CN112657483A - Catalyst and preparation method thereof - Google Patents
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- CN112657483A CN112657483A CN202011334408.4A CN202011334408A CN112657483A CN 112657483 A CN112657483 A CN 112657483A CN 202011334408 A CN202011334408 A CN 202011334408A CN 112657483 A CN112657483 A CN 112657483A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 117
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 claims abstract description 33
- 239000002184 metal Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000007864 aqueous solution Substances 0.000 claims abstract description 23
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 23
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 23
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract 2
- 238000001035 drying Methods 0.000 claims description 17
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 16
- 229910001447 ferric ion Inorganic materials 0.000 claims description 16
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 15
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 12
- 238000007598 dipping method Methods 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 23
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 23
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 229910000358 iron sulfate Inorganic materials 0.000 abstract description 8
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 abstract description 8
- 230000007774 longterm Effects 0.000 abstract 1
- 230000009257 reactivity Effects 0.000 abstract 1
- 239000004480 active ingredient Substances 0.000 description 15
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 10
- 239000011148 porous material Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 238000006384 oligomerization reaction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- -1 carbon chain olefin Chemical class 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000011208 chromatographic data Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JOJYUFGTMHSFEE-YONYXQDTSA-M Cytarabine ocfosphate Chemical compound [Na+].O[C@H]1[C@H](O)[C@@H](COP([O-])(=O)OCCCCCCCCCCCCCCCCCC)O[C@H]1N1C(=O)N=C(N)C=C1 JOJYUFGTMHSFEE-YONYXQDTSA-M 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及催化剂技术领域，更具体地，本发明涉及一种催化剂及其制备方法，所述催化剂的制备方法包括：将催化剂γ‑Al2O3载体浸渍到含有硫酸铁和硫酸镍金属活性成分混合物的水溶液中，10～48h后置于烘箱中干燥，再次经过焙烧，即得。本申请催化剂的制备方法简单，操作方便，同时制备得到的催化剂具有较高的反应活性和长时间的活性稳定性，使用该方法得到的催化剂在丙烯齐聚物的制备过程中丙烯的转化率高。The invention relates to the technical field of catalysts, and more particularly, the invention relates to a catalyst and a preparation method thereof. The preparation method of the catalyst comprises: impregnating a catalyst γ-Al 2 O 3 carrier into a metal active component containing iron sulfate and nickel sulfate In the aqueous solution of the mixture, it is dried in an oven after 10 to 48 hours, and then calcined again to obtain. The preparation method of the catalyst of the present application is simple, the operation is convenient, the prepared catalyst has high reactivity and long-term activity stability, and the catalyst obtained by using the method has a high conversion rate of propylene in the preparation process of propylene oligomer .
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a catalyst and a preparation method thereof.
Background
The long carbon chain olefin is an important chemical raw material in petroleum refining and fine chemical production. The production of nonenes and dodecenes by oligomerization over solid acid catalysts from propylene has attracted attention in recent years and the demand for products has increased dramatically.
The SPAC non-selective oligomerization process developed by the American Global oil products company (UOP) in the last 40 th century, and solid phosphoric acid-diatomite is adopted as a catalyst in the process. The process is one of the most widely used olefin oligomerization processes in the world at present. The catalyst has low price, high surface activity and selectivity; the method has the advantages of simple process flow, mature process technology, flexible raw materials and the like. The method has the main defects that the selectivity of the tetramer is low, the service life of the catalyst is short and is only 4-6 months, the catalyst cannot be regenerated, the water injection amount needs to be strictly controlled in the reaction process, otherwise, the catalyst is easy to be argillized and agglomerated, and the like. A typical process for olefin oligomerization using zeolite molecular sieves as catalysts is the MOGD process developed by Mobil corporation. The process adopts a medium-pore ZSM-5 molecular sieve (the molar ratio of silicon to aluminum is about 70) and Al with the mass fraction of 35 percent2O3Kneading the mixture into a strip catalyst. MOGD Process for C2-C4The olefin oligomerization reaction has flexible processing scheme, low arene content in the product, complex technological equipment and operation, reaction temperature higher than that of solid phosphoric acid catalyst and zeoliteMolecular sieve catalysts are prone to coking and deactivation, which is a major obstacle affecting the commercial implementation of this reaction process.
Disclosure of Invention
In view of the problems in the prior art, the first aspect of the present invention provides a method for preparing a catalyst, comprising: gamma-Al of the catalyst2O3And (3) soaking the carrier into an aqueous solution containing a mixture of iron sulfate and nickel sulfate metal active components, drying in an oven after 10-48 h, and roasting again to obtain the catalyst.
As a preferable technical scheme of the invention, the preparation method of the catalyst comprises the following steps:
(1) catalyst gamma-Al2O3Roasting the carrier to obtain a treated catalyst carrier;
(2) dipping the treated catalyst carrier into an aqueous solution containing a mixture of active components of ferric sulfate and nickel sulfate, wherein the dipping time is 10-48 h;
(3) and (3) placing the solid obtained in the step (2) in an oven for drying, and roasting again to obtain the catalyst.
As a preferable technical scheme of the invention, the roasting temperature in the step (1) is 300-500 ℃.
As a preferable technical scheme of the invention, the roasting time in the step (1) is 1-10 h.
As a preferable technical scheme of the invention, the volume ratio of the catalyst carrier treated in the step (2) to the aqueous solution containing the metal active ingredient mixture is (1-2): 1.
as a preferable technical scheme of the invention, the dipping time in the step (2) is 20-28 h.
As a preferable technical scheme of the invention, the drying temperature in the oven in the step (3) is 80-150 ℃.
As a preferable technical scheme of the invention, the roasting temperature in the step (3) is 300-700 ℃.
As a preferable technical scheme of the invention, the roasting temperature in the step (3) is 400-650 ℃.
As a preferable technical scheme of the invention, the proportion of the ferric ions in the metal active ingredient mixture is nFe3+/n(Fe3++Ni2+)＝0.6～0.95。
As a preferable technical scheme of the invention, the proportion of the ferric ions in the metal active ingredient mixture is nFe3+/n(Fe3++Ni2+)＝0.7。
The third aspect of the present invention provides a catalyst prepared according to the method for preparing the catalyst.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method of the catalyst is simple and convenient to operate, the prepared catalyst has high reaction activity and long-time activity stability, and the conversion rate of propylene in the preparation process of the propylene oligomer by using the catalyst obtained by the method is high.
Detailed Description
The present invention is illustrated by the following specific embodiments, but is not limited to the specific examples given below.
In a first aspect, the present invention provides a method for preparing a catalyst, comprising: gamma-Al of the catalyst2O3And (3) soaking the carrier into an aqueous solution containing a mixture of iron sulfate and nickel sulfate metal active components for 10-48 h, then placing the carrier into a drying oven for drying, and roasting again to obtain the catalyst.
In one embodiment, the method of preparing the catalyst comprises the steps of:
(1) gamma-Al for catalyst2O3Roasting the carrier to obtain a treated catalyst carrier;
(2) dipping the treated catalyst carrier into an aqueous solution containing a mixture of active components of ferric sulfate and nickel sulfate, wherein the dipping time is 10-48 h;
(3) and (3) placing the solid obtained in the step (2) in an oven for drying, and roasting again to obtain the catalyst.
Step (1)
In one embodiment, the catalyst support is γ -Al2O3。
Preferably, the gamma-Al2O3Has a particle diameter of 1 to 100 mesh and a specific surface area of 120 to 350m2(ii)/g, the average pore diameter is 8-20 nm, and the average pore volume is 0.7-1.6 mL/g; more preferably, the gamma-Al2O3Has a particle diameter of 80 mesh and a specific surface area of 302m2G, average pore diameter of 12nm and average pore volume of 1.6 mL/g.
In one embodiment, the calcination temperature in the step (1) is 300 to 500 ℃.
Preferably, the calcination temperature in the step (1) is 400 ℃.
In one embodiment, the calcination time in the step (1) is 1 to 10 hours.
Preferably, the roasting time in the step (1) is 3 h.
Step (2)
In one embodiment, the metal active ingredient is a mixture of iron sulfate and nickel sulfate.
Preferably, the ratio of the ferric ions in the metal active ingredient mixture is nFe3+/n(Fe3++Ni2+) 0.6-0.95% of the total weight; more preferably, the proportion of ferric ions in the metal active ingredient mixture is nFe3+/n(Fe3++Ni2+)＝0.7。
In one embodiment, the volume ratio of the catalyst carrier treated in the step (2) to the aqueous solution containing the metal active ingredient mixture is (1-2): 1.
preferably, the volume ratio of the catalyst carrier treated in the step (2) to the aqueous solution containing the metal active ingredient mixture is 1.7: 1.
in one embodiment, the dipping time in the step (2) is 20-28 h.
Preferably, the immersion time in step (2) is 24 h.
In the present application, the proportion of the ferric ions in the metal active ingredient is a molar ratio.
Step (3)
In one embodiment, the drying temperature in the oven in the step (3) is 80-150 ℃.
Preferably, the temperature for drying in the oven in the step (3) is 120 ℃.
In one embodiment, the drying time in the oven in the step (3) is 1 to 5 hours.
Preferably, the drying time in the oven in the step (3) is 2 h.
In one embodiment, the calcination temperature in the step (3) is 300 to 700 ℃.
Preferably, the roasting temperature in the step (3) is 400-650 ℃; more preferably, the calcination temperature in the step (3) is 550 ℃.
In one embodiment, the calcination time in the step (3) is 2 to 6 hours.
Preferably, the roasting time in the step (3) is 4 h.
The applicant considers that the possible reason is that under the condition, the load of the metal active component mixture in the pores of the catalyst carrier is good, the catalyst has stable load strength, and meanwhile, under the condition, some adsorbed water in the catalyst carrier can be effectively removed, the acidity of the catalyst is reduced, the conversion rate of the propylene is high, and under the condition, the catalyst carrier can be effectively combined with the metal active component, so that the conversion rate of the propylene and the service life of the catalyst are improved.
In addition, the applicant unexpectedly finds that the service life of the catalyst can be prolonged by drying the catalyst carrier impregnated with the metal active ingredient mixture and then roasting the dried catalyst carrier at 300-700 ℃, particularly 400-650 ℃.
In a second aspect, the present invention provides a catalyst prepared according to the method for preparing the catalyst.
In the catalyst obtained in the application, the total amount of the mixture of ferric sulfate and nickel sulfate accounts for 3-15 wt% of the catalyst.
Examples
Hereinafter, the present invention will be described in more detail by way of examples, but it should be understood that these examples are merely illustrative and not restrictive. The starting materials used in the examples which follow are all commercially available unless otherwise stated.
Example 1
Embodiment 1 of the present invention provides a method for preparing a catalyst, which comprises the following steps:
(1) for gamma-Al2O3Roasting at 300 ℃ for 10h to obtain a treated catalyst carrier;
(2) and (2) dipping the treated catalyst carrier into an aqueous solution containing a mixture of metal active components of ferric sulfate and nickel sulfate for 10h, wherein the volume ratio of the catalyst carrier to the aqueous solution containing the mixture of the metal active components is 1: 1;
(3) and (3) drying the solid obtained in the step (2) in an oven at 80 ℃ for 5h, and roasting at 400 ℃ for 6h again to obtain the catalyst.
The catalyst is gamma-Al2O3The carrier has a particle size of 80 meshes and a specific surface area of 310m2(iv)/g, average particle diameter of 10nm, and average pore volume of 0.89 mL/g.
In the mixture of the active ingredients of the iron sulfate and the nickel sulfate, the proportion of the ferric iron ions is nFe3+/n(Fe3++Ni2 +)＝0.7。
The total amount of the mixture of ferric sulfate and nickel sulfate accounts for 10 wt% of the catalyst.
Example 2
Embodiment 2 of the present invention provides a method for preparing a catalyst, which comprises the following steps:
(1) for gamma-Al2O3Roasting the carrier at 500 ℃ for 1h to obtain a treated catalyst carrier;
(2) and (2) dipping the treated catalyst carrier into a mixture aqueous solution containing metal active components of ferric sulfate and nickel sulfate for 48h, wherein the volume ratio of the catalyst carrier to the mixture aqueous solution containing the metal active components is 2: 1;
(3) and (3) drying the solid obtained in the step (2) in an oven at 150 ℃ for 1h, and roasting at 650 ℃ for 2h again to obtain the catalyst.
The catalyst is gamma-Al2O3The carrier has a particle size of 80 meshes and a specific surface area of 310m2(iv)/g, average particle diameter of 10nm, and average pore volume of 0.89 mL/g.
The proportion of the ferric iron ions in the mixture of the gold ferric sulfate and nickel sulfate metal active components is nFe3+/n(Fe3++Ni2+)＝0.7。
The total amount of the mixture of ferric sulfate and nickel sulfate accounts for 7 wt% of the catalyst.
Example 3
Embodiment 3 of the present invention provides a method for preparing a catalyst, which comprises the following steps:
(1) catalyst gamma-Al2O3Roasting the carrier at 400 ℃ for 3h to obtain a treated catalyst carrier;
(2) and (2) dipping the treated catalyst carrier into an aqueous solution containing a mixture of metal active components of ferric sulfate and nickel sulfate for 24h, wherein the volume ratio of the catalyst carrier to the aqueous solution containing the mixture of the metal active components is 1.7: 1;
(3) and (3) drying the solid obtained in the step (2) in a 120 ℃ oven for 2h, and roasting at 550 ℃ for 4h again to obtain the catalyst.
The catalyst is gamma-Al2O3The carrier has a particle size of 80 meshes and a specific surface area of 310m2(iv)/g, average particle diameter of 10nm, and average pore volume of 0.89 mL/g.
The proportion of the ferric iron ions in the mixture of the active ingredients of the ferric sulfate and the nickel sulfate is nFe3+/n(Fe3++Ni2 +)＝0.7。
The total amount of the mixture of ferric sulfate and nickel sulfate accounts for 8 wt% of the catalyst.
Example 4
Embodiment 4 of the present invention provides a method for preparing a catalyst, which comprises the following steps:
(1) the treated catalyst is gamma-Al2O3And (2) soaking the carrier into an aqueous solution containing a mixture of iron sulfate and nickel sulfate metal active components for 24h, wherein the volume ratio of the catalyst carrier to the aqueous solution containing the mixture of the metal active components is 1.7: 1;
(2) and (2) drying the solid obtained in the step (1) in a 120 ℃ oven for 2h, and roasting at 550 ℃ for 4h again to obtain the catalyst.
The total amount of the mixture of ferric sulfate and nickel sulfate accounts for 8 wt% of the catalyst.
Example 5
The embodiment 5 of the invention provides a preparation method of a catalyst, which is the same as the embodiment 3 in the specific implementation mode, and is different from the embodiment 3 in that the step (3) is to dry the solid obtained in the step (2) in a 120 ℃ oven for 2 hours and then calcine the solid at 300 ℃ for 4 hours.
Example 6
Embodiment 6 of the present invention provides a preparation method of a catalyst, which is the same as embodiment 3 in specific implementation manner, and is different from that in embodiment 3, in the step (3), the solid obtained in the step (2) is dried in an oven at 120 ℃ for 2 hours, and then baked at 700 ℃ for 4 hours, so as to obtain the catalyst.
Example 7
Example 7 of the present invention provides a method for preparing a catalyst, which is the same as example 3 except that the step (2) is to immerse the treated catalyst support in an aqueous solution containing a mixture of iron sulfate and nickel sulfate metal active components for 24 hours, wherein the volume ratio of the catalyst support to the aqueous solution containing the mixture of metal active components is 0.6: 1.
example 8
Example 8 of the present invention provides a method of preparing a catalyst, which is the same as example 3, except that the treated catalyst support is immersed in an aqueous solution containing a mixture of iron sulfate and nickel sulfate metal active ingredients for 32 hours, wherein the volume ratio of the catalyst support to the aqueous solution containing the mixture of metal active ingredients is 1.7: 1.
example 9
Example 9 of the present invention provides a method for preparing a catalyst, which is similar to example 3 in the following specific embodiment, except that nFe represents the ratio of ferric ions in the mixture of the active ingredients of ferric sulfate and nickel sulfate3+/n(Fe3++Ni2+)＝0.5。
Performance evaluation
1. Conversion of propylene: the catalysts obtained in the embodiments 1 to 9 are used for producing propylene oligomers from propylene, and are obtained by catalysis under the conditions of a reaction temperature of 67 ℃, a reaction pressure of 3.0MPa and a propylene flow rate of 1.2L/h. After the reaction of the propylene oligomer is finished, the product is separated by a gas-liquid separator, and tail gas is introduced into a chromatogram for detection at any time, and the real-time propylene reaction conversion rate is calculated. The method specifically comprises the following steps: the composition of the raw material and the reaction tail gas is analyzed by SP-6890 type chromatography, the analytical column is a dimethyl ether special analytical column, the column temperature is 30 ℃, and a thermal conductivity cell detector is used. After the reaction liquid product was collected, it was analyzed by using SP-6890 type chromatography with HP-PONA column and FID detector. The column temperature is increased from 35 ℃, the temperature increasing speed is 2 ℃/min, and the temperature is programmed to be increased to 270 ℃ and stopped. Data usage N2000+And (4) processing the chromatographic data by using a chromatographic data workstation, wherein the processing method is an area normalization method. The composition of each component in the liquid product was calculated from the peak area of each component.
2. Service life of the catalyst: the catalysts obtained in examples 1 to 9 were continuously used for producing propylene oligomers, and the conversion of propylene at each reaction time stage and the selectivity of the propylene oligomers having 6, 9, 12, 15, 18 carbon atoms in example 3 were recorded.
The propylene conversion rates for the propylene oligomers produced using the catalysts obtained in examples 1 to 9 are shown in Table 1.
TABLE 1
| Propylene conversion (wt%) | |
| Example 1 | 88.1 |
| Example 2 | 74.2 |
| Example 3 | 98.3 |
| Example 4 | 93.3 |
| Example 5 | 10.9 |
| Example 6 | 60.1 |
| Example 7 | 80.3 |
| Example 8 | 78.1 |
| Example 9 | 88.3 |
The catalysts obtained in examples 1-9 were continuously used for producing propylene oligomers, and the propylene conversion rates in different reaction time periods are shown in Table 2.
TABLE 2
The catalyst obtained in example 3 was used continuously for the production of propylene oligomers, the selectivity of propylene oligomers of different carbon numbers for different reaction time periods being shown in table 2.
TABLE 3
| Reaction time period | C6 | C9 | C12 | C15 | C18 |
| 0-380h | 8.1wt％ | 41.1wt％ | 32.2wt％ | 14.3wt％ | 4.3wt％ |
| 381-730h | 10.3wt％ | 42.2wt％ | 32.6wt％ | 12.5wt％ | 2.4wt％ |
| 731-1260h | 12.6wt％ | 40.0wt％ | 35.1wt％ | 10.3wt％ | 2.0wt％ |
| 1261-2000h | 11.6wt％ | 41.8wt％ | 36.0wt％ | 9.2wt％ | 1.4wt％ |
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (10)
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1193552A (en) * | 1998-04-13 | 1998-09-23 | 中国石油化工总公司 | Solid ziegler catalyst for olefins and preparation thereof |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1193552A (en) * | 1998-04-13 | 1998-09-23 | 中国石油化工总公司 | Solid ziegler catalyst for olefins and preparation thereof |
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