CN111375451B - Alumina carrier and carbon dioxide three-fraction selective hydrogenation catalyst - Google Patents
Alumina carrier and carbon dioxide three-fraction selective hydrogenation catalyst Download PDFInfo
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- CN111375451B CN111375451B CN201811633788.4A CN201811633788A CN111375451B CN 111375451 B CN111375451 B CN 111375451B CN 201811633788 A CN201811633788 A CN 201811633788A CN 111375451 B CN111375451 B CN 111375451B
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 28
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 10
- 239000011148 porous material Substances 0.000 claims abstract description 16
- 239000013078 crystal Substances 0.000 claims abstract description 13
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims description 45
- 150000001875 compounds Chemical class 0.000 claims description 44
- 229910052746 lanthanum Inorganic materials 0.000 claims description 36
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 36
- 239000004925 Acrylic resin Substances 0.000 claims description 29
- 229920000178 Acrylic resin Polymers 0.000 claims description 29
- 229910052782 aluminium Inorganic materials 0.000 claims description 29
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 29
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 24
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 239000011230 binding agent Substances 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 13
- 239000003607 modifier Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 6
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 6
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 6
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 6
- 229920002472 Starch Polymers 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 5
- -1 polyoxyethylene Polymers 0.000 claims description 5
- 239000008107 starch Substances 0.000 claims description 5
- 235000019698 starch Nutrition 0.000 claims description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 3
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 238000000034 method Methods 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 6
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 229960000583 acetic acid Drugs 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 241000219782 Sesbania Species 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- IFYDWYVPVAMGRO-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]tetradecanamide Chemical compound CCCCCCCCCCCCCC(=O)NCCCN(C)C IFYDWYVPVAMGRO-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical compound C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
Classifications
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- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B01J35/613—
-
- B01J35/633—
-
- B01J35/635—
-
- B01J35/651—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
- C07C7/167—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation for removal of compounds containing a triple carbon-to-carbon bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
- C07C2521/04—Alumina
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
- C07C2523/44—Palladium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to the field of catalyst carrier preparation, and discloses an alumina carrier and carbon dioxide three-fraction selective hydrogenation catalyst. The alumina carrier comprises alpha crystal form and theta crystal form, wherein theta-Al 2 O 3 10-30 wt% of total alumina, pore volume of the alumina carrier is 0.3-0.7mL/g, and specific surface area is 25m 2 More than g, and the average pore diameter is 40-300nm. The alumina carrier has stable performance, and the obtained carbon dioxide three-fraction selective hydrogenation catalyst has high selective hydrogenation conversion rate and good selectivity.
Description
Technical Field
The invention relates to the field of catalyst carrier preparation, in particular to an alumina carrier and carbon dioxide three-fraction selective hydrogenation catalyst.
Background
The cracked gas generated by cracking the liquid hydrocarbon steam contains 0.2-0.7mol% of acetylene and 0.2-0.9mol% of propyne and propadiene (MAPD). In order to obtain polymerization grade ethylene and propylene, acetylene and MAPD must be removed to required indexes. The catalytic hydrogenation method is the most commonly used method, and refers to that acetylene is hydrogenated to generate ethylene and propine is hydrogenated to generate propylene in the presence of a hydrogenation catalyst under certain process operation conditions, so that the purpose of purification is achieved.
The selective hydrogenation of three carbon-containing fractions generally adopts a multi-metal supported catalyst mainly comprising palladium, and the catalyst performance is improved mainly by a carrier and an added cocatalyst component, so that the aims of improving the ethylene selectivity, reducing the green oil generation amount and prolonging the catalyst operation period are fulfilled. The carbon dioxide three-fraction selective hydrogenation catalyst carrier is generally a toothed sphere or spherical particle, and the component is mainly alpha-Al 2 O 3 The preparation process mainly comprises the steps of powder mixing, kneading, strip extruding, grain cutting, drying, roasting and the like. The performance of the carrier directly determines the performance of the catalyst, so that the carrier with excellent performance is obtained in a crucial way.
Although the preparation of a catalyst support excellent in physical properties is an important approach for improving the catalyst performance, it is difficult to further improve the support performance today in the development of catalyst preparation technology. In the field of preparation of carbon two three-fraction selective hydrogenation catalyst carriers, no research aiming at carrying out technical improvement on the carbon two three-fraction selective hydrogenation catalyst carriers is seen at present.
CN 107970929A discloses an alkyne and dialkene liquid phase selective hydrogenation catalyst, its preparation method and application, and its carrier Al 2 O 3 The crystal form contains theta phase, wherein the proportion of the theta phase crystal form is>30%, preferably>45%, more preferably 45%>65％。
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide an alumina carrier and a carbon-two carbon three-fraction selective hydrogenation catalyst, wherein the alumina carrier has stable performance, and the obtained carbon-two carbon three-fraction selective hydrogenation catalyst has high selective hydrogenation conversion rate and good selectivity.
In order to achieve the purpose, the invention provides an alumina carrier which is characterized by comprising two crystal forms of alpha and theta, wherein theta-Al 2 O 3 Accounting for 10-30 wt% of the total alumina, the alumina carrier has a pore volume of 0.3-0.7mL/g and a specific surface area of 25m 2 More than g, and the average pore diameter is 40-300nm.
Preferably, theta-Al 2 O 3 15-25 wt.% of the total alumina.
Preferably, the pore volume of the alumina carrier is 0.3-0.65mL/g, and the specific surface area is 35-70m 2 (ii)/g, the average pore diameter is 100-300nm.
Preferably, the alumina carrier is obtained by sequentially forming, first drying and first roasting a mixture containing an aluminum-containing compound, a binder, an acid, a modifier and optionally lanthanum or a lanthanum-containing compound, wherein the modifier is polyethylene oxide and/or an acrylic resin.
Preferably, the aluminum-containing compound is aluminum hydroxide and/or pseudo-boehmite.
Preferably, the binder is one or more of sesbania powder, starch and hydroxypropyl methylcellulose.
Preferably, the acid is one or more of nitric acid, citric acid and acetic acid.
Preferably, the acid is used in an amount of 1 to 8% by weight relative to the weight of the aluminum-containing compound calculated as alumina.
Preferably, in the mixture, the weight ratio of the aluminum-containing compound, the binder and the acid is 1:0.03-0.1:0.015-0.08.
Preferably, the binder is used in an amount of 5 to 15% by weight relative to the weight of the aluminum-containing compound calculated as alumina.
Preferably, the lanthanum or lanthanum-containing compound is used in an amount of 0.35 to 1% by weight in terms of lanthanum element, relative to the weight of the aluminum-containing compound in terms of alumina.
Preferably, the molecular weight of the polyethylene oxide is 30 to 400 ten thousand, and the molecular weight of the acrylic resin is 500 to 700 ten thousand.
Preferably, the polyethylene oxide and the acrylic resin are used in an amount of 1 to 10% by weight, preferably 3 to 7% by weight, relative to the weight of the aluminum-containing compound, calculated as alumina.
Preferably, the weight ratio of the polyethylene oxide to the acrylic resin component is 1:9 to 9:1, preferably 2:8 to 5:5.
Preferably, after mixing the aluminum-containing compound, binder and acrylic resin, the acid and optionally lanthanum or a lanthanum-containing compound are added and mixed.
Preferably, the temperature of the mixing is 5-45 ℃ and the time of the mixing is 15-60 minutes.
Preferably, the conditions of the first drying include: the drying temperature is 80-150 ℃, and the drying time is 2-6 hours.
Preferably, the conditions of the first firing include: the roasting temperature is 400-650 ℃, and the roasting time is 5-15 hours.
Preferably, the first calcined support is impregnated with a potassium hydroxide solution, followed by second drying and second calcination.
Preferably, the concentration of the potassium hydroxide solution is 0.01-0.1mol/L.
Preferably, the potassium hydroxide solution is used in an amount of 30 to 100% by weight of the support after the first calcination.
Preferably, the conditions of the second drying include: the drying temperature is 80-150 ℃, and the drying time is 2-15 hours.
Preferably, the conditions of the second firing include: the roasting temperature is 1050-1300 ℃, and the drying time is 8-25 hours.
The second aspect of the present invention provides a selective hydrogenation catalyst for carbon-two three-fraction, which comprises the carrier of the present invention as described above, and an active metal component supported on the carrier.
The inventor of the invention unexpectedly discovers that the alumina carrier obtained by pretreating the alumina carrier in the carrier preparation process has alpha crystal form and theta crystal form, the proportion of the alumina with different crystal forms has obvious influence on the activity of the catalyst, and the theta-Al catalyst has obvious influence on the activity of the catalyst 2 O 3 When the proportion is 10-30 wt%, the conversion rate and selectivity of the prepared carbon dioxide three-fraction selective hydrogenation catalyst can be improved simultaneously. Moreover, the pretreatment method disclosed by the invention is simple in process, stable in carrier performance, free of the addition of operation steps and beneficial to large-scale production of the catalyst.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein. In the present invention, the "molecular weights" are all "number average molecular weights".
The alumina carrier provided by the invention comprises alpha crystal form and theta crystal form, wherein theta-Al 2 O 3 10-30 wt% of total alumina, pore volume of the alumina carrier is 0.3-0.7mL/g, and specific surface area is 25m 2 More than g, and the average pore diameter is 40-300nm.
Preferably, theta-Al 2 O 3 From 15 to 25 wt.%, more preferably from 17 to 20 wt.%, of the total alumina.
Preferably, the pore volume of the alumina carrier is 0.3-0.6mL/g; the specific surface area is 35-70m 2 Per g, more preferably from 40 to 60m 2 (iv) g; the average pore diameter is from 100 to 300nm, more preferably from 150 to 300nm.
In addition, the bulk density of the alumina carrier is 0.6-0.9g/mL, preferably 0.65-0.8g/mL.
According to a preferred embodiment of the present invention, the alumina support is obtained by subjecting a mixture containing an aluminum-containing compound, a binder, an acid, a modifier and optionally lanthanum or a lanthanum-containing compound to shaping, first drying and first calcination in this order; wherein the modifier is polyoxyethylene and/or acrylic resin.
In the present invention, the aluminum-containing compound may be any of various aluminum-containing compounds conventionally used for preparing an alumina carrier, and may be, for example, aluminum hydroxide and/or pseudo-boehmite.
In the present invention, the binder may use various binders that are currently used to prepare the alumina carrier, and may be, for example, one or more of sesbania powder, starch, and hydroxypropylmethylcellulose. Preferably, the binder is used in an amount of 5 to 15 wt.%, preferably 8 to 12 wt.%, more preferably 8 to 10 wt.%, relative to the weight of the aluminum-containing compound, calculated as alumina. According to one embodiment of the present invention, sesbania powder, starch and hydroxypropyl methylcellulose are preferably used together, and more preferably in a weight ratio of 1:0.5-0.7:0.1-0.3.
In the present invention, the acid may be one or more of nitric acid, citric acid and acetic acid. Preferably, the acid is used in an amount of 1 to 8 wt.%, preferably 4 to 6 wt.%, relative to the weight of the aluminium-containing compound, calculated as aluminium oxide. As the nitric acid, a commercially available concentrated nitric acid having a mass fraction of about 68%; as the above citric acid, commercially available solid citric acid (e.g., chemically pure or analytically pure citric acid) is preferably used; as the acetic acid, glacial acetic acid (e.g., 98% by mass) is preferably used. According to one embodiment of the present invention, nitric acid, citric acid and acetic acid are preferably used as the acid at the same time, and more preferably in a weight ratio of 1:0.9-1.1:0.1-0.3.
According to a preferred embodiment of the present invention, in the mixture, the weight ratio of the aluminum-containing compound, the binder and the acid is 1:0.03-0.1:0.015 to 0.08, more preferably 1:0.08-0.1:0.04-0.06. More preferably, the binder and the lanthanum or lanthanum-containing compound are used in an amount of 2 to 15 wt.%, preferably 8 to 12 wt.%, calculated as lanthanum element, relative to the weight of the aluminum-containing compound calculated as alumina.
The inventors of the present invention unexpectedly found that the alumina prepared by using the modifier in combination with lanthanum or a lanthanum-containing compound in the process of preparing the alumina carrier can simultaneously improve the conversion rate and selectivity of the catalyst in the selective hydrogenation reaction of carbon dioxide three-fraction.
According to the present invention, the lanthanum or lanthanum-containing compound may be a simple lanthanum or any lanthanum-containing compound capable of being fired to obtain lanthanum oxide, and it is preferable to use simple lanthanum from the viewpoint of operability. More preferably, the lanthanum or lanthanum containing compound is used in an amount of 0.35 to 1 wt.%, preferably 0.4 to 0.6 wt.%, more preferably 0.4 to 0.5 wt.%, relative to the weight of the aluminum containing compound, calculated as alumina.
In order to improve the conversion rate and selectivity of the selective hydrogenation catalyst for the carbon-two carbon three-cut, the molecular weight of the acrylic resin is preferably 100 ten thousand to 1000 ten thousand, more preferably 500 ten thousand to 700 ten thousand, and the molecular weight of the polyethylene oxide is preferably 200 ten thousand to 500 ten thousand, more preferably 300 ten thousand to 400 ten thousand. And the polyethylene oxide and the acrylic resin are used in an amount of 1 to 10% by weight, preferably 3 to 7% by weight, relative to the weight of the aluminum-containing compound in terms of alumina, in order to further improve the conversion and selectivity of the selective hydrogenation reaction. More preferably, the weight ratio of the polyethylene oxide to the acrylic resin component is 1:9 to 9:1, even more preferably 2:8 to 5:5, and still more preferably 1:0.4-0.7.
As a production process of the above-mentioned mixture containing the aluminum-containing compound, the binder, the acid, the acrylic resin and optionally lanthanum or the lanthanum-containing compound, for example, the aluminum-containing compound, the binder and the acrylic resin may be mixed, and then the acid and optionally lanthanum or the lanthanum-containing compound may be added and mixed. Preferably, the aluminum-containing compound, the binder and the acrylic resin are mixed using powder, and then the mixture is mixed with an aqueous solution in which an acid and optionally lanthanum or a lanthanum-containing compound are dissolved. When hydroxypropylmethylcellulose is used as the binder, it is preferably mixed in the form of an aqueous solution.
In order to achieve good mixing effect, the weight ratio of the added water to the aluminum-containing compound (based on the dry weight of the aluminum hydroxide) is preferably 1-4:1, preferably 1.8 to 2.2:1.
the mixing can achieve the effect of uniformly mixing the materials, preferably, the mixing temperature can be 5-45 ℃, and the mixing time can be 15-60 minutes.
In the present invention, the molding is used to form the mixed materials into the desired shape of the catalyst, and the molding method is not particularly limited, and may be specifically selected according to the use requirements of the catalyst. The shape of the molding may be, for example, a pellet shape, a clover shape, a cylinder shape, a spherical shape, a porous shape, or the like. From the viewpoint of producing the selective hydrogenation catalyst for the three-carbon fraction, preferred are denticular or spherical particles, generally 1 to 10mm in diameter.
In the present invention, the method of the first drying is not particularly limited, and any conventional method for producing an alumina support may be used. Preferably, the conditions of the first drying include: the drying temperature is 80-150 ℃, and the drying time is 2-6 hours; more preferably, the conditions of the first drying include: the drying temperature is 80-100 ℃, and the drying time is 3-5 hours. The first drying may be performed using a drying belt heater.
In the present invention, the method of the first calcination is not particularly limited, and any conventional method for producing an alumina carrier can be used. Preferably, the conditions of the first firing include: the roasting temperature is 400-650 ℃, and the roasting time is 5-15 hours; more preferably, the conditions of the first firing include: the roasting temperature is 450-550 ℃, and the roasting time is 8-12 hours. The first firing may be performed using, for example, a mesh belt kiln calciner.
In order to further improve the conversion rate and selectivity of the obtained carbo-two fraction selective hydrogenation catalyst, it is more preferable that the first calcined carrier is impregnated with a potassium hydroxide solution, and then the second drying and the second calcination are performed.
The potassium hydroxide solution used for impregnation has a concentration of preferably 0.01 to 0.1mol/L, more preferably 0.02 to 0.05mol/L, and is used in an amount of 30 to 100% by weight, more preferably 50 to 80% by weight, of the support after the first calcination.
As the conditions of the second drying, for example, there may be included: the drying temperature is 80-150 ℃, and the drying time is 2-15 hours; preferably, the drying temperature is 110-130 ℃ and the drying time is 6-10 hours. The second drying may be performed using a drying belt heater.
As the conditions of the second firing, for example, there may be included: the roasting temperature is 1050-1300 ℃, and the drying time is 8-25 hours; more preferably, the calcination temperature is 1100-1200 deg.C, more preferably 1130-1170 deg.C, and the calcination time is 12-18 hours. The second calcination may be performed using, for example, a mesh belt kiln calciner.
By immersing the potassium hydroxide solution under the above conditions, and performing the second drying and the second calcination, the conversion rate and the selectivity of the obtained carbo-dioxide three-fraction selective hydrogenation catalyst can be further improved.
The invention provides a selective hydrogenation catalyst for three carbon-dioxide fractions, which comprises the alumina carrier and an active metal component loaded on the carrier.
As the above active metal component, the active metal component of the existing carbo-two three-cut selective hydrogenation catalyst may be used, preferably comprising palladium and optionally a promoter component. As the promoter component, ga, ag, mn, W, cu, etc. may be mentioned, and among them, ag and Mn are preferable. The palladium may be used in an amount of 0.01 to 0.4 wt%, preferably 0.02 to 0.1 wt%, relative to the alumina support; the promoter component may be used in an amount of 0.02 to 0.2 wt%, preferably 0.04 to 0.1 wt%, relative to the alumina support. The loading method can adopt any method for preparing the supported catalyst, and the active metal component can be loaded on the carrier by adopting the known existing methods such as dipping, spraying and the like, and the loading can be carried out in a step-by-step mode or a synchronous mode. For example, the support may be impregnated with a solution of a salt of the active metal dissolved therein, and then dried and calcined.
The present invention will be described in detail below by way of examples. In the following examples, acrylic resins (molecular weight 500 ten thousand) were used from Shandong Yanggu Longquan chemical plant and polyethylene oxides (molecular weight 400 ten thousand) were used from ZiboKai Yuan Hengchang chemical Co., ltd.
In the following examples,. Theta. -Al 2 O 3 The ratio parameters were determined by X-ray diffraction testing (XRD).
Example 1
Aluminum hydroxide powder (20000 g calculated by alumina), sesbania powder 1000g, starch 600g and modifier 750g (polyoxyethylene 450g and acrylic resin 300 g) are sequentially added into a kneader and uniformly mixed, and then 41000g of deionized water dissolved with concentrated nitric acid 400g, citric acid 400g, glacial acetic acid 200g, rare earth element lanthanum 92g and hydroxypropyl methyl cellulose 200g (molecular weight 20 ten thousand) is added into the kneader in a spraying manner, and the kneading time is 25min. And adding the kneaded material into a bin of a granulator, and starting the granulator to granulate to prepare the toothed sphere particles with the outer diameter of 5 mm.
The drying belt heater, mesh belt kiln roaster and exhaust fan were started, the drying curve was checked, and the carrier particles were poured into the drying belt using the loading hopper. The temperature range of the drying zone is controlled to be 90 ℃, and the drying time is controlled to be 4 hours.
And roasting the dried carrier for 10 hours at 500 ℃ by a mesh belt kiln roasting furnace to obtain the carrier. 20000g of the carrier is immersed in 12000g of potassium hydroxide solution with the concentration of 0.04mol/L, dried at 120 ℃ for 8 hours and then calcined at 1150 ℃ for 15 hours to obtain the catalyst carrier 1.
Example 2
The carrier preparation process was the same as in example 1 except that the addition amounts of polyethylene oxide and acrylic resin were 600g and 400g, respectively, to prepare carrier 2.
Example 3
The carrier preparation process was the same as in example 1 except that the addition amounts of the polyethylene oxide and the acrylic resin were 700g and 300g, respectively, to prepare a carrier 3.
Example 4
The carrier preparation process was the same as in example 1 except that the amounts of polyethylene oxide and acrylic resin added were 780g and 520g, respectively, to prepare a carrier 4.
Example 5
The support preparation process was the same as in example 1 except that the rare earth element lanthanum was changed from 92g to 110g, to prepare a support 5.
Example 6
The procedure of preparing the carrier was the same as in example 1 except that the calcination temperature of the carrier was changed from 1150 ℃ to 1200 ℃ to prepare a carrier 6.
Example 7
The support preparation process was the same as in example 1 except that the modifier was only 750g of an acrylic resin, and support 7 was prepared.
Example 8
The support preparation process was the same as in example 1 except that the modifier was only 750g of polyethylene oxide, to prepare a support 8.
Comparative example 1
An alumina carrier was prepared by the same procedure as in example 1, except that the carrier D1 was prepared without adding polyethylene oxide and an acrylic resin.
Test example 1
The vehicle performance results are listed in table 1.
TABLE 1
As can be seen from Table 1, compared with the prior art, due to the addition of polyethylene oxide and acrylic resin as modifiers in the preparation process of the catalyst carrier of the present invention, the physical parameters of the catalyst, such as bulk density, pore volume, specific surface area and average pore diameter, are all superior to those of the catalyst without addition of polyethylene oxide and acrylic resin.
Test example 2
Preparation of the catalyst:
and taking 30mL of palladium nitrate solution with the concentration of 12mgPd/mL, adding 180mL of deionized water for dilution, spraying the solution on 1000g of the prepared catalyst carrier, drying the catalyst carrier at 120 ℃ for 7 hours, and roasting the catalyst carrier at 450 ℃ for 8 hours to obtain the catalyst.
Evaluation of catalyst Performance:
the prepared catalyst is used for the reaction of removing acetylene by selective hydrogenation of carbon-containing fraction.
20mL of catalyst is loaded into a fixed bed reactor, hydrogen is introduced for reduction, then feed gas is switched, the feed gas from the top of the deethanizing tower is introduced into the reactor after being matched with hydrogen, the hydrogen-acetylene ratio is 1.4, the concentration of acetylene at the inlet is 0.45mol%, and the gas phase volume space velocity is 10000h -1 . The composition of the tail gas of the reaction was monitored by gas chromatography, and the acetylene conversion and selectivity of the catalyst were determined and are shown in table 2.
TABLE 2
| Catalyst and process for producing the same | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | D1 |
| A conversion rate% | 97 | 100 | 100 | 99 | 96 | 95 | 96 | 96 | 88 |
| Selectively, according to | 79 | 82 | 80 | 79 | 72 | 77 | 72 | 77 | 65 |
As seen from Table 2, different θ -Al 2 O 3 The catalyst prepared by the carrier with the proportion shows different catalyst application performances, and because the polyoxyethylene and the acrylic resin are added as the modifiers in the preparation process of the catalyst carrier, the required theta-Al is obtained 2 O 3 The prepared catalyst has higher conversion rate and selectivity when being applied to a carbon two three-fraction selective hydrogenation process.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (23)
1. The alumina carrier is characterized by comprising alpha crystal form and theta crystal form, wherein theta-Al is in a crystal form 2 O 3 10-30 wt% of total alumina, pore volume of the alumina carrier is 0.3-0.7mL/g, and specific surface area is 25m 2 More than g, the average pore diameter is 40-300nm;
the alumina carrier is obtained by sequentially molding, first drying and first roasting a mixture containing an aluminum-containing compound, a binder, an acid, a modifier and lanthanum or a lanthanum-containing compound, impregnating the carrier subjected to the first roasting with a potassium hydroxide solution, and then performing second drying and second roasting, wherein the modifier is polyoxyethylene and/or acrylic resin.
2. The alumina support of claim 1 wherein θ -Al 2 O 3 15-25 wt.% of the total alumina.
3. The alumina carrier according to claim 1, wherein the pore volume is 0.3-0.65mL/g, and the specific surface area is 35-70m 2 G, the average pore diameter is 100-300nm.
4. The alumina support of claim 1 wherein the aluminum-containing compound is aluminum hydroxide and/or pseudoboehmite.
5. The alumina support of claim 1 wherein the binder is one or more of sesbania powder, starch and hydroxypropyl methylcellulose.
6. The alumina support of claim 1 wherein the acid is one or more of nitric acid, citric acid and acetic acid.
7. The alumina support according to claim 1, wherein the acid is present in an amount of 1 to 8% by weight relative to the weight of the aluminium-containing compound calculated as alumina.
8. The alumina support as claimed in claim 1, wherein the binder is present in an amount of 5 to 15 wt% relative to the weight of the aluminium-containing compound, calculated as alumina.
9. The alumina support as claimed in claim 1, wherein the lanthanum or lanthanum-containing compound is present in an amount of from 0.35 to 1% by weight, calculated as the lanthanum element, relative to the weight of the aluminium-containing compound, calculated as alumina.
10. The alumina carrier according to claim 1, wherein the molecular weight of the polyethylene oxide is 200 to 500 ten thousand, and the molecular weight of the acrylic resin is 100 to 1000 ten thousand.
11. The alumina support according to claim 1, wherein the polyethylene oxide and the acrylic resin are used in an amount of 1 to 10% by weight relative to the weight of the aluminum-containing compound in terms of alumina.
12. The alumina support according to claim 11, wherein the polyethylene oxide and the acrylic resin are used in an amount of 3 to 7% by weight relative to the weight of the aluminum-containing compound in terms of alumina.
13. The alumina support according to claim 1, wherein the weight ratio of the polyethylene oxide to the acrylic resin component is 1:9-9:1.
14. The alumina support according to claim 13, wherein the weight ratio of the polyethylene oxide to the acrylic resin component is 2:8-5:5.
15. The alumina support according to any one of claims 1 to 14 wherein after the aluminium-containing compound, the binder and the acrylic resin are mixed, the acid and lanthanum or a lanthanum-containing compound are added and mixed.
16. The alumina support of claim 15 wherein the temperature of mixing is 5-45 ℃ and the time of mixing is 15-60 minutes.
17. The alumina support of any one of claims 1 to 14, wherein the first drying conditions include: the drying temperature is 80-150 ℃, and the drying time is 2-6 hours.
18. The alumina support of any of claims 1 to 14, wherein the conditions of the first calcination include: the roasting temperature is 400-650 ℃, and the roasting time is 5-15 hours.
19. The alumina support according to any one of claims 1 to 14, wherein the concentration of the potassium hydroxide solution is 0.01 to 0.1mol/L.
20. The alumina support of any one of claims 1 to 14 wherein the potassium hydroxide solution is present in an amount of from 30 to 100% by weight of the first calcined support.
21. The alumina support of any one of claims 1 to 14, wherein the second drying conditions include: the drying temperature is 80-150 ℃, and the drying time is 2-15 hours.
22. The alumina support of any of claims 1 to 14, wherein the conditions of the second calcination include: the roasting temperature is 1050-1300 ℃, and the drying time is 8-25 hours.
23. A carbon-dioxide three-fraction selective hydrogenation catalyst, characterized in that it comprises the carrier of any one of claims 1 to 22, and an active metal component supported on the carrier.
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| CN102451685A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst and preparation method thereof |
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| CN105732260A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Selective hydrogenation method for C2 fraction |
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| CN101433841B (en) * | 2007-12-13 | 2010-04-14 | 中国石油天然气股份有限公司 | Selectively hydrogenating catalyst and preparation method thereof |
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| CN1238239A (en) * | 1998-06-10 | 1999-12-15 | 中国石化齐鲁石油化工公司 | Catalyst for selective hydrogenation of diolefin as raw material for alkylation of C4 and preparing method thereof |
| CN102451685A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst and preparation method thereof |
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