CN115970673A - Chromium-based alkane dehydrogenation catalyst and preparation method thereof - Google Patents
Chromium-based alkane dehydrogenation catalyst and preparation method thereof Download PDFInfo
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- CN115970673A CN115970673A CN202211660649.7A CN202211660649A CN115970673A CN 115970673 A CN115970673 A CN 115970673A CN 202211660649 A CN202211660649 A CN 202211660649A CN 115970673 A CN115970673 A CN 115970673A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 81
- 239000011651 chromium Substances 0.000 title claims abstract description 38
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 24
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 24
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 150000001335 aliphatic alkanes Chemical class 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000003381 stabilizer Substances 0.000 claims abstract description 12
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 6
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- 239000002243 precursor Substances 0.000 claims description 17
- 239000011148 porous material Substances 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 9
- 239000001099 ammonium carbonate Substances 0.000 claims description 9
- 238000001694 spray drying Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 239000004005 microsphere Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 6
- 238000001935 peptisation Methods 0.000 claims description 6
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims 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 description 4
- 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 4
- 239000000203 mixture Substances 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- -1 aluminum ions Chemical class 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000012047 saturated solution Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical group [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical group [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 2
- 239000012716 precipitator Substances 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 18
- 238000011069 regeneration method Methods 0.000 description 13
- 230000008929 regeneration Effects 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000001294 propane Substances 0.000 description 9
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 7
- GVHCUJZTWMCYJM-UHFFFAOYSA-N chromium(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GVHCUJZTWMCYJM-UHFFFAOYSA-N 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910000423 chromium oxide Inorganic materials 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 238000000465 moulding Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000011865 Pt-based catalyst Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000000306 component Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910019923 CrOx Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- VZJJZMXEQNFTLL-UHFFFAOYSA-N chloro hypochlorite;zirconium;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Zr].ClOCl VZJJZMXEQNFTLL-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention belongs to the field of alkane dehydrogenation catalysts, and particularly relates to a preparation method of a chromium-based alkane dehydrogenation catalyst. The catalyst prepared by the method comprises an active component Cr, a stabilizer A, an auxiliary agent B and a carrier, wherein A is one or more of Ti and Zr, and B is one or more of alkali metal or alkaline earth metal.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a chromium-based alkane dehydrogenation catalyst and a preparation method thereof.
Background
The alkane dehydrogenation technology has been industrialized, and the catalysts used at present mainly have two types: pt-based catalysts and CrOx-based catalysts. The cost of the Pt-based catalyst is too highAnd is sensitive to poisons such as sulfur, olefin and the like, so the requirements on raw materials are strict and the raw materials need to be pretreated. The Cr-based catalyst has the advantages of low price, high alkane conversion rate and the like, but is easy to coke and quickly deactivate, and needs to be repeatedly regenerated; in the industry, the one-way operation period of the Cr-based catalyst is only 15-30 min, and frequent scorching regeneration greatly influences the physical and chemical structure of the catalyst, thus finally leading to the deactivation of the catalyst. Firstly, the specific surface area of the catalyst is reduced with the increase of the reaction time, the increase of the reaction temperature and the increase of the number of reduction-dehydrogenation-regeneration cycles, and secondly, the frequent high-temperature regeneration easily causes the sintering of Cr active centers and easily causes the surface phase Cr to migrate to the bulk phase to form stable Cr 2 O 3 -Al 2 O 3 Spinel structure, thereby deactivating the catalyst.
CN 104148070 discloses a low-carbon alkane dehydrogenation catalyst containing framework silver, which adopts aluminum oxide containing silver as a carrier, chromium oxide as an active component, and sodium, potassium, calcium, copper, zirconium, silver and the like as auxiliaries, and can improve the stability and carbon deposition resistance of the catalyst. CN 103769156 discloses a dehydrogenation catalyst and its preparation method, which adopts ammonia-treated alumina as carrier, chromium as active component, and potassium and manganese, cobalt, iron, nickel, copper as auxiliary agent, and has the advantages of low content of chromium oxide, high activity, good propylene selectivity, etc. CN 102019178A reports a catalyst for preparing propylene by propane dehydrogenation, and preparation and application thereof, wherein the content of chromium oxide is 10-20%, the reaction temperature is 590 ℃, the absolute pressure is 0.105MPa, and the space velocity is 900 hours -1 Under the condition, the conversion rate of propane is 40% and the selectivity of propylene is 85% when the reaction is carried out for 5 min. CN101940922B reports a low-carbon alkane dehydrogenation catalyst and a preparation method thereof, wherein chromium is used as an active metal component, chromium-containing alumina is used as a carrier, the weight content of chromium oxide in the carrier is 2.0-15.0%, and the catalyst activity is improved. CN101940922A reports a low-carbon alkane dehydrogenation catalyst, which uses Cr as an active component and alkali metal as an auxiliary agent, and has a propane conversion rate of 47% and a propylene selectivity of about 89% when the catalyst is reacted for 30 minutes at a reaction temperature of 645 ℃ and a liquid hourly space velocity of 600 h-1 under normal pressure. The above patents mainly improve the conversion rate and selectivity of the catalystOr single pass stability, without concern for catalyst deactivation by cyclic regeneration at high temperatures.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a chromium-based alkane dehydrogenation catalyst which is a novel Cr-based alkane dehydrogenation catalyst and has higher conversion rate and selectivity.
It is another object of the present invention to provide a process for preparing the above-mentioned catalyst.
In order to realize the purpose of the invention, the following technical scheme is specifically adopted:
a chromium-based alkane dehydrogenation catalyst comprises an active component Cr, a stabilizer A, an auxiliary agent B and a carrier; the active component accounts for 10 to 35 percent of the total weight of the catalyst by the content of the oxide; the stabilizer A accounts for 0.1 to 5 percent of the total weight of the catalyst by the content of oxides; the auxiliary agent B accounts for 0.1 to 3 percent of the total weight of the catalyst by the content of the oxide; the balance of carrier, the sum of the total mass percentage is 100%.
Further, the oxide of the active component Cr is Cr 2 O 3 The precursor material is chromium nitrate.
Further, the stabilizer A is any one or a mixture of two of Ti and Zr; the precursor of the stabilizer A is any one or more of zirconium oxychloride, zirconyl nitrate and titanium tetrachloride.
Furthermore, the assistant B is any one or a mixture of more of alkali metals or alkaline earth metals; the precursor of the auxiliary agent B is nitrate or chloride of alkali metal or alkaline earth metal;
further, the carrier is alumina; the precursor of the carrier is aluminum nitrate and aluminum trichloride.
As a preferred embodiment of the present application, the preparation method of the chromium-based alkane dehydrogenation catalyst comprises the following steps:
a. dissolving a precursor of the active component, a precursor of the stabilizer A and a precursor of the carrier in water, and uniformly stirring to obtain a solution; then slowly dripping a precipitator to ensure that the pH value of the solution is 9.0-11.0;
b. heating the substance obtained in the step a to 50-90 ℃, and aging for 4-48 h; then, carrying out spray drying to obtain microsphere powder with peptization performance;
c. b, adding a proper amount of acid and a precursor solution of the auxiliary B into the powder obtained in the step B, uniformly mixing, extruding and forming; and then drying and roasting to obtain the catalyst.
Further, the solution in step a is a saturated solution of aluminum ions.
Further, the precipitant is any one of ammonium carbonate and ammonium bicarbonate.
Furthermore, the acid in the step c is any one of nitric acid and hydrochloric acid, and the mole number of the added acid is 3-20% of the total mole number of Al and Cr.
Preferably, the drying temperature in the step c is 80-120 ℃, and the drying time is 4-10 h; the roasting temperature is 600-1000 ℃, and the roasting time is 4-10 h.
A catalyst prepared by any one of the methods described above, the catalyst having a specific surface area of < 150m 2 Pore volume < 0.45ml/g.
Compared with the prior art, the positive effects of the invention are as follows:
the method comprises the following steps of (I) adding a proper amount of acid into powder, wherein the selected acid can not only enable the powder to generate viscosity and improve the strength of a catalyst, but also can act with part of chromium precipitates, so that the bulk phase and the surface phase of the catalyst are more reasonably distributed, and bulk phase chromium acts with aluminum, so that the action of a surface phase chromium element and aluminum oxide can be inhibited, and the stability of the catalyst is improved.
The invention avoids the pore channel blockage caused by soaking the chromium precursor, increases large pore channels by high-temperature roasting decomposition of the ammonium salt generated in the synthesis step, is beneficial to quick overflow of reaction products, and improves the selectivity of target products.
And (III) preparing an aluminum ion saturated solution and performing subsequent precipitation aging operation to obtain the catalyst with smaller specific surface area and smaller pore volume, so that the pore structure is more stable, and meanwhile, a stabilizer is added in the preparation process of the catalyst, so that the pore channel of the catalyst is not easy to collapse at high temperature, and the regeneration stability of the catalyst is favorably improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The test method for the evaluation results of the catalyst in the following examples is as follows: weighing 4.4g of the prepared catalyst, carrying out performance evaluation on a fixed bed device, feeding materials according to the volume ratio of propane to nitrogen being 1, wherein the reaction temperature is 575 ℃, and the propane mass space velocity is 0.7h -1 The evaluation result is instantaneous data at 5min of feeding.
Example 1
Weighing 68.45g of chromium nitrate nonahydrate, 618.10g of aluminum nitrate nonahydrate and 5.82g of zirconium oxychloride octahydrate, adding a proper amount of water to ensure that the aluminum nitrate nonahydrate is just completely dissolved, uniformly stirring, adding a proper amount of ammonium carbonate, adjusting the pH to 9.5, heating to 50 ℃, standing and aging for 24 hours, obtaining microsphere powder with peptizing performance by spray drying (the spray drying can be carried out by adopting the conventional technology in the industry), adding an aqueous solution containing 2.15g of potassium nitrate and 0.25mol of HNO into the powder 3 Extruding and forming, drying at 80 ℃ for 10h, and roasting at 600 ℃ for 6h to obtain a catalyst;
the specific surface area of the catalyst was determined to be 143m 2 The pore volume was 0.38ml/g. The catalyst evaluation results show that: the propane conversion was 44.26% with a selectivity of 90.33%.
Example 2
Weighing 94.77g of chromium nitrate nonahydrate, 210.55g of aluminum trichloride and 1.88g of zirconyl nitrate, adding a proper amount of water to ensure that the aluminum trichloride is just completely dissolved, uniformly stirring, adding a proper amount of ammonium bicarbonate, adjusting the pH to 10.2, then heating to 80 ℃, standing and aging for 12h, obtaining microsphere powder with peptization performance by spray drying, adding an aqueous solution containing 0.78g of magnesium nitrate hexahydrate and 0.71g of sodium chloride and 0.11mol of HCl, extruding, molding, drying at 120 ℃ for 4h, and roasting at 750 ℃ for 8h to obtain a catalyst;
the specific surface area of the catalyst is 128m2, and the pore volume is 0.33ml/g. The catalyst evaluation results show that: the propane conversion was 42.79% with a selectivity of 91.68%.
Example 3
Weighing 115.83g of chromium nitrate nonahydrate, 537.16g of aluminum nitrate nonahydrate, 3.42g of zirconyl nitrate and 2.80g of titanium tetrachloride, adding a proper amount of water to ensure that the aluminum nitrate nonahydrate is completely dissolved, uniformly stirring, adding a proper amount of ammonium bicarbonate, adjusting the pH to 10.8, heating to 70 ℃, standing and aging for 36 hours, obtaining microsphere powder with peptization performance by spray drying, adding an aqueous solution containing 3.96g of calcium chloride and 0.15mol of HNO 3 Extruding and molding, drying at 100 ℃ for 6h, and roasting at 900 ℃ for 5h to obtain a catalyst;
the specific surface area of the catalyst is 98m2, and the pore volume is 0.37ml/g. The catalyst evaluation results show that: the propane conversion was 43.79% with a selectivity of 92.74%.
Example 4
Weighing 136.89g of chromium nitrate nonahydrate, 192.50g of aluminum trichloride and 0.47g of titanium tetrachloride, adding a proper amount of water to ensure that the aluminum trichloride is just completely dissolved, uniformly stirring, adding a proper amount of ammonium bicarbonate, adjusting the pH to 9.2, heating to 90 ℃, standing and aging for 7 hours, spray-drying to obtain microsphere powder with peptization performance, adding an aqueous solution containing 0.92g of lithium nitrate and 0.16mol of HCl, extruding and molding, drying at 120 ℃ for 4 hours, and roasting at 800 ℃ for 5 hours to obtain a catalyst;
the specific surface area of the catalyst is 133m2, and the pore volume is 0.42ml/g. The catalyst evaluation results show that: the propane conversion was 45.79% with a selectivity of 90.21%.
Example 5
Weighing 94.77g of chromium nitrate nonahydrate, 588.67g of aluminum nitrate nonahydrate and 2.81g of zirconyl nitrate, adding a proper amount of water to ensure that the aluminum nitrate nonahydrate is just completely dissolved, uniformly stirring, adding a proper amount of ammonium bicarbonate, adjusting the pH to 10.4, heating to 70 ℃, standing and aging for 48 hours, obtaining microsphere powder with peptizing performance by spray drying, adding an aqueous solution containing 2.15g of potassium nitrate and 0.20mol of HNO 3 Extruding and forming, drying at 120 ℃ for 9h, and roasting at 950 ℃ for 7h to obtain a catalyst; the specific surface area of the catalyst is 92m2, and the pore volume is 0.35ml/g. The catalyst evaluation results were as follows:
| conversion rate | Selectivity is | |
| Initial | 45.42％ | 92.45％ |
| Regenerated ten times | 45.69％ | 92.40％ |
| Regenerated fifty times | 45.02％ | 92.68％ |
| Regeneration is carried out for one hundred times | 45.73％ | 92.78％ |
| Regeneration for two hundred times | 45.23％ | 92.36％ |
Comparative example 1
The difference from example 5 is that chromium nitrate nonahydrate was introduced by means of impregnation. The specific surface area of the catalyst is 82.48m 2 The pore volume is 0.24ml/g. The catalyst evaluation results were as follows
| Conversion rate | Selectivity is | |
| Initial | 42.70％ | 91.86％ |
| Regenerated ten times | 42.54％ | 92.38％ |
| Regeneration is carried out for fifty times | 42.69％ | 92.01％ |
| Regeneration is carried out for one hundred times | 41.92％ | 92.66％ |
| Regeneration for two hundred times | 41.48％ | 92.72％ |
The comparison of example 5 with comparative example 1 shows that the catalyst prepared in example 5 has better stability and higher conversion rate.
Comparative example 2
The difference from example 5 is: the amount of water in which the aluminum nitrate nonahydrate solution was dissolved in comparative example 2 wasExample 5 the amount of water of the solution was 3 times. Comparative example 2 the catalyst had a specific surface area of 167m 2 The pore volume was 0.55ml/g, and the catalyst evaluation results were as follows:
the comparison of example 5 with comparative example 2 shows that the catalyst prepared in example 5 has better stability and higher selectivity.
Comparative example 3
The difference from the example 5 is that the microsphere powder with peptization performance is directly obtained by spray drying without standing and aging for 48 hours. Specific surface area of the catalyst is 172.4m 2 Per g, pore volume 0.46ml/g.
| Conversion rate | Selectivity is | |
| Initial | 47.42％ | 91.33％ |
| Regenerated ten times | 46.69％ | 91.69％ |
| Regeneration is carried out for fifty times | 43.08％ | 92.97％ |
| Regenerating for one hundred times | 41.43％ | 93.06％ |
| Regeneration for two hundred times | 40.31％ | 93.22％ |
Example 5 compares to comparative example 3, and although comparative example 3 has a higher initial activity, the regeneration stability is inferior to example 5.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The chromium-based alkane dehydrogenation catalyst is characterized by comprising an active component Cr, a stabilizer A, an auxiliary agent B and a carrier; the active component accounts for 10 to 35 percent of the total weight of the catalyst by the content of the oxide; the stabilizer A accounts for 0.1 to 5 percent of the total weight of the catalyst by the content of oxides; the auxiliary agent B accounts for 0.1 to 3 percent of the total weight of the catalyst by the content of the oxide; the balance being carrier, the total mass being 100%.
2. The chromium-based alkane dehydrogenation catalyst of claim 1, wherein: the oxide of the active component Cr is Cr 2 O 3 The precursor material is chromium nitrate.
3. The chromium-based alkane dehydrogenation catalyst of claim 1, wherein: the stabilizer A is any one or a mixture of two of Ti and Zr; the precursor of the stabilizer A is any one or more of zirconium oxychloride, zirconyl nitrate and titanium tetrachloride.
4. The chromium-based alkane dehydrogenation catalyst of claim 1, wherein: the auxiliary agent B is any one or a mixture of more of alkali metals or alkaline earth metals; the precursor of the assistant B is nitrate or chloride of alkali metal or alkaline earth metal.
5. The chromium-based alkane dehydrogenation catalyst of claim 1, wherein: the carrier is alumina; the precursor of the carrier is aluminum nitrate or aluminum trichloride.
6. The method of preparing a chromium-based alkane dehydrogenation catalyst according to any one of claims 1 to 5, characterized by comprising the steps of:
a. dissolving a precursor of the active component, a precursor of the stabilizer A and a precursor of the carrier in water, and uniformly stirring to obtain a solution; then slowly dripping a precipitator to ensure that the pH value of the solution is 9.0-11.0;
b. heating the substance obtained in the step a to 50-90 ℃, and aging for 4-48 h; then, carrying out spray drying to obtain microsphere powder with peptization performance;
c. b, adding a proper amount of acid and a precursor solution of the auxiliary B into the powder obtained in the step B, uniformly mixing, extruding and forming; and then drying and roasting to obtain the catalyst.
7. The method of preparing a chromium-based alkane dehydrogenation catalyst of claim 6, wherein: the solution in the step a is saturated solution containing aluminum ions; the precipitant is one of ammonium carbonate and ammonium bicarbonate.
8. The method of preparing a chromium-based alkane dehydrogenation catalyst of claim 6, wherein: the acid in the step c is any one of nitric acid and hydrochloric acid, and the mole number of the added acid is 3-20% of the total mole number of Al and Cr.
9. The method of preparing a chromium-based alkane dehydrogenation catalyst of claim 6, wherein: the drying temperature in the step c is 80-120 ℃, and the drying time is 4-10 h; the roasting temperature is 600-1000 ℃, and the roasting time is 4-10 h.
10. A catalyst prepared according to the method of any one of claims 7 to 9, wherein: the specific surface area of the catalyst is less than 150m 2 Pore volume < 0.45ml/g.
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