CN115888797A - Catalyst for preparing ethylene and propylene by cracking of C, V and C-hexaalkane and preparation method and application thereof - Google Patents
Catalyst for preparing ethylene and propylene by cracking of C, V and C-hexaalkane and preparation method and application thereof Download PDFInfo
- Publication number
- CN115888797A CN115888797A CN202211391936.2A CN202211391936A CN115888797A CN 115888797 A CN115888797 A CN 115888797A CN 202211391936 A CN202211391936 A CN 202211391936A CN 115888797 A CN115888797 A CN 115888797A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- catalyst
- cracking
- metal
- propylene
- 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 238000005336 cracking Methods 0.000 title claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 25
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000005977 Ethylene Substances 0.000 title claims abstract description 24
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229910052720 vanadium Inorganic materials 0.000 title claims description 6
- 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 129
- 239000002808 molecular sieve Substances 0.000 claims abstract description 124
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- 229910052680 mordenite Inorganic materials 0.000 claims abstract description 15
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 12
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 11
- 239000011230 binding agent Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 14
- 230000032683 aging Effects 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical group [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- 229910052788 barium Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000004898 kneading Methods 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 28
- 239000002994 raw material Substances 0.000 abstract description 12
- 238000011069 regeneration method Methods 0.000 abstract description 12
- 230000008929 regeneration Effects 0.000 abstract description 11
- 125000004122 cyclic group Chemical group 0.000 abstract description 6
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 42
- 238000004523 catalytic cracking Methods 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- 239000011651 chromium Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 5
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000002844 continuous effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- -1 carbon olefin Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- WFLYOQCSIHENTM-UHFFFAOYSA-N molybdenum(4+) tetranitrate Chemical compound [N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WFLYOQCSIHENTM-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001502 supplementing effect Effects 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
Abstract
The invention relates to a catalyst for preparing ethylene and propylene by cracking C five-carbon hexaalkane, and a preparation method and application thereof. The catalyst mainly comprises a molecular sieve and modified metal, wherein the molecular sieve is formed by compounding one or two of Y-type molecular sieve and mordenite, an SAPO-34 molecular sieve, a ZSM-5 molecular sieve and a binder; the modified metal is selected from one or more of rare earth metal, IA, IIA, VIB and VIIB. Wherein, the Y-type molecular sieve and the mordenite are modified by rare earth metal, and the ZSM-5 molecular sieve is modified by VIB or VIIB and IA or IIA metal. The catalyst provided by the invention has the double functions of dehydrogenation and cracking, and can solve the problems of high investment cost, more byproducts in the reaction process, high heat loss, short service life of the catalyst and the like in the prior art; the catalyst can treat various mixed raw materials, has high selectivity to ethylene and propylene, can withstand repeated cyclic regeneration, and is suitable for repeated cyclic regeneration reaction devices.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a catalyst for preparing ethylene and propylene by cracking C five-carbon hexaalkane, and a preparation method and application thereof.
Background
In the petroleum refining industry, ethylene and propylene in low-carbon olefin are always the most basic raw materials in the petrochemical industry, and the development level of the petrochemical industry in one country is directly influenced by the yield of the low-carbon olefin. The catalytic cracking technology is an important technical means for solving the problem of low carbon olefin shortage at present.
Due to its stable solid acidity and specific pore structure, molecular sieves are widely used in the reaction of light hydrocarbon catalytic cracking to produce light olefins. Most of the raw materials used in the current catalytic cracking technology are light hydrocarbon mixtures with various components, and the molecular sieve catalyst with single pore diameter is not suitable for processing raw materials with complex components. In order to solve the problem, molecular sieves with different pore structure types can be compounded to prepare the composite molecular sieve catalyst, the defects are made up by utilizing the advantages of respective multi-stage pore channel structures, and the internal diffusion and the external diffusion of raw material and product molecules on the surface of the catalyst are facilitated, so that the pore continuous effect of the molecular sieve is maximized to deal with various complex reaction systems.
Patent CN105085144 discloses a method for producing ethylene propylene from C-hexaalkane, which connects a catalytic dehydrogenation reactor and a catalytic cracking reactor in series, wherein a raw material rich in C-hexaalkane from a refinery firstly enters the reactor filled with a dehydrogenation catalyst, and after alkane dehydrogenation reaction is carried out under a certain temperature and pressure condition, the raw material enters the reactor filled with the catalytic cracking catalyst for catalytic cracking reaction. The process combines catalytic dehydrogenation and catalytic cracking reactions, can improve the selectivity of ethylene and propylene in the obtained product, but has obvious defects, large occupied area and high investment cost by adopting two or even a plurality of reactors.
Patent CN106140266 discloses a preparation method of a metal modified ZSM-5 molecular sieve catalyst, and the invention mainly improves the cracking performance of the catalyst by introducing La or Ce rare earth elements into ZSM-5. At the reaction temperature of 627 ℃ and the reaction space velocity of 4h -1 The normal hexane is used as a raw material, so that the conversion rate is 99%, the ethylene selectivity is 23.2%, and the propylene selectivity is 25.7%. Although the selectivity of ethylene and propylene in the product is high, the reaction temperature is high, and meanwhile, the conversion rate of the normal hexane of 99 percent needs to absorb a large amount of heat, which causes difficulty in industrially supplementing heat for a reactor. Therefore, the selectivity of ethylene and propylene in the cracked product is considered in the light hydrocarbon cracking catalyst, and the conversion rate of the raw material is ensured not to be too high, so that the temperature in the reactor is prevented from being reduced too much, and the subsequent reaction effect is difficult to maintain.
At present, the reaction temperature for producing ethylene and propylene by cracking light hydrocarbon in industry is between 500 and 800 ℃, the reaction is a strong endothermic reaction, the conversion rate can reach 90 percent by adopting a molecular sieve catalyst to carry out catalytic cracking on the light hydrocarbon. Besides low-carbon olefin, the products obtained by cracking also can produce by-products such as methane, ethane, propane, butane, benzene and the like, and cause difficulty in the subsequent separation and purification process. The catalyst is easy to generate substances such as polycyclic aromatic hydrocarbon and the like to block the pore channels in the cracking reaction, so that the activity is reduced or the catalyst is inactivated, but the problem of pore channel blocking can be solved by injecting a certain amount of air for regeneration. Therefore, the above problems can be solved by developing a catalyst which is applicable to a cyclic regeneration reactor and has excellent cracking performance.
Disclosure of Invention
The invention aims to provide a catalyst for preparing ethylene and propylene by cracking C, V and C, and a preparation method and application thereof.
The invention is realized by the following technical scheme, and according to the catalyst for preparing ethylene and propylene by cracking the C-V-C-hexaalkane, the catalyst mainly comprises a molecular sieve and modified metals, wherein the molecular sieve comprises the following components in percentage by mass: one or two of Y-type molecular sieve and mordenite, the content is 0.01-10%; SAPO-34 molecular sieve with the content of 0.01 to 30 percent; ZSM-5 molecular sieve material, the content is 60% -80%; the balance being binder. The modified metal is selected from one or more of rare earth metal, IA, IIA, VIB and VIIB. Wherein, the Y-type molecular sieve and the mordenite are modified by rare earth metal, and the ZSM-5 molecular sieve is modified by VIB or VIIB and IA or IIA metal.
The invention discloses a preparation method of a catalyst for preparing ethylene and propylene by cracking C, V and C hexaalkanes, which comprises the following steps:
(1) Weighing a certain amount of one or two of Y-type molecular sieve and mordenite, carrying out metal modification, wherein the modified metal is rare earth metal, and drying and roasting to obtain a modified molecular sieve I;
(2) Weighing a certain amount of ZSM-5 molecular sieve, carrying out metal I and metal II loading, drying and roasting to obtain the modified ZSM-5 molecular sieve;
(3)、uniformly mixing the modified molecular sieve I, the modified ZSM-5 molecular sieve and a certain amount of SAPO-34 molecular sieve, and adding a binder and HNO 3 Mixing the solution and water, kneading, extruding, drying and roasting to obtain a compound formed molecular sieve catalyst;
(4) And carrying out hydrothermal aging treatment on the compounded and formed molecular sieve catalyst for 0.5-8 h under the conditions of normal pressure, 500-800 ℃ and 100% of water vapor to obtain the composite molecular sieve catalyst for preparing ethylene and propylene by cracking the C-V-C-hexaalkane.
Further preferably, the Y-type molecular sieve is SiO 2 /Al 2 O 3 An HY type molecular sieve with the molar ratio of 2-10; ZSM-5 molecular sieve uses SiO 2 /Al 2 O 3 HZSM-5 molecular sieve raw powder with the molar ratio of 60-300; the SAPO-34 molecular sieve adopts micron-sized molecular sieve raw powder; the binder can be pseudoboehmite.
More preferably, the rare earth metal in the step (1) is at least one selected from La, ce, pr and Nd, and the loading amount of the rare earth metal is 0.01 to 4%, preferably 1 to 3%.
The specific method for modifying the metal in the step (1) is to uniformly mix one or two of a certain amount of Y-type molecular sieve and mordenite with the salt solution of the rare earth metal element, stand for 10-12h, dry, and then place the mixture in a muffle furnace to roast at 500-600 ℃ for 4-6 h to obtain the modified molecular sieve I.
Preferably, in the step (2), the metal I is selected from VIB and VIIB metals, preferably one or more of Cr, mo and Mn; the metal loading is 0.1 to 5%, preferably 1 to 3%.
The metal II is selected from IA and IIA group metals, preferably one or more of K, mg and Ba; the metal loading is 0.01 to 10%, preferably 0.5 to 5%.
The specific method of the step (2) is that a certain amount of ZSM-5 molecular sieve is mixed with the salt solution of the metal I and the salt solution of the metal II in sequence uniformly, the mixture is dried after being kept stand for 10 to 12 hours, and then the mixture is placed in a muffle furnace to be roasted for 4 to 6 hours at 500 to 600 ℃ to obtain the modified ZSM-5 molecular sieve.
Preferably, the drying temperature in the step (3) is 80-150 ℃, the roasting temperature is 500-600 ℃, and the roasting time is 4-6 h; the temperature of the hydrothermal aging in the step (4) is 580-620 ℃, the flow rate of the steam is 15ml/h, and the time of the hydrothermal aging is 3-6 h.
The invention has the advantages that:
(1) The prepared catalyst is a composite molecular sieve catalyst, three molecular sieves with different structures are compounded, the advantages of respective pore channels of the molecular sieves can be exerted, the defects of the molecular sieves are overcome, and the internal diffusion and the external diffusion of raw material molecules and product molecules on the surface of the catalyst are facilitated, so that the pore continuous effect of the molecular sieves is maximized, and various complex reaction systems are responded.
(2) The catalyst prepared by the invention has the double functions of dehydrogenation and cracking, has good thermal stability, and can obtain higher ethylene propylene selectivity in light hydrocarbon cracking reaction. In addition, the catalyst can be subjected to repeated cyclic regeneration, and can be suitable for industrial cyclic regeneration reaction devices.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to specific embodiments, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention.
Example 1
(1) Respectively weighing 5.0g of HY molecular sieve, 5.0g of SAPO-34 molecular sieve and 50g of HZSM-5 molecular sieve (Si/Al = 150);
(2) Uniformly mixing 5.0g of HY molecular sieve and a lanthanum nitrate solution with a certain concentration in equal volume, standing for 10h, drying in an oven at 85 ℃ for 4h after standing, and then placing in a muffle furnace to roast at 500 ℃ for 4h to obtain an HY molecular sieve loaded with 1.5% of La;
(3) Respectively preparing a chromium nitrate solution with a certain concentration as a solution A and a potassium nitrate solution with a certain concentration as a solution B, uniformly mixing 50g of the HZSM-5 molecular sieve weighed in the step (1) with a certain amount of the solution A and the solution B in an isometric manner, standing for 10h, drying in an oven at 85 ℃ for 4h after standing, and then placing in a muffle furnace to roast for 4h at 500 ℃ to obtain the HZSM-5 molecular sieve loaded with 5% of Cr and 2%K;
(4) Uniformly mixing HY molecular sieve loaded with 1.5% of La, HZSM-5 molecular sieve loaded with 5% of Cr and 2%K and 5.0g of SAPO-34 molecular sieve, adding a certain amount of pseudoboehmite and a proper amount of HNO with the mass fraction of 5% 3 Solution and water, extruding and forming. Placing the obtained molded sample at room temperature for 12h, then placing the molded sample in a drying oven to dry for 6h at 120 ℃, and then placing the molded sample in a muffle furnace to bake for 4h at 500 ℃ to prepare the composite molecular sieve catalyst;
(5) And (3) carrying out hydrothermal aging on the prepared composite molecular sieve catalyst for 4 hours under the conditions of normal pressure, 600 ℃ and 100% of water vapor (the flow rate of the water vapor is 15 ml/h), thus obtaining the catalyst C-1.
Example 2
(1) Respectively weighing 5.0g of HY molecular sieve, 2.5g of SAPO-34 and 50g of HZSM-5 molecular sieve (Si/Al = 100);
(2) Uniformly mixing 5.0g of HY molecular sieve with a cerium nitrate solution with a certain concentration in equal volume, standing for 10h, drying in an oven at 85 ℃ for 4h after standing, and then placing in a muffle furnace to roast at 500 ℃ for 4h to obtain an HY molecular sieve loaded with 1% Ce;
(3) Preparing a molybdenum nitrate solution with a certain concentration as a solution A and a barium nitrate solution with a certain concentration as a solution B, mixing 50g of the HZSM-5 molecular sieve weighed in the step (1) with a certain amount of the solution A and the solution B in an isovolumetric manner, standing for 10h, drying in an oven at 85 ℃ after standing for 4h, and then placing in a muffle furnace to roast for 4h at 500 ℃ to obtain the HZSM-5 molecular sieve loaded with 2% of Mo and 1.5% of Ba;
(4) Mixing the HY molecular sieve of step (2) with 1% Ce and the HZSM-5 molecular sieve loaded with 2% Mo and 1.5% Ba obtained in step (3) with 2.5g SAPO-34 molecular sieve uniformly, and the other steps are the same as those of step (4) of example 1;
(5) The hydrothermal aging method of the composite molecular sieve was the same as in the step (5) of example 1, and finally, catalyst C-2 was obtained.
Example 3
(1) Respectively weighing 5.0g of HY molecular sieve, 5.0g of mordenite, 2.5g of SAPO-34 and 40g of HZSM-5 molecular sieve (Si/Al = 80);
(2) Uniformly mixing 5.0g of HY with 5.0g of mordenite, uniformly mixing with praseodymium nitrate solution with a certain concentration in equal volume, and standing for 10 hours; standing, drying in an oven at 85 deg.C for 4h, and calcining in a muffle furnace at 500 deg.C for 4h to obtain mixed molecular sieve raw powder loaded with 1.5% Pr;
(3) Respectively preparing a manganese nitrate solution with a certain concentration as a solution A and a magnesium nitrate solution with a certain concentration as a solution B, mixing 40g of the HZSM-5 molecular sieve weighed in the step (1) with a certain amount of the solution A and the solution B in an isometric manner, standing for 10h, drying in an oven at 85 ℃ for 4h after standing, then placing in a muffle furnace, and roasting at 500 ℃ for 4h to obtain the HZSM-5 molecular sieve loaded with 4% of Mn and 3% of Mg;
(4) Uniformly mixing the mixed molecular sieve raw powder loaded with 1.5% of Pr obtained in the step (2) and the HZSM-5 molecular sieve loaded with 4% of Mn and 3% of Mg obtained in the step (3) with the 2.5g SAPO-34 molecular sieve, and the other steps are the same as the step (4) of the example 1;
(5) The hydrothermal aging method of the composite molecular sieve was the same as in example 1, step (5), and finally catalyst C-3 was obtained.
Example 4
(1) Respectively weighing 2.5g of HY molecular sieve, 2.5g of mordenite, 2.5g of SAPO-34 and 40g of HZSM-5 molecular sieve (Si/Al = 60);
(2) Uniformly mixing 2.5g of HY molecular sieve and 2.5g of mordenite, then mixing with a neodymium nitrate solution with a certain concentration in an equal volume, standing for 10 hours, drying in an oven at 85 ℃ for 4 hours after standing, and then placing in a muffle furnace to roast at 500 ℃ for 4 hours to obtain mixed molecular sieve raw powder loaded with 1.5% of Nd;
(3) Respectively preparing a chromium nitrate solution with a certain concentration as a solution A and a barium nitrate solution with a certain concentration as a solution B, mixing 40g of HZSM-5 weighed in the step (1) with a certain amount of the solution A and the solution B in an isometric manner, standing for 10 hours, drying in an oven at 85 ℃ for 4 hours after standing, and then placing in a muffle furnace to roast at 500 ℃ for 4 hours to obtain the HZSM-5 molecular sieve loaded with 3% of Cr and 2% of Ba;
(4) The mixed molecular sieve raw powder loaded with 1.5% Nd obtained in step (2) and the HZSM-5 molecular sieve loaded with 3% Cr and 2% Ba obtained in step (3) were mixed uniformly with 2.5g of SAPO-34 molecular sieve, and the other steps were the same as in step (4) of example 1.
(5) The hydrothermal aging method of the composite molecular sieve was the same as in step (5) of example 1, and finally catalyst C-4 was obtained.
Example 5
(1) Weighing 5.0g of mordenite, 3.0g of SAPO-34 and 50g of HZSM-5 molecular sieve (Si/Al = 60);
(2) Mixing 5.0g of mordenite with a lanthanum nitrate solution with a certain concentration in an equal volume, standing for 10h, drying in an oven at 85 ℃ for 4h after standing, and then placing in a muffle furnace to roast at 500 ℃ for 4h to obtain the mordenite loaded with 2% of La;
(3) Respectively preparing a chromium nitrate solution with a certain concentration as a solution A and a magnesium nitrate solution with a certain concentration as a solution B, mixing 50g of HZSM-5 weighed in the step (1) with a certain amount of the solution A and the solution B in an isometric manner, standing for 10 hours, drying in an oven at 85 ℃ for 4 hours after standing, and then placing in a muffle furnace to roast at 500 ℃ for 4 hours to obtain the HZSM-5 molecular sieve loaded with 3% of Cr and 4% of Mg;
(4) Homogeneously mixing the mercerized molecular sieve loaded with 2% La obtained in step (2) and the HZSM-5 molecular sieve loaded with 3% Cr and 4% Mg obtained in step (3) with 3.0g SAPO-34 molecular sieves, the other steps being the same as in step (4) of example 1.
(5) The hydrothermal aging method of the composite molecular sieve was the same as in step (5) of example 1, and finally catalyst C-5 was obtained.
Comparative example 1
(1) 8.0g of SAPO-34 and 50g of HZSM-5 molecular sieve (Si/Al = 150) were weighed respectively;
(2) Uniformly mixing the HZSM-5 molecular sieve weighed in the step (1) with the SAPO-34 molecular sieve, adding a certain amount of pseudo-boehmite and a proper amount of HNO with the mass fraction of 5% 3 Solution and water, extruding and forming. The obtained molded sample is placed at room temperature for 12h, then placed in an oven to be dried at 120 ℃ for 6h, then placed in a muffle furnace to be roasted at 500 ℃ for 4h, and then subjected to hydrothermal aging at normal pressure, 600 ℃ and 100% of water vapor (the flow rate of the water vapor is 15 ml/h) for 4h to obtain the productCatalyst D-1.
Comparative example 2
(1) Weighing 8.0g HY molecular sieve and 50g HZSM-5 molecular sieve (Si/Al = 150);
(2) Uniformly mixing the two molecular sieves weighed in the step (1), mixing the two molecular sieves with a potassium nitrate solution with a certain concentration in an isometric manner, standing for 10 hours, drying in an oven at 85 ℃ for 4 hours after standing, and roasting in a muffle furnace at 600 ℃ for 4 hours to obtain the molecular sieve loaded with 2% K;
(3) Adding a certain amount of pseudo-boehmite and a proper amount of HNO with the mass fraction of 5% into the molecular sieve loaded with 2% K obtained in the step (2) 3 Solution and water, extruding and forming. The obtained molded sample was left at room temperature for 12 hours, then dried in an oven at 120 ℃ for 6 hours, further calcined in a muffle furnace at 500 ℃ for 4 hours, and then subjected to hydrothermal aging at normal pressure, 600 ℃ and 100% steam (steam flow rate 15 ml/h) for 4 hours to obtain catalyst D-2.
The performance of the catalyst prepared according to the present invention was evaluated as follows
The catalysts prepared in examples 1 to 5 were charged into a cyclically regenerable 10ml adiabatic fixed bed apparatus in which the feed and regeneration gas were freely switched by a valve. The raw materials are N-pentane, N-hexane and mixed carbon five-carbon six (N-hexane: N-pentane = 1:1) in sequence, and the regeneration gas is N 2 :O 2 =10/1, purge gas N 2 .5g of catalyst is filled in a reactor, the catalytic cracking reaction time is set to be 11min, after the reaction is finished, a valve switches purge gas, after 2-3 min of purge, the temperature is reduced to 500 ℃ of the catalyst regeneration temperature, and the regeneration gas is switched to, and the regeneration time is 15min. Reaction conditions are as follows: the reaction space velocity is 3.0h -1 The reaction temperature is 600 ℃, the reaction product is analyzed by on-line chromatography, and the experimental result is shown in tables 1-3.
TABLE 1 results of n-pentane cleavage
| Catalyst and process for producing the same | Per pass conversion/% | Ethylene selectivity/%) | Propylene selectivity/%) |
| C-1 | 62.5 | 16.5 | 30.3 |
| C-2 | 66.7 | 16.2 | 26.2 |
| C-3 | 69.4 | 17.2 | 21.5 |
| C-4 | 71.5 | 15.6 | 25.7 |
| C-5 | 67.8 | 16.7 | 28.4 |
| D-1 | 80.5 | 16.5 | 23.1 |
| D-2 | 76.1 | 15.8 | 19.0 |
TABLE 2 cracking results of n-hexane
| Catalyst and process for preparing same | Per pass conversion/% | Ethylene selectivity/%) | Propylene selectivity/%) |
| C-1 | 68.3 | 9.9 | 35.6 |
| C-2 | 72.7 | 10.5 | 29.4 |
| C-3 | 75.5 | 11.2 | 30.2 |
| C-4 | 76.8 | 10.9 | 29.4 |
| C-5 | 74.3 | 12.3 | 30.8 |
| D-1 | 85.0 | 11.7 | 25.7 |
| D-2 | 81.3 | 11.6 | 22.6 |
TABLE 3 Mixed carbon five six cracking results
After the catalyst prepared by the invention is subjected to a reaction-purging-regeneration cyclic process for 300 times, the conversion rate of raw materials and the selectivity of products are not obviously changed.
The above description is only an embodiment of the present invention, and is not intended to limit the present invention in any way, and the present invention may also have other embodiments according to the above structures and functions, and are not listed. Therefore, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention by those skilled in the art can be made within the technical scope of the present invention.
Claims (8)
1. The catalyst for preparing ethylene and propylene by cracking of C, V and C-hexaalkane is characterized in that a molecular sieve used by the catalyst is compounded by three different types of molecular sieves, and the composition and the mass fraction of the molecular sieves comprise: one or two of Y-type molecular sieve and mordenite, the content is 0.01-10%; SAPO-34 molecular sieve with the content of 0.01 to 30 percent; ZSM-5 molecular sieve, the content is 60% -80%; the balance of the binder.
2. The catalyst of claim 1, wherein the Y-type molecular sieve is SiO 2 /Al 2 O 3 An HY type molecular sieve with the molar ratio of 2-10; ZSM-5 molecular sieve uses SiO 2 /Al 2 O 3 HZSM-5 molecular sieve raw powder with the molar ratio of 60-300; the SAPO-34 molecular sieve adopts micron-sized molecular sieve raw powder.
3. A preparation method of a catalyst for preparing ethylene and propylene by cracking of C, V and C-hexaalkane is characterized by comprising the following steps:
(1) Weighing one or two of a certain amount of Y-type molecular sieve and mordenite, carrying out metal modification, wherein the modified metal is rare earth metal, and drying and roasting to obtain a modified molecular sieve I;
(2) Weighing a certain amount of ZSM-5 molecular sieve, carrying out metal I and metal II loading, drying and roasting to obtain the modified ZSM-5 molecular sieve;
(3) Uniformly mixing the modified molecular sieve I, the modified ZSM-5 molecular sieve and a certain amount of SAPO-34 molecular sieve, and adding a binder and HNO 3 Mixing the solution and water, kneading, extruding, drying and roasting to obtain a compound formed molecular sieve catalyst;
(4) And carrying out hydrothermal aging treatment on the compounded and formed molecular sieve catalyst for 0.5-8 h under the conditions of normal pressure, 500-800 ℃ and 100% of water vapor to obtain the composite molecular sieve catalyst for preparing ethylene and propylene by cracking the C-V-C-hexaalkane.
4. Root of herbaceous plantThe method of claim 3, wherein the Y-type molecular sieve is SiO 2 /Al 2 O 3 An HY type molecular sieve with the molar ratio of 2-10; ZSM-5 molecular sieve uses SiO 2 /Al 2 O 3 HZSM-5 molecular sieve raw powder with the molar ratio of 60-300; the SAPO-34 molecular sieve adopts micron-sized molecular sieve raw powder; the binder is pseudoboehmite.
5. The method for preparing the catalyst for cracking carbon five carbon six alkane to prepare the ethylene and the propylene according to claim 3, wherein the rare earth metal in the step (1) is at least one of La, ce, pr and Nd, and the loading amount of the rare earth metal is 0.01-4%, preferably 1-3%.
6. The method for preparing the catalyst for cracking the carbon five carbon six alkane to prepare the ethylene and the propylene according to the claim 3, wherein the metal I in the step (2) is selected from VIB and VIIB group metals, preferably one or more of Cr, mo and Mn; the metal loading is 0.1 to 5%, preferably 1 to 3%.
7. The method for preparing the catalyst for cracking the carbon five-carbon hexaalkane to prepare the ethylene and the propylene according to the claim 3, wherein the metal II in the step (2) is selected from IA and IIA group metals, preferably one or more of K, mg and Ba; the metal loading is 0.01 to 10%, preferably 0.5 to 5%.
8. The method for preparing the catalyst for cracking the carbon five-carbon hexaalkane to prepare the ethylene and the propylene according to claim 3, wherein the drying temperature in the step (3) is 80-150 ℃, the roasting temperature is 500-600 ℃, and the roasting time is 4-6 h; the temperature of the hydrothermal aging in the step (4) is 580-620 ℃, the flow rate of the steam is 15ml/h, and the time of the hydrothermal aging is 3-6 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211391936.2A CN115888797A (en) | 2022-11-08 | 2022-11-08 | Catalyst for preparing ethylene and propylene by cracking of C, V and C-hexaalkane and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211391936.2A CN115888797A (en) | 2022-11-08 | 2022-11-08 | Catalyst for preparing ethylene and propylene by cracking of C, V and C-hexaalkane and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115888797A true CN115888797A (en) | 2023-04-04 |
Family
ID=86481698
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211391936.2A Pending CN115888797A (en) | 2022-11-08 | 2022-11-08 | Catalyst for preparing ethylene and propylene by cracking of C, V and C-hexaalkane and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115888797A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20070020355A (en) * | 2005-08-15 | 2007-02-21 | 차이나 페트로리움 앤드 케미컬 코포레이션 | Fluid-bed catalyst for the preparation of ethylene and propylene by catalytic cracking |
| US20100145127A1 (en) * | 2007-04-04 | 2010-06-10 | Zaiku Xie | Catalytic composition for producing olefins by catalytic cracking |
| CN102746873A (en) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | Method for preparing ethylene and propylene through catalytic cracking of light hydrocarbons |
| CN105085144A (en) * | 2014-05-14 | 2015-11-25 | 中国石油天然气股份有限公司 | Production method of ethylene and propylene from C5 and C6 alkane |
| CN105085143A (en) * | 2014-05-14 | 2015-11-25 | 中国石油天然气股份有限公司 | C5 and C6 alkane and C4 mixing method for production of ethylene and propylene |
| CN105085145A (en) * | 2014-05-14 | 2015-11-25 | 中国石油天然气股份有限公司 | C5 and C6 alkane and C4 mixing process for production of ethylene and propylene |
| CN112588314A (en) * | 2020-12-14 | 2021-04-02 | 洛阳市科创石化科技开发有限公司 | Catalyst for producing propane by converting light hydrocarbon and preparation method and application thereof |
| CN112742456A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Dehydrogenation cracking catalyst, preparation method thereof and method for producing ethylene and propylene by using hydrocarbon four |
| CN114505097A (en) * | 2022-01-25 | 2022-05-17 | 中国科学院过程工程研究所 | Composite molecular sieve catalyst for light hydrocarbon cracking and high yield of low-carbon olefins and preparation method thereof |
-
2022
- 2022-11-08 CN CN202211391936.2A patent/CN115888797A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20070020355A (en) * | 2005-08-15 | 2007-02-21 | 차이나 페트로리움 앤드 케미컬 코포레이션 | Fluid-bed catalyst for the preparation of ethylene and propylene by catalytic cracking |
| US20100145127A1 (en) * | 2007-04-04 | 2010-06-10 | Zaiku Xie | Catalytic composition for producing olefins by catalytic cracking |
| CN102746873A (en) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | Method for preparing ethylene and propylene through catalytic cracking of light hydrocarbons |
| CN105085144A (en) * | 2014-05-14 | 2015-11-25 | 中国石油天然气股份有限公司 | Production method of ethylene and propylene from C5 and C6 alkane |
| CN105085143A (en) * | 2014-05-14 | 2015-11-25 | 中国石油天然气股份有限公司 | C5 and C6 alkane and C4 mixing method for production of ethylene and propylene |
| CN105085145A (en) * | 2014-05-14 | 2015-11-25 | 中国石油天然气股份有限公司 | C5 and C6 alkane and C4 mixing process for production of ethylene and propylene |
| CN112742456A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Dehydrogenation cracking catalyst, preparation method thereof and method for producing ethylene and propylene by using hydrocarbon four |
| CN112588314A (en) * | 2020-12-14 | 2021-04-02 | 洛阳市科创石化科技开发有限公司 | Catalyst for producing propane by converting light hydrocarbon and preparation method and application thereof |
| CN114505097A (en) * | 2022-01-25 | 2022-05-17 | 中国科学院过程工程研究所 | Composite molecular sieve catalyst for light hydrocarbon cracking and high yield of low-carbon olefins and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 朱宁: "轻烃催化裂解催化剂的催化机理及其动力学研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》, no. 4, 15 April 2012 (2012-04-15), pages 016 - 27 * |
| 江蕾: "基于ZSM-5分子筛的轻质链烷烃吸附分离与催化裂解制低碳烯烃研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, no. 1, 15 January 2021 (2021-01-15), pages 016 - 288 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11891347B2 (en) | Catalyzed alkylation, alkylation catalysts, and methods of making alkylation catalysts | |
| KR100228997B1 (en) | Process for producing aromatic hydrocarbon | |
| CN1915516A (en) | Catalytic cracking fluid bed catalyst containing molecular sieve | |
| CN101428235B (en) | Regeneration method of molecular sieve catalysts | |
| EP3305748A1 (en) | Process for converting naphtha | |
| CN105585401A (en) | Method for producing propylene | |
| CN103769207A (en) | Catalyst used for production of isobutene via isomerization of n-butene skeleton and combined production of propylene, and preparation method and applications thereof | |
| CN112588314B (en) | Catalyst for producing propane by converting light hydrocarbon and preparation method and application thereof | |
| TWI342306B (en) | ||
| CN110498725B (en) | Solid acid catalyzed alkylation method | |
| CN106925339A (en) | For the preparation method of the hierarchical pore molecular sieve catalyst of xylene isomerization reaction in C8 aronmatic | |
| CN101993320A (en) | Aromatization method for producing light aromatics | |
| CN100395314C (en) | Aromatization catalyst, preparation method, and application | |
| JP4344853B2 (en) | Dealuminated zeolite NU-86 and its use in hydrocarbon conversion | |
| JP6446033B2 (en) | Process for producing unsaturated hydrocarbons | |
| CN110947417B (en) | Catalyst for producing propane and gasoline from alkane, preparation method and application | |
| CN104109071B (en) | The method of cracked C 5 fraction propylene | |
| CN115888797A (en) | Catalyst for preparing ethylene and propylene by cracking of C, V and C-hexaalkane and preparation method and application thereof | |
| CN113385215B (en) | Preparation method and application of catalyst for preparing propane by hydro-upgrading | |
| CN100368356C (en) | Method for producing propylene through catalytic cracking C4 olefin | |
| CN1189433C (en) | Method for preparing ethene and propylene | |
| CN1123387C (en) | Zeolite catalyst for preparing alkylbenzene from olefin and benzene and preparing process thereof | |
| CN112642466A (en) | Butane aromatization catalyst and preparation method and application thereof | |
| CN113582801B (en) | Process for preparing isooctenes by mixing carbon four selective overlapping | |
| CN115518679B (en) | Aromatization catalyst, preparation method and application thereof and butane aromatization method |
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 |