CN1387947A - Low-carbon olefine synthesized C12-C18 ZrZSM-5 molecular sieve catalyst and its prepn - Google Patents
Low-carbon olefine synthesized C12-C18 ZrZSM-5 molecular sieve catalyst and its prepn Download PDFInfo
- Publication number
- CN1387947A CN1387947A CN01119414A CN01119414A CN1387947A CN 1387947 A CN1387947 A CN 1387947A CN 01119414 A CN01119414 A CN 01119414A CN 01119414 A CN01119414 A CN 01119414A CN 1387947 A CN1387947 A CN 1387947A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- solution
- hour
- zsm
- mixed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 41
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000003054 catalyst Substances 0.000 title claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 238000005342 ion exchange Methods 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 7
- 230000006698 induction Effects 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 238000006384 oligomerization reaction Methods 0.000 abstract description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910021536 Zeolite Inorganic materials 0.000 abstract description 3
- 239000002283 diesel fuel Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000010457 zeolite Substances 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract 1
- 238000005303 weighing Methods 0.000 description 15
- 239000000203 mixture Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000003502 gasoline Substances 0.000 description 8
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 230000008030 elimination Effects 0.000 description 5
- 238000003379 elimination reaction Methods 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 239000000446 fuel Substances 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 2
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- -1 propylene, butylene Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The ZrZSM-5 catalyst consists of Zr 2.0-7.0 wt% and ZSM-5 molecular sieve 93.0-98.0 wt%, and the ZSM-5 molecular sieve is a hydrogen type one with a Si-to-Al molar ratio of 24-78. Zr ion is introduced into zeolite through ion exchange in acid solution to regulate its performance and to make the strong acid active center of molecular sieve shift to weak acid center of mid and strong acid. The modified catalyst has higher oligomerization reaction activity and higher C12-C18 selectivity, increased from 40% to 78%, and this makes it possible to synthesize diesel oil from low-carbon olefine.
Description
Olefin oligomerization is a kind of the superimposed generation of olefinic monomer to be contained the important chemical reaction of the compound that one or more tectonic elements repeat to link to each other, and is the effective way of a class as synthetic liquid fuel, plastics, medicine, dyestuff, resin, washing composition, lubricating oil and additive.High grow the chief editor, point out that low-carbon alkene oligomerisation (as propylene, butylene) can be used for synthetic environment close friend's liquid fuel in " zeolite catalysis with separate " of Sinopec press, aromaticity content is very low in the product.Such catalyzer mainly can be divided into molecular sieve type and non-molecular sieve two big class an acidic catalysts; Molecular sieve type catalyst particularly wherein, have advantages such as active height, good, the stable height of selectivity and poison resistance are strong, can promote low-carbon alkene to change liquid fuels such as gasoline, diesel oil into, the SKP zeolite catalyst of present industrial application is mainly used in the process that gasoline is produced in olefin oligomerization, but diesel consumption and environmental requirement along with present rapid growth, the resource of China and the state of the art have determined to be that diesel and gasoline ratio was on the low side during the liquid fuel of raw material was produced with the oil, and grade is low, can not satisfy the demands far away.There is the lot of domestic and international investigator that the catalyzer and the catalytic process of low-carbon alkene oligomerisation have been carried out a large amount of research in the recent period.The Fan Hong of Dalian University of Technology flies to wait the people at petroleum journal, 2000,4 (16): 46-50 has introduced the compound serial olefin oligomerization catalyst of ferric sulfate-single nickel salt has been studied, and thinks that maturing temperature is 450 ℃ in reducing atmosphere, and adopting mean pore size is γ-Al of 9.6nm
2O
3During for carrier, with the Fe of co-impregnation preparation
(2/3) xNi
1-xSO
4-P
2O
5/ γ-Al
2O
3Catalyzer have good catalytic activity, the above selectivity of product of trimerization and stability.At 60 ℃, 3.0MPa and LHSV is 2h
-1Reaction conditions under the transformation efficiency of propylene oligomerization can reach 92.9%, C
9 =And C
12 =Selectivity reaches 42.9% and 51.8% respectively.People such as Qian Mingxing are at J Mol of catalysis A:Chem., and 2000,160 (2): 243-247 introduces them also to FeCl
2(PhCHO-NC
6H
4NCHPh) and the ethylene oligomerization on the EAO complex catalyst system study, its olefine reaction selectivity can reach 84.8%, and with C
4-C
10Be primary product.
The ZSM-5 molecular sieve is the catalyzer that reaction has obvious activity and is widely studied to olefin oligomerization catalysis synthetic gasoline as the hydrated aluminosilicate of highly crystalline.Shanxi coalification institute of the Chinese Academy of Sciences is reflected at coal based synthetic gas and is converted into low-carbon alkene (i.e. one section reaction) on the ferrum-based catalyst by F-T, the low-carbon alkene coal-based synthetic gasoline technological process of two-stage method that is converted into stop bracket gasoline (being second-stage reaction) in oligomerisation on the ZSM-5 molecular sieve catalyst has been passed through more than 3000 hours industrial single tube mould and is had a try and test then, and yield of gasoline reaches 140g/Nm
3[CO+H
2], gasoline octane rating reaches No. 90, and it is mainly C
5-C
12Product, this catalyzer is used for oligomerization of propene process, C
12-C
18Selectivity have only 40%.
The synthetic C of low-carbon alkene that the purpose of this invention is to provide a kind of highly selective and high conversion
12-C
18ZrZSM-5 molecular sieve catalyst and preparation method.
Catalyst weight per-cent of the present invention consists of:
Zr： 2.0-7.0％
ZSM-5 molecular sieve 93.0-98.0%
Aforesaid ZSM-5 molecular sieve is that the Si/Al mol ratio is the Hydrogen ZSM-5 molecular sieve of 24-78.
Preparation of catalysts method of the present invention comprises the steps:
(1) at first be with the Si/Al mol ratio Hydrogen ZSM-5 molecular sieve of 24-78 at 520-540 ℃ of following roasting 3-5 hour to remove the impurity of its physical adsorption;
(2) molecular sieve and auxiliary agent after the processing of (1) step are pressed 72-63: the mixed of 28-37, evenly grind;
(3) drips of solution that nitric acid is mixed with 2-4% adds to mix in the ground material of (2) step and pinches suitable back extrusion molding, 100-120 ℃ of oven dry down;
(4) material after the oven dry of (3) step is crushed to the 10-40 order, then at 500-520 ℃ of roasting 3-5 hour, to take off nitric acid and moisture;
(5) inorganic acids is mixed with the solution of 0.1-1.0mol concentration;
(6) again zirconates and above-mentioned acid solution are mixed with the ion-exchange upgrading liquid J of 0.1-1.0mol concentration;
(7) ratio that is not less than the 6ml ion exchange liquid in catalyst weight 1 gram is carried out 1-3 hour ion-exchange not being higher than under 80 ℃ the induction stirring;
(8) then solution is filtered that to be washed till the pH value with deionized water be it to be kept 3-8 hour behind the 6-7 in 100-120 ℃ baking oven, made catalyzer then at 200-300 ℃ of roasting 3-5 hour.
Advantage of the present invention is:
(1) adopt the catalyzer of upgrading molecular sieve ZrZSM-5 first, and the preparation method is simple as olefin oligomerization.
(2) catalyst selectivity height, diesel oil distillate C in the product
12-C
18Cut can reach 78%.
Embodiments of the invention are as follows:
Embodiment 1
(1) at first be that 28 Hydrogen ZSM-5 molecular sieve is 540 ℃ of following roastings 3 hours, to remove the impurity of its absorption with 20 gram Si/Al mol ratios;
(2) 13 mol sieve is restrained γ-Al with 7
2O
3, put into mortar simultaneously and mix, evenly grind;
(3) 3% salpeter solution is dripped in the good material of mill, mix and pinch suitably, be squeezed into the bar column type of Φ 2, insert in the baking oven and dry down in 120 ℃ with manual spiral banded extruder;
(4) again the strip molecular sieve is crushed to the 10-40 order and puts into retort furnace and be warming up to 520 ℃ of roastings 5 hours,, treat that temperature is reduced to below 60 ℃ can take out to take off nitric acid and moisture;
(5) accurately take by weighing 32% hydrochloric acid, 1.97 grams and put into volumetric flask, add deionized water is mixed with 0.1mol to 200ml solution J; Take by weighing zirconium oxychloride 6.4 gram again and add among the solution J, under stirring till the transparent liquid that becomes colorless;
(6) take by weighing 10 molecular sieves that make of gram (4) step and put into Erlenmeyer flask, add 120ml solution J, under 80 ℃, keeping 2 hours on the induction stirring well heater;
(7) the back elimination solution of waiting to lower the temperature washs to the pH value with deionized water and to be about 6;
(8) again it is inserted keep 5 hours in 110 ℃ the baking oven after, put into retort furnace and made catalyzer in 3 hours in 200 ℃ of roastings, its Zr content is 2.13%.
Embodiment 2
(1) at first be 52.5 Hydrogen ZSM-5 molecular sieve 540 ℃ of following roastings 3 hours to remove the impurity of its absorption with 20 gram Si/Al mol ratios;
(2) 14 mol sieve is restrained γ-Al with 6
2O
3Put into mortar simultaneously and mix, evenly grind;
(3) 3% salpeter solution is dripped in the good material of mill, mix and pinch suitably, be squeezed into the bar column type of Φ 2, insert in the baking oven and dry down in 105 ℃ with manual spiral banded extruder;
(4) again the strip molecular sieve is crushed to the 10-40 order and puts into retort furnace and be warming up to 510 ℃ of roastings 3 hours,, treat that temperature is reduced to below 60 ℃ can take out to take off nitric acid and moisture;
(5) accurately take by weighing 36% nitric acid, 7.0 grams and put into volumetric flask, add deionized water is mixed with 0.2mol to 200ml solution J; Take by weighing zirconium nitrate 8.0 gram again and add among the solution J, under stirring till the transparent liquid that becomes colorless;
(6) take by weighing 10 molecular sieves that make of gram (4) step and put into Erlenmeyer flask, add 150ml solution J, under 60 ℃, keeping 2 hours on the induction stirring well heater;
(7) the back elimination solution of waiting to lower the temperature washs to the pH value with deionized water and to be about 6;
(8) again it is inserted keep 7 hours in 105 ℃ the baking oven after, put into retort furnace and got final product in 3 hours in 200 ℃ of roastings, its Zr content is 3.65%.
Embodiment 3
(1) at first be 35.3 Hydrogen ZSM-5 molecular sieve 540 ℃ of following roastings 3 hours to remove the impurity of its absorption with 20 gram Si/Al mol ratios;
(2) 14.4 mol sieve is put into mortar simultaneously with the thin water aluminum oxide of 5.6 gram plans and mix, evenly grind;
(3) 2% salpeter solution is dripped in the good material of mill, mix and pinch suitably, be squeezed into the bar column type of Φ 2, insert in the baking oven and dry down in 115 ℃ with manual spiral banded extruder;
(4) again the strip molecular sieve is crushed to the 10-40 order and puts into retort furnace and be warming up to 520 ℃ of roastings 3 hours,, treat that temperature is reduced to below 60 ℃ can take out to take off nitric acid and moisture;
(5) accurately take by weighing 98% sulfuric acid, 4.0 grams and put into volumetric flask, add deionized water is mixed with 0.2mol to 200ml solution J; Take by weighing zirconium nitrate 12.89 gram again and add among the solution J, under stirring till the transparent liquid that becomes colorless;
(6) take by weighing 10 molecular sieves that make of gram (4) step and put into Erlenmeyer flask, add 180ml solution J, under 60 ℃, keeping 2 hours on the induction stirring well heater;
(7) the back elimination solution of waiting to lower the temperature washs to the pH value with deionized water and to be about 7;
(8) again it is inserted keep 8 hours in 120 ℃ the baking oven after, put into retort furnace and made catalyzer in 5 hours in 240 ℃ of roastings.Its Zr content is 5.98%.
Embodiment 4
(1) at first be 67.8 Hydrogen ZSM-5 molecular sieve 540 ℃ of following roastings 3 hours to remove the impurity of its absorption with 20 gram Si/Al mol ratios;
(2) 12.8 mol sieve is restrained γ-Al with 7.2
2O
3Put into mortar simultaneously and mix, evenly grind;
(3) 3% salpeter solution is dripped in the good material of mill, mix and pinch suitably, be squeezed into the bar column type of Φ 2, insert in the baking oven and dry down in 120 ℃ with manual spiral banded extruder;
(4) again the strip molecular sieve is crushed to the 10-40 order and puts into retort furnace and be warming up to 520 ℃ of roastings 3 hours,, treat that temperature is reduced to below 60 ℃ can take out to take off nitric acid and moisture;
(5) accurately take by weighing 85% phosphatase 24 .6 gram and put into volumetric flask, add deionized water is mixed with 0.2mol to 200ml solution J; Take by weighing zirconium nitrate 12.89 gram again and add among the solution J, under stirring till the transparent liquid that becomes colorless;
(6) take by weighing 10 molecular sieves that make of gram (4) step and put into Erlenmeyer flask, add 180ml solution J, under 80 ℃, keeping 2 hours on the induction stirring well heater;
(7) the back elimination solution of waiting to lower the temperature washs to the pH value with deionized water and to be about 7;
(8) again it is inserted keep 6 hours in 120 ℃ the baking oven after, put into retort furnace and made catalyzer in 3 hours in 200 ℃ of roastings, its Zr content is 6.32%.
Embodiment 5
(1) at first be 32.3 Hydrogen ZSM-5 molecular sieve 540 ℃ of following roastings 3 hours to remove the impurity of its absorption with 20 gram Si/Al mol ratios;
(2) 12.8 mol sieve is restrained γ-Al with 7.2
2O
3Put into mortar simultaneously and mix, evenly grind;
(3) 3% salpeter solution is dripped in the good material of mill, mix and pinch suitably, be squeezed into the bar column type of Φ 2, insert in the baking oven and dry down in 120 ℃ with manual spiral banded extruder;
(4) again the strip molecular sieve is crushed to the 10-40 order and puts into retort furnace and be warming up to 520 ℃ of roastings 3 hours,, treat that temperature is reduced to below 60 ℃ can take out to take off nitric acid and moisture;
(5) accurately take by weighing 85% phosphatase 24 .6 gram and put into volumetric flask, add deionized water is mixed with 0.2mol to 200ml solution J; Take by weighing zirconium nitrate 18.32 gram again and add among the solution J, under stirring till the transparent liquid that becomes colorless;
(6) take by weighing 10 molecular sieves that make of gram (4) step and put into Erlenmeyer flask, add 180ml solution J, under 60 ℃, keeping 2 hours on the induction stirring well heater;
(7) the back elimination solution of waiting to lower the temperature washs to the pH value with deionized water and to be about 7;
(8) again it is inserted keep 5 hours in 110 ℃ the baking oven after, put into retort furnace and made catalyzer in 3 hours in 240 ℃ of roastings, its Zr content is 6.86%.
Catalyst performance characterizes with reactive behavior and measures:
1, Zr content is 2.0-7.0%. in the employing elemental analyser mensuration molecular sieve
2, adopt NH
3-TPD measure the differing molecular sieve strong faintly acid Changing Pattern, see Table 1.
3, the characterization of adsorption of catalyzer sees Table 3.
Table 1
Activity rating of catalyst: on the pressurization static bed reaction unit of 2ml different content ZrZSM-5 is reacted, its condition is as follows: T=210 ℃ of P=2.5Mpa propylene LHSV=2.0hr
-1Product collection is taken out by sampling jug after the condensation in ice condenser, by day island proper Tianjin GC-7A hydrogen flame identifier analyze, chromatographic column is 0.25 * 50 meter the capillary column that is coated with stain OV1-101.Temperature by 30 ℃ of beginnings with 2 ℃/min temperature programming to 200 ℃.Its reaction result sees Table 2.
Table 2
Table 3
Claims (2)
1. a low-carbon alkene synthesizes C
12-C
18The ZrZSM-5 molecular sieve catalyst, it is characterized in that the weight percent of catalyzer consists of: Zr:2.0-7.0%
ZSM-5 molecular sieve 93.0-98.0%
Described ZSM-5 molecular sieve is that the Si/Al mol ratio is the Hydrogen ZSM-5 molecular sieve of 24-78.
2. a kind of low-carbon alkene as claimed in claim 1 synthesizes C
12-C
18The preparation method of ZrZSM-5 molecular sieve catalyst, it is characterized in that concrete steps are as follows:
(1) at first be with the Si/Al mol ratio Hydrogen ZSM-5 molecular sieve of 24-78 at 520-540 ℃ of following roasting 3-5 hour to remove the impurity of its physical adsorption;
(2) molecular sieve and auxiliary agent after the processing of (1) step are pressed 72-63: the mixed of 28-37, evenly grind;
(3) drips of solution that nitric acid is mixed with 2-4% adds to mix in the ground material of (2) step and pinches suitable back extrusion molding, 100-120 ℃ of oven dry down;
(4) material after the oven dry of (3) step is crushed to the 10-40 order, then at 500-520 ℃ of roasting 3-5 hour, to take off nitric acid and moisture;
(5) inorganic acids is mixed with the solution of 0.1-1.0mol concentration;
(6) again zirconates and above-mentioned acid solution are mixed with the ion-exchange upgrading liquid J of 0.1-1.0mol concentration;
(7) ratio that is not less than the 6ml ion exchange liquid in catalyst weight 1 gram is carried out 1-3 hour ion-exchange not being higher than under 80 ℃ the induction stirring;
(8) then solution is filtered that to be washed till the pH value with deionized water be it to be kept 3-8 hour behind the 6-7 in 100-120 ℃ baking oven, made catalyzer then at 200-300 ℃ of roasting 3-5 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN01119414A CN1128675C (en) | 2001-05-24 | 2001-05-24 | Low-carbon olefine synthesized C12-C18 ZrZSM-5 molecular sieve catalyst and its prepn |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN01119414A CN1128675C (en) | 2001-05-24 | 2001-05-24 | Low-carbon olefine synthesized C12-C18 ZrZSM-5 molecular sieve catalyst and its prepn |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1387947A true CN1387947A (en) | 2003-01-01 |
| CN1128675C CN1128675C (en) | 2003-11-26 |
Family
ID=4663639
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN01119414A Expired - Lifetime CN1128675C (en) | 2001-05-24 | 2001-05-24 | Low-carbon olefine synthesized C12-C18 ZrZSM-5 molecular sieve catalyst and its prepn |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1128675C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100337749C (en) * | 2003-11-11 | 2007-09-19 | 中科合成油技术有限公司 | Molecular sieve catalyst and preparation method thereof |
| CN103623860B (en) * | 2013-12-20 | 2016-03-02 | 上海兖矿能源科技研发有限公司 | For catalyst and the Synthesis and applications of the oligomerisation of Fischer-Tropsch synthetic low-carbon alkene |
| CN108246342A (en) * | 2018-01-16 | 2018-07-06 | 西南化工研究设计院有限公司 | A kind of in-situ synthetic method of Ni-based oligomerization of propene molecular sieve catalyst |
| CN110721733A (en) * | 2019-09-17 | 2020-01-24 | 中国科学院青岛生物能源与过程研究所 | Catalyst for preparing aviation oil by oligomerization of low-carbon hydrocarbon and preparation method and application thereof |
| CN112264106A (en) * | 2020-11-20 | 2021-01-26 | 中化泉州石化有限公司 | Ethylene selective oligomerization catalyst composition and application thereof |
| CN115400788A (en) * | 2022-08-30 | 2022-11-29 | 华东理工大学 | MCM-22 molecular sieve catalyst, and modification method and application thereof |
-
2001
- 2001-05-24 CN CN01119414A patent/CN1128675C/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100337749C (en) * | 2003-11-11 | 2007-09-19 | 中科合成油技术有限公司 | Molecular sieve catalyst and preparation method thereof |
| CN103623860B (en) * | 2013-12-20 | 2016-03-02 | 上海兖矿能源科技研发有限公司 | For catalyst and the Synthesis and applications of the oligomerisation of Fischer-Tropsch synthetic low-carbon alkene |
| CN108246342A (en) * | 2018-01-16 | 2018-07-06 | 西南化工研究设计院有限公司 | A kind of in-situ synthetic method of Ni-based oligomerization of propene molecular sieve catalyst |
| CN110721733A (en) * | 2019-09-17 | 2020-01-24 | 中国科学院青岛生物能源与过程研究所 | Catalyst for preparing aviation oil by oligomerization of low-carbon hydrocarbon and preparation method and application thereof |
| CN112264106A (en) * | 2020-11-20 | 2021-01-26 | 中化泉州石化有限公司 | Ethylene selective oligomerization catalyst composition and application thereof |
| CN115400788A (en) * | 2022-08-30 | 2022-11-29 | 华东理工大学 | MCM-22 molecular sieve catalyst, and modification method and application thereof |
| CN115400788B (en) * | 2022-08-30 | 2024-02-02 | 华东理工大学 | MCM-22 molecular sieve catalyst and modification method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1128675C (en) | 2003-11-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1128675C (en) | Low-carbon olefine synthesized C12-C18 ZrZSM-5 molecular sieve catalyst and its prepn | |
| CN101940928A (en) | Nickel-based catalyst for hydroisomerization of n-butene for preparing butene-2 or butene-1 | |
| CN1883798A (en) | Catalyst for direct preparation of dimethyl ether by using synthesis gas | |
| CN1218783C (en) | Catalyzer for preparing olefine in low carbon number through catalytic cracking and its preparing method and application | |
| CN1212376C (en) | Light hydrocarbon non-hydrogenation modified catalyst, preparing process and application thereof | |
| CN109304216B (en) | Catalyst for producing low-carbon olefin by synthesis gas one-step method | |
| CN1923366A (en) | Preparation of hydrocarbon molecular sieve catalyst by methanol transformation | |
| CN100337749C (en) | Molecular sieve catalyst and preparation method thereof | |
| CN1114955A (en) | Catalyzer for methanation of carbon dioxide and its preparation method | |
| CN109305871B (en) | Method for producing low-carbon olefin by synthesis gas one-step method | |
| CN1490081A (en) | Fixed bed catalyst for producing propene from butylene by disproportion | |
| CN109305870B (en) | Method for preparing low-carbon olefin by synthesis gas one-step method | |
| CN109647492B (en) | Catalyst for directly producing low-carbon olefin by synthesis gas | |
| CN109304215B (en) | Catalyst for preparing low-carbon olefin by synthesis gas one-step method | |
| CN1232071A (en) | Light hydrocarbon aromatization catalyst and its preparing process | |
| CN102247879A (en) | Catalyst for preparing olefins with same carbon atom number by dehydrogenizing alkane mixtures of C4 and above, and preparation method and application thereof | |
| CN1136298C (en) | Catalyst for producing middle fraction from Fischer-Tropsch synthetic heavy hydrocarbon and its prepn and use | |
| CN1157260C (en) | Preparation method of solid phosphoric acid catalyst for olefine oligopolymerization or hydrocarbylation | |
| CN1120750C (en) | Catalyst for synthesizing methyl isobutyl ketone and preparation process thereof | |
| CN109651031B (en) | Method for directly producing low-carbon olefin by using synthesis gas | |
| CN1136297C (en) | Catalyst for producing gasoline from Fischer-Tropsch synthetic heavy hydrocarbon and its prepn and use | |
| CN1159099C (en) | Solid super acidic catalyst and its preparation method | |
| CN1151104C (en) | Solid phosphoric acid catalyst for low carbon olefine oligomerization or polymerization | |
| CN1191120C (en) | Lawrencium base catalyst for preparing C2 oxygen-contained compound by using synthetic gas | |
| CN109647516B (en) | Catalyst for preparing polyformaldehyde dimethyl ether |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: ZHONGKE SYNTHETIC OIL TECHNOLOGY CO., LTD., DISTR Free format text: FORMER OWNER: SHANXI INST. OF COAL CHEMISTRY, CHINESE ACADEMY OF SCIENCES Effective date: 20070119 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20070119 Address after: 030006, Taiyuan hi tech Zone, Shanxi, South Central Cyberport, port 4, 2, A and B Patentee after: Zhongke Synthetic Oil Technology Co., Ltd. Address before: 165 mailbox 030001, Shanxi City, Taiyuan Province Patentee before: Shanxi Institute of Coal Chemistry, Chinese Academy of Sciences |
|
| C56 | Change in the name or address of the patentee | ||
| CP02 | Change in the address of a patent holder |
Address after: 101407 Beijing city Huairou District Yanqi Economic Development Zone C District No. 1 south two Street Park Patentee after: Zhongke Synthetic Oil Technology Co., Ltd. Address before: 030006, Taiyuan hi tech Zone, Shanxi, South Central Cyberport, port 4, 2, A and B Patentee before: Zhongke Synthetic Oil Technology Co., Ltd. |
|
| CX01 | Expiry of patent term |
Granted publication date: 20031126 |
|
| CX01 | Expiry of patent term |