CN103962172A - Method for preparing high-carbon hydrocarbon by using low-carbon oxygen containing compound as well as catalyst and preparation method thereof - Google Patents
Method for preparing high-carbon hydrocarbon by using low-carbon oxygen containing compound as well as catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a method for preparing high-carbon hydrocarbon by using a low-carbon oxygen containing compound as well as a catalyst and a preparation method thereof. The catalyst is prepared from the following components of Na2O, MxOy, Al2O3, SiO2 and H2O which are in the molar ratio of (0-0.2):(0.5-1.2):1:(10-40 ):(0-40), wherein MxOy is an oxide of the metallic element M, x is the number of the metallic element M, and y is the number of oxygen atoms required to meet the oxidation state of the metallic elements M; the metallic element M is one or more of Zn, Ag, Mo, Cu, Ni, Mn, Cr, Pt, Fe, W, Au, V and La. When the catalyst provided by the invention is used for preparing the high-carbon hydrocarbon by using the low-carbon oxygen containing compound, the operation is convenient, and the per-pass conversion of the catalyst is 99 percent. In the prepared high-carbon hydrocarbon, the yield of C5+hydrocarbon is higher than 84 percent, and the yield of aromatic hydrocarbon is higher than 45 percent.
Description
Technical field
The present invention relates to a kind of method by low-carbon oxygen-containing compound high-carbon hydrocarbon processed, Catalysts and its preparation method.
Background technology
Because the domestic air pollution problems inherent of fluctuation and China of World Oil Market price is on the rise, find and use green renewable alternative energy source to become the task of top priority in recent years.Biomass fuel oil tech is paid close attention to because its relatively ripe technique has obtained widely, and living beings ethanol is promoted the use of on as the market of the U.S., Brazil in American States at present, and some countries in Europe have also built biomass-making ethanol plant as Italy.
Taking biomass-making ethanol technology as example, this technique is produced and can be added the alcohol fuel using in gasoline, diesel oil to through zymotechnique taking corn, stalk or cassava as raw material.The subject matter that this technology aspect exists be at present exactly in product ethanol selectively not high, be generally 30% left and right; Accessory substance is many and assorted, except recyclable its economic worth such as xylitol, butanediol, in separation of ethanol distillate, also contain 90 many kinds of substances, be mainly organic oxygen-containing compound and comprise (the Gayubo A. such as polyalcohol, aldehydes, ketone, carboxylic acid and phenols and furans, etc., Ind.Eng.Chem.Res., 2004,43:2610).If these organic oxygen-containing accessory substances are further converted to fuel oil, not only can improve carbon source service efficiency but also can effectively solve organic blowdown problem in living beings ethanol.
The catalyst that current known can be used for is converted into organic oxygen-containing compound fuel hydrocarbons is the crystalline silico-alumino molecular sieve ZSM series of XOM's research and development, as ZSM-5, and ZSM-11, ZSM-12 etc.The use methanol/dimethyl ether of having reported is for raw material or set it as intermediate product and produce the MTG of Exxon Mobil Corporation technique (the Yurchak S. of automobile-use fuel oil, Stud.Surf.Sci.Catal, 1988,36:251) with Denmark Mortopl rope company's T IGAS technique (Topp-Jorgensen J., Stud.Surf.Sci.Catal, 1988,36:293) be all using ZSM-5 as catalyst, methanol/dimethyl ether is catalytically conveted to the hydrocarbon mixture with gasoline boiling range.From the material of publishing, ZSM catalyst series is that exothermic heat of reaction is violent for the problem of the chain growth polymerization maximum of catalysis low-carbon oxygen-containing compound, catalyst is easily because of carbon deposit inactivation, and the hydrone that in course of reaction, oxycompound removes at high temperature can cause permanent damage to aluminum-oxygen tetrahedron skeleton structure.For this problem, person skilled in art is devoted to the improvement of technology to reduce the dividing potential drop of carbon distribution and reduction water at present, and these effort can reduce the generation of problem, but also there is no breakthrough progress, cannot fundamentally avoid this problem.And, be that MTG technique or TIGAS technique all will directly or indirectly be produced gasoline taking methanol/dimethyl ether as raw material, wherein the concentration of MTG process feeds methyl alcohol is in 83wt% left and right.At present there are no using the report that low-carbon (LC) aldehyde, ketone, carboxylic acid, carbohydrate are raw material production hydrocarbon fuel.
Summary of the invention
The defect that technical problem to be solved by this invention is high to material purity requirement while being to overcome low-carbon oxygen-containing compound of the prior art high-carbon hydrocarbon processed, catalyst heat release is violent, and a kind of method by low-carbon oxygen-containing compound high-carbon hydrocarbon processed, Catalysts and its preparation method are provided.When catalyst provided by the present invention is used for low-carbon oxygen-containing compound high-carbon hydrocarbon processed, easy to operate, the conversion per pass of catalyst can reach 99%; In the high-carbon hydrocarbon making, C
5the yield of+hydro carbons is higher than 84%, and the yield of aromatic hydrocarbons is higher than 45%.
The invention provides a kind of Modified HZSM-5 Zeolite Catalyst; Mole consisting of of described Modified HZSM-5 Zeolite Catalyst: (0～0.2) Na
2o:(0.5～1.2) M
xo
y: Al
2o
3: (10～40) SiO
2: (0～40) H
2o, wherein M
xo
yfor the oxide of metallic element M, x is the number of metallic element M, and y is the required oxygen atom number of oxidation state that meets metallic element M, and described metallic element M is one or more in Zn, Ag, Mo, Cu, Ni, Mn, Cr, Pt, Fe, W, Au, V and La.
In the present invention, described metallic element M is preferably one or more in Mo, Cu, Ni, Mn, Cr, Pt, Fe, W, Au and V.
The present invention also provides the preparation method of aforesaid Modified HZSM-5 Zeolite Catalyst; Described preparation method comprises the steps:
(1) will mix with binding agent through pretreated HZSM-5 molecular sieve, grind, obtain abrasive;
(2) in described abrasive, drip the salpeter solution that mass concentration is 2%-8%, extrusion modling, at 90-150 DEG C, dry 1-2 hour, obtains molecular sieve;
(3) by described molecular sieve roasting 2-8h at 450-580 DEG C, cooling, be broken into 20-40 order, obtain catalyst carrier;
(4) get the described catalyst carrier of the quality such as two parts, in a catalyst carrier, add deionized water, mix with the salting liquid of described metallic element M, mix with another part of catalyst carrier again, dipping 12-36h, dry 4-12h at 90-150 DEG C, then at 450-580 DEG C roasting 2-8h.
In step (1), in described HZSM-5 molecular sieve, SiO
2with Al
2o
3mol ratio be preferably 30～120.
In step (1), described binding agent is the binding agent for catalytic cracking reaction and hydrocracking reaction of this area routine, is preferably one or more in kaolin, imvite, diatomite, alchlor, silica and silicon-aluminum sol.
In step (1), described pretreatment is this area routine operation, is preferably: in the Muffle furnace of 450-580 DEG C, HZSM-5 molecular sieve roasting 2-8h is removed to volatile impurity, deposit in drying box for subsequent use.
In step (1), the synthetic method of described HZSM-5 molecular sieve is this area routine, be preferably: will be configured to two parts of solution of first, second for the synthesis of the raw material of HZSM-5 molecular sieve, wherein first solution is made up of waterglass, directed agents and water, and second solution is made up of aluminium source, inorganic acid and water; Under 200～300r/min stir speed (S.S.), second solution is slowly joined in first solution, stirring reaction is until form uniform jel product; Continue to stir 15～20min and make jel product ageing, then rise to standing crystallization 20～30h at 180 DEG C with the speed of 5 DEG C/min by room temperature, rapid cold filtration after crystallization completes, with deionized water wash to filtrate pH value be 8～9, filter cake is dried at 120 DEG C.By filter cake and ammonium salt solution with 1 part of filter cake: (0.1～0.5) part ammonium salt: (8～10) part H
2weight ratio contact 20～30min of O carries out ion-exchange, and after being dried, under 450～580 DEG C of conditions, roasting 2～8h makes the HZSM-5 molecular sieve with reactivity.
Preferably, be (8～15) Na for the synthesis of the quality proportioning of the raw material of HZSM-5 molecular sieve
2o:Al
2o
3: (40～95) SiO
2: (18～39) directed agents: (2.5～6) inorganic acid: (2500～3900) H
2o.
Wherein, described directed agents is the directed agents of this area routine, is preferably one or more in isopropylamine, ethamine, ethylenediamine, n-butylamine, isopropyl alcohol and inorganic ammonium salt, is more preferably ethamine.Described aluminium source is the inorganic acid aluminium salt of this area routine, is preferably aluminum sulfate and/or aluminum nitrate, is more preferably aluminum sulfate.Described inorganic acid is preferably acid corresponding to described inorganic acid aluminium salt.In the time that described inorganic acid aluminium salt is aluminum sulfate, described inorganic acid is preferably sulfuric acid.
In step (2), the consumption of described salpeter solution is this area routine, is preferably the 20%-35% that accounts for the quality of described abrasive.
In step (2) and step (4), described dry equipment is this area routine, is preferably baking oven.
In step (3), described is cooling preferably for being cooled to room temperature.
In step (3) and step (4), the equipment of described roasting is this area routine, is preferably Muffle furnace.
In step (4), described dipping preferably at room temperature carries out.
Wherein, described room temperature is this area routine, is preferably 25-40 DEG C.
In step (4), the time of described dipping is preferably 20-36h.The described dry time is preferably 7-12h.The temperature of described roasting is preferably 500～550 DEG C.
In step (4), when described dipping, preferably also regulating the pH value of maceration extract with ammoniacal liquor is 7～8.
In step (4), the salting liquid of described metallic element M preferably comprises one or more in zinc nitrate, silver nitrate, ammonium molybdate, copper nitrate, nickel nitrate, manganese nitrate, chromic nitrate, chloroplatinic acid, gold chloride, ferric nitrate, phosphotungstic acid and lanthanum nitrate.The load concentration of the salting liquid of described metallic element M is preferably 0.5～10%, and described percentage is the mass percent that the salting liquid of described metallic element M accounts for Modified HZSM-5 Zeolite Catalyst.
In step (4), in the Modified HZSM-5 Zeolite Catalyst making, HZSM-5 molecular sieve accounts for 45～65%, and binding agent accounts for 25～45%, metallic element M accounts for 0.5～10%, and described percentage is the mass percent that accounts for Modified HZSM-5 Zeolite Catalyst.
The present invention also provides a kind of method by low-carbon oxygen-containing compound high-carbon hydrocarbon processed; The described method by low-carbon oxygen-containing compound high-carbon hydrocarbon processed comprises the steps:
(1) the deoxidation polymerisation of low-carbon oxygen-containing compound: the raw material of described deoxidation polymerisation comprises described low-carbon oxygen-containing compound and reproducibility carrier gas, described low-carbon oxygen-containing compound adopts reproducibility carrier gas forced feed, carries out deoxidation polymerisation, obtains C
1～C
12hydrocarbon mixture; The catalyst of described deoxidation polymerisation is aforesaid Modified HZSM-5 Zeolite Catalyst; Described reproducibility carrier gas comprises reducibility gas and inert gas, and described reducibility gas is H
2and/or CO;
(2) separation of hydrocarbon product: by described C
1～C
12hydrocarbon mixture cooling, then separate and obtain through the pressure of 0.3～0.6MPa: the gaseous products of light hydrocarbon components and reproducibility carrier gas composition, C
3above liquid hydrocarbon product, and the waste liquid of reaction generation;
Again described gaseous products is separated and is circulated:
When described reducibility gas is H
2or when CO, described gaseous products is passed into pressure-swing absorption apparatus (PSA) and isolate H
2or CO, by isolated H
2or CO and remaining ingredient are circulated to charging place as recycle stock;
When described reducibility gas is H
2during with CO, described gaseous products is passed into membrane separation device and isolate light hydrocarbon components, remaining ingredient is carried out to the synthetic reaction of low-carbon oxygen-containing compound, the product of described light hydrocarbon components and described synthetic reaction is circulated to charging place as recycle stock;
The volume ratio of the raw material of described recycle stock and described deoxidation polymerisation is (1～8): 1;
Finally, to described C
3above liquid hydrocarbon product is carried out low pressure separation and rectifying, obtains high-carbon hydrocarbon.
In step (1), described low-carbon oxygen-containing compound has this area conventional sense, and usually, it comprises C
1～C
3monohydric alcohol, polyalcohol, ether, carboxylic acid, aldehydes, ketone, ester class and carbohydrate in one or more, preferably comprise one or more in methyl alcohol, ethanol, ethylene glycol, dimethyl ether, acetaldehyde, glycerine, ether and acetic acid, more preferably comprise one or more in ethanol, ethylene glycol, acetaldehyde, glycerine, ether and acetic acid.
In a preferred embodiment of the present invention, described low-carbon oxygen-containing compound is that water content is not higher than the thick methyl alcohol of 30wt%.
In a preferred embodiment of the present invention, described low-carbon oxygen-containing compound is that water content is not higher than the dimethyl ether of 30wt%.
In a preferred embodiment of the present invention, described low-carbon oxygen-containing compound is the organic liquid waste of discharge during living beings ethanol is produced.
In step (1), when described reducibility gas is H
2during with the mixture of CO, described H
2with the volume ratio of CO be preferably 1.2～2.5.Described inert gas preferably comprises N
2, Ar and CO
2in one or more.
In step (1), the equipment of described deoxidation polymerisation is this area routine, is preferably multi-stage fixed-bed adiabatic reactor.
In step (1), the reaction pressure of described deoxidation polymerisation is preferably 1.5～4.0MPa.The reaction temperature of described deoxidation polymerisation is preferably 300～500 DEG C.The charging air speed of described deoxidation polymerisation is preferably 0.6～2.5Kg reactant/Kg catalyst/hr.
In step (2), described cooling is preferably for being cooled to 40～60 DEG C.
In step (2), described synthetic reaction is the reaction of the syngas catalytic conversion methanol of this area routine.
In step (2), described high-carbon hydrocarbon is the C that is rich in aromatic hydrocarbons
5～C
12hydrocarbons.
In the present invention, cooling, the separation and the rectifying that relate to can complete respectively in heat transmission equipment, separation equipment and the rectifying device of this area routine.
Meeting on the basis of this area general knowledge, above-mentioned each optimum condition, can be combined, and obtains the preferred embodiments of the invention.
Agents useful for same of the present invention and raw material be commercially available obtaining all.
Positive progressive effect of the present invention is: when catalyst provided by the present invention is used for low-carbon oxygen-containing compound high-carbon hydrocarbon processed, easy to operate, the conversion per pass of catalyst can reach 99%; In the high-carbon hydrocarbon making, C
5the yield of+hydro carbons is higher than 84%, and the yield of aromatic hydrocarbons is higher than 45%.
Detailed description of the invention
Mode below by embodiment further illustrates the present invention, but does not therefore limit the present invention among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example, according to conventional method and condition, or selects according to catalogue.
In following embodiment, the synthetic method of described HZSM-5 molecular sieve is as follows: raw material is configured to two parts of solution of first, second, and wherein first solution is made up of waterglass, directed agents and water, and second solution is made up of aluminium source, inorganic acid and water; Under 200～300r/min stir speed (S.S.), second solution is slowly joined in first solution, stirring reaction is until form uniform jel product; Continue to stir 15～20min and make jel product ageing, then rise to standing crystallization 20～30h at 180 DEG C with the speed of 5 DEG C/min by room temperature, rapid cold filtration after crystallization completes, with deionized water wash to filtrate pH value be 8～9, filter cake is dried at 120 DEG C.By filter cake and ammonium salt solution with 1 part of filter cake: (0.1～0.5) part ammonium salt: (8～10) part H
2weight ratio contact 20～30min of O carries out ion-exchange, and after being dried, under 450～580 DEG C of conditions, roasting 2～8h makes the HZSM-5 molecular sieve with reactivity.
Wherein, be (8～15) Na for the synthesis of the raw material proportioning of HZSM-5 molecular sieve
2o:Al
2o
3: (40～95) SiO
2: (18～39) directed agents: (2.5～6) inorganic acid: (2500～3900) H
2o.
Wherein, described directed agents is one or more in isopropylamine, ethamine, ethylenediamine, n-butylamine, isopropyl alcohol and inorganic ammonium salt.Described aluminium source is aluminum sulfate and/or aluminum nitrate.Described inorganic acid is acid corresponding to described inorganic acid aluminium salt.
In following embodiment, after described deoxidation polymerisation completes, also carry out the separation of hydrocarbon product: described hydrocarbon mixture is cooled, then separate and obtain through the pressure of 0.3～0.6MPa: the gaseous products of light hydrocarbon components and reproducibility carrier gas composition, C
3above liquid hydrocarbon product, and the waste liquid of reaction generation;
Again described gaseous products is separated and is circulated:
When described reducibility gas is H
2or when CO, described gaseous products is passed into pressure-swing absorption apparatus (PSA) and isolate H
2or CO, by isolated H
2or CO and remaining ingredient are circulated to charging place as recycle stock;
When described reducibility gas is H
2during with CO, described gaseous products is passed into membrane separation device and isolate light hydrocarbon components, remaining ingredient is carried out to the synthetic reaction of low-carbon oxygen-containing compound, the product of described light hydrocarbon components and described synthetic reaction is circulated to charging place as recycle stock;
The volume ratio of the raw material of described recycle stock and described deoxidation polymerisation is (1～8): 1;
Finally, to described C
3above liquid hydrocarbon product is carried out low pressure separation and rectifying, obtains high-carbon hydrocarbon.
Wherein, described pressure-swing absorption apparatus (PSA) is purchased from Beijing Peking University Pioneer Technology Co., Ltd., or Sichuan Tianyi Science & Technology Co., Ltd.Described membrane separation device is purchased from GE company, or MIT.
Embodiment 1
The preparation of catalyst:
Get SiO
2/ Al
2o
3=60 HZSM-5 molecular sieve 50g, at 520 DEG C, roasting 6h, with imurity-removal, makes pure catalyst carrier.Accurately take said catalyst carrier 20g and put into beaker A, in beaker B, add 20mL deionized water simultaneously.In beaker B, add a certain amount of zinc nitrate and copper nitrate respectively, magnetic agitation dissolves it in 10 minutes completely.Subsequently, the mixed solution of beaker B is poured in beaker A, and stirred into pasty state structure with glass bar.Under room temperature, place 12h.
Catalyst after dipping is completed is placed in 100 DEG C of baking ovens and maintains 6h, then dry catalyst is put into 520 DEG C of Muffle furnaces, with 2 DEG C/min temperature programming, roasting 8h.Finally obtain consist of (wt%) of catalyst:
In order to characterize design feature and the acid feature of the catalyst making, the present embodiment passes through NH
3-TPD, N
2the method such as adsorption/desorption, strength test obtains lower column data:
Methanol oxidation transforms hydrocarbon reaction processed:
It is reactor that the present embodiment adopts fixed bed, the thick methyl alcohol of certain flow (water that contains 5%-45%) is squeezed into reaction system with Micro-metering Pumps, reactant after vaporization, the molecular sieve catalyst of flowing through under the nitrogen of certain air speed carries.Methyl alcohol reacts and generates taking aromatic hydrocarbons as main hydrocarbon product in reactor, and through cooling liquid product and the gas-phase product collected of cold-trap, liquid product obtains oil-phase product and water through layering.Wherein reaction condition is as follows:
Reaction pressure: 0.1MPa
Reaction temperature: 450 DEG C
Raw material air speed: 3h
-1
Carrier gas flow rate: 30mL/min
Condenser temperature: 0 DEG C
Under this reaction condition, the conversion per pass of catalyst can reach 99%, and oil phase yield exceedes 80%, and wherein aromatics yield exceedes 65%.
Modified HZSM-5 Zeolite Catalyst prepared by the present invention is after metal-modified, aspect the acidity of catalyst and pore passage structure, be all improved, the exothermic heat of reaction that can effectively avoid conventional ZSM catalyst series to bring is violent, catalyst is easily because of carbon deposit inactivation, and the hydrone that in course of reaction, oxycompound removes at high temperature can cause to aluminum-oxygen tetrahedron skeleton structure the defect of permanent damage.
Embodiment 2
The preparation method of catalyst is completely with embodiment 1.
Alcohol catalysis transforms hydrocarbon reaction processed:
It is reactor that the present embodiment adopts fixed bed, the straight alcohol of certain flow is squeezed into reaction system with Micro-metering Pumps, reactant after vaporization, the molecular sieve catalyst of flowing through under the nitrogen of certain air speed carries.Ethanol reacts and generates taking aromatic hydrocarbons as main hydrocarbon product in reactor, and through cooling liquid product and the gas-phase product collected of cold-trap, liquid product obtains oil-phase product and water through layering.Wherein reaction condition is as follows:
Reaction pressure: 0.1MPa
Reaction temperature: 430 DEG C
Raw material air speed: 3h
-1
Carrier gas flow rate: 30mL/min
Condenser temperature: 0 DEG C
Under this reaction condition, oil phase yield exceedes 78%, and wherein aromatics yield exceedes 62%.
Embodiment 3
The preparation of catalyst:
Get SiO
2/ Al
2o
3=70 HZSM-5 molecular sieve 50g, at 520 DEG C, roasting 6h, with imurity-removal, makes pure catalyst carrier.Accurately take said catalyst carrier 20g and put into beaker A, in beaker B, add 20mL deionized water simultaneously.In beaker B, add a certain amount of zinc nitrate and lanthanum nitrate respectively, magnetic agitation dissolves it in 10 minutes completely.Subsequently, the mixed solution of beaker B is poured in beaker A, and stirred into pasty state structure with glass bar.Under room temperature, place 12h.
Catalyst after dipping is completed is placed in 100 DEG C of baking ovens and maintains 6h, then dry catalyst is put into 520 DEG C of Muffle furnaces, with 2 DEG C/min temperature programming, roasting 8h.Finally obtain consist of (wt%) of catalyst:
In order to characterize design feature and the acid feature of the catalyst making, the present embodiment passes through NH
3-TPD, N
2the method such as adsorption/desorption, strength test obtains lower column data:
Dimethyl ether catalysis transforms hydrocarbon reaction processed:
It is reactor that the present embodiment adopts fixed bed, and dimethyl ether air accumulator is connected to charging aperture, regulates pressure-reducing valve pressure, controls the flow of dimethyl ether.The carrier gas flux of certain flow is provided simultaneously.Dimethyl ether reacts and generates taking aromatic hydrocarbons as main hydrocarbon product in reactor, and through cooling liquid product and the gas-phase product collected of cold-trap, liquid product obtains oil-phase product and water through layering.Wherein reaction condition is as follows:
Reaction pressure: 0.15MPa
Reaction temperature: 425 DEG C
Raw material air speed: 2h
-1
Carrier gas flow rate: 20mL/min
Condenser temperature: 0 DEG C
Under this reaction condition, oil phase yield exceedes 77%, and wherein aromatics yield exceedes 64%.
Embodiment 4
The preparation method of catalyst is completely with embodiment 3.
Ether catalytic cracking hydrocarbon reaction:
It is reactor that the present embodiment adopts fixed bed, the absolute ether of certain flow is squeezed into reaction system with Micro-metering Pumps, reactant after vaporization, the molecular sieve catalyst of flowing through under the nitrogen of certain air speed carries.Ether reacts and generates taking aromatic hydrocarbons as main hydrocarbon product in reactor, and through cooling liquid product and the gas-phase product collected of cold-trap, liquid product obtains oil-phase product and water through layering.Wherein reaction condition is as follows:
Reaction pressure: 0.10MPa
Reaction temperature: 425 DEG C
Raw material air speed: 3h
-1
Carrier gas flow rate: 30mL/min
Condenser temperature: 0 DEG C
Under this reaction condition, oil phase yield exceedes 81%, and wherein aromatics yield exceedes 67%.
Embodiment 5
The preparation of catalyst:
Get SiO
2/ Al
2o
3=38 HZSM-5 molecular sieve 50g, at 520 DEG C, roasting 6h, with imurity-removal, makes pure catalyst carrier.Accurately take said catalyst carrier 20g and put into beaker A, in beaker B, add 20mL deionized water simultaneously.In beaker B, add a certain amount of zinc nitrate and nickel nitrate respectively, magnetic agitation dissolves it in 10 minutes completely.Subsequently, the mixed solution of beaker B is poured in beaker A, and stirred into pasty state structure with glass bar.Under room temperature, place 12h.
Catalyst after dipping is completed is placed in 100 DEG C of baking ovens and maintains 6h, then dry catalyst is put into 520 DEG C of Muffle furnaces, with 2 DEG C/min temperature programming, roasting 8h.Finally obtain consist of (wt%) of catalyst:
In order to characterize design feature and the acid feature of the catalyst making, the present embodiment passes through NH
3-TPD, N
2the method such as adsorption/desorption, strength test obtains lower column data:
Hardness: 70-101N
BET specific area: 325-415m
2/ g
Micro pore volume: 0.11-0.19cm
3/ g
Acid strength: 0.45-0.79mmoL/g
Ethylene glycol catalytic cracking hydrocarbon reaction:
It is reactor that the present embodiment adopts fixed bed, the pure ethylene glycol of certain flow is squeezed into reaction system with Micro-metering Pumps, reactant after vaporization, the molecular sieve catalyst of flowing through under the nitrogen of certain air speed carries.Ethylene glycol reacts and generates taking aromatic hydrocarbons as main hydrocarbon product in reactor, and through cooling liquid product and the gas-phase product collected of cold-trap, liquid product obtains oil-phase product and water through layering.Wherein reaction condition is as follows:
Reaction pressure: 0.10MPa
Reaction temperature: 500 DEG C
Raw material air speed: 5h
-1
Carrier gas flow rate: 20mL/min
Condenser temperature: 0 DEG C
Under this reaction condition, oil phase yield exceedes 60%, and wherein aromatics yield exceedes 55%.
Embodiment 6
The preparation of catalyst:
Get SiO
2/ Al
2o
3=80 HZSM-5 molecular sieve 50g, at 520 DEG C, roasting 6h, with imurity-removal, makes pure catalyst carrier.Accurately take said catalyst carrier 20g and put into beaker A, in beaker B, add 20mL deionized water simultaneously.In beaker B, add a certain amount of zinc nitrate and chromic nitrate respectively, magnetic agitation dissolves it in 10 minutes completely.Subsequently, the mixed solution of beaker B is poured in beaker A, and stirred into pasty state structure with glass bar.Under room temperature, place 12h.
Catalyst after dipping is completed is placed in 100 DEG C of baking ovens and maintains 6h, then dry catalyst is put into 520 DEG C of Muffle furnaces, with 2 DEG C/min temperature programming, roasting 8h.Finally obtain consist of (wt%) of catalyst:
In order to characterize design feature and the acid feature of the catalyst making, the present embodiment passes through NH
3-TPD, N
2the method such as adsorption/desorption, strength test obtains lower column data:
Hardness: 62-87N
BET specific area: 411-485m
2/ g
Micro pore volume: 0.12-0.18cm
3/ g
Acid strength: 0.35-0.60mmoL/g
Acetic acid catalysis transforms hydrocarbon reaction processed:
It is reactor that the present embodiment adopts fixed bed, the pure acetic acid of certain flow is squeezed into reaction system with Micro-metering Pumps, reactant after vaporization, the molecular sieve catalyst of flowing through under the nitrogen of certain air speed carries.Acetic acid reacts and generates taking aromatic hydrocarbons as main hydrocarbon product in reactor, and through cooling liquid product and the gas-phase product collected of cold-trap, liquid product obtains oil-phase product and water through layering.Wherein reaction condition is as follows:
Reaction pressure: 0.10MPa
Reaction temperature: 520 DEG C
Raw material air speed: 1h
-1
Carrier gas flow rate: 20mL/min
Condenser temperature: 0 DEG C
Under this reaction condition, oil phase yield exceedes 61%, and wherein aromatics yield exceedes 52%.
Comparative example 1
This comparative example adopts existing MTG technique to make methyl alcohol be converted into hydrocarbon mixture under acidic catalyst effect.Methyl alcohol is dehydration generation dimethyl ether (DME) under Bronsted acid catalytic action first, and DME further transforms and generates C
2-C
5alkene, C
2-C
5alkene is further realized and is selected type conversion reaction under the effect of ZSM-5 catalyst total acidic, comprising alkene generates, alkylation (hydrocarbonylation, refer to that an alkene is combined into reacting of a high collateralization alkane with an alkane), oligomerisation (the polymer of a kind of molecular weight lower (1500 below) of the degree of polymerization between monomer and final polymer, also referred to as oligomer), aromatisation (mainly cycloalkane processed or alkane change the process of aromatic hydrocarbon into), cracking (referring to that at high temperature strand chain rupture of hydro carbons becomes the process of the unsaturated hydrocarbons of little molecular weight) and disproportionation (also claim selfoxidation-reduction reaction, refer to by one or more hydrogen atoms from a molecular transfer to another molecule, make a molecular oxidation, the reduction of molecule) etc. multistep reaction, finally obtain alkane, the mixture of alkene and aromatic hydrocarbons, it is typical gasoline component.Methanol conversion be gasoline from stoichiometry, the yield of component is hydrocarbon 44% and water 56%.In 44% hydrocarbon product, some can not enter in the component of gasoline, and this part product type is similar to liquefied petroleum gas (LPG).
Claims (10)
1. a Modified HZSM-5 Zeolite Catalyst, is characterized in that, mole the consisting of of described Modified HZSM-5 Zeolite Catalyst: (0～0.2) Na
2o:(0.5～1.2) M
xo
y: Al
2o
3: (10～40) SiO
2: (0～40) H
2o, wherein M
xo
yfor the oxide of metallic element M, x is the number of metallic element M, and y is the required oxygen atom number of oxidation state that meets metallic element M, and described metallic element M is one or more in Zn, Ag, Mo, Cu, Ni, Mn, Cr, Pt, Fe, W, Au, V and La.
2. Modified HZSM-5 Zeolite Catalyst as claimed in claim 1, is characterized in that, described metallic element M is one or more in Mo, Cu, Ni, Mn, Cr, Pt, Fe, W, Au and V.
3. the preparation method of a Modified HZSM-5 Zeolite Catalyst as claimed in claim 1 or 2; Described preparation method comprises the steps:
(1) will mix with binding agent through pretreated HZSM-5 molecular sieve, grind, obtain abrasive;
(2) in described abrasive, drip the salpeter solution that mass concentration is 2%-8%, extrusion modling, at 90-150 DEG C, dry 1-2 hour, obtains molecular sieve;
(3) by described molecular sieve roasting 2-8h at 450-580 DEG C, cooling, be broken into 20-40 order, obtain catalyst carrier;
(4) get the described catalyst carrier of the quality such as two parts, in a catalyst carrier, add deionized water, mix with the salting liquid of described metallic element M, mix with another part of catalyst carrier again, dipping 12-36h, dry 4-12h at 90-150 DEG C, then at 450-580 DEG C roasting 2-8h.
4. preparation method as claimed in claim 3, is characterized in that, in step (1), and in described HZSM-5 molecular sieve, SiO
2with Al
2o
3mol ratio be 30～120;
And/or in step (1), described binding agent is one or more in kaolin, imvite, diatomite, alchlor, silica and silicon-aluminum sol;
And/or in step (1), described pretreatment is: in the Muffle furnace of 450-580 DEG C, HZSM-5 molecular sieve roasting 2-8h is removed to volatile impurity.
5. preparation method as claimed in claim 3, it is characterized in that, in step (1), the synthetic method of described HZSM-5 molecular sieve is: raw material is configured to two parts of solution of first, second, wherein first solution comprises waterglass, directed agents and water, and second solution comprises aluminium source, inorganic acid and water; Under the stir speed (S.S.) of 200～300r/min, second solution is joined in first solution, stir until form uniform jel product; Continue to stir 15～20min and make jel product ageing, then rise at 180 DEG C and leave standstill crystallization 20～30h by room temperature with the speed of 5 DEG C/min, cold filtration afterwards, with deionized water wash to filtrate pH value be 8～9, obtain filter cake, oven dry at 120 DEG C; By filter cake and ammonium salt solution with 1 part of filter cake: (0.1～0.5) part ammonium salt: (8～10) part H
2weight ratio contact 20～30min of O carries out ion-exchange, dry after under 450～580 DEG C of conditions roasting 2～8h, make the HZSM-5 molecular sieve with reactivity;
Wherein, described raw material is preferably: according to mass ratio meter, and (8～15) Na
2o:Al
2o
3: (40～95) SiO
2: (18～39) directed agents: (2.5～6) inorganic acid: (2500～3900) H
2o;
Wherein, described directed agents is preferably one or more in isopropylamine, ethamine, ethylenediamine, n-butylamine, isopropyl alcohol and inorganic ammonium salt; Described aluminium source is inorganic acid aluminium salt, is preferably aluminum sulfate and/or aluminum nitrate; Described inorganic acid is preferably acid corresponding to described inorganic acid aluminium salt.
6. preparation method as claimed in claim 3, is characterized in that, in step (2), the consumption of described salpeter solution is the 20%-35% that accounts for the quality of described abrasive;
And/or in step (2) and step (4), described dry equipment is baking oven;
And/or in step (3), described being cooled to is cooled to room temperature;
And/or in step (3) and step (4), the equipment of described roasting is Muffle furnace;
And/or in step (4), described dipping at room temperature carries out;
Wherein, described room temperature is preferably 25-40 DEG C;
And/or in step (4), the time of described dipping is 20-36h; The described dry time is 7-12h; The temperature of described roasting is 500～550 DEG C;
And/or in step (4), when described dipping, also regulating the pH value of maceration extract with ammoniacal liquor is 7～8;
And/or, in step (4), the salting liquid of described metallic element M comprises one or more in zinc nitrate, silver nitrate, ammonium molybdate, copper nitrate, nickel nitrate, manganese nitrate, chromic nitrate, chloroplatinic acid, gold chloride, ferric nitrate, phosphotungstic acid and lanthanum nitrate; The load concentration of the salting liquid of described metallic element M is preferably 0.5～10%, and described percentage is the mass percent that the salting liquid of described metallic element M accounts for Modified HZSM-5 Zeolite Catalyst;
And/or, in step (4), in the Modified HZSM-5 Zeolite Catalyst making, HZSM-5 molecular sieve accounts for 45～65%, binding agent accounts for 25～45%, and metallic element M accounts for 0.5～10%, and described percentage is the mass percent that accounts for Modified HZSM-5 Zeolite Catalyst.
7. by a method for low-carbon oxygen-containing compound high-carbon hydrocarbon processed, it is characterized in that, the described method by low-carbon oxygen-containing compound high-carbon hydrocarbon processed comprises the steps:
(1) the deoxidation polymerisation of low-carbon oxygen-containing compound: the raw material of described deoxidation polymerisation comprises described low-carbon oxygen-containing compound and reproducibility carrier gas, described low-carbon oxygen-containing compound adopts reproducibility carrier gas forced feed, carries out deoxidation polymerisation, obtains C
1～C
12hydrocarbon mixture; The catalyst of described deoxidation polymerisation is Modified HZSM-5 Zeolite Catalyst as claimed in claim 1 or 2; Described reproducibility carrier gas comprises reducibility gas and inert gas, and described reducibility gas is H
2and/or CO;
(2) separation of hydrocarbon product: by described C
1～C
12hydrocarbon mixture cooling, then separate and obtain through the pressure of 0.3～0.6MPa: the gaseous products of light hydrocarbon components and reproducibility carrier gas composition, C
3above liquid hydrocarbon product, and the waste liquid of reaction generation;
Again described gaseous products is separated and is circulated:
When described reducibility gas is H
2or when CO, described gaseous products is passed into pressure-swing absorption apparatus and isolate H
2or CO, by isolated H
2or CO and remaining ingredient are circulated to charging place as recycle stock;
When described reducibility gas is H
2during with CO, described gaseous products is passed into membrane separation device and isolate light hydrocarbon components, remaining ingredient is carried out to the synthetic reaction of low-carbon oxygen-containing compound, the product of described light hydrocarbon components and described synthetic reaction is circulated to charging place as recycle stock;
The volume ratio of the raw material of described recycle stock and described deoxidation polymerisation is (1～8): 1;
Finally, to described C
3above liquid hydrocarbon product is carried out low pressure separation and rectifying, obtains high-carbon hydrocarbon.
8. the method by low-carbon oxygen-containing compound high-carbon hydrocarbon processed as claimed in claim 7, is characterized in that, in step (1), described low-carbon oxygen-containing compound comprises C
1～C
3monohydric alcohol, polyalcohol, ether, carboxylic acid, aldehydes, ketone, ester class and carbohydrate in one or more, preferably comprise one or more in methyl alcohol, ethanol, ethylene glycol, dimethyl ether, acetaldehyde, glycerine, ether and acetic acid.
9. the method by low-carbon oxygen-containing compound high-carbon hydrocarbon processed as claimed in claim 7, is characterized in that, in step (1), when described reducibility gas is H
2during with the mixture of CO, described H
2with the volume ratio of CO be 1.2～2.5; And/or described inert gas comprises N
2, Ar and CO
2in one or more;
And/or in step (1), the equipment of described deoxidation polymerisation is multi-stage fixed-bed adiabatic reactor;
And/or in step (1), the reaction pressure of described deoxidation polymerisation is 1.5～4.0MPa; And/or the reaction temperature of described deoxidation polymerisation is 300～500 DEG C; And/or the charging air speed of described deoxidation polymerisation is 0.6～2.5Kg reactant/Kg catalyst/hr.
10. the method by low-carbon oxygen-containing compound high-carbon hydrocarbon processed as claimed in claim 7, is characterized in that, in step (2), described cooling is for being cooled to 40～60 DEG C;
And/or in step (2), described high-carbon hydrocarbon is the C that is rich in aromatic hydrocarbons
5～C
12hydrocarbons.
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Cited By (3)
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|---|---|---|---|---|
| CN106582795A (en) * | 2015-10-14 | 2017-04-26 | 中国石油化工股份有限公司 | Catalyst for alkylation reaction of ethane and benzene |
| CN106582796A (en) * | 2015-10-14 | 2017-04-26 | 中国石油化工股份有限公司 | Catalyst used for alkylation reaction of ethane and benzene |
| CN108043450A (en) * | 2017-11-09 | 2018-05-18 | 沈阳航空航天大学 | The preparation method and application of nickel, chromium Modified HZSM-5 Zeolite Catalyst |
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| CN101550352A (en) * | 2008-04-03 | 2009-10-07 | 中国石油化工股份有限公司 | Aromatizatian catalytic material and preparation method thereof |
| CN103521257A (en) * | 2013-10-25 | 2014-01-22 | 连云港阳方催化科技有限公司 | ZSM-5 molecular sieve modified catalyst as well as preparation method and application thereof |
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| US6051520A (en) * | 1998-05-19 | 2000-04-18 | Phillips Petroleum Company | Hydrotreating catalyst composition and processes therefor and therewith |
| CN101550352A (en) * | 2008-04-03 | 2009-10-07 | 中国石油化工股份有限公司 | Aromatizatian catalytic material and preparation method thereof |
| CN103521257A (en) * | 2013-10-25 | 2014-01-22 | 连云港阳方催化科技有限公司 | ZSM-5 molecular sieve modified catalyst as well as preparation method and application thereof |
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| CN106582795A (en) * | 2015-10-14 | 2017-04-26 | 中国石油化工股份有限公司 | Catalyst for alkylation reaction of ethane and benzene |
| CN106582796A (en) * | 2015-10-14 | 2017-04-26 | 中国石油化工股份有限公司 | Catalyst used for alkylation reaction of ethane and benzene |
| CN106582795B (en) * | 2015-10-14 | 2019-04-12 | 中国石油化工股份有限公司 | Catalyst for ethane and benzene alkylation reaction |
| CN106582796B (en) * | 2015-10-14 | 2019-07-09 | 中国石油化工股份有限公司 | The catalyst of ethane and benzene alkylation reaction |
| CN108043450A (en) * | 2017-11-09 | 2018-05-18 | 沈阳航空航天大学 | The preparation method and application of nickel, chromium Modified HZSM-5 Zeolite Catalyst |
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