CN117427669A - Preparation method of low-carbon alkane dehydrogenation reaction auxiliary agent - Google Patents
Preparation method of low-carbon alkane dehydrogenation reaction auxiliary agent Download PDFInfo
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- CN117427669A CN117427669A CN202311409414.5A CN202311409414A CN117427669A CN 117427669 A CN117427669 A CN 117427669A CN 202311409414 A CN202311409414 A CN 202311409414A CN 117427669 A CN117427669 A CN 117427669A
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- 239000012752 auxiliary agent Substances 0.000 title claims abstract description 62
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 16
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 40
- 239000010949 copper Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000011575 calcium Substances 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 24
- 229910052802 copper Inorganic materials 0.000 claims abstract description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 18
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 23
- 239000011148 porous material Substances 0.000 claims description 20
- 239000012043 crude product Substances 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 19
- 239000011812 mixed powder Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052684 Cerium Inorganic materials 0.000 claims description 15
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 15
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 14
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 claims description 5
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 4
- 229940116318 copper carbonate Drugs 0.000 claims description 3
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 3
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 238000010438 heat treatment Methods 0.000 abstract description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 239000011593 sulfur Substances 0.000 abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 abstract description 5
- 238000005338 heat storage Methods 0.000 abstract description 3
- 238000004898 kneading Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 25
- 230000008569 process Effects 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 11
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 150000001335 aliphatic alkanes Chemical class 0.000 description 8
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 239000001282 iso-butane Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- -1 polypropylene Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 3
- 241000219782 Sesbania Species 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 229940043430 calcium compound Drugs 0.000 description 2
- 150000001674 calcium compounds Chemical class 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 229910004247 CaCu Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000003915 liquefied petroleum gas Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000957 no side effect Toxicity 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000012360 testing method 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
-
- 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
- B01J37/28—Phosphorising
-
- 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)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a low-carbon alkane dehydrogenation reaction auxiliary agent, which consists of Ca, cu, ce, V, P, si, al elements, wherein the auxiliary agent comprises 5-28% of CaO, 2-22% of CuO, 0.8-3.3% of CeO ₂ and V according to the mass percentage of oxides 2 O 3 1 to 4.7% of P 2 O 5 0.5-2.7%, siO 2 5-12%, the rest of Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The Al is 2 O 3 Is a-Al 2 O 3 Taking the copper as a carrier type, kneading copper source, calcium source and the like, not only retaining a-Al 2 O 3 And realizes the heat storage function of CuO and H 2 The reaction releases heat to generate water, and the heating material absorbs water and releases heat, so that the three-layer heat release effect is achieved.After roasting, sulfur carrying treatment can passivate the pipeline and deactivate the dehydrogenation agent, so that the yield of dehydrogenation reaction is improved.
Description
Technical Field
The invention relates to a reaction auxiliary agent for preparing mono-olefin and diolefin by dehydrogenating low-carbon alkane, belonging to the field of petrochemical industry.
Background
The low-carbon alkane is mainly used as fuel for direct combustion, has extremely low utilization rate and small generated added value, and is converted into important chemical raw materials such as olefin and the like, so that the utilization rate and the added value of the low-carbon alkane are improved, and the research of the potential application prospect is increasingly paid attention to. For example, propylene is an important basic chemical raw material and is widely used for producing chemical products such as polypropylene, isopropanol, isopropylbenzene, carbonyl alcohol, propylene oxide, acrylic acid, acrylonitrile and the like; and another important low-carbon olefin butene is widely used, such as producing high-octane gasoline components from mixed butene, and products such as maleic anhydride, sec-butyl alcohol, heptene, polybutene, acetic anhydride and the like.
The method has the advantages that the method has abundant light hydrocarbon resources such as liquefied petroleum gas, condensate and the like, contains a large amount of low-carbon alkanes such as propane, butane and the like, can effectively convert the propane, butane and the like into propylene and butene directly, fully utilizes petroleum resources, relieves the problem of insufficient sources of low-carbon alkenes, particularly propylene, butene and the like, and can simultaneously obtain high-value hydrogen. Thus, there is a need to develop processes and catalysts for the dehydrogenation of light alkanes suitable for industrial applications, including various functional adjuvants.
The technology for preparing propylene by dehydrogenating propane has been known for more than 20 years so far, and industrial application is mature. The development of a catalytic dehydrogenation process for propane has been successful: the Oleflex process from UOP, the Catofin process from Lummes, the Fluidized Bed (FBD) process from Snamprogetti, the steam activated reforming (STAR) process from Uhde, the PDH process from Linde. More Oleflex process and the Catofin process of Lummes, UOP corporation, U.S. are used. The catalyst system is developed from butane dehydrogenation catalyst, mainly Cr-based catalyst and Pt-based catalyst. It is reported that the activity of the Cr-based catalyst is highest among the oxide catalysts for dehydrogenation of light alkanes. Compared with noble metal catalyst, it has lower requirement for impurity in raw material and low cost.
Alkane dehydrogenation reactions are typically endothermic and the overall process may be run as an adiabatic cyclic process. The inherent characteristics of the operation mode of the fixed bed reactor and the strong heat absorption of the dehydrogenation reaction are that the temperature distribution of the bed layer of the reaction system is uneven and has larger temperature difference. Therefore, the heat is supplemented to the reaction system in the reaction process, the temperature difference of the reaction system can be reduced, and the selectivity of the product is improved. Therefore, the dehydrogenation reaction auxiliary agent is called a heating element in the process of developing Crain, and the heating element, the inert porcelain ball and the dehydrogenation agent are mixed in a reactor, so that compared with the single dehydrogenation agent, the dehydrogenation reaction auxiliary agent has obvious supply of the system and the olefin yield.
CN 108176405B discloses an alkane dehydrogenation reaction reinforcing auxiliary agent which contains 15-18 m% of CaO and 70-80 m% of Al 2 O 3 6 to 15m% of CuO, and 0.01 to 3m% of an oxide of an element selected from the group consisting of group VIII, group VI, group IA, group IIA and rare earth elements or a mixture thereof; the preparation process includes forming aluminum compound and calcium compound, calcining at 800-1400 deg.c for 0.5-15 hr to prepare composite carrier, and soaking in Cu solution. The aluminum compound becomes a-Al at > 1500 DEG C 2 O 3 The water absorption rate is very low, the preparation of 6-15 m percent of CuO by one-time impregnation is basically impossible to realize, and the preparation is carried out by adopting multiple times of impregnation, thus greatly influencingThe efficiency and impregnation uniformity are poor, and the innermost layer is basically difficult to penetrate.
CN 108300430B discloses an exothermic additive for alkane dehydrogenation reaction, and a preparation method and a use method thereof. The composition of the composite material is 10 to 35 percent wt percent of CaO and 50 to 85 percent of Al by weight 2 O 3 5 to 30 wt percent of CuO, and 0 to 3 wt percent of a metal oxide selected from group VIII, group IIB, group IIIB, and group VIIB. The aluminum compound, the calcium compound and the solid copper compound are mixed, molded and baked for 0.2 to 24 hours at a high temperature of 800 to 1400 ℃ and Al 2 O 3 Reacts with CuO to form red aluminum bronze spinel, which is susceptible to aging during hydrothermal reaction but is not susceptible to reduction, thus greatly compromising the promoting effect.
CN 113388376B discloses an alkane dehydrogenation heating auxiliary agent, a preparation method and application thereof, and the auxiliary agent mainly comprises CaO, cuO and Al 2 O 3 Prepared from CaO, cuO and Al 2 O 3 The weight portions of the components are as follows: 35-90 parts, 10-40 parts and 5-40 parts; the Cu element in the alkane dehydrogenation heating auxiliary agent mainly exists in the forms of CaCu2O3 and Ca2CuO3, and the ratio of the number of Ca atoms to the number of Al atoms is more than or equal to 6/7. High Ca content and undoubtedly weakened Al 2 O 3 The main content of the catalyst is a-Al before the development of heating elements in the field of dehydrogenation heating auxiliary agents 2 O 3 Inert porcelain ball to store heat, so Al 2 O 3 And is also important in heating elements. Secondly, cu element is mainly CaCu 2 O 3 And Ca 2 CuO 3 In the form of (2) and cannot effectively utilize the redox exotherm of Cu.
In view of the above problems, the dehydrogenation auxiliary agent is basically not domesticated at present, is monopolized by foreign countries, and in order to break the situation, it is imperative to develop an auxiliary agent which can compensate the heat absorption loss of the dehydrogenation reaction with larger heating value.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a low-carbon alkane dehydrogenation reaction auxiliary agent.
The auxiliary agent consists of Ca, cu, ce, V, P, si, al elementsThe composition comprises, by mass, 5-28% of CaO, 2-22% of CuO and CeO 2 0.8 to 3.3% V 2 O 3 1 to 4.7% of P 2 O 5 0.5-2.7%, siO 2 5-12%, the rest of Al 2 O 3 。
Another object of the invention is to provide a method for preparing said adjuvant, comprising the steps of:
s1, roasting small-pore pseudo-boehmite at 1250 ℃ for 6 hours to prepare a-Al 2 O 3 ；
S2, a-Al in S1 2 O 3 Uniformly mixing with small-pore pseudo-boehmite, a calcium source, a copper source and a pore-forming agent to prepare mixed powder;
s3, uniformly mixing the metered phosphoric acid with a cerium source, a vanadium source, silica sol, nitric acid and water according to a certain proportion to prepare a mixed solution;
s4, adding the mixed solution in the step S3 into the mixed powder in the step S2, extruding strips, forming, maintaining, drying and roasting to obtain an auxiliary agent crude product;
s5, immersing the crude product of the auxiliary agent prepared in the S4 into an ammonium thiosulfate solution, and drying to prepare a finished auxiliary agent.
Further, a-Al in step S2 2 O 3 The dosage of the pseudo-boehmite with small holes is calculated by Al 2 O 3 The mass percentage is 6-9:1.
Further, in step S2, the calcium source is CaCO 3 、Ca(OH) 2 One or more of CaO, and Cu (OH) as copper source 2 One or more of CuO and basic copper carbonate.
Further, in the step S2, the pore-forming agent is one of CMC and sesbania powder, and the dosage of the pore-forming agent is 2-10% of the mixed powder in the step S2
Further, in step S3, ce (NO 3 ) 3 、CeCl 3 One or two of ammonium metavanadate and vanadyl oxalate as vanadium source.
Further, in the step S4, the curing condition is that the sealing system is treated for 2d at 60+/-5 ℃, and the roasting condition is that the sealing system is treated for 4-6 h at 600-1000 ℃.
Further, the concentration of the ammonium thiosulfate solution in the step S5 is determined by the fact that the sulfur-carrying element mass of the auxiliary agent crude product in the step S4 is 0.5-1.2%.
Further, in the step S5, the drying condition is 120-150 ℃ and the drying is carried out for 2-4 hours.
The invention has the beneficial effects that:
1. by using a-Al 2 O 3 Is used as a main carrier and is matched with a small amount of small-pore pseudo-boehmite and silica sol for forming, thereby retaining a-Al 2 O 3 The heat storage function of the catalyst is that a small amount of small-pore pseudo-boehmite ensures the strength of the auxiliary agent, silica sol further promotes the strength to be improved, and makes up for pure a-Al 2 O 3 The disadvantage of inability to shape is that the silica sol minimizes the amount of pore pseudo-boehmite which is gamma-Al prepared by firing in step S4 2 O 3 In this form, if the amount of acid is too large, side reactions such as cleavage occur simultaneously with the dehydrogenation reaction.
2. By using a-Al 2 O 3 The powder is molded, the strength is not high, and the step S4 of the invention utilizes the principle of cement maintenance, and the strength of the auxiliary agent is further improved by referring to the preparation of the catalyst in the field.
3. By first preparing a-Al 2 O 3 The powder is kneaded with copper source and calcium source and then baked at low temperature, thus ensuring the alpha-Al 2 O 3 The heat storage function of the alloy is guaranteed, no reaction similar to spinel structure occurs among copper, calcium and aluminum, and the heating characteristic of the alloy is guaranteed to the greatest extent. CuO and H 2 The reaction releases heat and produces water, the heating material absorbs water and releases heat, and the auxiliary agent serves as a heating medium to store a part of heat. The temperature distribution of the reactor for alkane dehydrogenation is effectively improved through triple heat release.
4. Cerium and vanadium have various valence states, and the characteristic can greatly promote the oxidation-reduction heat release of copper.
5. In the step S5, the ammonium thiosulfate solution is used for treating the crude product of the auxiliary agent in the step S4, so that the sulfur loading of the auxiliary agent is realized, and the auxiliary agent has multiple functions:
firstly, in the heating process, decomposing escaped sulfur to passivate a pipeline;
secondly, sulfur carries out a certain degree of inactivation treatment on the dehydrogenation agent, so that the occurrence of cracking side reaction is reduced;
thirdly, ca and Cu are contained in the auxiliary agent, sulfur can be stabilized, slow release of the auxiliary agent can be controlled, and excessive release of S at one time is avoided, so that adverse effects are generated. In the prior report, ca and Cu act with carrier Al, are spinel-like structures, and cannot realize the function.
Detailed Description
The following detailed examples illustrate the invention in order to make the objects, technical solutions and advantages of the invention more apparent.
Example 1
The additive comprises 12 mass percent of oxide, 5 mass percent of CaO, 5 mass percent of CuO and 5 mass percent of CeO 2 Is 3.3%, V 2 O 3 1%, P 2 O 5 1.1% of SiO 2 9% of the rest of Al 2 O 3 。
According to the component proportion, the low-carbon alkane dehydrogenation reaction auxiliary agent is prepared by adopting the following method:
s1, roasting small-pore pseudo-boehmite at 1250 ℃ for 6 hours to prepare a-Al 2 O 3 ；
S2, a-Al in S1 2 O 3 Uniformly mixing with small-pore pseudo-boehmite, a calcium source, a copper source and a pore-forming agent to prepare mixed powder; wherein a-Al 2 O 3 In proportion with the dosage of the small-pore pseudo-boehmite, by Al 2 O 3 The mass percentage is 8:1; the calcium source is Ca (OH) 2 The copper source is Cu (OH) 2 The porous ceramic powder and CuO are added in a mass ratio of 1:1, and the pore-forming agent is CMC, and the dosage of the pore-forming agent and the CuO is 8% of that of the mixed powder in S2.
S3, uniformly mixing the metered phosphoric acid with a cerium source, a vanadium source, silica sol, nitric acid and water according to a certain proportion to prepare a mixed solution; cerium source is Ce (NO) 3 ) 3 The vanadium source is vanadyl oxalate.
S4, adding the mixed solution in the step S3 into the mixed powder in the step S2, extruding strips, forming, maintaining, drying and roasting to obtain an auxiliary agent crude product; curing conditions are 60+/-5 ℃ for 2d under a sealing system, and roasting conditions are 800 ℃ for 5h.
S5, immersing the crude product of the auxiliary agent prepared in the S4 into an ammonium thiosulfate solution, and drying to prepare a finished auxiliary agent.
The concentration of the ammonium thiosulfate solution is determined by the sulfur-carrying element mass of the auxiliary agent crude product in the step S4 being 0.8%. The drying condition is 120 ℃ for 4 hours.
Comparative example 1
The only difference in the preparation is that no cerium source was added in step S3 as in example 1.
Example 2
The additive comprises 5 mass percent of CaO, 14 mass percent of CuO and 14 mass percent of CeO 2 0.8% of V 2 O 3 4.7%, P 2 O 5 0.5% of SiO 2 10% of the rest of Al 2 O 3 。
According to the component proportion, the low-carbon alkane dehydrogenation reaction auxiliary agent is prepared by adopting the following method:
s1, roasting small-pore pseudo-boehmite at 1250 ℃ for 6 hours to prepare a-Al 2 O 3 ；
S2, a-Al in S1 2 O 3 Uniformly mixing with small-pore pseudo-boehmite, a calcium source, a copper source and a pore-forming agent to prepare mixed powder; wherein a-Al 2 O 3 In proportion with the dosage of the small-pore pseudo-boehmite, by Al 2 O 3 The mass percentage is 9:1; the calcium source is CaCO 3 The copper source is basic copper carbonate, the pore-forming agent is CMC, and the dosage is 10% of the mixed powder in S2.
S3, uniformly mixing the metered phosphoric acid with a cerium source, a vanadium source, silica sol, nitric acid and water according to a certain proportion to prepare a mixed solution; the cerium source is CeCl 3 The vanadium source is vanadyl oxalate.
S4, adding the mixed solution in the step S3 into the mixed powder in the step S2, extruding strips, forming, maintaining, drying and roasting to obtain an auxiliary agent crude product; curing conditions are 60+/-5 ℃ for 2d under a sealing system, and roasting conditions are 600 ℃ for 5h.
S5, immersing the crude product of the auxiliary agent prepared in the S4 into an ammonium thiosulfate solution, and drying to prepare a finished auxiliary agent. The concentration of the ammonium thiosulfate solution is determined by the sulfur-carrying element mass of the auxiliary agent crude product in the step S4 being 0.5%.
The drying condition is 150 ℃ for 2 hours.
Comparative example 2
The only difference in the preparation is that no vanadium source is added in step S3 as in example 2.
Example 3
The additive comprises 28 mass percent of oxide, 28 mass percent of CaO, 2 mass percent of CuO and 2 mass percent of CeO 2 Is 1.6% V 2 O 3 3.1% of P 2 O 5 1.8%, siO 2 5% of the rest of Al 2 O 3 。
According to the component proportion, the low-carbon alkane dehydrogenation reaction auxiliary agent is prepared by adopting the following method:
s1, roasting small-pore pseudo-boehmite at 1250 ℃ for 6 hours to prepare a-Al 2 O 3 ；
S2, a-Al in S1 2 O 3 Uniformly mixing with small-pore pseudo-boehmite, a calcium source, a copper source and a pore-forming agent to prepare mixed powder; wherein a-Al 2 O 3 In proportion with the dosage of the small-pore pseudo-boehmite, by Al 2 O 3 The mass percentage is 7:1; the calcium source is CaCO 3 、Ca(OH) 2 The copper source is CuO, the pore-forming agent is sesbania powder, and the dosage of the pore-forming agent is 5% of the mixed powder in S2, wherein the calculated CaO content is 1:1.
S3, uniformly mixing the metered phosphoric acid with a cerium source, a vanadium source, silica sol, nitric acid and water according to a certain proportion to prepare a mixed solution; cerium source is Ce (NO) 3 ) 3 、CeCl 3 According to CeO 2 The mass ratio is 1:1, and the vanadium source is ammonium metavanadate.
S4, adding the mixed solution in the step S3 into the mixed powder in the step S2, extruding strips, forming, maintaining, drying and roasting to obtain an auxiliary agent crude product; curing conditions are 60+/-5 ℃ for 2d under a sealing system, and roasting conditions are 1000 ℃ for 6h.
S5, immersing the crude product of the auxiliary agent prepared in the S4 into an ammonium thiosulfate solution, and drying to prepare a finished auxiliary agent. The concentration of the ammonium thiosulfate solution is determined by the sulfur-carrying element mass of the auxiliary agent crude product in the step S4 being 1.0%.
The drying condition is 135 ℃ for 3 hours.
Comparative example 3
The preparation is identical to example 3, the only difference being that the preparation is completed until step S4, step S5 not being performed.
Example 4
The additive comprises 19 mass percent of CaO, 22 mass percent of CuO and 22 mass percent of CeO 2 Is 1.1% V 2 O 3 2.3%, P 2 O 5 2.7%, siO 2 12% of the rest of Al 2 O 3 。
According to the component proportion, the low-carbon alkane dehydrogenation reaction auxiliary agent is prepared by adopting the following method:
s1, roasting small-pore pseudo-boehmite at 1250 ℃ for 6 hours to prepare a-Al 2 O 3 ；
S2, a-Al in S1 2 O 3 Uniformly mixing with small-pore pseudo-boehmite, a calcium source, a copper source and a pore-forming agent to prepare mixed powder; wherein a-Al 2 O 3 In proportion with the dosage of the small-pore pseudo-boehmite, by Al 2 O 3 The mass percentage is 6:1; the calcium source is CaO, and the copper source is Cu (OH) 2 The pore-forming agent is sesbania powder, and the dosage of the pore-forming agent is 2% of the mixed powder in the S2.
S3, uniformly mixing the metered phosphoric acid with a cerium source, a vanadium source, silica sol, nitric acid and water according to a certain proportion to prepare a mixed solution; cerium source is Ce (NO) 3 ) 3 The vanadium source is ammonium metavanadate and vanadyl oxalate according to the conversion V 2 O 3 1:1 mass.
S4, adding the mixed solution in the step S3 into the mixed powder in the step S2, extruding strips, forming, maintaining, drying and roasting to obtain an auxiliary agent crude product; curing condition is that the treatment is carried out for 2d under a sealing system with 60+/-5 ℃, and roasting condition is that the treatment is carried out for 4h under 760 ℃.
S5, immersing the crude product of the auxiliary agent prepared in the S4 into an ammonium thiosulfate solution, and drying to prepare a finished auxiliary agent.
The concentration of the ammonium thiosulfate solution is determined by the sulfur-carrying element mass of the auxiliary agent crude product in the step S4 being 1.2%. The drying condition is 120 ℃ for 3 hours.
Comparative example 4
The preparation is the same as in example 4, the only difference being that no silica sol, siO, is added in step S3 2 Is of the quality of (1)In the amount of a-Al 2 O 3 Supplement the medicine.
Comparative example 5
The preparation is the same as in example 4, the only difference being that no silica sol, siO, is added in step S3 2 The quality of the product is supplemented by small-pore pseudo-boehmite.
Comparative example 6
The only difference in the preparation is that in the step S4, the curing is not carried out, and the extruded strips are directly dried after being molded.
Comparative example 7
Some dehydrogenation reaction auxiliary agent commodity is abroad.
Comparative example 8
Certain commercial a-Al 2 O 3 Porcelain ball.
Evaluation system:
a) Evaluation of Strength
Reference is made to HG/T2782-2011 determination of crushing resistance of chemical fertilizer catalyst particles.
TABLE 1 Strength test results
| Intensity (N/cm) | |
| Example 4 | 280 |
| Comparative example 4 | 115 |
| Comparative example 5 | 253 |
| Comparative example 6 | 235 |
Table 1 shows that the addition of silica sol can obviously promote the use of a-Al 2 O 3 The strength of the dehydrogenation reaction auxiliary agent of the kneading and extruding strip can be further increased by adopting a maintenance mode.
b) Activity evaluation
3mL of fresh dehydrogenation agent prepared by the company is taken and is respectively and uniformly mixed with 3mL of dehydrogenation reaction auxiliary agent prepared in examples 1-4 and auxiliary agent prepared in comparative examples 1-8, the mixture is placed in a quartz glass reactor, nitrogen is introduced, the temperature is raised to 580 ℃, 15mL/min of isobutane is introduced, an outlet gas is collected by using an air bag for 15min, the outlet gas enters a gas chromatography equipped with an alumina column for component analysis, isobutene is used as a target product, and the conversion rate and selectivity are calculated as shown in Table 2.
Conversion = (isobutane inlet-isobutane outlet)/isobutane inlet x 100%
Selectivity = isobutylene outlet/(isobutane inlet-isobutane outlet) ×100%
Table 2 conversion and selectivity in examples
| Conversion (%) | Selectivity (%) | |
| Example 1 | 62.8 | 93.1 |
| Comparative example 1 | 61.5 | 92.0 |
| Example 2 | 61.2 | 91.4 |
| Comparative example 2 | 60.9 | 90.6 |
| Example 3 | 59.7 | 88.9 |
| Comparative example 3 | 61.3 | 87.1 |
| Example 4 | 61.1 | 90.8 |
| Comparative example 4 | 61.2 | 90.6 |
| Comparative example 5 | 60.7 | 90.1 |
| Comparative example 6 | 61.1 | 90.5 |
| Comparative example 7 | 61.3 | 92.8 |
| Comparative example 8 | 59.8 | 87.3 |
Through the above examples 1-4 and comparative examples 1-8, it can be seen that the addition of cerium and vanadium has a tendency to increase the reactivity, and the reason for this is that cerium and vanadium have various valence states, and by utilizing this characteristic, the oxidation-reduction heat release of copper can be greatly promoted, and the reaction temperature deficiency caused by the heat absorption of dehydrogenation reaction is overcome.
In the embodiment 3 and the comparative example 3, the dehydrogenation reaction auxiliary agent is carried with S and migrates to the dehydrogenation agent, and the primary activity of the dehydrogenation agent is deactivated in a certain process, so that the occurrence of cracking side reaction is reduced, and the selectivity is improved.
Example 4 and comparative example 4 show that the addition of silica sol has almost no side effect on dehydrogenation reaction, while comparative example 5 replaces silica sol with pseudo-boehmite, and the carrier produced by roasting at 760 ℃ is a side reaction with a certain strong acidity, which can cause cracking of raw materials.
From comparative examples 7 to 8, it is apparent that the dehydrogenation reaction auxiliary agent of the present invention has significant advantages.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention.
Claims (8)
1. A preparation method of a low-carbon alkane dehydrogenation reaction auxiliary agent is characterized in that the auxiliary agent consists of Ca, cu, ce, V, P, si, al elements, wherein the auxiliary agent comprises 5-28% of CaO, 2-22% of CuO and 2-22% of CeO according to the mass percentage of oxide 2 0.8 to 3.3% V 2 O 3 1 to 4.7% of P 2 O 5 0.5-2.7%, siO 2 5-12%, the rest of Al 2 O 3 ；
The preparation method of the auxiliary agent comprises the following steps:
s1, roasting small-pore pseudo-boehmite at 1250 ℃ for 6 hours to prepare a-Al 2 O 3 ；
S2, a-Al in S1 2 O 3 Uniformly mixing with small-pore pseudo-boehmite, a calcium source, a copper source and a pore-forming agent to prepare mixed powder;
s3, uniformly mixing the metered phosphoric acid with a cerium source, a vanadium source, silica sol, nitric acid and water according to a certain proportion to prepare a mixed solution;
s4, adding the mixed solution in the step S3 into the mixed powder in the step S2, extruding strips, forming, maintaining, drying and roasting to obtain an auxiliary agent crude product;
s5, immersing the crude product of the auxiliary agent prepared in the S4 into an ammonium thiosulfate solution, and drying to prepare a finished auxiliary agent.
2. The method according to claim 1, wherein the a-Al is as described in step S2 2 O 3 The dosage of the pseudo-boehmite with small holes is calculated by Al 2 O 3 The mass percentage is 6-9:1.
3. The method according to claim 1, wherein the calcium source in step S2 is CaCO 3 、Ca(OH) 2 One or more of CaO, wherein the copper source is Cu (OH) 2 One or more of CuO and basic copper carbonate.
4. The preparation method of claim 1, wherein the pore-forming agent in the step S2 is one of CMC and sesbania powder, and the amount of the pore-forming agent is 2-10% of the mixed powder in the step S2.
5. The method according to claim 1, wherein the cerium source in step S3 is Ce (NO 3 ) 3 、CeCl 3 The vanadium source is one or two of ammonium metavanadate and vanadyl oxalate.
6. The preparation method according to claim 1, wherein the curing condition in the step S4 is that the curing is carried out for 2 days under a sealing system of 60+/-5 ℃, and the baking condition is that the curing is carried out for 4-6 hours under a temperature of 600-1000 ℃.
7. The preparation method according to claim 1, wherein the concentration of the ammonium thiosulfate solution in the step S5 is determined by the sulfur-carrying element mass of the auxiliary agent crude product in the step S4 being 0.5-1.2%.
8. The method according to claim 1, wherein the drying condition in step S5 is 120-150 ℃ for 2-4 hours.
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