CN103657707B - Preparation method of low carbon hydrocarbon aromatization catalyst - Google Patents
Preparation method of low carbon hydrocarbon aromatization catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 36
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 32
- 238000005899 aromatization reaction Methods 0.000 title claims abstract description 26
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- -1 carbon hydrocarbon Chemical class 0.000 title description 9
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000002808 molecular sieve Substances 0.000 claims abstract description 15
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 6
- 239000011230 binding agent Substances 0.000 claims abstract description 5
- 238000001802 infusion Methods 0.000 claims abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 229910001593 boehmite Inorganic materials 0.000 claims description 8
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000012018 catalyst precursor Substances 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 13
- 239000002243 precursor Substances 0.000 abstract description 11
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 239000011159 matrix material Substances 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 229910021529 ammonia Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- 238000005453 pelletization Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 239000011701 zinc Substances 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010306 acid treatment Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
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- 230000000903 blocking effect Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002288 cocrystallisation Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
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- 150000001993 dienes Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- AWCVTCIRPFTIPO-UHFFFAOYSA-N hexane hex-1-ene Chemical compound CCCCCC.CCCCC=C AWCVTCIRPFTIPO-UHFFFAOYSA-N 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003915 liquefied petroleum gas Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of preparation method of low-carbon hydrocarbon aromatization catalyst, mainly solve the problem that in prior art, aromatized catalyst reaction stability is bad.The present invention is comprised the following steps by employing: a) by 50 ~ 90 parts of ZSM-5 molecular sieves and 10 ~ 50 parts of binding agents kneaded and formed, obtain preformed catalyst presoma I; B) by mixture I normal pressure, temperature be 200 ~ 700 DEG C, air speed is 0.1 ~ 20 hour
-1water Under steam treated 0.1 ~ 40 hour, obtains precursor II; C) precursor II is placed in the acid solution that concentration is 0.1 ~ 5 mol/L, under temperature is 20 ~ 95 DEG C of conditions, processes 0.1 ~ 24 hour, obtains precursor III; D) to be selected from least one element in VIII, IIB or IIIA race by infusion process to precursor III load, namely to obtain described low-carbon hydrocarbon aromatization catalyst; Wherein, load capacity is that the technical scheme of 0.1 ~ 10% of precursor III weight solves this problem preferably, can be used for preparing in the industrial production of low-carbon (LC) hydrocarbon aromatization catalyst.
Description
Technical field
The present invention relates to a kind of preparation method of low-carbon hydrocarbon aromatization catalyst.
Background technology
Aromatic hydrocarbons is widely used in synthetic fibers, synthetic resin, synthetic rubber and various fine chemicals, is indispensable basic organic chemical industry raw material; In addition non-benzene aromatic hydrocarbons still produces the important mediation component of high-knock rating gasoline.In recent years, the development of aromatic hydrocarbons downstream product rapidly, causes domestic and international market to the demand sustainable growth of aromatic hydrocarbons, wherein China to aromatic hydrocarbons year the growth rate of demand more than 10%.
C4 ~ C6 lower carbon number hydrocarbons and the hydrocarbon mixture containing C4 ~ C6 lower carbon number hydrocarbons are the secondary liquid of petrochemical industry and oil refining industry, originate from ethylene project, oil plant and natural gas purification process.Except minority component is used as except industrial chemicals by extracting in numerous low-carbon (LC) hydro carbons, very major part is all used as cheap fuel, and main cause is that fuel price is higher.Along with the smooth enforcement of China's strategy to develop western regions and West-East National Gas Transmission Project, and from the extensive use of coal dimethyl ether synthesis technology, lower carbon number hydrocarbons is extruded commercial market gradually by more cheap fuel such as pipe natural gas at last.These low-carbon (LC) hydro carbons are converted into aromatic hydrocarbons by technology of aromatization, not only can be aromatics production and open up new raw material source, and can Optimum utilization lighter hydrocarbons resource, improve petroleum chemical enterprise's economic benefit.
Mainly molecular sieve catalyst is concentrated on to the research of aromatization of low carbon hydrocarbon, particularly on ZSM-5 molecular sieve at present.Patent CN101530813A discloses a kind of molecular sieve catalyst preparation method for carbon 4 liquid gas aromatization reaction, adopts rare earth-ZSM-5/ZSM-11 cocrystallization molecular sieve to be parent, obtained catalyst after alkali treatment-steam treatment-zinc supported.At 470 ~ 520 DEG C, pressure 0.3 ~ 0.9MPa, weight space velocity 0.5 ~ 1.5 hour
-1reaction condition under, catalyst single pass life investigates the 30th hour, and aromatics yield is about 62 % by weight.
Patent CN1586721A discloses a kind of molecular sieve catalyst preparation method for carbon four liquefied petroleum gas aromatisation, adopts grain size to be the silica-rich zeolite of 10 ~ 500nm, carries out steam treatment and organic acid reaming modification obtains catalyst, do not add metal component.400 DEG C, pressure 3MPa, weight space velocity 0.8 hour
-1reaction condition under, catalyst single pass life investigates the 10th day, and aromatics yield is about 49 % by weight.
Patent CN1232071A discloses one and is made up of Zn, rare earth, ZSM-5 and aluminium oxide, and has carried out the aromatized catalyst preparation method of steam treatment modification, and wherein Zn species are by [Zn (NH
3)
4]
2+form be introduced into molecular sieve catalyst.This catalyst at 520 ~ 550 DEG C, mass space velocity 0.6 ~ 1.5 hour
-1reaction condition under aromatization is carried out to mixing carbon four, one way duration of runs that aromatics yield is greater than 40% is 300 ~ 450 hours.
Patent CN1340601A discloses one and is made up of ZnO, ZSM-5 molecular sieve, aluminium oxide and VA or group vib oxide, and has carried out the aromatized catalyst preparation method of steam treatment modification, for n-hexane and the aromatization mixing carbon four.This catalyst at 450 ~ 600 DEG C, pressure 0.1-1.0MPa, mass space velocity 0.2 ~ 12 hour
-1reaction condition under aromatization is carried out to mixing carbon four, one way duration of runs that aromatics yield is greater than 41% is 470 hours.
In above-mentioned technology, the single pass life of catalyst is all within 500 hours, shows that the reaction stability of catalyst is undesirable, and it is frequent that this causes reactor in course of reaction to switch regeneration.
Summary of the invention
Technical problem to be solved by this invention is the problem that in prior art, aromatized catalyst reaction stability is bad, provides a kind of preparation method of new low-carbon hydrocarbon aromatization catalyst.Catalyst prepared by the method, in aromatization of low carbon hydrocarbon reaction, has good reactivity and stability.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of preparation method of low-carbon hydrocarbon aromatization catalyst, comprises the following steps:
A) by 50 ~ 90 parts of ZSM-5 molecular sieves and 10 ~ 50 parts of binding agents kneaded and formed, obtain preformed catalyst precursor mixture I;
B) by mixture I normal pressure, temperature be 200 ~ 700 DEG C, air speed is 0.1 ~ 20 hour
-1water Under steam treated 0.1 ~ 40 hour, obtains precursor II;
C) precursor II is placed in the acid solution that concentration is 0.1 ~ 5 mol/L, under temperature is 20 ~ 95 DEG C of conditions, processes 0.1 ~ 24 hour, obtains precursor III;
D) to be selected from least one element in VIII, IIB or IIIA race by infusion process to precursor III load, namely to obtain described low-carbon hydrocarbon aromatization catalyst; Wherein, load capacity is 0.1 ~ 10% of precursor III weight.
In technique scheme, described binding agent preferred version is be selected from least one in aluminium oxide or boehmite.Steam treatment temperature preferable range is 300 ~ 600 DEG C, and air speed preferable range is 1 ~ 18 hour
-1, processing time preferable range is 1 ~ 30 hour.Described sour preferred version is be selected from least one in oxalic acid or nitric acid.The concentration preferences of acid solution is 0.2 ~ 4 mol/L, and acid treatment temperature preferable range is 30 ~ 85 DEG C, and time preferable range is 1 ~ 20 hour.VIII element preferred version is at least one be selected from Fe, Co or Ni, and IIB race element preferred version is at least one be selected from Zn or Cd, and IIIA race element preferred version is at least one be selected from Al or Ga.The load capacity preferable range being selected from least one element in VIII, IIB or IIIA race is 0.5 ~ 8% of precursor III weight.The silica alumina ratio SiO of ZSM-5 molecular sieve
2/ Al
2o
3be 20 ~ 300.
Catalyst prepared by the present invention reacts for aromatization of low carbon hydrocarbon, generates the aromatic product containing benzene,toluene,xylene.Reaction condition is: reaction temperature 400 ~ 600 DEG C, and preferable range is 450 ~ 550 DEG C; Reaction pressure 0 ~ 2.0MPa, preferable range is 0.1 ~ 1.0MPa; Weight space velocity 0.01 ~ 10 hour
-1, preferable range is 0.3 ~ 5 hour
-1.Lower carbon number hydrocarbons described in the inventive method refers to C4 ~ C6 lower carbon number hydrocarbons, and wherein the percentage by weight of each component is: mono-olefin content 20 ~ 80%, and diolefin content is lower than 2%, and surplus is alkane.
Steam treatment is the acid method of adjustment that aromatized catalyst is conventional, but the non-framework aluminum produced in this process easily causes the blocking of molecular sieve pore passage, thus affects catalyst reaction performance.Part non-framework aluminum can be dissolved, dredging molecular sieve pore passage, the mass transfer diffusion of molecular screen material after improving steam treatment by suitable acid treatment.Introduce the sour type distributes on one or more metal species adjustment molecular sieve afterwards, suppress the carbon deposition rate on catalyst, and then realize obtaining more excellent reaction stability while ensureing aromatization of low carbon hydrocarbon reactivity.Catalyst prepared by the present invention can show preferably reactivity and stability in aromatization of low carbon hydrocarbon course of reaction, when adopting C4 ~ C6 mixing lower carbon number hydrocarbons to make raw material, catalyst single pass life reaches 700 hours, aromatics yield 48 % by weight, can alleviate reactor in existing commercial fixed bed device and switch and catalyst regeneration problem frequently.
Below by comparative example and embodiment, the present invention is further elaborated.
Detailed description of the invention
[comparative example 1]
NaZSM-5 molecular screen primary powder (silica alumina ratio is 20) is removed template in 4 hours 550 DEG C of roastings.Resulting materials mixes with 1:0.5 part by weight with boehmite.In mixture, add salpeter solution, pinch even and extruded moulding, pelletizing after dry and roasting.Resulting materials after ammonia exchanges, 300 DEG C, air speed 10 hours
-1water Under steam treated 15 hours, obtained catalyst.
[comparative example 2]
NaZSM-5 molecular screen primary powder (silica alumina ratio is 20) is removed template in 4 hours 550 DEG C of roastings.Resulting materials mixes with 1:0.5 part by weight with boehmite.In mixture, add salpeter solution, pinch even and extruded moulding, pelletizing after dry and roasting.Resulting materials after ammonia exchanges, 300 DEG C, air speed 10 hours
-1water Under steam treated 15 hours.By incipient impregnation normal direction matrix material load Zn metal species, load capacity is 5% of matrix material weight, obtained catalyst.
[embodiment 1]
NaZSM-5 molecular screen primary powder (silica alumina ratio is 20) is removed template in 4 hours 550 DEG C of roastings.Resulting materials mixes with 1:0.5 part by weight with boehmite.In mixture, add salpeter solution, pinch even and extruded moulding, pelletizing after dry and roasting.Resulting materials after ammonia exchanges, 300 DEG C, air speed 10 hours
-1water Under steam treated 15 hours.Resulting materials in the oxalic acid solution of 1.0mol/L 80 DEG C process 6 hours.By incipient impregnation normal direction matrix material load Zn metal species, load capacity is 5% of matrix material weight, obtained catalyst.
[comparative example 3]
NaZSM-5 molecular screen primary powder (silica alumina ratio is 100) is removed template in 4 hours 550 DEG C of roastings.Resulting materials mixes with 1:0.4 part by weight with boehmite.In mixture, add salpeter solution, pinch even and extruded moulding, pelletizing after dry and roasting.Resulting materials after ammonia exchanges, 400 DEG C, air speed 8 hours
-1water Under steam treated 10 hours, obtained catalyst.
[comparative example 4]
NaZSM-5 molecular screen primary powder (silica alumina ratio is 100) is removed template in 4 hours 550 DEG C of roastings.Resulting materials mixes with 1:0.4 part by weight with boehmite.In mixture, add salpeter solution, pinch even and extruded moulding, pelletizing after dry and roasting.Resulting materials after ammonia exchanges, 400 DEG C, air speed 8 hours
-1water Under steam treated 10 hours.By incipient impregnation normal direction matrix material load Ni metal species, load capacity is 1% of matrix material weight, obtained catalyst.
[embodiment 2]
NaZSM-5 molecular screen primary powder (silica alumina ratio is 100) is removed template in 4 hours 550 DEG C of roastings.Resulting materials mixes with 1:0.4 part by weight with boehmite.In mixture, add salpeter solution, pinch even and extruded moulding, pelletizing after dry and roasting.Resulting materials after ammonia exchanges, 400 DEG C, air speed 8 hours
-1water Under steam treated 10 hours.Resulting materials in the salpeter solution of 2.0mol/L 30 DEG C process 15 hours.By incipient impregnation normal direction matrix material load Ni metal species, load capacity is 1% of matrix material weight, obtained catalyst.
[comparative example 5]
NaZSM-5 molecular screen primary powder (silica alumina ratio is 150) is removed template in 4 hours 550 DEG C of roastings.Resulting materials mixes with 1:0.3 part by weight with aluminium oxide.In mixture, add salpeter solution, pinch even and extruded moulding, pelletizing after dry and roasting.Resulting materials after ammonia exchanges, 600 DEG C, air speed 4 hours
-1water Under steam treated 4 hours, obtained catalyst.
[comparative example 6]
NaZSM-5 molecular screen primary powder (silica alumina ratio is 150) is removed template in 4 hours 550 DEG C of roastings.Resulting materials mixes with 1:0.3 part by weight with aluminium oxide.In mixture, add salpeter solution, pinch even and extruded moulding, pelletizing after dry and roasting.Resulting materials after ammonia exchanges, 600 DEG C, air speed 4 hours
-1water Under steam treated 4 hours.By incipient impregnation normal direction matrix material load Al and Ga metal species, load capacity is respectively 0.8% and 0.5% of matrix material weight, obtained catalyst.
[embodiment 3]
NaZSM-5 molecular screen primary powder (silica alumina ratio is 150) is removed template in 4 hours 550 DEG C of roastings.Resulting materials mixes with 1:0.3 part by weight with aluminium oxide.In mixture, add salpeter solution, pinch even and extruded moulding, pelletizing after dry and roasting.Resulting materials after ammonia exchanges, 600 DEG C, air speed 4 hours
-1water Under steam treated 4 hours.Resulting materials in the mixed solution containing 0.5mol/L nitric acid and 0.5mol/L oxalic acid 50 DEG C process 10 hours.By incipient impregnation normal direction matrix material load Al and Ga metal species, load capacity is respectively 0.8% and 0.5% of matrix material weight, obtained catalyst.
[embodiment 4]
Catalyst performance examination is carried out on fixed-bed reactor, adopts internal diameter to be the stainless steel reactor of 10mm, loaded catalyst 10 milliliters, reaction temperature 500 DEG C, reaction pressure 0.5MPa, mass space velocity 5 hours
-1, raw material adopts C4 ~ C6 mixing lower carbon number hydrocarbons, specifically forms in table 1.
Product is analyzed respectively after gas-liquid separation, and gas-phase product adopts Agilent gas-chromatography 6820, Al
2o
3pillar, hydrogen flame detector; Liquid product adopts Agilent gas-chromatography 6820, FFAP pillar, hydrogen flame detector.Analysis result normalization.Reaction time be 20 and 60 little constantly the results are shown in Table 2.
[comparative example 7]
The performance of [comparative example 1 ~ 6] catalyst is investigated with [embodiment 4].
Table 1
| Raw material components | Butane | Butylene | Pentane | Amylene | Hexane | Hexene | Other |
| Percentage composition (% by weight) | 1.7 | 2.2 | 25.3 | 44.6 | 7.6 | 8.6 | 10.0 |
Table 2
Therefrom can find out, with adopt steam treatment merely, and adopt the catalyst of steam treatment loading metal to compare, the catalyst prepared through steam treatment, acid treatment and carried metal achieves better initial conversion and aromatics yield in aromatization of low carbon hydrocarbon course of reaction, and reaction stability obtains and significantly improves.
[embodiment 5]
The device of [embodiment 4] adopt C4 ~ C6 mixing lower carbon number hydrocarbons carry out stability examination as raw material to the catalyst prepared by [embodiment 2].
Examination condition is: synthesis under normal pressure, weight space velocity 1.2 hours
-1, reaction temperature 450 ~ 580 DEG C.Appraisal result is in table 3.
Table 3
| Reaction time, hour | Aromatics yield, % by weight |
| 100 | 50.3 |
| 200 | 49.2 |
| 300 | 49.0 |
| 400 | 48.7 |
| 500 | 48.7 |
| 600 | 48.3 |
| 700 | 47.9 |
Therefrom can find out, catalyst single pass life is greater than 700 hours, aromatics yield 48 % by weight.
Claims (4)
1. a preparation method for low-carbon hydrocarbon aromatization catalyst, comprises the following steps:
A) by 50 ~ 90 parts of ZSM-5 molecular sieves and 10 ~ 50 parts of binding agents kneaded and formed, obtain preformed catalyst precursor mixture I;
B) by mixture I normal pressure, temperature be 200 ~ 700 DEG C, air speed is 0.1 ~ 20 hour
-1water Under steam treated 0.1 ~ 40 hour, obtains presoma II;
C) presoma II is placed in the acid solution that concentration is 0.2 ~ 4 mol/L, under temperature is 30 ~ 85 DEG C of conditions, processes 1 ~ 20 hour, obtains presoma III;
D) to be selected from least one element in IIIA race by infusion process to presoma III load, namely to obtain described low-carbon hydrocarbon aromatization catalyst; Wherein, load capacity is 0.5 ~ 8% of presoma III weight;
IIIA race element is selected from least one in Al or Ga;
The silica alumina ratio SiO of ZSM-5 molecular sieve
2/ Al
2o
3be 20 ~ 300.
2. the preparation method of low-carbon hydrocarbon aromatization catalyst according to claim 1, is characterized in that described binding agent is selected from least one in aluminium oxide or boehmite.
3. the preparation method of low-carbon hydrocarbon aromatization catalyst according to claim 1, it is characterized in that steam treatment temperature is 300 ~ 600 DEG C, air speed is 1 ~ 18 hour
-1, the processing time is 1 ~ 30 hour.
4. the preparation method of low-carbon hydrocarbon aromatization catalyst according to claim 1, is characterized in that described acid is selected from least one in oxalic acid or nitric acid.
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|---|---|---|---|---|
| CN106552663A (en) * | 2015-09-24 | 2017-04-05 | 中国石油天然气股份有限公司 | Catalyst for aromatization of straight-run naphtha and preparation method thereof |
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