CN111744543B - Aviation kerosene catalyst prepared by olefin polymerization, preparation process thereof and olefin polymerization process - Google Patents
Aviation kerosene catalyst prepared by olefin polymerization, preparation process thereof and olefin polymerization process Download PDFInfo
- Publication number
- CN111744543B CN111744543B CN202010511976.0A CN202010511976A CN111744543B CN 111744543 B CN111744543 B CN 111744543B CN 202010511976 A CN202010511976 A CN 202010511976A CN 111744543 B CN111744543 B CN 111744543B
- Authority
- CN
- China
- Prior art keywords
- olefin polymerization
- catalyst
- aviation kerosene
- deionized water
- molecular sieve
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 39
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 28
- 239000003350 kerosene Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002808 molecular sieve Substances 0.000 claims abstract description 52
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910018054 Ni-Cu Inorganic materials 0.000 claims abstract description 10
- 229910018481 Ni—Cu Inorganic materials 0.000 claims abstract description 10
- 239000002105 nanoparticle Substances 0.000 claims abstract description 10
- 150000002500 ions Chemical class 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 84
- 239000008367 deionised water Substances 0.000 claims description 47
- 229910021641 deionized water Inorganic materials 0.000 claims description 47
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- 239000010949 copper Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 17
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 16
- 239000004202 carbamide Substances 0.000 claims description 16
- 239000011780 sodium chloride Substances 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 239000013067 intermediate product Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 150000001879 copper Chemical class 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 5
- 238000005119 centrifugation Methods 0.000 description 14
- 239000007788 liquid Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- 238000005406 washing Methods 0.000 description 13
- 239000012153 distilled water Substances 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 230000001105 regulatory effect Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000006384 oligomerization reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 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
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- -1 olefin hydrocarbon Chemical class 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses an aviation kerosene catalyst prepared by olefin polymerization, which comprises the following components in parts by weight: 0.1-2 parts of element M and/or oxide thereof, 0.1-3.5 parts of Ni-Cu nano particles and/or oxide thereof, and 80-99 parts of carrier Z; wherein, the element M is selected from one or more of Na, K and Cs, and the carrier Z is selected from at least one of silicon oxide and molecular sieve; the tetrahedral Ni ion content on the surface of the catalyst is 60-85%. The catalyst can obviously improve the long-period running stability of aviation kerosene prepared by olefin polymerization, and the selectivity of the aviation kerosene can be maintained for at least 12 hours by more than 90%. The invention also provides a preparation process for preparing the aviation kerosene catalyst by olefin polymerization and an olefin polymerization process.
Description
Technical Field
The invention relates to the field of catalysts, and in particular relates to an aviation kerosene catalyst prepared by olefin polymerization, a preparation process thereof and an olefin polymerization process.
Background
The catalytic cracking refinery in China is rich in low-carbon olefin, and a reasonable catalyst and process are found for processing, so that the problem of energy which is urgently needed can be solved, and the comprehensive economic benefit can be improved. The polymerization reaction using C5-C6 olefin hydrocarbon as raw material is an important way for preparing clean liquid fuel. The aviation industry in China is rapidly developed, the consumption of aviation fuel oil is increased sharply, and the annual consumption of the aviation fuel oil reaches more than 5000 ten thousand tons. Aviation fuel oil can be divided into aviation gasoline and aviation kerosene, and the carbon number distribution is respectively between C4-C12 and C9-C18. Therefore, the C5-C6 olefin resources are superposed into the C9-C18 resources, so that the method has good application prospect and practical value when being used for producing high-quality aviation fuel.
The prior olefin polymerization catalysts usually need to use solid phosphoric acid-diatomite as a main component to obtain solid phosphoric acid catalysts (De Klerk A, leckel D O, prnslo N M. Dense olefin polymerization by phosphoric acid catalysis: separating the effects of the temperature and the catalyst reaction on product selection [ J ]. Industrial and Engineering Chemistry Research,2006,45 (18): 6127-6136), and the catalysts have the problems of short catalyst life, equipment corrosion, regeneration and environmental pollution on the whole. In recent years, aluminosilicate catalysts (Agliulin M R, danilova I G, faizlin A V, et al. Sol-gel synthesis of Mesoporous alumina with a nano pore size distribution and catalytic activity thermal of in the oligomerization of Microporous and Mesoporous Materials,2016,230, 118-127.) have a high selectivity for olefin polymerization, but these Materials are amorphous, short-range disorder despite long-range, and thus have relatively poor hydrothermal stability, and their acidity is weak, which severely restricts their use in chemical production, and thus one of the difficulties facing the use of aluminosilicates. The molecular sieve catalyst has the characteristics of high reaction efficiency, no corrosion and good hydrothermal stability, and ZSM-5 molecular sieves are used as matrixes, and ZSM-5 molecular sieves with different grain sizes and similar acid amounts (0.2-3 mu m) are stacked in Popov et Al (Popopovv V S, ivanova I.Effect of crystal size on fibers oligomerization [ J ]. Journal of Catalysis,2016, 335. But the selectivity of the reaction process is unstable, and the selectivity of the superposed product of the conversion rate of the large-grain stacked ZSM-5 is reduced from 55 percent to 22 percent after 6 hours of reaction. The conversion rate of the superimposed product of the small-grain stacked molecular sieve is reduced to about 15 percent. Therefore, a catalyst with high selectivity and stability is needed.
Disclosure of Invention
The invention aims to solve the problems and provides an aviation kerosene catalyst prepared by olefin polymerization, a preparation process thereof and an olefin polymerization process.
The invention provides an aviation kerosene catalyst prepared by olefin polymerization, which comprises the following components in parts by weight:
0.1-2 parts of element M and/or its oxide
0.1-3.5 parts of Ni-Cu nano particles and/or oxides thereof
80-99 parts of a carrier Z;
wherein, the element M is selected from one or more of Na, K and Cs, and the carrier Z is selected from at least one of silicon oxide and molecular sieve;
the content of Ni ions of tetrahedrons on the surface of the catalyst is 60-85%.
Furthermore, the weight portion of the element M and/or the oxide thereof is 0.2 to 1 portion.
Further, the mass ratio of Ni to Cu in the Ni-Cu nanoparticles and/or the oxides thereof is (0.1-2.5): 1.
Further, the mass ratio of Ni to Cu in the Ni-Cu nanoparticles and/or the oxides thereof is (0.2-1.0): 1.
Further, the molecular sieve is at least one of H-ZSM-5 and H-IM-5 molecular sieves.
The invention also provides a preparation process for preparing the aviation kerosene catalyst by olefin polymerization, which comprises the following steps:
1) Mixing soluble salt containing element M, carrier Z and deionized water, adjusting to alkalinity by using urea, filtering and roasting to obtain an intermediate product; the element M is selected from one or more of Na, K and Cs, and the carrier Z is selected from at least one of silicon oxide and molecular sieve;
2) Mixing nickel salt, copper salt, the intermediate product obtained in the step 1) and deionized water, filtering and calcining to obtain the required catalyst.
Further, the soluble salt containing the element M is NaCl, and the weight ratio of the soluble salt containing the element M to the carrier Z to the deionized water is (0.02-0.08): 1:20.
further, the molar ratio between the nickel salt and the copper salt is (0.1-2.5): 1.
The invention also provides an olefin polymerization process, which comprises the step of carrying out contact reaction on olefin and the catalyst as described in claim 1 under the following reaction conditions: the reaction pressure is 0-4 MPa, the temperature is 120-300 ℃, and the mass space velocity is 0.1-10 h -1 。
Further, the olefin is selected from at least one of C5 olefins and C6 olefins.
The technical scheme of the invention can obviously improve the long-period running stability of the aviation kerosene prepared by olefin polymerization, and the aviation kerosene selectivity can be maintained for at least 12 hours by more than 90%.
Detailed Description
The following examples are only preferred embodiments of the present invention and are not intended to limit the present invention in any way. Various modifications and alterations to this invention will become apparent to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Example one
A preparation process for preparing an aviation kerosene catalyst by olefin polymerization is characterized by comprising the following steps: the method comprises the following steps:
1) Mixing soluble salt containing element M, carrier Z and deionized water, adjusting to alkalinity by using urea, filtering and roasting to obtain an intermediate product; the element M is selected from one or more of Na, K and Cs, and the carrier Z is selected from at least one of silicon oxide and molecular sieve;
2) Mixing nickel salt, copper salt, the intermediate product obtained in the step 1) and deionized water, filtering and calcining to obtain the required catalyst.
In the step 1), the element M is preferably Na, and the soluble salt containing the element M is NaCl; the molecular sieve is preferably at least one selected from H-ZSM-5 and H-IM-5 molecular sieves. The weight ratio of the soluble salt containing the element M, the carrier Z and the deionized water is preferably (0.02-0.08): 1:20. preferably, the alkaline adjustment by urea is specifically to adjust the pH to 7.5 to 9.0.
The filtration is preferably carried out by centrifugation, and the calcination is preferably carried out at 450 ℃ for 3h.
In step 2), the molar ratio between the nickel salt and the copper salt is preferably (0.1-2.5): 1, thereby controlling the mass ratio between Ni and Cu in the prepared catalyst. Mixing nickel salt, copper salt, the intermediate product obtained in the step 1) and deionized water, preferably placing the mixture in a constant-temperature water bath at 70 ℃ for stirring for 4 hours, and washing and filtering the mixture by warm deionized water. The calcination is preferably carried out at a ramp rate of 1 ℃/min in a muffle furnace at 450 ℃ for 3h.
Example two
The catalyst for preparing the aviation kerosene through olefin polymerization can be prepared by adopting the preparation process for preparing the aviation kerosene through olefin polymerization provided by the first embodiment, and comprises the following components in parts by weight:
0.1-2 parts of element M and/or oxide thereof
0.1-3.5 parts of Ni-Cu nano particles and/or oxides thereof
80-99 parts of a carrier Z;
wherein, the element M is selected from one or more of Na, K and Cs, and the carrier Z is selected from at least one of silicon oxide and molecular sieve;
the tetrahedral Ni ion content on the surface of the catalyst is 60-85%.
Preferably, the weight portion of the element M and/or the oxide thereof is 0.2 to 1 portion; the mass ratio of Ni to Cu in the Ni-Cu nanoparticles and/or the oxides thereof is (0.1-2.5): 1, and more preferably, the mass ratio of Ni to Cu in the Ni-Cu nanoparticles and/or the oxides thereof is (0.2-1.0): 1.
In some preferred embodiments, the support Z is selected from at least one of H-ZSM-5, H-IM-5 molecular sieves.
EXAMPLE III
Olefin polymerizationThe process comprises the step of carrying out contact reaction on olefin and the catalyst as described in example two under the following reaction conditions: the reaction pressure is 0-4 MPa, the temperature is 120-300 ℃, and the mass space velocity is 0.1-10 h -1 . More preferably, the olefin is selected from at least one of C5 olefins and C6 olefins.
Specific examples and comparative examples are provided below
Example 1
(1) NaCl, H-ZSM-5 and deionized water were mixed in a ratio of 0.02:1:20, regulating the pH value to 8.0 by using urea, stirring for 2 hours in a constant-temperature water bath kettle at the temperature of 60 ℃, removing the upper-layer liquid by centrifugal operation, washing for 3 times by using distilled water after centrifugation, drying, and roasting for 3 hours at the temperature of 450 ℃ to obtain the Na-HZSM-5 molecular sieve.
(2) Configuration of 0.01M Ni (NO) 3 ) 2 And 0.01M Cu (NO) 3 ) 2 10ml of each solution were mixed with 1g of molecular sieve and 10g of deionized water, stirred in a thermostatic water bath at 70 ℃ for 4 hours, the filtered molecular sieve was washed with warm deionized water after each treatment, and the sample was dried at 100 ℃ and this was repeated twice. Finally, all samples were calcined at a heating rate of 1 ℃/min in a muffle furnace at 450 ℃ for 3h.
Example 2
(1) NaCl, H-ZSM-5 and deionized water were mixed in a ratio of 0.03:1:20, regulating the pH value to 7.5 by using urea, stirring for 2 hours in a constant-temperature water bath kettle at the temperature of 60 ℃, removing the upper layer liquid by centrifugal operation, washing for 3 times by using distilled water after centrifugation, drying, and roasting for 3 hours at the temperature of 450 ℃ to obtain the Na-HZSM-5 molecular sieve.
(2) Configuration of 0.002M Ni (NO) 3 ) 2 And 0.002M Cu (NO) 3 ) 2 10ml of each solution were mixed with 1g of molecular sieve and 10g of deionized water, stirred in a thermostatic water bath at 70 ℃ for 4 hours, the filtered molecular sieve was washed with warm deionized water after each treatment, and the sample was dried at 100 ℃ and this was repeated twice. Finally, all samples were calcined at 450 ℃ for 3h in a muffle furnace at a heating rate of 1 ℃/min.
Example 3
(1) NaCl, H-ZSM-5 and deionized water were mixed in a ratio of 0.02:1:20, regulating the pH value to 8.0 by using urea, stirring for 2 hours in a constant-temperature water bath kettle at the temperature of 60 ℃, removing the upper-layer liquid by centrifugal operation, washing for 3 times by using distilled water after centrifugation, drying, and roasting for 3 hours at the temperature of 450 ℃ to obtain the Na-HZSM-5 molecular sieve.
(2) Configuration of 0.008M Ni (NO) 3 ) 2 And 0.008M Cu (NO) 3 ) 2 10ml of each solution were mixed with 1g of molecular sieve and 10g of deionized water, stirred in a thermostatic water bath at 70 ℃ for 4 hours, the filtered molecular sieve was washed with warm deionized water after each treatment, and the sample was dried at 100 ℃ and this was repeated twice. Finally, all samples were calcined at a heating rate of 1 ℃/min in a muffle furnace at 450 ℃ for 3h.
Example 4
(1) NaCl, H-ZSM-5 and deionized water were mixed in a ratio of 0.02:1:20, regulating the pH value to 7.5 by using urea, stirring for 2 hours in a constant-temperature water bath kettle at the temperature of 60 ℃, removing the upper layer liquid by centrifugal operation, washing for 3 times by using distilled water after centrifugation, drying, and roasting for 3 hours at the temperature of 450 ℃ to obtain the Na-HZSM-5 molecular sieve.
(2) Configuration of 0.01M Ni (NO) 3 ) 2 And 0.01M Cu (NO) 3 ) 2 10ml of each solution were mixed with 1g of molecular sieve and 10g of deionized water, stirred in a thermostatic water bath at 70 ℃ for 4 hours, the filtered molecular sieve was washed with warm deionized water after each treatment, and the sample was dried at 100 ℃ and this was repeated twice. Finally, all samples were calcined at a heating rate of 1 ℃/min in a muffle furnace at 450 ℃ for 3h.
Example 5
(1) NaCl, H-ZSM-5 and deionized water were mixed in a ratio of 0.05:1:20, regulating the pH value to 8.5 by using urea, stirring for 2 hours in a constant-temperature water bath kettle at the temperature of 60 ℃, removing the upper-layer liquid by centrifugal operation, washing for 3 times by using distilled water after centrifugation, drying, and roasting for 3 hours at the temperature of 450 ℃ to obtain the Na-HZSM-5 molecular sieve.
(2) Configuration 0.005M Ni (NO) 3 ) 2 And 0.014M Cu (NO) 3 ) 2 10ml of each solution was mixed with 1g of molecular sieve and 10g of deionized water, and then stirred in a thermostatic water bath at 70 ℃ for 4 hours, after each treatment, the filtered molecular sieve was washed with warm deionized water, and the sample was dried at 100 ℃ and this was repeated twice. Finally, theAll samples were calcined at 450 ℃ in a muffle furnace for 3h at a ramp rate of 1 ℃/min.
Example 6
(1) NaCl, H-ZSM-5 and deionized water were mixed in a ratio of 0.05:1:20, regulating the pH value to 9.0 by using urea, stirring for 2 hours in a constant-temperature water bath kettle at the temperature of 60 ℃, removing the upper layer liquid by centrifugal operation, washing for 3 times by using distilled water after centrifugation, drying, and roasting for 3 hours at the temperature of 450 ℃ to obtain the Na-HZSM-5 molecular sieve.
(2) Configuration of 0.01M Ni (NO) 3 ) 2 And 0.016M Cu (NO) 3 ) 2 10ml of each solution were mixed with 1g of molecular sieve and 10g of deionized water, stirred in a thermostatic water bath at 70 ℃ for 4 hours, the filtered molecular sieve was washed with warm deionized water after each treatment, and the sample was dried at 100 ℃ and this was repeated twice. Finally, all samples were calcined at a heating rate of 1 ℃/min in a muffle furnace at 450 ℃ for 3h.
Example 7
(1) NaCl, H-ZSM-5 and deionized water were mixed in a ratio of 0.04:1:20, regulating the pH value to 8.0 by using urea, stirring for 2 hours in a constant-temperature water bath kettle at the temperature of 60 ℃, removing the upper-layer liquid by centrifugal operation, washing for 3 times by using distilled water after centrifugation, drying, and roasting for 3 hours at the temperature of 450 ℃ to obtain the Na-HZSM-5 molecular sieve.
(2) Configuration 0.014M Ni (NO) 3 ) 2 And 0.017M Cu (NO) 3 ) 2 10ml of each solution were mixed with 1g of molecular sieve and 10g of deionized water, stirred in a thermostatic water bath at 70 ℃ for 4 hours, the filtered molecular sieve was washed with warm deionized water after each treatment, and the sample was dried at 100 ℃ and this was repeated twice. Finally, all samples were calcined at 450 ℃ for 3h in a muffle furnace at a heating rate of 1 ℃/min.
Example 8
(1) NaCl, H-ZSM-5 and deionized water were mixed in a ratio of 0.02:1:20, adjusting the pH value to 8.0 by using urea, stirring for 2 hours in a constant-temperature water bath kettle at the temperature of 60 ℃, removing the upper layer liquid by centrifugation, washing for 3 times by using distilled water after centrifugation, drying, and roasting for 3 hours at the temperature of 450 ℃ to obtain the Na-HZSM-5 molecular sieve.
(2) Configuration 0.04M Ni (NO) 3 ) 2 And 0.016M Cu (NO) 3 ) 2 10ml of each solution were mixed with 1g of molecular sieve and 10g of deionized water, stirred in a thermostatic water bath at 70 ℃ for 4 hours, the filtered molecular sieve was washed with warm deionized water after each treatment, and the sample was dried at 100 ℃ and this was repeated twice. Finally, all samples were calcined at a heating rate of 1 ℃/min in a muffle furnace at 450 ℃ for 3h.
Example 9
(1) NaCl, H-ZSM-5 and deionized water were mixed in a ratio of 0.02:1:20, regulating the pH value to 8.0 by using urea, stirring for 2 hours in a constant-temperature water bath kettle at the temperature of 60 ℃, removing the upper layer liquid by centrifugal operation, washing for 3 times by using distilled water after centrifugation, drying, and roasting for 3 hours at the temperature of 500 ℃ to obtain the Na-HZSM-5 molecular sieve.
(2) Configuration of 0.003M Ni (NO) 3 ) 2 And 0.02M Cu (NO) 3 ) 2 10ml of each solution was mixed with 1g of molecular sieve and 10g of deionized water, and then stirred in a thermostatic water bath at 90 ℃ for 4 hours, after each treatment, the filtered molecular sieve was washed with warm deionized water, and the sample was dried at 100 ℃ and this was repeated twice. Finally, all samples were calcined at 450 ℃ for 3h in a muffle furnace at a heating rate of 1 ℃/min.
Example 10
(1) NaCl, H-ZSM-5 and deionized water were mixed in a ratio of 0.02:1:20, regulating the pH value to 8.5 by using urea, stirring for 2 hours in a constant-temperature water bath kettle at the temperature of 60 ℃, removing the upper layer liquid by centrifugal operation, washing for 3 times by using distilled water after centrifugation, drying, and roasting for 3 hours at the temperature of 550 ℃ to obtain the Na-HZSM-5 molecular sieve.
(2) Configuration of 0.008M Ni (NO) 3 ) 2 And 0.008M Cu (NO) 3 ) 2 10ml of each solution was mixed with 1g of molecular sieve and 10g of deionized water, and then stirred in a thermostatic water bath at 70 ℃ for 4 hours, after each treatment, the filtered molecular sieve was washed with warm deionized water, and the sample was dried at 100 ℃ and this was repeated twice. Finally, all samples were calcined at a heating rate of 1 ℃/min in a muffle furnace at 450 ℃ for 3h.
Example 11
(1) NaCl, H-IM-5 and deionized water were mixed in a 0.02:1:20, regulating the pH value to 9.0 by using urea, stirring for 2 hours in a constant-temperature water bath kettle at the temperature of 60 ℃, removing the upper layer liquid by centrifugal operation, washing for 3 times by using distilled water after centrifugation, drying, and roasting for 3 hours at the temperature of 450 ℃ to obtain the Na-HZSM-5 molecular sieve.
(2) Configuration of 0.008M Ni (NO) 3 ) 2 And 0.02M Cu (NO) 3 ) 2 10ml of each solution were mixed with 1g of molecular sieve and 10g of deionized water, stirred in a thermostatic water bath at 70 ℃ for 4 hours, the filtered molecular sieve was washed with warm deionized water after each treatment, and the sample was dried at 100 ℃ and this was repeated twice. Finally, all samples were calcined at a heating rate of 1 ℃/min in a muffle furnace at 450 ℃ for 3h.
Comparative example 1
NaCl, H-ZSM-5 and deionized water were mixed in a ratio of 0.02:1:20, regulating the pH value to 8.0 by using urea, stirring for 2 hours in a constant-temperature water bath kettle at the temperature of 60 ℃, removing the upper-layer liquid by centrifugal operation, washing for 3 times by using distilled water after centrifugation, drying, and roasting for 3 hours at the temperature of 450 ℃ to obtain the Na-HZSM-5 molecular sieve.
Comparative example 2
Configuration of 0.002M Ni (NO) 3 ) 2 And 0.008M Cu (NO) 3 ) 2 10ml of each solution was mixed with 1g of H-ZSM-5 molecular sieve and 10g of deionized water, stirred in a thermostatic water bath at 70 ℃ for 4 hours, the filtered molecular sieve was washed with warm deionized water after each treatment, and the sample was dried at 100 ℃ and this was repeated twice. Finally, all samples were calcined at a heating rate of 1 ℃/min in a muffle furnace at 450 ℃ for 3h.
Comparative example 3
Ni and Cu were supported on 1g of H-ZSM-5 molecular sieve by impregnation in the same amount as in example 3, and the sample was dried at 100 ℃ and this was repeated twice. Finally, all samples were calcined at 450 ℃ for 3h in a muffle furnace at a heating rate of 1 ℃/min.
The catalysts obtained in examples 1 to 11 and comparative examples 1 to 3 were subjected to UV spectroscopy to determine the tetrahedral Ni content on the surface of the catalyst, the results are shown in Table 1, 0.1g of the catalyst was charged into a constant temperature zone of a reaction tube, and the bed height was about 8mm. In high purity N 2 And (50 mL/min) purging at 400 ℃ under normal pressure for 2h for activation. Then use the heightPure N 2 Pressurizing to 4MPa of reaction pressure 2 The flow rate is 100mL/min, and the liquid inlet amount is controlled to be 0.03mL/min. The reaction was continued for 12h and the aviation kerosene selectivity was recorded at 2h and 12h of catalytic reaction and the results are shown in table 1.
TABLE 1 tabulated results of catalytic reactions for catalysts of examples 1-11 and comparative examples 1-3
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (6)
1. A aviation kerosene catalyst prepared by C5 and C6 olefin polymerization is characterized in that: the catalyst comprises the following components in parts by weight:
0.1-2 parts of element M and/or oxide thereof
0.1-3.5 parts of Ni-Cu nano particles and/or oxides thereof
80-99 parts of a carrier Z;
wherein, the element M is selected from one or more of Na, K and Cs, and the carrier Z is H-ZSM-5 or H-IM-5 molecular sieve;
the content of Ni ions of tetrahedrons on the surface of the catalyst is 60 to 85 percent;
the catalyst is prepared by the following steps:
1) Mixing soluble salt containing element M, carrier Z and deionized water, adjusting to alkalinity by using urea, filtering and roasting to obtain an intermediate product;
2) Mixing nickel salt, copper salt, the intermediate product obtained in the step 1) and deionized water, and filtering and calcining to obtain the required catalyst.
2. The process for preparing aviation kerosene catalyst by C5, C6 olefin polymerization according to claim 1, wherein: the weight portion of the element M and/or the oxide thereof is 0.2 to 1 portion.
3. The C5, C6 olefin polymerization preparation aviation kerosene catalyst according to claim 2, wherein: the soluble salt containing the element M is NaCl, and the weight ratio of the soluble salt containing the element M to the carrier Z to the deionized water is (0.02-0.08): 1:20.
4. the C5, C6 olefin polymerization preparation aviation kerosene catalyst according to claim 1, wherein: the mass ratio of Ni to Cu in the Ni-Cu nano particles and/or the oxides thereof is (0.1-2.5): 1.
5. The C5, C6 olefin polymerization preparation aviation kerosene catalyst according to claim 3, wherein: the mass ratio of Ni to Cu in the Ni-Cu nano particles and/or the oxides thereof is (0.2-1.0): 1.
6. A C5 and C6 olefin polymerization process is characterized in that: contacting an olefin with the catalyst of claim 1 under the following reaction conditions: the reaction pressure is0 to 4MPa, the temperature of 120 to 300 ℃ and the mass space velocity of 0.1 to 10h -1 。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010511976.0A CN111744543B (en) | 2020-06-08 | 2020-06-08 | Aviation kerosene catalyst prepared by olefin polymerization, preparation process thereof and olefin polymerization process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010511976.0A CN111744543B (en) | 2020-06-08 | 2020-06-08 | Aviation kerosene catalyst prepared by olefin polymerization, preparation process thereof and olefin polymerization process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111744543A CN111744543A (en) | 2020-10-09 |
| CN111744543B true CN111744543B (en) | 2023-03-31 |
Family
ID=72676481
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010511976.0A Active CN111744543B (en) | 2020-06-08 | 2020-06-08 | Aviation kerosene catalyst prepared by olefin polymerization, preparation process thereof and olefin polymerization process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111744543B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87105159A (en) * | 1986-06-27 | 1988-03-23 | 无比石油公司 | The oligomerisation of alkene |
| US5883036A (en) * | 1995-03-29 | 1999-03-16 | Koa Oil Company, Ltd. | Olefin oligomerization catalyst, process for preparing the same, and olefin oligomerization process using the same |
| CN1398832A (en) * | 2001-07-20 | 2003-02-26 | 中国石油化工股份有限公司 | Low-carbon olefine oligomerizing or polymerizing process of producing C6 and over olefine |
| CN102215955A (en) * | 2008-11-19 | 2011-10-12 | 巴斯夫欧洲公司 | Oligomerisation of olefins |
| CN110721733A (en) * | 2019-09-17 | 2020-01-24 | 中国科学院青岛生物能源与过程研究所 | Catalyst for preparing aviation oil by oligomerization of low-carbon hydrocarbon and preparation method and application thereof |
-
2020
- 2020-06-08 CN CN202010511976.0A patent/CN111744543B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87105159A (en) * | 1986-06-27 | 1988-03-23 | 无比石油公司 | The oligomerisation of alkene |
| US5883036A (en) * | 1995-03-29 | 1999-03-16 | Koa Oil Company, Ltd. | Olefin oligomerization catalyst, process for preparing the same, and olefin oligomerization process using the same |
| CN1398832A (en) * | 2001-07-20 | 2003-02-26 | 中国石油化工股份有限公司 | Low-carbon olefine oligomerizing or polymerizing process of producing C6 and over olefine |
| CN102215955A (en) * | 2008-11-19 | 2011-10-12 | 巴斯夫欧洲公司 | Oligomerisation of olefins |
| CN110721733A (en) * | 2019-09-17 | 2020-01-24 | 中国科学院青岛生物能源与过程研究所 | Catalyst for preparing aviation oil by oligomerization of low-carbon hydrocarbon and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| "Propene oligomerization over Ni-exchanged Na-X zeolites";Anton N. Mlinar等;《Journal of Catalysis》;20121016;第296卷;第156-164页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111744543A (en) | 2020-10-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4499197A (en) | Co-gel catalyst manufacture | |
| TWI515045B (en) | Improved heavy metals trapping co-catalyst for fcc processes and method of metal passivation | |
| CN109967118B (en) | In-situ modification method of HZSM-5 molecular sieve catalyst for preparing aromatic hydrocarbon through methanol conversion | |
| CN101730673B (en) | Process for xylene production | |
| CN109433249B (en) | Method for modifying aluminum oxide by using Y-type molecular sieve structure directing agent and application of method | |
| WO1995012454A1 (en) | Modified microsphere fcc catalysts | |
| CN112960680B (en) | Modification method for improving hydrothermal stability of ZSM-5 molecular sieve | |
| JP5394064B2 (en) | Process for producing light olefins from hydrocarbon feedstock | |
| US20070010699A1 (en) | Process for production of light olefins from hydrocarbon feedstock | |
| CN112371167B (en) | Catalyst for producing high-octane component gasoline and preparation method and application thereof | |
| CN109746039B (en) | Hierarchical pore silicon-aluminum catalytic material and preparation method and application thereof | |
| CN101190864B (en) | Catalyst for preparing ethene and propene by catalysis cracking | |
| CN103657712A (en) | Catalytic cracking catalyst and preparation method thereof | |
| CN108097287B (en) | Catalytic cracking catalyst and preparation method thereof | |
| CN111744543B (en) | Aviation kerosene catalyst prepared by olefin polymerization, preparation process thereof and olefin polymerization process | |
| CN107971008B (en) | Catalytic cracking catalyst, preparation method thereof and petroleum hydrocarbon catalytic cracking method | |
| CN107344113B (en) | Hydrocracking catalyst for producing high aromatic hydrocarbon latent naphtha and preparation method and application thereof | |
| CN1297018A (en) | Catalytic cracking catalyst for preparing light oil with high yield and its preparing process | |
| CN102839010A (en) | Preparation method for modified magnesium aluminum spinel having acidity and alkality | |
| RU2603776C1 (en) | Method of hydrocracking hydrocarbon material | |
| CN111686787B (en) | Hydrocracking catalyst carrier, and preparation method and application thereof | |
| CN116265106A (en) | Preparation method of catalytic cracking catalyst for high yield of low carbon olefin | |
| CN107971005B (en) | Catalytic cracking catalyst, preparation method thereof and petroleum hydrocarbon catalytic cracking method | |
| CA1217160A (en) | Process for the dewaxing of hydrocarbon fractions | |
| JPH0286846A (en) | Catalyst composition for catalytic cracking of hydrocarbon oil and catalytic cracking method using same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |