CN106140198A - The preparation method of Performance of Isomerization Catalysts for Light n-Paraffin and the isomerization method of light paraffins - Google Patents
The preparation method of Performance of Isomerization Catalysts for Light n-Paraffin and the isomerization method of light paraffins Download PDFInfo
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Abstract
The invention discloses the preparation method of a kind of light n-alkane isomerization catalyst and the isomerization method of light normal paraffin, coprecipitation and hydrothermal treatment consists method synthesis of solid super acidic catalyst, this catalyst can be used for the isomerization of C4-C8 normal alkane isomerization, particularly pentane.In reaction atmosphere, hydrogen exists, and can obviously improve reactivity worth and the stability of catalyst.This catalyst for normal paraffin isomerization and reaction process have free from environmental pollution, not etching apparatus, the feature such as activity and selectivity is higher, reactivity worth is stable.
Description
Technical field
The present invention relates to the preparation method of Performance of Isomerization Catalysts for Light n-Paraffin and the isomerization method of light paraffins.
Background technology
Along with the fast development of World Economics, environmental conservation is the strictest to industrial requirement.In recent years
The automobile pollution coming China is continuously increased, increasing to the demand of gasoline.Within 2010, China performs
Gasoline standard in line with international standards, must limit more the alkene in gasoline, aromatic hydrocarbons, benzene and sulfur content
Strictly.Isomerized oil not olefin-containing, aromatic hydrocarbons and sulfur, be the clean gasoline of a kind of high-octane rating, low-steam pressure
Preferable blend component.
Late 1980s, the world's the most about 34.3Mt light paraffins is come by isomerization process
Producing high octane gasoline component, isomerization unit is concentrated mainly on the U.S., Japanese and European.20th century
The nineties, the ability of whole world isomerization unit increased rapidly, 1995-2010 world isomerization unit ability
Rate of increase can reach 7.6%.At present, have been obtained for extensively in U.S. C5/C6 alkane isomerization technology
General application, and not yet form bigger production capacity at China's C5/C6 isomerization process, and along with China
The increase of imported crude oil processing capacity and the raising of the level of crude oil processing, C5/C6 alkane in oil plant light oil
Amount will have and significantly increase, and the octane number of this fraction itself is the lowest, directly be certain to entering gasoline
Cause the decline of octane number.Therefore, as early as possible C5/C6 alkane isomerization technique is applied to commercial production,
To changing China's existing gasoline composition structure, improve quality of gasoline and environmental conservation all has important reality
Meaning.
Being restricted by thermodynamical equilibrium, isomerization reaction is the reaction of favors low temperature, and optimal conversion ratio is to connect
Near-thermal mechanical balance, favors low temperature is in isomerization reaction, but low temperature makes reaction rate reduce.Therefore temperature is reacted
Degree needs to consider equilibrium conversion and speed.Alkane isomerization needs the acid catalysis of stronger acid centre
Agent.The alumina load noble metal mainly having halogenation and the molecular sieve of current application of the most industrially succeeding are born
This two big type catalyst of supported noble metal.The aluminium oxide of halogenation has the strongest acidity, applies this kind of catalyst
The reaction temperature carrying out isomerization is relatively low, and the yield of isoparaffin is higher, but this type of catalyst is in raw material
To sulfur and water, very sensitive, it usually needs relatively low sulfur content and water content.And need constantly to mend
Chlorine operates, to remain acid.Catalyst with zeolite as carrier, owing to the acidity of zeolitic material is relatively low, different
Structureization reaction need to be carried out at a higher temperature, and isomerization yield when therefore reaching chemical equilibrium is relatively low.
But the advantage of this kind of catalyst is: to raw material has certain tolerance to sulfur and water, and will not corrode anti-
Answer equipment.
Recently, solid acid and super acids are paid close attention to the most widely, grinding of the catalyst of solid super-strong acid type
Studying carefully and increasingly increase, this kind of catalyst has that to be prone to same reactants separate, operation safe, low for equipment requirements etc. excellent
Gesture.
Studying more is SO4 2-/ZrO2The super acidic catalyst of type.Use this kind catalyst both can make different
Structureization reaction is carried out at a lower temperature, thus obtains higher isomerization yield, the most there is not the corruption of equipment
Erosion problem.
United States Patent (USP) US5157199 describes C4-C6 linear paraffin hysomer, and catalyst is Pt-
SO4 2-/ZrO2, isomerization reaction condition is: temperature is 200 DEG C；Pressure is 790kPa；H2Rubbing of/alkane
That ratio is 4.5:1.And in reaction mass, add the diamantane (obsolete) C of 0.1-0.8 weight %10HI6Help as reaction
Agent.
United States Patent (USP) US3032599 and European patent 0174836 also illustrate employing Pt-SO4 2-/ZrO2For
Catalyst carries out the method for C4-C6 linear paraffin hydro-refining isomery reaction.
United States Patent (USP) US6080904 describes the hydroisomerization reaction method of linear paraffin.Catalysis used
Agent is Pt-WO3/ZrO2。
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of Performance of Isomerization Catalysts for Light n-Paraffin.
Another object of the present invention is to provide the isomerization method of light paraffins.
The present invention provides the preparation method of a kind of light n-alkane isomerization catalyst, comprises the steps:
A. being dissolved in deionized water by the salt containing Zr, making mixed solution concentration is 0.5-2mol/L；
B. being dissolved in deionized water by the salt containing W, add strong aqua ammonia, being configured to W content is
0.2-2mol/L and the mixed solution of ammonia content 0.5-3mol/L；
The most under intense agitation, the solution solution in b being added drop-wise in step a for 30-45 minute
In, drip complete after, regulate pH=9 with ammonia, obtain the suspension having precipitation, be then stirred for 1.5-2
Hour；
D. the precipitate that obtained by c filters, washing, and then the product after washing is positioned in baking oven 110
DEG C-130 DEG C dry 8-16 hour；
E. with the H of 0.1-2.5mol/L2SO4Or (NH4)2SO4Dipping so that SO4 2-Pickup reaches one
Definite value, is then passed through 150 DEG C-280 DEG C after dry 18-36 hour, in 400-900 DEG C of roasting 4-12 hour；
F. iso volumetric impregnation method, is carried on Pt in e and obtains product, and the load capacity of Pt is 0.01-0.08wt%,
In terms of solid super acid catalyst gross weight；
G. the product obtained by f is in 110-130 DEG C after dry 8-16 hour, in 350-750 DEG C of roasting 8-16
Hour；
H. the product obtained by g is reducing 6-12 hour in 250-550 DEG C.
The preparation method of light n-alkane isomerization catalyst of the present invention, these, it is preferred to,
In step a, adding the salt containing Fe further, the salt containing Zr with the quality amount ratio of the salt containing Fe is
1.1:1～10:1.
The preparation method of light n-alkane isomerization catalyst of the present invention, wherein, the salt containing Fe
It is preferably ferrous sulfate or ferric nitrate.
The preparation method of light n-alkane isomerization catalyst of the present invention, wherein, in step a,
The described salt containing Zr is preferably zirconium nitrate or zirconium oxychloride.
The preparation method of light n-alkane isomerization catalyst of the present invention, wherein, in step b,
The described salt containing W is preferably ammonium metatungstate or sodium tungstate.
The preparation method of light n-alkane isomerization catalyst of the present invention, wherein, in step e,
Described SO4 2-Pickup preferably reaches 0.5～3.5wt%SO4 2-, in terms of solid super acid catalyst gross weight.
The preparation method of light n-alkane isomerization catalyst of the present invention, wherein, in step h also
Old terms is to reduce in mixed atmosphere, and hydrogen is preferably 1:10～4:6 with the volume ratio of nitrogen.
The present invention provides the isomerization method of a kind of light normal paraffin, described light normal paraffin to be the most simultaneously
The n-alkane of C4-C8, uses solid super acid catalyst, in the reaction atmosphere that there are hydrogen, makes
Reaction raw materials carries out isomerization process, and wherein, hydrogen partial pressure is 0.1-1.0MPa.
The isomerization method of light normal paraffin of the present invention, wherein, n-alkane in reaction raw materials
Percentage composition is preferably 20-100%.
The isomerization method of light normal paraffin of the present invention, wherein, the n-alkane in reaction raw materials
For preferred pentane.
The isomerization method of light normal paraffin of the present invention, wherein, isomerization reaction temperature is preferably
120-250 DEG C, isomerization reaction pressure is preferably 0.1-10MPa, and the air speed of isomerization reaction raw material is preferably
0.1-6h-1。
The preparation method is that, before preparing W-Zr or Fe promotion W-Zr oxide by coprecipitation
Driving body, hydrothermal aging produces WO3-ZrO2.Then will be by infusion process, by WO3-ZrO2Dipping and H2SO4
In solution, process through certain, obtain SO4 2-/WO3-ZrO2Carrier.Again by iso volumetric impregnation method, will
Pt load and SO4 2-/WO3-ZrO2On carrier, obtain Pt-SO4 2-/WO3-ZrO2。
The solid super acid catalyst of the normal alkane isomerization that the present invention proposes, can be used for the positive structure of C4-C8
Isomerization of paraffins.Reaction feed can be pure n-alkane, it is also possible to be different carbon number n-alkane and
The mixture of other hydro carbons, wherein the percetage by weight content of n-alkane is 20-100%.
When using pentane or the material containing pentane is reaction raw materials, reaction temperature is 120-250 DEG C,
Reaction pressure is 0.1-10MPa, and the air speed of pentane is 0.1-6 hour-1.Reaction temperature is the highest, pentane
Conversion ratio is the highest, but due to exothermic reaction when isomerization of paraffins reacts, is limited by thermodynamical equilibrium,
Under high temperature, conversion ratio then can decline.Low-speed is conducive to pentane conversion ratio, but not over thermodynamics pole
Limit.
Advantages of the present invention and effect:
1, solid ultra strong acid type catalyst is used to be used for the isomerization reaction of n-alkane particularly pentane,
Higher activity and selectivity can be obtained under higher alkane air speed.Certain hydrogen is kept in reaction atmosphere
Edema caused by disorder of QI pressure, can improve the normal alkane isomerization performance of solid super acid catalyst, and it is steady to be greatly improved it
Qualitative.
2, use solid ultra strong acid type catalyst and the isomerization reaction technique applied, have and do not pollute ring
The features such as border, not etching apparatus, reaction conversion ratio and selectivity are good, catalyst stabilization.
Detailed description of the invention
Hereinafter embodiments of the invention are elaborated: the present embodiment is premised on technical solution of the present invention
Under implement, give detailed embodiment and process, but protection scope of the present invention be not limited to following
Embodiment, the experimental technique of unreceipted actual conditions in the following example, generally according to normal condition.
Preparation method about Performance of Isomerization Catalysts for Light n-Paraffin
Salt containing Zr and the quality amount ratio of the salt containing Fe:
In the present invention, the quality amount ratio of the salt containing Zr with the salt containing Fe is not particularly limited, generally
In step a, adding the salt containing Fe further, the salt containing Zr with the quality amount ratio of the salt containing Fe is
1.1:1～10:1.
If the salt containing Zr is less than 1.1:1, due to the salt consumption containing Zr with the quality amount ratio of the salt containing Fe
Very few, cause H2SO4Load capacity is the lowest, and acidity is the most weak, and isomerization reaction activity reduces, and containing Zr's
Salt is more than 10:1 with the quality amount ratio of the salt containing Fe, owing to the salt consumption containing Zr is too much, causes waste,
And the H of load2SO4Acid strength reduces, and isomerization reaction activity reduces, and there is no other beneficial effects.
Salt containing Fe:
In the present invention, being not particularly limited the salt containing Fe, the generally salt containing Fe can be enumerated as chlorination
Ferrum or ferric nitrate.
Salt containing Zr:
In the present invention, the salt containing Zr is not particularly limited, in usual step a, the described salt containing Zr
Zirconium nitrate or zirconium oxychloride can be enumerated as.
Salt containing W:
In the present invention, the salt containing W is not particularly limited, in usual step b, the described salt containing W
Ammonium metatungstate or sodium tungstate can be enumerated as.
In step e, described SO
4
2-
Pickup:
In the present invention, in step e, described SO4 2-Pickup is not particularly limited, usual step e
In, described SO4 2-Pickup reaches 0.5～3.5wt%SO4 2, in terms of solid super acid catalyst gross weight.
If in step e, described SO4 2-Pickup is less than 0.5wt%SO4 2, due in step e, described
SO4 2-Pickup is too small, causes acid too low, it is impossible to meet the isomerization reaction needs to acid strength, and
In step e, described SO4 2-Pickup reaches more than 3.5wt%SO4 2, due in step e, described SO4 2-
Pickup is too much, and the loss causing acidity is serious, there is no other beneficial effect.
Hydrogen and the volume ratio of nitrogen:
In the present invention, the volume ratio of hydrogen with nitrogen is not particularly limited, reduction bar in usual step h
Part is to reduce in mixed atmosphere, and hydrogen is 1:10～4:6 with the volume ratio of nitrogen.
If hydrogen is less than 1:10 with the volume ratio of nitrogen, owing to hydrogen usage is very few, cause the expensive of load
Pt metal reduction is abundant not, and the volume ratio of hydrogen and nitrogen is more than 4:6, owing to hydrogen usage is too much,
Causing waste, and Pt reduction is too violent, cause Pt metal nanoparticle granule too big, isomerization is anti-
Activity should reduce, there is no other benefits.
Isomerization method about light paraffins
The percentage composition of n-alkane in reaction raw materials:
In the present invention, the percentage composition of n-alkane in reaction raw materials is not particularly limited, generally reacts
In raw material, the percentage composition of n-alkane is 20-100%, if the percentage composition of n-alkane in reaction raw materials
Less than 20%, owing in reaction raw materials, the percentage composition of n-alkane is the least, cause n-alkane conversion ratio
Too low and lose economy.
N-alkane in reaction raw materials is generally pentane.
Isomerisation conditions:
In the present invention, being not particularly limited isomerisation conditions, usual isomerization reaction temperature is 120-250
DEG C, isomerization reaction pressure is 0.1-10MPa, and the air speed of isomerization reaction raw material is 0.1-6h-1。
If reaction temperature is less than 120 DEG C, owing to reaction temperature is too low, reactivity is caused to reduce, and anti-
Answer temperature more than 250 DEG C, owing to temperature is too high, cause reactivity the highest, and cracking reaction occurs,
Reduce the selectivity of isomerization, there is no other beneficial effects.
If isomerization reaction pressure is less than 0.1MPa, due to isomerization reaction hypotony, cause isomery
Change reactivity to reduce, and isomerization reaction pressure is more than 10MPa, due to isomerization reaction hypertonia,
Cause the generation of cracking reaction, reduce isomerisation selectivity, increase cost simultaneously, there is no other useful
Effect.
If the air speed of isomerization reaction raw material is less than 0.1h-1, due to the air speed mistake of isomerization reaction raw material
Low, cause reaction efficiency the lowest, therefore lose economy, and the air speed of isomerization reaction raw material is more than 6h-1,
Owing to the air speed of isomerization reaction raw material is too high, causing catalyst loading too big, conversion ratio reduces, and loses
Economy, there is no other beneficial effects.
Embodiment 1 prepares catalyst
Preparing two parts of solution respectively, first part of solution is by 96.6gZrOCl2·8H2O is dissolved in 150mL and goes
In ionized water, it is configured to the solution that Zr content is 2mol/L；Second part of solution is, will
27.1g(NH4)6H2W12O40Being dissolved in 100mL deionized water, being configured to W content is 1.1mol/L's
Solution, adding 52g concentration is 1.5mol/L ammonia.After first part of solution prepares, at Quick mechanical
Under stirring, being slowly added dropwise in first part of solution by second part of solution, 30-45 minute used time was added dropwise to complete.
Then with ammonia by this solution adjustment PH=9, stirring 1.5-2 hour is continued afterwards.The precipitate that will obtain
Filter, be washed with deionized 4 times.Then the product after washing is positioned over 110 DEG C dry 12 in baking oven
Hour.The complete solid obtained afterwards will be dried with SO4 2-Load capacity be 2.0wt% standard dip in
The H of 1mol/L2SO4Solution 48 hours, 150 DEG C are positioned in Muffle furnace for dry 24 hours afterwards, and 900
DEG C roasting 4 hours.The solids that will obtain, with Pt load capacity for 0.01wt% iso volumetric impregnation in H2PtCl6
In solution 12 hours, then be positioned in the baking oven of 110 DEG C and be dried 12 hours, little through 350 DEG C of roastings 16
Time after, use hydrogen prereduction.Reducing gas is the gaseous mixture (H of hydrogen and nitrogen2:N2=1:10), stream
Speed is 30mL/min, and reduction temperature is 400 DEG C, and the recovery time is 6 hours.Obtain
0.01wt%Pt-SO4 2-/WO3-ZrO2Catalyst is labeled as catalyst A.
Embodiment 2 prepares catalyst
Preparing two parts of solution respectively, first part of solution is by 24.1gZrOCl2·8H2O is dissolved in 150mL and goes
In ionized water, it is configured to the solution that Zr content is 0.5mol/L；Second part of solution is, will
49.3g(NH4)6H2W12O40Being dissolved in 100mL deionized water, being configured to W content is the molten of 2mol/L
Liquid, adding 30g concentration is 1.5mol/L ammonia.After first part of solution prepares, stir at Quick mechanical
Mixing down, be slowly added dropwise in first part of solution by second part of solution, 30-45 minute used time was added dropwise to complete.Connect
This solution adjustment PH=9 with ammonia, continue stirring 1.5-2 hour afterwards.The precipitate mistake that will obtain
Filter, is washed with deionized 4 times.Then product after washing is positioned in baking oven 130 DEG C, and to be dried 8 little
Time.The complete solid obtained afterwards will be dried with SO4 2-Load capacity be 0.5wt% standard dip in
The H of 0.1mol/L2SO4Solution 12 hours, 280 DEG C are positioned in Muffle furnace for dry 36 hours afterwards, and 400
DEG C roasting 12 hours.The solids that will obtain, with Pt load capacity for 0.08wt% iso volumetric impregnation in H2PtCl6
In solution 12 hours, then be positioned in the baking oven of 130 DEG C and be dried 16 hours, little through 750 DEG C of roastings 8
Time after, use hydrogen prereduction.Reducing gas is the gaseous mixture (H of hydrogen and nitrogen2:N2=4:6), stream
Speed is 30mL/min, and reduction temperature is 250 DEG C, and the recovery time is 12 hours.Obtain
0.08wt%Pt-SO4 2-/WO3-ZrO2Catalyst is labeled as catalyst B.
Embodiment 3 prepares catalyst
Preparing two parts of solution respectively, first part of solution is by 58gZrOCl2·8H2O be dissolved in 150mL go from
In sub-water, it is configured to the solution that Zr content is 1.2mol/L, adds 5.8gFeSO4·7H2O is in above-mentioned
In solution, wherein the mass ratio of Zr salt and Fe salt is 10:1；Second part of solution is, will
4.9g(NH4)6H2W12O40Being dissolved in 100mL deionized water, being configured to W content is the molten of 0.2mol/L
Liquid, adding 21g concentration is 3mol/L ammonia.After first part of solution prepares, stir at Quick mechanical
Under, second part of solution is slowly added dropwise in first part of solution, 30-45 minute used time was added dropwise to complete.Then
With ammonia by this solution adjustment PH=9, continue stirring 1.5-2 hour afterwards.The precipitate obtained is filtered,
It is washed with deionized 4 times.Then the product after washing is positioned over 120 DEG C dry 16 hours in baking oven.
The complete solid obtained afterwards will be dried with H2SO4Load capacity is that the standard dip of 3.5wt% is in 2.5mol/L
H2SO4Solution 12 hours, 210 DEG C are positioned in Muffle furnace for dry 12 hours afterwards, 650 DEG C of roastings 8
Hour.The solids that will obtain, with Pt load capacity for 0.045wt% iso volumetric impregnation in H2PtCl6In solution
12 hours, then be positioned in the baking oven of 120 DEG C dry 8 hours, after 500 DEG C of roastings 8 hours,
Use hydrogen prereduction.Reducing gas is the gaseous mixture (H of hydrogen and nitrogen2:N2=1:3), flow velocity is
30mL/min, reduction temperature is 550 DEG C, and the recovery time is 8 hours.Obtain
0.045wt%Pt-SO4 2-/Fe-WO3-ZrO2Catalyst is labeled as catalyst C.
Embodiment 4 prepares catalyst
Preparing two parts of solution respectively, first part of solution is by 38.7gZrOCl2·8H2O is dissolved in 150mL and goes
In ionized water, it is configured to the solution that Zr content is 0.8mol/L, adds 35.2gFeSO4·7H2O in
In above-mentioned solution, wherein the mass ratio of Zr salt and Fe salt is 1.1:1；Second part of solution is, will
9.9g(NH4)6H2W12O40Being dissolved in 100mL deionized water, being configured to W content is the molten of 0.4mol/L
Liquid, adding 26g concentration is 1mol/L ammonia.After first part of solution prepares, stir at Quick mechanical
Under, second part of solution is slowly added dropwise in first part of solution, 30-45 minute used time was added dropwise to complete.Then
With ammonia by this solution adjustment PH=9, continue stirring 1.5-2 hour afterwards.The precipitate obtained is filtered,
It is washed with deionized 4 times.Then the product after washing is positioned over 115 DEG C dry 10 hours in baking oven.
The complete solid obtained afterwards will be dried with SO4 2-Load capacity is that the standard dip of 2.2wt% is in 1.2mol/L's
(NH4)2SO4Solution 30 hours, 180 DEG C are positioned in Muffle furnace for dry 36 hours afterwards, 450 DEG C of roastings
12 hours.The solids that will obtain, with Pt load capacity for 0.02wt% iso volumetric impregnation in H2PtCl6In solution
12 hours, then be positioned in the baking oven of 125 DEG C dry 10 hours, after 650 DEG C of roastings 10 hours,
Use hydrogen prereduction.Reducing gas is the gaseous mixture (H of hydrogen and nitrogen2:N2=1:4), flow velocity is
30mL/min, reduction temperature is 500 DEG C, and the recovery time is 6 hours.Obtain
0.02wt%Pt-SO4 2-/Fe-WO3-ZrO2Catalyst is labeled as catalyst D.
Embodiment 5 prepares catalyst
Preparing two parts of solution respectively, first part of solution is by 29gZrOCl2·8H2O be dissolved in 150mL go from
In sub-water, it is configured to the solution that Zr content is 0.6mol/L, adds 12.4gFeSO4·7H2O is in upper
Stating in solution, wherein the mass ratio of Zr salt and Fe salt is 7:3；Second part of solution is, will
14.8g(NH4)6H2W12O40Being dissolved in 100mL deionized water, being configured to W content is 0.6mol/L's
Solution, adding 10g concentration is 1mol/L ammonia.After first part of solution prepares, stir at Quick mechanical
Mixing down, be slowly added dropwise in first part of solution by second part of solution, 30-45 minute used time was added dropwise to complete.Connect
This solution adjustment PH=9 with ammonia, continue stirring 1.5-2 hour afterwards.The precipitate mistake that will obtain
Filter, is washed with deionized 4 times.Then the product after washing is positioned over 125 DEG C dry 14 in baking oven
Hour.The complete solid obtained afterwards will be dried with SO4 2-Load capacity be 0.5wt% standard dip in
(the NH of 0.1mol/L4)2SO4Solution 12 hours, 250 DEG C are positioned in Muffle furnace for dry 30 hours afterwards,
800 DEG C of roastings 10 hours.The solids that will obtain, with Pt load capacity for 0.03wt% iso volumetric impregnation in
H2PtCl6In solution 12 hours, then be positioned in the baking oven of 120 DEG C and be dried 16 hours, through 600 DEG C of roastings
After burning 8 hours, use hydrogen prereduction.Reducing gas is the gaseous mixture (H of hydrogen and nitrogen2:N2=3:7),
Flow velocity is 30mL/min, and reduction temperature is 450 DEG C, and the recovery time is 8 hours.Obtain
0.03wt%Pt-SO4 2-/Fe-WO3-ZrO2Catalyst is labeled as catalyst E.
Embodiment 6 prepares catalyst
Preparing two parts of solution respectively, first part of solution is by 48.3gZrOCl2·8H2O is dissolved in 150mL and goes
In ionized water, it is configured to the solution that Zr content is 1mol/L, adds 12.1gFeSO4·7H2O is in upper
Stating in solution, wherein the mass ratio of Zr salt and Fe salt is 8:2；Second part of solution is, will
19.7g(NH4)6H2W12O40Being dissolved in 100mL deionized water, being configured to W content is 0.8mol/L's
Solution, adding 12g concentration is 0.8mol/L ammonia.After first part of solution prepares, at Quick mechanical
Under stirring, being slowly added dropwise in first part of solution by second part of solution, 30-45 minute used time was added dropwise to complete.
Then with ammonia by this solution adjustment PH=9, stirring 1.5-2 hour is continued afterwards.The precipitate that will obtain
Filter, be washed with deionized 4 times.Then the product after washing is positioned over 130 DEG C dry 10 in baking oven
Hour.The complete solid obtained afterwards will be dried with SO4 2-Load capacity be 3.5wt% standard dip in
(the NH of 2.5mol/L4)2SO4Solution 48 hours, 220 DEG C are positioned in Muffle furnace for dry 36 hours afterwards,
900 DEG C of roastings 6 hours.The solids that will obtain, with Pt load capacity for 0.06wt% iso volumetric impregnation in H2PtCl6
In solution 12 hours, then be positioned in the baking oven of 120 DEG C and be dried 14 hours, little through 450 DEG C of roastings 10
Time after, use hydrogen prereduction.Reducing gas is the gaseous mixture (H of hydrogen and nitrogen2:N2=2:8), stream
Speed is 30mL/min, and reduction temperature is 550 DEG C, and the recovery time is 10 hours.Obtain
0.06wt%Pt-SO4 2-/Fe-WO3-ZrO2Catalyst is labeled as catalyst F.
Embodiment 7 prepares catalyst
Preparing two parts of solution respectively, first part of solution is by 67.7gZrOCl2·8H2O is dissolved in 150mL and goes
In ionized water, it is configured to the solution that Zr content is 1.4mol/L, adds 45.1gFeSO4·7H2O in
In above-mentioned solution, wherein the mass ratio of Zr salt and Fe salt is 6:4；Second part of solution is, will
32g(NH4)6H2W12O40Being dissolved in 100mL deionized water, being configured to W content is the molten of 1.3mol/L
Liquid, adding 47g concentration is 1.5mol/L ammonia.After first part of solution prepares, stir at Quick mechanical
Mixing down, be slowly added dropwise in first part of solution by second part of solution, 30-45 minute used time was added dropwise to complete.Connect
This solution adjustment PH=9 with ammonia, continue stirring 1.5-2 hour afterwards.The precipitate mistake that will obtain
Filter, is washed with deionized 4 times.Then the product after washing is positioned over 110 DEG C dry 16 in baking oven
Hour.The complete solid obtained afterwards will be dried with SO4 2-Load capacity is that the standard dip of 3wt% is in 2mol/L
(NH4)2SO4Solution 28 hours, 200 DEG C are positioned in Muffle furnace for dry 20 hours afterwards, 700 DEG C of roastings
Burn 8 hours.The solids that will obtain, with Pt load capacity for 0.07wt% iso volumetric impregnation in H2PtCl6Solution
In 12 hours, then be positioned in the baking oven of 125 DEG C and be dried 8 hours, through 550 DEG C of roastings 12 hours it
After, use hydrogen prereduction.Reducing gas is the gaseous mixture (H of hydrogen and nitrogen2:N2=1:9), flow velocity is
30mL/min, reduction temperature is 370 DEG C, and the recovery time is 8 hours.Obtain
0.07wt%Pt-SO4 2-/Fe-WO3-ZrO2Catalyst is labeled as catalyst G.
Embodiment 8 prepares catalyst
Changing the Zr salt in embodiment 4 into zirconium nitrate, W salt changes sodium tungstate into, and other step is identical,
After obtain catalyst H.
Embodiment 9 prepares catalyst
Changing the Fe salt in embodiment 6 into ferric nitrate, other step is identical, finally obtains catalyst I.
Embodiment 10 catalyst A is used for n-pentane isomerization reaction
5 grams of catalyst A are loaded in 10mL fixed bed reactors, at 200 DEG C, activate under hydrogen atmosphere
2 hours, then switching was reacted containing pentane.Reaction condition: temperature 120 DEG C, system pressure 10MPa,
Hydrogen partial pressure 1MPa, air speed 0.1h-1.Sample analysis after reacting 2 hours, pentane conversion ratio 65.2%,
Isopentane selectivity is 98.2%.
Embodiment 11 catalyst A is used for n-pentane isomerization reaction
5 grams of catalyst A are loaded in 10mL fixed bed reactors, at 250 DEG C, activate under hydrogen atmosphere
2 hours, then switching was reacted containing the pentane of the isopentane of 80%.Reaction condition: temperature 250 DEG C,
System pressure 5MPa, hydrogen partial pressure 0.5MPa, air speed 6h-1, hydrogen is 1:2 with the mol ratio of pentane.
After reaction different time, sample analysis see table 1.
Table 1
Embodiment 12 catalyst A is used for n-pentane isomerization reaction
5 grams of catalyst A are loaded in 10mL fixed bed reactors, at 190 DEG C, activate under hydrogen atmosphere
4 hours, then switching was reacted containing the pentane of the isopentane of 40%.Reaction condition: temperature 185 DEG C,
System pressure 0.1MPa, hydrogen partial pressure 0.1MPa, air speed 3h-1, hydrogen is 1:2 with the mol ratio of pentane.
After reaction different time, sample analysis see table 2.
Table 2
Embodiment 13 catalyst A is used for n-pentane isomerization reaction
5 grams of catalyst A are loaded in 10mL fixed bed reactors, at 180 DEG C, activate under hydrogen atmosphere
2 hours, then switching was reacted containing the pentane of the isopentane of 20%.Reaction condition: temperature 200 DEG C,
System pressure 2MPa, hydrogen partial pressure 0.8MPa, air speed 2h-1, hydrogen is 1:3 with the mol ratio of pentane.
Sample analysis after reacting 2 hours, pentane conversion ratio 48.3%, isopentane selectivity is 97.8%.
Embodiment 14 catalyst A is used for n-pentane isomerization reaction
5 grams of catalyst A are loaded in 10mL fixed bed reactors, at 230 DEG C, activate under hydrogen atmosphere
2 hours, then switching was reacted containing the pentane of the isopentane of 70%.Reaction condition: temperature 230 DEG C,
System pressure 7MPa, hydrogen partial pressure 0.85MPa, hydrogen is 1:1 with the mol ratio of pentane.Reaction 2
After hour, react sample analysis under different air speeds and see table 3.
Table 3
Embodiment 15 catalyst B is used for n-pentane isomerization reaction
5 grams of catalyst B are loaded in 10mL fixed bed reactors, at 220 DEG C, activate under hydrogen atmosphere
2 hours, then switching was reacted containing the pentane of the isopentane of 50%.Reaction condition: temperature 220 DEG C,
System pressure 6MPa, hydrogen partial pressure 1MPa, air speed 5h-1, hydrogen is 1:4 with the mol ratio of pentane.
Sample analysis after reacting 2 hours, pentane conversion ratio 55.3%, isopentane selectivity is 98.1%.
Embodiment 16 catalyst C is used for n-pentane isomerization reaction
5 grams of catalyst C are loaded in 10mL fixed bed reactors, at 220 DEG C, activate under hydrogen atmosphere
2 hours, then switching was reacted containing the pentane of the isopentane of 40%.Reaction condition: temperature 210 DEG C,
System pressure 5MPa, hydrogen partial pressure 1MPa, air speed 1.5h-1, hydrogen is 1:1 with the mol ratio of pentane.
Sample analysis after reacting 2 hours, pentane conversion ratio 58.0%, isopentane selectivity is 98.0%.
Embodiment 17 catalyst D is used for n-pentane isomerization reaction
5 grams of catalyst D are loaded in 10mL fixed bed reactors, at 220 DEG C, activate under hydrogen atmosphere
2 hours, then switching was reacted containing the pentane of the isopentane of 10%.Reaction condition: temperature 220 DEG C,
System pressure 4.5MPa, hydrogen partial pressure 0.7MPa, air speed 2.5h-1, hydrogen with the mol ratio of pentane is
1:2.Sample analysis after reacting 2 hours, pentane conversion ratio 60.4%, isopentane selectivity is 98.7%.
Embodiment 18 catalyst E is used for n-pentane isomerization reaction
5 grams of catalyst E are loaded in 10mL fixed bed reactors, at 220 DEG C, activate under hydrogen atmosphere
2 hours, then switching was reacted containing the pentane of the isopentane of 25%.Reaction condition: temperature 240 DEG C,
System pressure 8MPa, hydrogen partial pressure 0.9MPa, air speed 3.5h-1, hydrogen is 2:1 with the mol ratio of pentane.
Sample analysis after reacting 2 hours, pentane conversion ratio 63.5%, isopentane selectivity is 97.9%.
Embodiment 19 catalyst F is used for n-pentane isomerization reaction
5 grams of catalyst F are loaded in 10mL fixed bed reactors, at 220 DEG C, activate under hydrogen atmosphere
2 hours, then switching was reacted containing the pentane of the isopentane of 10%.Reaction condition: temperature 250 DEG C,
System pressure 3.5MPa, hydrogen partial pressure 1MPa, air speed 1.5h-1, hydrogen is 1:1 with the mol ratio of pentane.
Sample analysis after reacting 2 hours, pentane conversion ratio 59.2%, isopentane selectivity is 98.3%.
Embodiment 20 catalyst G is used for n-pentane isomerization reaction
5 grams of catalyst G are loaded in 10mL fixed bed reactors, at 220 DEG C, activate under hydrogen atmosphere
2 hours, then switching was reacted containing the pentane of the isopentane of 10%.Reaction condition: temperature 220 DEG C,
System pressure 2.5MPa, hydrogen partial pressure 0.3MPa, air speed 0.5h-1, hydrogen with the mol ratio of pentane is
1:3.Sample analysis after reacting 2 hours, pentane conversion ratio 55.5%, isopentane selectivity is 97.7%.
Embodiment 21 catalyst H is used for n-pentane isomerization reaction
5 grams of catalyst H are loaded in 10mL fixed bed reactors, at 160 DEG C, live under hydrogen atmosphere
Changing 4 hours, then switching is reacted containing the pentane of the isopentane of 65%.Reaction condition: temperature 130
DEG C, system pressure 6.5MPa, hydrogen partial pressure 0.8MPa, air speed 0.4h-1, hydrogen and pentane mole
Ratio is 1:2.Sample analysis after reacting 2 hours, pentane conversion ratio 26.7%, isopentane selectivity is 97.3%.
Embodiment 22 catalyst I is used for n-pentane isomerization reaction
5 grams of catalyst I are loaded in 10mL fixed bed reactors, at 220 DEG C, activate under hydrogen atmosphere
2 hours, then switching was reacted containing the pentane of the isopentane of 55%.Reaction condition: temperature 245 DEG C,
System pressure 6MPa, hydrogen partial pressure 1MPa, air speed 0.5h-1, hydrogen is 1:2 with the mol ratio of pentane.
Sample analysis after reacting 2 hours, pentane conversion ratio 50.9%, isopentane selectivity is 98.5%.
When using pentane or the material containing pentane is reaction raw materials, reaction temperature is the highest, pentane
Conversion ratio is the highest, but due to exothermic reaction when isomerization of paraffins reacts, is limited by thermodynamical equilibrium,
Under high temperature, conversion ratio then can decline.Low-speed is conducive to pentane conversion ratio, but not over thermodynamics pole
Limit.Solid ultra strong acid type catalyst is used to be used for the isomerization reaction of n-alkane particularly pentane, permissible
Higher activity and selectivity is obtained under higher alkane air speed.The hydrogen keeping certain in reaction atmosphere divides
Pressure, can improve the normal alkane isomerization performance of solid super acid catalyst, and be greatly improved its stability.
Claims (11)
1. a preparation method for light n-alkane isomerization catalyst, comprises the steps:
A. being dissolved in deionized water by the salt containing Zr, making mixed solution concentration is 0.5-2mol/L；
B. being dissolved in deionized water by the salt containing W, add strong aqua ammonia, being configured to W content is
0.2-2mol/L and the mixed solution of ammonia content 0.5-3mol/L；
The most under intense agitation, the solution solution in b being added drop-wise in step a for 30-45 minute
In, drip complete after, regulate pH=9 with ammonia, obtain the suspension having precipitation, be then stirred for 1.5-2
Hour；
D. the precipitate that obtained by c filters, washing, and then the product after washing is positioned in baking oven 110
DEG C-130 DEG C dry 8-16 hour；
E. with the H of 0.1-2.5mol/L2SO4Or (NH4)2SO4Impregnate 12-48 hour so that SO4 2-
Pickup reaches certain value, is then passed through 150 DEG C-280 DEG C after dry 12-36 hour, in 400-900 DEG C of roasting
Burn 4-12 hour；
F. iso volumetric impregnation method, is carried on Pt in e and obtains product, and the load capacity of Pt is 0.01-0.08wt%,
In terms of solid super acid catalyst gross weight；
G. the product obtained by f is in 110-130 DEG C after dry 8-16 hour, in 350-750 DEG C of roasting 8-16
Hour；
H. the product obtained by g is reducing 6-12 hour in 250-550 DEG C.
The preparation method of light n-alkane isomerization catalyst the most according to claim 1, it is special
Levying and be: in step a, add the salt containing Fe further, the quality of the salt containing Zr and the salt containing Fe is used
Amount ratio is 1.1:1～10:1.
The preparation method of light n-alkane isomerization catalyst the most according to claim 2, it is special
Levy and be: the described salt containing Fe is ferrous sulfate or ferric nitrate.
4. according to the preparation side of the light n-alkane isomerization catalyst described in any one of claims 1 to 3
Method, it is characterised in that: in step a, the described salt containing Zr is zirconium nitrate or zirconium oxychloride.
5. according to the preparation side of the light n-alkane isomerization catalyst described in any one of claims 1 to 3
Method, it is characterised in that: in step b, the described salt containing W is ammonium metatungstate or sodium tungstate.
6. according to the preparation side of the light n-alkane isomerization catalyst described in any one of claims 1 to 3
Method, it is characterised in that: in step e, described SO4 2-Pickup reaches 0.5～3.5wt%SO4 2-, with solid
Super acidic catalyst gross weight meter.
7. according to the preparation side of the light n-alkane isomerization catalyst described in any one of claims 1 to 3
Method, it is characterised in that: in step h, reducing condition is to reduce in mixed atmosphere, hydrogen and nitrogen
Volume ratio is 1:10～4:6.
8. an isomerization method for light normal paraffin, described light normal paraffin is the positive structure of C4-C8
Alkane, it is characterised in that: use solid super acid catalyst, in the reaction atmosphere that there are hydrogen, make
Reaction raw materials carries out isomerization process, and wherein, hydrogen partial pressure is 0.1-1.0MPa, and described solid super-strong acid is urged
Agent is for being prepared by preparation method described in claim 1-7.
The isomerization method of light normal paraffin the most according to claim 8, it is characterised in that: anti-
Answering the percentage composition of n-alkane in raw material is 20-100%.
The isomerization method of light normal paraffin the most according to claim 8, it is characterised in that: anti-
Answering the n-alkane in raw material is pentane.
The isomerization method of 11. light normal paraffins according to Claim 8～described in 10 any one, it is special
Levying and be: isomerization reaction temperature is 120-250 DEG C, isomerization reaction pressure is 0.1-10MPa, isomery
The air speed changing reaction raw materials is 0.1-6h-1。
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| CN111569861A (en) * | 2020-05-29 | 2020-08-25 | 河北工业大学 | Catalyst for reaction for converting isoparaffin into normal paraffin and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6080904A (en) * | 1993-07-22 | 2000-06-27 | Mobil Oil Corporation | Isomerization process |
| CN102407145A (en) * | 2011-10-24 | 2012-04-11 | 复旦大学 | Catalyst for normal heptane isomerization reaction and preparation method thereof |
| CN103055906A (en) * | 2011-10-18 | 2013-04-24 | 中国石油化工股份有限公司 | Solid superacid bifunctional catalyst and preparation method thereof |
-
2015
- 2015-03-24 CN CN201510130406.6A patent/CN106140198B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6080904A (en) * | 1993-07-22 | 2000-06-27 | Mobil Oil Corporation | Isomerization process |
| CN103055906A (en) * | 2011-10-18 | 2013-04-24 | 中国石油化工股份有限公司 | Solid superacid bifunctional catalyst and preparation method thereof |
| CN102407145A (en) * | 2011-10-24 | 2012-04-11 | 复旦大学 | Catalyst for normal heptane isomerization reaction and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| A.V. IVANOV ET AL: ""Isomerization of n-alkanes on Pt/WO3-SO4/ZrO2 systems"", 《CATALYSIS TODAY》 * |
| 李言 等: ""WO3/ZrO2固体酸催化剂的制备及应用研究进展"", 《分子催化》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111569861A (en) * | 2020-05-29 | 2020-08-25 | 河北工业大学 | Catalyst for reaction for converting isoparaffin into normal paraffin and preparation method thereof |
| CN111569861B (en) * | 2020-05-29 | 2023-04-07 | 河北工业大学 | Catalyst for reaction for converting isoparaffin into normal paraffin and preparation method thereof |
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