CN112023921A - Preparation method of Pt-based catalyst with high-dispersion active component - Google Patents
Preparation method of Pt-based catalyst with high-dispersion active component Download PDFInfo
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- 239000011865 Pt-based catalyst Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000006185 dispersion Substances 0.000 title claims abstract description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 55
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 238000001816 cooling Methods 0.000 claims abstract description 16
- XASWYPVFCVEQSU-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;potassium Chemical compound [K].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O XASWYPVFCVEQSU-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000010992 reflux Methods 0.000 claims abstract description 15
- 150000004032 porphyrins Chemical class 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 238000005520 cutting process Methods 0.000 claims abstract description 9
- 238000001704 evaporation Methods 0.000 claims abstract description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 9
- 238000000967 suction filtration Methods 0.000 claims abstract description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 8
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims abstract description 7
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 6
- 229910052718 tin Inorganic materials 0.000 claims abstract description 4
- 238000002791 soaking Methods 0.000 claims abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 45
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical group [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 34
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- 235000010333 potassium nitrate Nutrition 0.000 claims description 17
- 239000004323 potassium nitrate Substances 0.000 claims description 17
- 239000011148 porous material Substances 0.000 claims description 10
- VFMUXPQZKOKPOF-UHFFFAOYSA-N 2,3,7,8,12,13,17,18-octaethyl-21,23-dihydroporphyrin platinum Chemical group [Pt].CCc1c(CC)c2cc3[nH]c(cc4nc(cc5[nH]c(cc1n2)c(CC)c5CC)c(CC)c4CC)c(CC)c3CC VFMUXPQZKOKPOF-UHFFFAOYSA-N 0.000 claims description 8
- 229960001484 edetic acid Drugs 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 239000004005 microsphere Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 41
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 42
- 239000007787 solid Substances 0.000 description 34
- 239000000243 solution Substances 0.000 description 34
- 239000001294 propane Substances 0.000 description 21
- 238000006356 dehydrogenation reaction Methods 0.000 description 17
- 238000011156 evaluation Methods 0.000 description 14
- 238000005303 weighing Methods 0.000 description 13
- 230000032683 aging Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002846 Pt–Sn Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008542 thermal sensitivity Effects 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01J35/396—Distribution of the active metal ingredient
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
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Abstract
The invention relates to a preparation method of a Pt-based catalyst with a highly dispersed active component, which comprises the following steps: (1) adding a solution containing potassium ethylenediamine tetraacetate into Sn-containing alumina serving as a carrier, and performing suction filtration to obtain an Sn and K-containing alumina carrier sample; (2) vacuumizing the obtained product, adding an ethanol solution containing porphyrin Pt, heating and refluxing in a vacuum state, stopping refluxing, and continuously evaporating the solvent; (3) heating the obtained product in a nitrogen atmosphere, then cutting in nitrogen mixed gas containing HCl and water vapor, treating for a certain time, and then introducing nitrogen for cooling; (4) and (3) soaking the obtained product in an alkali metal assistant K, and drying and roasting to obtain the target product Pt-based catalyst with high-dispersion active components. The invention can realize high dispersion of Pt and reduce the Pt dosage, has stable active phase structure, good activity, high propylene selectivity and strong stability, and is beneficial to the industrial production of the catalyst.
Description
Technical Field
The invention relates to a preparation method of a high-dispersion dehydrogenation catalyst, in particular to a preparation method of a Pt-based catalyst with a high-dispersion active component.
Background
Propylene is one of the most important basic feedstocks for the chemical industry. Over the last 5 years, the annual rate of increase was 1.8 times that of GDP. The traditional process has serious shortage of propylene capacity, and an alternative process for producing propylene must be searched. The technology (PDH) for preparing propylene by propane dehydrogenation is the most competitive way and will become one of the key technologies for ensuring the core competitiveness in the global competition of petrochemical industry in various countries.
Propane dehydrogenation technology commonly uses supported Pt-based catalysts, and currently faces major problems: the Pt active component has high thermal sensitivity at high temperature, is easy to migrate, agglomerate and even sinter, so that the Pt active component is difficult to keep highly dispersed, the catalytic efficiency of the Pt active phase is rapidly reduced, the carbon deposition amount is rapidly increased, and even the Pt active phase is permanently inactivated due to sintering. At present, the aim of improving the selectivity and stability of the catalyst and delaying the deactivation of the catalyst is fulfilled by adding diluent gas hydrogen, performing negative pressure operation and other process strategies internationally. But the problems of poor high-temperature stability and rapid carbon deposit inactivation of the catalyst are not solved essentially. Therefore, how to realize the controllable preparation of the active phase, construct the Pt active phase with a high-temperature stable structure, and improve the catalytic efficiency and the service life of the Pt active phase is a main challenge facing the development of the Pt-based propane dehydrogenation catalyst.
CN1579616 patent provides a gamma-Al with macropore, low bulk ratio and double-pore structure2O3The pellets are used as a carrier for the catalyst for the dehydrogenation of the straight-chain alkane, and the reaction performance of the dehydrogenation of the low-carbon alkane can be improved by modulating the catalyst. USP4,914,075 discloses Pt-based catalysts supported on dehydrogenated aluminas of propane and other lower alkanes with high alkane conversion and olefin selectivity. The CN1201715 patent discloses Pt-Sn-K/Al for dehydrogenation of low carbon alkane2O3A method for preparing the catalyst. USP4,914,075, USP4,353,815, EP98,622Et al report Pt-based catalysts for propane and other lower alkanes dehydrogenation with high alkane conversion and olefin selectivity. Although these catalysts have high alkane conversion rate and olefin selectivity under certain reaction conditions, the catalysts have poor stability of catalytic reaction and short service life due to easy carbon deposition deactivation under high temperature conditions. A great deal of propane dehydrogenation research on Pt-Sn catalysts taking alumina as a carrier has been reported at home and abroad, but the activity, the stability, the product selectivity, the preparation economy and other aspects of the catalyst cannot be considered at the same time. The traditional Pt-based propane dehydrogenation catalyst takes alumina as a carrier, when Pt is introduced by adopting an impregnation method, the alumina carrier has a strong adsorption effect on a Pt precursor, although a competitive adsorbent is adopted, the Pt still cannot be highly dispersed, the Pt dosage cannot be reduced, aggregation and growth are easy to occur in the reaction process, and the propane conversion rate and the propylene selectivity are reduced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a Pt-based catalyst with a highly dispersed active component, and the catalyst prepared by the method can realize the high dispersion of Pt, has a stable active phase structure, and has better activity, selectivity and stability and lower raw material coking rate.
In order to solve the technical problem, the invention is realized as follows:
a preparation method of a Pt-based catalyst with high dispersion of active components comprises the following steps:
(1) adding a solution containing potassium ethylenediamine tetraacetate into Sn-containing alumina serving as a carrier, and performing suction filtration to obtain an Sn and K-containing alumina carrier sample;
(2) vacuumizing the product obtained in the step (1), adding an ethanol solution containing porphyrin Pt, heating and refluxing in a vacuum state, stopping refluxing, and continuously evaporating the solvent;
(3) heating the product obtained in the step (2) in a nitrogen atmosphere, then cutting into a nitrogen mixed gas containing HCl and water vapor, treating for a certain time, and then introducing nitrogen for cooling;
(4) and (4) soaking the product obtained in the step (3) in an alkali metal assistant K, and drying and roasting to obtain the target product Pt-based catalyst with high-dispersion active components.
As a preferable scheme, in the step (1), the Sn-containing alumina carrier is spherical, strip-shaped, microsphere or special-shaped; the specific surface of the Sn-containing alumina carrier is 170-260 m2A pore volume of 0.40-0.90 cm/g3/g。
The Sn in the alumina carrier containing Sn can be introduced in the gelling process of alumina, can also be introduced in a loading mode, and can also be introduced in the kneading process of alumina forming.
Further, in the step (1) of the present invention, the potassium ethylenediaminetetraacetate solution is prepared by mixing ethylenediaminetetraacetic acid, potassium hydroxide and water.
Further, the molar ratio of the ethylene diamine tetraacetic acid to the potassium hydroxide is 1: 4-10, preferably 1: 6-8; the concentration of the ethylene diamine tetraacetic acid potassium solution is 0.01-0.3 mol/L, preferably 0.05-0.2 mol/L based on the mass of ethylene diamine tetraacetic acid.
Furthermore, in the step (1), the addition amount of the Sn-containing alumina is 50-300 g, preferably 100-200 g, based on 1L of the EDTA potassium solution; fully stirring for 1-24 h, preferably 4-8 h.
Further, in the step (2), after the product obtained in the step (1) is vacuumized for 0.3-2 hours, preferably 0.5-1.2 hours, adding an ethanol solution containing porphyrin Pt, heating to 40-80 ℃ in a vacuum state, preferably 50-70 ℃, and keeping refluxing for 1-6 hours, preferably 2-4 hours; the volume ratio of the ethanol solution containing porphyrin Pt to the product obtained in the step (1) is 4-6: 1.
further, in the step (3), a nitrogen gas mixture containing HCl and water vapor is introduced at a temperature of 120-240 ℃, preferably 160-200 ℃, and the treatment is carried out for 1-8 hours, preferably 2-4 hours; the volume airspeed is 200-2000 h-1Preferably 500h-1-1000h-1(ii) a In the nitrogen mixed gas, the volume content of HCl is 1-10%; preferably 2-4%; the volume content of the water vapor is 5-30%, preferably 10-20%.
Further, in the step (4), the product obtained in the step (3) is further impregnated with an alkali metal additive K, aged at room temperature for 2-16 h, preferably 4-8 h, dried at 40-160 ℃ for 2-16 h, preferably dried at 80-120 ℃ for 4-8 h, and calcined at 400-800 ℃ for 2-20 h, preferably calcined at 500-700 ℃ for 4-8 h, preferably calcined at 450-600 ℃ for 6-18 h.
Furthermore, in the Pt-based catalyst with highly dispersed active components, the weight percentage content of Pt calculated by elements is 0.1-1.0%, and preferably 0.2-0.5%; the weight percentage of Sn is 0.2-10% calculated by element; preferably 0.5-5%; the percentage content of K is 0.3-4%, preferably 0.3-3% by weight of the element.
Further, in the step (2) of the present invention, the porphyrin Pt is platinum octaethylporphyrin; the alkali metal additive K is potassium nitrate. The alkali metal additive K is soluble K-containing salt, which can be inorganic salt or organic salt, and is preferably potassium nitrate.
In the invention, potassium ethylene diamine tetraacetate is highly dispersed on the surface of Sn-containing alumina in advance, porphyrin platinum with larger kinetic diameter is loaded, under the combined action of HCl and water vapor, in the presence of hydroxyl free radicals, porphyrin pi ring is destroyed, conjugation is lost, the stability of porphyrin platinum is reduced, chloride ions and platinum in the porphyrin platinum have stronger affinity, platinum is eluted from a coordination structure, then the platinum is migrated to the vicinity of ethylene diamine tetraacetate, potassium combined with the ethylene diamine tetraacetate is replaced, thus forming a coordination compound of the ethylene diamine tetraacetate and Pt, and the highly dispersed Pt-containing catalyst is obtained after drying and roasting. The preparation method can realize high dispersion of Pt and reduce the Pt dosage, and has the advantages of stable active phase structure, good activity, high propylene selectivity and strong stability. The catalyst of the invention has simple preparation method and mature process technology, and is beneficial to the industrial production of the catalyst.
Drawings
The invention is further described with reference to the following figures and detailed description. The scope of the invention is not limited to the following expressions.
FIG. 1 is a transmission electron micrograph of the catalyst obtained in example 2.
Detailed Description
Example 1
Respectively weighing certain amount of EDTA powder and solid potassium hydroxide in the molar ratio of 1 to 7, adding into deionized water, and stirring to obtain mixed solution containing EDTA and potassium hydroxide with molar concentration of 0.15 mol/L.
Weighing dried Sn-containing alumina carrier (spherical, diameter 1.6mm, pore volume 0.56 cm)3G, specific surface area 224m2The carrier was used in the following examples) 75g was added to 500mL of a solution containing potassium ethylenediaminetetraacetate, sufficiently stirred for 6 hours, and then filtered with suction. And placing the solid obtained after suction filtration in a rotary evaporator, vacuumizing for 1h, adding 375mL of ethanol solution containing a certain amount of octaethylporphyrin platinum, heating to 60 ℃ under a vacuum state, treating for 3h, stopping refluxing, continuously evaporating the solvent, cooling, and taking out the solid. Putting the obtained solid in a fixed bed reactor, heating to 180 ℃ in a nitrogen atmosphere, then cutting in nitrogen containing HCl with a volume concentration of 3% and water vapor with a volume concentration of 15%, wherein the volume space velocity is 750h-1And after 3h of treatment, switching to nitrogen and cooling. Preparing 75mL of potassium nitrate solution with a certain concentration, adding the potassium nitrate solution into 50g of solid which is treated by nitrogen and contains HCl and water vapor, aging for 10h, drying for 6h at 100 ℃, and roasting for 10h at 500 ℃ to obtain a catalyst C-1, wherein the catalyst comprises the following components in percentage by weight: 0.3 wt% of Pt, 1 wt% of Sn and 2 wt% of K. The grain size distribution of Pt grains in the range of 1nm-3nm is 93%. Evaluation conditions were as follows: at 600 ℃, the mass space velocity of propane is 2h-1The propane dehydrogenation reaction was carried out under normal pressure with the catalyst amount of 3 g. The evaluation results are shown in Table 1.
Example 2
Respectively weighing a certain amount of the following components in a molar ratio of 1: 6, adding the ethylenediamine tetraacetic acid powder and the solid potassium hydroxide into deionized water, and fully stirring to prepare a mixed solution containing the ethylenediamine tetraacetic acid and the potassium hydroxide, wherein the molar concentration of the mixed solution is 0.2 mol/L.
Weighing dried Sn-containing alumina carrier (spherical, diameter 1.6mm, pore volume 0.56 cm)3G, specific surface area 224m2Per g, following fruitThe carrier was used in all examples) was added to 500mL of a solution containing potassium ethylenediaminetetraacetate, sufficiently stirred for 4 hours, and then suction-filtered. And (3) placing the solid obtained after suction filtration in a rotary evaporator, vacuumizing for 1.2h, adding 400mL of ethanol solution containing a certain amount of octaethylporphyrin platinum, heating to 50 ℃ in a vacuum state, treating for 4h, stopping refluxing, continuously evaporating the solvent, cooling, and taking out the solid. Putting the obtained solid in a fixed bed reactor, heating to 160 ℃ in a nitrogen atmosphere, then cutting in nitrogen containing HCl with volume concentration of 4% and water vapor with volume concentration of 20%, wherein the volume space velocity is 500h-1And after 4 hours of treatment, switching to nitrogen and cooling. Preparing 75mL of potassium nitrate solution with a certain concentration, adding the potassium nitrate solution into 50g of solid which is treated by nitrogen and contains HCl and water vapor, aging for 16h, drying for 4h at 80 ℃, and roasting for 18h at 450 ℃ to obtain a catalyst C-2, wherein the catalyst comprises the following components in percentage by weight: 0.5 wt% of Pt, 5 wt% of Sn and 3 wt% of K. The grain size distribution of Pt grains in the range of 1nm-3nm is 96%. Evaluation conditions were as follows: at 600 ℃, the mass space velocity of propane is 2h-1The propane dehydrogenation reaction was carried out under normal pressure with the catalyst amount of 3 g. The evaluation results are shown in Table 1.
Example 3
Respectively weighing certain amount of EDTA powder and solid potassium hydroxide in the molar ratio of 1 to 8, adding into deionized water, and stirring to obtain mixed solution containing EDTA and potassium hydroxide with molar concentration of 0.05 mol/L.
Weighing dried Sn-containing alumina carrier (spherical, diameter 1.6mm, pore volume 0.56 cm)3G, specific surface area 224m2The carrier was used in the following examples) 50g, was added to 500mL of a solution containing potassium ethylenediaminetetraacetate, stirred well for 4 hours, and then filtered with suction. And (3) placing the solid obtained after suction filtration in a rotary evaporator, vacuumizing for 0.5h, adding 300mL of ethanol solution containing a certain amount of octaethylporphyrin platinum, heating to 70 ℃ in a vacuum state, treating for 2h, stopping refluxing, continuously evaporating the solvent, cooling, and taking out the solid. Putting the obtained solid in a fixed bed reactor, heating to 160 ℃ in the nitrogen atmosphere, then cutting in nitrogen containing HCl with the volume concentration of 2 percent and water vapor with the volume concentration of 10 percent, and emptyingThe speed is 1000h-1And after the treatment for 2 hours, switching to nitrogen and cooling. Preparing 75mL of potassium nitrate solution with a certain concentration, adding the potassium nitrate solution into 50g of solid which is treated by nitrogen and contains HCl and water vapor, aging for 10h, drying for 4h at 120 ℃, and roasting for 6h at 600 ℃ to obtain a catalyst C-3, wherein the catalyst comprises the following components in percentage by weight: 0.2% of Pt, 0.5% of Sn and 1.0% of K. The grain size distribution of Pt grains in the range of 1nm-3nm is 92%. Evaluation conditions were as follows: at 600 ℃, the mass space velocity of propane is 2h-1The propane dehydrogenation reaction was carried out under normal pressure with the catalyst amount of 3 g. The evaluation results are shown in Table 1.
Example 4
Respectively weighing certain amount of EDTA powder and solid potassium hydroxide in the molar ratio of 1 to 7, adding into deionized water, and stirring to obtain mixed solution containing EDTA and potassium hydroxide with molar concentration of 0.15 mol/L.
Weighing dried Sn-containing alumina carrier (spherical, diameter 1.6mm, pore volume 0.56 cm)3G, specific surface area 224m2Per g, the carrier is used in the following examples) 100g, added to 500mL of a solution containing potassium ethylenediaminetetraacetate, stirred well for 4h, and then filtered with suction. And (3) placing the solid obtained after suction filtration in a rotary evaporator, vacuumizing for 0.8h, adding 500mL of ethanol solution containing a certain amount of octaethylporphyrin platinum, heating to 60 ℃ in a vacuum state, treating for 3h, stopping refluxing, continuously evaporating the solvent, cooling, and taking out the solid. Putting the obtained solid in a fixed bed reactor, heating to 160 ℃ in a nitrogen atmosphere, then cutting in nitrogen containing 3% of HCl by volume and 15% of water vapor by volume, wherein the volume space velocity is 900h-1And after 4 hours of treatment, switching to nitrogen and cooling. Preparing 75mL of potassium nitrate solution with a certain concentration, adding the potassium nitrate solution into 50g of solid which is treated by nitrogen and contains HCl and water vapor, aging for 4h, drying for 6h at 100 ℃, and roasting for 8h at 500 ℃ to obtain a catalyst C-4, wherein the catalyst comprises the following components in percentage by weight: 0.3 wt% of Pt, 2 wt% of Sn and 1 wt% of K. The grain size distribution of Pt grains in the range of 1nm-3nm is 95%. Evaluation conditions were as follows: at 600 ℃, the mass space velocity of propane is 2h-1The propane dehydrogenation reaction was carried out under normal pressure with the catalyst amount of 3 g. The evaluation results are shown in Table 1。
Example 5
Respectively weighing certain amount of EDTA powder and solid potassium hydroxide in the molar ratio of 1 to 7, adding into deionized water, and stirring to obtain mixed solution containing EDTA and potassium hydroxide with molar concentration of 0.15 mol/L.
Weighing dried Sn-containing alumina carrier (spherical, diameter 1.6mm, pore volume 0.56 cm)3G, specific surface area 224m2The carrier was used in the following examples) 75g was added to 500mL of a solution containing potassium ethylenediaminetetraacetate, sufficiently stirred for 6 hours, and then filtered with suction. And (3) placing the solid obtained after suction filtration in a rotary evaporator, vacuumizing for 0.7h, adding 300mL of ethanol solution containing a certain amount of octaethylporphyrin platinum, heating to 60 ℃ in a vacuum state, treating for 3h, stopping refluxing, continuously evaporating the solvent, cooling, and taking out the solid. And (3) placing the obtained solid in a fixed bed reactor, heating to 180 ℃ in a nitrogen atmosphere, then cutting in nitrogen containing HCl with a volume concentration of 3% and water vapor with a volume concentration of 15%, wherein the volume space velocity is 800h, switching to nitrogen after 3h of treatment, and cooling. Preparing 75mL of potassium nitrate solution with a certain concentration, adding the potassium nitrate solution into 50g of solid which is treated by nitrogen and contains HCl and water vapor, aging for 4h, drying for 6h at 100 ℃, and roasting for 8h at 500 ℃ to obtain a catalyst C-4, wherein the catalyst comprises the following components in percentage by weight: pt 0.4 wt%, Sn 3.0 wt%, and K2.0 wt%. The grain size distribution of Pt grains in the range of 1nm-3nm is 94%. Evaluation conditions were as follows: at 600 ℃, the mass space velocity of propane is 2h-1The propane dehydrogenation reaction was carried out under normal pressure with the catalyst amount of 3 g. The evaluation results are shown in Table 1.
Comparative example 1
Weighing dried Sn-containing alumina carrier (spherical, diameter 1.6mm, pore volume 0.56 cm)3G, specific surface area 224m2The carrier is used in the following examples) 75g, the carrier is placed in a rotary evaporator, after vacuumization for 1h, 375mL of ethanol solution containing a certain amount of octaethylporphyrin platinum is added, the temperature is heated to 60 ℃ in a vacuum state, the treatment is carried out for 3h, the reflux is stopped, the solvent is continuously evaporated, and the solid is taken out after the temperature is reduced. Placing the obtained solid in a fixed bed reactor, and raising the temperature of the solid in a nitrogen atmosphereThe temperature is increased to 180 ℃, then nitrogen containing 3 percent of HCl by volume concentration and 15 percent of water vapor by volume concentration is cut in, and the volume space velocity is 750h-1And after 3h of treatment, switching to nitrogen and cooling. Preparing 75mL of potassium nitrate solution with a certain concentration, adding the potassium nitrate solution into 50g of solid which is treated by nitrogen and contains HCl and water vapor, aging for 10h, drying for 6h at 100 ℃, and roasting for 10h at 500 ℃ to obtain a catalyst D-1, wherein the catalyst comprises the following components in percentage by weight: 0.3 wt% of Pt, 1 wt% of Sn and 2 wt% of K. The grain size distribution of Pt grains in the range of 1nm-3nm is 52%. Evaluation conditions were as follows: at 600 ℃, the mass space velocity of propane is 2h-1The propane dehydrogenation reaction was carried out under normal pressure with the catalyst amount of 3 g. The evaluation results are shown in Table 1.
Comparative example 2
Respectively weighing a certain amount of the following components in a molar ratio of 1: 7 and solid potassium hydroxide are added into deionized water and fully stirred to prepare a solution containing the potassium ethylene diamine tetraacetate and having the molar concentration of 0.15 mol/L.
Weighing dried Sn-containing alumina carrier (spherical, diameter 1.6mm, pore volume 0.56 cm)3G, specific surface area 224m2The carrier was used in the following examples) 75g was added to 500mL of a solution containing potassium ethylenediaminetetraacetate, sufficiently stirred for 6 hours, and then filtered with suction. And placing the solid obtained after suction filtration in a rotary evaporator, vacuumizing for 1h, adding 375mL of aqueous solution containing a certain amount of chloroplatinic acid, heating at 60 ℃ in a vacuum state, treating for 3h, stopping refluxing, continuously evaporating the solvent, cooling and taking out the solid. Putting the obtained solid in a fixed bed reactor, heating to 180 ℃ in a nitrogen atmosphere, then cutting in nitrogen containing HCl with a volume concentration of 3% and water vapor with a volume concentration of 15%, wherein the volume space velocity is 750h-1And after 3h of treatment, switching to nitrogen and cooling. Preparing 75mL of potassium nitrate solution with a certain concentration, adding the potassium nitrate solution into 50g of solid which is treated by nitrogen and contains HCl and water vapor, aging for 10h, drying for 6h at 100 ℃, and roasting for 10h at 500 ℃ to obtain a catalyst D-2, wherein the catalyst comprises the following components in percentage by weight: 0.3 wt% of Pt, 1 wt% of Sn and 2 wt% of K. The grain size distribution of Pt grains in the range of 1nm-3nm is 72%. Evaluation conditions were as follows: at 600 ℃ the mass space velocity of propaneIs 2h-1The propane dehydrogenation reaction was carried out under normal pressure with the catalyst amount of 3 g. The evaluation results are shown in Table 1.
TABLE 1 reactivity of the catalysts
The description of the present invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the invention in the form disclosed. Many modifications and variations will be apparent to practitioners skilled in this art. The embodiment was chosen and described in order to best explain the principles of the invention and the practical application, and to enable others of ordinary skill in the art to understand the invention for various embodiments with various modifications as are suited to the particular use contemplated. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (10)
1. A preparation method of a Pt-based catalyst with a highly dispersed active component is characterized by comprising the following steps:
(1) adding a solution containing potassium ethylenediamine tetraacetate into Sn-containing alumina serving as a carrier, and performing suction filtration to obtain an Sn and K-containing alumina carrier sample;
(2) vacuumizing the product obtained in the step (1), adding an ethanol solution containing porphyrin Pt, heating and refluxing in a vacuum state, stopping refluxing, and continuously evaporating the solvent;
(3) heating the product obtained in the step (2) in a nitrogen atmosphere, then cutting into a nitrogen mixed gas containing HCl and water vapor, treating for a certain time, and then introducing nitrogen for cooling;
(4) and (4) soaking the product obtained in the step (3) in an alkali metal assistant K, and drying and roasting to obtain the target product Pt-based catalyst with high-dispersion active components.
2. The method for preparing a Pt-based catalyst having a highly dispersed active component according to claim 1, wherein: in the step (1), the Sn-containing alumina carrier is spherical, strip-shaped, microsphere or special-shaped; the specific surface of the Sn-containing alumina carrier is 170-260 m2A pore volume of 0.40-0.90 cm/g3/g。
3. The method for preparing a Pt-based catalyst having a highly dispersed active component according to claim 2, wherein: in the step (1), the potassium ethylene diamine tetraacetate solution is prepared by mixing ethylene diamine tetraacetic acid, potassium hydroxide and water.
4. The method for preparing a Pt-based catalyst having a highly dispersed active component according to claim 3, wherein: in the step (1), the Sn-containing alumina is added in an amount of 50-300 g based on 1L of the EDTA potassium solution, and the mixture is fully stirred for 1-24 hours.
5. The method for preparing a Pt-based catalyst having a highly dispersed active component according to claim 4, wherein: in the step (2), after the product obtained in the step (1) is vacuumized for 0.3-2 hours, adding an ethanol solution containing porphyrin Pt, heating to 40-80 ℃ in a vacuum state, keeping refluxing for 1-6 hours, and the volume ratio of the added ethanol solution containing porphyrin Pt to the product obtained in the step (1) is 4-6: 1.
6. The method for preparing a Pt-based catalyst having a highly dispersed active component according to claim 5, wherein: in the step (3), under the temperature of 120-240 ℃, a nitrogen mixed gas containing HCl and water vapor is cut in, and the treatment is carried out for 1-8 h, wherein the volume space velocity is 200-2000 h < -1 >; in the nitrogen mixed gas, the volume content of HCl is 1-10%; the volume content of the water vapor is 5-30%.
7. The method for preparing a Pt-based catalyst having a highly dispersed active component according to claim 6, wherein: in the step (4), the product obtained in the step (3) is dipped in the alkali metal additive K again, aged for 2-16 h at room temperature, dried for 2-16 h at 40-160 ℃, and roasted for 2-20 h at 400-800 ℃.
8. The method for preparing a Pt-based catalyst having a highly dispersed active component according to claim 7, wherein: in the Pt-based catalyst with a highly dispersed active component, the weight percentage of Pt calculated by elements is 0.1-1.0%; the weight percentage of Sn is 0.2-10% calculated by element; the percentage content of K is 0.3-4% by weight of the element.
9. The method for preparing a Pt-based catalyst with highly dispersed active components according to any one of claims 1 to 8, wherein: in the step (2), porphyrin Pt is octaethylporphyrin platinum; the alkali metal additive K is potassium nitrate.
10. The method for preparing a Pt-based catalyst having a highly dispersed active component according to claim 3, wherein: the molar ratio of the ethylene diamine tetraacetic acid to the potassium hydroxide is 1: 4-10; the concentration of the ethylene diamine tetraacetic acid potassium solution is 0.01-0.3 mol/L based on the mass of ethylene diamine tetraacetic acid.
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