CN110548538A - Preparation method and application of metal modified SAPO-34 molecular sieve - Google Patents
Preparation method and application of metal modified SAPO-34 molecular sieve Download PDFInfo
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- CN110548538A CN110548538A CN201810562127.0A CN201810562127A CN110548538A CN 110548538 A CN110548538 A CN 110548538A CN 201810562127 A CN201810562127 A CN 201810562127A CN 110548538 A CN110548538 A CN 110548538A
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 68
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 45
- 239000002184 metal Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 48
- 238000005342 ion exchange Methods 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 4
- -1 cesium ions Chemical class 0.000 claims description 26
- 239000007787 solid Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910001422 barium ion Inorganic materials 0.000 claims description 2
- 229910001451 bismuth ion Inorganic materials 0.000 claims description 2
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- 229910001424 calcium ion Inorganic materials 0.000 claims description 2
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 2
- 150000002602 lanthanoids Chemical class 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 claims description 2
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 2
- 229910001437 manganese ion Inorganic materials 0.000 claims description 2
- 229910001453 nickel ion Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 2
- 229910001414 potassium ion Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- 229910001419 rubidium ion Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- 229910001456 vanadium ion Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 229910052799 carbon Inorganic materials 0.000 abstract description 17
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 16
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 11
- 239000005977 Ethylene Substances 0.000 abstract description 11
- 238000009826 distribution Methods 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 230000001276 controlling effect Effects 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 7
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 101000642536 Apis mellifera Venom serine protease 34 Proteins 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011208 chromatographic data Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000010606 normalization Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
- C07C2529/85—Silicoaluminophosphates (SAPO 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
-
- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
-
- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The application discloses a preparation method of a metal modified SAPO-34 molecular sieve, which comprises the following steps: putting a hydrogen type SAPO-34 molecular sieve into a solution containing metal ions for ion exchange to obtain the metal modified SAPO-34 molecular sieve; the solvent of the solution containing the metal ions is an organic solvent. The method is simple and efficient, reduces the discharge of waste liquid, and accords with the principle of green chemistry. The application also discloses application of the modified SAPO-34 molecular sieve prepared by the method, and the modified SAPO-34 molecular sieve can be used as a catalyst in an oxygen-containing compound conversion reaction, such as a reaction for preparing low-carbon olefin (MTO) from methanol, so that the distribution of products can be effectively changed, the low-carbon olefin selectivity and the ethylene selectivity in the initial stage of the reaction can be improved, and the purpose of regulating and controlling the product selectivity can be achieved.
Description
Technical Field
The application relates to a preparation method and application of a metal modified SAPO-34 molecular sieve, belonging to the fields of chemical synthesis and catalyst preparation.
Background
Ethylene and propylene are important basic raw materials in modern petrochemical industry, and the market demand of the ethylene and propylene is continuously rising. At present, the method for obtaining ethylene and propylene mainly is a light oil cracking production method from crude oil. Petroleum has problems of price increase, unstable supply and the like in a short period of time, and has a problem of limited storage capacity in a long period of time. The research on the chemistry of C1 for producing lower olefins in a non-petroleum route has therefore received great attention from the industry. Wherein, the preparation of the low-carbon olefin (MTO) by the methanol is an ideal way for preparing the low-carbon olefin by replacing a petroleum route.
the SAPO-34 molecular sieve has medium acidity, good thermal stability and hydrothermal stability, and an ellipsoid cage structure and a three-dimensional pore channel structure which are formed by 8-membered ring orifices, so that the SAPO-34 molecular sieve has extremely high selectivity on ethylene and propylene, and shows excellent catalytic performance in the reaction of preparing low-carbon olefin (MTO) from methanol. According to the existing market demand, the demand and the market price of ethylene are increased and are higher than those of propylene, so that the regulation of the proportion of ethylene and propylene in the MTO reaction by using the metal modified SAPO-34 molecular sieve has important industrial production significance.
At present, in order to improve the selectivity of low-carbon olefin, the acidity of the SAPO-34 molecular sieve is usually modulated by metal modification, mainly through the following ways: (1) adding a metal salt solution in the gel process of synthesizing the SAPO-34 molecular sieve, namely isomorphous substitution modification; (2) the metal ions are exchanged to the SAPO-34 molecular sieve by conventional ion exchange methods. The metal salt of the former is mostly made of expensive metal, which is not beneficial to large-scale industrial application and has a great deal of environmental problems. The traditional ion exchange method of the SAPO-34 molecular sieve mainly comprises the following steps: (1) roasting SAPO-34 molecular sieve raw powder, and removing an organic structure template agent used in the synthesis process; (2) exchanging the hydrogen type SAPO-34 molecular sieve after roasting into an ammonium type SAPO-34 molecular sieve in an ammonium nitrate solution; (3) and exchanging the ammonium SAPO-34 molecular sieve in a metal salt solution to obtain the metal modified SAPO-34 molecular sieve. However, the ion exchange method is complicated and has a large amount of waste liquid.
Disclosure of Invention
According to one aspect of the application, the preparation method of the metal modified SAPO-34 molecular sieve is simple and efficient, reduces the discharge of waste liquid, and accords with the principle of green chemistry. The modified SAPO-34 molecular sieve prepared by the method is used as a catalyst in an oxygen-containing compound conversion reaction, such as a reaction of preparing low-carbon olefin (MTO) from methanol, can effectively change the distribution of products, improve the selectivity of the low-carbon olefin and the selectivity of ethylene at the initial stage of the reaction, and achieve the purpose of regulating and controlling the selectivity of the products.
The preparation method of the metal modified SAPO-34 molecular sieve is characterized in that the hydrogen type SAPO-34 molecular sieve is placed in a solution containing metal ions for ion exchange to obtain the metal modified SAPO-34 molecular sieve;
The solvent of the solution containing the metal ions is an organic solvent.
optionally, in the metal modified SAPO-34 molecular sieve, the metal ions are located at ion sites in the three-dimensional pore channels and/or the CHA cage structure of the SAPO-34 molecular sieve.
Optionally, the metal ions include at least one of group IA metal ions, group IIA metal ions, group IIIA metal ions, group VA metal ions, group IVB metal ions, group VB metal ions, group VIIB metal ions, group VIII metal ions, group IB metal ions, group IIB metal ions, lanthanide metal ions.
optionally, the metal ions include at least one of lithium ions, sodium ions, potassium ions, rubidium ions, cesium ions, magnesium ions, calcium ions, barium ions, aluminum ions, gallium ions, bismuth ions, zirconium ions, vanadium ions, cadmium ions, manganese ions, iron ions, cobalt ions, nickel ions, copper ions, zinc ions, platinum ions, gold ions, palladium ions, silver ions, rhodium ions, and ruthenium ions.
Optionally, the solution containing metal ions is a solution of a metal salt.
Optionally, the metal salt is an inorganic metal salt and/or an organometallic salt.
optionally, the organic solvent is selected from at least one of methanol, ethanol, n-propanol, and isopropanol.
Optionally, the temperature of the ion exchange is 30 ℃ to 120 ℃.
Alternatively, the lower temperature limit of the ion exchange may be independently selected from 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, and any point in a range consisting of any two of the above points.
Alternatively, the upper temperature limit of the ion exchange may be independently selected from 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, and any point in a range consisting of any two of the above points.
optionally, the temperature of the ion exchange is from 40 ℃ to 75 ℃.
optionally, the solid-to-liquid ratio of the ion exchange is 5-80: 1, and the time is 1-8 h.
Optionally, the solid-to-liquid ratio of the ion exchange is 10-50: 1, and the time is 2-6 h.
Alternatively, the lower solid-to-liquid ratio limit of the ion exchange may be independently selected from 5:1, 8:1, 10:1, 15:1, 20:1, 25:1, 30:1, 35:1, 40:1, 45:1, 55:1, 60:1, 65:1, 70:1, 75:1, 80:1, and any point in a range consisting of any two of the above points.
Alternatively, the ion exchange upper solid-to-liquid ratio limit may be independently selected from 5:1, 8:1, 10:1, 15:1, 20:1, 25:1, 30:1, 35:1, 40:1, 45:1, 55:1, 60:1, 65:1, 70:1, 75:1, 80:1, and any point in a range consisting of any two of the above points.
alternatively, the lower time limit for ion exchange may be independently selected from 1h, 1.5h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, and any point in a range consisting of any two of the above points.
Alternatively, the upper time limit for ion exchange may be independently selected from 1h, 1.5h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, and any point in a range consisting of any two of the above points.
Optionally, the SAPO-34 molecular sieve is a hydrogen type molecular sieve; the hydrogen type molecular sieve is obtained by roasting molecular sieve raw powder.
Optionally, the method comprises: and (3) placing the hydrogen type SAPO-34 molecular sieve in a solution containing metal ions, stirring, and carrying out ion exchange to obtain the metal modified SAPO-34 molecular sieve.
Optionally, the method comprises the steps of:
a) Obtaining a solution containing metal ions;
b) Placing a hydrogen type SAPO-34 molecular sieve in the solution containing metal ions obtained in the step a), and performing ion exchange for a set time at a set temperature according to a set solid-liquid ratio;
c) And (4) carrying out liquid-solid separation, and washing and drying the obtained solid to obtain the metal modified SAPO-34 molecular sieve.
Optionally, the washing comprises washing with an organic solvent for 1-5 times.
Optionally, the organic solvent for washing is the same as the solvent of the solution containing metal ions.
As a specific embodiment, the preparation method of the metal modified SAPO-34 molecular sieve at least comprises the following steps: and (3) placing the roasted hydrogen type SAPO-34 molecular sieve in an organic solvent containing metal ions for ion exchange, and centrifuging, washing and drying the obtained solid after the ion exchange to obtain the metal modified SAPO-34 molecular sieve.
As a specific embodiment, the preparation method of the metal modified SAPO-34 molecular sieve comprises the following steps:
(1) Dissolving a metal salt in an organic solvent to obtain a metal salt solution;
(2) Placing a hydrogen type SAPO-34 molecular sieve obtained by roasting SAPO-34 raw powder into the metal salt solution obtained in the step (1), and performing ion exchange for a certain time at a certain temperature and a certain liquid-solid ratio;
(3) And after ion exchange, performing centrifugal liquid-solid separation, washing, drying and roasting the obtained solid to obtain the metal modified SAPO-34 molecular sieve.
the metal salt is an inorganic metal salt and/or an organic metal salt.
According to another aspect of the present application, there is provided a catalyst obtained by calcining the metal-modified SAPO-34 molecular sieve prepared according to any one of the methods described above in air.
Alternatively, the temperature of the firing is not higher than 800 ℃.
Optionally, the roasting temperature is 450-800 ℃.
Alternatively, the lower temperature limit of the firing may be independently selected from 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, and any of the ranges consisting of any two of the above values.
Alternatively, the upper temperature limit for the firing may be independently selected from 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, and any point in a range consisting of any two of the above points.
According to yet another aspect of the present application, there is provided the use of the above catalyst in an oxygenate conversion reaction.
optionally, the catalyst is a catalyst for an oxygenate conversion reaction.
Optionally, the oxygenate conversion reaction includes a reaction for preparing low-carbon olefin from methanol, a reaction for preparing propylene from methanol, a reaction for preparing low-carbon olefin from dimethyl ether, and the like.
Benefits that can be produced by the present application include, but are not limited to:
1) The preparation method of the metal modified SAPO-34 molecular sieve is simple and efficient, effectively improves the exchange efficiency, saves the exchange time, reduces the discharge of waste liquid and accords with the principle of green chemistry compared with the traditional method of roasting the raw powder of the molecular sieve, exchanging ammonium nitrate solution and exchanging metal ion solution.
2) The metal modified SAPO-34 molecular sieve prepared by the preparation method provided by the application is used in the reaction of preparing low-carbon olefin from methanol, compared with the SAPO-34 molecular sieve which is not subjected to metal modification, the initial low-carbon olefin selectivity and the ethylene selectivity are obviously improved, the product distribution can be effectively changed, and the purpose of regulating and controlling the product selectivity is achieved.
drawings
FIG. 1 shows XRD spectra of samples 1 # -15 # of the present application.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, the starting materials in the examples of the present application were all purchased commercially, wherein the SAPO-34 molecular sieves used in the examples were purchased from south-opening catalyst plants.
The analysis method in the examples of the present application is as follows:
In the examples, the structure of the sample was characterized by X-ray powder diffraction, and the X-ray powder diffraction phase analysis (XRD) was performed using an X' Pert PRO X-ray diffractometer from PANalytical, the netherlands, a Cu target, a K α radiation source (λ ═ 0.15418nm), a voltage of 40KV, and a current of 40 mA.
In the examples, the concentrations of the reactants and products were analyzed by high performance gas chromatography, which was performed by model 6890N gas chromatography from Agilent.
the conversion, selectivity, in the examples of the present application were calculated as follows:
in the examples of the present application, the chromatographic data normalization, methanol conversion and product selectivity were calculated based on carbon moles:
The conversion C of methanol was calculated using equation (1):
C＝[(100-NORmethanol-NORDimethyl ether)/14]/[(100-NORMethanol-NORDimethyl ether)/14+NORMethanol/32+NORDimethyl ether/23] (1)；
Product selectivity S xi was calculated using equation (2)
Sxi＝NORxi/(100-NORMethanol-NORDimethyl ether) (2)；
Wherein NOR xi is the mass content of the product after normalization of chromatographic data.
EXAMPLE 1 preparation of hydrogen form SAPO-34 molecular sieves
2g of SAPO-34 molecular sieve raw powder is placed in a tubular furnace to be roasted for 2h at the constant temperature of 600 ℃, an organic structure template agent and water are removed, and the hydrogen type SAPO-34 molecular sieve is obtained and marked as a sample 1 #, and the sample also exists as a comparison sample.
Example 2 preparation of metal modified SAPO-34 molecular sieves
The hydrogen type SAPO-34 molecular sieve prepared in the embodiment 1 is placed in a solution containing metal ions according to a set liquid-solid ratio, the solution is stirred for 3 minutes, the temperature is raised to a set ion exchange temperature, after the ion exchange is carried out for a set time, a solid is obtained by centrifugal separation, and the metal modified SAPO-34 molecular sieve sample is obtained after washing for 3 times by a corresponding organic solvent in a metal solution and drying at 100 ℃.
The relationships between the serial number of the obtained metal modified SAPO-34 molecular sieve sample and the solid-liquid mass ratio, the ion exchange temperature and the ion exchange time of the solution containing metal ions, the molecular sieve raw powder and the solution containing metal ions are shown in Table 1.
TABLE 1
example 3 preparation of catalyst samples
The obtained samples 1 # -15 # were respectively calcined in an air atmosphere to obtain catalysts, and the catalysts obtained from samples 1 # -15 # and the preparation conditions are shown in table 2.
TABLE 2
Example 4 sample structural characterization
The structures of a 1 # hydrogen type SAPO-34 molecular sieve sample and a 2 # -15 # metal modified SAPO-34 molecular sieve sample are characterized by X-ray powder diffraction, an XRD spectrogram is shown in figure 1, XRD spectrograms of the samples 2 # -15 # are similar to those of the sample 1 # SP34 molecular sieve, namely, diffraction peak positions and shapes are the same, and the obtained product only contains a CHA structure diffraction peak and has no other impurity peaks, which indicates that metal ions are uniformly introduced into three-dimensional pore canals and/or ion sites in a CHA cage structure of the SAPO-34 molecular sieve.
Example 5 evaluation of catalyst Performance
The catalysts prepared from samples 1 # -15 # in example 3 were tabletted and crushed to 40-60 mesh for reaction of preparing low carbon olefin (MTO) from methanol.
the specific experimental procedures and conditions were as follows:
0.1g of catalyst sample is weighed and loaded into a fixed bed reactor, the reaction pressure is normal pressure, helium gas is activated for 45min at 500 ℃, and MTO reaction is carried out at 500 ℃.
The reaction raw material adopts pure methanol, the methanol takes helium as a carrying gas, the flow rate of the helium gas is 8mL/min, and the space velocity of the methanol is 2.0h -1.
The reaction product was analyzed on-line by an Agilent 6890N gas chromatograph, and the data of the product distribution, the initial low-carbon olefin selectivity, and the ethylene-propylene ratio on samples 1 # -15 # for 5min are shown in Table 3.
It can be seen from table 3 that, compared with comparative sample 1 # SP34, samples 2 # to 15 # after metal modification have significantly increased initial low carbon olefin selectivity, ethylene selectivity, and ethylene/propylene ratio, so the initial low carbon olefin selectivity and ethylene selectivity can be effectively improved by the metal-modified SAPO-34 molecular sieve method, and the ethylene/propylene selectivity ratio can be adjusted, thereby better meeting the market demand.
TABLE 3 initial reaction results for methanol conversion to olefins
Note: the data for 5min at the beginning of the reaction are shown in the table
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A preparation method of a metal modified SAPO-34 molecular sieve is characterized by comprising the following steps: putting a hydrogen type SAPO-34 molecular sieve into a solution containing metal ions for ion exchange to obtain the metal modified SAPO-34 molecular sieve;
the solvent of the solution containing the metal ions is an organic solvent.
2. The method of claim 1, wherein the metal modified SAPO-34 molecular sieve has the metal ions located at ion sites within the three-dimensional pore channels and/or the CHA cage structure of the SAPO-34 molecular sieve.
3. The method of claim 1, wherein the metal ions comprise at least one of group IA metal ions, group IIA metal ions, group IIIA metal ions, group VA metal ions, group IVB metal ions, group VB metal ions, group VIIB metal ions, group VIII metal ions, group IB metal ions, group IIB metal ions, lanthanide metal ions;
Preferably, the metal ions include at least one of lithium ions, sodium ions, potassium ions, rubidium ions, cesium ions, magnesium ions, calcium ions, barium ions, aluminum ions, gallium ions, bismuth ions, zirconium ions, vanadium ions, cadmium ions, manganese ions, iron ions, cobalt ions, nickel ions, copper ions, zinc ions, platinum ions, gold ions, palladium ions, silver ions, rhodium ions, and ruthenium ions.
4. The method according to claim 1, wherein the organic solvent is at least one selected from methanol, ethanol, n-propanol, and isopropanol.
5. The method of claim 1, wherein the temperature of the ion exchange is between 30 ℃ and 120 ℃;
Preferably, the temperature of the ion exchange is 40 ℃ to 75 ℃.
6. The method according to claim 1, wherein the solid-to-liquid ratio of the ion exchange is 5-80: 1, and the time is 1-8 h;
Preferably, the solid-liquid ratio of the ion exchange is 10-50: 1, and the time is 2-6 h.
7. Method according to any one of claims 1 to 6, characterized in that it comprises the following steps:
a) Obtaining a solution containing metal ions;
b) placing a hydrogen type SAPO-34 molecular sieve in the solution containing metal ions obtained in the step a), and performing ion exchange for a set time at a set temperature according to a set solid-liquid ratio;
c) And (4) carrying out liquid-solid separation, and washing and drying the obtained solid to obtain the metal modified SAPO-34 molecular sieve.
8. A catalyst, characterized in that the catalyst is obtained by calcining the metal modified SAPO-34 molecular sieve prepared by the method of any one of claims 1 to 7 in air.
9. The catalyst of claim 8, wherein the temperature of the calcination is not higher than 800 ℃;
Preferably, the roasting temperature is 450-800 ℃.
10. Use of the catalyst of claim 9 in an oxygenate conversion reaction.
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Application publication date: 20191210 |