CN107673383A - Hexa-aluminate, include its carrier and preparation method thereof and high-temperature methanation catalyst - Google Patents
Hexa-aluminate, include its carrier and preparation method thereof and high-temperature methanation catalyst Download PDFInfo
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- CN107673383A CN107673383A CN201710795738.5A CN201710795738A CN107673383A CN 107673383 A CN107673383 A CN 107673383A CN 201710795738 A CN201710795738 A CN 201710795738A CN 107673383 A CN107673383 A CN 107673383A
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- aluminate
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- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 22
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 22
- 239000012153 distilled water Substances 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 239000000725 suspension Substances 0.000 claims abstract description 13
- 239000004411 aluminium Substances 0.000 claims abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 10
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 9
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 9
- 238000004821 distillation Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 238000001556 precipitation Methods 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- 238000013019 agitation Methods 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 39
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 31
- 238000001035 drying Methods 0.000 claims description 25
- 238000002803 maceration Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 12
- 239000001099 ammonium carbonate Substances 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 11
- 241000219782 Sesbania Species 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000005516 engineering process Methods 0.000 claims description 8
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 7
- 239000000428 dust Substances 0.000 claims description 6
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 5
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 150000001447 alkali salts Chemical class 0.000 claims description 3
- XFBXDGLHUSUNMG-UHFFFAOYSA-N alumane;hydrate Chemical compound O.[AlH3] XFBXDGLHUSUNMG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 239000011812 mixed powder Substances 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229910002706 AlOOH Inorganic materials 0.000 claims 1
- 229910001648 diaspore Inorganic materials 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 8
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 8
- 229910052788 barium Inorganic materials 0.000 description 32
- -1 salt compound Chemical class 0.000 description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 26
- 229910052759 nickel Inorganic materials 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 12
- 239000000969 carrier Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 8
- 238000005470 impregnation Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 6
- 239000008236 heating water Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 230000002045 lasting effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000002459 sustained effect Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 235000019359 magnesium stearate Nutrition 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- QKYBEKAEVQPNIN-UHFFFAOYSA-N barium(2+);oxido(oxo)alumane Chemical compound [Ba+2].[O-][Al]=O.[O-][Al]=O QKYBEKAEVQPNIN-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000165940 Houjia Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 229910006415 θ-Al2O3 Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/16—Preparation of alkaline-earth metal aluminates or magnesium aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/168—Barium aluminates
-
- 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
- B01J21/005—Spinels
-
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/005—Spinels
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- 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
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
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- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/08—Production of synthetic natural gas
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Abstract
The present invention relates to hexa-aluminate, include its carrier and preparation method thereof and high-temperature methanation catalyst.The hexa-aluminate is prepared by following steps：(A) boehmite is scattered in distilled water under high velocity agitation, forms suspension, solid-to-liquid ratio 1:8‑1:40, preferably 1:10‑1:30, and warming-in-water is to 25 100 DEG C, preferably 25 80 DEG C；(B) alkaline-earth metal salt solution is added in suspension, it is 1 to control the mol ratio of alkaline-earth metal and aluminium:7 15, and pH value is adjusted to 0.1 6 with nitric acid, then alkali is added in suspension, and continue to react, precipitation；(C) by the filtering of gained precipitation plus distillation water washing, dry, roasting, hexa-aluminate needed for acquisition.
Description
Technical field
The present invention relates to oxycarbide methanation field, more particularly to a kind of high-temperature methanation catalyst and its preparation side
Method.
Technical background
Methanation reaction is simplest Fischer-Tropsch synthesis, then synthesizes ammonia, natural gas from coal, oven gas LNG, hydrogen combustion
Material field of batteries is all widely used, and particularly in natural gas from coal day and oven gas LNG fields, passes through technological means
Contain H by coal gasification further methanation, or by oven gas etc.2、CO、CO2Component gas methanation produces methane, can be effective
Fill up the situation of China's source of the gas shortage.
Methanation reaction mainly has CO methanations and CO2Methanation, two kinds of reactions are strong anti-thermal response.At present, external,
There are more ripe synthesis gas and coke-oven gas methanation technology in the country, but in actual process operation, in fact it could happen that because strong anti-
Answer heat release occur reaction temperature rise and cause catalyst high temperature sintering, or prolonged high temperature operation and cause catalyst carbon deposition, height
The generation of situations such as temperature sintering.Methanation catalyst is still the core of methane synthetic technology, and exploitation has excellent high-temperature stable
Property, the catalyst of anti-carbon be still methanation catalyst exploitation key.
Hexa-aluminate is the minute surface that the oxidation of the spinel layer and alkali metal or alkaline-earth metal that are formed by aluminum oxide is formed
What layer was alternately accumulated and formed, at high temperature with good heat endurance so that it is as support applications in high temperature
Catalytic field has may.Forefathers also possess some special knowledge for hexa-aluminate as high-temperature methanation catalyst carrier, patent
CN102674413A is that sol-gal process prepares hexa-aluminate, and uses substantial amounts of organic reagent, and step is more, preparation time length,
It is unfavorable for industry's enlarging production.Patent CN104907075 use for co-precipitation method, it is necessary to use substantial amounts of nine water nitre
Sour aluminium, raw material availability is low, and water requirement is big, and discharge is high.Two kinds of patents are to use first to introduce activearm preparing catalyst
Divide the method for aftershaping, this is unfavorable for the implementation of industrialized production.
The content of the invention
Present invention mainly solves prior art step is more, low production efficiency, high discharge the problem of, and provide a kind of high temperature first
The preparation method of Alkanizing catalyst.Prepare the catalyst with good high-temperature stability and mechanical performance.
The invention provides a kind of hexa-aluminate, the catalyst carrier comprising hexa-aluminate and preparation method thereof and methanation
Catalyst and preparation method thereof.
According to an aspect of the invention, there is provided a kind of preparation method of hexa-aluminate, the preparation method include：
(A) boehmite is scattered in distilled water under high velocity agitation, forms suspension, solid-to-liquid ratio 1:8-1:40,
It is preferred that 1:10-1:30, more preferably 1:15-1:20, and warming-in-water is to 25-100 DEG C, further 25-80 DEG C, preferably 40-60
℃；
(B) alkaline-earth metal salt solution is added in suspension, it is 1 to control the mol ratio of alkaline-earth metal and aluminium:7-15, preferably
1:9-12, preferably 1:10-11, and (preferably with nitric acid, such as the nitric acid that mass fraction is 40-65%) pH value is adjusted to 0.1-
6,0-2h (preferably 1-2 hours) is preferably maintained, then adds alkali (or alkali lye) in suspension, and continues reaction (such as 0-
2h, preferably 1-2 hours), precipitate (25-80 DEG C of precipitation temperature, preferably 40-60 DEG C)；
(C) by the filtering of gained precipitation plus distillation water washing, dry, roasting, hexa-aluminate needed for acquisition.
Preferably, the alkali salt is the one or more in barium nitrate, magnesium nitrate, calcium nitrate, strontium nitrate, preferably
Barium nitrate.
Further, the drying includes but is not limited in 100-120 DEG C of dry 5-8h.
Further, the roasting includes but is not limited to be calcined 2-6h at 1000-1300 DEG C.
Preferably, the alkaline-earth metal salt solution used in step (B) is concentration 0.1-0.3mol/L barium nitrate aqueous solution.
In step (B), alkali can be the form addition of aqueous slkali, it is preferable that the aqueous slkali is concentration 0.1-2mol/L
Ammonium carbonate and/or ammonium hydrogen carbonate the aqueous solution.Aqueous slkali is, for example, the mixed liquor or two of ammonium carbonate or ammonium hydrogen carbonate or both
Person is respectively at the mixed liquor of ammoniacal liquor or the mixed liquor of three.The addition of aqueous slkali, based on alkali cpd, preferably alkaline earth is golden
Belong to the 10-120%, more preferably preferably 20-90%, more preferably 30-80%, 40-60% of salt compound weight.
Boehmite described here is selected from common boehmite, extraordinary boehmite, a kind of SB powder (business
Product boehmite) in one or more, boehmite chemical formula is AlOOHnH2O, n=0.08~0.62, preferably
Refer to common boehmite (pore volume 0.38-0.5ml/g, specific surface area 240-260m2/g)。
The invention further relates to the hexa-aluminate prepared by the above method.It can contain in prepared barium aluminates micro-
The barium aluminate of amount, therefore alternatively referred to as composite Ba-Al oxide, in this application the two there is identical implication.
According to another aspect of the present invention, the invention provides a kind of preparation method of the carrier containing hexa-aluminate,
This method includes：
Hexa-aluminate is well mixed with common boehmite/macropore aluminium hydroxide, SB powder, sesbania powder, the mixed powder
By mass percentage, hexa-aluminate accounts for 10-98%, preferably 15-90% or 20-80%, common boehmite or macropore to material
Aluminium hydrate powder accounts for 0-70%, preferably 5-60% or 10-50% or 20-40%, SB powder account for 0-30%, preferably 2-25% or 5-
20% or 8-18%, sesbania powder account for 2-10%, preferably 3-8% or 4-7%, add the 50-110% of solid powder gross mass, excellent
60-100% dust technology (concentration such as 0.15-0.4mol/L) is selected to mediate uniform, drying (such as 80-120 DEG C, 0.5-2h)
After be granulated, the releasing agent for then adding above-mentioned granulation material gross weight 1.5-4% beats sheetmolding, fired (such as 450-1000
DEG C, 2-4h at preferably 500-900 DEG C) after obtain carrier.The oxidation of hexa-aluminate and 0-90% of the resulting vehicle containing 10-100%
Aluminium.
The invention further relates to the carrier prepared by above-mentioned preparation method.
According to a further aspect of the invention, the invention provides a kind of high-temperature methanation catalyst, the high temperature catalyst
It is to be prepared by following step：
Carrier made above is added in nickel salt solution and impregnated, by the carrier drying after dipping, roasting.
In a preferred embodiment, the catalyst through the following steps that prepare：
The carrier of above-mentioned preparation is added to the nickel nitrate solution that weight/mass percentage composition is 10-20%, preferably 14-
18%, dipping temperature is 40-70 DEG C, dip time 1-3h, is afterwards filtered out the maceration extract of excess, the 100-120 in baking oven
DEG C drying 1-5h, in Muffle furnace 400-650 DEG C roasting 2-4h, be made high-temperature methanation catalyst.
The high temperature catalyst can be through impregnating acquisition, by mass once or twice, and catalyst includes 6-20%, preferably 10-
The hexa-aluminate and 0-80% of 16% active component NiO, 10-90%, preferably 20-80%, preferably 10-70% aluminum oxide.
It is an advantage of the current invention that the use of boehmite being silicon source when preparing hexa-aluminate, raw material is easy to get, price just
Preferably, active principle content is high, and raw material usage amount is low, can with acid adjustment pH value after barium nitrate solution mixes with suspension containing aluminium
So that the suspension part gel, is advantageous to barium nitrate and is uniformly mixed with aluminium, be advantageous to obtain more perfect hexa-aluminate crystalline substance
Body, and not exclusively plastic is equally beneficial for follow-up precipitation and filtration washing process.With ammonium carbonate or ammonium bicarbonate precipitation by barium
It is precipitated out and the content of nitrate in filter cake then can be effectively reduced the step of passing through washing, reduces nitrogen oxidation in roasting process
The discharge of thing, therefore, have more that production efficiency is high, environment-friendly, sintering temperature using the preparation method of the hexa-aluminate of the present invention
The advantages of low, hexa-aluminate crystalline phase perfection.Common boehmite/macropore of a part is added when preparing catalyst carrier
Aluminium hydroxide or SB powder, γ-Al are formed after fired2O3Or η-Al2O3Or θ-Al2O3, this several aluminum oxide is respectively provided with higher
Specific surface area and pore volume, can effectively improve hexaaluminate carrier specific surface area and the less problem of pore volume, and gained
After active component and 500-650 DEG C of roasting is sufficiently impregnated, Ni ions can not only enter hexa-aluminate specular layer and improve carrier
Active component stability, simultaneous oxidation nickel can also form nickel aluminate microstructure with oxide contact face, can effectively carry
The anti-carbon performance of high catalyst.It is also an advantage of the present invention that first shaping is re-introduced into active component, reduce powder operation
Step, be advantageous to the industrialized production of catalyst.
The analysis and characterization means of catalyst have：
1st, using the hole size and pore structure of Merck ＆ Co., Inc of U.S. ASAP2460 devices measure catalyst；
2nd, using Rigaku D/max-2200PC X-ray diffractometer analysis of catalyst thing phases；
3rd, using U.S. PE companies Optima2100DV inductively coupled plasma Spectral Emission analysis instrument analysis of catalyst gold
Belong to content；
4th, formed using Agilent company of the U.S. 6890N gas chromatographic analysis product.
Brief description of the drawings
Fig. 1 is catalyst preparation general flow chart.
Fig. 2 is that the barium aluminates prepared in embodiment 1 are analyzed using Rigaku D/max-2200PC X-ray diffractometers
Catalyst thing phase result figure.
Fig. 3 is that the barium aluminates prepared in embodiment 2 are analyzed using Rigaku D/max-2200PC X-ray diffractometers
Catalyst thing phase result figure.
Embodiment
Embodiment 1
The preparation of barium aluminates：6.57g barium nitrates are dissolved in 100ml distilled water, by 20.5gSB powder in rapid mixing conditions
Under be scattered in 400ml water, warming-in-water is to 40 DEG C, and under lasting stirring condition, it is suspended that barium nitrate solution is added into SB powder
Liquid, the PH to 5.0 of the mixed liquor is adjusted with 40% nitric acid, stir 30min；3.0g ammonium carbonate is dissolved in 100ml distilled water
In, aqueous slkali is made, aqueous slkali is slowly added dropwise in above-mentioned mixed liquor, and sustained response 1h, filtering plus distillation water washing,
110 DEG C, 5h drying, 1200 DEG C, 3h roastings, are made 19.5g barium aluminates after grinding.
The barium aluminates prepared with this method use Rigaku D/max-2200PC X-ray diffractometer analysis of catalyst
Thing phase result is as shown in Fig. 2 have obvious barium aluminates (BaAl12O19) crystal structure, and it is brilliant with a small amount of barium aluminium point
Stone (BaAl2O4) structure.The specific surface area of Merck ＆ Co., Inc of U.S. ASAP2460 devices measure barium aluminates is used as 35.64m2/
G, pore volume 0.15cm3/ g, aperture 15.82nm, and there is typical meso-hole structure.Each item data is public with documents and materials
The data opened are suitable.
The preparation of catalyst carrier：By gained barium aluminates 19.5g and 16g common boehmite, 9.5g SB powder
And 1.8g sesbania powder is well mixed, 0.3mol/L dust technology 25ml kneadings are added, 120 DEG C, be granulated after 1h drying, then
The magnesium stearate for adding 0.94g beats sheetmolding, 500 DEG C, the obtained 38.5g carriers of 3h roastings as releasing agent.
Prepared carrier uses the specific surface area of Merck ＆ Co., Inc of U.S. ASAP2460 devices measure as 132.26m2/ g, pore volume
For 0.32cm3/ g, aperture 11.91nm.
The preparation of methanation catalyst：The water nickel nitrates of 70g six are taken to be dissolved in 12ml distilled water, heating water bath to 55 DEG C of preparations
Into the nickel impregnation liquid that nickel weight/mass percentage composition is 17.2%, 35g carriers made above are poured into maceration extract, impregnated
2h, the maceration extract of excess is filtered out, 110 DEG C of drying 2h, 450 DEG C of roasting 3h produce methanation catalyst.
The catalyst contains 11.4% NiO, 44.3% BaAl12O19And 44.3% Al2O3。
Embodiment 2
The preparation of barium aluminates：6.57g barium nitrates are dissolved in 100ml distilled water, the common boehmite powder of 20.5g is existed
It is scattered under rapid mixing conditions in 300ml water, warming-in-water is to 60 DEG C, and under lasting stirring condition, barium nitrate solution is added
Enter the PH to 1.0 for adjusting the mixed liquor with 40% nitric acid to boehmite powder suspension, stir 60min；By 3.0g carbon
Sour ammonium is dissolved in 100ml distilled water, and aqueous slkali is made, aqueous slkali is slowly added dropwise in above-mentioned mixed liquor, and sustained response
1h, filtering plus distillation water washing, 110 DEG C, 5h drying, 1200 DEG C, 3h roastings, 19.5g barium aluminates are made after grinding.
The barium aluminates prepared with this method use Rigaku D/max-2200PC X-ray diffractometer analysis of catalyst
Thing phase result is as shown in figure 3, have obvious barium aluminates (BaAl12O19) crystal structure, and it is brilliant with a small amount of barium aluminium point
Stone (BaAl2O4) structure, it is used as silicon source using boehmite, it is more difficult to which the mixing uniformity of plastic, aluminium and barium is poor, with implementation
Example 1 is compared, and the content of products therefrom barium aluminate is higher.Six aluminic acids are determined using Merck ＆ Co., Inc of U.S. ASAP2460 devices
The specific surface area of barium is 40.64m2/ g, pore volume 0.18cm3/ g, aperture 13.28nm.
The preparation of catalyst carrier：By gained barium aluminates 19.5g and 39g macropore aluminium hydrate powder, 20g SB powder and
2.3g sesbania powder is well mixed, and adds 0.2mol/L dust technology 50ml kneadings, 120 DEG C, be granulated after 1h drying, Ran Houjia
The life graphite for entering 1.6g beats sheetmolding, 500 DEG C, the obtained 45.8g carriers of 3h roastings as releasing agent.
Resulting vehicle uses Merck ＆ Co., Inc of U.S. ASAP2460 devices specific surface area as 172.41m2/ g, pore volume are
0.40cm3/ g, aperture 9.60nm.
The preparation of methanation catalyst：The water nickel nitrates of 70g six are taken to be dissolved in 12ml distilled water, heating water bath to 55 DEG C of preparations
Into the nickel impregnation liquid that nickel weight/mass percentage composition is 17.2%, 35g carriers made above are poured into maceration extract, impregnated
2h, the maceration extract of excess is filtered out, 110 DEG C of drying 2h, 550 DEG C of roasting 3h produce methanation catalyst.
The catalyst contains 16% NiO, 25.2% BaAl12O19And 58.8% Al2O3。
Embodiment 3
The preparation of barium aluminates：6.57g barium nitrates are dissolved in 100ml distilled water, by 20.5gSB powder in rapid mixing conditions
Under be scattered in 400ml water, warming-in-water is to 50 DEG C, and under lasting stirring condition, it is suspended that barium nitrate solution is added into SB powder
Liquid, the PH to 3.0 of the mixed liquor is adjusted with 65% nitric acid, stir 30min；3.0g ammonium carbonate is dissolved in 100ml distilled water
In, aqueous slkali is made, aqueous slkali is slowly added dropwise in above-mentioned mixed liquor, and sustained response 1h, filtering plus distillation water washing,
110 DEG C, 5h drying, 1200 DEG C, 3h roastings, are made 19.5g barium aluminates after grinding.
The barium aluminates prepared with this method use Rigaku D/max-2200PC X-ray diffractometer analysis of catalyst
Thing mutually finds that the hexa-aluminate has obvious barium aluminates (BaAl12O19) crystal structure, and it is brilliant with micro barium aluminium point
Stone (BaAl2O4) structure, the specific surface area of Merck ＆ Co., Inc of U.S. ASAP2460 devices measure barium aluminates is used as 32.48m2/
G, pore volume 0.14cm3/ g, aperture 16.12nm.
The preparation of catalyst carrier：By gained barium aluminates 19.5g and 3.6g common boehmite, 7.2g SB powder
And 0.9g sesbania powder is well mixed, 0.3mol/L dust technology 20ml kneadings are added, 110 DEG C, be granulated after 1h drying, then
The magnesium stearate for adding 0.62g beats sheetmolding, 500 DEG C, the obtained 27.6g carriers of 3h roastings as releasing agent.
The specific surface area of Merck ＆ Co., Inc of U.S. ASAP2460 devices measure carrier is used as 91.25m2/ g, pore volume are
0.22cm3/ g, aperture 13.28nm.
The preparation of methanation catalyst：The water nickel nitrates of 70g six are taken to be dissolved in 12ml distilled water, heating water bath to 60 DEG C of preparations
Into the nickel impregnation liquid that nickel weight/mass percentage composition is 17.2%, 25g carriers made above are poured into maceration extract, impregnated
2h, the maceration extract of excess is filtered out, repeated impregnations, drying, roasting process carry out two after 110 DEG C of drying 2h, 450 DEG C of roasting 3h
Secondary dipping.
The catalyst contains 18% NiO, 57.4% BaAl12O19And 24.6% Al2O3。
Embodiment 4
The preparation of barium aluminates：13.14g barium nitrates are dissolved in 200ml distilled water, by 41.0gSB powder in quick stirring bar
It is scattered under part in 600ml water, warming-in-water is to 40 DEG C, under lasting stirring condition, barium nitrate solution is added into SB powder and hanged
Turbid, the PH to 2.0 of the mixed liquor is adjusted with 65% nitric acid, stir 30min；6.0g ammonium carbonate is dissolved in 100ml distillations
In water, aqueous slkali is made, aqueous slkali is slowly added dropwise in above-mentioned mixed liquor, and sustained response 1h, filtering plus distillation washing
Wash, 110 DEG C, 5h drying, 1200 DEG C, 3h roastings, 50g barium aluminates are made after grinding.
The preparation of catalyst carrier：Gained barium aluminates 50g is well mixed with 1.85g sesbania powder, then added
1.0g life graphite beats sheetmolding, 500 DEG C, the obtained 49.3g carriers of 3h roastings as releasing agent.
The preparation of methanation catalyst：The water nickel nitrates of 70g six are taken to be dissolved in 12ml distilled water, heating water bath to 55 DEG C of preparations
Into the nickel impregnation liquid that nickel weight/mass percentage composition is 17.2%, 35g carriers made above are poured into maceration extract, impregnated
2h, the maceration extract of excess is filtered out, 110 DEG C of drying 2h, 600 DEG C of roasting 3h produce methanation catalyst.
The catalyst contains 8% NiO, 92% BaAl12O19。
Embodiment 5
The preparation of barium aluminates：6.57g barium nitrates are dissolved in 100ml distilled water, the mixed liquor is adjusted with 40% nitric acid
PH to 1.0,15.4g SB powder is scattered in 400ml water under rapid mixing conditions, warming-in-water is persistently being stirred to 40 DEG C
Under the conditions of mixing, barium nitrate solution is added to SB powder suspensions, stirs 30min；By 5.0g ammonium bicarbonate solubility in 100ml
In distilled water, aqueous slkali is made, aqueous slkali is slowly added dropwise in above-mentioned mixed liquor, and sustained response 1h, filtering plus distillation
Water washing, 110 DEG C, 5h drying, 1200 DEG C, 3h roastings, 16.2g barium aluminates are made after grinding.
The preparation of catalyst carrier：By gained 16.2g barium aluminates and 60g macropore aluminium hydroxide, 20g SB powder and 3g
Sesbania powder be well mixed, add 0.3mol/L dust technology 80ml kneadings, 120 DEG C, be granulated after 1h drying, then add
2.0g magnesium stearate beats sheetmolding, 600 DEG C, the obtained 80.3g carriers of 3h roastings as releasing agent.
The preparation of methanation catalyst：The water nickel nitrates of 70g six are taken to be dissolved in 12ml distilled water, heating water bath to 55 DEG C of preparations
Into the nickel impregnation liquid that nickel weight/mass percentage composition is 17.2%, 35g carriers are poured into maceration extract, impregnate 2h, by excess
Maceration extract filters out, and 110 DEG C of drying 2h, 450 DEG C of roasting 3h produce methanation catalyst.
The catalyst contains 15% NiO, 17% BaAl12O19And 68% Al2O3。
Comparative example 1
Take the sesbania powder of 60g macropore aluminium hydroxide, 20g SB powder and 3g to be well mixed, add 0.3mol/L dilute nitre
Sour 65ml kneadings, 110 DEG C, be granulated after 1h drying, the magnesium stearate for then adding 1.7g beats sheetmolding as releasing agent, and 600
DEG C, 3h roastings 60.1g carriers are made.The water nickel nitrates of 75g six are taken to be dissolved in 15ml distilled water, heating water bath is configured to 55 DEG C
Nickel weight/mass percentage composition is 17.2% nickel impregnation liquid, and 35g carriers are poured into maceration extract, impregnates 2h, by the leaching of excess
Stain liquid filters out, and 110 DEG C of drying 2h, 450 DEG C of roasting 3h produce methanation catalyst.
The catalyst contains 15% NiO and 85% Al2O3。
Activity and high-temperature stability will be carried out on the liquid high pressure micro fixed-bed reactor of four gas one by six kinds of catalyst above
Test, test condition are：By catalyst breakage into 40-60 mesh particles, weigh 10ml and load catalyst in reactor constant temperature
Section, is separated, catalyst is first in reducing atmosphere H with silica wool and quartz sand up and down2/N2=75, reduction air speed 2040h-1,
500 DEG C, reduce 5h under conditions of 1.0MPa, then be transferred to synthesis condition pressure 3.0MPa, air speed 8000h-1, air inlet composition H2/
CO/CO2/CH4/H2O=36.8/7.6/3.7/36.7/15.2, regulation reaction temperature are 650 DEG C, on-line chromatograph analysis product group
Into the continuance test 48h since being entered synthesis gas, then stopping air inlet, be passed through N2/H2(add a small amount of hydrogen is=99 gaseous mixtures
Prevent catalyst because of N2The micro amount of oxygen of middle carrying and be oxidized), flow 340ml/min, purge to system detectio less than CO, CO2
When, holding is passed through hydrogen nitrogen mixed gas and is warming up to 800 DEG C with 3 DEG C/min heating rate, and maintains 48h to enter under this condition
The processing of row high temperature ageing, cool after pending end and be transferred to synthesis condition progress catalyst activity detection again, same lasting survey
Try 48h and stop experiment, treat that device is cooled to less than the 50 DEG C measure for splitting out catalyst and carbon distribution content being carried out to catalyst.Survey
Shown in test result table 1.
Table 1
Wherein：
CO conversion ratio calculation formula：
CH4Selective calculation formula：
From test result as can be seen that there is good methanation reaction activity, choosing by inventive method prepared catalyst
Selecting property, and still there is the activity suitable with before processing, selectivity and reaction temperature rising after high temperature ageing is handled, illustrate catalysis
Agent has good high-temperature stability, and it is very low and do not occur obvious powder phenomenon-tion to test the carbon deposition quantity of rear catalyst, has very
Good anti-carbon and mechanical stability.
Claims (13)
1. a kind of preparation method of hexa-aluminate, the preparation method include：
(A) boehmite is scattered in distilled water under high velocity agitation, forms suspension, solid-to-liquid ratio 1:8-1:40, preferably
1:10-1:30, and warming-in-water is to 25-100 DEG C, preferably 25-80 DEG C；
(B) alkaline-earth metal salt solution is added in suspension, it is 1 to control the mol ratio of alkaline-earth metal and aluminium:7-15, and adjust pH
Then value adds alkali in suspension, and continue to react, precipitation to 0.1-6；
(C) by the filtering of gained precipitation plus distillation water washing, dry, roasting, hexa-aluminate needed for acquisition.
2. preparation method according to claim 1, wherein, the alkali salt be barium nitrate, magnesium nitrate, calcium nitrate,
One or more in strontium nitrate, preferably barium nitrate.
3. preparation method according to claim 1, wherein, in step (A), solid-to-liquid ratio 1:15-1:20, and warming-in-water is extremely
40-60℃；
In step (B), it is 1 to control the mol ratio of alkaline-earth metal and aluminium:9-12.
4. according to the preparation method any one of claim 1-3, wherein, the drying is included in 100-120 DEG C of drying
5-8h；And
The roasting is included in 1000-1300 DEG C of roasting 2-6h.
5. according to the preparation method any one of claim 1-3, wherein, the alkali salt used in step (B) is molten
Liquid is concentration 0.1-0.3mol/L barium nitrate aqueous solution.
6. according to the preparation method any one of claim 1-5, wherein, the aqueous slkali is concentration 0.1-2mol/L
The aqueous solution of ammonium carbonate and/or ammonium hydrogen carbonate.
7. according to the preparation method any one of claim 1-6, wherein, boehmite chemical formula is AlOOH
nH2O, n=0.08~0.62, the one or more being selected from common boehmite, extraordinary boehmite, SB powder.
8. the hexa-aluminate prepared by the preparation method any one of claim 1-6.
9. a kind of preparation method of the carrier containing hexa-aluminate, this method include：
Six aluminic acids described in hexa-aluminate or claim 8 prepared by the preparation method any one of claim 1-7
Salt and optional common boehmite (pore volume 0.38-0.5ml/g, specific surface area 240-260m2/ g) or macropore aluminium hydroxide,
Optional SB powder, sesbania powder are well mixed, and by mass percentage, hexa-aluminate accounts for 10-98% to the mixed powder, commonly intends thin
Diaspore or macropore aluminium hydrate powder account for 0-70%, and SB powder accounts for 0-30%, and sesbania powder accounts for 2-10%, adds solid powder gross mass
50-110% dust technology (concentration such as 0.15-0.4mol/L) mediate uniform, be granulated after drying, then add above-mentioned granulation
Material gross weight 1.5-4% releasing agent beats sheetmolding, and carrier is obtained after fired.Hexa-aluminate of the resulting vehicle containing 10-100%
And 0-90% aluminum oxide.
10. the carrier prepared by the preparation method described in claim 9.
11. a kind of high-temperature methanation catalyst, the catalyst is prepared by following step：
Carrier prepared by the preparation method described in claim 9 is added in nickel salt solution and impregnated, the carrier after dipping is done
Dry, roasting.
12. high-temperature methanation catalyst according to claim 11, wherein, the catalyst is through the following steps that prepare
's：
It is molten that carrier prepared by the preparation method described in claim 9 is added to the nickel nitrate that weight/mass percentage composition is 10-20%
Liquid, preferably 14-18%, dipping temperature are 40-70 DEG C, dip time 1-3h, are afterwards filtered out the maceration extract of excess, in baking
100-120 DEG C of drying 1-5h in case, 400-650 DEG C of roasting 2-4h, is made high-temperature methanation catalyst in Muffle furnace.
13. the high-temperature methanation catalyst according to claim 11 or 12, wherein, by mass, the catalyst includes 6-
20%, preferably 10-16% active component NiO, 10-90%, preferably 20-80% hexa-aluminate and 0-80%, preferably 10-
70% aluminum oxide.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180185822A1 (en) * | 2016-12-29 | 2018-07-05 | Saint-Gobain Ceramics & Plastics, Inc. | Catalyst carrier and methods of forming thereof |
| CN114345351A (en) * | 2020-10-13 | 2022-04-15 | 中石化南京化工研究院有限公司 | Preparation method of synthetic gas methanation catalyst carrier |
| CN115382536A (en) * | 2022-09-29 | 2022-11-25 | 北京服装学院 | Hexaaluminate monolithic catalyst and preparation method thereof |
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