hydrogenation catalyst is calculated as with the dosage of active component 0.1-5 moles of % of the self-condensation reaction product.
  36. 36. according to the method described in any one in claim 1-7, wherein, in step (3), the condition of the hydrogenation reaction It is 0.1-30MPa including pressure, temperature is 25-350 DEG C, and the time is 0.5-10 hours.
  37. 37. according to the method for claim 36, wherein, the condition of the hydrogenation reaction is 1-10MPa including pressure, temperature For 50-300 DEG C, the time is 1-5 hours.
  38. 38. according to the method described in any one in claim 1-7, wherein, in step (3), the 3rd solvent is selected from hydrocarbon At least one of class, alcohols and water.
  39. 39. according to the method for claim 38, wherein, the varsol is selected from ether, petroleum ether, dichloromethane, three At least one of chloromethanes, heptane, hexane, pentamethylene and hexamethylene.
  40. 40. according to the method for claim 38, wherein, the alcohols solvent in glycerine, ethanol and methanol at least It is a kind of.
  41. 41. according to the method described in any one in claim 1-7, wherein, it is described to be cracked into steam cracking in step (4).
  42. 42. according to the method for claim 41, wherein, the steam cracking is carried out in steam cracking furnace.
  43. 43. according to the method for claim 42, wherein, the condition of the steam cracking is carried out in the steam cracking furnace Coil outlet temperature including steam cracking furnace is 710-890 DEG C, the hydrogenation reaction product and the matter of water vapour that step (3) obtains Amount is than being 1：(0.3-1).
  44. 44. according to the method for claim 43, wherein, the condition of the steam cracking is carried out in the steam cracking furnace Coil outlet temperature including steam cracking furnace is 780-860 DEG C, the hydrogenation reaction product and the matter of water vapour that step (3) obtains Measure ratio 1：(0.4-0.8).
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