CN100457697C - Method for preparing propylene by catalytic cracking olefin with four carbon atoms or above - Google Patents
Method for preparing propylene by catalytic cracking olefin with four carbon atoms or above Download PDFInfo
- Publication number
- CN100457697C CN100457697C CNB2006100572294A CN200610057229A CN100457697C CN 100457697 C CN100457697 C CN 100457697C CN B2006100572294 A CNB2006100572294 A CN B2006100572294A CN 200610057229 A CN200610057229 A CN 200610057229A CN 100457697 C CN100457697 C CN 100457697C
- Authority
- CN
- China
- Prior art keywords
- catalytic cracking
- molecular sieve
- heteropolyacid
- raw material
- propylene
- 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.)
- Active
Links
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims description 35
- 238000004523 catalytic cracking Methods 0.000 title claims description 24
- 150000001336 alkenes Chemical class 0.000 title claims description 16
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title description 8
- 125000004432 carbon atom Chemical group C* 0.000 title description 2
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 17
- 238000005336 cracking Methods 0.000 claims abstract description 5
- 239000002808 molecular sieve Substances 0.000 claims description 31
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 8
- 239000005977 Ethylene Substances 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 150000001993 dienes Chemical class 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 238000004230 steam cracking Methods 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 7
- 241000196324 Embryophyta Species 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 5
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 229960001866 silicon dioxide Drugs 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- -1 halogen sodium salt Chemical class 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 241000219782 Sesbania Species 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pent-2-ene Chemical group CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 2
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 238000002288 cocrystallisation Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000012962 cracking technique Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 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
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000010457 zeolite Substances 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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
This invention discloses a method for producing propylene by catalyzing and cracking with C4olefin or over without dual-olefin as the raw material including taking ZSM molecular screen modified by heteropolyacid as the catalyst, and the volume of heteropolyacid is 5-20% to the gross weight of the raw material, which is mixed with vapour to generate propylene by catalysis and crack reaction in a fixed bed reactor.
Description
Technical field
The present invention relates to carbon four and carbon four above alkene is the method that propylene is produced in the catalytic material cracking.
Background technology
Propylene is one of important organic raw material that is only second to by ethene, along with fast development of national economy, its demand is also constantly increased.The present propylene of China situation that is in that supply falls short of demand, the method for conventional stimulation propylene more and more can not satisfy the demand in market.Hydrocarbon vapours cracking and catalytic cracking are two sources greatly of propylene, and the former can propylene enhancing by reducing cracking severity, but growth is limited in one's ability; The latter is by the improvement of aspects such as catalyzer, processing condition, apparatus structure, can propylene enhancing, but confirmed it is expensive and limited.Present how C excessive, that added value is lower to producing in refinery or the ethylene plant's production process
4And C
4Above olefin feedstock carries out processing and utilization, and producing propylene has become an emerging cracking technique.It is simple that this technology has technology, less investment, and the characteristics of instant effect are subjected to the favor of many petrochemical industry research department.
A kind of method of olefin catalytic cracking to produce propylene is proposed among Chinese patent CN1611471A and the CN1611472A.400～600 ℃ of temperature of reaction, reaction pressure 0～0.15Mpa, the liquid phase air speed is 2～30hr
-1Condition under, the former reaches the selectivity that improves propylene and the purpose of yield with the phosphorus modified low silicon-aluminum than the ZSM type molecular sieve catalyst of (＜100); This patent relates to the catalyst modification problem of low silica-alumina ratio molecular sieve, does not use the high silica alumina ratio molecular sieve.The latter is 230～600 ZSM type molecular sieve with the silica alumina ratio preferable range, grain size by control ZSM type molecular sieve, reduce the residence time of reactant and resultant and improve selectivity of catalyst and stable purpose to reach, at 500 ℃, liquid phase air speed 10hr
-1Condition under, propene yield is greater than 30%; This patent focuses on the synthetic of molecular screen primary powder, does not add other active ingredient and carries out modification.
Chinese patent CN1600757 adopts the ZSM-5/ZSM-11 cocrystallization molecular sieve after ammonium ion exchange, with the performance of K, Mg, La, Ce allotment molecular sieve, is raw material with the butylene, is 500～650 ℃ in temperature of reaction, and the liquid phase air speed is 1～50hr
-1, under the pressure 0.01-0.8Mpa, the overall yield of ethene and propylene reaches 40-55%.The catalytic cracking reaction time is short, and the stability of catalyzer is not investigated.
Chinese patent CN1490288 adds the halogen sodium salt in the crystallization process of ZSM type molecular screen primary powder, be reaction raw materials with carbon four and carbon four above alkene, and temperature of reaction is 400～600 ℃, and reaction pressure is 0～0.15Mpa, liquid phase air speed 10～50hr
-1, more detailed investigation the proportioning of molecular sieve different halogen sodium salts and silicon-dioxide in crystallization process to the influence of catalytic cracking reaction.This patent lays particular emphasis on the crystallization of molecular sieve synthesizes, and the selectivity of propylene in the reaction process and the stability of catalyzer are not further elaborated.
Summary of the invention
The purpose of this invention is to provide a kind of new carbon four and the method for carbon four above olefin catalytic cracking to produce propylene, it is good that this method has the propylene selectivity, good stability, and knot charcoal amount is few, the technical characterstic that life cycle is long.
Method of the present invention is that the alkene mixture more than four is a raw material with carbon four that does not contain diolefin and carbon, and water is cooked thinner, described raw material is converted into the method for propylene in the presence of zeolite catalyst.
Concrete, method of the present invention comprises:
With the carbon four and the carbon four above alkene mixtures that do not contain diolefin is raw material, and raw material mixes the back with water vapor and contact in the fixed-bed reactor catalyst neutralisation, and described catalyzer is for using the ZSM type molecular sieve of heteropolyacid modification; Wherein the consumption of heteropolyacid is 5-20%, and preferred 8.0-15.0% is in the raw material gross weight.
The described heteropolyacid of preferred method of the present invention is served as reasons and is selected from the heteroatoms of one of P, Si, Fe and Co, with the polyatom combination that is selected from one of Mo, W, V, Nb and Ta contain the oxygen polyacid.
Polyatom in the more preferably described heteropolyacid is W, and promptly tungsten is heteropolyacid; Heteroatoms in the more preferably described heteropolyacid is P, i.e. phospho-wolframic acid.
Preferred described molecular sieve is that silica alumina ratio is the ZSM type molecular sieve of 50-300, and more preferably the silica alumina ratio of molecular sieve is 180-300.
ZSM type molecular sieve used in the method for the present invention can be ZSM-5, ZSM-11; Preferred described ZSM type molecular sieve is a type ZSM 5 molecular sieve, and more preferably the silica alumina ratio of molecular sieve is 180-300.
In a specific embodiments of the present invention, more preferably use the molecular sieve of commercial ZRP series by name, this molecular sieve is the ZSM-5 molecular sieve of modification; Silica alumina ratio is 180-300.
Method of the present invention is that 400～600 ℃, pressure are 0.1～0.5Mpa in temperature of reaction preferably, and the water oil volume is than being 0.5-1.0, and weight space velocity is 1～10hr
-1Under carry out catalytic cracking reaction.Catalytic pyrolysis generates and contains propylene and ethylene reaction mixture, after refrigerated separation, obtains propylene.
Olefin feedstock described in the method for the present invention can be derived from the C-4-fraction of isolated C-4-fraction of plant catalytic cracking unit or preparing ethylene by steam cracking.It mainly consists of the straight or branched alkene that contains 4 or 5 carbon atoms and two keys, be the isomer of various butylene and amylene, comprise: 1-butylene, suitable-2-butylene, instead-2-butylene, different-butylene etc., the 1-amylene, suitable-the 2-amylene, instead-the 2-amylene, 3-methyl-1-butene, 2-methyl-2-butene, 2-methyl-1-butene alkene etc.
The method of modifying that can adopt conventional molecular sieve of the catalyzer that uses in the method for the present invention is prepared.Preferably, Preparation of catalysts method of the present invention is a kneading method, and concrete steps are as follows:
(1) in the ZSM molecular sieve that the present invention uses, directly mixes in proportion and add a certain amount of heteropolyacid, binding agent, extrusion aid; (2) behind the mixing, add an amount of nitric acid, stir evenly aftershaping, wherein the weight percent concentration of nitric acid is less than 10%; (3) 60-140 ℃ dry 5-20 hour, 450-650 ℃ roasting 0.5-15 hour, obtain described catalyzer.
The consumption of wherein said heteropolyacid is 5-20% (in the raw material gross weight), preferred 8.0-15.0%.
Wherein said binding agent can be selected from silicon-dioxide, aluminum oxide and their mixture, preferred silicon-dioxide.The consumption of the binding agent 0-50% (in the gross weight of raw material) that is weight percentage;
Described extrusion aid can be selected field mountain valley with clumps of trees and bamboo powder, polyacrylamide, silica gel etc. for use.
Catalyst system therefor shape of the present invention can be strip, and is granular, spherical and extrudate etc.
In the olefins by catalytic cracking reaction process, add heteropolyacid in the catalyzer, the inhibition of certain limit hydrogen transfer reactions, reduced the generation of alkane, avoided coking to give birth to carbon.500 ℃ of temperature of reaction, pressure 0.1-0.5MPa, water-oil ratio 0.5-1.0, weight space velocity are 3hr
-1Condition under, the high energy of the selectivity of purpose product propylene reaches 46%, productivity of propylene is up to 37%.Behind the reaction 500hr, the selectivity of propylene is still greater than 40%, and productive rate is greater than 31%, and the one way olefin conversion has been obtained technological achievement preferably greater than 80%.
Method of the present invention has following effect:
1, use method of the present invention, the selectivity of propylene is good, the transformation efficiency height;
2, use method of the present invention, react after 500 hours, used catalyst activity and good stability, knot charcoal amount is few, and life cycle is long, the life-span height;
3, method of the present invention is a raw material with carbon four and the carbon four above alkene mixtures that do not contain diolefin, carries out in fixed-bed reactor, and technology is simple, and is easy to operate;
4, the Preparation of catalysts method of using in the method for the present invention is simple.
Embodiment
Following example will give further instruction to the present invention, but be not restricted to the present invention.
Embodiment 1 preparation catalyst A
(provide SiO with 50g ZRP molecular sieve by economic technology trade center, Garden of Ten-Thousand Trees, Beijing
2/ Al
2O
3＞200), 50g silicon oxide (specific surface＞200m
2The high-purity silicon oxide of/g), 2g sesbania powder uniform mixing adds 5% nitric acid 80ml, extruded moulding 2mm cylinder shape, and cut into 2-3mm; 80 ℃ and 120 ℃ dry 10 hours respectively, 600 ℃ of calcinings 6 hours, take out and be cooled to room temperature then, it is standby to put into moisture eliminator.Zhi Bei catalyzer is expressed as catalyst A by this way.
Embodiment 2 preparation catalyst B
With 50g ZRP molecular sieve (SiO
2/ Al
2O
3＞200), 50g silicon oxide (specific surface＞200m
2The high-purity silicon oxide of/g), (Beijing chemical reagents corporation provides the 10g phospho-wolframic acid, molecular formula: H
3[P (W
3O
10)
4] XH
2O, molecular weight: 2880.17), and 2g sesbania powder uniform mixing, other operation is identical with embodiment 1.Zhi Bei catalyzer is expressed as catalyst B by this way.
Embodiment 3 preparation catalyzer C, D, E
Change the add-on of phospho-wolframic acid, take by weighing 12 grams, 14 grams and 16 grams respectively, with extruded moulding behind the ZRP molecular sieve uniform mixing, other step is identical with the method that embodiment 2 prepares catalyzer, and the catalyzer that makes successively is C, D, E.
Embodiment 4 preparation catalyzer F
Concrete steps are with embodiment 2, and the alternative phospho-wolframic acid of silicotungstic acid is prepared catalyzer, and (silicotungstic acid is provided by Beijing chemical reagents corporation, molecular formula SiO
212WO
226H
2O, molecular weight: 3117.69), obtain catalyzer F.
Embodiment 5 preparation catalyzer G
Concrete steps are with embodiment 2, and the alternative phospho-wolframic acid of phospho-molybdic acid is prepared catalyzer, and (phospho-molybdic acid is provided by Beijing chemical reagents corporation, molecular formula H
3PO
412M
0O
330H
2O, molecular weight 2365.71), obtain catalyzer G.
Embodiment 6 catalytic cracking reactions
C with the plant catalytic cracking unit
4Cut is raw material (the raw material composition sees Table 1), in the presence of catalyst A, B, C, D, E, F, G, and at 500 ℃, pressure 0.2Mpa, water-oil ratio is 0.5, weight space velocity 3hr
-1Following successive reaction 500 hours the results are shown in Table 2, table 3.
Table 1 plant catalytic cracking C
4The composition of olefin feedstock
| Project | Trimethylmethane | Normal butane | Instead-2-butylene | 1-butylene | Iso-butylene | Suitable-2-butylene | Iso-pentane |
| Raw material is formed wt% | 0.11 | 19.88 | 44.05 | 5.20 | 0.12 | 30.38 | 0.25 |
Table 2
Table 3
Table 3 (continuing)
Embodiment 7
Change unstripped gas, the C-4-fraction that adopts the ethylene plant to obtain is a catalyzer adopting catalyzer C, at 500 ℃, and pressure 0.2Mpa, water-oil ratio is 0.5, weight space velocity 3hr
-1Down, successive reaction was carried out catalytic cracking reaction in 500 hours, the results are shown in Table 5.
Table 4 ethylene plant C-4-fraction raw material
| Project | Trimethylmethane | Normal butane | Instead-2-butylene | 1-butylene | Iso-butylene | Suitable-2-butylene |
| Raw material is formed wt% | 2.44 | 8.49 | 9.29 | 26.76 | 45.43 | 7.59 |
Table 5
Claims (9)
1, a kind of is the method that propylene is produced in the catalytic material cracking with the carbon four that do not contain diolefin and carbon four above alkene, ZSM type molecular sieve with modification is a catalyzer, raw material mixes the back and reacts in fixed-bed reactor with water vapor, it is characterized in that described ZSM type molecular sieve is carried out modification with heteropolyacid, wherein the consumption of heteropolyacid is 5-20%, with the total restatement of raw material; Wherein said heteropolyacid is served as reasons and is selected from the heteroatoms of one of P, Si, Fe and Co, with the polyatom combination that is selected from one of Mo, W, V, Nb and Ta contain the oxygen polyacid.
2, the method for catalytic cracking for producing propylene using according to claim 1, the consumption that it is characterized in that heteropolyacid in the described catalyzer is 8-15%, with the total restatement of raw material.
3, the method for catalytic cracking for producing propylene using according to claim 1 is characterized in that the polyatom in the described heteropolyacid is W.
4, the method for catalytic cracking for producing propylene using according to claim 3 is characterized in that the heteroatoms in the described heteropolyacid is P.
5, the method for catalytic cracking for producing propylene using according to claim 1, the silica alumina ratio that it is characterized in that described ZSM type molecular sieve is 50-300.
6, the method for catalytic cracking for producing propylene using according to claim 1 is characterized in that described ZSM type molecular sieve is a type ZSM 5 molecular sieve.
7, the method for catalytic cracking for producing propylene using according to claim 6, the silica alumina ratio that it is characterized in that described ZSM type molecular sieve is 180-300.
8, according to the method for one of claim 1-7 described catalytic cracking for producing propylene using, it is characterized in that described raw material is that 400-600 ℃, reaction pressure are 0.1-0.5Mpa in temperature of reaction, water-oil ratio is 0.5-1.0, weight space velocity is 1-10hr
-1Under carry out catalytic cracking reaction.
9,, it is characterized in that described raw material is the C-4-fraction that isolated C-4-fraction of plant catalytic cracking unit or preparing ethylene by steam cracking obtain according to the method for one of claim 1-7 described catalytic cracking for producing propylene using.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100572294A CN100457697C (en) | 2006-03-09 | 2006-03-09 | Method for preparing propylene by catalytic cracking olefin with four carbon atoms or above |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100572294A CN100457697C (en) | 2006-03-09 | 2006-03-09 | Method for preparing propylene by catalytic cracking olefin with four carbon atoms or above |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101033166A CN101033166A (en) | 2007-09-12 |
| CN100457697C true CN100457697C (en) | 2009-02-04 |
Family
ID=38729935
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100572294A Active CN100457697C (en) | 2006-03-09 | 2006-03-09 | Method for preparing propylene by catalytic cracking olefin with four carbon atoms or above |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100457697C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101722025B (en) * | 2008-10-31 | 2011-10-12 | 中国石油化工股份有限公司 | Catalyst for mixing C4 olefins to prepare propylene and ethylene, and using method thereof |
| CN101857520B (en) * | 2009-04-10 | 2013-02-27 | 中国石油化工股份有限公司 | Method for increasing yield of propylene and ethylene |
| CN102463133B (en) * | 2010-11-04 | 2013-08-28 | 中国石油化工股份有限公司 | Catalyst for preparing olefin by catalytic cracking, preparation method and application thereof |
| CN102861604B (en) * | 2011-07-07 | 2014-06-25 | 中国石油化工股份有限公司 | Olefin catalytic agent prepared by naphtha catalytic cracking and preparation method and application thereof |
| CN113318773B (en) * | 2020-02-28 | 2023-09-08 | 中国石油化工股份有限公司 | Catalytic cracking auxiliary agent containing phosphotungstic acid modified mesoporous material, preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1413965A (en) * | 2001-10-22 | 2003-04-30 | 中国石油化工股份有限公司 | Method for producing propene using C4 and its above colefines |
| CN1413966A (en) * | 2001-10-22 | 2003-04-30 | 中国石油化工股份有限公司 | Method for producing propen of C4 and its above colefines catalytic cracking |
| CN1506342A (en) * | 2002-12-11 | 2004-06-23 | 中国石油化工股份有限公司 | Process of catalytically cracking C4 and above olefin to produce propylene |
| CN1506343A (en) * | 2002-12-11 | 2004-06-23 | 中国石油化工股份有限公司 | Propylene producing process |
| WO2004076596A1 (en) * | 2003-01-24 | 2004-09-10 | Idemitsu Kosan Co., Ltd. | Process of catalytic cracking of hydrocarbon |
| CN1611471A (en) * | 2003-10-27 | 2005-05-04 | 中国石油化工股份有限公司 | Method for producing propene for olefin catalytic cracking |
-
2006
- 2006-03-09 CN CNB2006100572294A patent/CN100457697C/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1413965A (en) * | 2001-10-22 | 2003-04-30 | 中国石油化工股份有限公司 | Method for producing propene using C4 and its above colefines |
| CN1413966A (en) * | 2001-10-22 | 2003-04-30 | 中国石油化工股份有限公司 | Method for producing propen of C4 and its above colefines catalytic cracking |
| CN1506342A (en) * | 2002-12-11 | 2004-06-23 | 中国石油化工股份有限公司 | Process of catalytically cracking C4 and above olefin to produce propylene |
| CN1506343A (en) * | 2002-12-11 | 2004-06-23 | 中国石油化工股份有限公司 | Propylene producing process |
| WO2004076596A1 (en) * | 2003-01-24 | 2004-09-10 | Idemitsu Kosan Co., Ltd. | Process of catalytic cracking of hydrocarbon |
| CN1611471A (en) * | 2003-10-27 | 2005-05-04 | 中国石油化工股份有限公司 | Method for producing propene for olefin catalytic cracking |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101033166A (en) | 2007-09-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101734987B (en) | Method for preparing ethylene and propylene from C4 hydrocarbons | |
| CN101928011B (en) | Method for preparing ZSM-35 molecular sieve | |
| CN107265478B (en) | A kind of boron modification ferrierite molecular sieve catalyst and the preparation method and application thereof | |
| CN100457697C (en) | Method for preparing propylene by catalytic cracking olefin with four carbon atoms or above | |
| CN103769207B (en) | A kind of n-butene skeletal isomerization preparing isobutene co-production propylene catalyst and its preparation method and application | |
| CN101172247B (en) | Catalyst for production of propylene and ethylene with carbon alkatetraenes, regeneration and uses thereof | |
| CN102276405B (en) | Method for preparing propylene as main product from C4 and high carbon olefins | |
| CN101619011A (en) | Method for producing ethylene and propylene by catalytic cracking | |
| CN102069007A (en) | Catalyst for use in preparation of propylene by olefin cracking | |
| CN1704390A (en) | Method for preparing olefin by conversion of methanol | |
| CN102040444A (en) | Method for preparing propylene by butylene and ethene | |
| CN100363314C (en) | A kind of method that produces diesel oil by overlapping of C4 component containing butene | |
| CN102464548A (en) | Method for preparing propylene by olefin disproportionation in fluidized bed | |
| CN103121899B (en) | Method for preparing propylene and ethylene from alcohol | |
| CN101172925A (en) | Method for producing propylene with dismutation of ethylene and butylene | |
| CN101148391A (en) | Method for producing propylene by butylene and ethylene dismutation | |
| CN100413826C (en) | Method for producing propylene | |
| CN100368359C (en) | Production system for increasing production of propylene | |
| CN105712830A (en) | Preparation method of isobutene | |
| CN100368356C (en) | Method for producing propylene through catalytic cracking C4 olefin | |
| CN108101727B (en) | Method for preparing ethylene by ethanol dehydration | |
| CN105712818A (en) | Method used for preparing isobutene from MTBE-TBA mixture | |
| CN101172919B (en) | Method for producing ethylene with ethyl alcohol | |
| CN110479362B (en) | Catalyst for high yield of diesel oil and low carbon olefin, and preparation method and application thereof | |
| CN1307132C (en) | Catalyst for producing diesel oil by carbon tetraolefin polymerization and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 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 |