CN105541534A - Method for preparing low-carbon olefin from plant haulm - Google Patents
Method for preparing low-carbon olefin from plant haulm Download PDFInfo
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Abstract
The present invention discloses a method for preparing low-carbon olefin from plant haulm. The method comprises that in the presence of a first solvent and a dehydration catalyst, mixed six-carbon monosaccharide prepared from plant haulm is subjected to a dehydration reaction; in the presence of a condensation catalyst, the obtained dehydration reaction product is subjected to a self-condensation reaction; in the presence of a third solvent and a hydrogenation catalyst, the obtained self-condensation reaction product is subjected to a hydrogenation reaction; and finally the obtained hydrogenation reaction product is subjected to splitting. According to the present invention, the plant haulm can be adopted as the raw material to produce the low-carbon olefin in the high-efficiency manner while the total yield of the low-carbon olefin of the high splitting furnace can be effectively improved, and the utilization rate and the utilization value of the natural resources are improved while the requirements of the low-carbon olefin production on the petroleum raw material are effectively reduced.
Description
Technical field
The present invention relates to the preparation field of low-carbon alkene, particularly, relate to a kind of method being prepared low-carbon alkene by plant haulm.
Background technology
Low-carbon alkene typically refers to the general name of the unsaturated hydrocarbon of carbon four and carbon less than four, mainly comprises the Organic Chemicals that ethene, propylene, iso-butylene, divinyl etc. have high economic worth.Along with China's expanding economy, the demand of these Organic Chemicals increases year by year.Although the industrial scale of low-carbon alkene is also increasing year by year, also growing demand cannot met.
For a long time, low-carbon alkene product is prepared with petroleum naphtha by China, along with the maximization of petroleum chemical enterprise's production equipment scale, the processing power of China's single cover oil refining apparatus is more than 1,000 ten thousand tons/year, and the ethylene production capacity of ethylene unit supporting with it also reaches 80 ~ 1,200,000 tons/year.But along with the minimizing day by day of fossil resources, the petrochemical industry production cost based on crude oil improves year by year.Therefore, in the urgent need to developing a kind of new raw material preparing low-carbon alkene and method.
Summary of the invention
In order to solve the raw materials requirement anxiety that existing petroleum base low-carbon alkene is produced and the cost increase problem continued, the present invention proposes a kind of method being prepared low-carbon alkene by plant haulm.The method can take plant haulm as raw material, high efficiency obtained low-carbon alkene, effectively can also improve the overall yield of pyrolyzer low-carbon alkene simultaneously, effectively reduces the demand to petroleum in the production of low-carbon alkene.
The present inventor is surprised to find that after deliberation afterwards, 5 hydroxymethyl furfural (the 5-hydroxymethylfurfural obtained after the mixing six carbon monose obtained from plant haulm is carried out dehydration reaction in ionic liquid, HMF) can the effect of catalyzer issue be conigenous condensation reaction generate 5, 5 '-dihydroxymethyl chaff accidental cause (5, 5 '-di (hydroxymethyl) furoin, DHMF), again to 5, 5 '-dihydroxymethyl chaff accidental cause carries out the saturated straight chain alkane that hydrogenation reaction can obtain C10-C12, finally steam cracking is carried out to the saturated straight chain alkane of C10-C12 and can obtain low-carbon alkene.The mixing six carbon monose obtained from plant haulm can be converted into low-carbon alkene by the method expeditiously, can also improve the overall yield of pyrolyzer low-carbon alkene, effectively reduces the production of low-carbon alkene to the demand of petroleum, thus completes the present invention.
The invention provides a kind of method being prepared low-carbon alkene by plant haulm, the method comprises the steps:
(1) under the existence of the first solvent and dehydration catalyst, the mixing six carbon monose obtained from plant haulm is carried out dehydration reaction;
(2) under the existence of condensation catalyst, the dehydration reaction product that step (1) obtains is carried out self-condensation reaction;
(3) under the existence of the 3rd solvent and hydrogenation catalyst, the self-condensation reaction product that step (2) obtains is carried out hydrogenation reaction;
(4) hydrogenation reaction product that step (3) obtains is carried out cracking.
The method preparing low-carbon alkene by plant haulm provided by the invention can take plant haulm as raw material, high efficiency obtained low-carbon alkene, effectively can also improving the overall yield of pyrolyzer low-carbon alkene simultaneously, improve the demand to also effectively reducing while the utilization ratio of natural resources and utility value to petroleum in the production of low-carbon alkene.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of method being prepared low-carbon alkene by plant haulm, the method comprises the steps:
(1) under the existence of the first solvent and dehydration catalyst, the mixing six carbon monose obtained from plant haulm is carried out dehydration reaction;
(2) under the existence of condensation catalyst, the dehydration reaction product that step (1) obtains is carried out self-condensation reaction;
(3) under the existence of the 3rd solvent and hydrogenation catalyst, the self-condensation reaction product that step (2) obtains is carried out hydrogenation reaction;
(4) hydrogenation reaction product that step (3) obtains is carried out cracking.
According to the present invention, in step (1), described plant haulm can be selected from least one in maize straw, rice straw, Wheat Straw, kaoliang stalk and culm.Described plant haulm has renewable, low stain and widely distributed feature, and all can produce with glucose after being degraded is the mixing six carbon monose of main component.
In step (1), the operation preparing mixing six carbon monose from plant haulm can comprise: degraded under degraded solvent and degradation catalyst existent condition by plant haulm.Then the degraded product of acquisition can be obtained after desolventizing process the crystallization of mixing six carbon monose.Preferably, described plant haulm is crushed to 10-60 order, after the particle of preferred 20-40 order size, carries out degraded operation.Wherein, described degraded solvent can be selected from least one in water, methyl alcohol, ethanol and ionic liquid, preferred ion liquid.Described ionic liquid can be selected from least one in 1-alkyl-3-Methylimidazole chlorine, 1-alkyl-3-Methylimidazole carboxylic acid and 1-alkyl-3-methylimidazolidinyl phosphoric acid ester.Preferably, described ionic liquid is selected from least one in 1-butyl-3-Methylimidazole chlorine, 1-allyl group-3-Methylimidazole chlorine, 1-allyl group-3-Methylimidazole formic acid, 1-ethyl-3-methylimidazole methyl orthophosphoric acid and 1-ethyl-3-methylimidazole acetic acid.Described degradation catalyst can be mineral acid and/or solid acid.Described mineral acid can be selected from least one in hydrochloric acid, sulfuric acid and nitric acid.Described solid acid can be selected from SiO
2-Al
2o
3, B
2o
3-Al
2o
3with γ-Al
2o
3in at least one.The consumption of described degradation catalyst can be the 5-70 quality % of plant haulm, preferred 10-60 quality %.It can be 25-120 DEG C, preferred 50-110 DEG C that the operational condition of described degraded comprises temperature, and the time can be 0.5-10 hour, preferred 2-4 hour.Usually, the mixing six carbon monose of acquisition take glucose as main component, and usually, the content of glucose is not less than 40 quality % of mixing six carbon monose total amount, is preferably 40-60 quality %.
In step (1), described first solvent can be ionic liquid.Described ionic liquid can be selected from least one in 1-alkyl-3-Methylimidazole chlorine, 1-alkyl-3-Methylimidazole carboxylic acid and 1-alkyl-3-methylimidazolidinyl phosphoric acid ester.Preferably, described ionic liquid is selected from least one in 1-butyl-3-Methylimidazole chlorine, 1-allyl group-3-Methylimidazole chlorine, 1-allyl group-3-Methylimidazole formic acid, 1-ethyl-3-methylimidazole methyl orthophosphoric acid and 1-ethyl-3-methylimidazole acetic acid.
In step (1), described dehydration catalyst can be selected from least one in mineral acid, organic acid and metal halide.Described mineral acid can be selected from least one in sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid.Described organic acid can be selected from least one in acetic acid, propionic acid, phenylformic acid, Phenylsulfonic acid, oxalic acid, toxilic acid, phthalic acid and terephthalic acid.Described metal halide can be selected from least one in the muriate of chromium, aluminium, sodium, iron, copper, vanadium, molybdenum, platinum, ruthenium and rhodium or bromide.Preferably, described dehydration catalyst is selected from least one in sulfuric acid, hydrochloric acid, acetic acid, phenylformic acid, Phenylsulfonic acid, chromium dichloride, chromium trichloride, aluminum chloride, sodium-chlor, iron trichloride, cupric chloride, vanadium chloride, molybdenum chloride, platinum dichloride, Tetrachloroplatinum, ruthenium chloride and rhodium chloride.The usage quantity of described dehydration catalyst can be the 0.01-10 % by mole of described six carbon monose, preferred 1-8 % by mole.
In step (1), it can be 50-200 DEG C, preferred 70-180 DEG C that the condition of described dehydration reaction comprises temperature, and the time can be 0.5-10 hour, preferred 2-6 hour.Described dehydration reaction can be carried out under agitation.After described dehydration reaction terminates, the mixture that can obtain after dehydration reaction, obtain dehydration reaction product 5 hydroxymethyl furfural.The mode obtaining 5 hydroxymethyl furfural from the mixture obtained after described dehydration reaction can comprise: in the mixture after dehydration reaction, add water and organic solvent, and the mixture after dehydration reaction, water and organic solvent are fully mixed, leaving standstill makes aqueous phase and organic solvent be separated again, and then concentrated organic solvent obtains 5 hydroxymethyl furfural mutually afterwards.Described organic solvent can be selected from least one in methylene dichloride, tetracol phenixin, chloroform, sherwood oil, ether and hexanaphthene.
According to the present invention, in step (2), described condensation catalyst can be organonitrogen heterocycle carbine.Preferably, described condensation catalyst is selected from least one in 1,3,4-tri-tert-1,2,4-triazole-5-Cabbeen, 1,3,4-triphenyl-1,2,4-triazole-5-Cabbeen and 1,3,4-tri-naphthyl-1,2,4-triazole-5-Cabbeen.The usage quantity of described condensation catalyst can be the 0.01-10 % by mole of described dehydration reaction product (5 hydroxymethyl furfural), preferred 1-5 % by mole.
In step (2), described self-condensation reaction can carry out under the condition of presence or absence second solvent.Described second solvent can be selected from least one in tetrahydrofuran (THF), DMF, dimethyl sulfoxide (DMSO) and ionic liquid.Described ionic liquid is identical with above-mentioned.
In step (2), it can be 30-200 DEG C, preferred 50-120 DEG C that the condition of described self-condensation reaction comprises temperature, and the time can be 0.1-10 hour, preferred 0.5-5 hour.After described self-condensation reaction terminates, the mixture that can obtain after self-condensation reaction, obtain self-condensation reaction product 5,5 '-dihydroxymethyl chaff accidental cause.5 are obtained the mixture obtained after described self-condensation reaction, the mode of 5 '-dihydroxymethyl chaff accidental cause can comprise: first steamed (if any) by the second solvent, then wash the solid obtained with hexanaphthene, can 5 be obtained after drying, 5 '-dihydroxymethyl chaff accidental cause.
According to the present invention, in step (3), the active ingredient of described hydrogenation catalyst can be palladium metal and/or platinum.The carrier of described hydrogenation catalyst can be at least one in mineral acid and/or inorganic acid salt, acid organic salt, gac and heteropolyacid and/or heteropolyacid salt.Described mineral acid can be selected from least one in sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid.Described inorganic acid salt can be phosphoric acid tantalum and/or niobium phosphate.Described acid organic salt can be selected from [bmim]
3pW
12o
40, [MIMPS]
3pW
12o
40, [PyPS]
3pW
12o
40[TEAPS]
3pW
12o
40in at least one.Described heteropolyacid can be H
3pW
12o
40.Described heteropolyacid salt can be selected from CsH
2pW
12o
40, NaH
2pW
12o
40, LiH
2pW
12o
40and KH
2pW
12o
40in at least one.Preferably, described hydrogenation catalyst is selected from the mixture of phosphoric acid and palladium carbon and/or the mixture of phosphoric acid tantalum and platinum carbon.Particularly, described hydrogenation catalyst can be selected from Pd/CH
3pO
4, Pt/CsH
2pW
12o
40, Pt/Cs
2.5h
0.5pW
12o
40and Pt/CTaOPO
4in at least one.The consumption of described hydrogenation catalyst can be the 0.01-10% % by mole of described self-condensation reaction product (5,5 '-dihydroxymethyl chaff accidental cause) with the use gauge of active ingredient, preferred 0.1-5 % by mole.
In step (3), it can be 0.1-30MPa, preferred 1-10MPa that the condition of described hydrogenation reaction comprises pressure, and temperature can be 25-350 DEG C, preferred 50-300 DEG C, and the time can be 0.5-10 hour, preferred 1-5 hour.Preferably, before carrying out described hydrogenation reaction, use the air in inert gas replacement reaction vessel.Described rare gas element can be nitrogen and/or zero group gas.Described hydrogenation reaction can be carried out under agitation.
In step (3), described 3rd solvent can be selected from least one in hydro carbons, alcohols and water.Described varsol can be selected from least one in ether, sherwood oil, methylene dichloride, trichloromethane, heptane, hexane, pentamethylene and hexanaphthene.Described alcoholic solvent can be selected from least one in glycerine, ethanol and methyl alcohol.After described hydrogenation reaction terminates, the mixture that can obtain after hydrogenation reaction, obtain the saturated straight chain alkane of C10-C12.The mode obtaining the saturated straight chain alkane of C10-C12 the mixture obtained after described hydrogenation reaction can comprise: filtered by the mixture obtained after hydrogenation reaction, filtering hydrogenation catalyst also reclaims, and then removes the 3rd solvent.
According to the present invention, in step (4), described cracking can be steam cracking.Described steam cracking can carry out in steam cracking furnace.Preferably, the coil outlet temperature that the condition of carrying out described steam cracking in described steam cracking furnace can comprise steam cracking furnace is 710-890 DEG C, preferred 780-860 DEG C, the mass ratio of the hydrogenation reaction product that step (3) obtains and water vapor is 1:(0.3-1), preferred 1:(0.4-0.8).
In step (4), low-carbon alkene can be obtained from split product.The working method that the mode obtaining low-carbon alkene from described split product can be commonly used for this area.The described mode obtaining low-carbon alkene from split product such as can be separated split product according to the flow process comprising following working order: split product isolates Pyrolysis fuel oil PFO and pyrolysis gasoline and the acidic substance removed in splitting gas through oil scrubber and water wash column, after compression, hydrogen and methane is isolated with demethanizing tower, ethene and propylene is isolated with deethanizing column, ethene and propylene is isolated with depropanizing tower, isolating carbon Four composition with debutanizing tower, obtaining corresponding low-carbon alkene by being separated each component obtained respectively by rectifying tower separation.
Below will be described the present invention by specific embodiment.
In following examples and comparative example:
In step (1), the method for calculation mixing the yield of six carbon monose (total monosaccharide) are as follows:
In step (1), the method for calculation of the yield of HMF are as follows:
In step (2), the method for calculation of the yield of DHMF are as follows:
The method of calculation of the yield of the saturated straight chain alkane of the C10-C12 that step (3) obtains are as follows:
In step (4), the method for calculation of the yield of each split product are as follows:
Embodiment 1
(1) the straw mixture (mass ratio is about 1:1) of maize straw and kaoliang stalk composition is pulverized with pulverizer, then the 20-40 object straw chip obtained after sieving is put into the microwave reactor of band stirring tank, in the microwave reactor of band stirring tank, add 1-alkyl-3-Methylimidazole chloride ion liquid again, stir into turbid solution.
The vitriol oil (massfraction is 98%) of the plant haulm chip 60 quality % accounting for the microwave reactor putting into band stirring tank is added in the microwave reactor of band stirring tank, open microwave source to heat, stirring reaction 60 minutes after question response liquid temp reaches 90 DEG C, obtains the solution containing mixing six carbon monose.Carried out by the solution of mixing six carbon monose concentrating, crystallization, obtain mixing six carbon monose after filtration and drying, the yield recording mixing six carbon monose (total monosaccharide) is 21.87%.
1-butyl-3-Methylimidazole chlorine (as solvent), massfraction are the vitriol oil (as catalyzer) of 98% and add (wherein in the vitriol oil, the content of sulfuric acid is 0.5 % by mole of mixing six carbon monose) in stirring tank by the mixing six carbon monose that aforesaid method obtains, then under agitation, react 3 hours at 80 DEG C; Take out the material obtained, add water and methylene dichloride and material, water and the methylene dichloride obtained fully is mixed, leaving standstill makes aqueous phase be separated with organic solvent phase (methylene dichloride phase) again, concentrated organic solvent obtains 5 hydroxymethyl furfural (HMF) mutually afterwards, in aqueous phase, add methyl alcohol, unreacted sugar is separated out.As calculated, the yield of HMF is 82%.
(2) using tetrahydrofuran (THF) (as solvent), 1,3, the HMF that 4-tri-tert-1,2,4-triazole-5-Cabbeen (as catalyzer) and step (1) obtain adds in stirring tank (wherein 1,3, the consumption of 4-tri-tert-1,2,4-triazole-5-Cabbeen is 1.0 % by mole of HMF), then under agitation, react 1 hour at 80 DEG C; Take out the material obtained, tetrahydrofuran (THF) is steamed again with the solid that hexanaphthene washing obtains after removing, then obtain 5 after drying, 5 '-dihydroxymethyl chaff accidental cause (DHMF).As calculated, the yield of DHMF is 89%.
(3) using methyl alcohol (as solvent), Pd/CH
3pO
4the DHMF that (as catalyzer) and step (2) obtain adds (wherein Pd/CH in autoclave pressure
3pO
43.2 % by mole that are DHMF in the consumption of Pd), then use the air in argon replaces autoclave pressure, then be filled with hydrogen in autoclave pressure, make the pressure in autoclave pressure reach 3.45MPa, then under agitation, react 6 hours at 200 DEG C; Take out the material obtained, remove catalyzer after filtration and distill the saturated straight chain paraffins mixture except obtaining the C10-C12 of oily after desolventizing.In the saturated straight chain paraffins mixture of the C10-C12 of this oily obtained through chromatogram and mass spectroscopy, the content of the content of the content of C10 alkane, C11 alkane, the content of C12 alkane, total alkane is in table 1.
(4) the saturated straight chain paraffins mixture of C10-C12 water vapour and step (3) obtained injects small-sized cracking simulator (purchased from Sinopec Beijing Research Institute of Chemical Industry) according to the ratio that mass ratio is 1:0.5 and carries out steam cracking reaction, maintains reaction 40 minutes at the coil outlet temperature of small-sized cracking simulator is 790 DEG C.Low-carbon alkene composition in the gas-phase product obtained by chromatogram detection reaction, and calculate the yield of each split product.The yield of each split product is in table 2.
Embodiment 2
Divided by outside lower operational condition, other are all identical with embodiment 1.
In step (1), the first solvent is changed into 1-allyl group-3-Methylimidazole chlorine, dehydration catalyst changes chromium dichloride into, and temperature of reaction changes 100 DEG C into.
In step (2), do not use the second solvent, condensation catalyst is changed into 1,3,4-triphenyl-1,2,4-triazole-5-Cabbeen, temperature of reaction changes 60 DEG C into simultaneously.
The yield of HMF, the yield of DHMF, in the saturated straight chain paraffins mixture of C10-C12, the content of the content of the content of C10 alkane, C11 alkane, the content of C12 alkane, total alkane is in table 1.
The composition of the low-carbon alkene of final acquisition and the yield of each split product are in table 2.
Embodiment 3
Divided by outside lower operational condition, other are all identical with embodiment 1.
In step (1), the first solvent is changed into 1-allyl group-3-Methylimidazole formic acid, dehydration catalyst changes chromium trichloride into, and temperature of reaction changes 120 DEG C into.
In step (2), do not use the second solvent, condensation catalyst is changed into 1,3,4-triphenyl-1,2,4-triazole-5-Cabbeen, temperature of reaction changes 60 DEG C into simultaneously.
In step (3), change hydrogenation catalyst into Pt/CsH
2pW
12o
40, temperature of reaction changes 250 DEG C into, and the pressure in autoclave pressure changes 3.20MPa into.
In step (4), the mass ratio of the saturated straight chain paraffins mixture of C10-C12 water vapour and step (3) obtained changes 1:0.6 into, changes the coil outlet temperature of small-sized cracking simulator into 820 DEG C.
The yield of HMF, the yield of DHMF, in the saturated straight chain paraffins mixture of C10-C12, the content of the content of the content of C10 alkane, C11 alkane, the content of C12 alkane, total alkane is in table 1.
The composition of the low-carbon alkene of final acquisition and the yield of each split product are in table 2.
Embodiment 4
Divided by outside lower operational condition, other are all identical with embodiment 1.
In step (1), the first solvent is changed into 1-ethyl-3-methylimidazole methyl orthophosphoric acid, dehydration catalyst changes aluminum chloride into, and temperature of reaction changes 180 DEG C into.
In step (2), the second solvent is changed into 1-ethyl-3-methylimidazole acetic acid, condensation catalyst changes 1,3,4-tri-naphthyl-1,2,4-triazole-5-Cabbeen into, and temperature of reaction changes 100 DEG C into.
In step (3), change hydrogenation catalyst into Pt/CsH
2pW
12o
40, temperature of reaction changes 300 DEG C into, and the pressure in autoclave pressure changes 5.00MPa into.
In step (4), the mass ratio of the saturated straight chain paraffins mixture of C10-C12 water vapour and step (3) obtained changes 1:0.6 into, changes the coil outlet temperature of small-sized cracking simulator into 820 DEG C.
The yield of HMF, the yield of DHMF, in the saturated straight chain paraffins mixture of C10-C12, the content of the content of the content of C10 alkane, C11 alkane, the content of C12 alkane, total alkane is in table 1.
The composition of the low-carbon alkene of final acquisition and the yield of each split product are in table 2.
Embodiment 5
Divided by outside lower operational condition, other are all identical with embodiment 1.
In step (2), the second solvent is changed into 1-ethyl-3-methylimidazole acetic acid, condensation catalyst changes 1,3,4-tri-naphthyl-1,2,4-triazole-5-Cabbeen into, and temperature of reaction changes 100 DEG C into.
In step (3), change hydrogenation catalyst into Pt/CTaOPO
4, the 3rd solvent changes water into, and temperature of reaction changes 300 DEG C into, and the pressure in autoclave pressure changes 3.45MPa into.
In step (4), the mass ratio of the saturated straight chain paraffins mixture of C10-C12 water vapour and step (3) obtained changes 1:0.7 into, changes the coil outlet temperature of small-sized cracking simulator into 850 DEG C.
The yield of HMF, the yield of DHMF, in the saturated straight chain paraffins mixture of C10-C12, the content of the content of the content of C10 alkane, C11 alkane, the content of C12 alkane, total alkane is in table 1.
The composition of the low-carbon alkene of final acquisition and the yield of each split product are in table 2.
Embodiment 6
Divided by outside lower operational condition, other are all identical with embodiment 1.
In step (2), do not use the second solvent, condensation catalyst is changed into 1,3,4-triphenyl-1,2,4-triazole-5-Cabbeen, temperature of reaction changes 60 DEG C into simultaneously.
In step (3), change hydrogenation catalyst into Pt/CTaOPO
4, the 3rd solvent changes water into, and temperature of reaction changes 300 DEG C into, and the pressure in autoclave pressure changes 3.45MPa into.
In step (4), the mass ratio of the saturated straight chain paraffins mixture of C10-C12 water vapour and step (3) obtained changes 1:0.7 into, changes the coil outlet temperature of small-sized cracking simulator into 850 DEG C.
The yield of HMF, the yield of DHMF, in the saturated straight chain paraffins mixture of C10-C12, the content of the content of the content of C10 alkane, C11 alkane, the content of C12 alkane, total alkane is in table 1.
The composition of the low-carbon alkene of final acquisition and the yield of each split product are in table 2.
Embodiment 7
Divided by outside lower operational condition, other are all identical with embodiment 6.
In step (1), change the straw mixture of maize straw and kaoliang stalk composition the straw mixture of rice straw and Wheat Straw composition into prepare mixing six carbon monose, the yield finally recording mixing six carbon monose is 25.12%; Dehydration catalyst changes molybdenum chloride into, and temperature of reaction changes 140 DEG C into.
The yield of HMF, the yield of DHMF, in the saturated straight chain paraffins mixture of C10-C12, the content of the content of the content of C10 alkane, C11 alkane, the content of C12 alkane, total alkane is in table 1.
The composition of the low-carbon alkene of final acquisition and the yield of each split product are in table 2.
Embodiment 8
Divided by outside lower operational condition, other are all identical with embodiment 6.
In step (1), change the straw mixture of maize straw and kaoliang stalk composition the straw mixture of maize straw, rice straw, Wheat Straw, kaoliang stalk and culm composition into prepare mixing six carbon monose, the yield finally recording mixing six carbon monose is 27.51%; Dehydration catalyst changes Tetrachloroplatinum into, and temperature of reaction changes 120 DEG C into.
The yield of HMF, the yield of DHMF, in the saturated straight chain paraffins mixture of C10-C12, the content of the content of the content of C10 alkane, C11 alkane, the content of C12 alkane, total alkane is in table 1.
The composition of the low-carbon alkene of final acquisition and the yield of each split product are in table 2.
Comparative example 1
The petroleum naphtha with physical property shown in table 3 is carried out steam cracking reaction according to the working method of embodiment 1 step (4).
The composition of the low-carbon alkene of final acquisition and the yield of each split product are in table 2.
Table 1
| HMF yield | DHMF yield | C10 yield | C11 yield | C12 yield | Total alkane yield | |
| Embodiment 1 | 82％ | 89％ | 18.6％ | 37.6％ | 32.2％ | 88.4％ |
| Embodiment 2 | 81％ | 99％ | 18.6％ | 37.6％ | 32.2％ | 88.4％ |
| Embodiment 3 | 80％ | 99％ | - | 24.3％ | 67.6％ | 91.9％ |
| Embodiment 4 | 79％ | 91％ | 4.3％ | 36.8％ | 38.6％ | 79.7％ |
| Embodiment 5 | 82％ | 91％ | 27.0％ | 22.9％ | 45.6％ | 95.5％ |
| Embodiment 6 | 82％ | 99％ | 27.0％ | 22.9％ | 45.6％ | 95.5％ |
| Embodiment 7 | 78％ | 99％ | 27.0％ | 22.9％ | 45.6％ | 95.5％ |
| Embodiment 8 | 80％ | 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 divinyl.
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％ |
| Embodiment 7 | 0.71％ | 42.82％ | 16.95％ | 3.47％ | 5.83％ | 69.07％ |
| Embodiment 8 | 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, in petroleum naphtha, the content of each component is mass percentage, and unit is " quality % ".
Table 3
| Normal paraffin | Isoparaffin | Naphthenic hydrocarbon | Alkene | Aromatic hydrocarbons | Be greater than the hydrocarbon of C12 | Other impurity |
| 37.83 | 35.23 | 16.16 | 0.10 | 10.33 | 0.32 | 0.03 |
As can be seen from Table 1, use provided by the invention by plant haulm prepare low-carbon alkene method can high efficiency from plant haulm obtained mixing six carbon monose, simultaneously high efficiency mixing six carbon monose is changed into HMF, DHMF is changed into by high efficiency for HMF, and further, by carrying out hydrogenation reaction to DHMF, can the saturated straight chain alkane of acquisition C10-C12 of high yield.
As can be seen from Table 2, compared with comparative example 1, use the method preparing low-carbon alkene by plant haulm provided by the invention can obtain higher low-carbon alkene total recovery.Meanwhile, the yield of the ethene and divinyl that have essential industry using value in embodiment 1-8 is significantly higher than comparative example 1.
Claims (17)
1. prepared a method for low-carbon alkene by plant haulm, it is characterized in that, the method comprises the steps:
(1) under the existence of the first solvent and dehydration catalyst, the mixing six carbon monose obtained from plant haulm is carried out dehydration reaction;
(2) under the existence of condensation catalyst, the dehydration reaction product that step (1) obtains is carried out self-condensation reaction;
(3) under the existence of the 3rd solvent and hydrogenation catalyst, the self-condensation reaction product that step (2) obtains is carried out hydrogenation reaction;
(4) hydrogenation reaction product that step (3) obtains is carried out cracking.
2. method according to claim 1, wherein, in step (1), described plant haulm is be selected from least one in maize straw, rice straw, Wheat Straw, kaoliang stalk and culm;
Preferably, the operation preparing mixing six carbon monose from plant haulm comprises degrades plant haulm under degraded solvent and degradation catalyst existent condition;
Preferably, described degraded solvent is selected from least one in water, methyl alcohol, ethanol and ionic liquid;
Preferably, described degradation catalyst is mineral acid and/or solid acid;
Preferably, it is 25-120 DEG C that the operational condition of described degraded comprises temperature, and preferred 50-110 DEG C, the time is 0.5-10 hour, preferred 2-4 hour.
3. method according to claim 1 and 2, wherein, in step (1), described first solvent is ionic liquid;
Preferably, described ionic liquid is selected from least one in 1-alkyl-3-Methylimidazole chlorine, 1-alkyl-3-Methylimidazole carboxylic acid and 1-alkyl-3-methylimidazolidinyl phosphoric acid ester;
Further preferably, described ionic liquid is selected from least one in 1-butyl-3-Methylimidazole chlorine, 1-allyl group-3-Methylimidazole chlorine, 1-allyl group-3-Methylimidazole formic acid, 1-ethyl-3-methylimidazole methyl orthophosphoric acid and 1-ethyl-3-methylimidazole acetic acid.
4. method according to claim 1 and 2, wherein, in step (1), described dehydration catalyst is selected from least one in mineral acid, organic acid and metal halide;
Preferably, described dehydration catalyst is selected from least one in sulfuric acid, hydrochloric acid, acetic acid, phenylformic acid, Phenylsulfonic acid, chromium dichloride, chromium trichloride, aluminum chloride, sodium-chlor, iron trichloride, cupric chloride, vanadium chloride, molybdenum chloride, platinum dichloride, Tetrachloroplatinum, ruthenium chloride and rhodium chloride.
5. method according to claim 4, wherein, in step (1), the usage quantity of described dehydration catalyst is the 0.01-10 % by mole of described six carbon monose, preferred 1-8 % by mole.
6. method according to claim 1 and 2, wherein, in step (1), it is 50-200 DEG C that the condition of described dehydration reaction comprises temperature, and preferred 70-180 DEG C, the time is 0.5-10 hour, preferred 2-6 hour.
7. method according to claim 1 and 2, wherein, in step (2), described condensation catalyst is organonitrogen heterocycle carbine;
Preferably, described condensation catalyst is selected from least one in 1,3,4-tri-tert-1,2,4-triazole-5-Cabbeen, 1,3,4-triphenyl-1,2,4-triazole-5-Cabbeen and 1,3,4-tri-naphthyl-1,2,4-triazole-5-Cabbeen.
8. method according to claim 7, wherein, in step (2), the usage quantity of described condensation catalyst is the 0.01-10 % by mole of described dehydration reaction product, preferred 1-5 % by mole.
9. method according to claim 1 and 2, wherein, in step (2), described self-condensation reaction carries out under the condition of presence or absence second solvent;
Preferably, when described self-condensation reaction carries out under the condition of existence second solvent, described second solvent is selected from least one in tetrahydrofuran (THF), DMF, dimethyl sulfoxide (DMSO) and ionic liquid.
10. method according to claim 1 and 2, wherein, in step (2), it is 30-200 DEG C that the condition of described self-condensation reaction comprises temperature, and preferred 50-120 DEG C, the time is 0.1-10 hour, preferred 0.5-5 hour.
11. methods according to claim 1 and 2, wherein, in step (3), the active ingredient of described hydrogenation catalyst is palladium metal and/or platinum.
12. methods according to claim 11, wherein, the carrier of described hydrogenation catalyst is at least one in mineral acid and/or inorganic acid salt, acid organic salt, gac and heteropolyacid and/or heteropolyacid salt;
Preferably, described mineral acid is selected from least one in sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid;
Preferably, described inorganic acid salt is phosphoric acid tantalum and/or niobium phosphate;
Preferably, described acid organic salt is selected from [bmim]
3pW
12o
40, [MIMPS]
3pW
12o
40, [PyPS]
3pW
12o
40[TEAPS]
3pW
12o
40in at least one;
Preferably, described heteropolyacid is H
3pW
12o
40;
Preferably, described heteropolyacid salt is selected from CsH
2pW
12o
40, NaH
2pW
12o
40, LiH
2pW
12o
40and KH
2pW
12o
40in at least one.
13. methods according to claim 12, wherein, described hydrogenation catalyst is selected from the mixture of phosphoric acid and palladium carbon and/or the mixture of phosphoric acid tantalum and platinum carbon;
Preferably, described hydrogenation catalyst is selected from Pd/CH
3pO
4, Pt/CsH
2pW
12o
40, Pt/Cs
2.
5h
0.
5pW
12o
40and Pt/CTaOPO
4in at least one.
14. methods according to claim 12 or 13, wherein, in step (3), the consumption of described hydrogenation catalyst counts the 0.01-10% % by mole of described self-condensation reaction product, preferred 0.1-5 % by mole with the consumption of active ingredient.
15. methods according to claim 1 and 2, wherein, in step (3), it is 0.1-30MPa that the condition of described hydrogenation reaction comprises pressure, preferred 1-10MPa, and temperature is 25-350 DEG C, preferred 50-300 DEG C, the time is 0.5-10 hour, preferred 1-5 hour.
16. methods according to claim 1 and 2, wherein, in step (3), described 3rd solvent is selected from least one in hydro carbons, alcohols and water;
Preferably, described varsol is selected from least one in ether, sherwood oil, methylene dichloride, trichloromethane, heptane, hexane, pentamethylene and hexanaphthene;
Preferably, described alcoholic solvent is selected from least one in glycerine, ethanol and methyl alcohol.
17. methods according to claim 1 and 2, wherein, in step (4), described in be cracked into steam cracking;
Preferably, described steam cracking carries out in steam cracking furnace;
Further preferably, the coil outlet temperature that the condition of carrying out described steam cracking in described steam cracking furnace comprises steam cracking furnace is 710-890 DEG C, preferred 780-860 DEG C, the mass ratio of the hydrogenation reaction product that step (3) obtains and water vapor is 1:(0.3-1), preferred 1:(0.4-0.8).
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| US20100292100A1 (en) * | 2009-05-14 | 2010-11-18 | Technion Research & Development Foundation Ltd. | Novel diarylphosphine-containing compounds, processes of preparing same and uses thereof as tridentate ligands |
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| WO2008151178A1 (en) * | 2007-06-04 | 2008-12-11 | Wisconsin Alumni Research Foundation | Production of liquid alkanes in the jet fuel range (c8-c15) from biomass-derived carbohydrates |
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