CN106179468B - A kind of solid acid catalyst and its application - Google Patents
A kind of solid acid catalyst and its application Download PDFInfo
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- CN106179468B CN106179468B CN201510226518.1A CN201510226518A CN106179468B CN 106179468 B CN106179468 B CN 106179468B CN 201510226518 A CN201510226518 A CN 201510226518A CN 106179468 B CN106179468 B CN 106179468B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 204
- 239000011973 solid acid Substances 0.000 title claims abstract description 87
- 229910052751 metal Inorganic materials 0.000 claims abstract description 82
- 239000002184 metal Substances 0.000 claims abstract description 82
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 80
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 83
- 229910052750 molybdenum Inorganic materials 0.000 claims description 54
- 229910052759 nickel Inorganic materials 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 31
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 27
- 239000011733 molybdenum Substances 0.000 claims description 27
- 239000010457 zeolite Substances 0.000 claims description 26
- 229910021536 Zeolite Inorganic materials 0.000 claims description 24
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 24
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 12
- 150000001336 alkenes Chemical class 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 6
- 239000001282 iso-butane Substances 0.000 claims description 6
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 claims description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 230000029936 alkylation Effects 0.000 abstract description 30
- 229910000510 noble metal Inorganic materials 0.000 abstract description 24
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000010953 base metal Substances 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 63
- 239000012492 regenerant Substances 0.000 description 55
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 40
- FLTJDUOFAQWHDF-UHFFFAOYSA-N trimethyl pentane Natural products CCCCC(C)(C)C FLTJDUOFAQWHDF-UHFFFAOYSA-N 0.000 description 40
- 238000011069 regeneration method Methods 0.000 description 35
- 230000008929 regeneration Effects 0.000 description 33
- 238000001035 drying Methods 0.000 description 30
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- 230000009467 reduction Effects 0.000 description 17
- 238000011065 in-situ storage Methods 0.000 description 16
- 239000007809 chemical reaction catalyst Substances 0.000 description 15
- 150000002739 metals Chemical class 0.000 description 14
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 12
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 12
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 10
- -1 VIB group metals Chemical class 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 230000009849 deactivation Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000011964 heteropoly acid Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
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- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
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- 238000005342 ion exchange Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
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- 238000002390 rotary evaporation Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
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- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of solid acid catalyst, it is characterized by comprising solid acid and the metal components for accounting for 0.01~5wt% of solid acid catalyst being carried on solid acid, the metal component is group VIII metal and group vib metal, and group vib metal and the mass values of group VIII metal are (2~4): 1.Solid acid catalyst of the invention replaces noble metal using base metal, close to the catalytic performance of the even up to alkylation catalyst of carried noble metal, for occupying cost advantage when alkylated reaction.
Description
Technical Field
The invention relates to a solid acid catalyst and application thereof, in particular to a non-noble metal-containing solid acid catalyst and an alkylation reaction method thereof in the presence of the catalyst.
Background
The alkylation reaction of branched saturated hydrocarbon (such as isobutane) and olefin (such as butylene) with 2-6 carbon atoms can obtain gasoline component with higher octane number, and the gasoline component has high octane number and low Reid steam pressure, and contains no sulfur, nitrogen, olefin and aromatic hydrocarbon.
At present, the alkylation industrial production process technology is mainly a liquid acid alkylation process, including sulfuric acid alkylation and hydrofluoric acid alkylation, but further development, popularization and application of the liquid acid alkylation process are restricted by the defects of corrosivity and toxicity of liquid acid, harm of waste acid discharge in the process to the environment and the like.
The solid acid catalyst has the advantages of safety, no pollution, convenience in separation from products, reproducibility and recycling and the like, so that the solid acid catalyst becomes a hot point of research and has the potential of replacing a liquid acid catalyst.
The solid acid catalyst including zeolite, heteropoly acid and super acid has the fatal weakness of quick deactivation and needs frequent regeneration. Researchers have made many improvements on solid acid catalysts, such as a solid acid alkylation catalyst disclosed in CN101631614A, which includes a multi-metal component performing a hydrogenation function for regenerating the catalyst in the presence of hydrogen, but includes noble metals, such as platinum and palladium, which uses inexpensive metals instead of a part of the noble metals to relieve the cost pressure, but in which not only the noble metals platinum or palladium are necessary components, but also the compounding relationship of various inexpensive metals is not considered.
Disclosure of Invention
The inventor surprisingly finds out through a large number of experiments that under the condition of not adopting noble metals, the alkylation performance of the solid acid catalyst loaded with noble metals can be approached to or even reached by selecting VIII group metals and VIB group metals to load on solid acids, and the solid acid catalyst obtained by selecting a special proportioning relationship between the VIII group metals and the VIB group metals has good regeneration effect, and the cost of alkylation reaction can be greatly reduced. Based on this, the present invention was made.
It is therefore an object of the present invention to provide a solid acid alkylation catalyst which does not support a noble metal but only a non-noble metal, and it is a second object of the present invention to provide a less costly alkylation process.
In order to achieve one purpose, the solid acid catalyst provided by the invention is characterized by comprising a solid acid and metal components which are loaded on the solid acid and account for 0.01-5 wt% of the solid acid catalyst, wherein the metal components are VIB group metals and VIII group metals, and the mass ratio of the VIB group metals to the VIII group metals is (2-4): 1.
In order to achieve the second purpose, the invention provides an alkylation reaction method, which is characterized by being carried out under the alkylation reaction condition and in the presence of a solid acid catalyst, wherein the solid acid catalyst comprises solid acid and metal components which are loaded on the solid acid and account for 0.01-5 wt% of the solid acid catalyst, the metal components are VIB group metals and VIII group metals, and the mass ratio of the VIB group metals to the VIII group metals is (2-4): 1.
The solid acid catalyst provided by the invention adopts two non-noble metals to be matched according to a specific proportion so as to completely replace noble metals, the reaction performance of the noble metal-loaded alkylation catalyst can be approached to or even reached when the solid acid catalyst is applied to alkylation reaction, and the regeneration effect of the deactivated catalyst can be approached to or even reached to the performance of the noble metal-loaded fresh alkylation catalyst, so that the solid acid catalyst provided by the invention has cost advantage when being applied to alkylation reaction.
Detailed Description
The solid acid catalyst provided by the invention is characterized by comprising a solid acid and metal components which are loaded on the solid acid and account for 0.01-5 wt% of the solid acid catalyst, wherein the metal components are VIB group metals and VIII group metals, and the mass ratio of the VIB group metals to the VIII group metals is (2-4): 1.
The catalyst provided by the invention comprises a solid acid used for alkylation reaction and a metal component.
A variety of solid acids are known to be applicable to alkylation processes in the art. Wherein, the solid acid can be selected from one or more of zeolite, silicon oxide, aluminum oxide, metal halide, sulfated oxide, supported heteropolyacid and clay. Among the solid acids, zeolites are preferred; further preferably one or more zeolites selected from beta, Y, MCM-22, ZSM-5, and Mordnite, and more preferably the solid acid is Y-type zeolite.
The metal is loaded on the solid acid by combining two metals according to a specific proportion, the two metals are respectively from cheap metals in VIB group and VIII group, and the specific proportion relation of the combination of the two metal components is a key factor for realizing the invention. The inventor finds that when the mass ratio of the metal of the VIB group to the metal of the VIII group is (2-4): 1, preferably (2.2-3.8): 1, more preferably (2.5-3.5): 1, and most preferably (2.8-3.2): 1, for example, 3:1, which can achieve the reaction effect and the regeneration effect with the supported noble metal.
In the catalyst of the present invention, the metal component accounts for 0.01 to 5 wt%, preferably 0.5 to 5 wt%, more preferably 0.5 to 4 wt% of the solid acid catalyst.
The group VIB metal is preferably molybdenum and the group VIII metal is preferably nickel. In a specific embodiment of the invention, the supported metal component accounts for 2 wt% of the solid acid catalyst, and the mass ratio of molybdenum to nickel is 3:1, and the service life of the catalyst is not reduced in the alkylation reaction after three times of circulation of the regenerant, which is equivalent to that of the catalyst loaded with 0.5 wt% of platinum.
The operation of supporting the catalyst, metal, of the present invention is carried out by a conventional technique such as equivalent volume impregnation, ion exchange, saturated rotary evaporation, etc. More preferably, the present invention employs an equivalent volume impregnation method to control the metal loading. The preparation of the metal impregnation liquid is mainly to prepare the solution concentration by the same calculation of the loading amount and the saturated water absorption of the catalyst. The impregnated catalyst is dried at 80-120 deg.C and calcined at 250-500 deg.C.
In order to impart mechanical strength and other physical properties to the catalyst, it is common to add some matrix component in combination with a solid acid. The matrix can be alumina, silica-alumina, zirconia, clay, etc. The matrix material is present in an amount of about 10 to 80 wt%, preferably 15 to 30 wt%.
The invention also provides the application of the solid acid catalyst in alkylation reaction. The catalyst provided by the invention is suitable for alkylation reaction of isoparaffin and olefin, for example, the isoparaffin comprises one or more of isobutane and isopentane, and the olefin comprises one or more of propylene, isobutene, 1-butene, 2-butene and pentene. The present invention preferably uses the solid acid catalyst provided for the alkylation of isobutane with a butene or mixture of butenes, such as isobutane with butene (2-butene), to produce a gasoline product having a high octane number, although the invention is not limited thereto.
The solid acid alkylation catalyst catalyzes the alkylation of isoparaffin and olefin in a variety of reaction evaluation devices such as fluidized, fixed, and slurry beds. In the present invention, the catalyst was evaluated using a fixed bed, but the catalyst application apparatus of the present invention is not limited thereto.
In the alkylation reaction, the reactants are generally carried out in the liquid phase or supercritical phase. The alkylation reaction is carried out at 50-150 ℃, preferably 60-90 ℃; the reaction pressure is 0.5 to 5.0MPa, preferably 2.5 to 4.0 MPa; the molar ratio of alkane to alkene in the reaction feed is higher than 7: 1. higher than 10: 1 or more; the alkylation feed space velocity is controlled to be in the range of 0.01 to 0.5, preferably in the range of 0.02 to 0.2. It should be understood that the use of the catalyst of the present invention is not limited to any particular reaction conditions, which are exemplary.
The invention adopts two indexes of cycle life and product distribution to evaluate the alkylation reaction performance of the catalyst. Wherein the cycle life is based on the complete conversion of the olefin and the product distribution is C8And TMP (trimethylpentane) as a benchmark. The alkylated product was analyzed on top of gas chromatography.
The invention also evaluates the regeneration effect of the catalyst through the reaction performance of the regenerated catalyst. Removing carbon deposit precursors on the catalyst by the hydrogen regeneration, wherein the regeneration is the hydrogen regeneration under certain temperature and pressure: the pressure of the regenerated hydrogen is between 0.1 and 5.0MPa, preferably between 1.5 and 3.5MPa, and the regeneration temperature is between 150 ℃ and 350 ℃, preferably between 200 ℃ and 300 ℃. Catalyst regeneration Effect as catalyst cycle Life at full olefin conversion and product C8And TMP (trimethylpentane) distribution for comparison.
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
The expression of the metal supported on the solid acid catalyst and the content thereof is abbreviated in combination as "percent metal content" and "metal symbol", for example, the solid acid catalyst containing 0.5 wt% of Pt is expressed as 0.5Pt, and other supported metals are similarly expressed.
Examples of the preparation of the catalyst and the comparative catalyst are described below.
Comparative example 1
This comparative example illustrates a solid acid catalyst without supported metal.
The comparative catalyst was a shaped zeolite catalyst containing 80 wt% of a modified Y-type zeolite and 20 wt% of a support matrix. The particle size of the catalyst is 20-40 meshes. The comparative catalyst was numbered D-1.
Note: the modified Y-type zeolite is synthesized in a laboratory, has the particle size of 100-500 nm and is regulated and controlled by acidity and pore channels.
Comparative example 2
This comparative example illustrates a solid acid catalyst loaded with noble metal Pt alone, containing 0.5 wt% Pt.
The D-1 catalyst is used as a carrier, and chloroplatinic acid is used as a platinum source. Loading 0.5 wt% Pt by an equal volume impregnation method, drying and roasting after impregnation. Wherein the catalyst is dried at 120 ℃, calcined and reduced at 450 ℃. The comparative catalyst was numbered D-2.
Comparative example 3
This comparative example illustrates a solid acid catalyst containing 0.5 wt% Ni supporting only non-noble metal Ni.
D-1 catalyst is used as a carrier, and nickel nitrate hexahydrate is used as a nickel source. Loading Ni 0.5 wt% by an equal volume impregnation method, drying and roasting after impregnation, wherein the drying and roasting conditions are the same as those of comparative example 2. The comparative catalyst was numbered D-3.
Comparative example 4
This comparative example illustrates a solid acid catalyst containing 1.5 wt% Mo supporting only non-noble metal Mo.
D-1 catalyst is used as a carrier, and ammonium molybdate tetrahydrate is used as a molybdenum source. Loading 1.5 wt% Mo by an equal volume impregnation method, drying and roasting after impregnation, wherein the drying and roasting conditions are the same as the comparative example 2. The comparative catalyst was numbered D-4.
Comparative example 5
This comparative example illustrates a solid acid catalyst containing 2 wt% Ni supporting only non-noble metal Ni.
D-1 catalyst is used as a carrier, and nickel nitrate hexahydrate is used as a nickel source. Loading 2 wt% Ni by an equal volume impregnation method, impregnating, drying and roasting, wherein the drying and roasting conditions are the same as those of comparative example 2. The comparative catalyst was numbered D-5.
Comparative example 6
This comparative example illustrates a solid acid catalyst containing 2 wt% Mo supporting only non-noble metal Mo.
D-1 catalyst is used as a carrier, and ammonium molybdate tetrahydrate is used as a molybdenum source. Loading 2 wt% Mo by an equal volume impregnation method, impregnating, drying and roasting, wherein the drying and roasting conditions are the same as those of comparative example 2. The comparative catalyst was numbered D-6.
Example 1
This example illustrates the preparation and composition of the solid acid catalyst of the present invention.
D-1 catalyst is used as a carrier, ammonium molybdate tetrahydrate is used as a molybdenum source, and nickel nitrate hexahydrate is used as a nickel source. Loading Ni and Mo by an isometric impregnation method, drying and roasting after impregnation to obtain the catalyst, wherein the drying and roasting conditions are the same as those of the comparative example 2.
The catalyst was numbered A-1. In the catalyst A-1, the solid acid was Y-type zeolite, and the metal component accounted for 2 wt%, wherein Ni accounted for 0.44 wt%, Mo accounted for 1.56 wt%.
Example 2
This example illustrates the preparation and composition of the solid acid catalyst of the present invention.
D-1 catalyst is used as a carrier, ammonium molybdate tetrahydrate is used as a molybdenum source, and nickel nitrate hexahydrate is used as a nickel source. Loading Ni and Mo by an isometric impregnation method, impregnating, drying and roasting to obtain the catalyst, wherein the drying and roasting conditions are the same as those of the comparative example 2.
The catalyst was numbered A-2. In the catalyst A-2, the solid acid was Y-type zeolite, and the metal component accounted for 2 wt%, wherein Ni accounted for 0.5 wt%, Mo accounted for 1.5 wt%.
Example 3
This example illustrates the preparation and composition of the solid acid catalyst of the present invention.
D-1 catalyst is used as a carrier, ammonium molybdate tetrahydrate is used as a molybdenum source, and nickel nitrate hexahydrate is used as a nickel source. Loading Ni and Mo by an isometric impregnation method, impregnating, drying and roasting to obtain the catalyst, wherein the drying and roasting conditions are the same as those of the comparative example 2.
The catalyst was numbered A-3. In the catalyst A-3, the solid acid was Y-type zeolite, and the metal component accounted for 2 wt%, wherein Ni accounted for 0.57 wt%, Mo accounted for 1.43 wt%.
Comparative example 7
This comparative example illustrates a solid acid catalyst that supports only non-noble metals, Mo and Ni, but the ratio of Mo and Ni is outside the scope of the present invention.
D-1 catalyst is used as a carrier, ammonium molybdate tetrahydrate is used as a molybdenum source, and nickel nitrate hexahydrate is used as a nickel source. Loading Ni and Mo by an isometric impregnation method, impregnating, drying and roasting to obtain the catalyst, wherein the drying and roasting conditions are the same as those of the comparative example 2.
The catalyst was numbered D-7. In the catalyst D-7, the solid acid is Y-type zeolite, and the metal component accounts for 2 wt%, wherein Ni accounts for 1 wt%, and Mo accounts for 1 wt%.
Comparative example 8
This comparative example illustrates a solid acid catalyst that supports only non-noble metals, Mo and Ni, but the ratio of Mo and Ni is outside the scope of the present invention.
D-1 catalyst is used as a carrier, ammonium molybdate tetrahydrate is used as a molybdenum source, and nickel nitrate hexahydrate is used as a nickel source. Loading Ni and Mo by an isometric impregnation method, impregnating, drying and roasting to obtain the catalyst, wherein the drying and roasting conditions are the same as those of the comparative example 2.
The catalyst was numbered D-8. In catalyst D-8, the solid acid was Y-type zeolite, the metal component accounted for 2 wt%, wherein Ni accounted for 0.25 wt%, Mo accounted for 1.75 wt%.
Example 4
This example illustrates the preparation and composition of the solid acid catalyst of the present invention.
The D-1 catalyst is used as a carrier, ammonium molybdate tetrahydrate is used as a molybdenum source, and nickel nitrate hexahydrate is used as a nickel source. Mo and Ni are loaded by an isometric impregnation method, and the catalyst is obtained by drying and roasting after impregnation, wherein the drying and roasting conditions are the same as those of the comparative example 2.
The catalyst was numbered A-4. In catalyst A-4, the solid acid was Y-type zeolite, the metal component accounted for 1 wt%, Ni accounted for 0.25 wt%, Mo accounted for 0.75 wt%.
Example 5
This example illustrates the preparation and composition of the solid acid catalyst of the present invention.
The D-1 catalyst is used as a carrier, ammonium molybdate tetrahydrate is used as a molybdenum source, and nickel nitrate hexahydrate is used as a nickel source. Mo and Ni are loaded by an isometric impregnation method, and the catalyst is obtained by drying and roasting after impregnation, wherein the drying and roasting conditions are the same as those of the comparative example 2.
The catalyst was numbered A-5. In the catalyst A-5, the solid acid is Y-type zeolite, the metal component accounts for 4 wt%, Ni accounts for 1 wt%, and Mo accounts for 3 wt%.
Example 6
This example illustrates the preparation and composition of the solid acid catalyst of the present invention.
The catalyst is prepared by using a carrier matrix forming catalyst containing 80 wt% of beta zeolite and 20 wt% of carrier matrix as a carrier, ammonium molybdate tetrahydrate as a molybdenum source and nickel nitrate hexahydrate as a nickel source. Mo and Ni are loaded by an isometric impregnation method, and the catalyst is obtained by drying and roasting after impregnation, wherein the drying and roasting conditions are the same as those of the comparative example 2.
The catalyst was numbered A-6. In catalyst A-6, the solid acid was zeolite beta, the metal component accounted for 2 wt%, Ni accounted for 0.5 wt%, Mo accounted for 1.5 wt%.
Example 7
This example illustrates the preparation and composition of the solid acid catalyst of the present invention.
The catalyst is prepared by taking a formed catalyst containing 80 wt% of ZSM-5 zeolite and 20 wt% of a carrier matrix as a carrier, taking ammonium molybdate tetrahydrate as a molybdenum source and taking nickel nitrate hexahydrate as a nickel source. Mo and Ni are loaded by an isometric impregnation method, and the catalyst is obtained by drying and roasting after impregnation, wherein the drying and roasting conditions are the same as those of the comparative example 2.
The catalyst was numbered A-7. In catalyst A-7, the solid acid was ZSM-5 zeolite, the metal component accounted for 2 wt%, Ni accounted for 0.5 wt%, Mo accounted for 1.5 wt%.
Example 8
This example illustrates the preparation and composition of the solid acid catalyst of the present invention.
The method is characterized in that a formed catalyst containing 80 wt% of MCM-22 zeolite and 20 wt% of carrier matrix is used as a carrier, ammonium molybdate tetrahydrate is used as a molybdenum source, and nickel nitrate hexahydrate is used as a nickel source. Mo and Ni are loaded by an isometric impregnation method, and the catalyst is obtained by drying and roasting after impregnation, wherein the drying and roasting conditions are the same as those of the comparative example 2.
The catalyst was numbered A-8. In the catalyst A-8, the solid acid is MCM-22 zeolite, the metal component accounts for 2 wt%, the Ni accounts for 0.5 wt%, and the Mo accounts for 1.5 wt%.
The following examples illustrate the use of the solid acid catalysts provided by the present invention in alkylation reaction processes.
In the examples, the solid acid catalyst was subjected to a drying treatment and an in-situ reduction treatment, and then used for the evaluation of alkylation reaction. The solid acid catalyst was evaluated over multiple alkylation reactions and multiple regeneration processes. The deactivated catalyst is regenerated in the reactor while the regeneration effect is compared with the result of alkylation reaction.
Comparative reaction example 1
The comparative catalyst D-1 was dried and calcined at 200 ℃ and 450 ℃.
Evaluation of alkylation reaction, conditions of alkylation reaction: the product was analyzed by gas chromatography at 75 ℃ under 3.0MPa and 200ml/h (I/O: 250, mass ratio).
Catalyst regeneration, regeneration conditions: 250 ℃, 3.0MPa, H2The flow rate was 200 ml/min.
Comparative reaction example 2
The comparative catalyst D-2 was subjected to in situ reduction treatment under the conditions: 3.0MPa, H2The flow rate was 200ml/min and the reduction temperature was 450 ℃.
In a fixed bed reactor, the alkylation reaction activity and selectivity of the catalyst were evaluated through multiple alkylation reaction-catalyst regeneration cycles.
Alkylation reaction and regeneration conditions were the same as in comparative example 1.
Comparative reaction example 3
Similarly, with respect to catalyst D-3, the alkylation reaction activity and selectivity of the catalyst was evaluated after in-situ reduction in the reactor and through multiple alkylation reaction-catalyst regeneration cycles.
Comparative reaction example 4
Similarly, with respect to catalyst D-4, the alkylation reaction activity and selectivity of the catalyst was evaluated after in-situ reduction in the reactor and through multiple alkylation reaction-catalyst regeneration cycles.
Comparative reaction example 5
Similarly, with respect to catalyst D-5, the alkylation reaction activity and selectivity of the catalyst was evaluated after in-situ reduction in the reactor and through multiple alkylation reaction-catalyst regeneration cycles.
Comparative reaction example 6
Similarly, with respect to catalyst D-6, the alkylation reaction activity and selectivity of the catalyst was evaluated after in-situ reduction in the reactor and through multiple alkylation reaction-catalyst regeneration cycles.
Reaction example 1
As above, for catalyst A-1, after in-situ reduction in the reactor, the alkylation reaction activity and selectivity of the catalyst were evaluated through multiple alkylation reaction-catalyst regeneration cycles.
Reaction example 2
As above, for catalyst A-2, after in-situ reduction in the reactor, the alkylation reaction activity and selectivity of the catalyst were evaluated through multiple alkylation reaction-catalyst regeneration cycles.
Reaction example 3
As above, for catalyst A-3, after in-situ reduction in the reactor, the alkylation reaction activity and selectivity of the catalyst were evaluated through multiple alkylation reaction-catalyst regeneration cycles.
Comparative reaction example 7
Similarly, with respect to catalyst D-7, the alkylation reaction activity and selectivity of the catalyst was evaluated after in-situ reduction in the reactor and multiple alkylation reaction-catalyst regeneration cycles.
Comparative reaction example 8
Similarly, with respect to catalyst D-8, the alkylation reaction activity and selectivity of the catalyst was evaluated after in-situ reduction in the reactor and multiple alkylation reaction-catalyst regeneration cycles.
EXAMPLE 4
As above, for catalyst A-4, after in-situ reduction in the reactor, the alkylation reaction activity and selectivity of the catalyst were evaluated through multiple alkylation reaction-catalyst regeneration cycles.
Example 5 reaction example
As above, for catalyst A-5, after in-situ reduction in the reactor, the alkylation reaction activity and selectivity of the catalyst were evaluated through multiple alkylation reaction-catalyst regeneration cycles.
Example 6 reaction example
As above, for catalyst A-6, after in-situ reduction in the reactor, the alkylation reaction activity and selectivity of the catalyst were evaluated through multiple alkylation reaction-catalyst regeneration cycles.
Example 7 reaction example
As above, for catalyst A-7, after in-situ reduction in the reactor, the alkylation reaction activity and selectivity of the catalyst were evaluated through multiple alkylation reaction-catalyst regeneration cycles.
EXAMPLE 8
As above, for catalyst A-8, after in-situ reduction in the reactor, the alkylation reaction activity and selectivity of the catalyst were evaluated through multiple alkylation reaction-catalyst regeneration cycles.
The following data in tables 1 to 6 illustrate the alkylation reaction of the catalyst of the present invention and the comparative catalyst. Wherein,
TABLE 1 shows the fresh and regenerant alkylation reaction cycle life, C, for comparative samples D-1, D-2, D-3, D-4 and sample A-28Selectivity, TMP selectivity comparison;
TABLE 2 freshness agent and Redox alkylation reaction lifetimes for comparative samples D-2, D-5, D-6 and sample A-2, C8Selectivity, TMP selectivity comparison;
table 3 is a pairAlkylation reaction cycle Life of the fresheners and Regenerants, C, over samples D-7, D-8 and sample A-28Selectivity, TMP selectivity comparison;
TABLE 4 shows the freshness agent and multiple regenerant alkylation reaction cycle life, C, for samples A-1, A-2 and A-38Selectivity, TMP selectivity comparison;
TABLE 5 shows the alkylation reaction cycle life, C, of the fresheners and regenerants for samples A-2, A-4, and A-58Selectivity, TMP selectivity comparison;
TABLE 6 shows the alkylation reaction cycle life, C, of the fresheners and regenerants for samples A-2, A-6, A-7, and A-88Selectivity, TMP selectivity comparison;
C8the selectivity is the mass percentage of the hydrocarbon with the carbon number of 8 in the alkylated gasoline; TMP selectivity is the mass percent TMP (trimethylpentane) based on the alkylated gasoline.
In the table, the alkylation reaction cycle life of the regenerant and the regenerant is measured in "h (hours)", C8Selectivity, TMP selectivity, in% of total product, is shown in the following table:
TABLE 1
| Catalyst numbering | D-1 | D-2 | D-3 | D-4 | A-2 |
| Metal component and content (wt%) | / | 0.5Pt | 0.5Ni | 1.5Mo | 0.5Ni1.5Mo |
| Fresh agent cycle life/h | 15 | 15 | 14 | 13 | 13 |
| Regenerant cycle life/h | 7 | 13 | 8 | 11 | 13 |
| Fresh agent C8Selectivity/%) | 75.34 | 73.59 | 74.35 | 72.04 | 73.58 |
| Regenerant C8Selectivity/%) | 63.48 | 74.28 | 63.41 | 67.28 | 73.17 |
| TMP selectivity/% of the novel agent | 62.27 | 60.90 | 60.08 | 60.09 | 59.83 |
| Regenerant TMP selectivity/%) | 54.13 | 61.72 | 49.70 | 56.19 | 59.55 |
As can be seen from Table 1, the catalyst sample D-1 which did not support any metal component had a poor regeneration effect, the comparative catalyst sample D-2 which supported 0.5Pt as a metal and the catalyst sample A-2 which supported 0.5Ni1.5Mo as a metal had the best cycle life recovery and the cycle life recovery was the same, while the comparative catalyst samples D-3 and D-4 which supported 0.5Ni and 1.5Mo alone had cycle lives which were not as good as those of the catalyst sample A-2 which supported 0.5Ni1.5Mo as provided by the present invention. Comparative catalyst sample D-2 supporting noble metal 0.5Pt and catalyst sample A-2 supporting metal 0.5Ni1.5Mo both regenerated C8The selectivity and TMP selectivity are the best and are relatively close.
TABLE 2
| Catalyst numbering | D-2 | D-5 | D-6 | A-2 |
| Metal component and content (wt%) | 0.5Pt | 2Ni | 2Mo | 0.5Ni1.5Mo |
| Fresh agent cycle life/h | 15 | 14 | 13 | 13 |
| Cycle life of primary regenerant/h | 13 | 13 | 11 | 13 |
| Cycle life of secondary regenerant/h | 13 | 11 | 10 | 13 |
| Three regenerant cycle life/h | 13 | 10 | 8 | 13 |
| Fresh agent C8Selectivity/%) | 73.59 | 73.85 | 71.53 | 73.58 |
| Primary regenerant C8Selectivity/%) | 74.28 | 73.04 | 69.97 | 73.17 |
| Secondary regenerant C8Selectivity/%) | 73.96 | 69.50 | 60.03 | 73.26 |
| Third regenerant C8Selectivity/%) | 74.06 | 65.53 | 52.19 | 73.24 |
| TMP selectivity/% of the novel agent | 60.90 | 60.86 | 58.49 | 59.83 |
| Primary regenerant TMP selectivity/%) | 61.72 | 61.28 | 49.53 | 59.55 |
| Secondary regenerant TMP selectivity/%) | 61.06 | 54.23 | 40.33 | 59.79 |
| Triple regenerant TMP selectivity/%) | 61.50 | 48.69 | 35.06 | 60.03 |
As can be seen from Table 2, after three reaction-regeneration cycles of the supported metal 0.5Pt control catalyst sample D-2 and the supported metal 0.5Ni1.5Mo catalyst sample A-2, the regenerant cycle life was not reduced; the catalyst sample A-2 in which the total amount of the supported metal was 2 wt% and the metallic nickel and molybdenum were supported in a weight ratio of 1:3 achieved the same or similar regeneration effect as the comparative catalyst sample D-2 in which 0.5Pt was supported, thereby saving the cost.
It can also be seen from Table 2 that the cycle life of comparative catalyst sample D-5, which was loaded with only 2 wt% of nickel, or comparative catalyst sample D-6, which was loaded with only 2 wt% of Mo, exhibited a significant decay. Comparative catalyst sample D-2 supporting noble metal 0.5Pt and catalyst sample A-2 supporting metal 0.5Ni1.5Mo8The selectivity, TMP selectivity were superior to those of the comparative catalyst sample D-5 supporting only the metal 2Ni and the comparative catalyst sample D-6 supporting only the metal 2 Mo.
TABLE 3
| Catalyst numbering | D-7 | D-8 | A-2 |
| Metal component and content (wt%) | 1Ni1Mo | 0.25Ni1.75Mo | 0.5Ni1.5Mo |
| Fresh agent cycle life/h | 13 | 13 | 13 |
| Cycle life of primary regenerant/h | 11 | 11 | 13 |
| Cycle life of secondary regenerant/h | 10 | 10 | 13 |
| Three regenerant cycle life/h | 8 | 9 | 13 |
| Fresh agent C8Selectivity/%) | 72.03 | 71.76 | 73.58 |
| Primary regenerant C8Selectivity/%) | 69.22 | 70.47 | 73.17 |
| Secondary regenerant C8Selectivity/%) | 65.03 | 66.33 | 73.26 |
| Third regenerant C8Selectivity/%) | 59.11 | 60.12 | 73.24 |
| TMP selectivity/% of the novel agent | 56.81 | 56.23 | 59.83 |
| Primary regenerant TMP selectivity/%) | 49.21 | 54.26 | 59.55 |
| Secondary regenerant TMP selectivity/%) | 45.02 | 50.56 | 59.79 |
| Triple regenerant TMP selectivity/%) | 39.58 | 46.23 | 60.03 |
As can be seen from table 3, the total amount of supported metal is 2 wt%, and the ratio of nickel to molybdenum is in the range of 1: in addition to the ratio of 2 to 4, for example, the regenerant cycle life and the distribution of the alkylate were not as good as those of the catalyst sample A-2 in which the ratio of nickel to molybdenum was 1:3, for example, the comparative catalyst sample D-7 in which the ratio of nickel to molybdenum was 1:1 and the comparative catalyst sample D-8 in which the ratio of nickel to molybdenum was 1: 7.
TABLE 4
| Catalyst numbering | A-1 | A-2 | A-3 |
| Metal component and content (wt%) | 0.44Ni1.56Mo | 0.5Ni1.5Mo | 0.57Ni1.43Mo |
| Fresh agent cycle life/h | 13 | 13 | 13 |
| Cycle life of primary regenerant/h | 13.5 | 13 | 13 |
| Cycle life of secondary regenerant/h | 13 | 13 | 12.5 |
| Three regenerant cycle life/h | 13 | 13 | 13 |
| Fresh agent C8Selectivity/%) | 73.52 | 73.58 | 73.19 |
| Primary regenerant C8Selectivity/%) | 73.43 | 73.17 | 73.26 |
| Secondary regenerant C8Selectivity/%) | 74.06 | 73.26 | 73.63 |
| Third regenerant C8Selectivity/%) | 73.58 | 73.24 | 73.96 |
| TMP selectivity/% of the novel agent | 59.66 | 59.83 | 60.00 |
| Primary regenerant TMP selectivity/%) | 59.45 | 59.55 | 59.94 |
| Secondary regenerant TMP selectivity/%) | 59.69 | 59.79 | 60.15 |
| Triple regenerant TMP selectivity/%) | 60.12 | 60.03 | 59.86 |
As can be seen from table 4, the total amount of supported metal was 2 wt%, and the ratio of nickel to molybdenum was 1: catalyst samples A-1, A-2 and A-3, which were loaded at ratios of 3.5, 1:3 and 1:2.5, were all regenerated after deactivation and the alkylation performance (cycle life, C) after regeneration8Selectivity, TMP selectivity) are similar.
TABLE 5
| Catalyst numbering | A-2 | A-4 | A-5 |
| Metal component and content (wt%) | 0.5Ni1.5Mo | 0.25Ni0.75Mo | 1Ni3Mo |
| Fresh agent cycle life/h | 13 | 13 | 13 |
| Cycle life of primary regenerant/h | 13 | 12.5 | 13 |
| Cycle life of secondary regenerant/h | 13 | 13 | 12.5 |
| Three regenerant cycle life/h | 13 | 13 | 13 |
| Fresh agent C8Selectivity/%) | 73.58 | 73.46 | 73.60 |
| Primary regenerant C8Selectivity/%) | 73.17 | 73.10 | 73.07 |
| Secondary regenerant C8Selectivity/%) | 73.26 | 73.33 | 73.97 |
| Third regenerant C8Selectivity/%) | 73.24 | 73.69 | 74.05 |
| TMP selectivity/% of the novel agent | 59.83 | 59.18 | 60.19 |
| Primary regenerant TMP selectivity/%) | 59.55 | 59.39 | 59.91 |
| Secondary regenerant TMP selectivity/%) | 59.79 | 59.23 | 60.23 |
| Triple regenerant TMP selectivity/%) | 60.03 | 59.40 | 60.15 |
As can be seen from Table 5, the catalyst samples A-2, A-4, A-5, in which the total amount of metallic nickel and molybdenum was 2 wt%, 1 wt% and 4 wt% were supported in a ratio of 1:3, were regenerated after deactivation, and the alkylation performance (cycle life, C) after regeneration was obtained8Selectivity, TMP selectivity) are similar.
TABLE 6
| Catalyst numbering | A-2 | A-6 | A-7 | A-8 |
| Zeolite | Y | β | ZSM-5 | MCM-22 |
| Metal component and content (wt%) | 0.5Ni1.5Mo | 0.5Ni1.5Mo | 0.5Ni1.5Mo | 0.5Ni1.5Mo |
| Fresh agent cycle life/h | 13 | 9 | 11 | 6 |
| Cycle life of primary regenerant/h | 13 | 9 | 11 | 6 |
| Cycle life of secondary regenerant/h | 13 | 8.5 | 10.5 | 6 |
| Three regenerant cycle life/h | 13 | 9 | 11 | 6 |
| Fresh agent C8Selectivity/%) | 73.58 | 63.52 | 68.52 | 50.17 |
| Primary regenerant C8Selectivity/%) | 73.17 | 63.58 | 68.58 | 50.10 |
| Secondary regenerant C8Selectivity/%) | 73.26 | 63.19 | 68.19 | 50.07 |
| Third regenerant C8Selectivity/%) | 73.24 | 63.17 | 68.17 | 50.26 |
| TMP selectivity/% of the novel agent | 59.83 | 49.16 | 53.66 | 38.55 |
| Primary regenerant TMP selectivity/%) | 59.55 | 49.33 | 53.83 | 38.39 |
| Secondary regenerant TMP selectivity/%) | 59.79 | 49.50 | 54.00 | 38.91 |
| Triple regenerant TMP selectivity/%) | 60.03 | 49.68 | 54.18 | 39.03 |
As can be seen from Table 6, the catalyst samples A-2, A-6, A-7 and A-8 in which the total amount of metallic nickel and molybdenum was 2 wt% were supported in a ratio of 1:3 were regenerated after deactivation of all the solid acids (Y, β, ZSM-5 and MCM-22) and the catalyst activity and product selectivity were recovered, particularly the catalyst sample A-2 containing zeolite Y as a solid acid component was most effective.
Claims (9)
1. An alkylation reaction method is characterized by being carried out under the alkylation reaction condition and in the presence of a solid acid catalyst, wherein the solid acid catalyst comprises a solid acid and a metal component which is loaded on the solid acid and accounts for 0.01-5 wt% of the solid acid catalyst, the metal component is molybdenum and nickel, and the mass ratio of the molybdenum to the nickel is (2-4): 1; wherein the solid acid is selected from one or more of beta zeolite, Y-type zeolite, MCM-22, ZSM-5 and Mordnite.
2. The process of claim 1 wherein said metal component comprises 0.5 to 5 wt% of the solid acid catalyst.
3. The method according to claim 1, wherein the mass ratio of molybdenum to nickel is (2.2-3.8): 1.
4. The method according to claim 1, wherein the mass ratio of molybdenum to nickel is (2.5-3.5): 1.
5. The method according to claim 1, wherein the mass ratio of molybdenum to nickel is (2.8-3.2): 1.
6. The process of claim 1 wherein said solid acid is zeolite Y.
7. The process of claim 1 wherein said alkylation reaction is the reaction of contacting an alkane with an alkene to produce an alkylated gasoline.
8. The method according to claim 7, wherein the alkane is isoparaffin comprising one or more of isobutane and isopentane, and the alkene comprises one or more of propylene, isobutene, 1-butene, 2-butene and pentene.
9. The process of claim 8 wherein said isoparaffin is isobutane and said olefin is predominantly a mixture of butenes.
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