CN113385187A - Pyrolysis gas deoxidation catalyst and preparation method and application thereof - Google Patents
Pyrolysis gas deoxidation catalyst and preparation method and application thereof Download PDFInfo
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- CN113385187A CN113385187A CN202110805728.1A CN202110805728A CN113385187A CN 113385187 A CN113385187 A CN 113385187A CN 202110805728 A CN202110805728 A CN 202110805728A CN 113385187 A CN113385187 A CN 113385187A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 91
- 238000000197 pyrolysis Methods 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000007789 gas Substances 0.000 claims abstract description 93
- 229910052751 metal Inorganic materials 0.000 claims abstract description 60
- 239000002184 metal Substances 0.000 claims abstract description 60
- 239000011230 binding agent Substances 0.000 claims abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- 150000001336 alkenes Chemical class 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 17
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 20
- 238000006392 deoxygenation reaction Methods 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 14
- 239000011572 manganese Substances 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- 239000004568 cement Substances 0.000 claims description 13
- 239000011656 manganese carbonate Substances 0.000 claims description 13
- 229940093474 manganese carbonate Drugs 0.000 claims description 13
- 235000006748 manganese carbonate Nutrition 0.000 claims description 13
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 13
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000012266 salt solution Substances 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 238000004523 catalytic cracking Methods 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 6
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005336 cracking Methods 0.000 claims description 3
- 230000003635 deoxygenating effect Effects 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 16
- 239000002994 raw material Substances 0.000 abstract description 14
- 238000000746 purification Methods 0.000 abstract description 8
- 238000007233 catalytic pyrolysis Methods 0.000 abstract description 5
- 230000003993 interaction Effects 0.000 abstract description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- 239000008367 deionised water Substances 0.000 description 18
- 229910021641 deionized water Inorganic materials 0.000 description 18
- 239000000203 mixture Substances 0.000 description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 11
- 229910017604 nitric acid Inorganic materials 0.000 description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 9
- 239000005977 Ethylene Substances 0.000 description 9
- 238000005470 impregnation Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000005303 weighing Methods 0.000 description 8
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 7
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 230000008929 regeneration Effects 0.000 description 6
- 238000011069 regeneration method Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- MEKDPHXPVMKCON-UHFFFAOYSA-N ethane;methane Chemical compound C.CC MEKDPHXPVMKCON-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- NKCVNYJQLIWBHK-UHFFFAOYSA-N carbonodiperoxoic acid Chemical compound OOC(=O)OO NKCVNYJQLIWBHK-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- JTXAHXNXKFGXIT-UHFFFAOYSA-N propane;prop-1-ene Chemical group CCC.CC=C JTXAHXNXKFGXIT-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention provides a pyrolysis gas deoxidation catalyst and a preparation method and application thereof; the pyrolysis gas deoxidation catalyst is prepared by mixing a metal active component and a binder; the metal active component is Mn3O4And a composite oxide of metal MO; the metal MO is NiO and/or CuO; the Mn is3O4And the metal MO is in a mass ratio of 1: (0.05-0.15). Compared with the prior art, the pyrolysis gas deoxidation catalyst provided by the invention adopts components with specific contents, and realizes better integral interaction; the pyrolysis gas deoxidation catalyst has mild application conditions and high deoxidation precision and capacity, is suitable for purification and deoxidation of olefin raw materials containing hydrogen, and is particularly suitable for oxygen removal of the catalytic pyrolysis gas with the content of less than 0.1%.
Description
Technical Field
The invention relates to the technical field of olefin purification, in particular to a pyrolysis gas deoxidation catalyst and a preparation method and application thereof.
Background
Ethylene and propylene are important basic raw materials of downstream polyolefin materials, and the performance of a polymerization catalyst and a synthetic material is seriously influenced by the impurity containing trace oxygen, and the trace oxygen content in the ethylene and the propylene is required to be less than 1ppm in the polymerization process. In the petrochemical industry, advanced catalytic cracking processes replace steam cracking to increase the production of ethylene and propylene, and generally require deoxygenation and purification of the cracked gas prior to the ethylene and propylene separation unit. The cracked gas contains high content of hydrogen, olefin and less than 0.1% of oxygen, so that it is necessary to develop a deoxygenation catalyst which can meet the requirements of subsequent separation of ethylene and propylene, and can be used for polymerization, and has no loss of olefin content and long service life.
The deoxidizer is widely applied to the removal of oxygen in various industrial gases such as coal-produced synthesis gas, natural gas, high-purity gas, fine chemical industry, polyester, electron and the like. According to the deoxidation mechanism, the method is mainly divided into two categories of catalytic deoxidation and chemisorption deoxidation, wherein the catalytic dehydrogenation is mainly divided into consumption of activated carbon and consumption of H2Deoxidation mechanisms consuming CO, hydrocarbons and the like. The hydrogen consumption deoxidation catalyst for industrial application mainly uses Pt and Pd as active components and noble metal supported catalyst, and the deoxidant has high deoxidation activity and large deoxidation capacity, but the catalyst is expensive and easy to produce hydrogenation side reaction. In addition, in the field of ethylene and propylene purification, a deoxidizer taking Ni as an active component is also provided, but the deoxidizer is easy to damage due to temperature runaway caused by hydrogenation of olefin in the processes of activation regeneration and olefin feeding. The chemical adsorption type deoxidation catalyst is mainly copper series and manganese series, and the deoxidant has no hydrogenation side reaction, but is suitable for low-oxygen-content raw gas, and has small deoxidation capacity and frequent regeneration.
The deoxidant prepared with CuO as one active component has very low heat resisting temperature, and is sintered at 200 deg.c to form crystal grains and thus to lose activity. The reduction regeneration is an exothermic reaction, and the temperature of the bed layer is easily over 200 ℃ without paying attention, so that the reduction regeneration is easySintering occurs and the deoxidation activity is lost; the deoxidizer prepared by single active component NiO is easy to generate hydrogenation reaction after being reduced by introducing higher hydrogen and olefin raw materials, so that material loss and bed temperature runaway are caused; with a single active component Mn3O4The prepared deoxidizer has higher temperature during reduction and regeneration, consumes large heat energy and is not beneficial to large-scale industrial application.
The downstream high molecular materials of olefin in China are rapidly developed, and the requirements on ethylene and propylene are increased year by year. In recent years, the process of advanced catalytic cracking for increasing the yield of olefin is widely applied, and a pyrolysis gas deoxygenation catalyst matched with the process is not deeply developed.
Patent CN101745391 discloses a deoxidizer which takes Pd as a main active component and Ag, Au, Co, Cr as auxiliary active components, and is used for removing trace oxygen from catalytic cracking dry gas, but inevitably causes 0.5% -1.7% loss of ethylene gas.
Patent CN108620063 discloses a Mn-based active component, added with rare earth metal and binder, for removing trace oxygen from refinery dry gas. The deoxidizer is suitable for removing 100-200 ppm of oxygen in dry gas of a refinery, and the increase of the oxygen content of raw materials can lead to frequent regeneration of the deoxidizer.
Disclosure of Invention
In view of the above, the present invention aims to provide a pyrolysis gas deoxygenation catalyst, and a preparation method and an application thereof, and the pyrolysis gas deoxygenation catalyst provided by the present invention is suitable for purification and deoxygenation of an olefin raw material containing hydrogen, and is particularly suitable for removing oxygen with a content of catalytic pyrolysis gas of less than 0.1%.
The invention provides a pyrolysis gas deoxidation catalyst which is prepared by mixing a metal active component and a binder;
the metal active component is Mn3O4And a composite oxide of metal MO; the metal MO is NiO and/or CuO; the Mn is3O4And the metal MO is in a mass ratio of 1: (0.05-0.15).
Preferably, the metal MO is NiO and CuO, wherein the mass ratio of NiO to CuO is (0.1-0.3): 1.
preferably, the binder is selected from one or more of pseudo-boehmite, kaolin and high alumina cement.
Preferably, the metal active component accounts for 40-80 wt% of the pyrolysis gas deoxidation catalyst.
The invention also provides a preparation method of the pyrolysis gas deoxygenation catalyst, which comprises the following steps:
a) mixing a precursor of the metal MO, acid and water to obtain a metal salt solution;
b) adding Mn3O4Uniformly mixing the precursor and a binder, adding the metal salt solution obtained in the step a), and after forming, sequentially airing, drying and roasting to obtain the pyrolysis gas deoxidation catalyst.
Preferably, said Mn in step b)3O4The precursor is selected from one or more of manganese dioxide, manganese carbonate, manganese nitrate, manganese acetate and manganese hydroxide.
Preferably, the airing temperature in the step b) is 20-30 ℃, and the airing time is 8-12 hours; the drying temperature is 80-120 ℃, and the drying time is 4-8 h; the roasting temperature is 400-500 ℃, and the roasting time is 3-6 h.
The invention also provides a method for deoxidizing the pyrolysis gas, which comprises the following steps:
filling a catalyst into a fixed bed reactor, drying and reducing the catalyst in sequence, and performing deoxidation reaction on the pyrolysis gas to be treated by the catalyst to obtain deoxidized purified gas;
the catalyst is the pyrolysis gas deoxidation catalyst in the technical scheme.
Preferably, the pyrolysis gas to be treated is pyrolysis gas containing hydrogen and olefin after catalytic cracking of naphtha; the oxygen content of the cracking gas to be treated is below 0.1 percent.
Preferably, the gas space velocity of the deoxidation reaction is 1000h-1～3000h-1The temperature is 110-180 ℃, and the pressure is 0.1-2.0 MPa.
The invention provides a pyrolysis gas deoxidation catalyst and a preparation method and application thereof; the pyrolysis gas deoxidation catalyst consists of metal active componentsMixing with binder; the metal active component is Mn3O4And a composite oxide of metal MO; the metal MO is NiO and/or CuO; the Mn is3O4And the metal MO is in a mass ratio of 1: (0.05-0.15). Compared with the prior art, the pyrolysis gas deoxidation catalyst provided by the invention adopts components with specific contents, and realizes better integral interaction; the pyrolysis gas deoxidation catalyst has mild application conditions and high deoxidation precision and capacity, is suitable for purification and deoxidation of olefin raw materials containing hydrogen, and is particularly suitable for oxygen removal of the catalytic pyrolysis gas with the content of less than 0.1%.
In addition, the preparation method provided by the invention has the advantages of simple process, mild condition, easiness in control and wide application prospect.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a pyrolysis gas deoxidation catalyst which is prepared by mixing a metal active component and a binder;
the metal active component is Mn3O4And a composite oxide of metal MO; the metal MO is NiO and/or CuO; the Mn is3O4And the metal MO is in a mass ratio of 1: (0.05-0.15).
In the invention, the pyrolysis gas deoxidation catalyst is prepared by mixing a metal active component and a binder. In the present invention, the metal active component is Mn3O4And a composite oxide of metal MO; wherein, the metal MO is NiO and/or CuO; the Mn is3O4And the metal MO is in a mass ratio of 1: (0.05-0.15).
In the present invention, the metal MO is preferably NiO and CuO; wherein the mass ratio of NiO to CuO is preferably (0.1-0.3): 1.
in the present invention, the binder is preferably selected from one or more of pseudo-boehmite, kaolin and high alumina cement. The source of the binder is not particularly limited in the present invention, and commercially available products of the above pseudo-boehmite, kaolin and high alumina cement, which are well known to those skilled in the art, may be used.
In the invention, the metal active component preferably accounts for 40-80 wt% of the pyrolysis gas deoxidation catalyst; correspondingly, the binder preferably accounts for 60-20 wt% of the pyrolysis gas deoxygenation catalyst.
The pyrolysis gas deoxidation catalyst provided by the invention adopts components with specific contents, and realizes better integral interaction; the pyrolysis gas deoxidation catalyst has mild application conditions and high deoxidation precision and capacity, is suitable for purification and deoxidation of olefin raw materials containing hydrogen, and is particularly suitable for oxygen removal of the catalytic pyrolysis gas with the content of less than 0.1%.
The invention also provides a preparation method of the pyrolysis gas deoxygenation catalyst, which comprises the following steps:
a) mixing a precursor of the metal MO, acid and water to obtain a metal salt solution;
b) adding Mn3O4Uniformly mixing the precursor and a binder, adding the metal salt solution obtained in the step a), and after forming, sequentially airing, drying and roasting to obtain the pyrolysis gas deoxidation catalyst.
The method comprises the steps of firstly mixing a precursor of metal MO, acid and water to obtain a metal salt solution. In the present invention, the precursor of the metal MO is preferably any one of a soluble nitrate, chloride, acetate, hydroxycarbonate or oxalate of the metal MO, and the present invention is not particularly limited in kind and source thereof. As is clear from the description that the metal MO is NiO and/or CuO, the precursor of the metal MO is a precursor of NiO and/or a precursor of CuO.
In the present invention, the acid is preferably nitric acid, citric acid or acetic acid; the present invention is not particularly limited in terms of the source of the acid, and commercially available products of the above-mentioned nitric acid, citric acid and acetic acid, which are well known to those skilled in the art, may be used. In the invention, the addition amount of the acid is excellentSelected as Mn in step b)3O40.5-5% of the total mass of the mixture of the precursor and the binder.
After the metal salt solution is obtained, Mn is added in the invention3O4And uniformly mixing the precursor and the binder, adding the obtained metal salt solution, and after molding, sequentially airing, drying and roasting to obtain the pyrolysis gas deoxidation catalyst. In the present invention, the Mn is3O4The precursor is preferably selected from one or more of manganese dioxide, manganese carbonate, manganese nitrate, manganese acetate and manganese hydroxide. The invention is for the Mn3O4The source of the precursor is not particularly limited, and commercially available products of manganese dioxide, manganese carbonate, manganese nitrate, manganese acetate and manganese hydroxide mentioned above, which are well known to those skilled in the art, may be used.
In the present invention, the metal MO precursor and Mn3O4The dosage of the precursor is specifically weighed according to the content of the metal active component in the pyrolysis gas deoxidation catalyst.
In the invention, the binder is the same as that in the technical scheme, and is not described again; the dosage of the binder is specifically weighed according to the content of the binder in the pyrolysis gas deoxygenation catalyst.
In the invention, the forming mode is preferably extrusion molding or rolling ball molding.
In the invention, the airing temperature is preferably 20-30 ℃, and the airing time is preferably 8-12 h; the drying temperature is preferably 80-120 ℃, and the drying time is preferably 4-8 h; the roasting temperature is preferably 400-500 ℃, and the time is preferably 3-6 h; the air atmosphere is adopted.
The preparation method provided by the invention has the advantages of simple process, mild condition, easiness in control and wide application prospect.
The invention also provides a method for deoxidizing the pyrolysis gas, which comprises the following steps:
filling a catalyst into a fixed bed reactor, drying and reducing the catalyst in sequence, and performing deoxidation reaction on the pyrolysis gas to be treated by the catalyst to obtain deoxidized purified gas;
the catalyst is the pyrolysis gas deoxidation catalyst in the technical scheme.
In the invention, the deoxidation method of the pyrolysis gas is the application of the pyrolysis gas deoxidation catalyst in the technical scheme.
In the invention, the catalyst is preferably shaped before being filled, and the shaped catalyst is specifically particles with 10-20 meshes, so that the catalyst is convenient to fill. In the present invention, the loading amount of the catalyst in the fixed bed reactor is preferably 10mL to 10mL, more preferably 50 mL.
In the present invention, the gas used for the drying is preferably nitrogen; the drying temperature is preferably 110-130 ℃, and more preferably 120 ℃; the drying time is preferably 1 to 2 hours.
In the present invention, the gas used for the reduction is preferably hydrogen; the reduction temperature is preferably 280-400 ℃, the time is preferably 4-8 h, and the gas space velocity is preferably 800h-1～1200h-1。
In the invention, the pyrolysis gas to be treated is preferably pyrolysis gas containing hydrogen and olefin after catalytic cracking of naphtha; the oxygen content of the cracking gas to be treated is below 0.1 percent; i.e. the oxygen containing feed gas in the examples.
In the present invention, the gas space velocity of the deoxidation reaction is preferably 1000h-1～3000h-1The temperature is preferably 110 ℃ to 180 ℃, and more preferably 120 ℃ to 170 ℃; the pressure is preferably 0.1MPa to 2.0MPa, more preferably 1.5 MPa.
Aiming at the technical problems of the existing catalyst, the invention utilizes the hydrogenation catalytic activity of Ni and Cu and Mn on the basis of the material characteristics of pyrolysis gas and the matching property of the process3O4The chemical adsorption performance of the catalyst is considered, and CuO is easy to sinter and Mn is considered3O4The reduction temperature is high, and the like, and provides a pyrolysis gas deoxidation catalyst, a preparation method and application thereof.
The invention provides a pyrolysis gas deoxidation catalyst and a preparation method and application thereof; the pyrolysis gas deoxidation catalyst is prepared by mixing a metal active component and a binder; the metal active component is Mn3O4And a composite oxide of metal MO; the metal MO is NiO and/or CuO; the Mn is3O4And the metal MO is in a mass ratio of 1: (0.05-0.15). Compared with the prior art, the pyrolysis gas deoxidation catalyst provided by the invention adopts components with specific contents, and realizes better integral interaction; the pyrolysis gas deoxidation catalyst has mild application conditions and high deoxidation precision and capacity, is suitable for purification and deoxidation of olefin raw materials containing hydrogen, and is particularly suitable for oxygen removal of the catalytic pyrolysis gas with the content of less than 0.1%.
In addition, the preparation method provided by the invention has the advantages of simple process, mild condition, easiness in control and wide application prospect.
To further illustrate the present invention, the following examples are provided for illustration. The raw materials used in the following examples of the present invention are all commercially available; wherein the specific surface area of the pseudoboehmite is 300m2/g～350m2Per g, pore volume of 0.50cm3/g～0.75cm3The dry basis is more than or equal to 70wt percent.
Example 1
Weighing 39.90g of deionized water, dissolving 0.40g of 65 wt% concentrated nitric acid, 1.77g of nickel nitrate and 7.14g of copper nitrate in the deionized water, and uniformly stirring to obtain a transparent solution; then weighing 76.12g of manganese carbonate, 59.85g of pseudo-boehmite and 6.65g of high alumina cement, uniformly mixing solid powder, putting the prepared impregnation solution, uniformly kneading, extruding into a 2mm cylinder, airing for 8h at room temperature, drying for 6h at 120 ℃, and roasting for 4h at 500 ℃ in an air atmosphere to obtain the catalyst C-1.
Example 2
Weighing 42.00g of deionized water, dissolving 0.42g of 65 wt% concentrated nitric acid, 3.93g of nickel nitrate and 11.91g of copper nitrate in the deionized water, and uniformly stirring to obtain a transparent solution; then 68.50g of manganese carbonate, 63.00g of pseudo-boehmite and 7.00g of high alumina cement are weighed, solid powder is uniformly mixed, the prepared impregnation solution is put in, the mixture is uniformly kneaded and then extruded into a 2mm cylinder, the cylinder is dried at room temperature for 6h, dried at 110 ℃ for 8h, and roasted at 450 ℃ in air atmosphere for 4h, and the catalyst C-2 is obtained.
Example 3
31.29g of deionized water is weighed, 0.32g of 65 wt% concentrated nitric acid and 8.34g of copper nitrate are dissolved in the deionized water, and the solution is stirred uniformly and is transparent. Then 91.34g of manganese carbonate, 46.93g of pseudo-boehmite and 5.21g of high alumina cement are weighed, solid powder is uniformly mixed, the prepared impregnation solution is put in, the mixture is uniformly kneaded and extruded into a 2mm cylinder, the cylinder is dried at room temperature for 6h, dried at 120 ℃ for 8h, and roasted at 500 ℃ in air atmosphere for 4h, and the catalyst C-3 is obtained.
Example 4
Weighing 31.71g of deionized water, dissolving 0.32g of 65 wt% concentrated nitric acid and 11.80g of nickel nitrate in the deionized water, and uniformly stirring to obtain a transparent solution; then 91.34g of manganese carbonate, 47.57g of pseudo-boehmite and 5.29g of high-alumina cement solid powder are weighed and uniformly mixed, the prepared impregnation solution is put in, and after uniform kneading, the mixture is extruded into a 2mm cylinder, and is dried at room temperature for 10h, dried at 100 ℃ for 8h, and roasted at 500 ℃ in air atmosphere for 5h, thus obtaining the catalyst C-4.
Example 5
41.57g of deionized water is weighed, 0.42g of 65 wt% concentrated nitric acid and 15.48g of copper nitrate are dissolved in the deionized water, and the mixture is uniformly stirred, so that the solution is transparent; then 68.50g of manganese carbonate, 62.36g of pseudo-boehmite and 6.93g of high-alumina cement solid powder are weighed and uniformly mixed, the prepared impregnation solution is put into the mixture, the mixture is uniformly kneaded and extruded into a 2mm cylinder, the cylinder is dried at room temperature for 8h, dried at 120 ℃ for 8h, and roasted at 450 ℃ in air atmosphere for 6h to obtain the catalyst C-5.
Example 6
Weighing 43.71g of deionized water, dissolving 0.44g of 65 wt% concentrated nitric acid and 15.73g of nickel nitrate in the deionized water, and uniformly stirring to obtain a transparent solution; then 68.50g of manganese carbonate, 65.57g of pseudo-boehmite and 7.29g of high-alumina cement solid powder are weighed and uniformly mixed, the prepared impregnation solution is put in, and is extruded into a 2mm cylinder after being uniformly kneaded, the cylinder is dried at room temperature for 6h, dried at 120 ℃ for 6h, and roasted at 450 ℃ in air atmosphere for 6h, and the catalyst C-6 is obtained.
Example 7
38.14g of deionized water is weighed, 0.39g of 65 wt% concentrated nitric acid, 3.93g of nickel nitrate and 10.72g of copper nitrate are dissolved in the deionized water, and the mixture is uniformly stirred, so that the solution is transparent; then weighing 76.12g of manganese carbonate, 57.21g of pseudo-boehmite and 6.36g of high-alumina cement solid powder, uniformly mixing, putting the prepared impregnation solution, uniformly kneading, extruding into a 2mm cylinder, airing for 8h at room temperature, drying for 4h at 120 ℃, and roasting for 4h at 500 ℃ in an air atmosphere to obtain the catalyst C-7.
Example 8
Weighing 35.36g of deionized water, dissolving 0.36g of 65 wt% concentrated nitric acid, 2.95g of nickel nitrate and 7.14g of copper nitrate in the deionized water, and uniformly stirring to obtain a transparent solution; then 83.73g of manganese carbonate, 53.04g of pseudo-boehmite and 5.89g of high-alumina cement solid powder are weighed and uniformly mixed, the prepared impregnation solution is put into the mixture, the mixture is uniformly kneaded and extruded into a 2mm cylinder, the cylinder is dried at room temperature for 8h, dried at 110 ℃ for 7h, and roasted at 500 ℃ for 5h in an air atmosphere to obtain the catalyst C-8.
Example 9
26.06g of deionized water is weighed, 0.26g of 65 wt% concentrated nitric acid, 2.36g of nickel nitrate and 9.53g of copper nitrate are dissolved in the deionized water, and the mixture is stirred uniformly, so that the solution is transparent. Then weighing 98.95g of manganese carbonate, 39.09g of pseudo-boehmite and 4.34g of high-alumina cement solid powder, uniformly mixing, putting the prepared impregnation solution, uniformly kneading, extruding into a 2mm cylinder, airing at room temperature for 4h, drying at 120 ℃ for 4h, and roasting at 450 ℃ in an air atmosphere for 5h to obtain the catalyst C-9.
The physical composition properties of the catalyst prepared in the above example are shown in table 1.
Table 1 data of the physical composition properties of the catalysts prepared in the examples
| Catalyst and process for preparing same | C-1 | C-2 | C-3 | C-4 | C-5 | C-6 | C-7 | C-8 | C-9 |
| Mn3O4，m％ | 50 | 45 | 60 | 60 | 45 | 45 | 50 | 55 | 65 |
| NiO，m％ | 0.5 | 1.0 | 0.0 | 3.0 | 0.0 | 4.0 | 1.0 | 0.8 | 0.6 |
| CuO，m％ | 3.0 | 5.0 | 3.5 | 0.0 | 6.5 | 0.0 | 4.5 | 3.0 | 4.0 |
Application examples
The activity of the catalyst prepared in the example was evaluated; the reaction system is as follows:
the raw material gas was prepared by using a simulated cracked gas as shown in table 2.
Table 2 evaluation of feed gas composition data
| Components | Methane | Ethane (III) | Ethylene | Hydrogen gas | Propane | Propylene (PA) | Oxygen gas | Nitrogen gas |
| Raw material gas 1 composition (volume fraction)% | 15 | 12 | 28 | 20 | 5 | 15 | 0.05 | Filling in |
| Feed gas 2 composition (volume fraction)% | 12 | 10 | 19 | 10 | 7 | 25 | 0.02 | Filling in |
Shaping 20-mesh particles of the catalyst, filling 50mL of the catalyst, drying the catalyst for 1.5h at 120 ℃ in nitrogen before use, and reducing the catalyst with 99 percent of hydrogen and 1000h of gas space velocity-1And the condition is that the temperature is 280 ℃ for reduction for 4 h.
The oxygen content is detected by adopting a portable online detector, the reaction pressure is 1.5MPa, the feed gas 1 is used as an evaluation raw material, and the performance of the catalyst is shown in table 3; the catalyst performance is shown in Table 4 using feed gas 2 as the evaluation feed.
TABLE 3 reaction conditions and results for different catalysts starting from feed gas 1
TABLE 4 reaction conditions and results for different catalysts with feed gas 2 as feed
As can be seen from tables 3 and 4, the pyrolysis gas deoxygenation catalyst provided by the invention has high deoxygenation precision and no olefin loss under the condition of specific raw material gas, and the stability of the raw material 1 and C-8 catalyst basis is examined, and the volume space velocity is 2000h-1The reaction temperature is 150 ℃, and the deoxidation capacity is more than 35 mL/g.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A deoxidation catalyst for cracked gas is prepared by mixing metal active components and a binder;
the metal active component is Mn3O4And a composite oxide of metal MO; the metal MO is NiO and/or CuO; the Mn is3O4And the metal MO is in a mass ratio of 1: (0.05-0.15).
2. The deoxygenation catalyst for cracked gas according to claim 1, wherein the metal MO is NiO and CuO, and the mass ratio of NiO to CuO is (0.1-0.3): 1.
3. the deoxygenation catalyst of claim 1, wherein the binder is selected from one or more of pseudo-boehmite, kaolin, and high alumina cement.
4. The pyrolysis gas deoxygenation catalyst of claim 1, wherein the metal active component comprises 40 wt% to 80 wt% of the pyrolysis gas deoxygenation catalyst.
5. A preparation method of the pyrolysis gas deoxygenation catalyst according to any one of claims 1 to 4, comprising the following steps:
a) mixing a precursor of the metal MO, acid and water to obtain a metal salt solution;
b) adding Mn3O4Uniformly mixing the precursor and a binder, adding the metal salt solution obtained in the step a), and after forming, sequentially airing, drying and roasting to obtain the pyrolysis gas deoxidation catalyst.
6. The method according to claim 5, wherein the Mn in step b) is3O4The precursor is selected from one or more of manganese dioxide, manganese carbonate, manganese nitrate, manganese acetate and manganese hydroxide.
7. The preparation method according to claim 5, wherein the airing temperature in the step b) is 20-30 ℃ and the airing time is 8-12 h; the drying temperature is 80-120 ℃, and the drying time is 4-8 h; the roasting temperature is 400-500 ℃, and the roasting time is 3-6 h.
8. A method for deoxygenating a cracked gas, comprising the steps of:
filling a catalyst into a fixed bed reactor, drying and reducing the catalyst in sequence, and performing deoxidation reaction on the pyrolysis gas to be treated by the catalyst to obtain deoxidized purified gas;
the catalyst is the pyrolysis gas deoxidation catalyst of any one of claims 1 to 4.
9. The deoxidation method according to claim 8, characterized in that the pyrolysis gas to be treated is a pyrolysis gas containing hydrogen and olefins after catalytic cracking of naphtha; the oxygen content of the cracking gas to be treated is below 0.1 percent.
10. The deoxygenation method of claim 8, wherein the gas space velocity of the deoxygenation reaction is 1000h-1～3000h-1The temperature is 110-180 ℃, and the pressure is 0.1-2.0 MPa.
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| US20120003132A1 (en) * | 2009-07-23 | 2012-01-05 | Shudong Wang | Process for catalytic deoxygenation of coal mine methane |
| CN104888798A (en) * | 2015-06-10 | 2015-09-09 | 西南化工研究设计院有限公司 | High-activity catalyst for sulfur-tolerant deoxidization of CO-rich gas and preparation method of high-activity catalyst |
| CN112495389A (en) * | 2020-11-09 | 2021-03-16 | 大连圣得环保新材料有限公司 | Efficient multifunctional deoxidation catalyst, preparation method and application thereof |
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| US20120003132A1 (en) * | 2009-07-23 | 2012-01-05 | Shudong Wang | Process for catalytic deoxygenation of coal mine methane |
| CN104888798A (en) * | 2015-06-10 | 2015-09-09 | 西南化工研究设计院有限公司 | High-activity catalyst for sulfur-tolerant deoxidization of CO-rich gas and preparation method of high-activity catalyst |
| CN112495389A (en) * | 2020-11-09 | 2021-03-16 | 大连圣得环保新材料有限公司 | Efficient multifunctional deoxidation catalyst, preparation method and application thereof |
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| CN113952962A (en) * | 2021-11-11 | 2022-01-21 | 山东京博石油化工有限公司 | Catalytic pyrolysis gas deoxidation catalyst, preparation method thereof and pyrolysis gas deoxidation method |
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