CN104258855A - Preparation method and use of difunctional low-carbon alkane dehydrogenation catalyst - Google Patents
Preparation method and use of difunctional low-carbon alkane dehydrogenation catalyst Download PDFInfo
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Abstract
The invention discloses a preparation method and use of a difunctional low-carbon alkane dehydrogenation catalyst. The difunctional low-carbon alkane dehydrogenation catalyst is prepared by a dipping method, utilizes gamma-Al2O3 as a carrier, Pt as an active component, and Sn, Na, La and Zn as auxiliary agents, and optionally contains Cl as a modifier. Under the low-carbon alkane dehydrogenation conditions, hydrogen-vapor-low carbon alkane mixed gas and an oxygen-containing compound are simultaneously injected into a reactor, and the catalyst in the reactor has dual functions of low-carbon alkane dehydrogenation and hydrogen selective combustion. Through selective combustion of hydrogen, dehydrogenation reaction equilibrium is shifted toward right and simultaneously, the released combustion heat can be supplied for a dehydrogenation reaction. Through use of the difunctional low-carbon alkane dehydrogenation catalyst, a dehydrogenation reaction conversion rate and selectivity are high and stability is good.
Description
Technical field
The present invention relates to a kind of method for making and purposes of difunctional catalyst for dehydrogenation of low-carbon paraffin, be applicable to gas-solid catalysis, belong to Industrial Catalysis technical field.
Background technology
Dehydrogenating low-carbon alkane reaction is process amount low-carbon alkanes inexpensive greatly being changed into the corresponding alkene of market high added value in short supply, has important Research Significance and economic worth.
Dehydrogenating low-carbon alkane divides oxidative dehydrogenation and faces hydrogen dehydrogenation two kinds of forms.Oxidative dehydrogenation enthalpy change is less than zero, is exothermic reaction, without the need to external world's heating, and economize energy, and reaction is not by the restriction of thermodynamical equilibrium.But, because alkene is easier than alkane oxidized, cause the olefine selective of oxidative dehydrogenation very low.In addition, be easy to the complete oxidation that alkane occurs in course of reaction, cause temperature sharply to rise, thus alkane and alkene be more easily oxidized to CO and CO
2; Facing hydrogen dehydrogenation and can obtain higher olefine selective, is also the Hot Contents of current petrochemical industry low-carbon alkanes efficiency utilization research.By now, existing numerous face the preparation of hydrogen dehydrogenation and technology is open in this area, as USP 4513162, USP 5321192, USP 7405338, ZL 96115049.1, CN 101380587A, CN 1395506A, CN 103420768A etc.Face the reversible reaction that hydrogen dehydrogenation is heat absorption, molecular number increases, need the reaction condition of high temperature, low pressure.Therefore, certain embodiments energy consumption is higher.
If by oxidative dehydrogenation and the advantages of facing hydrogen dehydrogenation, and bifunctional catalyst can be designed.Introduce a small amount of oxygen facing in hydrogen dehydrogenation reactor system, while dehydrating alkanes, realize the selective combustion of hydrogen, moving to right of dehydrogenation reaction balance can be realized.In addition, heat can also be provided for dehydrogenation reaction self, for dehydrogenation of isobutane, 1mol dehydrogenation of isobutane needs the heat of 122kJ, and the oxygen of 0.5mol and hydrogen reaction can produce the heat of 242kJ, namely the oxygen of 1mol and the heat of hydrogen reaction generation can be the dehydrogenation of isobutane heat supply of 4mol, this reduces the energy consumption of dehydrogenating technology.
USP4418237 discloses a kind of method of ethylbenzene dehydrogenation, and the method passes into oxidation catalyst bed by after the product after ethylbenzene dehydrogenation and oxygen mix, and hydrogen partial is fallen in selective combustion.USP 4717781 discloses a kind of method of ethylbenzene dehydrogenation, is also applicable to propane and dehydrogenation of isobutane simultaneously.The method establishes oxidation reaction zone between two dehydrogenation reaction zones, and hydrogen partial is fallen in selective combustion.Above-mentioned two disclosed methods achieve oxidative dehydrogenation and face the combination of hydrogen dehydrogenation, but the dehydrogenation used is different with oxidation catalyst.
CN 1170397A discloses and makes dehydrogenatable hydrocarbons, especially C by hydrogen oxide selectively
3and C
4the catalyzed dehydrogenation of hydrocarbon becomes the reactor of unsaturated hydrocarbons.Catalyst Pt SnCs/ θ-Al used
2o
3play a part dehydrogenation and hydroxide with PtSn/Mg (Al) O simultaneously.
CN 1466558A discloses a kind of method of dehydrogenating of hydro carbons.The method is carried out at least one reaction zone, simultaneously with by hydrogen, one or more can the C of dehydrogenation
2~ C
30the liter heat that hydro carbons and/or the exothermic reaction of carbon under oxygen-containing gas exists cause.The burning of dehydrogenation used general yet catalysis hydro carbons and hydrogen and oxygen, does not need specific oxidation catalyst in principle.
Summary of the invention
technical problem:the object of the present invention is to provide a kind of method for making and purposes of difunctional catalyst for dehydrogenation of low-carbon paraffin.This bifunctional catalyst has selective combustion hydrogen functional and dehydrogenating low-carbon alkane function, under dehydrogenating low-carbon alkane process conditions, can obtain higher alkane conversion and olefine selective, have higher using value and economic benefit.
technical scheme:the method for making of difunctional catalyst for dehydrogenation of low-carbon paraffin of the present invention and purposes, difunctional catalyst for dehydrogenation of low-carbon paraffin is with γ-Al
2o
3bead is carrier, is active component, with Sn, Na, La and Zn for auxiliary agent at supported on carriers Pt; Cl is also contained as modifier in catalyst; Described low-carbon alkanes is C
2~ C
5alkane; Under dehydrogenating low-carbon alkane process conditions, pass in reactor by the gaseous mixture of hydrogen, steam and low-carbon alkanes, in reactor, inject oxygenatedchemicals, catalyst shows dehydrogenating low-carbon alkane function and selective combustion hydrogen functional simultaneously simultaneously.
The method for making of above-mentioned difunctional catalyst for dehydrogenation of low-carbon paraffin, is characterized in that comprising the following steps:
Step a, the γ-Al prepared with known ball forming method
2o
3bead is carrier, under 60 ~ 120 ° of C, and dipping zinc nitrate aqueous solution 2 ~ 6h, then at 60 ~ 150 ° of C, dry 2 ~ 10h;
Step b, the catalyst carrier being loaded with Metal Zn ion that obtains with step a under 60 ~ 120 ° of C, dipping lanthanum nitrate aqueous solution 2 ~ 6h, then at 60 ~ 150 ° of C, dry 2 ~ 10h; 400 ~ 600 ° of C, preferably 450 ~ 550 ° of C, roasting 1 ~ 10h, preferably 5 ~ 8h;
Step c, the γ-Al being loaded with Metal Zn ion, La ion obtained with step b
2o
3bead carrier, again under 60 ~ 120 ° of C, floods sodium-chloride water solution 2 ~ 6h, then at 60 ~ 150 ° of C, and dry 2 ~ 10h; 400 ~ 600 ° of C, preferably 450 ~ 550 ° of C, roasting 1 ~ 10h, preferably 5 ~ 8h;
Steps d, the γ-Al being loaded with Metal Zn ion, La ion and Na ion obtained with step c
2o
3bead carrier, again under 60 ~ 120 ° of C, floods the aqueous hydrochloric acid solution 2 ~ 6h of chloroplatinic acid aqueous solution and the butter of tin aqueous solution and 1.5 ~ 25wt%, then at 60 ~ 150 ° of C, and dry 2 ~ 10h; Again at 400 ~ 600 ° of C, preferably 450 ~ 550 ° of C, roasting 1 ~ 10h, preferably 5 ~ 8h, obtain catalyst precarsor, and then in hydrogen atmosphere, 400 ~ 600 ° of C, preferably 500 ~ 550 ° of C, reduction 1 ~ 10h, preferably 5 ~ 10h, namely obtain difunctional catalyst for dehydrogenation of low-carbon paraffin.
The method for making of above-mentioned difunctional catalyst for dehydrogenation of low-carbon paraffin and purposes, under dehydrogenating low-carbon alkane process conditions, pass in reactor by the gaseous mixture of hydrogen, steam and low-carbon alkanes, injects oxygenatedchemicals in reactor simultaneously; Oxygenatedchemicals can be gas, is oxygen or air; Can also be liquid, be aqueous hydrogen peroxide solution.
The method for making of above-mentioned difunctional catalyst for dehydrogenation of low-carbon paraffin and purposes, the oxygen in injecting reactor and the mol ratio of hydrogen are 0 ~ 0.05, preferably 0 ~ 0.025, the injection rate of oxygenatedchemicals calculates in this ratio.
The method for making of above-mentioned difunctional catalyst for dehydrogenation of low-carbon paraffin, catalyst can also be standby by total immersion legal system; By γ-Al
2o
3the liquid that the aqueous hydrochloric acid solution that bead is placed in lanthanum nitrate aqueous solution, zinc nitrate aqueous solution, sodium-chloride water solution, chloroplatinic acid aqueous solution, the butter of tin aqueous solution and 1.5 ~ 25wt% is made into, under 60 ~ 120 ° of C, dipping 2 ~ 6h.Then at 60 ~ 150 ° of C, dry 2 ~ 10h; 400 ~ 600 ° of C, preferred 450-550 ° C, roasting 1 ~ 10h, preferably 5 ~ 10h, obtain catalyst precarsor, and then in hydrogen atmosphere, 400 ~ 600 ° of C, preferably 500 ~ 550 ° of C, reduction 1 ~ 10h, preferably 5 ~ 10h, namely obtain difunctional catalyst for dehydrogenation of low-carbon paraffin.
Above-mentioned difunctional catalyst for dehydrogenation of low-carbon paraffin, is characterized in that: in this catalyst, is just calculated as based on the metal element weight in catalyst gross mass: the mass percentage of Pt element is 0.3 ~ 0.5%; The mass percentage of Sn element is 0.6 ~ 1.0%; The mass percentage of Na element is 0.75 ~ 1.0%; The mass percentage of La element is 0.8 ~ 1.0%; The mass percentage of Zn element is 0.3 ~ 1.0%; The mass percentage of Cl element is 0.1 ~ 0.2%.
The dehydrogenating low-carbon alkane process program of above-mentioned difunctional dehydrogenation is: catalyst filling precursor in the reactor, pass into hydrogen, 400 ~ 600 ° of C reduction 1 ~ 10 hour, preferably 500 ~ 550 ° of C reduction 5 ~ 10h, catalyst precarsor is made to be reduced into catalyst for dehydrogenation of low-carbon paraffin, then hydrogen is passed into, the gaseous mixture of water vapour and low-carbon alkanes, in reactor, inject oxygenatedchemicals simultaneously, at 500 ~ 700 ° of C, carry out dehydrogenating low-carbon alkane reaction, wherein: the mol ratio of hydrogen and low-carbon alkanes is 0.33 ~ 4.0, the mol ratio of water vapour and low-carbon alkanes is 0.1 ~ 5, reaction pressure is 0.05 ~ 0.3Mpa, the mass space velocity of the low-carbon alkanes of charging is 2 ~ 10h
-1, product is after isolating hydrogen, water, pyrolysis product and alkene, and unreacted raw material low-carbon alkanes loops back reactor outlet.
Above-mentioned dehydrogenating low-carbon alkane process program, dehydrogenation reaction is carried out in fixed bed reactors, and this reactor both can adopt isothermal reactor, also can adopt adiabatic reactor; Both can adopt A reactor, also can adopt multistage reactor, preferred multistage radial adiabatic reactor, by the heat needed for heater postreaction between each stage reactor.
beneficial effect:the invention provides a kind of method for making and purposes of difunctional catalyst for dehydrogenation of low-carbon paraffin.This bifunctional catalyst is under dehydrogenating low-carbon alkane process conditions, and alkane conversion and the olefine selective of catalyst are higher.
Feature of the present invention is:
(1) catalyst for dehydrogenation of low-carbon paraffin is bifunctional catalyst, has selective combustion hydrogen functional and dehydrogenating low-carbon alkane function concurrently.In reactor, catalyst is while catalysis dehydrogenating low-carbon alkane, and hydrogen partial is fallen in selective combustion, promotes that dehydrogenating low-carbon alkane molecular balance moves to right, improves low-carbon alkanes conversion ratio and olefine selective.
(2) dehydrogenation reaction technique is note oxygen technique, namely while pass into hydrogen, steam and low-carbon alkanes in reactor, injects a certain amount of oxygenatedchemicals.The combustion heat that the hydrogen catalyzed burning of bifunctional catalyst discharges can be dehydrogenating low-carbon alkane reaction additional heat, promotes the carrying out of dehydrogenation reaction, and reduces the energy consumption of dehydrogenation process systems.
(3) difunctional catalyst for dehydrogenation of low-carbon paraffin adopts infusion process preparation, and Surface acidity is low, and in dehydrogenation reaction process, side reaction is few, and carbon distribution not easily deposits at catalyst surface.Further, the steam injected in dehydrogenating low-carbon alkane course of reaction, can effectively suppress the carbon distribution of catalyst surface to generate.After dehydrogenating low-carbon alkane reaction terminates, the carbon deposition quantity of catalyst is lower.
Detailed description of the invention
Following examples are further illustrating of being given the present invention by the renovation process of catalyst for dehydrogenation of low-carbon paraffin, but not limitation of the present invention.
comparative example 1:
Catalyst preparation process is as follows:
Step a, the γ-Al prepared with known ball forming method
2o
3bead is carrier, and under 80 ° of C, dipping zinc nitrate aqueous solution 3h, then at 80 ° of C, dry 10h;
Step b, the catalyst carrier being loaded with Metal Zn ion that obtains with step a are under 80 ° of C, and dipping lanthanum nitrate aqueous solution 3h, then at 80 ° of C, dry 10h; 450 ° of C, roasting 8h;
Step c, the γ-Al being loaded with Metal Zn ion, La ion obtained with step b
2o
3bead carrier is again under 80 ° of C, and dipping sodium-chloride water solution 3h, then at 80 ° of C, dry 10h; 450 ° of C, roasting 8h;
Steps d, the γ-Al being loaded with Metal Zn ion, La ion and Na ion obtained with step c
2o
3bead carrier is again under 80 ° of C, and the aqueous hydrochloric acid solution 3h of dipping chloroplatinic acid aqueous solution and the butter of tin aqueous solution and 1.5wt%, then at 80 ° of C, dry 10h; 450 ° of C, roasting 8h, obtains catalyst precarsor, and then in hydrogen atmosphere, 500 ° of C, reduction 10h, namely obtains difunctional catalyst for dehydrogenation of low-carbon paraffin.
In catalyst, be just calculated as based on the metal element weight in catalyst gross mass: the mass percentage of Pt element is 0.35%; The mass percentage of Sn element is 0.6%; The mass percentage of Na element is 1.0%; The mass percentage of La element is 1.0%; The mass percentage of Zn element is 0.8%; The mass percentage of Cl element is 0.1%.
Dehydrogenating propane process program is: catalyst filling precursor in isothermal reactor, pass into hydrogen, reduce 10 hours at 500 ° of C, make catalyst precarsor be reduced into catalyst for dehydrogenation of low-carbon paraffin, then pass into the gaseous mixture of hydrogen, water vapour and propane, at 580 ~ 640 ° of C, carry out dehydrogenating propane reaction, wherein: the mol ratio of hydrogen and propane is 0.33, the mol ratio of water vapour and propane is 0.3, reaction pressure is 0.3Mpa, and the mass space velocity of the propane of charging is 8h
-1, product is after isolating hydrogen, water, pyrolysis product and alkene, and unreacted propane cycles returns reactor outlet.
Catalyst evaluates 30d continuously, conversion of propane 29.7%, Propylene Selectivity 95.5%.
comparative example 2:
Catalyst preparation process is as follows:
Step a, the γ-Al prepared with known ball forming method
2o
3bead is carrier, and under 90 ° of C, dipping zinc nitrate aqueous solution 4h, then at 120 ° of C, dry 5h;
Step b, the catalyst carrier being loaded with Metal Zn ion that obtains with step a are under 90 ° of C, and dipping lanthanum nitrate aqueous solution 4h, then at 120 ° of C, dry 5h; 550 ° of C, roasting 5h;
Step c, the γ-Al being loaded with Metal Zn ion, La ion obtained with step b
2o
3bead carrier is again under 90 ° of C, and dipping sodium-chloride water solution 4h, then at 120 ° of C, dry 5h; 550 ° of C, roasting 5h;
Steps d, the γ-Al being loaded with Metal Zn ion, La ion and Na ion obtained with step c
2o
3bead carrier is again under 90 ° of C, and the aqueous hydrochloric acid solution 4h of dipping chloroplatinic acid aqueous solution and the butter of tin aqueous solution and 12.5wt%, then at 120 ° of C, dry 5h; 550 ° of C, roasting 5h, obtains catalyst precarsor, and then in hydrogen atmosphere, 550 ° of C, reduction 5h, namely obtains difunctional catalyst for dehydrogenation of low-carbon paraffin.
In catalyst, be just calculated as based on the metal element weight in catalyst gross mass: the mass percentage of Pt element is 0.5%; The mass percentage of Sn element is 1.0%; The mass percentage of Na element is 0.75%; The mass percentage of La element is 0.8%; The mass percentage of Zn element is 0.3%; The mass percentage of Cl element is 0.2%.
Dehydrogenation of isobutane process program is: adopt adiabatic radial reactor, establishes the heat needed for heater postreaction before reactor.Catalyst filling precursor in reactor, pass into hydrogen, reduce 5 hours at 550 ° of C, make catalyst precarsor be reduced into catalyst for dehydrogenation of low-carbon paraffin, then pass into the gaseous mixture of hydrogen, water vapour and iso-butane, at 570 ~ 620 ° of C, carry out dehydrogenation of isobutane reaction, wherein: the mol ratio of hydrogen and iso-butane is 2.0, the mol ratio of water vapour and iso-butane is 0.1, reaction pressure is 0.1Mpa, and the mass space velocity of the iso-butane of charging is 5h
-1, product is after isolating hydrogen, water, pyrolysis product and alkene, and unreacted iso-butane loops back reactor outlet.
Catalyst evaluates 35d continuously, iso-butane conversion ratio 31.2%, selective isobutene 96.5%.
embodiment 1:
The preparation of catalyst is with comparative example 1.
Dehydrogenating propane process program is: catalyst filling precursor in isothermal reactor, pass into hydrogen, reduce 10 hours at 500 ° of C, catalyst precarsor is made to be reduced into catalyst for dehydrogenation of low-carbon paraffin, then the gaseous mixture of hydrogen, water vapour and propane is passed into, in reactor, inject air simultaneously, at 580 ~ 640 ° of C, carry out dehydrogenating propane reaction, wherein: the mol ratio of hydrogen and propane is 0.33, the mol ratio of water vapour and propane is 0.3, and reaction pressure is 0.3Mpa, and the mass space velocity of the propane of charging is 8h
-1, the oxygen in injecting reactor and the mol ratio of hydrogen are 0.025, and the injection rate of oxygenatedchemicals calculates in this ratio.Product is after isolating hydrogen, water, pyrolysis product and alkene, and unreacted propane cycles returns reactor outlet.
Catalyst evaluates 36d continuously, conversion of propane 33.7%, Propylene Selectivity 97.5%.Process energy consumption is 78.7% of comparative example 1 process energy consumption.
embodiment 2:
The preparation of catalyst is with comparative example 2.
Dehydrogenation of isobutane process program is: adopt adiabatic radial reactor, establishes the heat needed for heater postreaction before reactor.Catalyst filling precursor in reactor, pass into hydrogen, reduce 5 hours at 550 ° of C, make catalyst precarsor be reduced into catalyst for dehydrogenation of low-carbon paraffin, then the gaseous mixture of hydrogen, water vapour and iso-butane is passed into, in reactor, inject air simultaneously, at 570 ~ 620 ° of C, carry out dehydrogenation of isobutane reaction, wherein: the mol ratio of hydrogen and iso-butane is 2.0, the mol ratio of water vapour and iso-butane is 0.1, and reaction pressure is 0.1Mpa, and the mass space velocity of the iso-butane of charging is 5h
-1, the oxygen in injecting reactor and the mol ratio of hydrogen are 0.02, and the injection rate of oxygenatedchemicals calculates in this ratio.Product is after isolating hydrogen, water, pyrolysis product and alkene, and unreacted iso-butane loops back reactor outlet.
Catalyst evaluates 40d continuously, iso-butane conversion ratio 35.6%, selective isobutene 98.1%.Process energy consumption is 84.2% of comparative example 2 process energy consumption.
embodiment 3:
Catalyst preparation process is as follows:
Step a, the γ-Al prepared with known ball forming method
2o
3bead is carrier, and under 70 ° of C, dipping zinc nitrate aqueous solution 6h, then at 100 ° of C, dry 8h;
Step b, the catalyst carrier being loaded with Metal Zn ion that obtains with step a are under 70 ° of C, and dipping lanthanum nitrate aqueous solution 6h, then at 100 ° of C, dry 8h; 500 ° of C, roasting 6h;
Step c, the γ-Al being loaded with Metal Zn ion, La ion obtained with step b
2o
3bead carrier is again under 70 ° of C, and dipping sodium-chloride water solution 6h, then at 100 ° of C, dry 8h; 500 ° of C, roasting 6h;
Steps d, the γ-Al being loaded with Metal Zn ion, La ion and Na ion obtained with step c
2o
3bead carrier is again under 70 ° of C, and the aqueous hydrochloric acid solution 6h of dipping chloroplatinic acid aqueous solution and the butter of tin aqueous solution and 25wt%, then at 100 ° of C, dry 8h; 500 ° of C, roasting 6h, obtains catalyst precarsor, and then in hydrogen atmosphere, 500 ° of C, reduction 8h, namely obtains difunctional catalyst for dehydrogenation of low-carbon paraffin.
In catalyst, be just calculated as based on the metal element weight in catalyst gross mass: the mass percentage of Pt element is 0.4%; The mass percentage of Sn element is 0.9%; The mass percentage of Na element is 0.9%; The mass percentage of La element is 0.8%; The mass percentage of Zn element is 0.6%; The mass percentage of Cl element is 0.1%.
Ethane dehydrogenation process program is: catalyst filling precursor in insulation fix bed reactor, pass into hydrogen, reduce 5 hours at 550 ° of C, catalyst precarsor is made to be reduced into catalyst for dehydrogenation of low-carbon paraffin, then the gaseous mixture of hydrogen, water vapour and ethane is passed into, in reactor, inject oxygen simultaneously, at 580 ~ 650 ° of C, carry out ethane dehydrogenation reaction, wherein: the mol ratio of hydrogen and ethane is 0.5, the mol ratio of water vapour and ethane is 0.5, and reaction pressure is 0.2Mpa, and the mass space velocity of the ethane of charging is 3h
-1, the oxygen in injecting reactor and the mol ratio of hydrogen are 0.005, and product is after isolating hydrogen, water, pyrolysis product and alkene, and unreacted ethane recycle returns reactor outlet.
Catalyst evaluates 25d continuously, ethane conversion 28.7%, ethylene selectivity 92.4%.
embodiment 4:
Catalyst preparation process is as follows:
Step a, the γ-Al prepared with known ball forming method
2o
3bead is carrier, and under 80 ° of C, dipping zinc nitrate aqueous solution 5h, then at 120 ° of C, dry 5h;
Step b, the catalyst carrier being loaded with Metal Zn ion that obtains with step a are under 80 ° of C, and dipping lanthanum nitrate aqueous solution 5h, then at 120 ° of C, dry 5h; 550 ° of C, roasting 5h;
Step c, the γ-Al being loaded with Metal Zn ion, La ion obtained with step b
2o
3bead carrier is again under 80 ° of C, and dipping sodium-chloride water solution 5h, then at 120 ° of C, dry 5h; 550 ° of C, roasting 5h;
Steps d, the γ-Al being loaded with Metal Zn ion, La ion and Na ion obtained with step c
2o
3bead carrier is again under 80 ° of C, and the aqueous hydrochloric acid solution 5h of dipping chloroplatinic acid aqueous solution and the butter of tin aqueous solution and 10wt%, then at 120 ° of C, dry 5h; 550 ° of C, roasting 5h, obtains catalyst precarsor, and then in hydrogen atmosphere, 500 ° of C, reduction 7h, namely obtains difunctional catalyst for dehydrogenation of low-carbon paraffin.
In catalyst, be just calculated as based on the metal element weight in catalyst gross mass: the mass percentage of Pt element is 0.3%; The mass percentage of Sn element is 0.7%; The mass percentage of Na element is 0.75%; The mass percentage of La element is 0.8%; The mass percentage of Zn element is 0.5%; The mass percentage of Cl element is 0.1%.
Dehydrogenation of isobutane process program is: adopt three grades of adiabatic radial reactor tandem process, by the heat needed for heater postreaction between each stage reactor.First catalyst filling precursor in each stage reactor, pass into hydrogen, reduce 7 hours at 500 ° of C, make catalyst precarsor be reduced into catalyst for dehydrogenation of low-carbon paraffin, then the gaseous mixture of hydrogen, water vapour and iso-butane is passed into, in reactor, inject aqueous hydrogen peroxide solution simultaneously, at 570 ~ 640 ° of C, carry out dehydrogenation of isobutane reaction, wherein: the mol ratio of hydrogen and iso-butane is 3.0, the mol ratio of water vapour and iso-butane is 3, and reaction pressure is 0.25Mpa, and the mass space velocity of the iso-butane of charging is 4h
-1, the oxygen in injecting reactor and the mol ratio of hydrogen are 0.015, and the injection rate of oxygenatedchemicals calculates in this ratio.Product is after isolating hydrogen, water, pyrolysis product and alkene, and unreacted iso-butane loops back reactor outlet.
Catalyst evaluates 38d continuously, iso-butane conversion ratio 34.9%, selective isobutene 97.2%.
Claims (8)
1. the method for making of difunctional catalyst for dehydrogenation of low-carbon paraffin and a purposes, is characterized in that: this difunctional catalyst for dehydrogenation of low-carbon paraffin is with γ-Al
2o
3bead is carrier, is active component, with Sn, Na, La and Zn for auxiliary agent at supported on carriers Pt; Cl is also contained as modifier in catalyst; Described low-carbon alkanes is C
2~ C
5alkane; Under dehydrogenating low-carbon alkane process conditions, pass in reactor by the gaseous mixture of hydrogen, steam and low-carbon alkanes, meanwhile, in reactor, inject oxygenatedchemicals, catalyst shows dehydrogenating low-carbon alkane function and selective combustion hydrogen functional simultaneously.
2. the method for making of difunctional catalyst for dehydrogenation of low-carbon paraffin as claimed in claim 1, is characterized in that comprising the following steps:
Step a, the γ-Al prepared with known ball forming method
2o
3bead is carrier, under 60 ~ 120 ° of C, and dipping zinc nitrate aqueous solution 2 ~ 6h, then at 60 ~ 150 ° of C, dry 2 ~ 10h;
Step b, the catalyst carrier being loaded with Metal Zn ion that obtains with step a under 60 ~ 120 ° of C, dipping lanthanum nitrate aqueous solution 2 ~ 6h, then at 60 ~ 150 ° of C, dry 2 ~ 10h; 400 ~ 600 ° of C, roasting 1 ~ 10h;
Step c, the γ-Al being loaded with Metal Zn ion and La ion obtained with step b
2o
3bead carrier, again under 60 ~ 120 ° of C, floods sodium-chloride water solution 2 ~ 6h, then at 60 ~ 150 ° of C, and dry 2 ~ 10h; 400 ~ 600 ° of C, roasting 1 ~ 10h;
Steps d, the γ-Al being loaded with Metal Zn ion, La ion and Na ion obtained with step c
2o
3bead carrier, again under 60 ~ 120 ° of C, floods the aqueous hydrochloric acid solution 2 ~ 6h of chloroplatinic acid aqueous solution and the butter of tin aqueous solution and 1.5 ~ 25wt%, then at 60 ~ 150 ° of C, and dry 2 ~ 10h; 400 ~ 600 ° of C, roasting 1 ~ 10h, obtains catalyst precarsor, and then in hydrogen atmosphere, 400 ~ 600 ° of C, reduction 1 ~ 10h, namely obtains difunctional catalyst for dehydrogenation of low-carbon paraffin.
3. the method for making of difunctional catalyst for dehydrogenation of low-carbon paraffin as claimed in claim 1 and purposes, it is characterized in that: under dehydrogenating low-carbon alkane process conditions, the gaseous mixture of hydrogen, steam and low-carbon alkanes is passed in reactor, in reactor, injects oxygenatedchemicals simultaneously; Oxygenatedchemicals can be gas, is oxygen or air; Also can be liquid, be aqueous hydrogen peroxide solution.
4. the method for making of difunctional catalyst for dehydrogenation of low-carbon paraffin as claimed in claim 1 and purposes, it is characterized in that: the oxygen in injecting reactor and the mol ratio of hydrogen are 0 ~ 0.05, the injection rate of oxygenatedchemicals calculates in this ratio.
5. the method for making of difunctional catalyst for dehydrogenation of low-carbon paraffin as claimed in claim 1, is characterized in that: catalyst can also be standby by total immersion legal system; By γ-Al
2o
3the liquid that the aqueous hydrochloric acid solution that bead is placed in lanthanum nitrate aqueous solution, zinc nitrate aqueous solution, sodium-chloride water solution, chloroplatinic acid aqueous solution, the butter of tin aqueous solution and 1.5 ~ 25wt% is made into, under 60 ~ 120 ° of C, dipping 2 ~ 6h; Then at 60 ~ 150 ° of C, dry 2 ~ 10h; 400 ~ 600 ° of C, roasting 1 ~ 10h, obtains catalyst precarsor, and then in hydrogen atmosphere, 400 ~ 600 ° of C, reduction 1 ~ 10h, namely obtains difunctional catalyst for dehydrogenation of low-carbon paraffin.
6. difunctional catalyst for dehydrogenation of low-carbon paraffin as claimed in claim 1, is characterized in that: in this catalyst, is just calculated as based on the metal element weight in catalyst gross mass: the mass percentage of Pt element is 0.3 ~ 0.5%; The mass percentage of Sn element is 0.6 ~ 1.0%; The mass percentage of Na element is 0.75 ~ 1.0%; The mass percentage of La element is 0.8 ~ 1.0%; The mass percentage of Zn element is 0.3 ~ 1.0%; The mass percentage of Cl element is 0.1 ~ 0.2%.
7. the method for making of difunctional catalyst for dehydrogenation of low-carbon paraffin as claimed in claim 1 and purposes, it is characterized in that: the dehydrogenating low-carbon alkane process program of difunctional dehydrogenation is: fill the catalyst precarsor that claim 2 or 5 obtains in the reactor, pass into hydrogen, at 400 ~ 600 ° of C, reduce 1 ~ 10 hour, catalyst precarsor is made to be reduced into catalyst for dehydrogenation of low-carbon paraffin, then hydrogen is passed into, the gaseous mixture of water vapour and low-carbon alkanes, in reactor, inject oxygenatedchemicals simultaneously, at 500 ~ 700 ° of C, carry out dehydrogenating low-carbon alkane reaction, wherein: the mol ratio of hydrogen and low-carbon alkanes is 0.33 ~ 4.0, the mol ratio of water vapour and low-carbon alkanes is 0.1 ~ 5, reaction pressure is 0.05 ~ 0.3Mpa, the mass space velocity of the low-carbon alkanes of charging is 2 ~ 10h
-1, product is after isolating hydrogen, water, pyrolysis product and alkene, and unreacted raw material low-carbon alkanes loops back reactor outlet.
8. dehydrogenating low-carbon alkane process program as claimed in claim 7, it is characterized in that: dehydrogenation reaction is carried out in fixed bed reactors, this reactor both can adopt isothermal reactor, also can adopt adiabatic reactor; Both can adopt A reactor, also can adopt multistage reactor; By the heat needed for heater postreaction between each stage reactor.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107970924A (en) * | 2017-12-08 | 2018-05-01 | 杭州凯明催化剂股份有限公司 | A kind of preparation method of granular pattern catalyst suitable for VOCs catalysis burnings |
| CN108300430A (en) * | 2018-02-06 | 2018-07-20 | 四川润和催化新材料股份有限公司 | A kind of dehydrating alkanes heat release auxiliary agent and preparation method thereof and application method |
| CN110496630A (en) * | 2018-05-17 | 2019-11-26 | 中国石油化工股份有限公司 | The method of dehydrogenation of isobutane catalyst and preparation method thereof and preparing isobutene through dehydrogenation of iso-butane |
| CN110614113A (en) * | 2018-06-20 | 2019-12-27 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst with rod-shaped mesoporous molecular sieve silica gel composite material as carrier, preparation method and application |
| CN110813285A (en) * | 2018-08-14 | 2020-02-21 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst with spherical surface-surrounded mesoporous material silica gel composite material as carrier and preparation method and application thereof |
| CN110813286A (en) * | 2018-08-14 | 2020-02-21 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst with carrier being composite material containing donut mesoporous material and silica gel, preparation method and application thereof |
| CN112218842A (en) * | 2018-07-05 | 2021-01-12 | 陶氏环球技术有限责任公司 | Chemical treatment of catalyst treatment with hydrogen-containing supplemental fuel |
| CN112237929A (en) * | 2019-07-19 | 2021-01-19 | 中国石油化工股份有限公司 | Catalyst for preparing olefin by dehydrogenating light alkane and method for preparing olefin |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4506032A (en) * | 1983-03-22 | 1985-03-19 | Uop Inc. | Dehydrogenation catalyst composition |
| CN1466558A (en) * | 2000-09-26 | 2004-01-07 | �����ɷ� | Method for the dehydrogenation of hydrocarbons |
| CN102698750A (en) * | 2012-05-22 | 2012-10-03 | 南京沃来德能源科技有限公司 | Catalyst for catalytic dehydrogenation of alkane and preparation method and application thereof |
-
2014
- 2014-08-20 CN CN201410409656.9A patent/CN104258855A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4506032A (en) * | 1983-03-22 | 1985-03-19 | Uop Inc. | Dehydrogenation catalyst composition |
| CN1466558A (en) * | 2000-09-26 | 2004-01-07 | �����ɷ� | Method for the dehydrogenation of hydrocarbons |
| CN102698750A (en) * | 2012-05-22 | 2012-10-03 | 南京沃来德能源科技有限公司 | Catalyst for catalytic dehydrogenation of alkane and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| YIWEI ZHANG等: ""Effect of zinc addition on catalytic properties of PtSnK/γ-Al2O3 catalyst for isobutene dehydrogenation"", 《FUEL PROCESSING TECHNOLOGY》, vol. 96, 30 January 2012 (2012-01-30), pages 220 - 227 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107970924A (en) * | 2017-12-08 | 2018-05-01 | 杭州凯明催化剂股份有限公司 | A kind of preparation method of granular pattern catalyst suitable for VOCs catalysis burnings |
| CN108300430A (en) * | 2018-02-06 | 2018-07-20 | 四川润和催化新材料股份有限公司 | A kind of dehydrating alkanes heat release auxiliary agent and preparation method thereof and application method |
| CN108300430B (en) * | 2018-02-06 | 2021-02-02 | 四川润和催化新材料股份有限公司 | Alkane dehydrogenation heat release auxiliary agent and preparation method and use method thereof |
| CN110496630A (en) * | 2018-05-17 | 2019-11-26 | 中国石油化工股份有限公司 | The method of dehydrogenation of isobutane catalyst and preparation method thereof and preparing isobutene through dehydrogenation of iso-butane |
| CN110496630B (en) * | 2018-05-17 | 2021-10-19 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst, preparation method thereof and method for preparing isobutene through isobutane dehydrogenation |
| CN110614113A (en) * | 2018-06-20 | 2019-12-27 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst with rod-shaped mesoporous molecular sieve silica gel composite material as carrier, preparation method and application |
| CN112218842A (en) * | 2018-07-05 | 2021-01-12 | 陶氏环球技术有限责任公司 | Chemical treatment of catalyst treatment with hydrogen-containing supplemental fuel |
| CN112218842B (en) * | 2018-07-05 | 2023-11-28 | 陶氏环球技术有限责任公司 | Chemical treatment of catalyst treatment with hydrogen-containing supplemental fuel |
| CN110813285A (en) * | 2018-08-14 | 2020-02-21 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst with spherical surface-surrounded mesoporous material silica gel composite material as carrier and preparation method and application thereof |
| CN110813286A (en) * | 2018-08-14 | 2020-02-21 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst with carrier being composite material containing donut mesoporous material and silica gel, preparation method and application thereof |
| CN112237929A (en) * | 2019-07-19 | 2021-01-19 | 中国石油化工股份有限公司 | Catalyst for preparing olefin by dehydrogenating light alkane and method for preparing olefin |
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