CN102019178A - Propane dehydrogenation to propylene catalyst and preparation and applications thereof - Google Patents
Propane dehydrogenation to propylene catalyst and preparation and applications thereof Download PDFInfo
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- CN102019178A CN102019178A CN2009101699953A CN200910169995A CN102019178A CN 102019178 A CN102019178 A CN 102019178A CN 2009101699953 A CN2009101699953 A CN 2009101699953A CN 200910169995 A CN200910169995 A CN 200910169995A CN 102019178 A CN102019178 A CN 102019178A
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- catalyst
- oxide
- chromium
- propane dehydrogenation
- propane
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 239000001294 propane Substances 0.000 title claims abstract description 54
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 47
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 239000011651 chromium Substances 0.000 claims abstract description 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 10
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 3
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract 2
- 150000001340 alkali metals Chemical class 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 16
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical group [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- 235000010333 potassium nitrate Nutrition 0.000 claims description 4
- 239000004323 potassium nitrate Substances 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 150000001844 chromium Chemical class 0.000 claims description 3
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- FQHYQCXMFZHLAE-UHFFFAOYSA-N 25405-85-0 Chemical compound CC1(C)C2(OC(=O)C=3C=CC=CC=3)C1C1C=C(CO)CC(C(C(C)=C3)=O)(O)C3C1(O)C(C)C2OC(=O)C1=CC=CC=C1 FQHYQCXMFZHLAE-UHFFFAOYSA-N 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 238000005299 abrasion Methods 0.000 claims description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 150000002603 lanthanum Chemical class 0.000 claims description 2
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229940072033 potash Drugs 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 238000001694 spray drying Methods 0.000 claims description 2
- -1 chromic acetate Chemical class 0.000 claims 3
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims 2
- 229910052746 lanthanum Inorganic materials 0.000 claims 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims 2
- 239000007788 liquid Substances 0.000 claims 1
- 159000000001 potassium salts Chemical class 0.000 claims 1
- 238000001035 drying Methods 0.000 abstract description 6
- 239000012530 fluid Substances 0.000 abstract description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- UOUJSJZBMCDAEU-UHFFFAOYSA-N chromium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Cr+3].[Cr+3] UOUJSJZBMCDAEU-UHFFFAOYSA-N 0.000 abstract 2
- 229910052593 corundum Inorganic materials 0.000 abstract 2
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 2
- 239000011440 grout Substances 0.000 abstract 1
- 229910017604 nitric acid Inorganic materials 0.000 abstract 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 1
- 238000005507 spraying Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 238000005516 engineering process Methods 0.000 description 16
- 238000003756 stirring Methods 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 7
- 206010013786 Dry skin Diseases 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 150000002823 nitrates Chemical class 0.000 description 5
- 235000011837 pasties Nutrition 0.000 description 5
- 238000012216 screening Methods 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- IUGSMAXPUJKGKM-UHFFFAOYSA-N [Cr].[La] Chemical compound [Cr].[La] IUGSMAXPUJKGKM-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical class [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000003915 liquefied petroleum gas Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical class [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical class [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 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)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a propane dehydrogenation to propylene catalyst and preparation and applications thereof. The propane dehydrogenation to propylene catalyst is characterized by being a composition prepared from Gamma-Al2O3, a kind or many kinds of chromium oxides, a kind or many kinds of rare earth oxides and a kind or many kinds of alkali metal oxides, wherein the Gamma-Al2O3 accounts for 30-95%, the chromium oxides account for 1-50%, the rare earth oxides account for 0-30%, and the alkali metal oxides account for 0-10%. The preparation process comprises the following steps of: adding active components, such as chromium, rare earth, alkali metal and the like into aluminum oxide grout, regulating the pH value of 1-5 to form gelatum with concentrated nitric acid, and spraying and drying to form microballoons; then roasting for 0-5 hours at 250-750 DEG C in a nitrogen atmosphere; and roasting for 0.1-20 hours at 250-1000 DEG C in an air atmosphere. The obtained catalyst is in a fluid bed reactor, and reaction conditions comprise 400-700 DEG C of temperature, 0.01-3MPa of absolute pressure and 10-10000 h-1 of volume hourly space velocity.
Description
Technical field
The present invention relates to a kind of preparing propylene by dehydrogenating propane catalyst for reaction its preparation method that is used for, and the application in the preparing propylene by dehydrogenating propane reaction.
Background technology
Propylene is as a kind of important Organic Chemicals, and since the nineties in 20th century, the demand rate of rise of propylene has surpassed ethene.Point out that according to american chemical product market company (CMAI) latest survey report global propylene supply will be increased to 8,030 ten thousand t/a in 2010 by 5,670 ten thousand t/a in 2003, the average growth rate per annum of demand is 5%.Wherein, market, Asia, especially the propylene demand growth of Chinese market is the rapidest, and existing production of propylene device can not satisfy the demand growth of petrochemical iy produced to propylene, and the price of propylene is progressively soaring.The propylene main source has at present: the coproduction of naphtha vapor cracking ethylene preparation, oil plant FCC technology by-product and dehydrogenating propane.Along with rising steadily of International Crude Oil, the preparing propylene by dehydrogenating propane technology comes into one's own in recent years gradually.China is again the relatively abundant country of propane resource, and is about 6% as containing propane in the casing-head gas such as grand celebration, Tarim Basin, contains propane 3～6% in the condensate, and it is about 60% to contain propane in the liquefied petroleum gas, contains propane about 15% in the natural gas moisture.The utilization of propane at present mainly is to burn as fuel, and added value is not high.If can effectively the direct catalytic dehydrogenation of propane wherein be changed into propylene, can alleviate the problem of propylene source deficiency, and can obtain high value simultaneously and get hydrogen.Therefore, need exploitation to be fit to the propane dehydrogenation catalyst of commercial Application.
The catalyst system of preparing propylene by dehydrogenating propane mainly contains oxidative dehydrogenation type catalyst, chromium-based catalysts and platinum group catalyst etc.For the chromium-based catalysts and the platinum based catalyst that have had the allied industry makeup to put abroad.Industrialized in the world dehydrogenating propane technology mainly contains the FBD fluid bed preparing propylene by dehydrogenating propane technology of Oleflex technology, Catofin technology, STAR technology, Linde technology and Milan, ITA Snamprogetti company and the cooperative development of Russian Yarsintez company.It is at present, industrial that to use morely be " Catofin " technology of ABB Lummus company and " Oleflex " technology of Uop Inc..Two kinds of preparing propylene by dehydrogenating propane technologies of Oleflex and Catofin are identical substantially, different just dehydrogenation and catalyst regeneration part, Oleflex technology is used Pt/Al
2O
3The moving-bed of catalyst reactor, and Catofin technology is used Cr
2O
3/ Al
2O
3Catalyst fixed bed reactor.
Adopt the dehydrogenating propane technology of fixed bed reactors, conversion zone wherein, a plurality of reactors parallel operations, a part of reactor production, simultaneously a part of reactor regeneration, the regeneration period of catalyst is generally several hrs.Dehydrogenating propane reaction is the endothermic reaction that molecule increases, and therefore, high temperature and low pressure help the carrying out that react.At present, the outstanding problem that adopts the dehydrogenating propane technology existence of fixed bed reactors is that the catalyst heap is than big, the space that bed can supply reactant or product to pass through is little and resistance is big, the reaction pressure drop is bigger, reaction velocity is lower, mass-and heat-transfer causes the even product of reaction bed temperature skewness that side reaction further takes place slowly easily, make the reaction selectivity variation, and carrying out along with reaction, because the catalyst mechanical strength changes the beds structure is changed, normally carrying out of influence reaction shortened the service life of catalyst, and the mechanical strength to catalyst has proposed high requirement like this.
Adopt fluidized-bed process can solve mass transfer and the heat transfer problem that exists in the fixed bed reactors, use the ciculation fluidized bed process of riser can solve the cyclic regeneration problem of catalyst, but activity of such catalysts, hardness etc. is had higher requirement.The GB2177317A patent disclosure employing immersion process for preparing Cr/Al fluid catalyst, but the loaded down with trivial details cost height of the procedure that this patent provides, the not high and catalyst of selectivity can not be produced continuously.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of new optionally catalyst for preparing propylene with propane dehydrogenation and its production and application of higher conversion of propane and propylene that has.
The composition of this catalyst for preparing propylene with propane dehydrogenation comprises, γ-Al
2O
3, the oxide of one or more chromium, one or more rare earth oxides, a kind of composition that one or more alkali metal oxides constitute, wherein γ-Al
2O
3Account for 50-95%, the oxide of chromium accounts for 3-40%, and rare earth oxide accounts for 0-20%, and alkaline-earth metal accounts for 0-10%.
The preparation method of this catalyst for preparing propylene with propane dehydrogenation adopts and add the method preparation that active component solution is regulated pH value generation gel then in alumina sol, and method is simple, and cost of material is low, is easy to large-scale production.
Catalyst provided by the invention carries out the preparing propylene by dehydrogenating propane reaction in circulating fluid bed reactor, help the carrying out of mass transfer and heat transfer, and reaction can be carried out continuously, and the conversion ratio and the selectivity of reaction are higher.
The specific embodiment
The composition of this dehydrogenating propane system propylene catalyst for reaction comprises γ-Al
2O
3, the oxide of one or more chromium, one or more rare earth oxides, one or more alkali metal oxides.γ-Al wherein
2O
3Account for 50-95%, preferred 80-92%.The oxide of chromium accounts for 3-40%, preferred 10-20%.Rare earth oxide accounts for 0-20%, preferred 1-10%.Alkaline-earth metal accounts for 0-10%, preferred 1-6%.。γ-Al
2O
3Can adopt aluminium hydroxide, aluminium colloidal sol or sour molten boehmite etc.Chromium salt solution is a chromic nitrate, solubility chromic salts such as chromic acetate.Rare earths salt is a lanthanum nitrate, solubility lanthanum salt or other rare earth metal soluble-salts such as lanthanum acetate, and for example: cerous nitrate, neodymium nitrate and ytterbium nitrate, alkaline-earth metal salt solution are potassium nitrate, potassium acetate, soluble potassium salt or otheralkali metal salt such as potash.After spray-dried, at first in nitrogen atmosphere 450-650 ℃ roasting 0-5 hour, then in the air atmosphere 550-800 ℃ roasting 1-20 hour, the valence state of chromium is+2 ,+3 ,+4 ,+6 price ratio surface areas are 145m
2/ g, apparent bulk density is 0.8-1.0g/ml, 0-40 micron＜22%v% in the size distribution, 0-140 micron＞90%v%, abrasion index＜3.0m%/h.
A method for optimizing of catalyst for preparing propylene with propane dehydrogenation provided by the present invention may further comprise the steps:
(1), boehmite is added the water making beating.
(2), add as chromium lanthanum, potassium isoreactivity component, stirring
(3), regulate pH value to 3 with red fuming nitric acid (RFNA).
(4), be spray dried to microballoon, roasting.
Wherein, active component can be with different charging sequence.Spray drying forming adopts conventional method and condition, and generally being controlled at exhaust temperature is 160-260 ℃, and atomisation pressure is to carry out under 50-60 the atmospheric condition.At first in nitrogen atmosphere 450-650 ℃ roasting 0-5 hour, nitrogen linear velocity 0-200cm/min, then in the air atmosphere 550-800 ℃ roasting 1-20 hour, the linear velocity 20-200cm/min of air.
Dehydrogenating propane reaction of the present invention can be carried out on fluidized-bed reactor, and reaction condition comprises: temperature is 500-700 ℃, and absolute pressure 0.01-0.2Mpa, volume space velocity are 300-2000h
-1The product of reaction is through supercooling, and pressurization separates and the refining propylene that obtains.
Method provided by the invention is particularly suitable for dehydrogenating propane and produces propylene, and described propane can be pure propane flammable gas, also can be liquefied gas or the casing-head gas that is rich in propane.
Conversion ratio and selectivity and productive rate calculate with following formula:
(Mi: the molal quantity of certain product; Ni: institute's carbon atom quantity in certain product molecule)
Further specify the present invention below by example, the composition of propane and product obtains with gas chromatographic analysis in embodiment and the Comparative Examples.
Embodiment 1
66 gram boehmites are added water 250ml water, stir 2 hours one-tenth pasty states, add 17.08 gram chromic nitrates and stirred 1 hour, adding 1.74 gram lanthanum nitrates then stirred one hour, regulate pH value to 3 with concentrated hydrochloric acid, when continuing to stir after 2 hours ageing 2,120 ℃ of dryings 10 hours.Be rapidly heated 550 ℃ and kept 5 hours under nitrogen atmosphere, the linear velocity of nitrogen is 100cm/min.Then nitrogen is switched to air, continue to be warmed up to 700 ℃ and keep cooling naturally after 1 hour.Screening 40-80 purpose is urged the specific area 146m of catalyst
2/ g,, apparent bulk density 1.0.
Embodiment 2
66 gram boehmites are added water 250ml water, stir 2 hours one-tenth pasty states, add 8.08 gram chromic nitrates and stirred 1 hour, adding 1.74 gram lanthanum nitrates then stirred one hour, regulate pH value to 3 with concentrated hydrochloric acid, when continuing to stir after 2 hours ageing 2,120 ℃ of dryings 10 hours.Be rapidly heated 550 ℃ and kept 5 hours under nitrogen atmosphere, the linear velocity of nitrogen is 100cm/min.Then nitrogen is switched to air, continue to be warmed up to 700 ℃ and keep cooling naturally after 1 hour.Screening 40-80 purpose is urged the specific area 144m of catalyst
2/ g,, apparent bulk density 1.0.
Embodiment 3
66 gram boehmites are added water 250ml water, stir 2 hours one-tenth pasty states, add 17.08 gram chromic nitrates and stirred 1 hour, add 1.74 gram lanthanum nitrates and 0.1 gram potassium nitrate stirring one hour then, regulate pH value to 3 with concentrated hydrochloric acid, when continuing to stir after 2 hours ageing 2,120 ℃ of dryings 10 hours.Be rapidly heated 550 ℃ and kept 5 hours under nitrogen atmosphere, the linear velocity of nitrogen is 100cm/min.Then nitrogen is switched to air, continue to be warmed up to 700 ℃ and keep cooling naturally after 1 hour.Screening 40-80 purpose is urged the specific area 144m of catalyst
2/ g,, apparent bulk density 1.0.
Embodiment 4
66 gram boehmites are added water 250ml water, stirs and became pasty state in 2 hours, add 17.08 gram chromic nitrates and stirred 1 hour, regulate pH value to 3, continue stirring after 2 hours during ageing 2,120 ℃ of dryings 10 hours with concentrated hydrochloric acid.Be rapidly heated 550 ℃ and kept 5 hours under nitrogen atmosphere, the linear velocity of nitrogen is 100cm/min.Then nitrogen is switched to air, continue to be warmed up to 700 ℃ and keep cooling naturally after 1 hour.Screening 40-80 purpose is urged the specific area 144m of catalyst
2/ g,, apparent bulk density 1.0.
Embodiment 5
66 gram boehmites are added water 250ml water, stir 2 hours one-tenth pasty states, add 17.08 gram chromic nitrates and stirred 1 hour, adding 0.1 gram potassium nitrate then stirred one hour, regulate pH value to 3 with concentrated hydrochloric acid, when continuing to stir after 2 hours ageing 2,120 ℃ of dryings 10 hours.Be rapidly heated 550 ℃ and kept 5 hours under nitrogen atmosphere, the linear velocity of nitrogen is 100cm/min.Then nitrogen is switched to air, continue to be warmed up to 700 ℃ and keep cooling naturally after 1 hour.Screening 40-80 purpose is urged the specific area 144m of catalyst
2/ g,, apparent bulk density 1.0.
Embodiment 6
With embodiment 1 catalyst in the small-sized fluidized bed reactor.Reaction condition: 590 ℃ of temperature, absolute pressure 0.105Mpa, air speed 900h-1.Calculate the conversion ratio of propane and the selectivity of propylene, the results are shown in table 1.
Embodiment 7
With embodiment 2 catalyst in the small-sized fluidized bed reactor.Reaction condition: 590 ℃ of temperature, absolute pressure 0.105Mpa, air speed 900h-1.Calculate the conversion ratio of propane and the selectivity of propylene, the results are shown in table 1.
Embodiment 8
With embodiment 3 catalyst in the small-sized fluidized bed reactor.Reaction condition: 590 ℃ of temperature, absolute pressure 0.105Mpa, air speed 900h-1.Calculate the conversion ratio of propane and the selectivity of propylene, the results are shown in table 1.
Embodiment 9
With embodiment 4 catalyst in the small-sized fluidized bed reactor.Reaction condition: 590 ℃ of temperature, absolute pressure 0.105Mpa, air speed 900h-1.Calculate the conversion ratio of propane and the selectivity of propylene, the results are shown in table 1.
Embodiment 10
With embodiment 5 catalyst in the small-sized fluidized bed reactor.Reaction condition: 590 ℃ of temperature, absolute pressure 0.105Mpa, air speed 900h-1.Calculate the conversion ratio of propane and the selectivity of propylene, the results are shown in table 1.
Comparative Examples 1
Make catalyst by patent GB2177317A method, in the small-sized fluidized bed reactor.Reaction condition: 590 ℃ of temperature, absolute pressure 0.105Mpa, air speed 900h-1.Calculate the conversion ratio of propane and the selectivity of propylene, the results are shown in table 1.
Comparative Examples 2
With embodiment 1 catalyst in the small-sized fluidized bed reactor.Reaction condition: 590 ℃ of temperature, absolute pressure 0.105Mpa, air speed 1600h-1.Calculate the conversion ratio of propane and the selectivity of propylene, the results are shown in table 1.
Comparative Examples 3
With embodiment 1 catalyst in the small-sized fluidized bed reactor.Reaction condition: 570 ℃ of temperature, absolute pressure 0.105Mpa, air speed 900h-1.Calculate the conversion ratio of propane and the selectivity of propylene, the results are shown in table 1.
Table 1
Claims (15)
1. one kind is used for dehydrogenating propane system propylene catalyst for reaction, and it is characterized by: this catalyst is by γ-Al
2O
3, the oxide of one or more chromium, one or more rare earth oxides, a kind of composition that one or more alkali metal oxides constitute, wherein γ-Al
2O
3Account for 30-95%, the oxide of chromium accounts for 1-50%, and rare earth oxide accounts for 0-30%, and alkaline-earth metal accounts for 0-10%.
2. preparation method by the described catalyst for preparing propylene with propane dehydrogenation of claim 1, it is characterized by: in alumina sol, add chromium salt solution, stirred 0-2 hour, add rare earth metal salt solutions again, stirred 0-2 hour, add alkali metal karst liquid again and stirred 0-2 hour, adjust pH becomes gel, spray-drying then to 1-5.Metal salt solution can adopt different addition sequences.In nitrogen atmosphere 250-750 ℃ roasting 0-5 hour, then in the air atmosphere 250-1000 ℃ roasting 0.1-20 hour.
3. according to the catalyst for preparing propylene with propane dehydrogenation of claim 1, it is characterized by γ-Al
2O
3Account for 30-95%, preferred 80-92%.
4. according to the catalyst for preparing propylene with propane dehydrogenation of claim 1, the oxide that it is characterized by chromium accounts for 1-50%, preferred 10-20%.
5. according to the catalyst for preparing propylene with propane dehydrogenation of claim 1, it is characterized by rare earth oxide and account for 0-30%, preferred 1-10%.
6. according to the catalyst for preparing propylene with propane dehydrogenation of claim 1, it is characterized by alkaline earth oxide and account for 0-10%, preferred 1-6%.
7. according to the catalyst for preparing propylene with propane dehydrogenation of claim 1, it is characterized by the oxide that rare earth oxide is a lanthanum.
8. according to the catalyst for preparing propylene with propane dehydrogenation of claim 1, it is characterized by the oxide that alkaline earth oxide is a potassium.
9. according to the catalyst for preparing propylene with propane dehydrogenation of claim 1, the oxide valence state that it is characterized by chromium is+2 ,+3 ,+4, and+6 valencys.
10. according to claim 1 and 2 described methods, it is characterized by chromium salt solution is chromic nitrate, solubility chromic salts such as chromic acetate, and in roasting process, form the oxide of different valence state chromium.
11. according to claim 1 and 2 described methods, it is characterized by rare earths salt is lanthanum nitrate, solubility lanthanum salt such as lanthanum acetate, and in roasting process, form the oxide of lanthanum.
12. according to claim 1 and 2 described methods, it is characterized by alkaline-earth metal salt solution is potassium nitrate, potassium acetate, and soluble potassium salts such as potash, and in roasting process, form the oxide of potassium.
13., it is characterized in that the specific area of this catalyst is＞50m according to the catalyst for preparing propylene with propane dehydrogenation of claim 1
2/ g, apparent bulk density is 0.5-1.5g/ml, in the size distribution, 0-140 micron＞90%v%, abrasion index＜10.0m%/h.
14., it is characterized in that the used reactor of described dehydrogenation reaction is a fluidized-bed reactor according to each described method of claim 1-13.
15. according to each described method of claim 1-13, it is characterized in that described dehydrogenation reaction conditions comprises: temperature is 400-700 ℃, absolute pressure 0.01-3.Mpa, volume space velocity are 10-10000h
-1
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