CN106140198B - 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 a kind of preparation method of light n-alkane isomerization catalyst and the isomerization methods of light normal paraffin, coprecipitation and hydro-thermal process method synthesis of solid super acidic catalyst, the catalyst can be used for the isomerization of C4-C8 normal alkane isomerization, especially pentane.Hydrogen exists in reaction atmosphere, can obviously improve the reactivity worth and stability of catalyst.The catalyst for normal paraffin isomerization and reaction process have the characteristics that it is free from environmental pollution, do not corrode that equipment, activity and selectivity are 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 methods of light paraffins.
Background technique
With the fast development of world economy, environmental protection is also increasingly stringent to industrial requirement.China in recent years
Car ownership be continuously increased, it is increasing to the demand of gasoline.China performs gasoline in line with international standards within 2010
Standard must limit alkene, aromatic hydrocarbons, benzene and the sulfur content in gasoline more stringent.Isomerized oil not olefin-containing, aromatic hydrocarbons and
Sulphur is the clean gasoline ideal blend component of a kind of high-octane rating, low-steam pressure.
Late 1980s, about 34.3Mt light paraffins produce higher octane by isomerization process every year in the world
It is worth gasoline component, isomerization unit is concentrated mainly on the U.S., Japan and Europe.The 1990s whole world isomerization unit
Ability increases rapidly, and the growth rate of the world 1995-2010 isomerization unit ability can achieve 7.6%.Currently, in the U.S.
C5/C6 alkane isomerization technology, which has been obtained, to be widely applied, and is not yet formed in China's C5/C6 isomerization process biggish
Production capacity, and with the raising of the increase of China's imported crude oil processing capacity and the level of crude oil processing, C5/ in oil plant light oil
The amount of C6 alkane, which will have, significantly to be increased, and the octane number of this fraction itself is very low, directly is certain to lead to entering gasoline
Cause the decline of octane number.Therefore, C5/C6 alkane isomerization technique is applied to industrial production as early as possible, it is existing to China is changed
There is gasoline composed structure, improves quality of gasoline and environmental protection all has important practical significance.
It is restricted by thermodynamical equilibrium, isomerization reaction is the reaction of favors low temperature, and optimal conversion ratio is close to heating power
Balance is learned, favors low temperature is in isomerization reaction, but low temperature reduces reaction rate.Therefore reaction temperature needs comprehensively consider balance
Conversion ratio and rate.Alkane isomerization needs the acid catalyst of stronger acid centre.Current application of industrially succeeding
The alumina load noble metal for mainly having halogenation and molecular sieve carried noble metal this two major classes type catalyst.The aluminium oxide of halogenation
With very strong acidity, the reaction temperature for carrying out isomerization using this kind of catalyst is lower, and the yield of isoparaffin is higher, but this
Class catalyst in raw material to sulphur and water, it is very sensitive, it usually needs lower sulfur content and water content.And it needs continuous
It carries out mending chlorine operation, to remain acid.Using zeolite as the catalyst of carrier, since the acidity of zeolitic material is lower, isomerization is anti-
It should need to carry out at a higher temperature, therefore it is relatively low to reach isomerization yield when chemical balance.But this kind of catalyst is excellent
Gesture is: having certain tolerance to sulphur and water in raw material, and will not corrosion reaction equipment.
Recently, solid acid and super acids are all widely paid close attention to, and the research of the catalyst of solid super-strong acid type is increasingly
Increase, this kind of catalyst, which has, is easy to the advantages such as same reactants separate, safe operation, low for equipment requirements.
Studying more is SO4 2-/ZrO2The super acidic catalyst of type.Both isomerization can be made anti-using this type catalyst
It should carry out at a lower temperature, to obtain higher isomerization yield, and the etching problem of equipment be not present.
United States Patent (USP) US5157199 describes C4-C6 linear paraffin hysomer, catalyst Pt-SO4 2-/ZrO2,
Isomerization reaction condition are as follows: temperature is 200 DEG C；Pressure is 790kPa；H2The molar ratio of/alkane is 4.5:1.And in reaction mass
The middle adamantane C that 0.1-0.8 weight % is added10HI6As reaction promoter.
United States Patent (USP) US3032599 and European patent 0174836 are also illustrated using Pt-SO4 2-/ZrO2For catalyst into
The method of row C4-C6 linear paraffin hydro-refining isomery reaction.
United States Patent (USP) US6080904 describes the hydroisomerization reaction method of linear paraffin.Used catalyst is Pt-
WO3/ZrO2。
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of Performance of Isomerization Catalysts for Light n-Paraffin.
Yet another object of that present invention is to provide the isomerization method of light paraffins.
The present invention provides a kind of preparation method of light n-alkane isomerization catalyst, includes the following steps:
A. in deionized water by the salt dissolution containing Zr, it is 0.5-2mol/L that mixed solution concentration, which is made,；
B. the salt containing W is dissolved in deionized water, adds concentrated ammonia liquor, being configured to W content is 0.2-2mol/L and ammonium hydroxide
The mixed solution of content 0.5-3mol/L；
C. under intense agitation, the solution in b was added drop-wise in the solution in step a with 30-45 minutes, is dripped
After finishing, pH=9 is adjusted with ammonium hydroxide, the suspension of precipitating is obtained, is then stirred for 1.5-2 hours；
D. sediment c obtained filters, then the product after washing is placed in baking oven 110 DEG C -130 DEG C by washing
It is 8-16 hours dry；
E. the H of 0.1-2.5mol/L is used2SO4Or (NH4)2SO4Dipping, so that SO4 2-Impregnation increment reaches certain value, then
By 150 DEG C -280 DEG C after dry 18-36 hours, in 400-900 DEG C roasting 4-12 hours；
Pt is carried in e and obtains product by f. iso volumetric impregnation method, and the load capacity of Pt is 0.01-0.08wt%, super with solid
Strong acid catalyst total weight；
G. product f obtained in 110-130 DEG C after dry 8-16 hours, in 350-750 DEG C roasting 8-16 hours；
H. product g obtained is in 250-550 DEG C in reduction 6-12 hours.
The preparation method of light n-alkane isomerization catalyst of the present invention, wherein preferably, in step a,
The salt containing Fe is further added, the quality amount ratio of the salt containing Zr and 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 is preferably sulphur
Sour ferrous or ferric nitrate.
The preparation method of light n-alkane isomerization catalyst of the present invention, wherein described to contain Zr in step a
Salt be preferably zirconium nitrate or zirconium oxychloride.
The preparation method of light n-alkane isomerization catalyst of the present invention, wherein described containing W's in step b
Salt is preferably ammonium metatungstate or sodium tungstate.
The preparation method of light n-alkane isomerization catalyst of the present invention, wherein in step e, the SO4 2-
Impregnation increment preferably reaches 0.5~3.5wt%SO4 2-, with solid super acid catalyst total weight.
The preparation method of light n-alkane isomerization catalyst of the present invention, wherein reducing condition is in step h
It is restored in mixed atmosphere, the volume ratio of hydrogen and nitrogen is preferably 1:10~4:6.
The present invention goes back while providing a kind of isomerization method of light normal paraffin, and the light normal paraffin is C4-C8
N-alkane, using solid super acid catalyst, in the reaction atmosphere there are hydrogen, make reaction raw materials carry out isomerization
Processing, wherein hydrogen partial pressure 0.1-1.0MPa.
The isomerization method of light normal paraffin of the present invention, wherein the percentage of n-alkane contains in reaction raw materials
Amount is preferably 20-100%.
The isomerization method of light normal paraffin of the present invention, wherein the n-alkane in reaction raw materials is 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 preparing W-Zr or Fe with coprecipitation promotes W-Zr oxide precursor, hydro-thermal
WO is produced in aging3-ZrO2.Then infusion process will be used, by WO3-ZrO2Dipping and H2SO4In solution, by centainly handling, obtain
SO4 2-/WO3-ZrO2Carrier.Again by iso volumetric impregnation method, by Pt load and SO4 2-/WO3-ZrO2On carrier, Pt-SO is obtained4 2-/
WO3-ZrO2。
The solid super acid catalyst of normal alkane isomerization proposed by the present invention can be used for the different of C4-C8 n-alkane
Structure.Reaction feed can be pure n-alkane, be also possible to the mixture of different carbon number n-alkanes and other hydro carbons,
The weight percent content of middle n-alkane is 20-100%.
When using pentane or material containing pentane is reaction raw materials, reaction temperature is 120-250 DEG C, reaction pressure
Power is 0.1-10MPa, and the air speed of pentane is 0.1-6 hours-1.Reaction temperature is higher, and pentane conversion ratio is higher, but due to
Exothermic reaction when isomerization of paraffins reacts, is limited, under high temperature, conversion ratio can then decline by thermodynamical equilibrium.Low-speed has
It conducive to pentane conversion ratio, but not is more than thermodynamic limit.
Advantages of the present invention and effect:
1, using solid ultra strong acid type catalyst be used for n-alkane especially pentane isomerization reaction, can compared with
Higher activity and selectivity is obtained under high alkane air speed.Certain hydrogen partial pressure is kept in reaction atmosphere, can be improved solid
The normal alkane isomerization performance of body super acidic catalyst, and greatly improve its stability.
2, using solid ultra strong acid type catalyst and applied isomerization reaction technique, have it is free from environmental pollution, be stale-proof
The features such as losing equipment, reaction conversion ratio and selectivity good, catalyst stabilization.
Specific embodiment
Elaborate below to the embodiment of the present invention: the present embodiment carries out under the premise of the technical scheme of the present invention
Implement, gives detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation
Test method without specific conditions in example, usually according to normal condition.
Preparation method about Performance of Isomerization Catalysts for Light n-Paraffin
The quality amount ratio of salt containing Zr and the salt containing Fe:
In the present invention, the quality amount ratio of salt and the salt containing Fe containing Zr is not particularly limited, in usual step a,
The salt containing Fe is further added, the quality amount ratio of the salt containing Zr and the salt containing Fe is 1.1:1~10:1.
It is caused if the quality amount ratio of the salt containing Zr and the salt containing Fe is less than 1.1:1 since the salt dosage containing Zr is very few
H2SO4Load capacity is too low, and acid too weak, isomerization reaction activity reduces, and the quality amount ratio of the salt containing Zr and the salt containing Fe is big
The H for causing to waste since the salt dosage containing Zr is excessive in 10:1, and loading2SO4Acid strength reduces, isomerization reaction activity drop
It is low, have no other beneficial effects.
Salt containing Fe:
In the present invention, the salt containing Fe is not particularly limited, usually the salt containing Fe can be enumerated as iron chloride or nitric acid
Iron.
Salt containing Zr:
In the present invention, the salt containing Zr is not particularly limited, in usual step a, the salt containing Zr can be enumerated as
Zirconium nitrate or zirconium oxychloride.
Salt containing W:
In the present invention, the salt containing W is not particularly limited, in usual step b, the salt containing W can be enumerated as partially
Ammonium tungstate or sodium tungstate.
In step e, the SO4 2-Impregnation increment:
In the present invention, in step e, the SO4 2-Impregnation increment is not particularly limited, in usual step e, the SO4 2-
Impregnation increment reaches 0.5~3.5wt%SO4 2, with solid super acid catalyst total weight.
If in step e, the SO4 2-Impregnation increment is less than 0.5wt%SO4 2, due in step e, the SO4 2-Impregnation increment mistake
It is small, it causes acidity too low, is not able to satisfy isomerization reaction to the needs of acid strength, and in step e, the SO4 2-Impregnation increment reaches super
Cross 3.5wt%SO4 2, due in step e, the SO4 2-Impregnation increment is excessive, causes acid loss serious, has no other beneficial to effect
Fruit.
The volume ratio of hydrogen and nitrogen:
In the present invention, the volume ratio of hydrogen and nitrogen is not particularly limited, reducing condition is mixed in usual step h
It closes and is restored in atmosphere, the volume ratio of hydrogen and nitrogen is 1:10~4:6.
If the volume ratio of hydrogen and nitrogen is less than 1:10, since hydrogen usage is very few, the precious metals pt of load is caused also
Original is not enough, and the volume ratio of hydrogen and nitrogen is greater than 4:6 and causes to waste since hydrogen usage is excessive, and Pt reduction is too
Acutely, cause Pt metal nanoparticle particle too big, isomerization reaction activity reduces, and has 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, in usual reaction raw materials
The percentage composition of n-alkane is 20-100%, if the percentage composition of n-alkane is less than 20% in reaction raw materials, due to anti-
It answers the percentage composition of n-alkane in raw material too small, causes n-alkane conversion ratio too low and lose economy.
N-alkane in reaction raw materials is generally pentane.
Isomerisation conditions:
In the present invention, isomerisation conditions are not particularly limited, usual isomerization reaction temperature is 120-250 DEG C, different
Structure reaction pressure is 0.1-10MPa, and the air speed of isomerization reaction raw material is 0.1-6h-1。
If reaction temperature, since reaction temperature is too low, causes reactivity to reduce less than 120 DEG C, and reaction temperature is super
250 DEG C are crossed, since temperature is excessively high, causes reactivity too high, and cracking reaction occurs, reduces the selectivity of isomerization, and
Without other beneficial effects.
If isomerization reaction pressure is less than 0.1MPa, due to isomerization reaction hypotony, cause isomerization reaction living
Property reduce, and isomerization reaction pressure is more than 10MPa, due to isomerization reaction hypertonia, causes the generation of cracking reaction, is dropped
Low isomerisation selectivity, while increasing cost, have no other beneficial effects.
If the air speed of isomerization reaction raw material is less than 0.1h-1, since the air speed of isomerization reaction raw material is too low, cause anti-
It answers efficiency too low, therefore loses economy, and the air speed of isomerization reaction raw material is more than 6h-1, due to isomerization reaction raw material
Air speed is excessively high, causes catalyst loading too big, and conversion ratio reduces, and loses economy, has no other beneficial effects.
Embodiment 1 prepares catalyst
Prepare two parts of solution respectively, first part of solution is by 96.6gZrOCl2·8H2O is dissolved in 150mL deionized water, is matched
It is set to the solution that Zr content is 2mol/L；Second part of solution is, by 27.1g (NH4)6H2W12O40It is dissolved in 100mL deionized water,
It is configured to the solution that W content is 1.1mol/L, adding 52g concentration is 1.5mol/L ammonium hydroxide.After first part of solution prepares,
Under Quick mechanical stirring, second part of solution is slowly added dropwise in first part of solution, used time 30-45 minute is added dropwise to complete.Then
With ammonium hydroxide by solution adjustment PH=9, continue stirring 1.5-2 hours later.Obtained sediment is filtered, is washed with deionized water
It washs 4 times.Then the product after washing is placed in 110 DEG C drying 12 hours in baking oven.The solid that will be obtained after dry finish
With SO4 2-Load capacity is the standard dip of 2.0wt% in the H of 1mol/L2SO4Solution 48 hours, 150 DEG C put for drying 24 hours later
It is placed in Muffle furnace, 900 DEG C roast 4 hours.The solids that will be obtained, with Pt load capacity be 0.01wt% iso volumetric impregnation in
H2PtCl612 hours in solution, then drying 12 hours in 110 DEG C of baking oven are placed in, after being roasted 16 hours by 350 DEG C, used
Hydrogen prereduction.Reducing gas is the gaseous mixture (H of hydrogen and nitrogen2:N2=1:10), flow velocity 30mL/min, reduction temperature is
400 DEG C, the recovery time is 6 hours.Obtained 0.01wt%Pt-SO4 2-/WO3-ZrO2Catalyst is labeled as catalyst A.
Embodiment 2 prepares catalyst
Prepare two parts of solution respectively, first part of solution is by 24.1gZrOCl2·8H2O is dissolved in 150mL deionized water, is matched
It is set to the solution that Zr content is 0.5mol/L；Second part of solution is, by 49.3g (NH4)6H2W12O40It is dissolved in 100mL deionized water
In, it is configured to the solution that W content is 2mol/L, adding 30g concentration is 1.5mol/L ammonium hydroxide.After first part of solution prepares,
Under Quick mechanical stirring, second part of solution is slowly added dropwise in first part of solution, used time 30-45 minute is added dropwise to complete.It connects
With ammonium hydroxide by the solution adjust PH=9, continue later stirring 1.5-2 hours.Obtained sediment is filtered, deionized water is used
Washing 4 times.Then the product after washing is placed in 130 DEG C drying 8 hours in baking oven.The solid that will be obtained after dry finish
With SO4 2-Load capacity is the standard dip of 0.5wt% in the H of 0.1mol/L2SO4Solution 12 hours, 280 DEG C after drying 36 hours
It is placed in Muffle furnace, 400 DEG C roast 12 hours.The solids that will be obtained, with Pt load capacity be 0.08wt% iso volumetric impregnation in
H2PtCl612 hours in solution, then drying 16 hours in 130 DEG C of baking oven are placed in, after being roasted 8 hours by 750 DEG C, used
Hydrogen prereduction.Reducing gas is the gaseous mixture (H of hydrogen and nitrogen2:N2=4:6), flow velocity 30mL/min, reduction temperature is
250 DEG C, the recovery time is 12 hours.Obtained 0.08wt%Pt-SO4 2-/WO3-ZrO2Catalyst is labeled as catalyst B.
Embodiment 3 prepares catalyst
Prepare two parts of solution respectively, first part of solution is by 58gZrOCl2·8H2O is dissolved in 150mL deionized water, configuration
The solution for being 1.2mol/L at Zr content, adds 5.8gFeSO4·7H2O is in above-mentioned solution, the wherein matter of Zr salt and Fe salt
Amount is than being 10:1；Second part of solution is, by 4.9g (NH4)6H2W12O40It is dissolved in 100mL deionized water, being configured to W content is
The solution of 0.2mol/L, adding 21g concentration is 3mol/L ammonium hydroxide.After first part of solution prepares, under Quick mechanical stirring,
Second part of solution is slowly added dropwise in first part of solution, used time 30-45 minute is added dropwise to complete.Then with ammonium hydroxide by the solution tune
Agent PH=9 continues stirring 1.5-2 hours later.Obtained sediment is filtered, is washed with deionized 4 times.It then will washing
Product afterwards is placed in 120 DEG C drying 16 hours in baking oven.By the solid obtained after dry finish with H2SO4Load capacity is
The standard dip of 3.5wt% is in the H of 2.5mol/L2SO4Solution 12 hours, 210 DEG C were placed in Muffle furnace in drying 12 hours later
In, 650 DEG C roast 8 hours.The solids that will be obtained is 0.045wt% iso volumetric impregnation in H with Pt load capacity2PtCl6In solution
12 hours, then drying 8 hours in 120 DEG C of baking oven are placed in, after being roasted 8 hours by 500 DEG C, with hydrogen prereduction.Also
Raw-gas is the gaseous mixture (H of hydrogen and nitrogen2:N2=1:3), flow velocity 30mL/min, reduction temperature is 550 DEG C, the recovery time
It is 8 hours.Obtained 0.045wt%Pt-SO4 2-/Fe-WO3-ZrO2Catalyst is labeled as catalyst C.
Embodiment 4 prepares catalyst
Prepare two parts of solution respectively, first part of solution is by 38.7gZrOCl2·8H2O is dissolved in 150mL deionized water, is matched
It is set to the solution that Zr content is 0.8mol/L, adds 35.2gFeSO4·7H2O is in above-mentioned solution, wherein Zr salt and Fe salt
Mass ratio is 1.1:1；Second part of solution is, by 9.9g (NH4)6H2W12O40It is dissolved in 100mL deionized water, is configured to W content
For the solution of 0.4mol/L, adding 26g concentration is 1mol/L ammonium hydroxide.After first part of solution prepares, stirred in Quick mechanical
Under, second part of solution is slowly added dropwise in first part of solution, used time 30-45 minute is added dropwise to complete.Then with ammonium hydroxide that this is molten
Liquid adjustment PH=9, continues stirring 1.5-2 hours later.Obtained sediment is filtered, is washed with deionized 4 times.Then will
Product after washing is placed in 115 DEG C drying 10 hours in baking oven.By the solid obtained after dry finish with SO4 2-Load capacity
For 2.2wt% standard dip in the (NH of 1.2mol/L4)2SO4Solution 30 hours, 180 DEG C were placed in horse in drying 36 hours later
Not in furnace, 450 DEG C are roasted 12 hours.The solids that will be obtained is 0.02wt% iso volumetric impregnation in H with Pt load capacity2PtCl6It is molten
12 hours in liquid, then drying 10 hours in 125 DEG C of baking oven are placed in, after being roasted 10 hours by 650 DEG C, are gone back in advance with hydrogen
It is former.Reducing gas is the gaseous mixture (H of hydrogen and nitrogen2:N2=1:4), flow velocity 30mL/min, reduction temperature is 500 DEG C, also
The former time is 6 hours.Obtained 0.02wt%Pt-SO4 2-/Fe-WO3-ZrO2Catalyst is labeled as catalyst D.
Embodiment 5 prepares catalyst
Prepare two parts of solution respectively, first part of solution is by 29gZrOCl2·8H2O is dissolved in 150mL deionized water, configuration
The solution for being 0.6mol/L at Zr content, adds 12.4gFeSO4·7H2O is in above-mentioned solution, the wherein matter of Zr salt and Fe salt
Amount is than being 7:3；Second part of solution is, by 14.8g (NH4)6H2W12O40It is dissolved in 100mL deionized water, being configured to W content is
The solution of 0.6mol/L, adding 10g concentration is 1mol/L ammonium hydroxide.After first part of solution prepares, under Quick mechanical stirring,
Second part of solution is slowly added dropwise in first part of solution, used time 30-45 minute is added dropwise to complete.Then with ammonium hydroxide by the solution tune
Agent PH=9 continues stirring 1.5-2 hours later.Obtained sediment is filtered, is washed with deionized 4 times.It then will washing
Product afterwards is placed in 125 DEG C drying 14 hours in baking oven.By the solid obtained after dry finish with SO4 2-Load capacity is
The standard dip of 0.5wt% is in (the NH of 0.1mol/L4)2SO4Solution 12 hours, 250 DEG C were placed in Muffle in drying 30 hours later
In furnace, 800 DEG C are roasted 10 hours.The solids that will be obtained is 0.03wt% iso volumetric impregnation in H with Pt load capacity2PtCl6Solution
In 12 hours, then be placed in 120 DEG C of baking oven it is 16 hours dry, after being roasted 8 hours by 600 DEG C, with hydrogen prereduction.
Reducing gas is the gaseous mixture (H of hydrogen and nitrogen2:N2=3:7), flow velocity 30mL/min, reduction temperature is 450 DEG C, when reduction
Between be 8 hours.Obtained 0.03wt%Pt-SO4 2-/Fe-WO3-ZrO2Catalyst is labeled as catalyst E.
Embodiment 6 prepares catalyst
Prepare two parts of solution respectively, first part of solution is by 48.3gZrOCl2·8H2O is dissolved in 150mL deionized water, is matched
It is set to the solution that Zr content is 1mol/L, adds 12.1gFeSO4·7H2O is in above-mentioned solution, the wherein matter of Zr salt and Fe salt
Amount is than being 8:2；Second part of solution is, by 19.7g (NH4)6H2W12O40It is dissolved in 100mL deionized water, being configured to W content is
The solution of 0.8mol/L, adding 12g concentration is 0.8mol/L ammonium hydroxide.After first part of solution prepares, stirred in Quick mechanical
Under, second part of solution is slowly added dropwise in first part of solution, used time 30-45 minute is added dropwise to complete.Then with ammonium hydroxide that this is molten
Liquid adjustment PH=9, continues stirring 1.5-2 hours later.Obtained sediment is filtered, is washed with deionized 4 times.Then will
Product after washing is placed in 130 DEG C drying 10 hours in baking oven.By the solid obtained after dry finish with SO4 2-Load capacity
For 3.5wt% standard dip in the (NH of 2.5mol/L4)2SO4Solution 48 hours, 220 DEG C were placed in horse in drying 36 hours later
Not in furnace, 900 DEG C are roasted 6 hours.The solids that will be obtained is 0.06wt% iso volumetric impregnation in H with Pt load capacity2PtCl6Solution
In 12 hours, then be placed in 120 DEG C of baking oven it is 14 hours dry, after being roasted 10 hours by 450 DEG C, in advance also with hydrogen
It is former.Reducing gas is the gaseous mixture (H of hydrogen and nitrogen2:N2=2:8), flow velocity 30mL/min, reduction temperature is 550 DEG C, also
The former time is 10 hours.Obtained 0.06wt%Pt-SO4 2-/Fe-WO3-ZrO2Catalyst is labeled as catalyst F.
Embodiment 7 prepares catalyst
Prepare two parts of solution respectively, first part of solution is by 67.7gZrOCl2·8H2O is dissolved in 150mL deionized water, is matched
It is set to the solution that Zr content is 1.4mol/L, adds 45.1gFeSO4·7H2O is in above-mentioned solution, wherein Zr salt and Fe salt
Mass ratio is 6:4；Second part of solution is, by 32g (NH4)6H2W12O40It is dissolved in 100mL deionized water, being configured to W content is
The solution of 1.3mol/L, adding 47g concentration is 1.5mol/L ammonium hydroxide.After first part of solution prepares, stirred in Quick mechanical
Under, second part of solution is slowly added dropwise in first part of solution, used time 30-45 minute is added dropwise to complete.Then with ammonium hydroxide that this is molten
Liquid adjustment PH=9, continues stirring 1.5-2 hours later.Obtained sediment is filtered, is washed with deionized 4 times.Then will
Product after washing is placed in 110 DEG C drying 16 hours in baking oven.By the solid obtained after dry finish with SO4 2-Load capacity
For 3wt% standard dip in the (NH of 2mol/L4)2SO4Solution 28 hours, 200 DEG C were placed in Muffle furnace in drying 20 hours later
In, 700 DEG C roast 8 hours.The solids that will be obtained is 0.07wt% iso volumetric impregnation in H with Pt load capacity2PtCl612 in solution
Hour, then drying 8 hours in 125 DEG C of baking oven are placed in, after being roasted 12 hours by 550 DEG C, with hydrogen prereduction.Reduction
Gas is the gaseous mixture (H of hydrogen and nitrogen2:N2=1:9), flow velocity 30mL/min, reduction temperature is 370 DEG C, and the recovery time is
8 hours.Obtained 0.07wt%Pt-SO4 2-/Fe-WO3-ZrO2Catalyst is labeled as catalyst G.
Embodiment 8 prepares catalyst
Change the Zr salt in embodiment 4 into zirconium nitrate, W salt changes sodium tungstate into, and other steps are identical, finally obtain catalyst
H。
Embodiment 9 prepares catalyst
Change the Fe salt in embodiment 6 into ferric nitrate, other steps are identical, finally obtain catalyst I.
10 catalyst A of embodiment is used for n-pentane isomerization reaction
5 grams of catalyst A are fitted into 10mL fixed bed reactors, at 200 DEG C, activates 2 hours under hydrogen atmosphere, then cuts
It changes and is reacted containing pentane.Reaction condition: 120 DEG C of temperature, system pressure 10MPa, hydrogen partial pressure 1MPa, air speed 0.1h-1.Instead
Sampling analysis after answering 2 hours, pentane conversion ratio 65.2%, isopentane are selectively 98.2%.
11 catalyst A of embodiment is used for n-pentane isomerization reaction
5 grams of catalyst A are fitted into 10mL fixed bed reactors, at 250 DEG C, activates 2 hours under hydrogen atmosphere, then cuts
The pentane for changing the isopentane containing 80% is reacted.Reaction condition: 250 DEG C of temperature, system pressure 5MPa, hydrogen partial pressure
0.5MPa, air speed 6h-1, the molar ratio of hydrogen and pentane is 1:2.Sampling analysis see the table below 1 after reaction different time.
Table 1
12 catalyst A of embodiment is used for n-pentane isomerization reaction
5 grams of catalyst A are fitted into 10mL fixed bed reactors, at 190 DEG C, activates 4 hours under hydrogen atmosphere, then cuts
The pentane for changing the isopentane containing 40% is reacted.Reaction condition: 185 DEG C of temperature, system pressure 0.1MPa, hydrogen partial pressure
0.1MPa, air speed 3h-1, the molar ratio of hydrogen and pentane is 1:2.Sampling analysis see the table below 2 after reaction different time.
Table 2
13 catalyst A of embodiment is used for n-pentane isomerization reaction
5 grams of catalyst A are fitted into 10mL fixed bed reactors, at 180 DEG C, activates 2 hours under hydrogen atmosphere, then cuts
The pentane for changing the isopentane containing 20% is reacted.Reaction condition: 200 DEG C of temperature, system pressure 2MPa, hydrogen partial pressure
0.8MPa, air speed 2h-1, the molar ratio of hydrogen and pentane is 1:3.Sampling analysis after reaction 2 hours, pentane conversion ratio
48.3%, isopentane is selectively 97.8%.
14 catalyst A of embodiment is used for n-pentane isomerization reaction
5 grams of catalyst A are fitted into 10mL fixed bed reactors, at 230 DEG C, activates 2 hours under hydrogen atmosphere, then cuts
The pentane for changing the isopentane containing 70% is reacted.Reaction condition: 230 DEG C of temperature, system pressure 7MPa, hydrogen partial pressure
The molar ratio of 0.85MPa, hydrogen and pentane is 1:1.After reaction 2 hours, reaction sampling analysis under different air speeds be see the table below
3。
Table 3
15 catalyst B of embodiment is used for n-pentane isomerization reaction
5 grams of catalyst B are fitted into 10mL fixed bed reactors, at 220 DEG C, activates 2 hours under hydrogen atmosphere, then cuts
The pentane for changing the isopentane containing 50% is reacted.Reaction condition: 220 DEG C of temperature, system pressure 6MPa, hydrogen partial pressure
1MPa, air speed 5h-1, the molar ratio of hydrogen and pentane is 1:4.Sampling analysis after reaction 2 hours, pentane conversion ratio
55.3%, isopentane is selectively 98.1%.
16 catalyst C of embodiment is used for n-pentane isomerization reaction
5 grams of catalyst C are fitted into 10mL fixed bed reactors, at 220 DEG C, activates 2 hours under hydrogen atmosphere, then cuts
The pentane for changing the isopentane containing 40% is reacted.Reaction condition: 210 DEG C of temperature, system pressure 5MPa, hydrogen partial pressure
1MPa, air speed 1.5h-1, the molar ratio of hydrogen and pentane is 1:1.Sampling analysis after reaction 2 hours, pentane conversion ratio
58.0%, isopentane is selectively 98.0%.
17 catalyst D of embodiment is used for n-pentane isomerization reaction
5 grams of catalyst D are fitted into 10mL fixed bed reactors, at 220 DEG C, activates 2 hours under hydrogen atmosphere, then cuts
The pentane for changing the isopentane containing 10% is reacted.Reaction condition: 220 DEG C of temperature, system pressure 4.5MPa, hydrogen partial pressure
0.7MPa, air speed 2.5h-1, the molar ratio of hydrogen and pentane is 1:2.Sampling analysis after reaction 2 hours, pentane conversion ratio
60.4%, isopentane is selectively 98.7%.
18 catalyst E of embodiment is used for n-pentane isomerization reaction
5 grams of catalyst E are fitted into 10mL fixed bed reactors, at 220 DEG C, activates 2 hours under hydrogen atmosphere, then cuts
The pentane for changing the isopentane containing 25% is reacted.Reaction condition: 240 DEG C of temperature, system pressure 8MPa, hydrogen partial pressure
0.9MPa, air speed 3.5h-1, the molar ratio of hydrogen and pentane is 2:1.Sampling analysis after reaction 2 hours, pentane conversion ratio
63.5%, isopentane is selectively 97.9%.
19 catalyst F of embodiment is used for n-pentane isomerization reaction
5 grams of catalyst F are fitted into 10mL fixed bed reactors, at 220 DEG C, activates 2 hours under hydrogen atmosphere, then cuts
The pentane for changing the isopentane containing 10% is reacted.Reaction condition: 250 DEG C of temperature, system pressure 3.5MPa, hydrogen partial pressure
1MPa, air speed 1.5h-1, the molar ratio of hydrogen and pentane is 1:1.Sampling analysis after reaction 2 hours, pentane conversion ratio
59.2%, isopentane is selectively 98.3%.
20 catalyst G of embodiment is used for n-pentane isomerization reaction
5 grams of catalyst G are fitted into 10mL fixed bed reactors, at 220 DEG C, activates 2 hours under hydrogen atmosphere, then cuts
The pentane for changing the isopentane containing 10% is reacted.Reaction condition: 220 DEG C of temperature, system pressure 2.5MPa, hydrogen partial pressure
0.3MPa, air speed 0.5h-1, the molar ratio of hydrogen and pentane is 1:3.Sampling analysis after reaction 2 hours, pentane conversion ratio
55.5%, isopentane is selectively 97.7%.
21 catalyst H of embodiment is used for n-pentane isomerization reaction
5 grams of catalyst H are fitted into 10mL fixed bed reactors, at 160 DEG C, activates 4 hours under hydrogen atmosphere, then cuts
The pentane for changing the isopentane containing 65% is reacted.Reaction condition: 130 DEG C of temperature, system pressure 6.5MPa, hydrogen partial pressure
0.8MPa, air speed 0.4h-1, the molar ratio of hydrogen and pentane is 1:2.Sampling analysis after reaction 2 hours, pentane conversion ratio
26.7%, isopentane is selectively 97.3%.
22 catalyst I of embodiment is used for n-pentane isomerization reaction
5 grams of catalyst I are fitted into 10mL fixed bed reactors, at 220 DEG C, activates 2 hours under hydrogen atmosphere, then cuts
The pentane for changing the isopentane containing 55% is reacted.Reaction condition: 245 DEG C of temperature, system pressure 6MPa, hydrogen partial pressure
1MPa, air speed 0.5h-1, the molar ratio of hydrogen and pentane is 1:2.Sampling analysis after reaction 2 hours, pentane conversion ratio
50.9%, isopentane is selectively 98.5%.
When using pentane or material containing pentane is reaction raw materials, reaction temperature is higher, pentane conversion ratio
It is higher, but due to exothermic reaction when isomerization of paraffins reacts, limited by thermodynamical equilibrium, under high temperature, conversion ratio then can
Decline.Low-speed is conducive to pentane conversion ratio, but not is more than thermodynamic limit.It is used for using solid ultra strong acid type catalyst
The isomerization reaction of n-alkane especially pentane can obtain higher activity and selectivity under higher alkane air speed.
Certain hydrogen partial pressure is kept in reaction atmosphere, and the normal alkane isomerization performance of solid super acid catalyst can be improved,
And greatly improve its stability.
Claims (11)
1. a kind of preparation method of light n-alkane isomerization catalyst, includes the following steps:
A. in deionized water by the salt dissolution containing Zr, it is 0.5-2mol/L that mixed solution concentration, which is made,；
B. the salt containing W is dissolved in deionized water, adds concentrated ammonia liquor, being configured to W content is 0.2-2mol/L and ammonium hydroxide content
The mixed solution of 0.5-3mol/L；
C. under intense agitation, the solution in b was added drop-wise in the solution in step a with 30-45 minutes, it is added dropwise
Afterwards, pH=9 is adjusted with ammonium hydroxide, obtains the suspension of precipitating, is then stirred for 1.5-2 hours；
D. sediment c obtained filters, then the product after washing is placed in 110 DEG C of -130 DEG C of dryings in baking oven by washing
8-16 hours；
E. the H of 0.1-2.5mol/L is used2SO4Or (NH4)2SO4Dipping 12-48 hours, so that SO4 2-Impregnation increment reaches certain value,
Then by 150 DEG C -280 DEG C after dry 12-36 hours, in 400-900 DEG C roasting 4-12 hours；
Pt is carried in e and obtains product by f. iso volumetric impregnation method, and the load capacity of Pt is 0.01-0.08wt%, with solid super-strong acid
Overall catalyst weight meter；
G. product f obtained in 110-130 DEG C after dry 8-16 hours, in 350-750 DEG C roasting 8-16 hours；
H. product g obtained in 250-550 DEG C reduction 6-12 hours.
2. the preparation method of light n-alkane isomerization catalyst according to claim 1, it is characterised in that: step a
In, the salt containing Fe is further added, the quality amount ratio of the salt containing Zr and the salt containing Fe is 1.1:1~10:1.
3. the preparation method of light n-alkane isomerization catalyst according to claim 2, it is characterised in that: described to contain
The salt of Fe is ferrous sulfate or ferric nitrate.
4. the preparation method of described in any item light n-alkane isomerization catalysts, feature exist according to claim 1~3
In: in step a, the salt containing Zr is zirconium nitrate or zirconium oxychloride.
5. the preparation method of described in any item light n-alkane isomerization catalysts, feature exist according to claim 1~3
In: in step b, the salt containing W is ammonium metatungstate or sodium tungstate.
6. the preparation method of described in any item light n-alkane isomerization catalysts, feature exist according to claim 1~3
In: in step e, the SO4 2-Impregnation increment reaches 0.5~3.5wt%SO4 2-, with solid super acid catalyst total weight.
7. the preparation method of described in any item light n-alkane isomerization catalysts, feature exist according to claim 1~3
In: reducing condition is restored in mixed atmosphere in step h, and the volume ratio of hydrogen and nitrogen is 1:10~4:6.
8. a kind of isomerization method of light normal paraffin, the light normal paraffin is the n-alkane of C4-C8, and feature exists
In: solid super acid catalyst is used, in the reaction atmosphere there are hydrogen, reaction raw materials is made to carry out isomerization processing,
In, hydrogen partial pressure 0.1-1.0MPa, the solid super acid catalyst is to prepare as described in any one of claim 1~7
Method is made.
9. the isomerization method of light normal paraffin according to claim 8, it is characterised in that: N-alkanes in reaction raw materials
The mass percentage of hydrocarbon is 20-100%.
10. the isomerization method of light normal paraffin according to claim 8, it is characterised in that: in reaction raw materials just
Structure alkane is pentane.
11. according to the isomerization method of the described in any item light normal paraffins of claim 8~10, it is characterised in that: isomery
Changing reaction temperature is 120-250 DEG C, and isomerization reaction pressure is 0.1-10MPa, and the air speed of isomerization reaction raw material is 0.1-6h-1。
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|---|---|---|---|---|
| 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 |
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| 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 |
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| Title |
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| "Isomerization of n-alkanes on Pt/WO3-SO4/ZrO2 systems";A.V. Ivanov et al;《Catalysis Today》;20020401;第73卷;摘要，第1-2节 |
| "WO3/ZrO2固体酸催化剂的制备及应用研究进展";李言 等;《分子催化》;20111031;第25卷(第5期);第1节：WO3/ZrO2固体酸的制备方法 |
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