CN107398267A - A kind of catalyst for dehydrogenation of low-carbon paraffin and its preparation method and application - Google Patents
A kind of catalyst for dehydrogenation of low-carbon paraffin and its preparation method and application Download PDFInfo
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- CN107398267A CN107398267A CN201610343423.2A CN201610343423A CN107398267A CN 107398267 A CN107398267 A CN 107398267A CN 201610343423 A CN201610343423 A CN 201610343423A CN 107398267 A CN107398267 A CN 107398267A
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- catalyst
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- dehydrogenation
- carbon
- bead
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- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 36
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 24
- 239000012188 paraffin wax Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims description 13
- 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 30
- 239000011324 bead Substances 0.000 claims abstract description 26
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 150000001399 aluminium compounds Chemical class 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
- 238000001802 infusion Methods 0.000 claims abstract description 5
- 239000004411 aluminium Substances 0.000 claims abstract 2
- 229910052782 aluminium Inorganic materials 0.000 claims abstract 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000011651 chromium Substances 0.000 claims description 50
- 238000006243 chemical reaction Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 7
- 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 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 6
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910001593 boehmite Inorganic materials 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- -1 halide salt Chemical class 0.000 claims description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 3
- 239000001282 iso-butane Substances 0.000 claims description 3
- 235000013847 iso-butane Nutrition 0.000 claims description 3
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910001648 diaspore Inorganic materials 0.000 claims description 2
- 238000006197 hydroboration reaction Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 235000011837 pasties Nutrition 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 238000009938 salting Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229910006415 θ-Al2O3 Inorganic materials 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 238000005360 mashing Methods 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 238000009825 accumulation Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 235000013844 butane Nutrition 0.000 description 6
- QFSKIUZTIHBWFR-UHFFFAOYSA-N chromium;hydrate Chemical compound O.[Cr] QFSKIUZTIHBWFR-UHFFFAOYSA-N 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- 239000012279 sodium borohydride Substances 0.000 description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011796 hollow space material Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005839 oxidative dehydrogenation 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
- 239000012071 phase Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/24—Chromium, molybdenum or tungsten
- C07C2523/26—Chromium
-
- 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 present invention relates to one kind mixing aluminium compound and hollow hexagonal Cr (OH)3Bead prepares the methods and applications of catalyst for dehydrogenation of low-carbon paraffin.The technical scheme is that using aluminium compound as raw material, hollow hexagonal Cr (OH) is added3Carrier is made in bead, then loads to co-catalysis component by infusion process and the catalyst is obtained on carrier.The present invention adds hollow hexagonal Cr (OH) in aluminium compound3Bead, the co-catalysis component of alkali metal can be evenly distributed in the body phase of catalyst carrier after calcining；Adding alkali metal reduces the surface acidity of alumina material, so as to improve Cr series catalysts carbon accumulation resisting abilities, improves catalyst performance.
Description
Technical field
The present invention relates to a kind of catalyst for dehydrogenation of low-carbon paraffin and preparation method thereof, and in particular to one kind mixing calorize
Compound and hollow hexagonal Cr (OH)3Bead prepares the methods and applications of catalyst for dehydrogenation of low-carbon paraffin.
Background technology
China is an oil refining production capacity big country, and rising year by year for refining capacity causes the substantial amounts of C3-C4 hydrocarbon of by-product,
And China is very low to the utilization rate of refinery's mixed C4 hydrocarbon.In recent years, low-carbon alkene demand increases year by year, stone
Cerebrol rise in price, increasingly attracted attention with the technique of cheap manufacturing olefin by low-carbon alkane dehydrogenation, low-carbon alkanes take off
Hydrogen conversion can alleviate the low-carbon alkene contradiction that supply falls short of demand, be to realize natural gas, refinery gas and associated gas money
The important channel that source optimization utilizes, following application market have a extensive future.
Dehydrogenating low-carbon alkane reaction is limited by thermodynamical equilibrium, it is necessary to high temperature, low pressure reaction condition under
Carry out.Precious metals pt has been used to the industrialization of alkane alkene as a kind of excellent alkane dehydrogenating catalyst
In production, it is mainly that easily carbon distribution is made under its cost height and hot conditions to restrict its wide variety of factor at present
Into catalyst poisoning inactivation.Cr series catalysts costs are low, use Cr2O3/Al2O3During as dehydrogenation,
With higher catalytic activity, but due to the strong interaction between Cr and carrier so that active component is carrying
The decentralization in body surface face is relatively low, causes catalyst activity to reduce；Exist on simultaneous oxidation alumina supporter in substantial amounts of acid
The heart, cause in dehydrogenation reaction process rapid coking and cracking the problems such as, it is necessary to which repeated regeneration, shortens catalysis
The service life of agent, adds production cost.Therefore, using different activities component presoma, introducing alkali metal
Modifying agent is improved to catalyst, improves its catalytic activity and stability.
Chinese patent CN103933906 discloses a kind of chromium hydroxide nano-hollow with good catalytic
Structure.At room temperature, the nano-hollow material for possessing shell structurre is prepared using the method for liquid phase self assembly, and is transported
During using low-carbon alkanes low-temperature oxidative dehydrogenation.The catalyst prepared with the method takes off under the conditions of high temperature anaerobic
Hydrogen poor-performing, intensity is relatively low, and the structural stability difference problem of catalyst cannot be solved effectively.
Chinese patent CN668555A disclose it is a kind of containing aluminum oxide, chromium oxide, potassium oxide dehydrogenation,
The catalyst preferentially prepares alumina support, is then loaded to active component on carrier using infusion process, activity
Effect between component and carrier is weaker, and specific surface area of catalyst is small, active component in carrier surface skewness,
Catalyst activity is relatively low under the conditions of high-temperature low-pressure.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides that a kind of activity is high, stability is good, carbon accumulation resisting ability is strong
Catalyst for dehydrogenation of low-carbon paraffin and preparation method thereof.The present invention adds hollow hexagonal using aluminium compound as raw material
Cr(OH)3Carrier is made in bead, then loads to co-catalysis component by infusion process and the catalysis is obtained on carrier
Agent.The preparation process of the present invention is as follows：
(1) hollow hexagonal Cr (OH) is prepared3Bead：The hydroboration of various concentrations is added dropwise in soluble chromium salting liquid
Sodium solution forms blue suspension, and bead particle size increases and increased with the pH value of suspension, passes through regulation
The pH value control Cr (OH) of suspension3The granular size scope of bead is 10-1000 nanometers；
(2) alumina support containing Cr is prepared：With hollow hexagonal Cr (OH)3Bead uniformly mixes with aluminium compound,
Pasty state is beaten into water, then extrusion, drying, calcining；
(3) impregnate：The soluble-salt of co-catalysis component is miscible in solvent, and be added to that step (2) obtains contains
Cr alumina supports, co-catalysis component is supported on alumina support containing Cr using infusion process, passed through
100-120 DEG C of dry 12h, 500-550 DEG C of calcining 4h, produces catalyst for dehydrogenation of low-carbon paraffin.
Aluminium compound in the present invention is one kind in hydrated alumina or activated alumina；Using active metal as
Co-catalysis component；On the basis of the quality of catalyst, the content of chromic salts is calculated as 10-50wt% with chromium oxide,
The content of metal is calculated as 0.5-20wt% with oxide.
The hydrated alumina is the one or more in boehmite, boehmite, promise diaspore；It is described
Activated alumina is γ-Al2O3、θ-Al2O3、ρ-Al2O3、η-Al2O3、κ-Al2O3In one or more.
The metal as co-catalysis component be potassium, sodium, lithium, calcium, magnesium, lanthanum, zirconium, one kind in cerium or
It is several, its soluble-salt is prepared into solution.The soluble-salt of these metals is selected from nitrate, halide salt, carbon
One or more in hydrochlorate, acetate and sulfate.
Catalyst for dehydrogenation of low-carbon paraffin in the present invention can be applied to low-carbon alkanes catalytic dehydrogenation production low-carbon alkene
In the reaction of hydrocarbon, lower carbon number hydrocarbons includes one or more of mixtures in ethane, propane or iso-butane.
Hollow hexagonal Cr (OH) in the present invention3The preparation method of bead improves existing nano hollow structure system
Standby technical process is cumbersome, the problems such as environmental pollution, available for industrial substantial amounts of production；Prepared hollow six side
Shape Cr (OH)3Structure is a kind of new nano hollow structure, is not only also equipped with the characteristics of low-density excellent
The performances such as good heat endurance, big ratio surface, and the Cr formed afterwards through high-temperature roasting activation2O3As urging
Change the activated centre of reaction, be highly dispersed in the form of hallow nanoparticles on carrier, and form Cr- alkali and help
Agent-γ-Al2O3" sandwich " structure, experiment prove that this structure is more suitable for catalytic dehydrogenating reaction, show height
Active, selective and outstanding anti-carbon performance；On the other hand the co-catalysis component of alkali metal after calcining is promoted
It is evenly distributed in the body phase of catalyst carrier.Alkali metal is added in the present invention reduces the surface of alumina material
Acidity, so as to improve Cr series catalysts carbon accumulation resisting abilities, improve catalyst performance.
Embodiment
Technical scheme is further described with reference to embodiment, but embodiments of the present invention are not
The description being only limitted in embodiment.
Embodiment 1
(1) 10.63g six water chromium sulfates are weighed, 5ml water is dissolved in and forms solution A；2.19g NaBH4It is dissolved in 5
Ml water forms solution B, B is poured into Cr (OH) is formed in A3Bead, adjust Ph values using NaOH and change Cr (OH)3
Granular size is to 114 nanometers；
(2) by the Cr (OH) in step (1)3Bead be uniformly mixed into extrusion in 10g boehmites, drying,
Calcining generation alumina support containing Cr；
(3) 1.18g K are pressed2Liquor kalii acetici is added dropwise in O addition, then the stirring dipping 24 in 25 DEG C of water-baths
After hour, take out sample and be put into 100 DEG C of baking ovens dry 12h, then sample is put into Muffle furnace at 550 DEG C
Under the conditions of roasting 4h obtain required catalyst.
(4) catalyst efficiency is evaluated：Isobutane gas is put into preheating zone to be mixed, subsequently into reaction zone plus
Heat, reach predetermined temperature, it is formed gas into gas chromatographic analysis by drainer after reaction；By 10g
The catalyst of left and right is fitted into above-mentioned reactor, synthesis under normal pressure, 580 DEG C of mass space velocity 1.5/h, reaction temperature,
Evaluation result is as follows：Butanes conversion 54% during being somebody's turn to do, Propylene Selectivity 93.2%.
Embodiment 2
(1) the six water chromium sulfates for weighing 14.54g are dissolved in 5ml water formation solution A；10.96g NaBH4It is dissolved in 5ml
Water forms solution B, B is poured into Cr (OH) is formed in A3Bead, adjust Ph values using NaOH and change Cr (OH)3
Granular size is to 159 nanometers；
(2) by the Cr (OH) in step (1)3Bead be uniformly mixed into extrusion in 10g boehmites, drying,
Calcining generation alumina support containing Cr；
(3) 1.18g Na are pressed2Sodium carbonate liquor is added dropwise in O addition, and dipping is then stirred in 25 DEG C of water-baths
After 24 hours, take out sample and be put into 100 DEG C of baking ovens dry 12h, then sample is put into Muffle furnace at 550 DEG C
Under the conditions of roasting 4h obtain required catalyst；
(4) evaluating catalyst condition is as a result as follows with embodiment 1：Butanes conversion 52.6% during being somebody's turn to do, propylene
Selectivity is 92%.
Embodiment 3
(1) 1.2g Cr are pressed2O3Addition weigh six water chromium sulfates be dissolved in 10ml water formed solution A；0.76g
NaBH4It is dissolved in 10ml water and forms solution B, B is poured into Cr (OH) is formed in A3Bead, adjusted using NaOH
Save Ph values and change Cr (OH)3Granular size is to 222 nanometers；
(2) by the Cr (OH) in step (1)3Bead is uniformly mixed into the γ-Al that 10g particle diameters are 10nm2O3In
Extrusion, drying, calcining generation alumina support containing Cr；
(3) magnesium nitrate solution is added dropwise by 1.18g CaO addition, then the stirring dipping 24 in 25 DEG C of water-baths
After hour, take out sample and be put into 100 DEG C of baking ovens dry 12h, then sample is put into Muffle furnace at 550 DEG C
Under the conditions of roasting 4h obtain required catalyst；
(4) evaluating catalyst condition is as a result as follows with embodiment 1：Butanes conversion 50.8% during being somebody's turn to do, propylene
Selectivity is 92.3%.
Embodiment 4
(1) 1.2g Cr are pressed2O3Addition weigh six water chromium sulfates be dissolved in 10ml water formed solution A；0.76g
NaBH4It is dissolved in 10ml water and forms solution B, B is poured into Cr (OH) is formed in A3Bead, adjusted using NaOH
Save Ph values and change Cr (OH)3Granular size is to 114 nanometers；
(2) by the Cr (OH) in step (1)3Bead is uniformly mixed into the θ-Al that 10g particle diameters are 60nm2O3In
Extrusion, drying, calcining generation alumina support containing Cr；
(3) magnesium chloride solution is added dropwise by 1.18g MgO addition, then the stirring dipping 24 in 25 DEG C of water-baths
After hour, take out sample and be put into 100 DEG C of baking ovens dry 12h, then sample is put into Muffle furnace at 550 DEG C
Under the conditions of roasting 4h obtain required catalyst；
(4) evaluating catalyst condition is as a result as follows with embodiment 1：Butanes conversion 49.3% during being somebody's turn to do, propylene
Selectivity is 88.5%.
Embodiment 5
(1) 1.2g Cr are pressed2O3Addition weigh six water chromium sulfates be dissolved in 10ml water formed solution A；0.76g
NaBH4It is dissolved in 10ml water and forms solution B, B is poured into Cr (OH) is formed in A3Bead, adjusted using NaOH
Save Ph values and change Cr (OH)3Granular size is to 114 nanometers；
(2) by the Cr (OH) in step (1)3Bead is uniformly mixed into the η-Al that 10g particle diameters are 80nm2O3In
Extrusion, drying, calcining generation alumina support containing Cr；
(3) 1.18g ZrO are pressed2Addition be added dropwise chlorination zirconium solution, then in 25 DEG C of water-baths stir dipping
After 24 hours, take out sample and be put into 100 DEG C of baking ovens dry 12h, then sample is put into Muffle furnace at 550 DEG C
Under the conditions of roasting 4h obtain required catalyst；
(4) evaluating catalyst condition is as a result as follows with embodiment 1：Butanes conversion 48% during being somebody's turn to do, propylene choosing
Selecting property is 89.2%.
Embodiment 6
(1) 1.2g Cr are pressed2O3Addition weigh six water chromium sulfates be dissolved in 10ml water formed solution A；0.76g
NaBH4It is dissolved in 10ml water and forms solution B, B is poured into Cr (OH) is formed in A3Bead, adjusted using NaOH
Save Ph values and change Cr (OH)3Granular size is to 114 nanometers；
(2) by the Cr (OH) in step (1)3Bead is uniformly mixed into the κ-Al that 10g particle diameters are 10nm2O3In squeeze
Bar, drying, calcining generation alumina support containing Cr；
(3) 0.52g K are pressed2Sodium nitrate solution is added dropwise in O addition, then the stirring dipping 24 in 25 DEG C of water-baths
After hour, take out sample and be put into 100 DEG C of baking ovens dry 12h, then sample is put into Muffle furnace at 550 DEG C
Under the conditions of roasting 4h obtain required catalyst；
(4) evaluating catalyst condition is as a result as follows with embodiment 1：Butanes conversion 45.7% during being somebody's turn to do, propylene
Selectivity is 93.7%.
Claims (9)
- A kind of 1. catalyst for dehydrogenation of low-carbon paraffin, it is characterised in that：By the hollow hexagonal that particle diameter is 10-1000nm Cr(OH)3Bead is uniformly mixed with aluminium compound, and carrier is obtained by mashing, extrusion, drying and calcination, The one or more in potassium, sodium, lithium, calcium, magnesium, lanthanum, zirconium, cerium are loaded again as co-catalysis component.
- 2. a kind of preparation method of catalyst for dehydrogenation of low-carbon paraffin, it is characterised in that preparation process is as follows：(1) hollow hexagonal Cr (OH) is prepared3Bead：The hydroboration of various concentrations is added dropwise in soluble chromium salting liquid Sodium solution, blue suspension is formed, Cr (OH) is controlled by the pH value for adjusting suspension3The particle of bead is big Small is 10-1000nm；(2) alumina support containing Cr is prepared：With hollow hexagonal Cr (OH)3Bead uniformly mixes with aluminium compound, Pasty state is beaten into water, then extrusion, drying, calcining；(3) impregnate：Will be one or more of in co-catalysis component of potassium, sodium, lithium, calcium, magnesium, lanthanum, zirconium, cerium Soluble-salt is miscible in solvent, the alumina support containing Cr that step (2) obtains is added to, using infusion process Co-catalysis component is supported on alumina support containing Cr, by 100-120 DEG C of dry 12h, 500-550 DEG C 4h is calcined, produces catalyst for dehydrogenation of low-carbon paraffin.
- A kind of 3. preparation method of catalyst for dehydrogenation of low-carbon paraffin as claimed in claim 2, it is characterised in that：Institute Aluminium compound is stated as the one of which in hydrated alumina or activated alumina.
- A kind of 4. preparation method of catalyst for dehydrogenation of low-carbon paraffin as claimed in claim 3, it is characterised in that：Institute Hydrated alumina is stated as the one or more in boehmite, boehmite, promise diaspore；The active oxygen Change aluminium is γ-Al2O3、θ-Al2O3、ρ-Al2O3、η-Al2O3、κ-Al2O3In one or more.
- A kind of 5. preparation method of catalyst for dehydrogenation of low-carbon paraffin as claimed in claim 2, it is characterised in that：Institute Co-catalysis component is stated as the one or more in alkali metal potassium, sodium, lithium, calcium, magnesium, lanthanum, zirconium, cerium.
- A kind of 6. preparation method of catalyst for dehydrogenation of low-carbon paraffin as claimed in claim 2, it is characterised in that：Institute State one of the soluble-salt of co-catalysis component in nitrate, halide salt, carbonate, acetate and sulfate Kind is several.
- A kind of 7. preparation method of catalyst for dehydrogenation of low-carbon paraffin as claimed in claim 2, it is characterised in that：With On the basis of the gross mass of catalyst, the content of chromium oxide is 10-50wt%, and the content of co-catalysis component is with metal Oxide is calculated as 0.5-20wt%.
- A kind of 8. application of catalyst for dehydrogenation of low-carbon paraffin, it is characterised in that：The catalyst is applied to low-carbon alkanes In the reaction of catalytic dehydrogenation production low-carbon alkene.
- A kind of 9. application of catalyst for dehydrogenation of low-carbon paraffin as claimed in claim 8, it is characterised in that：It is described low Carbon hydrocarbon includes the one or more in ethane, propane or iso-butane.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113226540A (en) * | 2018-12-28 | 2021-08-06 | Sk燃气 株式会社 | Catalyst for the production of olefins comprising an oxygen carrier material and a dehydrogenation catalyst |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113226540A (en) * | 2018-12-28 | 2021-08-06 | Sk燃气 株式会社 | Catalyst for the production of olefins comprising an oxygen carrier material and a dehydrogenation catalyst |
| CN113226540B (en) * | 2018-12-28 | 2024-03-26 | Sk燃气 株式会社 | Catalyst for olefin production comprising oxygen carrier material and dehydrogenation catalyst |
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