CN118162186B - Propane dehydrogenation catalyst and preparation method and application thereof - Google Patents
Propane dehydrogenation catalyst and preparation method and application thereof Download PDFInfo
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 239000003054 catalyst Substances 0.000 title claims abstract description 139
- 239000001294 propane Substances 0.000 title claims abstract description 73
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 218
- 239000000243 solution Substances 0.000 claims description 64
- 238000001354 calcination Methods 0.000 claims description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 53
- 229910001868 water Inorganic materials 0.000 claims description 53
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 45
- BNKWCSJBOZKTJL-UHFFFAOYSA-N [Co].[N].[S] Chemical compound [Co].[N].[S] BNKWCSJBOZKTJL-UHFFFAOYSA-N 0.000 claims description 37
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 34
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 27
- 239000011259 mixed solution Substances 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 25
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 23
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 239000003513 alkali Substances 0.000 claims description 21
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 20
- 235000010413 sodium alginate Nutrition 0.000 claims description 20
- 239000000661 sodium alginate Substances 0.000 claims description 20
- 229940005550 sodium alginate Drugs 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 18
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 17
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 17
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 16
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 238000000498 ball milling Methods 0.000 claims description 14
- 229960002089 ferrous chloride Drugs 0.000 claims description 14
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 14
- 239000011575 calcium Substances 0.000 claims description 12
- 230000001804 emulsifying effect Effects 0.000 claims description 12
- 239000002077 nanosphere Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- INDBQWVYFLTCFF-UHFFFAOYSA-L cobalt(2+);dithiocyanate Chemical compound [Co+2].[S-]C#N.[S-]C#N INDBQWVYFLTCFF-UHFFFAOYSA-L 0.000 claims description 10
- 239000002585 base Substances 0.000 claims description 9
- 239000003995 emulsifying agent Substances 0.000 claims description 9
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 9
- 229920000053 polysorbate 80 Polymers 0.000 claims description 9
- 230000005307 ferromagnetism Effects 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 229910001424 calcium ion Inorganic materials 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 3
- 239000008157 edible vegetable oil Substances 0.000 claims description 3
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 3
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 3
- 239000012495 reaction gas Substances 0.000 claims description 3
- -1 tween-40 Polymers 0.000 claims description 3
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 31
- 230000000694 effects Effects 0.000 abstract description 18
- 229910052751 metal Inorganic materials 0.000 abstract description 13
- 239000002184 metal Substances 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 238000006555 catalytic reaction Methods 0.000 abstract description 9
- 238000011068 loading method Methods 0.000 abstract description 6
- 230000002035 prolonged effect Effects 0.000 abstract description 6
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 22
- 238000000151 deposition Methods 0.000 description 20
- 230000008021 deposition Effects 0.000 description 19
- 239000011148 porous material Substances 0.000 description 17
- 239000011651 chromium Substances 0.000 description 10
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 230000006872 improvement Effects 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 239000003549 soybean oil Substances 0.000 description 8
- 235000012424 soybean oil Nutrition 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 239000012752 auxiliary agent Substances 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 229910052718 tin Inorganic materials 0.000 description 6
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 5
- 229910000423 chromium oxide Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000011865 Pt-based catalyst Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 230000003313 weakening effect Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000002285 corn oil Substances 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention provides a propane dehydrogenation catalyst, a preparation method and application thereof, and belongs to the technical field of organic catalysis. The preparation method is simple, the loading amount of active metal and the adsorption amount of propane are improved, the reaction activity is improved, the selectivity of the catalyst to propane is high, the reaction yield is high, the reaction temperature is reduced, the generation of carbon deposit is reduced, the catalytic service life of the catalyst is greatly prolonged, the catalyst is convenient to separate and reuse, the catalytic activity for reuse is high, the thermal stability is good, noble metal does not need to be added, the cost is low, and the catalyst has wide application prospect.
Description
Technical Field
The invention relates to the technical field of organic catalysis, in particular to a propane dehydrogenation catalyst and a preparation method thereof, and a method for preparing propylene by propane dehydrogenation.
Background
The propane dehydrogenation technology is industrialized at present, the catalyst systems are Pt-based catalyst and Cr-based catalyst, the main dehydrogenation technology comprises an Oleflex process of UOP, a Catofin process of Lummas, a STAR process of Uhde, a PDH process of Linde, an FBD process cooperatively developed by Snamprogetti-Yarsintez and the like, wherein the most industrialized devices are the Oleflex technology and the Catofin technology, and the catalysts applied by the two technologies are Pt-based catalyst and Cr-based catalyst respectively. The Pt-based dehydrogenation catalyst is used for dehydrogenating low-carbon alkane, has the advantages of environmental friendliness, higher activity and the like, but has higher price, higher preparation complexity and higher purity requirement on reaction raw materials, and the catalyst is easy to have the phenomena of aggregation, sintering, enlarged Pt particles and the like of Pt components at high temperature, so that the problems of quicker activity reduction, poorer stability and the like are caused; and the agglomeration of Pt component and particle size during the reaction process become large, resulting in an irreversible regeneration process. The Cr catalyst has low price, relatively high activity and lower requirement on raw material purity, but has certain influence on the environment, meanwhile, the carbon deposition condition on the surface of the catalyst is more serious than that of Pt, the reaction process needs frequent regeneration, particularly the dehydrogenation conditions such as rapid coking, frequent carbon burning and cyclic regeneration of hot air in the reaction are harsh, and the performance requirements on all aspects of the Cr catalyst are higher, so that the dehydrogenation catalyst with excellent performance needs to be actively researched and developed for propane dehydrogenation reaction.
The dehydrogenation catalyst described in CN100406415C has a chromium oxide content of 5-30% and in example 1 the actual chromium oxide content is about 24%, which is a high Cr catalyst. The Catofin process developed by american chemical company, reported in patent No. EP192059, GB2162082, uses a chromia-alumina catalyst, activated aluminum pellets impregnated with 18-20wt% chromium, and, at a slight negative pressure of 49KPa, fresh propane and recycled propane are mixed and then preheated to a temperature of 550-750 ℃ (which preferably ranges from 620-670 ℃), operating at an absolute propane conversion per pass of 55-60mol% with a propylene concentration of around 52%. Patent No. CN102019178A reports a catalyst for preparing propylene by dehydrogenating propane, the content of chromium oxide is 10-20%, the reaction temperature is 590 ℃, the absolute pressure is 0.105MPa, the conversion rate of propane is 40% when the reaction is carried out for 5min under the condition of space velocity of 900 hours -1, and the propylene selectivity is 85%. Patent number 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 the chromium oxide in the carrier is 2.0-15.0%, the activity of the catalyst is improved, and the like. The patent No. CN101940922A reports a low-carbon alkane dehydrogenation catalyst, which takes Cr as an active component and alkali metal as an auxiliary agent, and the conversion rate of propane is 47% and the selectivity of propylene is about 89% when the reaction is carried out for 30 minutes at the reaction temperature of 645 ℃ and the liquid hourly space velocity of 600 hours -1 under normal pressure. The catalyst has better activity, but the content of the chromium oxide is up to 10-45% based on the weight of the catalyst, and no doubt, the catalyst has higher requirements on environmental protection. According to laboratory verification of the inventor, the catalyst is easy to accumulate carbon and has lower stability.
The propane dehydrogenation catalyst has been greatly developed at present, but has problems of low catalyst activity and the like, and particularly the existing Cr dehydrogenation catalyst has insufficient selectivity, stability and the like although the activity of the catalyst is improved by using alkali metal elements or transition metal elements as auxiliary agents.
Disclosure of Invention
The invention aims to provide a propane dehydrogenation catalyst, a preparation method thereof and a method for preparing propylene by propane dehydrogenation, which overcome the defects of the prior art, and have the advantages of simple preparation method, high selectivity, high reaction yield, reduced reaction temperature, reduced carbon deposition, convenient separation and repeated use, high catalytic activity, good thermal stability, no need of adding noble metal and low cost, wherein the loading amount of active metal and the adsorption amount of propane are improved, and the catalyst is prepared by the method.
The technical scheme of the invention is realized as follows:
The invention provides a preparation method of a propane dehydrogenation catalyst, which comprises the steps of preparing a spherical Al 2O3/ZrO2 carrier, sequentially immersing the spherical Al 2O3/ZrO2 carrier in an ethanol solution containing tin chloride and a solution containing Ga 2O3, calcining, adding the spherical Al 2O3/ZrO2 carrier into water containing cobalt thiocyanate, calcining, depositing magnetic ferroferric oxide on the surface, immersing the spherical Al 2O3/ZrO2 carrier in an immersion liquid containing alkali, zirconium nitrate and magnesium nitrate, volatilizing a solvent, and calcining to obtain the propane dehydrogenation catalyst.
As a further improvement of the invention, the method comprises the following steps:
S1, preparing a spherical Al 2O3/ZrO2 carrier containing Sn/Ga: uniformly mixing pseudo-boehmite and zirconia powder by ball milling, and adding the mixture into an aqueous solution containing sodium alginate and an emulsifier to obtain a water phase; dropwise adding the water phase into edible oil, emulsifying, dropwise adding a calcium ion solution, solidifying at normal temperature, centrifuging, adding the prepared nanospheres into an acetic acid solution, stirring for reaction, centrifuging, washing, drying and calcining to obtain a spherical Al 2O3/ZrO2 carrier; dissolving tin chloride in ethanol, adding Ga 2O3 to obtain a mixed solution, immersing a spherical Al 2O3/ZrO2 carrier in the mixed solution, and calcining to obtain a spherical Al 2O3/ZrO2 carrier containing Sn/Ga;
S2, doping cobalt sulfur nitrogen: dispersing the spherical Al 2O3/ZrO2 carrier containing Sn/Ga prepared in the step S1 in water, adding cobalt thiocyanate, volatilizing a solvent, and calcining to prepare a cobalt-sulfur-nitrogen doped spherical Al 2O3/ZrO2 catalyst containing Sn/Ga;
s3, ferromagnetism modification: dispersing the cobalt sulfur nitrogen doped Sn/Ga containing spherical Al 2O3/ZrO2 catalyst prepared in the step S2 in water, adding ferric chloride and ferrous chloride under the protection of inert gas, regulating the pH value of the solution, heating, stirring, reacting, centrifuging, washing, drying and calcining to obtain the magnetic cobalt sulfur nitrogen doped Sn/Ga containing spherical Al 2O3/ZrO2 catalyst;
s4, preparing an impregnating solution: dissolving alkali, zirconium nitrate and magnesium nitrate in water to obtain an impregnating solution;
S5, preparing a propane dehydrogenation catalyst: and (3) adding the magnetic cobalt sulfur nitrogen doped Sn/Ga-containing spherical Al 2O3/ZrO2 catalyst prepared in the step (S3) into the impregnating solution prepared in the step (S4), heating to volatilize the solvent, and calcining to prepare the propane dehydrogenation catalyst.
As a further improvement of the invention, in the step S1, the mass ratio of the pseudo-boehmite to the zirconia powder is 12-15:3-5, the ball milling time is 2-4 hours, the concentration of sodium alginate in the aqueous solution containing sodium alginate and an emulsifier is 15-20wt%, the concentration of the emulsifier is 1-2wt%, the emulsifier is at least one of Tween-20, tween-40, tween-60 and Tween-80, the concentration of the acetic acid solution is 10-12wt%, and the mass ratio of the stannic chloride, ga 2O3 and ethanol is 7-10:3-5:50.
As a further improvement of the invention, the mass ratio of the Sn/Ga-containing spherical Al 2O3/ZrO2 carrier to the cobalt thiocyanate in the step S2 is 15-20:3-5, the calcination is carried out under the protection of inert gas, the calcination temperature is 800-900 ℃, and the calcination time is 1-3h.
As a further improvement of the invention, in the step S3, the mass ratio of the cobalt sulfur nitrogen doped Sn/Ga-containing spherical Al 2O3/ZrO2 catalyst to the ferric chloride is 15-20:5-7, the molar ratio of the ferric chloride to the ferrous chloride is 2:1, the pH value of the solution is adjusted to 9-10, the temperature of the heating and stirring reaction is 75-85 ℃, the time is 3-5h, the calcining temperature is 500-700 ℃, and the time is 1-3h.
As a further improvement of the present invention, the mass ratio of the alkali, zirconium nitrate, magnesium nitrate and water in step S4 is 2-4:5-7:10-15:100, and the alkali is at least one selected from potassium carbonate, naOH, KOH, ca (OH) 2 and sodium carbonate, preferably a mixture of NaOH and Ca (OH) 2, and the mass ratio is 5-7:2.
As a further improvement of the invention, the mass ratio of the magnetic cobalt sulfur nitrogen doped Sn/Ga-containing spherical Al 2O3/ZrO2 catalyst to the impregnating solution in the step S5 is 15-20:70, the heating temperature is 70-80 ℃, the calcining temperature is 600-800 ℃ and the time is 2-4h.
As a further improvement of the invention, the method specifically comprises the following steps:
S1, preparing a spherical Al 2O3/ZrO2 carrier containing Sn/Ga: ball milling 12-15 parts by weight of pseudo-boehmite and 3-5 parts by weight of zirconia powder for 2-4 hours, uniformly mixing, and adding into 100 parts by weight of aqueous solution containing 15-20wt% of sodium alginate and 1-2wt% of emulsifier to obtain a water phase; dropwise adding the water phase into 200 parts by weight of edible oil, emulsifying, dropwise adding 15-20 parts by weight of 3-5wt% calcium ion solution, solidifying at normal temperature for 20-30min, centrifuging, adding the prepared nanospheres into 100 parts by weight of 10-12wt% acetic acid solution, stirring and reacting for 2-3h, centrifuging, washing, drying, and calcining at 500-600 ℃ for 1-2h to obtain a spherical Al 2O3/ZrO2 carrier; dissolving 7-10 parts by weight of tin chloride in 50 parts by weight of ethanol, adding 3-5 parts by weight of Ga 2O3, uniformly mixing to obtain a mixed solution, immersing 10 parts by weight of spherical Al 2O3/ZrO2 carrier in 50 parts by weight of the mixed solution, heating to 70-80 ℃ to volatilize solvent, and calcining at 600-700 ℃ for 2-4 hours to obtain the spherical Al 2O3/ZrO2 carrier containing Sn/Ga;
S2, doping cobalt sulfur nitrogen: dispersing 15-20 parts by weight of the spherical Al 2O3/ZrO2 carrier containing Sn/Ga prepared in the step S1 in 100 parts by weight of water, adding 3-5 parts by weight of cobalt thiocyanate, volatilizing a solvent, and calcining at 800-900 ℃ for 1-3 hours under the protection of inert gas to prepare a cobalt-sulfur-nitrogen doped spherical Al 2O3/ZrO2 catalyst containing Sn/Ga;
S3, ferromagnetism modification: dispersing 15-20 parts by weight of the cobalt sulfur nitrogen doped Sn/Ga containing spherical Al 2O3/ZrO2 catalyst prepared in the step S2 in 100 parts by weight of water, adding 5-7 parts by weight of ferric chloride and ferrous chloride under the protection of inert gas, adjusting the molar ratio of the ferric chloride to the ferrous chloride to be 2:1, adjusting the pH value of the solution to be 9-10, heating to 75-85 ℃, stirring and reacting for 3-5 hours, centrifuging, washing, drying, and calcining at 500-700 ℃ for 1-3 hours to prepare the magnetic cobalt sulfur nitrogen doped Sn/Ga containing spherical Al 2O3/ZrO2 catalyst;
s4, preparing an impregnating solution: dissolving 2-4 parts by weight of alkali, 5-7 parts by weight of zirconium nitrate and 10-15 parts by weight of magnesium nitrate in 100 parts by weight of water to obtain an impregnating solution;
the alkali is a mixture of NaOH and Ca (OH) 2, and the mass ratio is 5-7:2;
S5, preparing a propane dehydrogenation catalyst: adding 15-20 parts by weight of the magnetic cobalt sulfur nitrogen doped Sn/Ga-containing spherical Al 2O3/ZrO2 catalyst prepared in the step S3 into 70 parts by weight of the impregnating solution prepared in the step S4, heating to 70-80 ℃, volatilizing the solvent, and calcining at 600-800 ℃ for 2-4 hours to prepare the propane dehydrogenation catalyst.
The invention further protects the propane dehydrogenation catalyst prepared by the preparation method.
The invention further protects a method for preparing propylene by dehydrogenating propane, which comprises the steps of introducing mixed reaction gas of propane, hydrogen and nitrogen in a volume ratio of 8-10:8-10:50 into a fixed bed reactor loaded with the propane dehydrogenation catalyst, heating to 450-550 ℃ under normal pressure for reacting for 4-7h, wherein the reaction space velocity is 700-800h -1, and obtaining the product.
The invention has the following beneficial effects:
According to the invention, sodium alginate is used as an adhesive and an inclusion agent, pseudo-boehmite and zirconia powder are adhered and wrapped in sodium alginate microspheres, water-in-oil tiny liquid drops are formed through emulsification, a shell layer is formed on the surface under the crosslinking action of calcium ions, and then under the action of acetic acid and calcination, the surface sodium alginate and an internal sodium alginate adhesive react to be removed, so that a spherical Al 2O3/ZrO2 carrier with rich specific surface area and pore channels is obtained, the dispersity of active metals can be increased, the interaction between the metals and the carrier is enhanced, the metal loading capacity is improved, and the activity of the catalyst is improved.
The carrier is immersed in a mixed solution containing Sn and Ga, and calcined, so that the spherical Al 2O3/ZrO2 carrier containing Sn/Ga is prepared. The addition of Ga increases propylene selectivity during propane dehydrogenation, and the catalyst is slow to deactivate and carbon deposit is reduced during reaction. Sn is easy to be reduced to a metal state, and the action of the carrier and Sn is enhanced, so that the activity and selectivity of the catalyst are improved. After the two are synergistically modified, the selectivity and the conversion rate of the catalyst to propane are improved, the reaction can be carried out at a lower temperature, and the generation of carbon deposit is reduced.
Furthermore, the synergistic effect between Co-S-N, co nano particles and S/N elements is carried out on the surface, so that the catalytic performance of the composite material is improved, the cyclic stability is improved, and the composite material can be used for multiple catalytic applications without great reduction of activity. Meanwhile, the Co-doping of Co, N and S forms a network structure, which increases the specific surface area of the catalyst and the acid center of the surface, improves the adsorptivity and promotes the catalytic reaction. Due to the introduction of the S/N element, the selectivity of the catalyst to propylene can be improved, the reaction temperature can be reduced, the generation of carbon deposit can be reduced, and the catalytic service life of the catalyst can be greatly prolonged.
The deposition of ferroferric oxide in ferromagnetism is convenient for magnetic separation, and the ferroferric oxide can modify the activities of acid and metal phases, so that carbon deposit on a catalyst is reduced, fe can promote the change of the geometric structure of the catalyst, the energy of d-electron occupied state is reduced, and the energy of unoccupied state is increased, thereby weakening the adsorption of a product and improving the stability and selectivity of the catalyst.
On one hand, the addition of Na reduces the B acid center and the L strong/strong acid center in the catalyst, inhibits the occurrence of carbon deposit, improves the stability of catalytic reaction, and improves the exposure and the reactivity of active components Sn, zr and Mg on the surface of the catalyst. On the other hand, the addition of Ca can lead Sn, zr and Mg particles in the catalyst to be uniformly dispersed, the particle size is reduced, and part of the particles enter the pore canal of the molecular sieve; the reaction carbon deposition is reduced, and meanwhile, the generated carbon deposition is mainly deposited on the surface of the carrier and does not cover the active center of the catalyst, so that the catalyst poisoning caused by the carbon deposition is avoided to reduce the reaction activity, and the addition of the carbon deposition and the catalyst has a synergistic effect.
According to the invention, through loading the proper content of the active component (Mg) and the auxiliary agent (alkali and Zr), a strong interaction is formed among Mg, zr and O atoms, the thermal stability of an alumina crystal structure can be improved, the characteristics of excellent thermal stability, surface acid structure and the like of the carrier are fully exerted, the dispersity of the active component and the auxiliary agent on the surface of the carrier is good, the agglomeration rate is low, the catalyst has high propylene selectivity, the rate of carbon deposition generation can be reduced, the stability of the catalyst is enhanced, and the service period of the catalyst is prolonged.
The propane dehydrogenation catalyst prepared by the invention has the advantages of simple preparation method, large specific surface area and rich pore channels, high selectivity to propane catalysis, high reaction yield, reduced reaction temperature, reduced carbon deposition, greatly prolonged catalytic service life, convenient separation and repeated use, high catalytic activity for repeated use, good thermal stability, no need of adding noble metal, low cost and wide application prospect.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Pseudoboehmite with an average pore diameter of 10-15nm and a particle size of 5-10 microns purchased from Wuhan Hua Xiangke Jiete Biotechnology Co., ltd; zirconia powder with purity >99% was purchased from south Gong Shiying tai metal materials limited.
Example 1
The embodiment provides a preparation method of a propane dehydrogenation catalyst, which specifically comprises the following steps:
S1, preparing a spherical Al 2O3/ZrO2 carrier containing Sn/Ga: ball-milling 12 parts by weight of pseudo-boehmite and 3 parts by weight of zirconia powder for 2 hours, stirring and mixing for 15 minutes, and adding 100 parts by weight of aqueous solution containing 15wt% of sodium alginate and 1wt% of tween-20 to obtain a water phase; dripping the water phase into 200 parts by weight of corn oil, emulsifying for 15min at 10000r/min, dripping 15 parts by weight of 3wt% calcium chloride solution, solidifying for 20min at normal temperature, centrifuging, adding the prepared nanospheres into 100 parts by weight of 10wt% acetic acid solution, stirring and reacting for 2h, centrifuging, washing, drying, calcining for 1h at 500 ℃ to obtain a spherical Al 2O3/ZrO2 carrier; dissolving 7 parts by weight of tin chloride in 50 parts by weight of ethanol, adding 3 parts by weight of Ga 2O3, uniformly mixing to obtain a mixed solution, immersing 10 parts by weight of spherical Al 2O3/ZrO2 carrier in 50 parts by weight of the mixed solution, heating to 70 ℃ to volatilize solvent, and calcining at 600 ℃ for 2 hours to obtain a spherical Al 2O3/ZrO2 carrier containing Sn/Ga;
S2, doping cobalt sulfur nitrogen: 15 parts by weight of the spherical Al 2O3/ZrO2 carrier containing Sn/Ga prepared in the step S1 are dispersed in 100 parts by weight of water, 3 parts by weight of cobalt thiocyanate is added, the solvent is volatilized, and the cobalt-sulfur-nitrogen doped spherical Al 2O3/ZrO2 catalyst containing Sn/Ga is prepared by calcining at 800 ℃ for 1h under the protection of nitrogen;
s3, ferromagnetism modification: dispersing 15 parts by weight of the cobalt sulfur nitrogen doped Sn/Ga containing spherical Al 2O3/ZrO2 catalyst prepared in the step S2 in 100 parts by weight of water, adding 5 parts by weight of ferric chloride and ferrous chloride under the protection of nitrogen, adjusting the molar ratio of the ferric chloride to the ferrous chloride to be 2:1, adjusting the pH value of the solution to be 9, heating to 75 ℃, stirring and reacting for 3 hours, centrifuging, washing, drying, and calcining at 500 ℃ for 1 hour to prepare the magnetic cobalt sulfur nitrogen doped Sn/Ga containing spherical Al 2O3/ZrO2 catalyst;
S4, preparing an impregnating solution: 2 parts by weight of alkali, 5 parts by weight of zirconium nitrate and 10 parts by weight of magnesium nitrate are dissolved in 100 parts by weight of water to obtain an impregnating solution;
the alkali is a mixture of NaOH and Ca (OH) 2, and the mass ratio is 5:2;
S5, preparing a propane dehydrogenation catalyst: 15 parts by weight of the magnetic cobalt sulfur nitrogen doped Sn/Ga containing spherical Al 2O3/ZrO2 catalyst prepared in the step S3 is added into 70 parts by weight of the impregnating solution prepared in the step S4, the impregnating solution is heated to 70 ℃, the solvent is volatilized, and the calcining is carried out at 600 ℃ for 2 hours, so that the propane dehydrogenation catalyst is prepared.
Example 2
The embodiment provides a preparation method of a propane dehydrogenation catalyst, which specifically comprises the following steps:
S1, preparing a spherical Al 2O3/ZrO2 carrier containing Sn/Ga: ball-milling 15 parts by weight of pseudo-boehmite and 5 parts by weight of zirconia powder for 4 hours, stirring and mixing for 15 minutes, and adding into 100 parts by weight of an aqueous solution containing 20wt% of sodium alginate and 2wt% of tween-40 to obtain a water phase; dropwise adding the water phase into 200 parts by weight of soybean oil, emulsifying for 15min at 10000r/min, dropwise adding 20 parts by weight of 5wt% calcium chloride solution, solidifying for 30min at normal temperature, centrifuging, adding the prepared nanospheres into 100 parts by weight of 12wt% acetic acid solution, stirring and reacting for 3h, centrifuging, washing, drying, and calcining at 600 ℃ for 2h to obtain a spherical Al 2O3/ZrO2 carrier; dissolving 10 parts by weight of tin chloride in 50 parts by weight of ethanol, adding 5 parts by weight of Ga 2O3, uniformly mixing to obtain a mixed solution, immersing 10 parts by weight of spherical Al 2O3/ZrO2 carrier in 50 parts by weight of the mixed solution, heating to 80 ℃ to volatilize solvent, and calcining at 700 ℃ for 4 hours to obtain the spherical Al 2O3/ZrO2 carrier containing Sn/Ga;
S2, doping cobalt sulfur nitrogen: dispersing 20 parts by weight of the spherical Al 2O3/ZrO2 carrier containing Sn/Ga prepared in the step S1 in 100 parts by weight of water, adding 5 parts by weight of cobalt thiocyanate, volatilizing a solvent, and calcining at 900 ℃ for 3 hours under the protection of nitrogen to prepare a cobalt-sulfur-nitrogen doped spherical Al 2O3/ZrO2 catalyst containing Sn/Ga;
S3, ferromagnetism modification: dispersing 20 parts by weight of the cobalt sulfur nitrogen doped Sn/Ga containing spherical Al 2O3/ZrO2 catalyst prepared in the step S2 in 100 parts by weight of water, adding 7 parts by weight of ferric chloride and ferrous chloride under the protection of nitrogen, adjusting the molar ratio of the ferric chloride to the ferrous chloride to be 2:1, adjusting the pH value of the solution to be 10, heating to 85 ℃, stirring and reacting for 5 hours, centrifuging, washing, drying, and calcining at 700 ℃ for 3 hours to prepare the magnetic cobalt sulfur nitrogen doped Sn/Ga containing spherical Al 2O3/ZrO2 catalyst;
S4, preparing an impregnating solution: dissolving 4 parts by weight of alkali, 7 parts by weight of zirconium nitrate and 15 parts by weight of magnesium nitrate in 100 parts by weight of water to obtain an impregnating solution;
the alkali is a mixture of NaOH and Ca (OH) 2, and the mass ratio is 7:2;
S5, preparing a propane dehydrogenation catalyst: and (3) adding 20 parts by weight of the magnetic cobalt sulfur nitrogen doped Sn/Ga-containing spherical Al 2O3/ZrO2 catalyst prepared in the step (S3) into 70 parts by weight of the impregnating solution prepared in the step (S4), heating to 80 ℃, volatilizing the solvent, and calcining at 800 ℃ for 4 hours to prepare the propane dehydrogenation catalyst.
Example 3
The embodiment provides a preparation method of a propane dehydrogenation catalyst, which specifically comprises the following steps:
S1, preparing a spherical Al 2O3/ZrO2 carrier containing Sn/Ga: ball-milling 13 parts by weight of pseudo-boehmite and 4 parts by weight of zirconia powder for 3 hours, stirring and mixing for 15 minutes, and adding 100 parts by weight of aqueous solution containing 17wt% of sodium alginate and 1.5wt% of tween-80 to obtain a water phase; dropwise adding the water phase into 200 parts by weight of soybean oil, emulsifying for 15min at 10000r/min, dropwise adding 17 parts by weight of 4wt% calcium chloride solution, solidifying for 25min at normal temperature, centrifuging, adding the prepared nanospheres into 100 parts by weight of 11wt% acetic acid solution, stirring and reacting for 2.5h, centrifuging, washing, drying, and calcining at 550 ℃ for 1.5h to obtain a spherical Al 2O3/ZrO2 carrier; dissolving 8.5 parts by weight of tin chloride in 50 parts by weight of ethanol, adding 4 parts by weight of Ga 2O3, uniformly mixing to obtain a mixed solution, immersing 10 parts by weight of spherical Al 2O3/ZrO2 carrier in 50 parts by weight of the mixed solution, heating to 75 ℃ to volatilize solvent, and calcining at 650 ℃ for 3 hours to obtain the spherical Al 2O3/ZrO2 carrier containing Sn/Ga;
S2, doping cobalt sulfur nitrogen: dispersing 17 parts by weight of the spherical Al 2O3/ZrO2 carrier containing Sn/Ga prepared in the step S1 in 100 parts by weight of water, adding 4 parts by weight of cobalt thiocyanate, volatilizing a solvent, and calcining at 850 ℃ for 2 hours under the protection of nitrogen to prepare a cobalt-sulfur-nitrogen doped spherical Al 2O3/ZrO2 catalyst containing Sn/Ga;
S3, ferromagnetism modification: dispersing 17 parts by weight of the cobalt sulfur nitrogen doped Sn/Ga containing spherical Al 2O3/ZrO2 catalyst prepared in the step S2 in 100 parts by weight of water, adding 6 parts by weight of ferric chloride and ferrous chloride under the protection of nitrogen, adjusting the molar ratio of the ferric chloride to the ferrous chloride to be 2:1, adjusting the pH value of the solution to be 9.5, heating to 80 ℃, stirring and reacting for 4 hours, centrifuging, washing, drying, and calcining at 600 ℃ for 2 hours to prepare the magnetic cobalt sulfur nitrogen doped Sn/Ga containing spherical Al 2O3/ZrO2 catalyst;
S4, preparing an impregnating solution: 3 parts by weight of alkali, 6 parts by weight of zirconium nitrate and 12 parts by weight of magnesium nitrate are dissolved in 100 parts by weight of water to obtain an impregnating solution;
the alkali is a mixture of NaOH and Ca (OH) 2, and the mass ratio is 6:2;
S5, preparing a propane dehydrogenation catalyst: and (3) adding 17 parts by weight of the magnetic cobalt sulfur nitrogen doped Sn/Ga-containing spherical Al 2O3/ZrO2 catalyst prepared in the step (S3) into 70 parts by weight of the impregnating solution prepared in the step (S4), heating to 75 ℃, volatilizing the solvent, and calcining at 700 ℃ for 3 hours to prepare the propane dehydrogenation catalyst.
Example 4
The difference compared to example 3 is that the base is NaOH alone.
Example 5
The difference compared to example 3 is that the base is Ca (OH) 2 alone.
Comparative example 1
The difference from example 3 is that no zirconia powder was added in step S1.
The method comprises the following steps:
S1, preparing a spherical Al 2O3 carrier containing Sn/Ga: ball-milling 17 parts by weight of pseudo-boehmite for 3 hours, and adding 100 parts by weight of pseudo-boehmite into an aqueous solution containing 17wt% of sodium alginate and 1.5wt% of tween-80 to obtain a water phase; dropwise adding the water phase into 200 parts by weight of soybean oil, emulsifying for 15min at 10000r/min, dropwise adding 17 parts by weight of 4wt% calcium chloride solution, solidifying for 25min at normal temperature, centrifuging, adding the prepared nanospheres into 100 parts by weight of 11wt% acetic acid solution, stirring and reacting for 2.5h, centrifuging, washing, drying, and calcining at 550 ℃ for 1.5h to obtain a spherical Al 2O3 carrier; 8.5 parts by weight of tin chloride is dissolved in 50 parts by weight of ethanol, 4 parts by weight of Ga 2O3 is added, the mixture is uniformly mixed to obtain a mixed solution, 10 parts by weight of spherical Al 2O3 carrier is immersed in 50 parts by weight of the mixed solution, the mixed solution is heated to 75 ℃ to volatilize solvent, and the mixed solution is calcined at 650 ℃ for 3 hours, so that the spherical Al 2O3 carrier containing Sn/Ga is prepared.
Comparative example 2
In comparison with example 3, the difference is that no tin chloride was added in step S1.
The method comprises the following steps:
S1, preparing a Ga-containing spherical Al 2O3/ZrO2 carrier: ball-milling 13 parts by weight of pseudo-boehmite and 4 parts by weight of zirconia powder for 3 hours, stirring and mixing for 15 minutes, and adding 100 parts by weight of aqueous solution containing 17wt% of sodium alginate and 1.5wt% of tween-80 to obtain a water phase; dropwise adding the water phase into 200 parts by weight of soybean oil, emulsifying for 15min at 10000r/min, dropwise adding 17 parts by weight of 4wt% calcium chloride solution, solidifying for 25min at normal temperature, centrifuging, adding the prepared nanospheres into 100 parts by weight of 11wt% acetic acid solution, stirring and reacting for 2.5h, centrifuging, washing, drying, and calcining at 550 ℃ for 1.5h to obtain a spherical Al 2O3/ZrO2 carrier; adding 12.5 parts by weight of Ga 2O3 into 50 parts by weight of ethanol, uniformly mixing to obtain a mixed solution, immersing 10 parts by weight of spherical Al 2O3/ZrO2 carrier into 50 parts by weight of the mixed solution, heating to 75 ℃ to volatilize solvent, and calcining at 650 ℃ for 3 hours to obtain the spherical Al 2O3/ZrO2 carrier containing Ga.
Comparative example 3
In comparison with example 3, the difference is that Ga 2O3 is not added in step S1.
The method comprises the following steps:
S1, preparing a spherical Al 2O3/ZrO2 carrier containing Sn: ball-milling 13 parts by weight of pseudo-boehmite and 4 parts by weight of zirconia powder for 3 hours, stirring and mixing for 15 minutes, and adding 100 parts by weight of aqueous solution containing 17wt% of sodium alginate and 1.5wt% of tween-80 to obtain a water phase; dropwise adding the water phase into 200 parts by weight of soybean oil, emulsifying for 15min at 10000r/min, dropwise adding 17 parts by weight of 4wt% calcium chloride solution, solidifying for 25min at normal temperature, centrifuging, adding the prepared nanospheres into 100 parts by weight of 11wt% acetic acid solution, stirring and reacting for 2.5h, centrifuging, washing, drying, and calcining at 550 ℃ for 1.5h to obtain a spherical Al 2O3/ZrO2 carrier; 12.5 parts by weight of tin chloride is dissolved in 50 parts by weight of ethanol to obtain a mixed solution, 10 parts by weight of spherical Al 2O3/ZrO2 carrier is immersed in 50 parts by weight of the mixed solution, the solvent is volatilized by heating to 75 ℃, and the spherical Al 2O3/ZrO2 carrier containing Sn is prepared by calcining at 650 ℃ for 3 hours.
Comparative example 4
In comparison with example 3, the difference is that tin chloride and Ga 2O3 are not added in step S1.
The method comprises the following steps:
S1, preparing a spherical Al 2O3/ZrO2 carrier: ball-milling 13 parts by weight of pseudo-boehmite and 4 parts by weight of zirconia powder for 3 hours, stirring and mixing for 15 minutes, and adding 100 parts by weight of aqueous solution containing 17wt% of sodium alginate and 1.5wt% of tween-80 to obtain a water phase; adding the water phase into 200 parts by weight of soybean oil, emulsifying for 15min at 10000r/min, adding 17 parts by weight of 4wt% calcium chloride solution dropwise, solidifying for 25min at normal temperature, centrifuging, adding the prepared nanospheres into 100 parts by weight of 11wt% acetic acid solution, stirring and reacting for 2.5h, centrifuging, washing, drying, and calcining at 550 ℃ for 1.5h to obtain the spherical Al 2O3/ZrO2 carrier.
Comparative example 5
In comparison with example 3, the difference is that step S2 is not performed.
The method comprises the following steps:
S1, preparing a spherical Al 2O3/ZrO2 carrier containing Sn/Ga: ball-milling 13 parts by weight of pseudo-boehmite and 4 parts by weight of zirconia powder for 3 hours, stirring and mixing for 15 minutes, and adding 100 parts by weight of aqueous solution containing 17wt% of sodium alginate and 1.5wt% of tween-80 to obtain a water phase; dropwise adding the water phase into 200 parts by weight of soybean oil, emulsifying for 15min at 10000r/min, dropwise adding 17 parts by weight of 4wt% calcium chloride solution, solidifying for 25min at normal temperature, centrifuging, adding the prepared nanospheres into 100 parts by weight of 11wt% acetic acid solution, stirring and reacting for 2.5h, centrifuging, washing, drying, and calcining at 550 ℃ for 1.5h to obtain a spherical Al 2O3/ZrO2 carrier; dissolving 8.5 parts by weight of tin chloride in 50 parts by weight of ethanol, adding 4 parts by weight of Ga 2O3, uniformly mixing to obtain a mixed solution, immersing 10 parts by weight of spherical Al 2O3/ZrO2 carrier in 50 parts by weight of the mixed solution, heating to 75 ℃ to volatilize solvent, and calcining at 650 ℃ for 3 hours to obtain the spherical Al 2O3/ZrO2 carrier containing Sn/Ga;
S2, ferromagnetism modification: dispersing 17 parts by weight of the spherical Al 2O3/ZrO2 carrier containing Sn/Ga, which is prepared in the step S1, in 100 parts by weight of water, adding 6 parts by weight of ferric chloride and ferrous chloride under the protection of nitrogen, wherein the molar ratio of the ferric chloride to the ferrous chloride is 2:1, adjusting the pH value of the solution to 9.5, heating to 80 ℃, stirring and reacting for 4 hours, centrifuging, washing, drying, and calcining at 600 ℃ for 2 hours to prepare the spherical Al 2O3/ZrO2 catalyst containing Sn/Ga;
s3, preparing an impregnating solution: 3 parts by weight of alkali, 6 parts by weight of zirconium nitrate and 12 parts by weight of magnesium nitrate are dissolved in 100 parts by weight of water to obtain an impregnating solution;
the alkali is a mixture of NaOH and Ca (OH) 2, and the mass ratio is 6:2;
S4, preparing a propane dehydrogenation catalyst: and (3) adding 17 parts by weight of the magnetic Sn/Ga-containing spherical Al 2O3/ZrO2 catalyst prepared in the step (S2) into 70 parts by weight of the impregnating solution prepared in the step (S3), heating to 75 ℃, volatilizing the solvent, and calcining at 700 ℃ for 3 hours to prepare the propane dehydrogenation catalyst.
Comparative example 6
In comparison with example 3, the difference is that step S3 is not performed.
The method comprises the following steps:
S1, preparing a spherical Al 2O3/ZrO2 carrier containing Sn/Ga: ball-milling 13 parts by weight of pseudo-boehmite and 4 parts by weight of zirconia powder for 3 hours, stirring and mixing for 15 minutes, and adding 100 parts by weight of aqueous solution containing 17wt% of sodium alginate and 1.5wt% of tween-80 to obtain a water phase; dropwise adding the water phase into 200 parts by weight of soybean oil, emulsifying for 15min at 10000r/min, dropwise adding 17 parts by weight of 4wt% calcium chloride solution, solidifying for 25min at normal temperature, centrifuging, adding the prepared nanospheres into 100 parts by weight of 11wt% acetic acid solution, stirring and reacting for 2.5h, centrifuging, washing, drying, and calcining at 550 ℃ for 1.5h to obtain a spherical Al 2O3/ZrO2 carrier; dissolving 8.5 parts by weight of tin chloride in 50 parts by weight of ethanol, adding 4 parts by weight of Ga 2O3, uniformly mixing to obtain a mixed solution, immersing 10 parts by weight of spherical Al 2O3/ZrO2 carrier in 50 parts by weight of the mixed solution, heating to 75 ℃ to volatilize solvent, and calcining at 650 ℃ for 3 hours to obtain the spherical Al 2O3/ZrO2 carrier containing Sn/Ga;
S2, doping cobalt sulfur nitrogen: dispersing 17 parts by weight of the spherical Al 2O3/ZrO2 carrier containing Sn/Ga prepared in the step S1 in 100 parts by weight of water, adding 4 parts by weight of cobalt thiocyanate, volatilizing a solvent, and calcining at 850 ℃ for 2 hours under the protection of nitrogen to prepare a cobalt-sulfur-nitrogen doped spherical Al 2O3/ZrO2 catalyst containing Sn/Ga;
s3, preparing an impregnating solution: 3 parts by weight of alkali, 6 parts by weight of zirconium nitrate and 12 parts by weight of magnesium nitrate are dissolved in 100 parts by weight of water to obtain an impregnating solution;
the alkali is a mixture of NaOH and Ca (OH) 2, and the mass ratio is 6:2;
s4, preparing a propane dehydrogenation catalyst: and (3) adding 17 parts by weight of the cobalt sulfur nitrogen doped Sn/Ga-containing spherical Al 2O3/ZrO2 catalyst prepared in the step (S2) into 70 parts by weight of the impregnating solution prepared in the step (S3), heating to 75 ℃, volatilizing the solvent, and calcining at 700 ℃ for 3 hours to prepare the propane dehydrogenation catalyst.
Comparative example 7
The difference from example 3 is that no base is added in step S4.
The method comprises the following steps:
s4, preparing an impregnating solution: 7 parts by weight of zirconium nitrate and 14 parts by weight of magnesium nitrate were dissolved in 100 parts by weight of water to obtain an impregnation solution.
Comparative example 8
The difference from example 3 is that zirconium nitrate is not added in step S4.
The method comprises the following steps:
s4, preparing an impregnating solution: 3 parts by weight of a base and 18 parts by weight of magnesium nitrate were dissolved in 100 parts by weight of water to obtain an impregnation solution.
Comparative example 9
In comparison with example 3, the difference is that magnesium nitrate is not added in step S4.
The method comprises the following steps:
S4, preparing an impregnating solution: 3 parts by weight of a base and 18 parts by weight of zirconium nitrate were dissolved in 100 parts by weight of water to obtain an impregnating solution.
Comparative example 10
In comparison with example 3, the difference is that zirconium nitrate and magnesium nitrate are not added in step S4.
The method comprises the following steps:
S4, preparing an impregnating solution: 21 parts by weight of alkali was dissolved in 100 parts by weight of water to obtain an impregnating solution.
Test example 1
The parameters such as specific surface area, pore volume of the propane dehydrogenation catalysts prepared in examples 1 to 5 and comparative examples 1 to 10 were measured using ASAP2460 type full-automatic specific surface area and porosity analyzer manufactured by Micromeritics instruments, inc. of America. The results are shown in Table 1.
TABLE 1
As shown in the table above, the propane dehydrogenation catalysts prepared in examples 1-3 of the present invention have larger specific surface area and total pore volume, and the average pore diameter is more suitable, and have a certain pore canal limiting effect.
Experimental examples 1 to 5 and comparative experimental examples 1 to 10
A method for preparing propylene by dehydrogenating propane comprises the steps of introducing mixed reaction gas of propane, hydrogen and nitrogen in a volume ratio of 9:9:50 into a fixed bed reactor loaded with 0.5g of propane dehydrogenation catalyst prepared in examples 1-5 or comparative examples 1-10, heating to 500 ℃ under normal pressure for reaction for 5 hours, and obtaining a product, wherein the reaction space velocity is 750h -1. The results of propane conversion, propane selectivity, and propylene yield are shown in Table 2.
TABLE 2
As is clear from the above table, in the reaction of the propane dehydrogenation catalysts prepared in examples 1 to 3 of the present invention for the preparation of propylene by dehydrogenation of propane, the conversion rate of propane was high and the selectivity was high.
Test example 2
The propane dehydrogenation catalysts prepared in examples 1 to 5 or comparative examples 1 to 10 of the present invention were continuously subjected to catalytic reaction at 700℃for 200 hours, and the specific surface areas before and after the catalysts were measured. The results are shown in Table 3.
TABLE 3 Table 3
As is clear from the above table, the propane dehydrogenation catalysts prepared in examples 1-3 of the present invention have small differences in specific surface areas after continuous catalytic reaction for 200 hours at 700 ℃ reaction temperature, which indicates that carbon deposition is hardly generated and the catalytic effect is good.
Examples 4 and 5 compare with example 3 in which the base is NaOH or Ca (OH) 2 alone. Comparative example 7 compared with example 3, no base was added in step S4. The average pore diameter is improved, the selectivity and conversion rate of propane are reduced, the yield of propylene is reduced, and carbon deposition is increased. On one hand, the addition of Na reduces the B acid center and the L strong/strong acid center in the catalyst, inhibits the occurrence of carbon deposit, improves the stability of catalytic reaction, and improves the exposure and the reactivity of active components Sn, zr and Mg on the surface of the catalyst. On the other hand, the addition of Ca can lead Sn, zr and Mg particles in the catalyst to be uniformly dispersed, the particle size is reduced, and part of the particles enter the pore canal of the molecular sieve; the reaction carbon deposition is reduced, and meanwhile, the generated carbon deposition is mainly deposited on the surface of the carrier and does not cover the active center of the catalyst, so that the catalyst poisoning caused by the carbon deposition is avoided to reduce the reaction activity, and the addition of the carbon deposition and the catalyst has a synergistic effect.
Comparative example 1 in comparison with example 3, no zirconia powder was added in step S1. The specific surface area and the total pore volume are reduced, the average pore diameter is increased, the selectivity and conversion of propane are reduced, and the yield of propylene is reduced. The preparation example of the spherical Al 2O3/ZrO2 carrier with rich specific surface area and pore canal can increase the dispersity of active metal, strengthen the interaction between the metal and the carrier, and improve the loading capacity of the metal, thereby improving the activity of the catalyst.
In comparative examples 2 and 3, tin chloride or Ga 2O3 was not added in step S1, as compared with example 3. Comparative example 4 in contrast to example 3, no tin chloride and Ga 2O3 were added in step S1. The specific surface area and the total pore volume are reduced, the selectivity and conversion rate of propane are reduced, the yield of propylene is reduced, and carbon deposition is increased. The carrier is immersed in a mixed solution containing Sn and Ga, and calcined, so that the spherical Al 2O3/ZrO2 carrier containing Sn/Ga is prepared. The addition of Ga increases propylene selectivity during propane dehydrogenation, and the catalyst is slow to deactivate and carbon deposit is reduced during reaction. Sn is easy to be reduced to a metal state, and the action of the carrier and Sn is enhanced, so that the activity and selectivity of the catalyst are improved. After the two are synergistically modified, the selectivity and the conversion rate of the catalyst to propane are improved, the reaction can be carried out at a lower temperature, and the generation of carbon deposit is reduced.
Comparative example 5 compared to example 3, step S2 was not performed. The specific surface area and the total pore volume are reduced, the average pore diameter is improved, the selectivity and conversion rate of propane are reduced, the yield of propylene is reduced, and carbon deposition is increased. The synergistic effect between Co-S-N, co nano particles and S/N elements is carried out on the surface, so that the catalytic performance of the composite material is improved, the cyclic stability is improved, and the composite material can be used for multiple catalytic applications without great reduction of activity. Meanwhile, the Co-doping of Co, N and S forms a network structure, which increases the specific surface area of the catalyst and the acid center of the surface, improves the adsorptivity and promotes the catalytic reaction. Due to the introduction of the S/N element, the selectivity of the catalyst to propylene can be improved, the reaction temperature can be reduced, the generation of carbon deposit can be reduced, and the catalytic service life of the catalyst can be greatly prolonged.
Comparative example 6 compared to example 3, step S3 was not performed. The specific surface area and the total pore volume decrease, the selectivity and conversion of propane decrease, and the yield of propylene decreases. The ferroferric oxide can also modify the activity of the acid and metal phases, reduce carbon deposit on the catalyst, ensure that Fe can promote the change of the geometric structure of the catalyst, reduce the energy of d-electron occupied state and increase the energy of unoccupied state, thereby weakening the adsorption of products and improving the stability and selectivity of the catalyst.
In comparative examples 8 and 9, zirconium nitrate or magnesium nitrate was not added in step S4, as compared with example 3. In comparative example 10, in contrast to example 3, zirconium nitrate and magnesium nitrate were not added in step S4. The selectivity and conversion of propane are reduced, the yield of propylene is reduced, and carbon deposition is increased. According to the invention, through loading the proper content of the active component (Mg) and the auxiliary agent (alkali and Zr), a strong interaction is formed among Mg, zr and O atoms, the thermal stability of an alumina crystal structure can be improved, the characteristics of excellent thermal stability, surface acid structure and the like of the carrier are fully exerted, the dispersity of the active component and the auxiliary agent on the surface of the carrier is good, the agglomeration rate is low, the catalyst has high propylene selectivity, the rate of carbon deposition generation can be reduced, the stability of the catalyst is enhanced, and the service period of the catalyst is prolonged.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (8)
1. A process for preparing a propane dehydrogenation catalyst comprising the steps of:
S1, preparing a spherical Al 2O3/ZrO2 carrier containing Sn/Ga: uniformly mixing pseudo-boehmite and zirconia powder by ball milling, and adding the mixture into an aqueous solution containing sodium alginate and an emulsifier to obtain a water phase; dropwise adding the water phase into edible oil, emulsifying, dropwise adding a calcium ion solution, solidifying at normal temperature, centrifuging, adding the prepared nanospheres into an acetic acid solution, stirring for reaction, centrifuging, washing, drying and calcining to obtain a spherical Al 2O3/ZrO2 carrier; dissolving tin chloride in ethanol, adding Ga 2O3 to obtain a mixed solution, immersing a spherical Al 2O3/ZrO2 carrier in the mixed solution, and calcining to obtain a spherical Al 2O3/ZrO2 carrier containing Sn/Ga; the mass ratio of the pseudo-boehmite to the zirconia powder is 12-15:3-5; the mass ratio of the stannic chloride to the Ga 2O3 to the ethanol is 7-10:3-5:50;
S2, doping cobalt sulfur nitrogen: dispersing the spherical Al 2O3/ZrO2 carrier containing Sn/Ga prepared in the step S1 in water, adding cobalt thiocyanate, volatilizing a solvent, and calcining to prepare a cobalt-sulfur-nitrogen doped spherical Al 2O3/ZrO2 catalyst containing Sn/Ga; the mass ratio of the Sn/Ga-containing spherical Al 2O3/ZrO2 carrier to the cobalt thiocyanate is 15-20:3-5; the calcination is carried out under the protection of inert gas, the calcination temperature is 800-900 ℃ and the calcination time is 1-3h;
S3, ferromagnetism modification: dispersing the cobalt sulfur nitrogen doped Sn/Ga containing spherical Al 2O3/ZrO2 catalyst prepared in the step S2 in water, adding ferric chloride and ferrous chloride under the protection of inert gas, regulating the pH value of the solution, heating, stirring, reacting, centrifuging, washing, drying and calcining to obtain the magnetic cobalt sulfur nitrogen doped Sn/Ga containing spherical Al 2O3/ZrO2 catalyst; the mass ratio of the cobalt sulfur nitrogen doped Sn/Ga-containing spherical Al 2O3/ZrO2 catalyst to the ferric chloride is 15-20:5-7, the molar ratio of the ferric chloride to the ferrous chloride is 2:1, the calcining temperature is 500-700 ℃, and the calcining time is 1-3h;
S4, preparing an impregnating solution: dissolving alkali, zirconium nitrate and magnesium nitrate in water to obtain an impregnating solution; the mass ratio of the alkali to the zirconium nitrate to the magnesium nitrate to the water is 2-4:5-7:10-15:100;
S5, preparing a propane dehydrogenation catalyst: adding the magnetic cobalt sulfur nitrogen doped Sn/Ga-containing spherical Al 2O3/ZrO2 catalyst prepared in the step S3 into the impregnating solution prepared in the step S4, heating to volatilize the solvent, and calcining to prepare a propane dehydrogenation catalyst; the mass ratio of the magnetic cobalt sulfur nitrogen doped Sn/Ga-containing spherical Al 2O3/ZrO2 catalyst to the impregnating solution is 15-20:70; the calcination temperature is 600-800 ℃ and the calcination time is 2-4h.
2. The method according to claim 1, wherein the ball milling time in the step S1 is 2-4 hours, the concentration of sodium alginate in the aqueous solution containing sodium alginate and an emulsifier is 15-20wt%, the concentration of the emulsifier is 1-2wt%, the emulsifier is at least one selected from tween-20, tween-40, tween-60 and tween-80, and the concentration of the acetic acid solution is 10-12wt%.
3. The method according to claim 1, wherein the solution is adjusted to a pH of 9-10 in step S3, and the reaction is carried out at a temperature of 75-85 ℃ for 3-5 hours.
4. The method according to claim 1, wherein the base in step S4 is at least one selected from the group consisting of potassium carbonate, naOH, KOH, ca (OH) 2, and sodium carbonate.
5. The method according to claim 4, wherein the base is a mixture of NaOH and Ca (OH) 2 in a mass ratio of 5-7:2.
6. The method of claim 1, wherein the heating in step S5 is at a temperature of 70-80 ℃.
7. A propane dehydrogenation catalyst prepared by the preparation method as set forth in any one of claims 1 to 6.
8. A method for preparing propylene by dehydrogenating propane is characterized in that mixed reaction gas of propane and nitrogen with the volume ratio of 8-10:1 is introduced into a fixed bed reactor carrying propane dehydrogenation catalyst as claimed in claim 7, and is heated to 450-550 ℃ for reaction for 4-7h under normal pressure, and the reaction space velocity is 700-800h -1, so that the product is prepared.
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| CN110801861A (en) * | 2019-11-21 | 2020-02-18 | 西南化工研究设计院有限公司 | Environment-friendly catalyst for preparing propylene by direct dehydrogenation of propane and preparation method thereof |
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| CN110801861A (en) * | 2019-11-21 | 2020-02-18 | 西南化工研究设计院有限公司 | Environment-friendly catalyst for preparing propylene by direct dehydrogenation of propane and preparation method thereof |
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