CN114426450B - Method for preparing propylene by oxidative dehydrogenation of propane, reaction regeneration method and reaction regeneration device - Google Patents
Method for preparing propylene by oxidative dehydrogenation of propane, reaction regeneration method and reaction regeneration device Download PDFInfo
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- CN114426450B CN114426450B CN202011185070.0A CN202011185070A CN114426450B CN 114426450 B CN114426450 B CN 114426450B CN 202011185070 A CN202011185070 A CN 202011185070A CN 114426450 B CN114426450 B CN 114426450B
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- catalyst
- propane
- reaction
- oxidative dehydrogenation
- propylene
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 198
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 165
- 239000001294 propane Substances 0.000 title claims abstract description 98
- 238000011069 regeneration method Methods 0.000 title claims abstract description 82
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 title claims abstract description 75
- 230000008929 regeneration Effects 0.000 title claims abstract description 72
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 62
- 239000003054 catalyst Substances 0.000 claims abstract description 244
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 71
- 239000002699 waste material Substances 0.000 claims abstract description 58
- 229910052751 metal Inorganic materials 0.000 claims abstract description 51
- 239000002184 metal Substances 0.000 claims abstract description 51
- 239000000203 mixture Substances 0.000 claims abstract description 32
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 65
- 239000007789 gas Substances 0.000 claims description 58
- 239000007800 oxidant agent Substances 0.000 claims description 57
- 230000001590 oxidative effect Effects 0.000 claims description 50
- 239000002994 raw material Substances 0.000 claims description 46
- 238000000926 separation method Methods 0.000 claims description 30
- 239000007787 solid Substances 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 19
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 239000000376 reactant Substances 0.000 claims description 14
- 230000000694 effects Effects 0.000 claims description 13
- 238000004064 recycling Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 239000007795 chemical reaction product Substances 0.000 claims description 11
- 229910052720 vanadium Inorganic materials 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000002808 molecular sieve Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 4
- -1 rare earth metal ion Chemical class 0.000 claims description 4
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical group O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000001272 nitrous oxide Substances 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims 1
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 13
- 238000001465 metallisation Methods 0.000 abstract description 3
- 238000005299 abrasion Methods 0.000 abstract description 2
- 238000004458 analytical method Methods 0.000 description 16
- 239000011541 reaction mixture Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 238000002156 mixing Methods 0.000 description 15
- 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 14
- 238000002474 experimental method Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 239000003546 flue gas Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 230000009849 deactivation Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 239000002283 diesel fuel Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 238000003483 aging Methods 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000002826 coolant Substances 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
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Abstract
A method for preparing propylene by oxidative dehydrogenation of propane, a reaction regeneration method and a reaction regeneration device thereof, wherein the method for preparing propylene by oxidative dehydrogenation of propane adopts a mixture of a supported metal oxidative dehydrogenation catalyst and a waste catalytic cracking catalyst. The invention can effectively utilize the catalytic cracking catalyst which cannot be regenerated due to heavy metal deposition, and further reduce the abrasion of the special supported metal propane oxidative dehydrogenation catalyst in the fluidized bed reactor while obviously reducing the dosage of the special supported metal propane oxidative dehydrogenation catalyst.
Description
Technical Field
The invention relates to the fields of waste catalyst recycling and low-carbon olefin production, in particular to a method for preparing low-carbon olefin by oxidative dehydrogenation of low-carbon alkane by using a catalytic cracking device deactivated catalyst.
Background
In China, the catalytic cracking catalyst accounts for about 85% of the total consumption of the oil refining catalyst, after the catalytic cracking catalyst is repeatedly regenerated and used on the device, part of the catalyst is irreversibly deactivated due to the fact that excessive heavy metals such as vanadium and nickel are adsorbed, and the part of the nonrenewable deactivated catalytic cracking catalyst is listed in the national hazardous waste directory and belongs to hazardous wastes. The annual production of waste deactivated catalytic cracking catalyst in China is about 10 ten thousand tons, and in order to prevent environmental pollution, the waste deactivated catalytic cracking catalyst must be subjected to harmless treatment or resource utilization.
At present, most of domestic enterprises mainly adopt a magnetic separation method to treat the metal-poisoned deactivated catalytic cracking catalyst so as to select the catalytic cracking catalyst which has lighter heavy metal pollution, better performance and continuous use from the catalytic cracking balance agent by a physical method, but the method can not fundamentally solve the treatment problem of the metal-poisoned deactivated catalytic cracking catalyst. The preparation of building products by using the metal-poisoned deactivated catalytic cracking catalyst is another common idea for performing innocuous treatment or recycling on the building products at present, for example, patent CN108609857A, CN109305823A, CN109305778A, CN109304150A discloses a series of methods for preparing microcrystalline glass, high-strength ceramsite, baking-free bricks and harmless adsorption materials by taking the catalytic cracking waste catalyst as a raw material. However, since the deactivated catalysts from different catalytic cracking units have large differences in particle size distribution, heavy metal pollution degree and the like, the recycling process is difficult to ensure continuous and stable product quality reaching standards under the same technological process and preparation parameters.
In addition, another part of researchers realize the recycling of the heavy metals deposited on the poisoned and deactivated catalytic cracking catalyst by removing the heavy metals by a series of chemical treatment means so as to restore part of the cracking activity.
CN101219390a discloses a method for reactivating a catalytic cracking catalyst by using a coupling method of inorganic acid and organic acid, which utilizes the hole expanding effect of inorganic acid and the coordination function of organic acid to cooperatively complete the removal of polluted metal and the repair of pore structure of the deactivated catalytic cracking catalyst, but the method can cause the loss of active components on the catalyst while removing the polluted metal, and does not solve the problem of insufficient activity and stability of the catalyst after the reactivation caused by irreversible deactivation of molecular sieve framework damage.
CN102247880a discloses a method for recycling waste cracking agent through 'in-situ crystallization', catalytic cracking catalyst is synthesized in-situ by using catalytic cracking waste catalyst as raw material, heavy metal components such as vanadium and nickel deposited in the waste catalyst are removed by acid washing method, and catalytic cracking catalyst product is obtained through high temperature alkali fusion activation, spray drying to ball, crystallization and modification.
The recycling method deposits heavy metals on the deactivated catalyst, and heavy metal salt acid-containing wastewater can be generated to cause secondary pollution in the process of recovering the cracking activity, so that a method capable of comprehensively utilizing the heavy metals deposited on the deactivated catalytic cracking catalyst and the molecular sieve structure thereof is necessary to be developed.
Propylene is an important basic organic chemical raw material and is mainly used for producing chemical products such as polypropylene, isopropylbenzene, propylene oxide, acrylonitrile, acrylic acid, carbonyl alcohol and the like. At present, the propylene supply in China is mainly from natural gas, liquefied gas produced in the process of cracking petroleum to prepare ethylene and petroleum catalytic cracking, and the like. Because the traditional propylene production mode can not meet the increasing market demand, the contradiction between propylene supply and demand in China is increasingly prominent.
At present, the direct dehydrogenation (PDH) of propane has been industrialized, but because the direct dehydrogenation of propane is an endothermic reaction, a large amount of external heat supply is needed, and the direct dehydrogenation is performed under severe reaction conditions (about 1000K) to obtain a higher propane conversion rate, but the deep cracking of propylene product and the selective reduction of propylene caused by the deep dehydrogenation reaction are also easy to occur, and the deactivation of carbon deposition of the catalyst is caused, so that the catalyst needs to be regenerated frequently.
CN10920392a discloses a process for producing propylene from propane using a fixed fluidized bed reactor, employing a noble metal catalyst and a plurality of fixed fluidized bed reactors, in which, during normal operation, one part of the plurality of reactors is subjected to catalytic dehydrogenation reaction and the other part is subjected to catalyst regeneration to achieve operational continuity of the whole reaction process. The method can improve the conversion rate of the propane from about 30% to 45% -50%, and simultaneously ensure that the selectivity of the propylene is improved to about 90%. However, the method does not solve the problem of too fast deactivation of the catalyst, and because the reaction regeneration operation conditions are different, the operation is performed by frequently switching between different reactors, and the catalyst material is also required to be heated and cooled frequently, so that the operation is complicated.
The propane oxidative dehydrogenation (OPDH) reaction is exothermic and breaks thermodynamic limitation, so that higher conversion rate can be obtained under milder reaction conditions (less than 800K), meanwhile, the deactivation of carbon deposition of a catalyst is effectively avoided, and the regeneration frequency of the catalyst is reduced, so that the propylene (OPDH) prepared by the propane oxidative dehydrogenation is used as a novel propylene production process in recent years, and the research is continuously in progress. The high performance propane oxidative dehydrogenation catalyst systems reported so far mainly comprise vanadium-based, nickel-based, chromium-based and molybdenum-based catalysts.
CN109153621a discloses an oxidative dehydrogenation method of C2-C6 low-carbon alkane and a related reaction system, which is characterized in that a tube reactor is adopted, and cooling medium is introduced into the reactor shell to remove reaction heat release, so as to control the reaction temperature. Because the process utilizes oxygen as the oxidant, the reactor needs to be divided into an upstream region for dehydrogenation and a downstream region for oxygen removal to avoid the reduction of propylene selectivity caused by deep oxidation of propylene. Although the method can realize high conversion rate of propane and high yield of propylene at the same time, the reactor structure is complex, and the continuous operation of the device during the deactivation of the catalyst is difficult to ensure.
US20190194092A1 discloses a process method for preparing propylene by oxidative dehydrogenation of propane coupled with a catalytic cracker, which uses CO 2 in regenerated flue gas of the catalytic cracker as an oxidant and separates propane contained in catalytic cracking liquefied gas to be used as one of raw materials of the oxidative dehydrogenation device. However, the method cannot realize the recycling of the catalytic cracking deactivated catalyst, and the operation stability of the method is greatly influenced by the fluctuation of the catalytic cracking device due to the high coupling with the catalytic cracking device.
Disclosure of Invention
One of the technical problems to be solved by the invention is to provide a method for preparing propylene by oxidative dehydrogenation of propane based on the prior art, which utilizes a heavy metal deposition deactivated catalytic cracking catalyst in a catalytic cracking device and simultaneously reduces the dosage of a supported metal catalyst of the oxidative dehydrogenation device of propane.
The second technical problem to be solved by the invention is to provide a reaction regeneration method and a device for preparing propylene by oxidative dehydrogenation of propane.
The method for preparing propylene by oxidative dehydrogenation of propane provided by the invention comprises the steps of introducing a propane raw material and an oxidant into a dehydrogenation reactor, contacting the propane raw material and the oxidant with a catalyst, performing oxidative dehydrogenation reaction to generate propylene, separating a reactant flow from the catalyst gas and solid, and further separating propylene, propane and the oxidant by the separated reactant flow into a product separation device, wherein the propane and the oxidant are circulated back into the dehydrogenation reactor for continuous reaction, and the catalyst is a mixture of a supported metal oxidative dehydrogenation catalyst and a waste catalytic cracking catalyst.
The invention provides a reaction regeneration method for preparing propylene by oxidative dehydrogenation of propane, which adopts the method for preparing propylene by oxidative dehydrogenation of propane, wherein the dehydrogenation reactor is a fluidized bed dehydrogenation reactor, reactant flow and catalyst are separated in a gas-solid manner, the separated reactant flow enters a product separation device to further separate propylene, propane and oxidant, a part of separated spent catalyst is returned to the fluidized bed dehydrogenation reactor after steam stripping, the other part of the spent catalyst enters a catalyst regenerator for burning and regenerating, the regenerated catalyst is returned to the fluidized bed reactor for recycling, and the catalyst is a mixture of a supported metal oxidative dehydrogenation catalyst and a waste catalytic cracking catalyst.
The invention provides a reaction regenerating device for preparing propylene by oxidative dehydrogenation of propane, which comprises the following components: the device comprises a fluidized bed dehydrogenation reactor, gas-solid separation equipment, a stripper, a catalyst regenerator and a pressure swing adsorption separation device which are sequentially communicated, wherein the top of the fluidized bed dehydrogenation reactor is provided with the gas-solid separation equipment, a solid phase outlet of the gas-solid separation equipment is communicated with the catalyst regenerator through the stripper, a regenerated catalyst outlet of the catalyst regenerator is communicated with the bottom of the fluidized bed dehydrogenation reactor, and a gas phase outlet of the gas-solid separation equipment is communicated with the pressure swing adsorption separation device.
The method for preparing propylene by oxidative dehydrogenation of propane has the beneficial effects that:
The method for preparing propylene by oxidative dehydrogenation of propane provided by the invention effectively utilizes the catalytic cracking catalyst which cannot be regenerated due to heavy metal deposition, and has no emission of secondary pollutants such as heavy metal salt acid-containing wastewater. The invention can obviously reduce the consumption of the special supported metal propane oxidative dehydrogenation catalyst and further reduce the abrasion of the catalyst in the fluidized bed reactor, and the oxidant in the catalyst regeneration tail gas can be recycled, so that the emission index of the propylene preparation process by propane oxidative dehydrogenation can be further effectively reduced.
The dehydrogenation reactor in the reaction regeneration method and device for preparing propylene by oxidative dehydrogenation of propane adopts the fluidized bed dehydrogenation reactor, so that the reaction and regeneration recycling of the catalyst can be realized, and meanwhile, oxygen and carbon dioxide in the catalyst regeneration tail gas can be used as an oxidant for recycling.
Drawings
The attached drawing is a schematic flow chart of the method for preparing propylene by oxidative dehydrogenation of propane.
Reference numerals illustrate:
I-dehydrogenation reactor II-catalyst regenerator
III-reaction product/raw material heat exchanger IV-product separation system
VI-reactor stripping section of V-regenerated flue gas separation system
I-catalyst circulation slide valve ii-spent slide valve
Iii-regeneration slide iv-reaction raw material mixing valve
V-oxidizing gas mixing valve vi-circulation feeding mixing valve
1-23 Are material pipelines.
Detailed Description
The following describes specific embodiments of the present invention in detail.
In the first aspect, the method for preparing propylene by oxidative dehydrogenation of propane is provided by the invention, a propane raw material and an oxidant are introduced into a dehydrogenation reactor, the propane raw material and the oxidant are contacted with a catalyst to perform oxidative dehydrogenation reaction to generate propylene, a reactant flow and the catalyst are subjected to gas-solid separation, the separated reactant flow enters a product separation device to further separate propylene, propane and the oxidant, wherein the propane and the oxidant are recycled to the dehydrogenation reactor to continue the reaction, and the catalyst is a mixture of a supported metal oxidative dehydrogenation catalyst and a waste catalytic cracking catalyst.
In the method, the supported metal oxidative dehydrogenation catalyst contains 5-15wt% of metal active components and a heat-resistant inorganic oxide carrier based on the total weight of the catalyst, wherein the metal active components are selected from one or more of Cr, co, ni, mo and RE, and the heat-resistant inorganic oxide carrier is selected from one or a mixture of more of Al 2O3、TiO2、CeO2、SiO2, MCF molecular sieve and SBA-15 molecular sieve.
Optionally, in the catalyst, the proportion of the supported metal oxidative dehydrogenation catalyst is 50-95 wt%, and the proportion of the waste catalytic cracking catalyst is 5-50 wt%, preferably 15-35 wt%.
Optionally, the waste catalytic cracking catalyst is a catalytic cracking catalyst for depositing Ni and V metals, and the micro-reaction activity is less than 65; the catalytic cracking catalyst contains a Y-type molecular sieve or a rare earth metal ion modified Y-type molecular sieve; preferably, the total content of Ni and V in the waste catalytic cracking catalyst is not less than 2wt%. The micro-reaction activity is to take standard light diesel oil as raw material, react the light diesel oil with catalytic cracking catalyst deactivated by water vapor at 800 ℃ for 4 hours at 482 ℃ and calculate the total conversion rate of the weight of the diesel oil, and the total conversion rate of the diesel oil is taken as the micro-reaction activity index.
Optionally, the spent catalytic cracking catalyst is treated by an activation process comprising:
(1) Removing residual oil on the surface of the waste catalytic cracking catalyst;
(2) The method of impregnation is adopted to load metal active components on the waste catalytic cracking catalyst, wherein the metal active components are selected from one or more of V, cr, co, ni, mo and RE.
Preferably, the method for activating the waste catalytic cracking catalyst comprises the following steps:
(1) Removing residual oil on the surface of the waste catalytic cracking catalyst, pickling and roasting;
(2) Impregnating the roasted waste catalytic cracking catalyst with an aqueous solution containing a first metal active component salt, and obtaining a precursor after impregnation, ageing, drying and roasting;
(3) The aqueous solution containing the salt of the second metal active component and the precursor obtained in the step (2) are put into a high-pressure reaction kettle to react under the conditions of hydrogen pressure of 2-4 MPa and 100-200 ℃;
(4) Adding the solid reaction product obtained in the step (3) into a citric acid aqueous solution, standing for 1-2 hours, filtering, drying and roasting to obtain a treated waste catalytic cracking catalyst;
wherein the first metal active component and the second metal active component are selected from one or more of V, cr, co, ni, mo and RE.
Preferably, in the step (3), the aqueous solution containing the auxiliary metal salt and the aqueous solution containing the second metal active component salt are put into a high-pressure reaction kettle together with the precursor obtained in the step (2) and react under the conditions of the hydrogen pressure of 2-4 MPa and the temperature of 100-200 ℃; the auxiliary metal is La and/or Ce.
Optionally, the dehydrogenation reactor is a fluidized bed reactor; preference is given to fluidized-bed reactors provided with heat exchange jackets. The fluidized bed reactor comprises a dense bed reactor, a fast fluidized bed reactor or a dilute bed reactor.
Optionally, the oxidizing agent is selected from oxygen, carbon dioxide or nitrous oxide. The propane content in the propane raw material is not lower than 85%, and the consumption of the oxidant is 1-30 times of the stoichiometric amount of the propane; preferably, the oxidant is used in an amount of 3 to 5 times the stoichiometric amount of propane.
Optionally, the dehydrogenation reactor is operated under the following conditions: the reaction temperature is 350-750 ℃, the reaction pressure is 0.005-0.50 MPa, the mass ratio of catalyst to reaction raw material is 5-50, and the volume airspeed is 100-4500 h -1; preferably, the dehydrogenation reactor is operated under the following conditions: the reaction temperature is 450-600 ℃, the reaction pressure is 0.10-0.20 MPa, the mass ratio of the catalyst to the reaction raw materials is 30-50, and the volume airspeed is 3000-4000 h -1. Wherein the reaction raw material refers to a mixed gas of a propane raw material and an oxidant.
In a second aspect, the reaction regeneration method for preparing propylene by oxidative dehydrogenation of propane provided by the invention adopts the method for preparing propylene by oxidative dehydrogenation of propane, the dehydrogenation reactor is a fluidized bed dehydrogenation reactor, reactant flow and catalyst are separated in a gas-solid manner, the separated reactant flow enters a product separation device to further separate propylene, propane and oxidant, a part of separated spent catalyst is returned to the fluidized bed dehydrogenation reactor after steam stripping, the other part of the catalyst enters a catalyst regenerator for burning regeneration, the regenerated catalyst is returned to the fluidized bed reactor for recycling, and the catalyst is a mixture of a supported metal oxidative dehydrogenation catalyst and a waste catalytic cracking catalyst.
Optionally, the operating conditions of the catalyst regenerator are: the temperature is 550-700 ℃, the pressure is 0.01-0.55 MPa, and the linear velocity of the regeneration gas is 0.1-1.0 m/s.
Preferably, the operating conditions of the regenerator are: the temperature is 600-650 ℃, the pressure is 0.11-0.25 MPa, and the linear velocity of the regeneration gas is 0.1-0.5 m/s.
In a third aspect, the present invention provides a reaction regeneration device for producing propylene by oxidative dehydrogenation of propane, comprising: the device comprises a fluidized bed dehydrogenation reactor, gas-solid separation equipment, a stripper, a catalyst regenerator and a pressure swing adsorption separation device which are sequentially communicated, wherein the top of the fluidized bed dehydrogenation reactor is provided with the gas-solid separation equipment, a solid phase outlet of the gas-solid separation equipment is communicated with the catalyst regenerator through the stripper, a regenerated catalyst outlet of the catalyst regenerator is communicated with the bottom of the fluidized bed dehydrogenation reactor, and a gas phase outlet of the gas-solid separation equipment is communicated with the pressure swing adsorption separation device.
Preferably, the fluidized bed dehydrogenation reactor is a riser reactor, and the solid phase outlet of the gas-solid separation device is communicated with the catalyst inlet at the bottom of the fluidized bed dehydrogenation reactor. And a regeneration tail gas outlet of the catalyst regenerator is communicated with the fluidized bed dehydrogenation reactor.
In the method, propane raw material is preheated and then introduced into the bottom of a dehydrogenation reactor, and is fully mixed with oxidizing gas which is also introduced into the bottom of the reactor, and then is contacted with a catalyst from a stripping section of the dehydrogenation reactor and a catalyst regenerator, and the oxidation dehydrogenation reaction occurs in the upward movement process of reactant flow. Comprising separating the reactant stream, which produces propylene, unreacted propane and oxidant, and catalyst by a cyclone in a settler: after the separated spent catalyst enters a stripping section for stripping, one part of the catalyst returns to the bottom of the dehydrogenation reactor through a circulating vertical pipe, and the other part of the catalyst enters a catalyst regenerator through a spent inclined pipe for regeneration. And (3) feeding the gas mixture obtained by gas-solid separation into a product separation device to obtain a propylene product, and recycling unreacted propane and oxidant back to the dehydrogenation reactor for re-reaction. The oxidant contained in the regenerated tail gas separated by the catalyst regenerator is circulated and returned to the dehydrogenation reactor for re-reaction.
In the method of the present invention, the propane raw material is a mixture of a recycle feed and additional fresh propane, and the fresh propane feed amount is determined by the propane content in the recycle feed, so that the propane content in the reaction raw material obtained by mixing is not less than 85%, preferably not less than 95%.
In the method of the present invention, the oxidizing agent may be selected from one or a mixture of several of oxygen, carbon dioxide and nitrous oxide. The oxidizing gas is the mixture of the regenerated flue gas oxidizing agent and the fresh oxidizing agent, the feeding amount of the fresh oxidizing agent is determined according to the propane content in the reaction raw material entering the dehydrogenation reactor, and the volume ratio of the sum of the oxidizing agent in the circulating feeding agent and the oxidizing gas to the propane in the reaction raw material is 1-30 times of the stoichiometric consumption.
In the process of the present invention, the reaction material is preheated to 150-600 deg.c, preferably 450-500 deg.c, either directly by heat source or through heat exchange with the reaction product or other hot material or through a combination of the two.
In the invention, one or more catalyst circulation risers are arranged from the lower part of the stripping section of the fluidized bed dehydrogenation reactor to the lower part of the dehydrogenation reactor so as to adjust the apparent catalyst density in the dehydrogenation reactor.
In the invention, a coil is arranged in the dense bed of the catalyst regenerator, heating or cooling medium can be selectively introduced according to the overall heat balance condition of the reaction system, and the temperature of the regenerated catalyst returned to the dehydrogenation reactor can be regulated.
In the invention, the flow rate of the spent catalyst entering the catalyst regenerator is determined by the analysis result of the activity of the catalyst, the spent catalyst passes through the inclined tube of the spent catalyst and is controlled to the lower part of the catalyst regenerator by the sliding valve of the spent catalyst from the lower part of the gas section of the dehydrogenation reactor, and enters the catalyst regenerator to complete regeneration under the lifting of the regeneration gas.
In the invention, the regenerated catalyst passes through a regenerated catalyst inclined pipe from the upper part of the dense bed layer of the catalyst regenerator and is controlled by a regenerated slide valve to return to the lower part of the fluidized bed dehydrogenation reactor.
The method provided by the present invention is further described below with reference to the accompanying drawings, but the present invention is not limited thereto.
FIG. 1 is a schematic flow chart of the regeneration method for the reaction of preparing propylene by oxidative dehydrogenation of propane. As shown in fig. 1, the circulating propane from the product separation system IV is mixed into circulating feed through a pipeline 9 and circulating oxidant through a pipeline 10 by a circulating feed mixing valve vi, and is mixed with fresh propane from a pipeline 2 into reaction feed through a reaction raw material mixing valve IV by a pipeline 1, wherein the opening direction and opening degree of the reaction raw material mixing valve IV are controlled by the detection result of an online analyzer of the composition of the circulating feed, the reaction raw material is heat-exchanged with the reaction product to 450-500 ℃ through a product/raw material heat exchanger III by a pipeline 3, the preheated reaction raw material is introduced into the bottom of a fluidized bed dehydrogenation reactor I through a pipeline 4, and is fully mixed with oxidizing gas introduced into the bottom of the reactor from a pipeline 12, the regenerated catalyst from the reactor stripping section VI via line 32 and from the catalyst regenerator II via line 36 is contacted in the lower portion of the dehydrogenation reactor I and the reaction mixture undergoes oxidative dehydrogenation during the gas-to-agent contact and co-upward movement. After propylene, unreacted complete propane, oxidant and catalyst which are produced by the reaction leave the reactor, gas-solid separation is carried out by a cyclone separator in a settler above the reactor: the obtained gas mixture exchanges heat with the reaction raw material through a product/raw material heat exchanger III by a pipeline 5, and the reaction product after heat exchange enters a product separation device IV by a pipeline 6 to be separated to obtain a product propylene 7, unreacted propane 9 and an oxidant 10, wherein the obtained unreacted propane and the oxidant are circulated and returned to the dehydrogenation reactor for reaction again. After the spent catalyst obtained by separation enters the stripping section VI of the reactor to complete stripping, part of the spent catalyst returns to the bottom of the dehydrogenation reactor through circulating risers 31 and 32 (wherein i is a catalyst circulation slide valve which can be used for controlling the flow rate of the circulating catalyst, and the opening degree of the catalyst circulation slide valve i is controlled by the apparent density of the catalyst in the dehydrogenation reactor), and the other part of the spent catalyst returns to the lower part of the catalyst regenerator II through spent inclined tubes 33 and 34 (wherein II is a spent slide valve which can be used for controlling the flow rate of the spent catalyst, and the opening degree of the spent slide valve II is controlled according to the detection result of catalyst activity analysis) and enters the catalyst regenerator II for regeneration under the lifting of regenerated gas from a pipeline 21. After the regenerated catalyst is regenerated, the regenerated catalyst is returned to the lower part of the dehydrogenation reactor from the upper part of the dense bed of the catalyst regenerator through regeneration inclined pipes 35 and 36 (wherein iii is a regeneration slide valve which can be used for controlling the flow rate of the regenerated catalyst, and the opening degree of the regeneration slide valve ii is controlled by the apparent density of the catalyst of the dehydrogenation reactor). And a coil is arranged in the dense bed of the catalyst regenerator, heating medium or cooling medium can be selectively introduced, and the overall heat balance adjustment of the reaction system is realized by adjusting the temperature of the regenerated catalyst returned to the dehydrogenation reactor. The catalyst regenerator pressure may be controlled by a regeneration flue gas separation system using the amount of exhaust emissions from the regeneration tail gas 23. The carbon dioxide and oxygen separated by the catalyst regeneration flue gas through the regeneration flue gas separation system V can be used as an oxidant, and the carbon dioxide and the oxygen are mixed with a fresh oxidant 11 through an oxidation gas mixing valve V and then recycled back to the dehydrogenation reactor I for re-reaction. The opening of the oxidizing gas mixing valve v is determined according to the content of propane in the reaction raw material entering the dehydrogenation reactor, so that the volume ratio of the sum of the oxidizing agent in the circulating feed and the oxidizing agent in the oxidizing gas to the propane in the reaction raw material is 3-5 times of the stoichiometric consumption.
The process provided by the present invention is further illustrated by the following examples, which are not intended to limit the invention.
Examples and comparative examples:
the catalytic cracking catalyst has a trade name CR022 and is produced by Qilu division of China petrochemical catalyst. CR022-1 and CR022-2 are waste catalytic cracking catalysts taken from a catalytic cracking device, and the micro-inverse activity is 58.
The oxalic acid, ammonium metavanadate, 85wt% phosphoric acid reagent, nickel nitrate, cerium nitrate, ammonium metavanadate, citric acid, chromium nitrate and cerium nitrate are all analytically pure and are produced by Beijing Limited company, national pharmaceutical group chemical reagent.
Preparation example 1
The preparation method of the supported metal oxidative dehydrogenation catalyst A comprises the following steps:
Firstly adding oxalic acid as a complexing agent and a reducing agent to dissolve ammonium metavanadate, preparing a solution according to a set V load, soaking with gamma-Al 2O3, carrying out ultrasonic treatment for 0.5h, standing for 12h, drying at 110 ℃ for 10h, placing the dried precursor in a muffle furnace, programming to be heated to 600 ℃ under an air atmosphere, and calcining for 4h. The content of V 2O5 in the oxidative dehydrogenation catalyst A of the Al 2O3 -supported metal V based on the weight of the catalyst was 6wt% based on the metal oxide, and the specific surface was 203m 2/g and the pore volume was 0.450cm 3/g as determined by analysis.
Preparation example 2
(1) The waste catalytic cracking catalyst CR022-1 is dried for 2 hours after oil on the surface of the catalyst is removed by extraction.
(2) And adding a 20wt% phosphoric acid aqueous solution into the dried waste catalyst, reacting for 2 hours at 85 ℃, filtering, drying, and roasting for 8 hours at 600 ℃ in a muffle furnace.
(3) Dissolving a first metal active component precursor nickel nitrate in deionized water to obtain a nickel nitrate solution with the weight percent of 13 percent, adding the waste catalytic cracking catalyst roasted in the step (2) into the solution, soaking for 2 hours, ageing for 4 hours, drying at 80 ℃ for 12 hours, and roasting at 650 ℃ for 4 hours to obtain a precursor;
(4) Dissolving an auxiliary precursor cerium nitrate in deionized water to obtain a cerium nitrate solution with the weight percent of 7 percent;
(5) Dissolving a second active component precursor ammonium metavanadate in deionized water to obtain a 2wt% ammonium metavanadate solution;
(6) Putting the solution obtained in the step (4) and the solution obtained in the step (5) and the precursor obtained in the step (3) into a high-pressure reaction kettle, and reacting for 3 hours under the conditions of hydrogen pressure of 3MPa and 180 ℃ after hydrogen replacement;
(7) And (3) adding the solid reaction product obtained in the step (6) into an 8w% citric acid aqueous solution, standing for 2 hours, filtering, drying, and roasting in a muffle furnace at 600 ℃ for 10 hours to obtain the treated waste agent-1.
Preparation example 3
The waste catalytic cracking catalyst CR022-2 was treated in the same manner as in preparation example 2 to obtain a treated waste agent-2.
Preparation example 4
(1) The waste catalytic cracking catalyst CR022-1 is dried for 2 hours after oil on the surface of the catalyst is removed by extraction.
(2) And adding a 20wt% phosphoric acid aqueous solution into the dried waste catalyst, reacting for 2 hours at 85 ℃, filtering, drying, and roasting for 8 hours at 600 ℃ in a muffle furnace.
(3) Dissolving an active component precursor chromium nitrate in deionized water to obtain a chromium nitrate solution with the concentration of 16.3w percent, adding a roasted waste catalytic cracking catalyst into the solution, and carrying out impregnation, ageing, drying and roasting treatment to obtain a precursor;
(4) Dissolving an auxiliary precursor cerium nitrate in deionized water to obtain cerium nitrate solution with the concentration of 7w percent, and uniformly mixing the cerium nitrate solution with a furfural aqueous solution with the mass of 5 times;
(5) Putting the solution obtained in the step (4) and the precursor obtained in the step (3) into a high-pressure reaction kettle, and reacting for 3 hours under the conditions of hydrogen pressure of 3MPa and 180 ℃ after hydrogen replacement;
(6) And (3) adding the solid reaction product obtained in the step (5) into 8w% citric acid aqueous solution, standing for 2 hours, filtering, drying, and roasting in a muffle furnace at 600 ℃ for 10 hours. The treated waste agent-3 is obtained.
Preparation example 5
(1) The waste catalytic cracking catalyst CR022-2 is extracted to remove oil on the surface of the catalyst, and then is dried for 2 hours.
(2) And adding a 20wt% phosphoric acid aqueous solution into the dried waste catalyst, reacting for 2 hours at 85 ℃, filtering, drying, and roasting for 8 hours at 600 ℃ in a muffle furnace. And obtaining the treated waste agent-4.
TABLE 1 Properties of spent catalytic cracking catalyst
TABLE 2 Properties of spent catalytic cracking catalyst after treatment
Comparative example 1
Comparative example 1 illustrates the effect of oxidative dehydrogenation of propane to propylene using a supported metal oxidative dehydrogenation catalyst.
The reaction results were examined using a small-sized fixed fluidized bed reactor, the flow is shown in FIG. 2, the fixed fluidized bed reactor 201 is a stainless steel reactor, and the effective portion phi is 30mm×600mm. The experiment adopts a reaction and regeneration alternating intermittent operation mode: during the reaction, a certain amount of oxidative dehydrogenation catalyst A (the amount is calculated according to the mass ratio of the agent to the gas) is firstly filled in a stainless steel reactor, after the temperature is raised to the set reaction temperature, the reaction mixed gas containing the oxidant and the propane from a pipeline 202 is introduced into a fixed fluidized bed reactor 201 from the lower part through a pipeline 204, unconverted oxidant, propane and reaction product propylene leave the fixed fluidized bed reactor from the upper part through a pipeline 210, and after the reaction product is cooled 205 by a water tank, the composition of the reaction product is analyzed by an online gas chromatograph 206. During regeneration, after 3 times of replacement by N 2, the temperature is raised to a set regeneration temperature, regeneration air from the pipeline 203 is introduced from the lower part of the reactor, regeneration flue gas leaves the reactor from the upper part of the reactor, after passing through the CO reformer 207, the composition of the regeneration flue gas is analyzed by the CO 2 analyzer 209, and the calibration CO 2 from the pipeline 208 can calibrate the CO 2 analyzer.
The composition of the reaction mixture is shown in Table 3 using CO 2 as the oxidant. The feed amount was 0.6Nm 3/h.
The reaction conditions are as follows: the reaction temperature is 550 ℃, the reaction pressure is 0.10MPa, the mass ratio of the catalyst to the gas (reaction raw material) is 30, and the volume airspeed is 3220h -1.
The regeneration operating conditions were: the regeneration temperature is 650 ℃, the regeneration pressure is 0.20MPa, and the linear velocity of the regenerated air is 0.5m/s.
The reaction results obtained are shown in Table 5 by analysis using an on-line gas chromatograph.
TABLE 3 reaction mixture gas composition
| Component (A) | C3H8 | O2 | CO2 | N2 | H2O |
| Content/v% | 24.2 | 0.7 | 72.8 | 2.1 | 0.20 |
Examples 1-12 illustrate the effect of the process for producing propylene by dehydrogenation of propane provided by the present invention.
Example 1
The small-sized fixed fluidized bed reaction apparatus and experimental procedure used were the same as in comparative example 1.
15Wt% of treated waste agent-1 and 85wt% of supported metal oxidative dehydrogenation catalyst A are adopted to be used as a catalyst after being compatible.
The composition of the reaction mixture is shown in Table 3 using CO 2 as the oxidant. The feed amount was 0.6Nm 3/h.
The reaction conditions are as follows: the reaction temperature is 550 ℃, the reaction pressure is 0.10MPa, the mass ratio of the catalyst to the gas (reaction raw material) is 30, and the volume airspeed is 3220h -1.
The regeneration operating conditions were: the temperature is 650 ℃, the pressure is 0.20MPa, and the linear velocity of regenerated air is 0.5m/s.
The reaction results obtained are shown in Table 5 by analysis using an on-line gas chromatograph.
Example 2
The small-sized fixed fluidized bed reaction apparatus and experimental procedure used were the same as in comparative example 1.
25Wt% of treated waste agent-1 (the properties are shown in Table 3) was used as a catalyst after being compatible with 75wt% of the supported metal oxidative dehydrogenation catalyst A.
The composition of the reaction mixture is shown in Table 3 using CO 2 as the oxidant. The feed amount was 0.6Nm 3/h.
The reaction conditions are as follows: the reaction temperature is 550 ℃, the reaction pressure is 0.10MPa, the mass ratio of the catalyst to the gas (reaction raw material) is 30, and the volume airspeed is 3220h -1.
The regeneration operating conditions were: the regeneration temperature is 650 ℃, the regeneration pressure is 0.20MPa, and the linear velocity of the regenerated air is 0.5m/s.
The reaction results obtained are shown in Table 5 by analysis using an on-line gas chromatograph.
Example 3
The small-sized fixed fluidized bed reaction apparatus and the experimental method used were the same as in comparative example 1.
35Wt% of treated waste agent-1 (the properties are shown in Table 3) was used as a catalyst after being compatible with 65wt% of the supported metal oxidative dehydrogenation catalyst A.
The composition of the reaction mixture is shown in Table 3 using CO 2 as the oxidant. The feed amount was 0.6Nm 3/h.
The reaction conditions are as follows: the reaction temperature is 550 ℃, the reaction pressure is 0.10MPa, the mass ratio of the catalyst to the gas (reaction raw material) is 30, and the volume airspeed is 3220h -1.
The regeneration operating conditions were: the regeneration temperature is 650 ℃, the regeneration pressure is 0.20MPa, and the linear velocity of the regenerated air is 0.5m/s.
The reaction results obtained are shown in Table 5 by analysis using an on-line gas chromatograph.
Example 4
The small-sized fixed fluidized bed reaction apparatus and the experimental method used were the same as in comparative example 1.
60Wt% of treated waste agent-1 and 40wt% of supported metal oxidative dehydrogenation catalyst A are adopted to be used as a catalyst after being compatible.
The composition of the reaction mixture is shown in Table 3 using CO 2 as the oxidant. The feed amount was 0.6Nm 3/h.
The reaction conditions are as follows: the reaction temperature is 550 ℃, the reaction pressure is 0.10MPa, the mass ratio of the catalyst to the gas (reaction raw material) is 30, and the volume airspeed is 3220h -1.
The regeneration operating conditions were: the regeneration temperature is 650 ℃, the regeneration pressure is 0.20MPa, and the linear velocity of the regenerated air is 0.5m/s.
The reaction results obtained are shown in Table 5 by analysis using an on-line gas chromatograph.
Example 5
The small-sized fixed fluidized bed reaction apparatus and the experimental method used were the same as in comparative example 1.
The treated waste agent-1 is used as a catalyst.
The composition of the reaction mixture is shown in Table 3 using CO 2 as the oxidant. The feed amount was 0.6Nm 3/h.
The reaction conditions are as follows: the reaction temperature is 550 ℃, the reaction pressure is 0.10MPa, the mass ratio of the catalyst to the gas (reaction raw material) is 30, and the volume airspeed is 3220h -1.
The regeneration operating conditions were: the regeneration temperature is 650 ℃, the regeneration pressure is 0.20MPa, and the linear velocity of the regenerated air is 0.5m/s.
The reaction results obtained are shown in Table 6 by analysis using an on-line gas chromatograph.
Example 6
The small-sized fixed fluidized bed reaction apparatus and experimental procedure used were the same as in comparative example 1.
The catalyst is prepared by mixing 25wt% of treated waste agent-1 with 75wt% of supported metal oxidative dehydrogenation catalyst A.
The composition of the reaction mixture is shown in Table 3 using CO 2 as the oxidant. The feed amount was 0.6Nm 3/h.
The reaction conditions are as follows: the reaction temperature is 650 ℃, the reaction pressure is 0.10MPa, the mass ratio of the catalyst to the gas (reaction raw material) is 30, and the volume space velocity is 3610h -1.
The regeneration reaction conditions are as follows: the regeneration temperature is 650 ℃, the regeneration pressure is 0.20MPa, and the linear velocity of the regenerated air is 0.5m/s.
The reaction results obtained are shown in Table 6 by analysis using an on-line gas chromatograph.
Example 7
The small-sized fixed fluidized bed reaction apparatus and experimental procedure used were the same as in comparative example 1.
The catalyst is prepared by mixing 25wt% of treated waste agent-1 with 75wt% of supported metal oxidative dehydrogenation catalyst A.
The composition of the reaction mixture is shown in Table 3 using CO 2 as the oxidant. The feed amount was 0.6Nm 3/h.
The reaction conditions are as follows: the reaction temperature is 550 ℃, the reaction pressure is 0.30MPa, the mass ratio of the catalyst to the gas (reaction raw material) is 30, and the volume space velocity is 1615h -1.
The regeneration reaction conditions are as follows: the regeneration temperature is 650 ℃, the regeneration pressure is 0.20MPa, and the linear velocity of the regenerated air is 0.5m/s.
The reaction results obtained are shown in Table 6 by analysis using an on-line gas chromatograph.
Example 8
The small-sized fixed fluidized bed reaction apparatus and experimental procedure used were the same as in comparative example 1.
The catalyst is prepared by mixing 25wt% of treated waste agent-1 with 75wt% of supported metal oxidative dehydrogenation catalyst A.
The composition of the reaction mixture is shown in Table 3 using CO 2 as the oxidant. The feed amount was 0.6Nm 3/h.
The reaction conditions are as follows: the reaction temperature is 550 ℃, the reaction pressure is 0.10MPa, the mass ratio of the catalyst to the gas (reaction raw material) is 50, and the volume airspeed is 3220h -1.
The regeneration operating conditions were: the regeneration temperature is 650 ℃, the regeneration pressure is 0.20MPa, and the linear velocity of the regenerated air is 0.5m/s.
The reaction results obtained are shown in Table 6 by analysis using an on-line gas chromatograph.
Example 9
The small-sized fixed fluidized bed reaction apparatus and experimental procedure used were the same as in comparative example 1.
The catalyst is prepared by mixing 25wt% of treated waste agent-2 with 75wt% of supported metal oxidative dehydrogenation catalyst A.
The composition of the reaction mixture is shown in Table 3 using CO 2 as the oxidant. The feed amount was 0.6Nm 3/h.
The reaction conditions are as follows: the reaction temperature is 550 ℃, the reaction pressure is 0.10MPa, the mass ratio of the catalyst to the gas (reaction raw material) is 30, and the volume airspeed is 3220h -1.
The regeneration operating conditions were: the regeneration temperature is 650 ℃, the regeneration pressure is 0.20MPa, and the linear velocity of the regenerated air is 0.5m/s.
The reaction results obtained are shown in Table 6 by analysis using an on-line gas chromatograph.
Example 10
The small-sized fixed fluidized bed reaction apparatus and experimental procedure used were the same as in comparative example 1.
The catalyst is prepared by mixing 25wt% of treated waste agent-1 with 75wt% of supported metal oxidative dehydrogenation catalyst A.
The composition of the reaction mixture is shown in Table 4 using O 2 as an oxidizing agent. The feed amount was 0.6Nm 3/h.
TABLE 4 second reaction mixture composition
| Component (A) | C3H8 | O2 | CO2 | N2 | H2O |
| Content/v% | 24.2 | 72.8 | 0.5 | 2.2 | 0.3 |
The reaction conditions are as follows: the reaction temperature is 550 ℃, the reaction pressure is 0.10MPa, the mass ratio of the catalyst to the gas (reaction raw material) is 30, and the volume airspeed is 3220h -1.
The regeneration operating conditions were: the regeneration temperature is 650 ℃, the regeneration pressure is 0.20MPa, and the linear velocity of the regenerated air is 0.5m/s.
The reaction results obtained are shown in Table 7 by analysis using an on-line gas chromatograph.
Example 11
The small-sized fixed fluidized bed reaction apparatus and experimental procedure used were the same as in comparative example 1.
25Wt% of the treated waste agent-3 is adopted to be compatible with 75wt% of the supported metal oxidative dehydrogenation catalyst A to be used as a catalyst.
The composition of the reaction mixture is shown in Table 3 using CO 2 as the oxidant. The feed amount was 0.6Nm 3/h.
The reaction conditions are as follows: the reaction temperature is 550 ℃, the reaction pressure is 0.10MPa, the mass ratio of the catalyst to the gas (reaction raw material) is 30, and the volume airspeed is 3220h -1.
The regeneration operating conditions were: the regeneration temperature is 650 ℃, the regeneration pressure is 0.20MPa, and the linear velocity of the regenerated air is 0.5m/s.
The reaction results obtained are shown in Table 7 by analysis using an on-line gas chromatograph.
Example 12
The small-sized fixed fluidized bed reaction apparatus and experimental procedure used were the same as in comparative example 1.
25Wt% of the treated waste agent-4 is adopted to be compatible with 75wt% of the supported metal oxidative dehydrogenation catalyst A to be used as a reaction catalyst.
The composition of the reaction mixture is shown in Table 3 using CO 2 as the oxidant. The feed amount was 0.6Nm 3/h.
The reaction conditions are as follows: the reaction temperature is 550 ℃, the reaction pressure is 0.10MPa, the mass ratio of the catalyst to the gas (reaction raw material) is 30, and the volume airspeed is 3220h -1.
The regeneration operating conditions were: the regeneration temperature is 650 ℃, the regeneration pressure is 0.20MPa, and the linear velocity of the regenerated air is 0.5m/s.
The reaction results obtained are shown in Table 7 by analysis using an on-line gas chromatograph.
TABLE 5 reaction results summary-1
TABLE 6 reaction results summary Table-2
TABLE 7 reaction results summary Table-3
Note that: tables 5 to 7
Propane conversion C Propane : is defined as
Propylene selectivity S Propylene : is defined as
Propylene yield Y Propylene : defined as C Propane ×S Propylene .
As can be seen from the data in tables 5 to 7: although the different kinds of oxidants, the waste catalytic cracking catalyst treatment methods and the reaction conditions are adopted, the propylene yield is different, the treated waste catalytic cracking catalyst obtained by the method can effectively replace a special supported metal propane dehydrogenation catalyst.
According to the estimated proportion of 25wt% dead catalyst, the treatment cost per ton of deactivated FCC agent is 2000 yuan/ton, the market price per ton of propane dehydrogenation catalyst is 110000 yuan/ton when the method is used for dangerous waste treatment, and the economic benefit of 29500 yuan/ton (deactivated FCC agent) can be created. Therefore, the invention can create objective environmental and economic benefits.
Claims (13)
1. A method for preparing propylene by oxidative dehydrogenation of propane is characterized in that a propane raw material and an oxidant are introduced into a dehydrogenation reactor and are contacted with a catalyst to perform oxidative dehydrogenation reaction to generate propylene, a reactant flow is separated from the catalyst in a gas-solid manner, the separated reactant flow enters a product separation device to further separate propylene, propane and the oxidant, wherein the propane and the oxidant are recycled to the dehydrogenation reactor to continue the reaction, and the catalyst is a mixture of a supported metal oxidative dehydrogenation catalyst and a waste catalytic cracking catalyst; in the catalyst, the proportion of the waste catalytic cracking catalyst is 15-35 wt%;
the supported metal oxidative dehydrogenation catalyst comprises 5-15wt% of metal active components and a heat-resistant inorganic oxide carrier, wherein the metal active components are selected from one or more of Cr, co, ni, mo and RE, and the heat-resistant inorganic oxide carrier is selected from one or a mixture of more of Al 2O3、TiO2、CeO2、SiO2, MCF molecular sieve and SBA-15 molecular sieve;
the waste catalytic cracking catalyst is treated by an activation method, which comprises the following steps:
(1) Removing residual oil on the surface of the waste catalytic cracking catalyst, pickling and roasting;
(2) Impregnating the roasted waste catalytic cracking catalyst with an aqueous solution containing a first metal active component salt, and drying and roasting to obtain a precursor;
(3) The aqueous solution of the salt of the second metal active component and the precursor obtained in the step (2) are put into a high-pressure reaction kettle to react under the conditions of hydrogen pressure of 2-4 MPa and 100-200 ℃;
(4) Adding the solid reaction product obtained in the step (3) into a citric acid aqueous solution, standing for 1-2 hours, filtering, drying and roasting to obtain a treated waste catalytic cracking catalyst;
wherein the first metal active component and the second metal active component are selected from one or more of V, cr, co, ni, mo and Re.
2. The method for preparing propylene by oxidative dehydrogenation of propane according to claim 1, wherein the waste catalytic cracking catalyst is a catalytic cracking catalyst deposited with Ni and V metals, and the micro-reaction activity is less than 65; the catalytic cracking catalyst contains a Y-type molecular sieve or a rare earth metal ion modified Y-type molecular sieve.
3. The method for producing propylene by oxidative dehydrogenation of propane according to claim 2, wherein the total content of Ni and V in the spent catalytic cracking catalyst is not less than 2wt%.
4. A process for the oxidative dehydrogenation of propane to propylene according to claim 1, 2 or 3, characterized in that the dehydrogenation reactor is a fluidized bed reactor.
5. The process for producing propylene by oxidative dehydrogenation of propane according to claim 4, wherein a fluidized bed reactor provided with a heat exchange jacket is preferred.
6. A process for the oxidative dehydrogenation of propane to propylene according to any one of claims 1 to 3 characterised in that the oxidising agent is selected from oxygen, carbon dioxide or nitrous oxide.
7. The process for producing propylene by oxidative dehydrogenation of propane according to any one of claims 1 to 3, wherein the propane content in the propane raw material is not less than 85%, and the amount of the oxidizing agent is 1 to 30 times the stoichiometric amount of propane.
8. The method for producing propylene by oxidative dehydrogenation of propane according to claim 7, wherein the amount of the oxidizing agent is 3 to 5 times the stoichiometric amount of propane.
9. A process for the oxidative dehydrogenation of propane to propylene according to any one of claims 1 to 3, characterized in that the dehydrogenation reactor is operated under the following conditions: the reaction temperature is 350-750 ℃, the reaction pressure is 0.005-0.50 MPa, the mass ratio of the catalyst to the reaction raw materials is 5-50, and the volume space velocity is 100-4500 h -1.
10. The process for the oxidative dehydrogenation of propane to propylene according to claim 9, wherein the dehydrogenation reactor is operated under the following conditions: the reaction temperature is 450-600 ℃, the reaction pressure is 0.10-0.20 MPa, the mass ratio of the catalyst to the reaction raw materials is 30-50, and the volume space velocity is 3000-4000 h -1.
11. A reaction regeneration method for preparing propylene by oxidative dehydrogenation of propane is characterized in that the method for preparing propylene by oxidative dehydrogenation of propane is adopted in any one of claims 1-10, the dehydrogenation reactor is a fluidized bed dehydrogenation reactor, reactant flow and catalyst are separated in a gas-solid manner, the separated reactant flow enters a product separation device to further separate propylene, propane and oxidant, a part of separated spent catalyst is returned to the fluidized bed dehydrogenation reactor after steam stripping, the other part of the spent catalyst enters a catalyst regenerator for burning regeneration, the regenerated catalyst is returned to the fluidized bed reactor for recycling, and the catalyst is a mixture of a supported metal oxidative dehydrogenation catalyst and a waste catalytic cracking catalyst.
12. The process for regenerating a reaction for producing propylene by oxidative dehydrogenation of propane according to claim 11, wherein the catalyst regenerator is operated under the following conditions: the temperature is 550-700 ℃, the pressure is 0.01-0.55 MPa, and the linear velocity of the regeneration gas is 0.1-1.0 m/s.
13. The reactive regeneration process for the oxidative dehydrogenation of propane to propylene of claim 12 wherein the operating conditions of said regenerator are: the temperature is 600-650 ℃, the pressure is 0.11-0.25 MPa, and the linear velocity of the regeneration gas is 0.1-0.5 m/s.
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