CN117258819A - One-dimensional nitrogen-phosphorus-oxygen catalyst, preparation thereof and application thereof in preparation of alkene-containing compound by dehydrogenation - Google Patents
One-dimensional nitrogen-phosphorus-oxygen catalyst, preparation thereof and application thereof in preparation of alkene-containing compound by dehydrogenation Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 32
- SJWUULVPYAMRCJ-UHFFFAOYSA-N [N].[O].[P] Chemical compound [N].[O].[P] SJWUULVPYAMRCJ-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 10
- 150000001875 compounds Chemical class 0.000 title claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000004321 preservation Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical group 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 36
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 16
- 238000011068 loading method Methods 0.000 description 12
- 238000011056 performance test Methods 0.000 description 11
- 238000001354 calcination Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 8
- 230000002238 attenuated effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052582 BN Inorganic materials 0.000 description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- -1 alkyl compound Chemical class 0.000 description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical group [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000003837 high-temperature calcination Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 description 3
- 239000006012 monoammonium phosphate Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZSPTYLOMNJNZNG-UHFFFAOYSA-N 3-Buten-1-ol Chemical group OCCC=C ZSPTYLOMNJNZNG-UHFFFAOYSA-N 0.000 description 1
- 229910052580 B4C Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- PDNNQADNLPRFPG-UHFFFAOYSA-N N.[O] Chemical compound N.[O] PDNNQADNLPRFPG-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002113 nanodiamond Substances 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/24—Nitrogen compounds
-
- 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)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of catalysis, and in particular discloses a preparation method of a one-dimensional nitrogen-phosphorus-oxygen catalyst, which comprises the steps of mixing raw materials of a formula 1Performing two-stage heat treatment in a mixed atmosphere containing ammonia and oxygen to prepare the one-dimensional nitrogen-phosphorus-oxygen catalyst; in the mixed atmosphere, the volume content of ammonia is 85-98%; the two-stage heat treatment process comprises a T1 heat preservation section and a T2 heat preservation section, wherein the temperature of T1 is 100-130 ℃; t2 is 750-950 ℃. The invention also comprises the catalyst prepared by the preparation method and the dehydrogenation preparation method thereofUse in olefins. The invention prepares a brand-new catalyst, and the catalyst can obtain better catalytic selectivity and stability based on a brand-new action mode.
Description
Technical Field
The invention relates to the field of industrial catalysis, in particular to the field of alkyl compound dehydrogenation catalysts.
Background
At present, styrene is used as an industrial raw material and has wide application market in a plurality of industries. The related data show that since 2014, the imported amount of Chinese styrene is maintained to be more than 150 ten thousand tons per year, and the exported amount is only less than 25 ten thousand tons, which indicates that the yield of styrene in China cannot meet the demand amount and needs to rely on import. Therefore, the research of a novel catalyst for improving the yield of styrene is of great importance.
At present, the preparation of styrene is mainly obtained by catalytic dehydrogenation of ethylbenzene under high temperature conditions, while ethylbenzene dehydrogenation by using potassium-containing ferric oxide as a catalyst under the condition that water vapor is used as a high temperature dehydrogenation medium is the most widely used technology in industry at present, and the main problems of the technology at present are as follows: firstly, the catalyst is easy to accumulate carbon, so that a large amount of steam is required to be introduced simultaneously to eliminate the carbon accumulation, thereby generating larger energy consumption; secondly, the introduction of water vapor also tends to cause loss of potassium element in the catalyst, resulting in reduced stability of the catalyst. The catalysts reported in patents CN200910057803, CN101829576a, CN102040466a, CN103028419a, CN101279263, CN10142273 and european patent 0177832 are based on the potassium-containing iron oxide catalyst, and heavy metal elements such as cerium, molybdenum, lead and copper are added to reduce the water-hydrocarbon ratio, but the addition of heavy metals not only increases the cost of the catalyst, but also causes more pollution to the environment. In addition, the addition of various metal elements makes the preparation process of the catalysts more complicated, and the corresponding cost is increased.
In a short period of time, researchers expand the research direction to nonmetallic catalysts, such as boron carbide reported by CN109126843A, nano-diamond reported by CN112717972A, phosphorus doped boron nitride reported by CN201910739798.4 and CN202110541901.1, and the like, and all show good alkane dehydrogenation capability under the condition of no water vapor. The invention of the catalyst greatly promotes the research of the application of the nonmetallic catalyst in ethylbenzene dehydrogenation, but the preparation process of the carbon material and the boron nitride material is complicated, the steps are more, and the industrialized catalyst is not easy to amplify. Therefore, on the basis of ensuring certain performance, the preparation flow of the catalyst is simplified, and the method has important significance for popularization of the catalyst.
Disclosure of Invention
Aiming at the problems of complex preparation and unsatisfactory performance of the traditional nonmetallic dehydrogenation catalyst, the first aim of the invention is to provide a preparation method of a one-dimensional nitrogen-phosphorus-oxygen catalyst, aiming at obtaining a brand new dehydrogenation catalyst with excellent dehydrogenation capability.
The second object of the invention is to provide the one-dimensional nitrogen-phosphorus-oxygen catalyst prepared by the preparation method.
The third object of the present invention is to provide the application of the one-dimensional nitrogen-phosphorus-oxygen catalyst for preparing vinyl (c=c) by dehydrogenation of ethyl (C-C).
The preparation method of the one-dimensional nitrogen-phosphorus-oxygen catalyst comprises the steps of carrying out two-stage heat treatment on a raw material of the formula 1 in a mixed atmosphere containing ammonia and oxygen to prepare the one-dimensional nitrogen-phosphorus-oxygen catalyst;
in the mixed atmosphere, the volume content of ammonia is 85-98%;
the two-stage heat treatment process comprises a T1 heat preservation section and a T2 heat preservation section, wherein the temperature of T1 is 90-150 ℃; t2 is 750-950 ℃.
The research of the invention shows that the two-stage calcination treatment (two-stage heat treatment) of the compound shown in the formula 1 under the mixed atmosphere of ammonia and oxygen is innovatively combined with the joint control of the structure shown in the formula 1, the atmosphere proportion of the mixed gas and the temperature parameters of the two-stage calcination, so that the synergy can be realized, and the nitrogen-phosphorus-oxygen metal-free catalyst with a one-dimensional structure can be obtained unexpectedly. The research of the invention also shows that the prepared catalyst has excellent application performance in the aspect of olefin preparation by dehydrogenation, and particularly can show excellent product selectivity and running stability.
In the invention, the raw material of the formula 1 can be placed in a conventional tube furnace with heating equipment, and the temperature is raised to the T1 temperature from the initial temperature (usually room temperature) for one section, and then is raised to the T2 section after heat preservation treatment at the temperature, and the heat preservation is continued, so that the catalyst is prepared.
In the invention, the combined control of the structure of the formula 1, the ammonia-oxygen mixed atmosphere and the content proportion thereof, the two-stage calcination mechanism and the temperature is the key for integrally and synergistically improving the performance of the prepared material in the aspect of olefin production by dehydrogenation.
In the invention, the volume content of ammonia in the mixed atmosphere is preferably 90-95%. The research of the invention shows that the conversion rate and the product selectivity of the prepared material in the aspect of dehydrogenation alkene preparation can be further improved by carrying out the two-stage heat treatment under the mixed atmosphere with the preferable proportion.
The rate of temperature rise in the heat treatment stage is not particularly limited and may be, for example, 1 to 10℃per minute;
in the invention, the temperature of T1 is 100-130 ℃, and more preferably 100-120 ℃;
the heat preservation time of the T1 heat preservation section can be adjusted according to the requirements, and the heat preservation time of the T1 heat preservation section is 20-200 min, can be further 40-90 min, and can be further 50-70 min in consideration of treatment efficiency.
Preferably, the temperature of T2 is 800-900 ℃;
the heat preservation time of the T2 heat preservation section can be adjusted according to the requirement, and the heat preservation time of the T2 heat preservation section is 20-300 min, further can be 50-130 min, and further preferably is 80-100 min in consideration of treatment efficiency.
The invention also provides a one-dimensional nitrogen-phosphorus-oxygen catalyst prepared by the preparation method.
According to the research of the invention, the preparation method can endow the product with special physical and chemical characteristics and morphology, so that the product is favorable for endowing the product with excellent selectivity and stability in dehydrogenation and alkene preparation.
The one-dimensional nitrogen-phosphorus-oxygen catalyst has a nano tubular structure;
preferably, in the one-dimensional nitrogen-phosphorus-oxygen catalyst, the element mole ratio of phosphorus, nitrogen and oxygen is 1: x: y, where x is preferably from 1.4 to 2.6, preferably from 1.5 to 2.1, and y is from 0.25 to 5, preferably from 0.3 to 0.5.
The invention also provides application of the one-dimensional nitrogen-phosphorus-oxygen catalyst prepared by the preparation method, a raw material containing an ethyl group is contacted with the one-dimensional nitrogen-phosphorus-oxygen catalyst prepared by the preparation method, dehydrogenation reaction is carried out, and the ethyl group (C-C) in the raw material is dehydrogenated to prepare a corresponding olefin product (C=C).
For example, in the present invention, the raw material containing an ethyl group is a compound having a structural formula of formula 2;
2, 2
Wherein R is 1 ～R 4 H, C alone 1 ～C 10 Alkyl, C of (2) 3 ～C 10 Cycloalkyl or aryl groups of (a); alternatively, R 1 And R is R 4 Mutually ring-closing to form a ring base;
the alkyl, cycloalkyl, cyclic or aryl radicals being allowed toWith substituents C 1 ～C 6 Alkyl, C of (2) 1 ～C 6 At least one substituent selected from the group consisting of alkoxy, halogen, phenyl, nitro, trifluoromethyl;
preferably, the aryl is benzene ring, five-membered heterocyclic aryl, six-membered heterocyclic aryl, or condensed ring formed by combining two or more aromatic rings in benzene ring, five-membered heterocyclic aryl and six-membered heterocyclic aryl.
In a more specific embodiment of the present invention, the feedstock containing an ethyl group is a compound having the structure of formula 2-A;
in the formula 2-A, R 1 H, C of a shape of H, C 1 ～C 2 Alkyl, isopropyl, phenyl or substituted phenyl; the benzene ring of the substituted phenyl contains C 1 ～C 2 Alkyl, isopropyl, C 1 ～C 3 At least one substituent selected from the group consisting of alkoxy, halogen, phenyl, nitro, trifluoromethyl;
said R is 3 Is H or C 1 ～C 2 Is a hydrocarbon group.
In the application of the invention, the one-dimensional nitrogen-phosphorus-oxygen catalyst and the carrier are compounded, and then the dehydrogenation reaction is carried out.
In the invention, the temperature of dehydrogenation reaction is 500-700 ℃; preferably 550-650 ℃;
preferably, the dehydrogenation reaction is carried out under anhydrous conditions;
preferably, the dehydrogenation reaction is carried out in the absence of oxygen.
The beneficial effects are that:
according to the invention, the compound of the formula 1 is subjected to two-stage calcination treatment under the mixed atmosphere of ammonia and oxygen, and the combination control of the structure of the formula 1, the atmosphere proportion in the mixed atmosphere and the temperature parameters of the two-stage calcination is further matched, so that the synergy can be realized, and the nitrogen-phosphorus-oxygen metal-free catalyst with a one-dimensional structure can be obtained unexpectedly. And the research shows that the prepared catalyst has excellent application performance in the aspect of olefin preparation by dehydrogenation, and particularly can show better selectivity and stability than the prior similar catalyst.
The research shows that under the test condition of the invention, the ethylbenzene conversion rate can reach more than 54%, and the selectivity of the styrene can reach 94-98%, the stability exceeds 50 hours, and the excellent selectivity and stability are both achieved.
Compared with the existing carbon-based and boron nitride-based catalysts, the nitrogen-phosphorus-oxygen catalyst has the obvious advantage of simple preparation.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of the catalyst of example 1;
FIG. 2X-ray photoelectron Spectrometry (XPS) Total spectrum of the catalyst of example 1.
Detailed Description
In the following cases, the heat treatment process was performed in a tube furnace.
The ratio of the mixed atmospheres in the heat treatment stage is referred to as the volume ratio.
The room temperature is 5-45 ℃.
In the following cases, steady operation is indicated to refer to maintaining the conversion and the run time at selectivity.
Example 1
Weighing 10.90g of commercial formula, loading into corundum ark, placing into a tube furnace, and introducing 60mL/min of mixed gas (90% ammonia gas-10% oxygen gas) for high-temperature calcination. The high-temperature calcination is divided into two stages, the first stage is to raise from room temperature to 120 ℃ at a rate of 5 ℃/min (marked as T1) and hold for 60min, the second stage is to raise from 120 ℃ to 800 ℃ at a rate of 5 ℃/min (marked as T2) and hold for 90min and then cool naturally to room temperature, and the obtained catalyst is named PN-60-800-90. The molar ratio of the elements in the obtained catalyst is tested as P, N, O=1: 2.1:0.48.
the test method of the catalyst performance comprises the following steps: 50mg of PN-60-800-90 catalyst is weighed, added with 2ml of quartz sand with granularity of 40-60 meshes for dilution, and filled into a fixed bed quartz reaction tube with granularity of phi 8 mm. And (3) introducing 20mL/min of nitrogen, heating the catalytic bed to 600 ℃ from room temperature at a speed of 4 ℃/min, and then introducing mixed feed gas with the volume fraction of ethylbenzene of 2.8% at a speed of 20mL/min, wherein the carrier gas is nitrogen, so as to carry out the reaction. The reaction product was collected with ethanol at 5℃and analyzed for its composition by gas chromatography. The ethylbenzene conversion rate is 54%, the styrene selectivity is 95%, and the stable operation can be performed for more than 50 hours.
Example 2
The difference from example 1 was that the mixture was changed to a mixture of 95% ammonia and 5% oxygen, and the other production steps were the same as in example 1. The catalyst obtained was still subjected to sample loading, reaction and performance test by the method of example 1, and the performance of the catalyst was measured as follows: the ethylbenzene conversion rate is 50%, the styrene selectivity is 96%, and the stable operation can be performed for more than 50 hours.
Example 3
The difference from example 1 was that the mixture was changed to 85% ammonia-15% oxygen mixture, and the other production steps were identical to those of example 1. The catalyst obtained was still subjected to sample loading, reaction and performance test by the method of example 1, and the performance of the catalyst was measured as follows: the ethylbenzene conversion rate is 45%, the styrene selectivity is 98%, and the stable operation can be performed for more than 50 hours.
Example 4
The difference compared to example 1 is only that the temperature of T2 was changed to 900 ℃, and the other preparation steps were identical to example 1.
The molar ratio of the elements in the obtained catalyst is tested as P, N, O=1: 1.5:0.3. the catalyst obtained was still subjected to sample loading, reaction and performance test by the method of example 1, and the performance of the catalyst was measured as follows: the ethylbenzene conversion rate is 45%, the styrene selectivity is 94%, and the stable operation can be performed for more than 50 hours.
Example 5
The difference compared to example 1 is only that the temperature of T1 is changed to 100 ℃, and other preparation steps remain the same as example 1.
The catalyst obtained was still subjected to sample loading, reaction and performance test by the method of example 1, and the performance of the catalyst was measured as follows: the ethylbenzene conversion rate is 53%, the styrene selectivity is 95%, and the stable operation can be performed for more than 50 hours.
Comparative example 1
The other preparation steps remain the same as in example 1, except that formula 1 in example 1 is replaced with hydroxyethylethylene binary phosphonic acid (HEDP). The catalyst obtained was still subjected to sample loading, reaction and performance test by the method of example 1, and the performance of the catalyst was measured as follows: the ethylbenzene conversion rate is 11%, and the styrene selectivity is 93%.
Comparative example 2
The other preparation steps were consistent with example 1, except that formula 1 in example 1 was replaced with monoammonium phosphate (MAP). The catalyst obtained was still subjected to sample loading, reaction and performance test by the method of example 1, and the performance of the catalyst was measured as follows: the ethylbenzene conversion was 9.7% and the styrene selectivity was 84%.
Comparative example 3
The difference compared to example 1 is only that the mixture was changed to pure nitrogen (99.9% nitrogen), and other production steps were kept identical to example 1. Catalyst products were hardly obtained and the preparation failed.
Comparative example 4
The difference from example 1 was that the air-fuel mixture was changed to air, and the other production steps were the same as in example 1. Catalyst products were hardly obtained and the preparation failed.
Comparative example 5
The difference from example 1 was that the mixture was changed to 99.9% ammonia gas, and the other production steps were identical to those of example 1. The catalyst obtained was still subjected to sample loading, reaction and performance test by the method of example 1, and the performance of the catalyst was measured as follows: the ethylbenzene conversion rate is 39%, the styrene selectivity is 94%, and the dehydrogenation performance is obviously attenuated after 20 hours of operation.
Comparative example 6
The difference compared to example 1 is only that the temperature of T2 was changed to 700 ℃, and the other preparation steps remained the same as in example 1. The molar ratio of the elements in the obtained catalyst is tested as P, N, O=1: 2.9:0.36. the catalyst obtained was still subjected to sample loading, reaction and performance test by the method of example 1, and the performance of the catalyst was measured as follows: the ethylbenzene conversion rate is 33%, the styrene selectivity is 94%, and the dehydrogenation performance is obviously attenuated after 20 hours of operation.
Comparative example 7
The difference compared to example 1 is only that the temperature of T2 is changed to 1000 ℃, and the other preparation steps remain the same as example 1. The molar ratio of the elements in the obtained catalyst is tested as P, N, O=1: 1.3:0.2. the catalyst obtained was still subjected to sample loading, reaction and performance test by the method of example 1, and the performance of the catalyst was measured as follows: the ethylbenzene conversion rate is 23% and the styrene selectivity is 94%.
Comparative example 8
The first stage of high temperature calcination in example 1 was eliminated from the incubation and the temperature was directly raised to 800 ℃, with other preparation steps consistent with example 1. The amount of the catalyst obtained is very small, and the preparation fails.
Comparative example 9
The difference compared to example 1 is only that the temperature of T1 is changed to 80 ℃, and the other preparation steps remain the same as example 1. The catalyst obtained was still subjected to sample loading, reaction and performance test by the method of example 1, and the performance of the catalyst was measured as follows: the ethylbenzene conversion rate is 26%, the styrene selectivity is 92%, and the dehydrogenation performance is obviously attenuated after 20 hours of operation.
Comparative example 10
Sample loading, reaction and performance testing were performed using commercial phosphorus nitride as a catalyst, still using the method of example 1, and the performance of the catalyst was measured as: ethylbenzene conversion was 25%, styrene selectivity was 96%, and dehydrogenation performance was significantly attenuated after 20 hours of operation.
TABLE 1 comparison of the Main preparation conditions and Properties of the catalysts of the examples
TABLE 2 comparison of the Main preparation conditions and Property of the comparative catalyst
From example 1, comparative examples 1-2, it can be seen that the use of formula 1 is critical to the performance of the resulting material, which is much higher than the ethylbenzene conversion on the HEDP and MAP obtained catalysts.
It can be seen from examples 1, 2, 3 and comparative examples 3 to 5 that the calcining atmosphere greatly affects the performance of the catalyst. Calcination in nitrogen and air atmosphere hardly resulted in catalyst product failure. Under the mixed atmosphere of ammonia and oxygen, better catalyst performance can be obtained. Wherein the concentration of ammonia is 85-95%, and the conversion rate of the catalyst can be maintained at a higher level of 45-54%. An oxygen-free or excessively high oxygen atmosphere is not conducive to the performance of the catalyst.
It can be seen from examples 1, 4 and comparative examples 6 to 7 that the calcination temperature in the second stage also has a great influence on the performance of the catalyst. Calcination at 800-900 c may result in better catalyst performance. Too low or too high a temperature is detrimental to the performance of the catalyst.
It can be seen from examples 1, 5 and comparative examples 8 to 9 that the calcination temperature in the first stage has a large influence on the performance of the catalyst. Better catalyst performance can be obtained by residence for a period of time at 100-120 ℃. If the residence time is not taken or the temperature is too low (e.g., 80 ℃ C.) at this stage, a catalyst product of sufficient quality is not obtained, the preparation fails, and the performance test thereof cannot be performed.
As can be seen from examples and comparative example 10, the commercial phosphorus nitride powder, without oxygen, had significantly lower performance.
Claims (10)
1. A preparation method of a one-dimensional nitrogen-phosphorus-oxygen catalyst is characterized in that a raw material of a formula 1 is subjected to two-stage heat treatment in a mixed atmosphere containing ammonia and oxygen to prepare the one-dimensional nitrogen-phosphorus-oxygen catalyst;
in the mixed atmosphere, the volume content of ammonia is 85-98%;
the two-stage heat treatment process comprises a T1 heat preservation section and a T2 heat preservation section, wherein the temperature of T1 is 90-150 ℃; t2 is 750-950 ℃.
2. The method for preparing a one-dimensional nitrogen-phosphorus-oxygen catalyst according to claim 1, wherein the volume content of ammonia gas in the mixed atmosphere is 90-95%.
3. The method for preparing a one-dimensional nitrogen-phosphorus-oxygen catalyst according to claim 1, wherein the temperature of T1 is 100-130 ℃, and more preferably 100-120 ℃;
preferably, the heat preservation time of the T1 heat preservation section is 20-200 min, and more preferably 40-90 min.
4. The method for preparing a one-dimensional nitrogen-phosphorus-oxygen catalyst according to claim 1, wherein the temperature of T2 is 800-900 ℃;
preferably, the heat preservation time of the T2 heat preservation section is 20-300 min, and more preferably 50-130 min.
5. A one-dimensional nitrogen-phosphorus-oxygen catalyst produced by the production method of any one of claims 1 to 4;
preferably, the one-dimensional nitrogen-phosphorus-oxygen catalyst has a nano tubular structure;
preferably, in the one-dimensional nitrogen-phosphorus-oxygen catalyst, the element mole ratio of phosphorus, nitrogen and oxygen is 1: x: y, where x is preferably from 1.4 to 2.6 and y is from 0.25 to 5.
6. Use of the one-dimensional nitrogen-phosphorus-oxygen catalyst prepared by the preparation method according to any one of claims 1 to 4, characterized in that raw materials containing ethyl groups are contacted with the one-dimensional nitrogen-phosphorus-oxygen catalyst prepared by the preparation method according to any one of claims 1 to 4, dehydrogenation reaction is carried out, and the ethyl groups in the raw materials are dehydrogenated, so that corresponding olefin products are prepared.
7. The use according to claim 6, wherein the starting material containing an ethyl group is a compound of formula 2;
wherein R is 1 ～R 4 H, C alone 1 ～C 10 Alkyl, C of (2) 3 ～C 10 Cycloalkyl or aryl groups of (a); alternatively, R 1 And R is R 4 Mutually ring-closing to form a ring base;
the alkyl, cycloalkyl, cyclic or aryl groups are allowed to bear substituents which are C 1 ～C 6 Alkyl, C of (2) 1 ～C 6 At least one substituent selected from the group consisting of alkoxy, halogen, phenyl, nitro, trifluoromethyl;
preferably, the aryl is benzene ring, five-membered heterocyclic aryl, six-membered heterocyclic aryl, or condensed ring formed by combining two or more aromatic rings in benzene ring, five-membered heterocyclic aryl and six-membered heterocyclic aryl.
8. The use according to claim 7, wherein the starting material containing an ethyl group is a compound having the structure of formula 2-a;
in the formula 2-A, R 1 H, C of a shape of H, C 1 ～C 2 Alkyl, isopropyl, phenyl or substituted phenyl; the benzene ring of the substituted phenyl contains C 1 ～C 2 Alkyl, isopropyl, C 1 ～C 3 At least one substituent selected from the group consisting of alkoxy, halogen, phenyl, nitro, trifluoromethyl;
said R is 3 Is H or C 1 ～C 2 Is a hydrocarbon group.
9. The use according to claim 7, wherein the one-dimensional nitrogen phosphorus oxygen catalyst is used alone or in combination with a support, followed by said dehydrogenation.
10. Use according to any one of claims 7 to 9, wherein the dehydrogenation reaction is carried out at a temperature of 500 to 700 ℃; preferably 550-650 ℃;
preferably, the dehydrogenation reaction is carried out under anhydrous conditions;
preferably, the dehydrogenation reaction is carried out in the absence of oxygen.
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