CN109908944A - A kind of oligomerization of propene prepares the catalyst and preparation method thereof of nonene and laurylene - Google Patents
A kind of oligomerization of propene prepares the catalyst and preparation method thereof of nonene and laurylene Download PDFInfo
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Abstract
The invention belongs to chemical fields, and in particular to a kind of oligomerization of propene prepares the catalyst and preparation method thereof of nonene and laurylene.After active component is carried on alumina support by the present invention, then in alumina support periphery load molecular sieve, form the core-shell structure of molecular sieve coated alumina.Under the premise of giving full play to molecular sieve catalytic performance, increases support inside alumina support, effectively increase the intensity of catalyst, avoid the dusting of simple molecular sieve；Active component is located inside molecular sieve, it is not easy to which the loss for causing active component improves stability and the service life of catalyst；Since molecular sieve and Alumina spheres form nucleocapsid shape, and the aluminium oxide of molecular sieve and the active component of load all has catalytic activity, form step catalytic action, unreacted raw material enters aluminum oxide molecular sieve and further reacts on peripheral molecular sieve, the catalytic action of the aluminium oxide of molecular sieve and the active component of load forms addition, the further promotion of active and selectivity.
Description
Technical field
The invention belongs to chemical fields, and in particular to a kind of oligomerization of propene prepares the catalyst and its system of nonene and laurylene
Preparation Method.
Background technique
The trimer nonene of the importance that propylene comprehensively utilizes when propylene oligomerization, the third refining can be used as higher octane
Be worth gasoline addO-on therapy, and nonyl it is dilute can also be used in manufacture nonyl phenol, nonyl phenol is the original for preparing agricultural emulsifier and detergent
Material；Propylene tetramer 12 is dilute also an extensive use, for example, as 12 it is dilute made from vulcanization dodecylphenol calcium be exactly one
The good lube oil additive of kind.
The preparation of catalyst is the emphasis of oligomerization of propene research, and an important factor for influence oligomerization of propene Technique Popularizing.
The catalyst for being currently used for oligomerization of propene mainly has solid acid catalyst, carried molecular sieve catalyst and based on ion liquid type
Catalyst.Catalyst for oligomerization most widely used at present is exactly solid phosphoric acid catalyst, and solid phosphoric acid catalyst is although at low cost, living
Property it is high, but the disadvantages of catalyst easily argillization blocks pipeline, and equipment is be easy to cause to corrode, and the reaction service life is short, and technological operation is difficult.
Industrial applications are still not implemented because expensive in the Ni-based complex compound of the similar ionic liquid of Inst Francais Du Petrole's exploitation.And support type point
Sub- sieve catalyst type is especially more, and has many advantages, such as that preparation method is simple and thermal stability is good.In recent years, it is widely used
In the research of olefin oligomerization.But mostly research is that lab scale is studied in laboratory, is unable to satisfy the work of high load capacity, enlargement
Intensity and activity after industry application requirement, especially shaping of catalyst can not meet industrial application requirement simultaneously, therefore be badly in need of opening
Hair is high-intensitive, the novel propylene catalyst for oligomerization of high activity and service life length.
Summary of the invention
The present invention above-mentioned propene oligomer catalyst there are aiming at the problem that, invention provides a kind of oligomerization of propene preparation nonyl
Alkene, catalyst of laurylene and preparation method thereof, the catalyst of invention preparation have high-intensitive, high activity and highly selective excellent
Point, and catalyst long service life.
The technical solution adopted by the invention is as follows:
The invention also includes the preparation methods of above-mentioned catalyst, comprising the following steps:
S1, suitable active component presoma is carried on γ-Al2O3It is calcined after sphere, obtains the forerunner of modified catalyst
Body；
S2, ammonium hydroxide and template are uniformly mixed, obtain solution A；
S3, aluminium salt is dissolved in deionized water, while the resulting catalyst precursor of step 1 is added, stirring a period of time
After obtain solution B；
S4, it is stirred solution A and solution B to obtain solution C；
S5, solution C is slowly added in silicon source solution, obtains collosol and gel, while be added into the collosol and gel inorganic
Acid solution or ammonia spirit adjust pH value to 9.0~11.0, obtain solution D；
S6, the solution D is transferred in autoclave, takes out reaction product after crystallization a few hours at a certain temperature
And be filtered, washed solution to neutrality and obtain filter cake, by filtration cakes torrefaction, roasting, obtain composite catalyst.
Further, the presoma of the active component include its sulfate, nitrate, chloride, in metal form
One or more mixing.
Further, the active component is supported on γ-Al2O3On method include infusion process, the precipitation method, physical mixed
The combination of one or more of method.When the presoma of active component is salt, it can be used and salt is configured to solution, pass through leaching
Stain is supported on carrier, is roasted after being subsequently dried；Or alkali, such as the formation of sodium carbonate, sodium hydroxide is added in salting liquid
Precipitating, is deposited metal on carrier using the precipitation method；When the presoma of active component is solid-oxide, object can use
Manage mixing method mixing.If active component is variant for the presoma of multicomponent or each component, a variety of methods can be selected to join
With being loaded step by step.
Further, the template is tetrabutylammonium bromide, tetrabutylammonium hydroxide, in tetraethylammonium bromide and tetrem
At least one of base ammonium hydroxide.
Further, source of aluminium is at least one of aluminium chloride, aluminum sulfate or aluminum nitrate, and wherein silicon source is with Al2O3
Meter；The silicon source is at least one of silica solution, ethyl orthosilicate/butyl silicate, and wherein silicon source is with SiO2Meter；With quality
Meter, silica alumina ratio SiO2/Al2O3=50~200, template/SiO2=0.01~0.2.The temperature of the crystallization is 80 DEG C~200
DEG C, time of crystallization is 2h~for 24 hours.The drying temperature of filter cake is 100 DEG C~120 DEG C, and maturing temperature is 400 DEG C~600 DEG C, roasting
The burning time is 2h~10h.
Further, the inorganic acid solution is the one or more of hydrochloric acid, sulfuric acid or nitric acid.
The invention also includes the catalyst that a kind of oligomerization of propene prepares nonene and laurylene, are prepared using the above method, institute
State active component presoma and γ-Al2O3Mass ratio are as follows: 0.02-0.3；The aluminium salt with γ-Al2O3Mass ratio are as follows:
0.5-2.By aluminium salt and γ-Al2O3Limited proportion, then by system with molecular sieve for preparing for when silica alumina ratio limit, then define molecule
The ratio of sieve and alumina support.Molecular sieve is excessively unfavorable for the promotion of catalyst strength, outer layer under the conditions of long-play
The easy dusting of molecular sieve is so that service life reduction；Molecular sieve content is lower, is unfavorable for giving full play to the catalytic action of molecular sieve,
It cannot be to γ-Al2O3Effective package is formed, it can be less than preferable protection, so that under operation stability so that active component is exposed
Drop.
Further, the γ-Al2O3Sphere has carried out the washing of Na ion, and γ-Al2O3Sphere diameter is 2-5mm.
Sodium ion will affect catalyst to the selectivity of target product, it is therefore desirable to avoid being added in synthesis.
The invention has the benefit that the present invention is prepared for the composite catalyst structure of case type, molecule is being given full play to
Under the premise of sieving catalytic performance, increases support inside alumina support, mixed compared to traditional carrier, effectively increase catalysis
The intensity of agent avoids the dusting of simple molecular sieve；And active component auxiliary agent is loaded on alumina support, due to aluminium oxide
Special aperture, improves the dispersibility of active component, and then improves the activity and selectivity of catalyst；Active component is loaded
On the alumina support, periphery is protected by molecular sieve, it is not easy to which the loss for causing active component improves the steady of catalyst
The qualitative and service life；Since molecular sieve and Alumina spheres form nucleocapsid shape, and molecular sieve and the oxidation for loading active component
Aluminium all has catalytic activity, therefore forms step catalytic action, and some raw materials unreacted on peripheral molecular sieve enter oxidation
Aluminum molecular screen further reacts, and the catalytic action of the aluminium oxide of molecular sieve and the active component of load forms addition, activity and choosing
Selecting property is further promoted.
Specific embodiment
All features disclosed in this specification or disclosed all methods or in the process the step of, in addition to mutually exclusive
Feature and/or step other than, can combine in any way.
Embodiment 1
1, in terms of mass parts, 0.1 part of nickel nitrate is dissolved in 1 part of deionized water, 1 part of γ-Al is added2O3Sphere stirring leaching
120 DEG C of drying, 500 DEG C of calcining 4h, obtain the presoma of modified catalyst after stain；
2,10 parts of ammonium hydroxide and 5 parts of tetrabutylammonium bromide, 200 parts of deionized waters are uniformly mixed, obtain solution A；
3,1 part of aluminum sulfate and 200 parts of deionized waters are uniformly mixed, while before above-mentioned 1 resulting catalyst is added
Body is driven, obtains solution B after stirring a period of time；
4, it is stirred solution A and solution B to obtain solution C；
5, solution C is slowly added in 50 parts of silica solution (25%) solution, obtains collosol and gel, while to the collosol and gel
Middle addition dilute nitric acid solution or ammonia spirit adjust pH value to 9.0~11.0, obtain solution D；
6, the solution D is transferred in autoclave, takes out reaction product after crystallization 12h at being 180 DEG C in temperature
And be filtered, washed solution to neutrality and obtain filter cake, by 110 DEG C of dryings of filter cake, 500 DEG C of roasting 5h, obtain the composite catalyst.
Embodiment 2:
1, in terms of mass parts, 0.05 part of lead chloride is dissolved in 1 part of deionized water, 1 part of γ-Al is added2O3Sphere stirring leaching
120 DEG C of stain drying, 500 DEG C of calcining 4h, obtain the presoma of modified catalyst；
2,10 parts of ammonium hydroxide and 5 parts of tetrabutylammonium hydroxide, 200 parts of deionized waters are uniformly mixed, obtain solution A；
3,1 part of aluminum nitrate and 200 parts of deionized waters are uniformly mixed, while before above-mentioned 1 resulting catalyst is added
Body is driven, obtains solution B after stirring a period of time；
4, it is stirred solution A and solution B to obtain solution C；
5, solution C is slowly added in 100 teos solutions, obtains collosol and gel, while into the collosol and gel
Dilute nitric acid solution or ammonia spirit is added, adjusts pH value to 9.0~11.0, obtains solution D；
6, the solution D is transferred in autoclave, crystallization takes out reaction product simultaneously afterwards for 24 hours at 150 DEG C of temperature
It is filtered, washed solution to neutrality and obtains filter cake, by 110 DEG C of dryings of filter cake, 500 DEG C of roasting 5h, obtain the composite catalyst.
Embodiment 3:
1, in terms of mass parts, 0.2 part of nickel nitrate is dissolved in 1 part of deionized water, 1 part of γ-Al is added2O3Sphere stirring leaching
120 DEG C of drying, 500 DEG C of calcining 4h, obtain the presoma of modified catalyst after stain；
2,10 parts of ammonium hydroxide and 5 parts of tetraethylammonium bromides, 200 parts of deionized waters are uniformly mixed, obtain solution A；
3,1 part of aluminum sulfate and 200 parts of deionized waters are uniformly mixed, while before above-mentioned 1 resulting catalyst is added
Body is driven, obtains solution B after stirring a period of time；
4, it is stirred solution A and solution B to obtain solution C；
5, solution C is slowly added in 150 parts of silica solution (25%) solution, obtains collosol and gel, while solidifying to the colloidal sol
Dilute nitric acid solution or ammonia spirit are added in glue, adjusts pH value to 9.0~11.0, obtains solution D；
6, the solution D is transferred in autoclave, takes out reaction product simultaneously after crystallization 12h at 150 DEG C of temperature
It is filtered, washed solution to neutrality and obtains filter cake, by 110 DEG C of dryings of filter cake, 500 DEG C of roasting 5h, obtain the composite catalyst.
Embodiment 4:
1, in terms of mass parts, 0.03 part of nickel chloride is dissolved in 1 part of deionized water, 1 part of γ-Al is added2O3Sphere stirring leaching
120 DEG C of drying, 500 DEG C of calcining 4h, obtain the presoma of modified catalyst after stain；
2,10 parts of ammonium hydroxide and 5 parts of mould tetraethyl ammonium hydroxides, 200 parts of deionized waters are uniformly mixed, obtain solution
A；
3,1 part of aluminium chloride and 200 parts of deionized waters are uniformly mixed, while before above-mentioned 1 resulting catalyst is added
Body is driven, obtains solution B after stirring a period of time；
4, it is stirred solution A and solution B to obtain solution C；
5, solution C is slowly added in 200 parts of silica solution (25%) solution, obtains collosol and gel, while solidifying to the colloidal sol
Dilute hydrochloric acid solution or ammonia spirit are added in glue, adjusts pH value to 9.0~11.0, obtains solution D；
6, the solution D is transferred in autoclave, crystallization takes out reaction product simultaneously afterwards for 24 hours at 200 DEG C of temperature
It is filtered, washed solution to neutrality and obtains filter cake, by 110 DEG C of dryings of filter cake, 500 DEG C of roasting 5h, obtain the composite catalyst.
Embodiment 5:
1, in terms of mass parts, 0.03 part of zirconium chloride is dissolved in 1 part of deionized water, 1 part of γ-Al is added2O3Sphere stirring leaching
120 DEG C of drying, 500 DEG C of calcining 4h, obtain the presoma of modified catalyst after stain；
2,10 parts of ammonium hydroxide and 5 parts of tetraethylammonium bromides, 200 parts of deionized waters are uniformly mixed, obtain solution A；
3,1 part of aluminium chloride and 200 parts of deionized waters are uniformly mixed, while before above-mentioned 1 resulting catalyst is added
Body is driven, obtains solution B after stirring a period of time；
4, it is stirred solution A and solution B to obtain solution C；
5, solution C is slowly added in 200 parts of silica solution (25%) solution, obtains collosol and gel, while solidifying to the colloidal sol
Dilution heat of sulfuric acid or ammonia spirit are added in glue, adjusts pH value to 9.0~11.0, obtains solution D；
6, the solution D is transferred in autoclave, crystallization takes out reaction product simultaneously afterwards for 24 hours at 200 DEG C of temperature
It is filtered, washed solution to neutrality and obtains filter cake, by 110 DEG C of dryings of filter cake, 500 DEG C of roasting 5h, obtain the composite catalyst.
Embodiment 6:
1, in terms of mass parts, 0.02 part of zirconium chloride and 0.02 part of nickel chloride are dissolved in 1 part of deionized water, 1 part of γ-is added
Al2O3120 DEG C of drying, 500 DEG C of calcining 4h after sphere stirring dipping, obtain the presoma of modified catalyst；
2,10 parts of ammonium hydroxide and 5 parts of tetrabutylammonium bromide, 200 parts of deionized waters are uniformly mixed, obtain solution A；
3,1 part of aluminium chloride and 200 parts of deionized waters are uniformly mixed, while before above-mentioned 1 resulting catalyst is added
Body is driven, obtains solution B after stirring a period of time；
4, it is stirred solution A and solution B to obtain solution C；
5, solution C is slowly added in 200 parts of silica solution (25%) solution, obtains collosol and gel, while solidifying to the colloidal sol
Dilute nitric acid solution or ammonia spirit are added in glue, adjusts pH value to 9.0~11.0, obtains solution D；
6, the solution D is transferred in autoclave, crystallization takes out reaction product simultaneously afterwards for 24 hours at 200 DEG C of temperature
It is filtered, washed solution to neutrality and obtains filter cake, by 110 DEG C of dryings of filter cake, 500 DEG C of roasting 5h, obtain the composite catalyst.
Embodiment 7
1, in terms of mass parts, 0.04 part of lanthanum nitrate is dissolved in 1 part of deionized water, 1 part of γ-Al is added2O3Sphere stirring leaching
120 DEG C of drying, 500 DEG C of calcining 4h, obtain the presoma of modified catalyst after stain；
2,10 parts of ammonium hydroxide and 5 parts of tetrabutylammonium bromide, 200 parts of deionized waters are uniformly mixed, obtain solution A；
3,1 part of aluminum sulfate and 200 parts of deionized waters are uniformly mixed, while before above-mentioned 1 resulting catalyst is added
Body is driven, obtains solution B after stirring a period of time；
4, it is stirred solution A and solution B to obtain solution C；
5, solution C is slowly added in 150 parts of silica solution (25%) solution, obtains collosol and gel, while solidifying to the colloidal sol
Dilute nitric acid solution or ammonia spirit are added in glue, adjusts pH value to 9.0~11.0, obtains solution D；
6, the solution D is transferred in autoclave, takes out reaction product simultaneously after crystallization 12h at 150 DEG C of temperature
It is filtered, washed solution to neutrality and obtains filter cake, by 110 DEG C of dryings of filter cake, 500 DEG C of roasting 5h, obtain the composite catalyst.
Comparative example 1:
1, in terms of mass parts, 10 parts of ammonium hydroxide and 5 parts of tetraethylammonium bromides, 200 parts of deionized waters is uniformly mixed, are obtained
To solution A；
2,1 part of aluminum sulfate, 0.2 part of nickel nitrate and 200 parts of deionized waters are uniformly mixed, while above-mentioned 1 institute is added
The catalyst precursor obtained obtains solution B after stirring a period of time；
3, it is stirred solution A and solution B to obtain solution C；
4, solution C is slowly added in 150 parts of silica solution (25%) solution, obtains collosol and gel, while solidifying to the colloidal sol
Dilute nitric acid solution or ammonia spirit are added in glue, adjusts pH value to 9.0~11.0, obtains solution D；
5, the solution D is transferred in autoclave, takes out reaction product simultaneously after crystallization 12h at 150 DEG C of temperature
It is filtered, washed solution to neutrality and obtains filter cake, by 110 DEG C of dryings of filter cake, 500 DEG C of roasting 5h, obtain the composite catalyst
It by gained oligomerization of propene molecular sieve catalyst tabletting and sieves, takes 20~40 mesh particles for propylene oligomerization
Activity rating, activity rating data are shown in Table 1.
Comparative example 2
1, in terms of mass parts, 10 parts of ammonium hydroxide and 5 parts of tetraethylammonium bromides, 200 parts of deionized waters is uniformly mixed, are obtained
To solution A；
2,1 part of aluminum sulfate and 200 parts of deionized waters are uniformly mixed, while before above-mentioned 1 resulting catalyst is added
Body is driven, obtains solution B after stirring a period of time；
3, it is stirred solution A and solution B to obtain solution C；
4, solution C is slowly added in 150 parts of silica solution (25%) solution, obtains collosol and gel, while solidifying to the colloidal sol
Dilute nitric acid solution or ammonia spirit are added in glue, adjusts pH value to 9.0~11.0, obtains solution D；
5, the solution D is transferred in autoclave, takes out reaction product simultaneously after crystallization 12h at 150 DEG C of temperature
It is filtered, washed solution to neutrality and obtains filter cake, by 110 DEG C of dryings of filter cake, 500 DEG C of roasting 5h, obtain molecular sieve.
6, it takes above-mentioned molecular sieve powder to be added to the water, obtains homogeneous slurry；1 part of γ-Al is added into slurries2O3Powder is mixed
It closes, water bath with thermostatic control is simultaneously stirred；0.2 part of nickel nitrate solution is added into above-mentioned slurries and obtains mixed serum, mixed serum is placed in
It is stirred to react in water bath with thermostatic control, obtains finished catalyst through 120 DEG C of dryings, 500 DEG C of roasting 4h, molding.
Comparative example 3
1, in terms of mass parts, 10 parts of ammonium hydroxide and 5 parts of tetraethylammonium bromides, 200 parts of deionized waters is uniformly mixed, are obtained
To solution A；
2,1 part of aluminum sulfate, 0.2 part of nickel nitrate and 200 parts of deionized waters are uniformly mixed, while above-mentioned 1 institute is added
The catalyst precursor obtained, adds 1 part of γ-Al2O3Sphere obtains solution B after stirring a period of time；
3, it is stirred solution A and solution B to obtain solution C；
4, solution C is slowly added in 150 parts of silica solution (25%) solution, obtains collosol and gel, while solidifying to the colloidal sol
Dilute nitric acid solution or ammonia spirit are added in glue, adjusts pH value to 9.0~11.0, obtains solution D；
5, the solution D is transferred in autoclave, takes out reaction product simultaneously after crystallization 12h at 150 DEG C of temperature
It is filtered, washed solution to neutrality and obtains filter cake, by 110 DEG C of dryings of filter cake, 500 DEG C of roasting 5h, obtain the composite catalyst.
Comparative example 4
1, in terms of mass parts, 0.1 part of nickel nitrate is dissolved in 1 part of deionized water, 1 part of γ-Al is added2O3Sphere stirring leaching
120 DEG C of drying, 500 DEG C of calcining 4h, obtain the presoma of modified catalyst after stain；
2,4 parts of ammonium hydroxide and 2 parts of tetrabutylammonium bromide, 80 parts of deionized waters are uniformly mixed, obtain solution A；
3,0.4 part of aluminum sulfate and 80 parts of deionized waters are uniformly mixed, while before above-mentioned 1 resulting catalyst is added
Body is driven, obtains solution B after stirring a period of time；
4, it is stirred solution A and solution B to obtain solution C；
5, solution C is slowly added in 20 parts of silica solution (25%) solution, obtains collosol and gel, while to the collosol and gel
Middle addition dilute nitric acid solution or ammonia spirit adjust pH value to 9.0~11.0, obtain solution D；
6, the solution D is transferred in autoclave, takes out reaction product after crystallization 12h at being 180 DEG C in temperature
And be filtered, washed solution to neutrality and obtain filter cake, by 110 DEG C of dryings of filter cake, 500 DEG C of roasting 5h, obtain the composite catalyst.
Comparative example 5
1, in terms of mass parts, 0.2 part of nickel nitrate is dissolved in 1 part of deionized water, 1 part of γ-Al is added2O3Sphere stirring leaching
120 DEG C of drying, 500 DEG C of calcining 4h, obtain the presoma of modified catalyst after stain；
2,25 parts of ammonium hydroxide and 12.5 parts of tetraethylammonium bromides, 500 parts of deionized waters are uniformly mixed, obtain solution A；
3,2.5 parts of aluminum sulfate and 500 parts of deionized waters are uniformly mixed, while above-mentioned 1 resulting catalyst is added
Presoma obtains solution B after stirring a period of time；
4, it is stirred solution A and solution B to obtain solution C；
5, solution C is slowly added in 375 parts of silica solution (25%) solution, obtains collosol and gel, while solidifying to the colloidal sol
Dilute nitric acid solution or ammonia spirit are added in glue, adjusts pH value to 9.0~11.0, obtains solution D；
6, the solution D is transferred in autoclave, takes out reaction product simultaneously after crystallization 12h at 150 DEG C of temperature
It is filtered, washed solution to neutrality and obtains filter cake, by 110 DEG C of dryings of filter cake, 500 DEG C of roasting 5h, obtain the composite catalyst.
Activity rating
It by gained oligomerization of propene molecular sieve catalyst tabletting and sieves, takes 20~40 mesh particles for propylene oligomerization
Activity rating, activity rating data are shown in Table 1.The activity rating condition of table 1: using propylene as reaction raw materials, reaction temperature
For 120 DEG C, 2.5MPa, mass space velocity 2.0h-1Reaction condition under, load catalyst 6g obtained by each example respectively, it is to be evaluated
After device stable operation for 24 hours, following catalyst activity data are measured.
The activity rating tables of data of 1 catalyst of table
By data in table 1 as it can be seen that the oligomerization of propene composite catalyst that the method for the present invention is prepared can significantly improve catalyst
Oligomerization of propene performance, propylene conversion, nonene and laurylene selectivity are higher.
Strength test
Intensity workouts are implemented to above-mentioned each catalyst using DL3 intelligence detector for strength of particles, the intensity of adsorbent is with diameter
It is indicated to anti-crushing power, detection method is carried out referring to HB/T2782-1996.Testing machine range is (0~300) N, sample measurement
Granule number is 50, the mechanical strength of sample is calculated with the arithmetic mean of instantaneous value of 50 measurement results, numerical value is with newton (N/ per cm
Cm it) indicates.
The intensity data table of 2 catalyst of table
By data in table 2 as it can be seen that the oligomerization of propene composite catalyst that the method for the present invention is prepared can significantly improve catalyst
Intensity solves the problems, such as that catalytic mechanical intensity is low and uses easy dusting, so that having a possibility that large-scale industrial application.
Life experiment
Using above-mentioned condition, catalyst life test is carried out to embodiment 3, comparative example 2, comparative example 3, continuous operation 96 is small
It is as shown in table 3 to test its activity rating data by Shi Hou:
Catalyst activity after table 3 is run 96 hours evaluates tables of data
As shown in table 3, after running 96 hours, the propylene conversion of the catalyst of embodiment 3 is dropped to by 94.3%
89.4%, nearly 5 percentage points are had dropped, and comparative example 1, comparative example 2, comparative example 3, comparative example 4 and comparative example 5 have dropped respectively
Percentage point more than 8,8 percentage points, 11 percentage points, it is 8 percentage points and 9 percentage points nearly nearly.Therefore, long-play condition
Under, the service life is longer for catalyst of the invention, and stability is more preferable.
The invention is not limited to specific embodiments above-mentioned.The present invention, which expands to, any in the present specification to be disclosed
New feature or any new combination, and disclose any new method or process the step of or any new combination.
Claims (10)
1. the preparation method that a kind of oligomerization of propene prepares the catalyst of nonene and laurylene, which comprises the following steps:
S1, the presoma of one or more of suitable Zr, Ni, Pb, Fe and rare earth element active component is carried on γ-
Al2O3It is calcined after sphere, obtains the presoma of modified catalyst；
S2, ammonium hydroxide and template are uniformly mixed, obtain solution A；
S3, aluminium salt is dissolved in deionized water, while the resulting catalyst precursor of step 1 is added, obtained after stirring a period of time
To solution B；
S4, it is stirred solution A and solution B to obtain solution C；
S5, solution C is slowly added in silicon source solution, obtains collosol and gel, while addition inorganic acid is molten into the collosol and gel
Liquid or ammonia spirit adjust pH value to 9.0~11.0, obtain solution D；
S6, the solution D is transferred in autoclave, reaction product and mistake is taken out after crystallization a few hours at a certain temperature
Filter, washing solution to neutrality obtain filter cake, by filtration cakes torrefaction, roasting, obtain composite catalyst.
2. preparation method according to claim 1, which is characterized in that the presoma of the active component includes its sulfuric acid
The mixing of one or more of salt, nitrate, chloride, metal form.
3. preparation method according to claim 1, which is characterized in that the active component is supported on γ-Al2O3On side
Method includes the combination of one or more of infusion process, the precipitation method, physical mixed method.
4. preparation method according to claim 1, which is characterized in that the template is tetrabutylammonium bromide, the tetrabutyl
In ammonium hydroxide, tetraethylammonium bromide and at least one of tetraethyl ammonium hydroxide.
5. preparation method according to claim 1, which is characterized in that source of aluminium is aluminium chloride, aluminum sulfate or aluminum nitrate
At least one of, wherein silicon source is with Al2O3Meter；The silicon source is silica solution, at least one in ethyl orthosilicate/butyl silicate
Kind, wherein silicon source is with SiO2Meter；In mass, silica alumina ratio SiO2/Al2O3=50~200, template/SiO2=0.01~0.2.
6. preparation method according to claim 1, which is characterized in that the temperature of the crystallization is 80 DEG C~200 DEG C, crystallization
Time be 2h~for 24 hours；The drying temperature of filter cake is 100 DEG C~120 DEG C, and maturing temperature is 400 DEG C~600 DEG C, calcining time
For 2h~10h.
7. preparation method according to claim 1-6, which is characterized in that the inorganic acid solution is hydrochloric acid, sulphur
It is sour or nitric acid one or more.
8. a kind of oligomerization of propene prepares the composite catalyst of nonene and laurylene, using described in the claims any one of 1-7
Preparation method preparation.
9. composite catalyst according to claim 8, it is characterised in that: in the catalyst, the active component forerunner
Body and γ-Al2O3Mass ratio are as follows: 0.02-0.3；The aluminium salt and γ-Al2O3Mass ratio be 0.5-2.
10. catalyst according to claim 9, it is characterised in that: the γ-Al2O3Sphere using preceding carried out Na from
The washing of son, and γ-Al2O3Sphere diameter is 2-5mm.
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| CN112657482A (en) * | 2020-11-24 | 2021-04-16 | 大连理工大学 | Solid acid catalyst and propylene oligomer obtained by using same |
| CN114602536A (en) * | 2020-12-03 | 2022-06-10 | 万华化学集团股份有限公司 | Preparation method of catalyst and method for reducing VOC content in polyether polyol |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111714975A (en) * | 2020-06-10 | 2020-09-29 | 浙江工业大学 | Plate type air inlet purifier, air inlet system and method of vehicle-mounted fuel cell |
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| CN114602536A (en) * | 2020-12-03 | 2022-06-10 | 万华化学集团股份有限公司 | Preparation method of catalyst and method for reducing VOC content in polyether polyol |
| CN114602536B (en) * | 2020-12-03 | 2023-07-11 | 万华化学集团股份有限公司 | Preparation method of catalyst and method for reducing VOC content in polyether polyol |
| CN115193397A (en) * | 2022-07-22 | 2022-10-18 | 润和科华催化剂(上海)有限公司 | Shell silver mercury remover and preparation method thereof |
| CN115193397B (en) * | 2022-07-22 | 2023-10-27 | 润和科华催化剂(上海)有限公司 | Shell silver mercury remover and preparation method thereof |
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