WO2011050505A1 - 一种提高水热稳定性的双组元改性分子筛及制备方法 - Google Patents
一种提高水热稳定性的双组元改性分子筛及制备方法 Download PDFInfo
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- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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- B01J37/0201—Impregnation
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
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- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
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- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- C07C2529/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
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- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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- C07C2529/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
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- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
Definitions
- Double-twist modified molecular sieve for improving water heat stability and preparation method thereof Double-twist modified molecular sieve for improving water heat stability and preparation method thereof
- the invention belongs to the technical field of molecular sieve modification, and particularly relates to a two-component modified molecular sieve and a preparation method for improving hydrothermal stability.
- ZSM-5 zeolite molecular sieves USP 3,702,886
- ZSM-5 zeolite molecular sieves have been developed due to their high silicon to aluminum ratio, unique pore structure and excellent thermal and hydrothermal stability. It has been widely used in petrochemical processes such as selective cracking of hydrocarbons (CN 1872415A), thiolation, isomerization, disproportionation, catalytic dewaxing, and etherification.
- the addition of ZSM-5 zeolite in particular to conventional catalytic cracking catalysts or auxiliaries, can substantially increase the yield and enthalpy of low olefins (USP 5,997,728).
- ZSM-5 zeolite molecular sieves are easily deactivated under catalytic cracking hydrothermal conditions, affecting their stability and selectivity. Therefore, a lot of research has been done on the modification of ZSM-5 zeolite molecular sieves.
- diammonium hydrogen phosphate or ammonium dihydrogen phosphate is mixed with NHU-ZSM-5 and dried, and then calcined at 500 ° C to prepare phosphorus-modified ZSM-5.
- the zeolite is used in the xylene isomerization reaction to significantly improve the selectivity of its para-product.
- a modified ZSM-5 molecular sieve impregnated with a phosphorus compound is disclosed in USP 5,171,921, which is useful as a catalytically active component for the conversion of olefins or aliphatic hydrocarbons to C 2 -C 5 olefins.
- HZSM-5 is modified with trimethyl phosphite to increase the selectivity of the reaction.
- CN85102828 reports that the ZSM-5 molecular sieve is modified by impregnation and evaporation, and the shape-selective catalytic activity of the alkylation of methylstyrene by the modification of phosphorus is greatly improved.
- CN97120271 reports a phosphorus-containing faujasite hydrocarbon cracking catalyst prepared by uniformly mixing faujasite with an aqueous solution of a phosphorus-containing compound, drying, and baking at 450-600 ° C for 0.5 hours or more. And has good catalytic activity.
- CN98117286 reports a phosphorus-containing zeolite containing 90-99.9 by weight of aluminosilicate zeolite and 0.1 to 10% by weight of phosphorus in terms of P 2 0 5 , which has high hydrocarbon conversion activity and selectivity to diesel. And better resistance to heavy metals such as vanadium and nickel.
- CN 1211469A and CN 1211470A report a molecular sieve composition for the production of propylene and ethylene, characterized in that a five-membered ring molecular sieve is added to an aqueous solution of a compound containing phosphorus and an alkaline earth metal ion and/or a transition metal ion.
- the mixture is uniformly mixed and obtained by an immersion reaction, and the composition is composed of 85 to 95% by weight of a five-membered ring molecular sieve, 2 to 10% by weight of phosphorus, 0.3 to 5% by weight of an alkaline earth metal, and an oxide. It is composed of 0.3-5 wt% of transition metal elements.
- CN 1072031C and CN 1072032C also report a five-membered ring molecular sieve composition for producing propylene and ethylene (especially ethylene) from 88 to 95% by weight of a five-membered ring molecular sieve, 2 to 8% by weight of an oxide.
- the preparation method of the composition is a one-step impregnation method, the process is simple, the stability is good, and the ethylene yield is obviously improved.
- the catalytic cracking catalysts for industrial applications have low yields of low-carbon olefins, especially propylene, and cannot meet the actual needs of refining and chemical production. Therefore, it is of great significance to greatly increase the yield of propylene.
- the modification of functional shape-selective cracking molecular sieves is the most effective way to increase the production of low-carbon olefins by catalytic cracking.
- the object of the present invention is to provide a two-component modified molecular sieve and a preparation method for greatly improving hydrothermal stability against existing molecular sieve materials and techniques.
- a method for modifying a two-component modified molecular sieve for improving hydrothermal stability, adding a molecular sieve to a phosphorus-containing aqueous solution, followed by filtering, drying and calcining comprising adding a molecular sieve to a phosphorus-containing aqueous solution, Reaction pressure conditions at pH 1 to 10 (preferably 2 to 7), reaction temperature 70 to 200 ° C (preferably 90 to 160 ° C), and 0.2 to 1.2 MPa (preferably 0.2 to 0.8 MPa)
- the reaction is carried out for 10 to 200 minutes, and then filtered, dried and calcined to obtain a phosphorus-modified molecular sieve; the phosphorus-modified molecular sieve is added to an aqueous solution containing silver ions at a reaction temperature of 0 to 100 ° C (preferably 20 to 60 ° C).
- the reaction is protected from light for 30 to 150 minutes, and then filtered, dried and calcined to obtain a two-component modified mo
- the filtration, drying and roasting in the modification process are all in the prior art.
- the present invention is not particularly limited in terms of the process and technical parameters used, and the recommended drying temperature is
- the baking temperature is 200 ⁇ 800 °C
- the baking time is 0.5 ⁇ 10 hours.
- the invention is distinguished from the modification conditions required by the conventional phosphorus modification method, which is high temperature and has a certain pressure at the same time, and the synergistic effect of high temperature and pressure can further enhance the diffusion of the modified component in the pores of the molecular sieve, so that the modification The component enters the deeper molecular sieve pores and reacts with the B acid sites on the surface, but the high temperature or low temperature pressure does not achieve satisfactory results.
- the premise is that water is required as the medium.
- the phosphorus-containing aqueous solution is not particularly limited in the method of the present invention, and usually a phosphorus-containing aqueous solution used for the phosphorus-modified molecular sieve may be used.
- the phosphorus compound in the phosphorus-containing aqueous solution is not particularly limited as long as it is soluble in water.
- the phosphorus-containing aqueous solution may be a phosphoric acid solution, a phosphorous acid solution, a soluble phosphate aqueous solution, an aqueous phosphite solution, or the like, and may be one or more of them, and the soluble phosphate aqueous solution and the aqueous phosphite solution may be ammonium phosphate or hydrogen phosphate.
- An aqueous solution of a phosphate or a phosphite such as diammonium or ammonium dihydrogen phosphate.
- the weight ratio of the phosphorus-containing aqueous solution to the molecular sieve is preferably (2 ⁇ 5):1.
- the aqueous silver ion-containing solution of the present invention may be an aqueous solution of one or a mixture of silver nitrate and silver acetate.
- the weight ratio of the aqueous solution containing silver ions to the molecular sieve is preferably (2 ⁇ 10):1, and the concentration of the aqueous solution containing silver ions is preferably 0.01-0.1 mol/L.
- the present invention does not need to limit the molecular sieve species and composition thereof, the composition of phosphorus, and the composition of silver in the process, depending on the needs.
- the molecular sieve is preferably one of ZSM type, ⁇ type, Y type, MCM type molecular sieves, preferably ZSM type and ⁇ type molecular sieve, and the ratio of silicon to aluminum is 15 ⁇ 100, preferably 15 ⁇ 60.
- the present invention also claims a modified molecular sieve obtained by applying the modification method of the present invention. And providing a modified molecular sieve obtained by using the modification method of the invention: a molecular sieve having a dry content of 88 to 99% by weight, a silica to alumina ratio of 15 to 60, and a phosphorus content of 0.5 to 10% by weight of the oxide The oxide is 0.012% by weight of silver, and the two-component modified molecular sieve has good hydrothermal stability and activity.
- Elemental analysis was carried out by X-ray fluorescence spectrometry (XRF).
- XRF X-ray fluorescence spectrometry
- the instrument used was a ZSX primus X-ray fluorescence spectrometer.
- Stability evaluation was judged by the change of relative crystallinity (ZSM-5%) before and after hydrothermal aging at 800 ° C for 4 hours and 800 ° C for 7 hours.
- the crystallinity was determined on D/max-3C X-ray diffractometer of Rigaku Co., Japan. . 3.
- the activity evaluation was determined by the micro-reverse assessment device produced by Beijing Huayang Company.
- the raw material oil was Dagang light diesel oil.
- the evaluation conditions were as follows: The catalyst was treated at 800 ° C and 100% steam for 4 hours and 17 hours. 5 g, reaction temperature 460 ° C, reaction time 70 seconds, the ratio of agent to oil was 3.2.
- PZ-3 molecular sieve was added to the silver-containing solution, and the reaction was stirred at 60 ° C for 60 minutes in the dark, filtered, dried, and then calcined at 500 ° C for 2 hours to obtain a two-component modification.
- Molecular sieve APZ-3 Then kaolin (45%), aluminum sol (15%) and APZ-3 (40%) It was added to steaming water in a fixed proportion, beaten, dried at 120 Torr, calcined at 450 ° C for 1 hour, and then crushed and sieved. The obtained catalyst sample was recorded as C-3. Take 20 ⁇ 40 mesh particle catalyst for micro activity investigation. The composition of the sample, the crystallinity before and after aging, and the microreactor activity of the model catalyst are shown in Tables 1-3.
- the invention provides a modified molecular sieve obtained by using the modification method of the invention: a molecular sieve having a dry content of 88-99% by weight and a silica-alumina ratio of 15 ⁇ 60, 0.5-10% by weight of the oxide Phosphorus and oxide are 0.01 to 2% by weight of silver.
- Crystallinity retention rate Relative crystallinity after hydrothermal treatment Relative crystallinity before ice heat treatment X 100% Table 2 Hydrothermal stability of two-component modified molecular sieve
- Crystallinity retention rate Relative crystallinity after hydrothermal treatment / Relative crystallinity before hydrothermal treatment X 100%
- CD-5 25 24 It was found through research that the introduction of phosphorus inhibits the dealuminization of the ZSM-5 zeolite framework under hydrothermal conditions, significantly increasing the acid retention on the zeolite, thereby increasing its catalytic activity and selectivity; In order to further greatly improve the hydrothermal stability of the molecular sieve and at the same time realize the surface acidity of the modified zeolite, it is necessary to introduce a second modified element to modify it. After the transition metal silver ion is introduced into the ZSM-5 molecular sieve, its oxidation is beneficial to the formation of normal carbon ions, which makes the reaction easier to initiate, thereby increasing the reactivity; compared with other transition metals, the adsorption of silver on olefins is weak.
- the invention has the advantages that the method can prevent the phosphorus-modified molecular sieve from losing a large amount of the phosphorus component in the transition metal ion exchange modification, and the modified two-component modified molecular sieve and the model catalyst thereof are excellent. Hydrothermal stability and catalytic activity.
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- Crystallography & Structural Chemistry (AREA)
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Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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US13/505,219 US9895686B2 (en) | 2009-10-30 | 2009-12-01 | Double-component modified molecular sieve with improved hydrothermal stability and production method thereof |
JP2012535574A JP5677446B2 (ja) | 2009-10-30 | 2009-12-01 | 改善された熱水安定性を有するニ成分修飾モレキュラーシーブ |
CA2779312A CA2779312C (en) | 2009-10-30 | 2009-12-01 | Double-component modified molecular sieve with improved hydrothermal stability and production method thereof |
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CN200910237007.4 | 2009-10-30 | ||
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US9895686B2 (en) | 2009-10-30 | 2018-02-20 | Petrochina Company Limited | Double-component modified molecular sieve with improved hydrothermal stability and production method thereof |
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CN110116021A (zh) * | 2018-02-07 | 2019-08-13 | 中国石油天然气股份有限公司 | 一种fcc催化剂中分子筛的双组元改性方法及其改性分子筛 |
KR102079063B1 (ko) * | 2018-06-20 | 2020-04-13 | 한국화학연구원 | 경질올레핀 제조용 촉매, 이의 제조방법, 및 이를 이용하여 경질올레핀을 제조하는 방법 |
CN112206810B (zh) * | 2019-07-09 | 2022-01-04 | 中国石油化工股份有限公司 | 一种制备方法和一种稀土y型分子筛 |
CN113526522B (zh) * | 2020-04-13 | 2023-02-21 | 中国石油化工股份有限公司 | 磷改性mfi结构分子筛及其制备方法 |
CN114715911B (zh) * | 2021-01-05 | 2024-03-12 | 中国石油化工股份有限公司 | 含磷和金属的多级孔zsm-5分子筛及其制备方法 |
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US20120275994A1 (en) | 2012-11-01 |
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CA2779312C (en) | 2016-09-20 |
JP2013509344A (ja) | 2013-03-14 |
US9895686B2 (en) | 2018-02-20 |
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CA2779312A1 (en) | 2011-05-05 |
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