CN101722025B - Catalyst for mixing C4 olefins to prepare propylene and ethylene, and using method thereof - Google Patents
Catalyst for mixing C4 olefins to prepare propylene and ethylene, and using method thereof Download PDFInfo
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- CN101722025B CN101722025B CN2008102253589A CN200810225358A CN101722025B CN 101722025 B CN101722025 B CN 101722025B CN 2008102253589 A CN2008102253589 A CN 2008102253589A CN 200810225358 A CN200810225358 A CN 200810225358A CN 101722025 B CN101722025 B CN 101722025B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 23
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000005977 Ethylene Substances 0.000 title claims abstract description 5
- 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 37
- 239000002808 molecular sieve Substances 0.000 claims abstract description 34
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 20
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 11
- 239000000853 adhesive Substances 0.000 claims abstract description 8
- 230000001070 adhesive effect Effects 0.000 claims abstract description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 238000006555 catalytic reaction Methods 0.000 claims description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 8
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 239000011575 calcium Substances 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 239000011777 magnesium Substances 0.000 claims description 8
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 8
- 239000010452 phosphate Substances 0.000 claims description 8
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 5
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 5
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 10
- 238000006276 transfer reaction Methods 0.000 abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 4
- 239000011574 phosphorus Substances 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 206010027476 Metastases Diseases 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 235000013847 iso-butane Nutrition 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000009401 metastasis Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000005504 petroleum refining 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
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon 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
- 230000001131 transforming effect Effects 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
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- Catalysts (AREA)
Abstract
The invention provides a catalyst for mixing C4 olefins to prepare propylene and ethylene, and a using method thereof. The catalyst consists of ZSM molecular sieve, a modified component and adhesives, wherein modified elements of the modified component are alkaline-earth metal and phosphorus. Compared with unmodified molecular sieve catalysts and the molecular sieve catalysts modified only with alkaline-earth metal, in the process of catalyzing C4 mixed olefins to prepare propylene and ethylene, the catalyst of the invention has the advantages of obviously raising the yield of propylene and obviously reducing the yield of C3 alkane serving as a byproduct of hydrogen transfer reaction, along with good stability.
Description
Technical field
The present invention relates to the catalyst that uses in a kind of Chemical Manufacture, more particularly, relate to a kind of mixed C that is used for
4The catalyst of olefins to prepare propylene and ethene and using method thereof.
Background technology
A considerable amount of mixed C are arranged in petroleum refining process
4Generate.In recent years, along with China to the propylene growth of requirement, be that the production technology of main purpose product comes into one's own with the propylene, by C
4The technology that alkene transform to generate propylene is one of research contents wherein.
In mixed C
4In the preparing propylene transformed process of olefin catalytic, generally adopt molecular sieve catalyst.Because the character and the reaction characteristics thereof of molecular sieve, catalytic reaction process is accompanied by the generation of catalyst carbon deposit with being difficult to avoid, causes catalyst activity and stability decreases; And, generate the accessory substance alkane of corresponding carbon number in the catalytic reaction process inevitably owing to the existence of hydrogen transfer reaction.
Usually, in course of reaction, add inert component as diluent, perhaps improve the air speed of charging, control is reflected under the gentle as far as possible condition carries out (low-temp low-pressure), and molecular sieve carried out various forms of modifications or preliminary treatment, to reach coke content that reduces on the catalyst and the purpose that suppresses hydrogen transfer reaction.
In the prior art, Chinese patent CN1284109A and U.S. Pat 6646176B1 by heating in water vapour with aluminium complexant pretreatment catalyst, reach more than 180 the final silicon/aluminum ratio of molecular sieve; Make this molecular sieve at 500～600 ℃, 0.01～0.2MPa, 10～30h
-1Carry out catalytic reaction under the condition,, do not use diluent in the course of reaction owing to adopted higher air speed.Chinese patent CN1274342A, adopting the silica alumina ratio that contains proton hardly is 200～5000 molecular sieves, metal-modified with IB family; Use this molecular sieve at 400～700 ℃, 0.01～1.0MPa, 1～1000hr
-1Carry out catalytic reaction under the condition.Chinese patent CN1506342A, adopting alkaline-earth metal is that 38～1000 ZSM-5 is molecular sieve modified to silica alumina ratio; Use this molecular sieve at 540～580 ℃, 10～30hr
-1Carry out catalytic reaction under the condition.Chinese patent CN1490287A, adopt contain Mo, W, P, La are metal and alkaline-earth metal, are that 50～300 ZSM-5 is molecular sieve modified to silica alumina ratio; At 350～500 ℃ of reaction temperatures, reaction pressure 0.6～1MPa, liquid phase air speed 1～10hr
-1Carry out catalytic reaction under the condition.Chinese patent CN1676499A adopts rare earth metal, alkaline-earth metal, zirconium and P elements, is that 50～300 ZSM-5 molecular sieve carries out modification to silica alumina ratio; At 450～600 ℃ of reaction temperatures, reaction pressure 0.1～0.5MPa, liquid phase air speed 1～10hr
-1Carry out catalytic reaction under the condition; Adopting water in the course of reaction is diluent.
Above-mentioned prior art, the main high silica alumina ratio molecular sieve that adopts is done the catalyst key component, though the modifying element and the preprocess method that adopt are different, but the ability of the stability of the catalytic reaction effect, particularly catalyst of system propylene, ethene and inhibition hydrogen transfer reaction still has much room for improvement.
Summary of the invention
For when having high propylene+yield of ethene, make catalyst have high stability and low hydrogen metastasis degree, the invention provides a kind of mixed C that is used for
4The catalyst of olefins to prepare propylene and ethene and using method thereof.The mixed C that is used for of the present invention
4The catalyst of olefins to prepare propylene and ethene is achieved in that
A kind of mixed C that is used for
4The catalyst of olefins to prepare propylene and ethene is characterized in that:
Described catalyst is made up of ZSM molecular sieve, modified component and adhesive; Wherein
Described ZSM molecular screening is from the molecular sieve of ZSM-5, ZSM-8 or ZSM-11 structure type, and the silica alumina ratio of described ZSM molecular sieve is 301～1000:1;
Described adhesive is that aluminium oxide is or/and silica;
The modifying element of described modified component is alkaline-earth metal and P elements.
In the specific implementation, described ZSM molecular sieve accounts for 20～80wt% of total catalyst weight, 15～75wt% of described binder constitutes total catalyst weight, and the modifying element of described modified component accounts for 0.02～20wt% of total catalyst weight.
In the specific implementation, the alkali earth metal in the described modified component is selected from one or more in the nitrate, chloride, acetate, sulfate of alkaline-earth metal, and described alkali earth metal accounts for 0.01～10wt% of total catalyst weight; P elements in the described modified component is selected from phosphoric acid or/and phosphate, and described P elements accounts for 0.01～10wt% of total catalyst weight.
In the specific implementation, described alkaline-earth metal is that calcium is or/and magnesium; Described phosphate is that diammonium hydrogen phosphate is or/and ammonium dihydrogen phosphate (ADP).
Embodiment preferred of the present invention is:
The molecular sieve of the ZSM-5 structure type that described ZSM molecular sieve is silica alumina ratio 310～800:1, described ZSM molecular sieve accounts for 20～80wt% of total catalyst weight;
Described adhesive is an aluminium oxide, 15～75wt% of described binder constitutes total catalyst weight;
Alkali earth metal in the described modified component is selected from calcium or/and one or more in the nitrate of magnesium, chloride, acetate or the sulfate, and described alkali earth metal accounts for 0.01～10wt% of total catalyst weight; P elements in the described modified component is selected from phosphoric acid or/and phosphate, and wherein phosphate is diammonium hydrogen phosphate or/and ammonium dihydrogen phosphate (ADP), and described P elements accounts for 0.01～10wt% of total catalyst weight.
The present invention adopts than the high silica alumina ratio molecular sieve, and big more its acidity of molecular sieve silica alumina ratio is weak more, the acid amount is low more, compares with the low silica-alumina ratio molecular sieve, and its hydrogen transfer reaction degree is weak, accessory substance alkane content is lower, the carbon deposit degree is also lower, is easy to modification.The introducing of modifying element of the present invention can be adopted conventional methods such as ion-exchange, infusion process, mixing method; The moulding of catalyst can be adopted conventional methods such as adding the adhesive extruded moulding,
Mixed C of the present invention
4The using method of olefins to prepare propylene and catalyst for ethylene is achieved in that
Adopt the described catalyst of claim 1～5, carry out mixed C
4The catalytic reaction of olefins to prepare propylene and ethene, the temperature of this reaction are that 450～600 ℃, pressure are that 0.01～0.3MPa, water hydrocarbon weight ratio are 0～1, weight space velocity is 1～20h
-1
Catalyst provided by the invention and using method thereof not only have higher propylene+yield of ethene, while catalyst stability height, and the hydrogen transfer reaction degree is low.This catalyst can be used for transforming the process of producing propylene, ethene by containing high carbon number alkene.
The specific embodiment
Be described in further detail technical scheme of the present invention below in conjunction with embodiment, protection scope of the present invention is not limited to the following specific embodiment.
Embodiment 1
Catalytic reaction is carried out in tubular fixed-bed reactor.The used mixed C of catalytic reaction
4The raw material composition of alkene sees Table 1.
Table 1
| Iso-butane (wt%) | Normal butane (wt%) | Butene-1 (wt%) | Isobutene (wt%) | Anti-butylene (wt%) | Maleic (wt%) | ∑ butylene (wt%) |
| 0.75 | 26.66 | 13.70 | 5.10 | 30.25 | 23.60 | 72.64 |
Preparation of catalysts
Hydrogen ZSM-5 molecular sieve (silica alumina ratio is 380, and market is bought) is mixed with 3:1 with aluminium oxide, stir and mediate, extruded moulding.100 ℃ of dry 10h, 560 ℃ of roasting 4h.The above-mentioned bar 2h of solution impregnation that will contain diammonium hydrogen phosphate, calcium nitrate and magnesium nitrate filters, and 100 ℃ of dry 10h, 560 ℃ of roasting 4h make catalyst.Phosphorus, calcium and magnesium account for 0.26wt%, 2.20wt% and the 1.23wt% of total catalyst weight respectively.
Evaluating catalyst:
Carry out at tubular fixed-bed reactor.Reaction condition is: 520 ℃ of reaction temperatures, reaction pressure 0.1MPa, water hydrocarbon weight ratio 0.5, feed weight air speed 2.5h
-1Reaction result sees Table 2, and (the product weight yield is with C in the raw material
4Alkene is that benchmark calculates).
Table 2
| Yield of ethene (wt%) | Propane yield (wt%) | Propene yield (wt%) | Butene conversion (wt%) |
| 10.25 | 4.36 | 31.05 | 74.50 |
Catalyst stability is estimated
(product yield is with C in the raw material for the product yield of differential responses time
4Alkene is that benchmark calculates) see Table 3.
Table 3
| Reaction time (hour) | Yield of ethene (wt%) | Propane yield (wt%) | Propene yield (wt%) | Butene conversion (wt%) |
| 10 | 10.25 | 4.36 | 31.05 | 74.50 |
| 100 | 8.31 | 3.17 | 30.02 | 73.56 |
| 500 | 6.93 | 2.63 | 30.24 | 71.82 |
| 800 | 6.02 | 1.87 | 30.51 | 69.72 |
Embodiment 2
In catalyst: phosphorus, calcium, magnesium account for 0.51 (wt) %, 2.55 (wt) % and 2.54 (wt) % of total catalyst weight respectively.
Type of reactor, reaction raw materials, catalyst preparation step and evaluating catalyst condition are with embodiment 1.Reaction result sees Table 4.
Embodiment 3
In catalyst: phosphorus, calcium and magnesium account for 0.25 (wt) %, 1.25 (wt) % and 2.25 (wt) % of total catalyst weight respectively.
Type of reactor, reaction raw materials, catalyst preparation step and evaluating catalyst condition are with embodiment 1.Reaction result sees Table 4.
Comparative Examples 1
Preparation of Catalyst: Hydrogen ZSM-5 molecular sieve and aluminium oxide are mixed with 3:1, stir and mediate, extruded moulding.100 ℃ of dry 10h, 560 ℃ of roasting 4h.
The evaluating catalyst condition is with embodiment 1, and reaction result sees Table 4.
Comparative Examples 2
Hydrogen ZSM-5 molecular sieve and aluminium oxide are mixed with 3:1, stir and mediate, extruded moulding.100 ℃ of dry 10h, 560 ℃ of roasting 4h.The above-mentioned bar 2h of solution impregnation that will contain calcium nitrate and magnesium nitrate filters, and 100 ℃ of dry 10h, 560 ℃ of roasting 4h make catalyst.Calcium and magnesium account for 2.22 (wt) % and 1.25 (wt) % of total catalyst weight respectively.
The evaluating catalyst condition is with embodiment 1.Reaction result sees Table 4.
Table 4
| Yield of ethene (wt%) | Propane yield (wt%) | Propene yield (wt%) | Butene conversion (wt%) | |
| Embodiment 1 | 10.25 | 4.36 | 31.05 | 74.50 |
| Embodiment 2 | 8.48 | 2.34 | 30.59 | 70.44 |
| Embodiment 3 | 10.78 | 3.45 | 31.11 | 73.98 |
| Comparative Examples 1 | 11.97 | 15.04 | 22.94 | 84.29 |
| Comparative Examples 2 | 12.83 | 7.92 | 30.76 | 77.74 |
As can be seen from Table 4, with unmodified molecular sieve with only compare with alkali-earth metal modified molecular sieve, catalyst of the present invention is at catalysis C
4Mixed olefins is produced in the process of propylene and ethene, and propene yield improves, accessory substance C
3The alkane productive rate obviously reduces.
Claims (5)
1. one kind is used for mixed C
4The catalyst of olefins to prepare propylene and ethene is characterized in that:
Described catalyst is made up of ZSM molecular sieve, modified component and adhesive; Wherein
The silica alumina ratio of described ZSM molecular sieve is: 301～1000; 1, described ZSM molecular screening is from the molecular sieve of ZSM-5, ZSM-8 or ZSM-11 structure type, and described ZSM molecular sieve accounts for 20～80wt% of total catalyst weight;
Described adhesive is an aluminium oxide or/and silica, 15～75wt% of described binder constitutes total catalyst weight;
The modifying element of described modified component is alkaline-earth metal and P elements, and the modifying element of described modified component accounts for 0.02～20wt% of total catalyst weight.
2. catalyst according to claim 1 is characterized in that:
Alkali earth metal in the described modified component is selected from: one or more in the nitrate of alkaline-earth metal, chloride, acetate, the sulfate, and described alkali earth metal accounts for 0.01～10wt% of total catalyst weight;
P elements in the described modified component is selected from phosphoric acid or/and phosphate, and described P elements accounts for 0.01～10wt% of total catalyst weight.
3. catalyst according to claim 2 is characterized in that:
Described alkaline-earth metal is that calcium is or/and magnesium; Described phosphate is that diammonium hydrogen phosphate is or/and ammonium dihydrogen phosphate (ADP).
4. catalyst according to claim 1 is characterized in that:
Described ZSM molecular sieve is a silica alumina ratio 310～800: the molecular sieve of 1 ZSM-5 structure type, and described ZSM molecular sieve accounts for 20～80wt% of total catalyst weight;
Described adhesive is an aluminium oxide, 15～75wt% of described binder constitutes total catalyst weight;
Alkali earth metal in the described modified component is selected from calcium or/and one or more in the nitrate of magnesium, chloride, acetate or the sulfate, and described alkali earth metal accounts for 0.01～10wt% of total catalyst weight; P elements in the described modified component is selected from phosphoric acid or/and phosphate, and wherein phosphate is diammonium hydrogen phosphate or/and ammonium dihydrogen phosphate (ADP), and described P elements accounts for 0.01～10wt% of total catalyst weight.
5. mixed C
4The using method of olefins to prepare propylene and catalyst for ethylene adopts one of claim 1～4 described catalyst, carries out mixed C
4The catalytic reaction of olefins to prepare propylene and ethene, the temperature of this reaction are that 450～600 ℃, pressure are that 0.01～0.3MPa, water hydrocarbon weight ratio are 0～1, weight space velocity is 1～20h
-1
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| Application Number | Priority Date | Filing Date | Title |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102253589A CN101722025B (en) | 2008-10-31 | 2008-10-31 | Catalyst for mixing C4 olefins to prepare propylene and ethylene, and using method thereof |
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| Publication Number | Publication Date |
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| CN101722025B true CN101722025B (en) | 2011-10-12 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10016750B1 (en) | 2017-01-10 | 2018-07-10 | King Fahd University Of Petroleum And Minerals | Method of producing propylene and ethylene with a core-shell ZSM catalyst |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102649084A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Catalyst used in double-bond isomerization of n-butene |
| CN102649085B (en) * | 2011-02-25 | 2016-02-10 | 中国石油化工股份有限公司 | The catalyst of butylenes double-bond isomerization |
| CN102872902A (en) * | 2011-07-12 | 2013-01-16 | 中国石油化工股份有限公司 | Catalytic cracking assistant for propylene yield increase |
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Cited By (7)
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|---|---|---|---|---|
| US10016750B1 (en) | 2017-01-10 | 2018-07-10 | King Fahd University Of Petroleum And Minerals | Method of producing propylene and ethylene with a core-shell ZSM catalyst |
| US10112190B2 (en) | 2017-01-10 | 2018-10-30 | King Fahd University Of Petroleum And Minerals | Fluidized-bed cracking of butene to form propylene and ethylene |
| US10112191B2 (en) | 2017-01-10 | 2018-10-30 | King Fahd University Of Petroleum And Minerals | Method for cracking butene |
| US10159967B1 (en) | 2017-01-10 | 2018-12-25 | King Fahd University Of Petroleum And Minerals | Method for making a catalyst and cracking a hydrocarbon stream to form propylene/ethylene |
| US10159968B1 (en) | 2017-01-10 | 2018-12-25 | King Fahd University Of Petroleum And Minerals | Method of making ZSM-based catalyst and forming a propylene/ethylene mixture |
| US10166535B1 (en) | 2017-01-10 | 2019-01-01 | King Fahd University Of Petroleum And Minerals | Method of treating butene to form propylene/ethylene mixture |
| US10166536B1 (en) | 2017-01-10 | 2019-01-01 | King Fahd University of Petroleum and Minerals. | Method of making and separating a propylene/ethylene mixture from butene |
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