CN106316742B - The method for producing C 4 olefin - Google Patents
The method for producing C 4 olefin Download PDFInfo
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Abstract
The present invention relates to a kind of methods for producing C 4 olefin, so that raw material is contacted generation catalysis reaction with catalyst and generate the logistics containing C 4 olefin；Wherein, the raw material has structure formula (I):In formula (I), R1For the C optionally replaced1‑8Linear or branched alkyl group, R2For hydrogen, optionally the C replaced1‑10Linear or branched alkyl group, the positive integer that n is 1~6；The catalyst based on parts by weight, including following component: a) 20~80 parts of molecular sieve；The molecular sieve is selected from least one of ZSM-5, beta, Y, MCM-22, MCM-41 or mordenite molecular sieve；B) 20~80 parts of binder；C) 0.1~20 part of silica inactive surfaces coating.This method can be used for non-fossil sources alkene field.
Description
Technical field
The present invention relates to a kind of method for producing C 4 olefin, in particular to a kind of acetyl-propionic acid compound produces carbon four
The method of alkene.
Background technique
Alkene is the important basic material of national economy, occupy in petrochemical industry and development of chemical industry it is important strategically
One of the basic industry and mainstay industry of position and national economy.Alkene industry is clearly included in hair by 12 planning of country
In exhibition planning.Basic compound and a national oil chemical industry are important using ethylene and propylene as the olefin product of representative
The staple product of industry development level, alkene industrial expansion drive the development of other Organic chemical products.It is main at present
Olefin form is ethylene, propylene, C4 alkene etc..For ethylene product, can by the polymerization of ethylene, alkylation with benzene and with
The addition reaction of water, oxygen, halogen, a series of available valuable derivatives, wherein polyethylene, ethylene oxide, vinyl chloride,
Styrene is the most important consumer goods.Propylene dosage is only second to ethylene.The maximum downstream product of propylene is polypropylene, accounts for the whole world third
50% or more of alkene consumption figure, in addition propylene may further be used to prepare acrylonitrile, isopropanol, phenol and acetone, butanol and octanol, third
Olefin(e) acid and its esters, propylene oxide and propylene glycol, epoxychloropropane and synthetic glycerine etc..The acquisition of alkene at present is mainly with can not
Regenerated naphtha obtains.Therefore the restriction that petroleum resources produce alkene is very big.China's ethylene production needs within 2010
About 50,000,000 tons of chemical industry light oil.China's oil shortage of resources, energy demand increase comparatively fast, and crude oil external dependence degree reaches within 2010
53%, with the unstable concussion and internal supply aggravation of contradictions of international crude oil price, olefin feedstock is in short supply, constrains alkene
The development of hydrocarbon industry.Therefore positive development, which produces reproducible alkene by renewable resource, important meaning.
The plant that nature is widely present is a kind of typical renewable resource, belongs to one kind of biomass.Global biology
The annual yield of matter is about 200,000,000,000 tons, and rich reserves are from a wealth of sources, cheap and easy to get.From reproducible biomass resource
It is prepared with the extensive concern that widely applied olefin product causes scientific circles and industry.
Levulic acid (4-Oxyvalerate, levulonic acid or valeric acid) is a kind of short chain non-volatile fatty acid.Acetyl
Propionic acid low toxicity, has hygroscopicity, distills under normal pressure and hardly decompose, and carbonyl and carboxyl is contained in molecule, it is prone at salt, ester
Change, add the series of chemical such as hydrogen, condensation, oxidation and halogenation, is the important centre for preparing a variety of chemical products with high added-value
Body is widely used in the industrial circles such as fragrance, solvent, oil dope, medicine and plasticizer.Levulinate is short-chain
Aliphatic ester, generally colourless liquid, boiling point is higher, and a kind of important organic chemicals, can be directly used as fragrance, food
Additive, gasoline additive and biological liquid fuel etc. can be used for the row such as food, cosmetics, medicine, plastics and communications and transportation
Industry.
Currently, people expand research to the utilization of levulic acid.United States Patent (USP) (US 20140171688A1) describes
The ketones solvents such as methyl ethyl ketone are converted by levulic acid.After the process converts levulic acid and formic acid for hexose first, warp
It crosses alkali process and forms metal salt, obtain can be used as the methyl ethyl ketone of solvent after electrolytic decarbodylation in electrolytic cell again later.Beauty
State's patent (US 20060247444A1), which is described, converts N- alkyl pyrrolidone for levulic acid.N- alkyl pyrrolidone can
For use as solvent, surfactant, dispersing agent and emulsifier, can be used for the maintenance of oil well and gas well, the synthesis of polymer and
Medical aspect.That patent describes 2 step processes, and catalytic hydrogenation prepares 5- first under hydrogen after levulic acid and organic amine are mixed
- 2 pyrrolidones of base-N- alkyl.Chinese patent (CN200910073688.5), which is described, prepares angelica lactone for levulic acid
Method.The inorganic liquid acid or solid acid catalyst of its weight 1-10%, at a temperature of 100-150 DEG C, control are added in levulic acid
Vacuum degree processed is 20-150mmHg, and the levulic acid and alpha-angelica lactone in reaction system gas phase are separated by rectifying, second
Acyl propionic acid is back to reaction system, and alpha-angelica lactone condensation controls 60-90 DEG C of condensation temperature, separation and purification obtains product.
On the whole, the conversion of levulic acid, which is concentrated mainly on, is converted into the fine chemicals such as pure and mild ester, by levulic acid
The method that class compound is converted into alkene is seldom, the method for especially controllably converting C 4 olefin for levulic acid.
Summary of the invention
The present invention intends to provide a kind of method for producing C 4 olefin.
For achieving the above object, the technical solution adopted by the present invention is as follows: a method of producing C 4 olefin, make
Raw material contacts generation catalysis reaction with catalyst and generates the logistics containing C 4 olefin；Wherein, the raw material has structure formula (I):
In formula (I), R1For the C optionally replaced1-8Linear or branched alkyl group, R2For hydrogen, optionally the C replaced1-10Straight chain or branch
Alkyl group, the positive integer that n is 1~6；
The catalyst based on parts by weight, including following component:
A) 20~80 parts of molecular sieve；The molecular sieve is selected from ZSM-5, beta, Y, MCM-22, MCM-41 or modenite
At least one of molecular sieve；
B) 20~80 parts of binder；
C) 0.1~20 part of silica inactive surfaces coating.
In above-mentioned technical proposal, it is preferable that in formula (I), R1For the C optionally replaced1-4Linear or branched alkyl group；R2For hydrogen,
The C optionally replaced1-5Linear or branched alkyl group；The positive integer that n is 1~4.
In above-mentioned technical proposal, it is preferable that based on parts by weight, the dosage of molecular sieve is 30~70 parts in catalyst, is glued
The dosage for tying agent is 30~70 parts, and the dosage of silica inactive surfaces coating is 1~15 part.
In above-mentioned technical proposal, it is preferable that the molecular sieve is selected from least one of ZSM-5 or Y molecular sieve.
In above-mentioned technical proposal, it is preferable that beta and mordenite molecular sieve silica alumina ratio SiO2/Al2O3=10~
300, it is highly preferred that SiO2/Al2O3=10~65；ZSM-5, Y, MCM-22 and MCM-41 molecular sieve silica alumina ratio SiO2/
Al2O3=2~500, it is highly preferred that SiO2/Al2O3=3~150.
In above-mentioned technical proposal, it is preferable that the catalytic reaction condition are as follows: 200~800 DEG C of reaction temperature, Hydrogen Vapor Pressure
0.1~5MPa in terms of gauge pressure, hydrogen flowing quantity be 3~500 ml/mins, raw material weight air speed 0.3~10 hour-1。
In above-mentioned technical proposal, it is preferable that the raw material comes from biological material.
In above-mentioned technical proposal, it is preferable that the raw material comes from xylitol, glucose, cellobiose, hemicellulose or wood
At least one of quality.
In above-mentioned technical proposal, it is preferable that the raw material is in bagasse, glucose, timber, corn stalk or straw straw
At least one.
In above-mentioned technical proposal, it is preferable that the C 4 olefin in 1- butylene, 2- butylene or isobutene at least one
Kind.
Catalyst described in the method for the present invention the preparation method is as follows: molecular sieve, binder, extrusion aid, expanding agent are mixed
It pinches, extruded moulding, 100~200 DEG C drying 1~24 hour after molding roasts 1~10 hour at 400~700 DEG C.Wherein,
The extrusion aid is at least one of sesbania powder, polyethylene glycol or sodium carboxymethylcellulose, and the expanding agent is citric acid, grass
At least one of acid or ethylenediamine tetra-acetic acid, the extrusion aid of addition and the total amount of expanding agent are no more than mixture weight
10%.Acid is added when molding to be mediated, the acid of addition includes at least one of inorganic acid or acetic acid, and inorganic acid includes nitre
At least one of acid, sulfuric acid or phosphoric acid, the amount for the acid solution being added are the 50~90% of mixture weight.Silica is lazy
Property surface covering introduced by the method for liquid deposition.Specifically, it is introduced by dipping-roasting program.In liquid deposition
In scheme, obtained catalyst Precursors are immersed in nonpolar solvent, the mass ratioes of nonpolar solvent and catalyst Precursors is 1~
20, nonpolar solvent is one of the chain alkane of C5~C10 and the cycloalkane of C5~C10 or a variety of, and is added and is selected from four
One of methoxyl group silicon, tetraethoxy-silicane, tetrapropoxy-silicane, silicon tetrachloride or a variety of dressing agents are reacted, dressing agent
Quality is the 1~150% of catalyst Precursors quality, dry at 80~150 DEG C after processing, and is roasted at 300~600 DEG C
0.5~8 hour, obtain the catalyst.
As an embodiment of the invention, raw material of the present invention is biomass based compound.Such compound
It can be obtained by biomass material from a wealth of sources, rich reserves, it can be with large scale preparation.For example, levulic acid can be in zirconium
In the presence of oxide, metal chloride, organic acid or inorganic acid, produced by the biomass substrate such as cellulose, stalk
(Efficient Conversion of Cellulose to Levulinic Acid by Hydrothermal
Treatment Using Zirconium Dioxide as a Recyclable Solid Acid Catalyst,
Ind.Eng.Chem.Res.,2014,53(49),pp 18796–18805；Production of levulinic acid
from cellulose by hydrothermal decomposition combined with aqueous phase
Dehydration with a solid acid catalyst, Energy Environ.Sci., 2012,5,7559-7574；
Effective Production of Levulinic Acid from Biomass through Pretreatment
Using Phosphoric Acid, Hydrochloric Acid, or Ionic Liquid, Ind.Eng.Chem.Res.,
2014,53(29),pp 11611–11621)。
The method of the present invention further improves catalyst to the selectivity of alkene by the silylation modification to molecular sieve, adopts
With the method for the present invention, feed stock conversion can reach 98%；The selectivity of target product C 4 olefin reaches as high as 91%, takes
Obtained preferable technical effect.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
[comparative example 1]
60 grams of corn stalks are weighed, is placed in autoclave pressure and is added 700 grams of water, add the sulphur of the 5mol/L of water quality 7%
Acid solution is warming up at 180 DEG C and reacts 45 minutes, cools down later, reaction solution after cooling is filtered, filter cake and filtering are obtained
Liquid, filtered fluid are that the hydrolyzate of cellulose uses mass spectrum to carry out identifying primary product for acetyl to reaction result after reaction
Propionic acid, yield are 18 grams.
It weighs the ZSM-5 molecular sieve that 35 grams of silica alumina ratios are 50 to be mixed with 35 grams of gama-alumina auxiliary agents, sesbania powder is added
It 2.7 grams, is uniformly mixed.48 grams of aqueous solution of nitric acid that nitric acid mass percentage is 5.5%, kneading and compacting, extrusion are added later.
It is 8 hours dry at 120 DEG C to obtain catalyst precarsor, is roasted 2 hours by 500 DEG C, obtains molecular sieve catalyst.
Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is second
Acyl propionic acid, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 300 DEG C of temperature.After reaction, instead
1 should be the results are shown in Table, reaction substrate conversion ratio is 98%, and the selectivity of C 4 olefin is 5%.
[comparative example 2]
It weighs the Y molecular sieve that 35 grams of silica alumina ratios are 8 to be mixed with 35 grams of gama-alumina auxiliary agents, sesbania powder 2.7 is added
Gram, it is uniformly mixed.48 grams of aqueous solution of nitric acid that nitric acid mass percentage is 5.5%, kneading and compacting, extrusion are added later.?
It is 8 hours dry at 120 DEG C to catalyst precarsor, it is roasted 2 hours by 500 DEG C, obtains molecular sieve catalyst.
Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is second
Acyl propionic acid, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 300 DEG C of temperature.After reaction, instead
1 should be the results are shown in Table, reaction substrate conversion ratio is 97%, and the selectivity of C 4 olefin is 7%.
[comparative example 3]
It weighs the beta molecular sieve that 35 grams of silica alumina ratios are 20 to be mixed with 35 grams of gama-alumina auxiliary agents, sesbania powder is added
It 2.7 grams, is uniformly mixed.48 grams of aqueous solution of nitric acid that nitric acid mass percentage is 5.5%, kneading and compacting, extrusion are added later.
It is 8 hours dry at 120 DEG C to obtain catalyst precarsor, is roasted 2 hours by 500 DEG C, obtains molecular sieve catalyst.
Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is second
Acyl propionic acid, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 300 DEG C of temperature.After reaction, instead
1 should be the results are shown in Table, reaction substrate conversion ratio is 99%, and the selectivity of C 4 olefin is 4%.
[comparative example 4]
Weigh gross mass be 35 gram molecules sieve mixture, including 17.5 grams of silica alumina ratios be 50 ZSM-5 molecular sieve, 17.5 grams
The beta that silica alumina ratio is 30, is mixed with 35 grams of gama-alumina auxiliary agents, is added 2.7 grams of sesbania powder, is uniformly mixed.Later plus
Enter 48 grams of aqueous solution of nitric acid that nitric acid mass fraction is 5.5%, kneading and compacting, extrusion.Catalyst precarsor is obtained to do at 120 DEG C
It dry 8 hours, is roasted 2 hours by 500 DEG C, obtains catalyst.
Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is second
Acyl propionic acid, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 300 DEG C of temperature.After reaction, instead
It answers the result shows that reaction substrate conversion ratio is 95%, the selectivity of C 4 olefin is 10%.
[comparative example 5]
Weigh gross mass be 35 gram molecules sieve mixture, including 24.5 grams of silica alumina ratios be 50 ZSM-5 molecular sieve, 10.5 grams
The beta that silica alumina ratio is 30, is mixed with 35 grams of gama-alumina auxiliary agents, is added 2.7 grams of sesbania powder, is uniformly mixed.Later plus
Enter 48 grams of aqueous solution of nitric acid that nitric acid mass fraction is 5.5%, kneading and compacting, extrusion.Catalyst precarsor is obtained to do at 120 DEG C
It dry 8 hours, is roasted 2 hours by 500 DEG C, obtains catalyst.
Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is second
Acyl methyl propionate, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 280 DEG C of temperature.Reaction terminates
Afterwards, reaction result shows that reaction substrate conversion ratio is 93%, and the selectivity of C 4 olefin is 10%.
[comparative example 6]
Weighing gross mass is that 35 gram molecules sieve mixture, Y molecular sieve, 24.5 grams of sial including 10.5 grams of silica alumina ratios for 10
It than the beta for 30, is mixed with 35 grams of gama-alumina auxiliary agents, is added 2.7 grams of sesbania powder, be uniformly mixed.Nitre is added later
48 grams of aqueous solution of nitric acid that acid mass fraction is 5.5%, kneading and compacting, extrusion.Catalyst precarsor is obtained dry 8 at 120 DEG C
Hour, it is roasted 2 hours by 500 DEG C, obtains catalyst.
Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is second
Acyl methyl propionate, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 400 DEG C of temperature.Reaction terminates
Afterwards, reaction result shows that reaction substrate conversion ratio is 99%, and the selectivity of C 4 olefin is 6%.
[embodiment 1]
Weighing gross mass is that 35 gram molecules sieve mixture, Y molecular sieve, 17.5 grams of sial including 17.5 grams of silica alumina ratios for 10
It than the ZSM-5 for 50, is mixed with 35 grams of gama-alumina auxiliary agents, is added 2.7 grams of sesbania powder, be uniformly mixed.Nitre is added later
48 grams of aqueous solution of nitric acid that acid mass fraction is 5.5%, kneading and compacting, extrusion.Catalyst precarsor is obtained dry 8 at 120 DEG C
Hour, it is roasted 2 hours by 500 DEG C, obtains catalyst Precursors.The precursor catalyst is immersed into containing for 5 times of molecular sieve parents
In the heptane solvent for having 4% tetramethoxy-silicane, 5h is stirred at room temperature.It takes out and after drying, roasts and urged at 550 DEG C at 80 DEG C
Agent.
Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is second
Acyl methyl propionate, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 300 DEG C of temperature.Reaction terminates
Afterwards, reaction result shows that reaction substrate conversion ratio is 91%, and the selectivity of C 4 olefin is 87%.
[embodiment 2]
Weighing gross mass is that 35 gram molecules sieve mixture, Y molecular sieve, 17.5 grams of sial including 17.5 grams of silica alumina ratios for 10
It than the beta for 30, is mixed with 35 grams of gama-alumina auxiliary agents, is added 2.7 grams of sesbania powder, be uniformly mixed.Nitre is added later
48 grams of aqueous solution of nitric acid that acid mass fraction is 5.5%, kneading and compacting, extrusion.Catalyst precarsor is obtained dry 8 at 120 DEG C
Hour, it is roasted 2 hours by 500 DEG C, obtains catalyst Precursors.The precursor catalyst is immersed into containing for 5 times of molecular sieve parents
In the heptane solvent for having 4% tetraethoxy-silicane, 5h is stirred at room temperature.It takes out and after drying, roasts and urged at 550 DEG C at 80 DEG C
Agent.
Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is second
Acyl methyl propionate, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 350 DEG C of temperature.Reaction terminates
Afterwards, reaction result shows that reaction substrate conversion ratio is 94%, and the selectivity of C 4 olefin is 91%.
[embodiment 3]
Weighing gross mass is that 35 gram molecules sieve mixture, Y molecular sieve, 17.5 grams of sial including 17.5 grams of silica alumina ratios for 8
It than the beta for 30, is mixed with 35 grams of gama-alumina auxiliary agents, is added 2.7 grams of sesbania powder, be uniformly mixed.Nitre is added later
48 grams of aqueous solution of nitric acid that acid mass fraction is 5.5%, kneading and compacting, extrusion.Catalyst precarsor is obtained dry 8 at 120 DEG C
Hour, it is roasted 2 hours by 500 DEG C, obtains catalyst Precursors.The precursor catalyst is immersed into containing for 5 times of molecular sieve parents
In the heptane solvent for having 4% silicon tetrachloride, 5h is stirred at room temperature.It takes out and after drying, roasts and be catalyzed at 550 DEG C at 80 DEG C
Agent.
Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is second
Acyl methyl propionate, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 350 DEG C of temperature.Reaction terminates
Afterwards, reaction result shows that reaction substrate conversion ratio is 93%, and the selectivity of C 4 olefin is 88%.
[embodiment 4]
Weigh gross mass be 35 gram molecules sieve mixture, including 17.5 grams of silica alumina ratios be 100 ZSM-5 molecular sieve, 17.5
The beta that gram silica alumina ratio is 30, is mixed with 35 grams of gama-alumina auxiliary agents, is added 2.7 grams of sesbania powder, is uniformly mixed.Later
48 grams of aqueous solution of nitric acid that nitric acid mass fraction is 5.5%, kneading and compacting, extrusion is added.Catalyst precarsor is obtained at 120 DEG C
It is 8 hours dry, it is roasted 2 hours by 500 DEG C, obtains catalyst Precursors.The precursor catalyst is immersed into 5 times of molecular sieve parents
The heptane solvent containing 4% silicon tetrachloride in, 5h is stirred at room temperature.It takes out and after drying, roasts and obtain at 550 DEG C at 80 DEG C
Catalyst.
Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is second
Acyl methyl propionate, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 350 DEG C of temperature.Reaction terminates
Afterwards, reaction result shows that reaction substrate conversion ratio is 97%, and the selectivity of C 4 olefin is 84%.
[embodiment 5]
Weighing gross mass is that 35 gram molecules sieve mixture, Y molecular sieve, 17.5 grams of sial including 17.5 grams of silica alumina ratios for 6
It than the beta for 30, is mixed with 45 grams of gama-alumina auxiliary agents, is added 3.2 grams of sesbania powder, be uniformly mixed.Nitre is added later
48 grams of aqueous solution of nitric acid that acid mass fraction is 5.5%, kneading and compacting, extrusion.Catalyst precarsor is obtained dry 8 at 120 DEG C
Hour, it is roasted 2 hours by 500 DEG C, obtains catalyst Precursors.The precursor catalyst is immersed into containing for 5 times of molecular sieve parents
In the heptane solvent for having 4% silicon tetrachloride, 5h is stirred at room temperature.It takes out and after drying, roasts and be catalyzed at 550 DEG C at 80 DEG C
Agent.
Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is second
Acyl butyl propionate, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 300 DEG C of temperature.Reaction terminates
Afterwards, reaction result shows that reaction substrate conversion ratio is 91%, and the selectivity of C 4 olefin is 82%.
[embodiment 6]
Weighing gross mass is that 35 gram molecules sieve mixture, Y molecular sieve, 17.5 grams of sial including 17.5 grams of silica alumina ratios for 10
It than the beta for 30, is mixed with 35 grams of gama-alumina auxiliary agents, is added 2.7 grams of sesbania powder, be uniformly mixed.Nitre is added later
48 grams of aqueous solution of nitric acid that acid mass fraction is 5.5%, kneading and compacting, extrusion.Catalyst precarsor is obtained dry 8 at 120 DEG C
Hour, it is roasted 2 hours by 500 DEG C, obtains catalyst Precursors.The precursor catalyst is immersed into containing for 5 times of molecular sieve parents
In the heptane solvent for having 4% silicon tetrachloride, 5h is stirred at room temperature.It takes out and after drying, roasts and be catalyzed at 550 DEG C at 80 DEG C
Agent.
Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is second
Acyl butyl propionate, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 300 DEG C of temperature.Reaction terminates
Afterwards, reaction result shows that reaction substrate conversion ratio is 94%, and the selectivity of C 4 olefin is 79%.
[embodiment 7]
Weighing gross mass is that 35 gram molecules sieve mixture, Y molecular sieve, 17.5 grams of sial including 17.5 grams of silica alumina ratios for 8
It than the beta for 30, is mixed with 35 grams of gama-alumina auxiliary agents, is added 2.7 grams of sesbania powder, be uniformly mixed.Nitre is added later
48 grams of aqueous solution of nitric acid that acid mass fraction is 5.5%, kneading and compacting, extrusion.Catalyst precarsor is obtained dry 8 at 120 DEG C
Hour, it is roasted 2 hours by 500 DEG C, obtains catalyst Precursors.The precursor catalyst is immersed into containing for 5 times of molecular sieve parents
In the heptane solvent for having 4% silicon tetrachloride, 5h is stirred at room temperature.It takes out and after drying, roasts and be catalyzed at 550 DEG C at 80 DEG C
Agent.
Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is second
Methyl acetoacetate, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 400 DEG C of temperature.Reaction terminates
Afterwards, reaction result shows that reaction substrate conversion ratio is 90%, and the selectivity of C 4 olefin is 82%.
[embodiment 8]
Weighing gross mass is that 35 gram molecules sieve mixture, Y molecular sieve, 17.5 grams of sial including 17.5 grams of silica alumina ratios for 10
It than the beta for 30, is mixed with 35 grams of gama-alumina auxiliary agents, is added 2.7 grams of sesbania powder, be uniformly mixed.Nitre is added later
48 grams of aqueous solution of nitric acid that acid mass fraction is 5.5%, kneading and compacting, extrusion.Catalyst precarsor is obtained dry 8 at 120 DEG C
Hour, it is roasted 2 hours by 500 DEG C, obtains catalyst Precursors.The precursor catalyst is immersed into containing for 5 times of molecular sieve parents
In the heptane solvent for having 4% silicon tetrachloride, 5h is stirred at room temperature.It takes out and after drying, roasts and be catalyzed at 550 DEG C at 80 DEG C
Agent.
Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is second
Acyl propyl propionate, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 350 DEG C of temperature.Reaction terminates
Afterwards, reaction result shows that reaction substrate conversion ratio is 92%, and the selectivity of C 4 olefin is 83%.
[embodiment 9]
Weighing gross mass is that 35 gram molecules sieve mixture, Y molecular sieve, 17.5 grams of sial including 17.5 grams of silica alumina ratios for 8
It than the modenite for 30, is mixed with 35 grams of gama-alumina auxiliary agents, is added 2.7 grams of sesbania powder, be uniformly mixed.Later plus
Enter 48 grams of aqueous solution of nitric acid that nitric acid mass fraction is 5.5%, kneading and compacting, extrusion.Catalyst precarsor is obtained to do at 120 DEG C
It dry 8 hours, is roasted 2 hours by 500 DEG C, obtains catalyst Precursors.The precursor catalyst is immersed into 5 times of molecular sieve parents
In heptane solvent containing 4% tetramethoxy-silicane, 5h is stirred at room temperature.It takes out and after drying, roasts and obtain at 550 DEG C at 80 DEG C
Catalyst.
Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is second
Acyl propyl propionate, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 300 DEG C of temperature.Reaction terminates
Afterwards, reaction result shows that reaction substrate conversion ratio is 92%, and the selectivity of C 4 olefin is 80%.
[embodiment 10]
Weighing gross mass is that 35 gram molecules sieve mixture, beta, 17.5 grams of silica alumina ratios including 17.5 grams of silica alumina ratios for 30
It for 20 mercerising, is mixed with 8.75 grams of gama-alumina auxiliary agents, is added 2.7 grams of sesbania powder, be uniformly mixed.Nitre is added later
48 grams of aqueous solution of nitric acid that acid mass fraction is 5.5%, kneading and compacting, extrusion.Catalyst precarsor is obtained dry 8 at 120 DEG C
Hour, it is roasted 2 hours by 500 DEG C, obtains catalyst Precursors.The precursor catalyst is immersed into containing for 5 times of molecular sieve parents
In the heptane solvent for having 4% tetramethoxy-silicane, 5h is stirred at room temperature.It takes out and after drying, roasts and urged at 550 DEG C at 80 DEG C
Agent.
Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is second
Acyl propyl propionate, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 400 DEG C of temperature.Reaction terminates
Afterwards, reaction result shows that reaction substrate conversion ratio is 98%, and the selectivity of C 4 olefin is 88%.
[embodiment 11]
Weighing gross mass is that 35 gram molecules sieve mixture, beta, 17.5 grams of silica alumina ratios including 17.5 grams of silica alumina ratios for 30
It for 100 MCM-22, is mixed with 35 grams of gama-alumina auxiliary agents, is added 2.7 grams of sesbania powder, be uniformly mixed.Nitre is added later
48 grams of aqueous solution of nitric acid that acid mass fraction is 5.5%, kneading and compacting, extrusion.Catalyst precarsor is obtained dry 8 at 120 DEG C
Hour, it is roasted 2 hours by 500 DEG C, obtains catalyst Precursors.The precursor catalyst is immersed into containing for 5 times of molecular sieve parents
In the heptane solvent for having 4% tetramethoxy-silicane, 5h is stirred at room temperature.It takes out and after drying, roasts and urged at 550 DEG C at 80 DEG C
Agent.
Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is second
Acyl methyl propionate, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 280 DEG C of temperature.Reaction terminates
Afterwards, reaction result shows that reaction substrate conversion ratio is 94%, and the selectivity of C 4 olefin is 84%.
[embodiment 12]
Weighing gross mass is that 35 gram molecules sieve mixture, beta, 17.5 grams of silica alumina ratios including 17.5 grams of silica alumina ratios for 30
It for 100 MCM-41, is mixed with 35 grams of gama-alumina auxiliary agents, is added 2.7 grams of sesbania powder, be uniformly mixed.Nitre is added later
48 grams of aqueous solution of nitric acid that acid mass fraction is 5.5%, kneading and compacting, extrusion.Catalyst precarsor is obtained dry 8 at 120 DEG C
Hour, it is roasted 2 hours by 500 DEG C, obtains catalyst Precursors.The precursor catalyst is immersed into containing for 5 times of molecular sieve parents
In the heptane solvent for having 4% silicon tetrachloride, 5h is stirred at room temperature.It takes out and after drying, roasts and be catalyzed at 550 DEG C at 80 DEG C
Agent.
Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is second
Acyl methyl propionate, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 300 DEG C of temperature.Reaction terminates
Afterwards, reaction result shows that reaction substrate conversion ratio is 92%, and the selectivity of C 4 olefin is 83%.
[embodiment 13]
Weighing gross mass is that 35 gram molecules sieve mixture, mercerising, 17.5 grams of silica alumina ratios including 17.5 grams of silica alumina ratios for 20
It for 50 MCM-41, is mixed with 35 grams of gama-alumina auxiliary agents, is added 2.7 grams of sesbania powder, be uniformly mixed.Nitre is added later
48 grams of aqueous solution of nitric acid that acid mass fraction is 5.5%, kneading and compacting, extrusion.Catalyst precarsor is obtained dry 8 at 120 DEG C
Hour, it is roasted 2 hours by 500 DEG C, obtains catalyst Precursors.The precursor catalyst is immersed into containing for 5 times of molecular sieve parents
In the heptane solvent for having 4% silicon tetrachloride, 5h is stirred at room temperature.It takes out and after drying, roasts and be catalyzed at 550 DEG C at 80 DEG C
Agent.
Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is second
Acyl methyl propionate, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 320 DEG C of temperature.Reaction terminates
Afterwards, reaction result shows that reaction substrate conversion ratio is 97%, and the selectivity of C 4 olefin is 87%.
[embodiment 14]
Weighing gross mass is that 35 gram molecules sieve mixture, Y molecular sieve, 17.5 grams of sial including 17.5 grams of silica alumina ratios for 10
It than the beta for 30, is mixed with 35 grams of gama-alumina auxiliary agents, is added 2.7 grams of sesbania powder, be uniformly mixed.Nitre is added later
48 grams of aqueous solution of nitric acid that acid mass fraction is 5.5%, kneading and compacting, extrusion.Catalyst precarsor is obtained dry 8 at 120 DEG C
Hour, it is roasted 2 hours by 500 DEG C, obtains catalyst Precursors.The precursor catalyst is immersed into containing for 5 times of molecular sieve parents
In the heptane solvent for having 8% tetramethoxy-silicane, 5h is stirred at room temperature.It takes out and after drying, roasts and urged at 550 DEG C at 80 DEG C
Agent.
Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is second
Acyl methyl propionate, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 300 DEG C of temperature.Reaction terminates
Afterwards, reaction result shows that reaction substrate conversion ratio is 98%, and the selectivity of C 4 olefin is 80%.
[embodiment 15]
Weighing gross mass is that 35 gram molecules sieve mixture, Y molecular sieve, 17.5 grams of sial including 17.5 grams of silica alumina ratios for 10
It than the beta for 30, is mixed with 35 grams of gama-alumina auxiliary agents, is added 2.7 grams of sesbania powder, be uniformly mixed.Nitre is added later
48 grams of aqueous solution of nitric acid that acid mass fraction is 5.5%, kneading and compacting, extrusion.Catalyst precarsor is obtained dry 8 at 120 DEG C
Hour, it is roasted 2 hours by 500 DEG C, obtains catalyst Precursors.The precursor catalyst is immersed into containing for 5 times of molecular sieve parents
In the heptane solvent for having 12% tetramethoxy-silicane, 5h is stirred at room temperature.It takes out and after drying, roasts and obtain at 550 DEG C at 80 DEG C
Catalyst.
Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is second
Acyl methyl propionate, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 300 DEG C of temperature.Reaction terminates
Afterwards, reaction result shows that reaction substrate conversion ratio is 91%, and the selectivity of C 4 olefin is 82%.
[embodiment 16]
Weigh gross mass be 35 gram molecules sieve mixture, including 17.5 grams of silica alumina ratios be 100 ZSM-5 molecular sieve, 17.5
The beta that gram silica alumina ratio is 30, is mixed with 35 grams of gama-alumina auxiliary agents, is added 2.7 grams of sesbania powder, is uniformly mixed.Later
48 grams of aqueous solution of nitric acid that nitric acid mass fraction is 5.5%, kneading and compacting, extrusion is added.Catalyst precarsor is obtained at 120 DEG C
It is 8 hours dry, it is roasted 2 hours by 500 DEG C, obtains catalyst Precursors.The precursor catalyst is immersed into 5 times of molecular sieve parents
The heptane solvent containing 24% tetramethoxy-silicane in, 5h is stirred at room temperature.It takes out and after drying, is roasted at 550 DEG C at 80 DEG C
Obtain catalyst.
Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is second
Acyl methyl propionate, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 300 DEG C of temperature.Reaction terminates
Afterwards, reaction result shows that reaction substrate conversion ratio is 93%, and the selectivity of C 4 olefin is 80%.
Table 1
| Embodiment | Molecular sieve | Silica alumina ratio | Silylating reagent | Substrate | Conversion ratio/% | Selectivity/% |
| Comparative example 1 | ZSM-5 | 50 | - | Levulic acid | 98 | 5 |
| Comparative example 2 | Y | 8 | - | Levulic acid | 97 | 7 |
| Comparative example 3 | Beta | 20 | - | Levulic acid | 99 | 4 |
| Comparative example 4 | ZSM-5+beta | 50/30 | - | Levulic acid | 95 | 11 |
| Comparative example 5 | ZSM-5+beta | 50/30 | - | Methyl ester levulinate | 93 | 10 |
| Comparative example 6 | Y+beta | 10/30 | - | Methyl ester levulinate | 99 | 6 |
| 1 | Y+ZSM-5 | 10/50 | 4% tetramethoxy-silicane | Methyl ester levulinate | 91 | 87 |
| 2 | Y+beta | 10/30 | 4% Ethoxysilane | Methyl ester levulinate | 94 | 91 |
| 3 | Y+beta | 8/30 | 4% silicon tetrachloride | Methyl ester levulinate | 93 | 88 |
| 4 | ZSM-5+beta | 100/30 | 4% silicon tetrachloride | Methyl ester levulinate | 98 | 84 |
| 5 | Y+beta | 6/30 | 4% silicon tetrachloride | Butyl acetylpropanoate | 91 | 82 |
| 6 | Y+beta | 10/30 | 4% silicon tetrachloride | Butyl acetylpropanoate | 94 | 79 |
| 7 | Y+beta | 8/30 | 4% silicon tetrachloride | Methyl acetoacetate | 90 | 82 |
| 8 | Y+beta | 10/30 | 4% silicon tetrachloride | Levulic acid propyl ester | 92 | 83 |
| 9 | Y+ mercerising | 8/30 | 4% tetramethoxy-silicane | Levulic acid propyl ester | 92 | 80 |
| 10 | Beta+ mercerising | 30/20 | 4% tetramethoxy-silicane | Levulic acid propyl ester | 98 | 88 |
| 11 | beta+MCM-22 | 30/100 | 4% tetramethoxy-silicane | Methyl ester levulinate | 94 | 84 |
| 12 | beta+MCM-41 | 30/100 | 4% silicon tetrachloride | Methyl ester levulinate | 92 | 83 |
| 13 | Mercerising+MCM-41 | 20/50 | 4% silicon tetrachloride | Methyl ester levulinate | 97 | 87 |
| 14 | Y+beta | 10/30 | 8% tetramethoxy-silicane | Methyl ester levulinate | 98 | 80 |
| 15 | Y+beta | 10/30 | 12% tetramethoxy-silicane | Methyl ester levulinate | 91 | 82 |
| 16 | ZSM-5+beta | 100/30 | 24% tetramethoxy-silicane | Methyl ester levulinate | 93 | 80 |
Claims (9)
1. a kind of method for producing C 4 olefin makes raw material contact generation catalysis reaction with catalyst and generates the object containing C 4 olefin
Stream；Wherein, the raw material has structure formula (I):
In formula (I), R1For the C optionally replaced1-8Linear or branched alkyl group, R2For hydrogen, optionally the C replaced1-10Linear chain or branched chain alkane
Base, the positive integer that n is 1~6；
The catalyst based on parts by weight, including following component:
A) 20~80 parts of molecular sieve；The molecular sieve is selected from ZSM-5, beta, Y, MCM-22, MCM-41 or modenite molecule
At least one of sieve；
B) 20~80 parts of binder；
C) 0.1~20 part of silica inactive surfaces coating；
Wherein, the catalytic reaction condition are as follows: 200~800 DEG C of reaction temperature, Hydrogen Vapor Pressure 0.1~5MPa in terms of gauge pressure, hydrogen
Flow be 3~500 ml/mins, raw material weight air speed 0.3~10 hour -1.
2. producing the method for C 4 olefin according to claim 1, it is characterised in that in formula (I), R1For the C optionally replaced1-4
Linear or branched alkyl group；R2For hydrogen, optionally the C replaced1-5Linear or branched alkyl group；The positive integer that n is 1~4；The carbon tetraene
Hydrocarbon is selected from least one of 1- butylene, 2- butylene or isobutene.
3. producing the method for C 4 olefin according to claim 1, it is characterised in that based on parts by weight, molecule in catalyst
The dosage of sieve is 30~70 parts, and the dosage of binder is 30~70 parts, and the dosage of silica inactive surfaces coating is 1~15
Part.
4. producing the method for C 4 olefin according to claim 1, it is characterised in that the molecular sieve is selected from ZSM-5 or Y points
At least one of son sieve.
5. producing the method for C 4 olefin according to claim 1, it is characterised in that beta and mordenite molecular sieve sial
Molar ratio SiO2/Al2O3=10~300, ZSM-5, Y, MCM-22 and MCM-41 molecular sieve silica alumina ratio SiO2/Al2O3=2~
500。
6. producing the method for C 4 olefin according to claim 5, it is characterised in that beta and mordenite molecular sieve sial
Molar ratio SiO2/Al2O3=10~65, ZSM-5, Y, MCM-22 and MCM-41 molecular sieve silica alumina ratio SiO2/Al2O3=3~
150。
7. producing the method for C 4 olefin according to claim 1, it is characterised in that the raw material comes from biological material.
8. producing the method for C 4 olefin according to claim 1, it is characterised in that the raw material comes from xylitol, grape
At least one of sugar, cellobiose, hemicellulose or lignin.
9. aromatization method according to claim 1, it is characterised in that the raw material comes from bagasse, glucose, timber, jade
Rice at least one of straw or straw straw.
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| Stainless Steel As a Catalyst for the Total Deoxygenation of Glycerol and Levulinic Acid in Aqueous Acidic Medium;Domenico Di Mondo,et al.;《ACS Catalysis》;20110303(第1期);355-364 |
| Utilization of biomass: Conversion of model compounds to hydrocarbons over zeolite H-ZSM-5;Uffe V. Mentzela，et al;《Applied Catalysis A: General》;20110203(第396期);59-67 |
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