WO2019010812A1 - Cu-SAPO分子筛合成方法及合成的Cu-SAPO分子筛和应用 - Google Patents

Cu-SAPO分子筛合成方法及合成的Cu-SAPO分子筛和应用 Download PDF

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WO2019010812A1
WO2019010812A1 PCT/CN2017/102095 CN2017102095W WO2019010812A1 WO 2019010812 A1 WO2019010812 A1 WO 2019010812A1 CN 2017102095 W CN2017102095 W CN 2017102095W WO 2019010812 A1 WO2019010812 A1 WO 2019010812A1
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molecular sieve
sapo
sapo molecular
source
copper
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French (fr)
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杨淼
孙丽婧
田鹏
刘中民
曹毅
向骁
桑石云
曹磊
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中国科学院大连化学物理研究所
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/54—Phosphates, e.g. APO or SAPO compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/90—Injecting reactants
    • 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]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
    • C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/86—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by NMR- or ESR-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM

Definitions

  • the invention belongs to the field of chemistry and chemical industry, and relates to the field of molecular sieves and preparation methods thereof, in particular to a method for synthesizing a copper-containing silicoaluminophosphate molecular sieve (Cu-SAPO), a product obtained by the method and a use thereof.
  • Cu-SAPO can be used as a catalyst for the oxynitride purification process.
  • SAPO-n silicoaluminophosphate molecular sieves
  • USP 4,440,871 silicoaluminophosphate molecular sieves
  • Cu-SAPO-34 or Cu-SSZ-13 catalyst prepared by using SAPO-34 as a carrier (SSZ-13 is a molecular sieve having the same topology as SAPO-34, the difference being that the former is a silica-alumina molecular sieve and the latter is a silicoaluminophosphate
  • SSZ-13 is a molecular sieve having the same topology as SAPO-34, the difference being that the former is a silica-alumina molecular sieve and the latter is a silicoaluminophosphate
  • Molecular sieves have high activity and excellent hydrothermal stability in the process of purifying nitrogen oxides by the diesel exhaust gas selective catalytic reduction technology (Urea-SCR) system. At present, most of the introduction of copper ions in SAPO molecular sieve catalysts is carried out by ion exchange method.
  • the obtained molecular sieves are first calcined to remove the template, ion exchange with ammonium nitrate solution to obtain ammonia samples, and then mixed with a certain concentration of copper salt solution. After several hours, filtration, washing, drying, and high temperature calcination gave Cu-SAPO-34. Due to the poor low-temperature hydrothermal stability of SAPO molecular sieves, the molecular sieve framework tends to undergo partial hydrolysis during the ion exchange process, resulting in a decrease in the specific surface area of the molecular sieve. At the same time, the ion exchange process is cumbersome. In the exchange process, the utilization rate of copper ions in the copper salt solution is low, the washing process consumes a large amount of pure water and is converted into sewage, and the high temperature roasting process consumes time and energy.
  • CN 102259892 A discloses a method for synthesizing a silicoaluminophosphate molecular sieve catalyst using a metal-amine complex as a templating agent, avoiding a cumbersome ion exchange process.
  • the one-step synthesis of Cu-SAPO-34 has poor hydrothermal stability and limits its industrial application. For example, Corma et al. synthesized Cu-SAPO-34 molecular sieve with copper amine complex and diethylamine as template, the copper loading was controlled at 3.4-10.4%, and the crystal size was about 6-10 ⁇ m.
  • the amount and distribution of the negative charge of the skeleton is directly derived from the amount of introduction of silicon atoms and their distribution.
  • a single substitution of a P atom by a Si atom can form a Si(4Al) linkage to form an acid center.
  • Si atoms simultaneously replace adjacent P and Al atoms Si-rich regions or even silicon islands are formed, resulting in an uneven distribution of negative charges of the skeleton, which is not conducive to the stable existence of copper ions.
  • the present application firstly uses a copper amine complex as a synthetic template to obtain a high copper content of Cu-SAPO, which is then directly used as a Cu source, a partial silicon phosphorus aluminum source, and a seed crystal for Cu-SAPO molecular sieve.
  • the method avoids the competition between copper amine complexes and other synthetic templates when copper-amine complexes and other templating agents are directly used as a co-template to synthesize Cu-SAPO, and better guides the synthesis of other organic templating agents.
  • the crystal grain size, Cu content and silicon content and distribution of the molecular sieve product can be effectively regulated, so that the obtained copper-containing molecular sieve has more excellent catalytic performance and hydrothermal stability.
  • the present invention provides a method for synthesizing a Cu-SAPO molecular sieve, comprising the steps of:
  • the Cu loading is 5-20 wt%, preferably 5-15 wt%;
  • the high copper content Cu-SAPO molecular sieve obtained in the step (1) is used as a raw material and mixed with the crystallization liquid obtained in the step (2), and hydrothermally crystallized to obtain a Cu-SAPO molecular sieve product.
  • the Cu-SAPO molecular sieve in the step (1) is synthesized using a templating agent containing a copper amine complex or by an ion exchange method from a SAPO molecular sieve.
  • the Cu-SAPO molecular sieve in the step (1) is a copper template, a source of aluminum, a source of phosphorus, and water through a water using a copper amine complex as a single template or together with an organic amine template R1 as a mixed template.
  • the silicon source may be selected from one or more of tetraethyl orthosilicate, silica sol and white carbon
  • the aluminum source may be selected from aluminum isopropoxide, pseudo-boehmite One or more of aluminum sol and aluminum hydroxide
  • the phosphorus source may be selected from one or more of phosphoric acid, phosphorous acid and phosphorus pentoxide
  • the organic amine template R1 may be selected from triethylamine, two Mixture of one or more of ethylamine, morpholine, tetraethylammonium hydroxide, propylamine, diisopropylamine, N,N diisopropylethylamine, trimethylamine, diethanolamine, and piperazine.
  • the copper amine complex in the step (1) comprises a copper-polyethylene polyamine complex, preferably a Cu-tetraethylene pentamine complex, a Cu-triethylenetetramine complex, and a Cu-di An ethylene triamine complex and a Cu-pentaethylene hexamine complex.
  • step (1) the synthesis of the high copper content Cu-SAPO molecular sieve in step (1) is carried out in the presence of SAPO seed crystals.
  • the silicon source used in the step (2) may be selected from one or more of tetraethyl orthosilicate, silica sol and white carbon;
  • the aluminum source may be selected from aluminum isopropoxide, pseudo-thick aluminum One or more of stone, aluminum sol and aluminum hydroxide;
  • the phosphorus source may be selected from one or more of phosphoric acid, phosphorous acid and phosphorus pentoxide;
  • the organic amine templating agent R may be selected from triethylamine, A mixture of one or more of diethylamine, morpholine, tetraethylammonium hydroxide, propylamine, diisopropylamine, N,N diisopropylethylamine, trimethylamine, diethanolamine, and piperazine.
  • the Cu-SAPO feedstock having a high copper content in the step (3) is fed in an amount of from 2 to 200% by weight based on the total mass of the solid oxides in the crystallization solution.
  • the temperature for hydrothermal crystallization in the step (3) is 140-240 ° C for 0.5-72 hours.
  • a more preferred crystallization temperature is from 150 to 200 °C.
  • the Cu loading of the Cu-SAPO molecular sieve product prepared in the step (3) is reduced by more than 10% compared with the copper content of the Cu-SAPO raw material having a high copper content, preferably a Cu-SAPO raw material having a high copper content. 10-70% of copper content.
  • the Cu-SAPO molecular sieve comprises any one of Cu-SAPO-34 molecular sieve, Cu-SAPO-42 molecular sieve, Cu-SAPO-18 and Cu-DNL-6 (RHO).
  • the present invention provides a Cu-SAPO molecular sieve raw powder prepared by the above method, preferably a Cu-SAPO-34 molecular sieve raw powder, which is rhombohedral, preferably having a particle size ranging from 1 to 2 ⁇ m.
  • the present invention provides a catalyst for a NO x selective reduction removal reaction obtained by calcining a molecular sieve synthesized according to the above method in air at 500 to 800 °C.
  • the catalyst exhibits good catalytic properties especially in the catalytic removal reaction of nitrogen oxides.
  • the catalyst still maintained excellent catalytic activity after treatment with saturated steam at 800 ° C for 16 hours.
  • the present invention provides a method for improving high temperature hydrothermal stability of a Cu-SAPO molecular sieve, characterized in that the method comprises: high copper synthesized by using a templating agent comprising a copper amine complex
  • the content of Cu-SAPO molecular sieve is mixed with a crystallization solution and hydrothermally crystallized, wherein the crystallization solution is prepared by mixing an organic amine tempering agent R with water and optionally a silicon source, an aluminum source and a phosphorus source. of.
  • a novel method for synthesizing Cu-SAPO molecular sieves is provided, which achieves high yield synthesis of Cu-SAPO with high hydrothermal stability and efficient utilization of Cu source. Its crystal size, Cu content and silicon content and distribution can be effectively regulated;
  • the prepared molecular sieve can be used as a catalyst for the catalytic removal reaction of nitrogen oxides and exhibits good catalytic performance. After the catalyst was treated with steam at 800 ° C for 16 hours, the catalytic performance was still improved or remained unchanged.
  • Example 1 is an XRD pattern of a high copper content Cu-SAPO-34 synthesized in Example 1.
  • Example 2 is a scanning electron micrograph (SEM) of the high copper content Cu-SAPO-34 synthesized in Example 1.
  • Figure 3 is an XRD pattern of the product of Example 3.
  • Figure 4 is a scanning electron micrograph (SEM) of the product of Example 5.
  • Figure 5 is a solid 29 Si nuclear magnetic spectrum of Example 3.
  • Figure 6 is a graph showing the results of NH 3 -SCR reaction evaluation of Examples 3, 5, and 8.
  • Fig. 7 is a comparison of evaluation results of NH 3 -SCR reaction of the sample of Example 5 before high temperature hydrothermal treatment (Example 5) and after (Example 5-H).
  • Figure 8 is an XRD pattern of a sample of Example 13.
  • Figure 9 is an XRD pattern of a sample of Example 16.
  • Figure 10 is a scanning electron micrograph (SEM) of the product of Example 16.
  • Figure 11 is a SEM electron micrograph of a sample of Comparative Example 3.
  • Figure 12 is a solid 29 Si nuclear magnetic spectrum of a sample of Comparative Example 3.
  • the invention is further illustrated below in conjunction with the examples. It is to be understood that the examples are not intended to limit the scope of the invention.
  • the experimental methods in the following examples which do not specify the specific conditions are usually carried out according to conventional conditions or according to the conditions recommended by the manufacturer. Unless otherwise specified, the raw materials used in this application are purchased commercially and used without special treatment.
  • the Cu-SAPO-34 molecular sieve raw material is a high copper content Cu-SAPO-34 synthesized by using a copper amine complex as a single template or as a mixed template together with other organic amines, and has a Cu loading of 5-20% by weight.
  • the synthetic method reference is Applied Catalysis B: Environmental 127 (2012) 273-280, but is not limited to this method.
  • test conditions of this application are as follows:
  • Elemental composition was determined using a Philips Magix X X-ray Fluorescence Analyzer (XRF).
  • X-ray powder diffraction phase analysis using PANalytical, the Netherlands
  • the company's X'Pert PRO X-ray diffractometer, Cu target, K ⁇ radiation source ( ⁇ 0.141618 nm), voltage 40KV, current 40mA.
  • the specific surface area and pore size distribution of the samples were determined using a Micromeritics ASAP Model 2020 physical adsorber. Before the analysis, the sample was preheated at 350 ° C for 6 h, and the free volume of the sample tube was measured with He as the medium. When the sample was analyzed, the adsorption and desorption measurements were carried out at a liquid nitrogen temperature (77 K) using nitrogen as an adsorption gas. The specific surface area of the material was determined using the BET formula; the total pore volume of the material was calculated using the amount of adsorption of N 2 at a relative pressure (P/P 0 ) of 0.99. The micropore surface area and micropore volume were calculated by the t-plot method. When calculated, the cross-sectional area of the N 2 molecule was taken to be 0.162 nm 2 .
  • Solid NMR experiments of the samples were performed on a Bruker Avance III 600 (14.1 Tesla) spectrometer.
  • the 29 Si MAS NMR experiment used a 7 mm dual resonance probe with a speed of 6 kHz.
  • the sampling frequency is 5000-6000
  • the pulse width of ⁇ /4 is 2.5 ⁇ s
  • the sampling delay is 10s
  • the sodium 4,4-dimethyl-4-propane sulfonate (DSS) is used as the chemistry.
  • Displacement reference corrected to 0ppm.
  • Quasi-boehmite (65 wt%), water, phosphoric acid (85 wt%), silica sol (31 wt%), copper sulfate pentahydrate, tetraethylenepentamine (TEPA), optional, added to a 2 L synthesis kettle
  • the organic templating agent R1 and SAPO-34 are seeded, uniformly stirred, then sealed, heated to 140-200 ° C under stirring, and crystallized for 5-24 h.
  • the solid product was centrifuged, and the sample was washed with deionized water to neutrality.
  • the seed crystal is added to the synthesis in order to reduce the particle size of the synthesized high copper Cu-SAPO-34, so that it can participate in the subsequent crystallization, and play the role of seed crystal and copper source. The addition of seed crystal is also beneficial to improve the product. Yield.
  • the seed crystal is nano-scale SAPO-34 synthesized by reference patent CN104340986B.
  • the XRD of the four high-copper Cu-SAPO-34 samples synthesized is shown in Fig. 1, and the SEM of the sample Cu-34-a is shown in Fig. 2, and the particle size is 300-500 nm.
  • a seed seeding amount (M seed crystal / (M P2O5 + M Al2O3 + M SiO2 )) * 100%
  • product yield (M product original powder * 85% / (M P2O5 + M Al2O3 +M SiO2 )*100%
  • the aluminum source is first dissolved by mixing with water, and then an optional phosphorus source, silicon source, and templating agent R are sequentially added thereto.
  • a sample of Cu-SAPO-34 prepared in Example 1 was added to the above mixture. After stirring at room temperature, the gel was transferred to a stainless steel reaction vessel. After the reactor was placed in an oven, the temperature was raised to 160-200 ° C for 0.5-72 h, and the crystallization was completed. The solid product was centrifuged, washed, and dried in air at 120 ° C to obtain a sample of the molecular sieve raw powder.
  • the sample was subjected to XRD analysis, the peak shape showed a typical CHA structural characteristic peak, and the XRD diffraction spectrum of Example 3 is shown in FIG.
  • FIG. 4 shows an SEM photograph of the Cu-SAPO-34 molecular sieve prepared in Example 5. It can be seen that the morphology of the obtained sample is rhombohedral and the particle size ranges from 1-2 ⁇ m. It can be seen that the particle size of the sample prepared by the synthesis method of the present invention is smaller than that of the conventional hydrothermally synthesized SAPO molecular sieve. This is directly related to the use of copper-containing Cu-SAPO-34 as a raw material and seed crystal. After the sample was calcined and the template was removed, the specific surface area and pore volume were measured.
  • the sample had a high BET specific surface area of 560.7 m 2 g -1 and a large pore volume of 0.29 cm 3 g -1 , which was calculated according to the t-plot method.
  • the obtained micropore specific surface area and micropore volume were 542.5 m 2 g -1 and 0.25 cm 3 g -1 , respectively .
  • Figure 5 shows a solid nuclear magnetic 29 Si spectrum of the sample of Example 7, which shows that the sample showed a single peak at 90 ppm, respectively, which was assigned to the Si(4Al) coordination environment of the sample.
  • Examples 3, 5 and 8 samples will be implemented in a high-temperature calcination 650 °C 2h, after removal of the template agent for removing NH 3 reacts with NO x selective reduction catalyst performance tests.
  • the specific experimental procedures and conditions are as follows: After calcination, the sample is tableted, and 0.1 g of a 60 to 80 mesh sample is weighed and mixed with 0.4 g of quartz sand (60 to 80 mesh), and charged into a fixed bed reactor. The reaction was started by nitrogen at 600 ° C for 40 min, then the temperature was lowered to 120 ° C, and the temperature was raised to 550 ° C.
  • the reaction raw material gas was: NO: 500 ppm, NH 3 : 500 ppm, O 2 : 5%, H 2 O: 5%, N 2 as a balance gas, and a gas flow rate of 300 mL/min.
  • the reaction tail gas was analyzed by online FTIR using a Bruker Tensor 27 instrument. The results are shown in Fig. 6. It can be seen that the sample of Example 3 has a lower activity in the temperature range below 200 ° C due to the lower copper content, and the conversion of NO gradually increases with increasing temperature, and the conversion rate remains close to 100% at 500 ° C. In Example 5, the copper content of the sample was increased, thus increasing its low-temperature reactivity.
  • the NO conversion rate was further increased with increasing temperature, the conversion rate was close to 100% at 350 ° C, and the temperature was increased to 450-500 ° C. The rate has dropped slightly, but it remains above 90%.
  • the sample of Example 8 has a higher Cu content, and therefore, its low temperature activity is high, but a high Cu content causes a side reaction in the high temperature section to occur, so that the NO conversion rate slightly decreases after higher than 400 °C.
  • Example 5 Sample 650 °C high temperature firing 2h, after removal of the templating agent, further heat treated 16 hours at 800 °C high temperature water, were designated as sample 5-H followed by removal of NH 3 reacts with NO x selective reduction catalyst performance tests.
  • the test conditions were the same as in Example 10, and the results are shown in Fig. 7. It can be seen that the SCR reactivity of the sample is well maintained after high temperature water treatment, indicating that the Cu-SAPO-34 prepared by the method described in the present application has excellent high temperature hydrothermal stability and has practical progress. The conditions of the application.
  • Quasi-boehmite (65 wt%), water, phosphoric acid (85 wt%), silica sol (31 wt%), copper sulfate pentahydrate, tetraethylenepentamine (TEPA), diethanolamine were sequentially added to a 2 L synthesis kettle.
  • Trimethylamine (33% by weight), hydrofluoric acid (40% by weight) and SAPO-42 seed crystals.
  • the aluminum source is mixed with water to dissolve, and then an optional phosphorus source and silicon source are sequentially added thereto.
  • Diethanolamine, trimethylamine and hydrofluoric acid A sample of Cu-SAPO-42 prepared in Example 12 was added to the above mixture. After stirring at room temperature, the gel was transferred to a stainless steel reaction vessel. After the reaction vessel was placed in an oven, the temperature was raised to 200 ° C for 48 hours, and the crystallization was completed. The solid product was centrifuged, washed, and dried in air at 120 ° C to obtain a sample of the molecular sieve raw powder. The sample was subjected to XRD analysis, the peak shape showed a typical LTA structural characteristic peak, and the XRD diffraction spectrum of Example 13 is shown in Fig. 8.
  • the aluminum source is mixed with water, and then a phosphorus source, a silicon source, and N,N diisopropylethylamine are sequentially added thereto.
  • FIG. 10 shows an SEM photograph of the Cu-SAPO-18 molecular sieve prepared in Example 16.
  • the molar ratio of each raw material and the crystallization conditions are shown in Table 3.
  • the specific steps are as follows: a pseudo-boehmite (65% by weight), water, phosphoric acid (85% by weight), silica sol (31% by weight), copper sulfate pentahydrate, tetraethylene pentamine and two are sequentially added to a 100 mL synthesis kettle. Ethylamine (DEA).
  • DEA Ethylamine
  • the amount of SAPO-34 seed crystal added was 5% by weight of the solid content of the reaction mixture, and the mixture was uniformly stirred, then sealed, and heated to 170 ° C under stirring for 3 days.
  • the solid product was separated by centrifugation.
  • the sample was washed with deionized water to neutrality and dried in air at 120 ° C to obtain a Cu-SAPO-34 molecular sieve sample.
  • Figure 11 shows a SEM electron micrograph of Comparative Sample 3, which shows that the sample has a particle size of 5-10 microns.
  • Figure 12 shows the 29 Si NMR solid NMR spectrum of Comparative Sample 3. It can be seen that in addition to the Si (4Al) signal, the sample has a significant signal at 110 ppm, which is attributed to Si (0Al). Copper amine complex templating agents tend to cause formation of silicon islands. From the results of the four comparative examples, it is known that for the Cu-SAPO-34 molecular sieve synthesized by using a copper amine complex with other organic amines, reducing the amount of the copper amine complex can reduce the copper content in the product.
  • the copper content of the synthesized product is also controlled by the amount of silica charged in the synthesis system.
  • the amount of silicon oxide is reduced, the amount of copper in the product is reduced to a limited extent.
  • the simultaneous loading of the silica and copper amine complexes also resulted in a slower crystallization rate of the SAPO molecular sieve and a significant decrease in yield (Comparative Example 4).
  • the method provided by the present invention solves the above problems. Firstly, the Cu-SAPO molecular sieve raw material with high copper content is prefabricated, and the amount of copper amine complex input during the synthesis is high, and the crystallization speed and product yield are improved. Then, the pre-formed Cu-SAPO-34 raw material was used as a copper source, a part of silicon aluminophosphate and a seed crystal for the synthesis of Cu-SAPO-34. During the synthesis of this step, the problem of competition between the copper amine complex and other organic amine template agents is avoided, and the silicon content and silicon atom distribution of the product are basically controlled by the selected organic amine template.
  • the Cu content can also be controlled over a relatively wide range to achieve controlled synthesis of Cu-SAPO-34.
  • the improvement in the amount of silicon and the coordination environment in the Cu-SAPO molecular sieve provides the possibility of improving the hydrothermal stability of the synthesized Cu-SAPO-34.

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Abstract

本发明涉及一种合成Cu-SAPO分子筛的方法及其产品和用途。更具体地，涉及的方法包括将使用铜胺络合物为模板剂合成的高Cu含量的Cu-SAPO分子筛作为Cu源和部分硅磷铝源和晶种，进行Cu-SAPO分子筛的合成。该方法不但可以在较宽范围内控制SAPO分子筛中的铜含量，还可以有效调控硅含量及其硅原子分布，产品收率高。所得Cu-SAPO分子筛催化剂表现出优异的高温水热稳定性和对NOx的催化选择还原脱除性能。

Description

Cu-SAPO分子筛合成方法及合成的Cu-SAPO分子筛和应用 技术领域
本发明属于化学化工领域，涉及分子筛及其制备方法领域，尤其涉及一种合成含铜磷酸硅铝分子筛(Cu-SAPO)的方法和通过该方法获得的产品及其用途。所述Cu-SAPO可用于氮氧化合物净化过程的催化剂。
背景技术
1984年，美国联合碳化物公司(UCC)开发了系列由PO2 +、AlO2 -和SiO2四面体构成三维开放骨架结构的新型磷酸硅铝分子筛(SAPO-n)(USP4,440,871)。Si原子通过取代方式进入中性磷酸铝骨架结构，使骨架产生净的负电荷，引起质子酸性，因而赋予SAPO分子筛催化性能。以SAPO-34为载体制备的Cu-SAPO-34或Cu-SSZ-13催化剂(SSZ-13是与SAPO-34具有相同拓扑结构的分子筛，区别在于前者是硅铝分子筛，后者是磷酸硅铝分子筛)在柴油车尾气选择催化还原技术(Urea-SCR)系统净化氮氧化合物过程中，具有高活性和优异的水热稳定性。目前SAPO分子筛催化剂中铜离子的引入绝大部分采用离子交换法，即将得到的分子筛先焙烧除去模板剂，与硝酸铵溶液进行离子交换获得氨型样品，然后再和一定浓度的铜盐溶液混合搅拌数小时，过滤、洗涤、干燥、高温焙烧后得到Cu-SAPO-34。由于SAPO分子筛具有较差的低温水热稳定性，离子交换过程中分子筛骨架往往会发生部分水解导致分子筛比表面积下降。同时，离子交换法过程繁琐，在交换过程中铜盐溶液中铜离子的利用率低，洗涤过程耗费大量的纯净水并转化成污水，高温焙烧过程耗时耗能。
相比离子交换法，一步法合成含铜分子筛具有明显优势。CN 102259892A公开了一种以金属-胺络合物为模板剂合成磷酸硅铝分子筛催化剂的方法，避免了繁琐的离子交换工艺。但是，一步合成的Cu-SAPO-34的高温水热稳定性较差，限制其工业应用。如Corma等以铜胺络合物和二乙胺为模板剂合成Cu-SAPO-34分子筛，铜负载量控制在3.4-10.4％，晶体粒度约6-10μm。研究表明，该方法合成的低铜负载量催 化剂(铜含量3.4％)经750℃水热老化13h后活性明显下降，而对于具有中(铜含量6.0％)、高(10.4％)铜含量的Cu-SAPO-34催化剂，750℃水热老化13h后骨架结构全部倒塌(Applied CatalysisB:Environmental,2012,127:273)。除Cu负载量影响分子筛水热稳定性外，骨架负电荷的分布也影响骨架外铜离子的稳定性，从而影响铜负载分子筛样品的水热稳定性。对于SAPO分子筛，骨架负电荷的量及分布直接源于硅原子的引入量及其分布。如Si原子单一取代P原子可以形成Si(4Al)连接，形成酸中心。而当Si原子同时取代相邻的P和Al原子时，就会形成富Si区域甚至硅岛，导致骨架负电荷的不均匀分布，这不利于铜离子的稳定存在。为了进一步改进合成Cu-SAPO-34分子筛的水热稳定性，大量研究工作尝试使用各种有机模板剂与铜胺络合物复配合成Cu-SAPO-34，以期调变其铜含量和分子筛中的硅量及硅原子分布(J.Catalysis 2014，314，73-82；Chemical Engineering Journal 2016，294，254-263；CN 104209141A；CN 103818927A)。这些工作显示，铜胺络合物作为合成模板，容易使SAPO分子筛骨架中产生硅岛。但如果为了避免硅岛形成并控制铜负载量，同时降低铜胺络合物模板剂和硅源的量，又将影响产品收率和结晶度。
发明内容
为解决上述问题，本申请首先使用铜胺络合物作为合成模板剂得到高铜含量的Cu-SAPO，然后将其直接作为Cu源、部分硅磷铝源以及晶种，进行Cu-SAPO分子筛的合成。该方法避免了直接使用铜胺络合物和其他模板剂作为共模板合成Cu-SAPO时，铜胺络合物与其他合成模板的竞争，更好地发挥其他有机模板剂在合成中的导向作用，并且分子筛产品的晶体粒度、Cu含量及硅含量和分布都可以得到有效调控，从而获得的含铜分子筛具有更优异的催化性能和水热稳定性。
在一个方面，本发明提供一种Cu-SAPO分子筛的合成方法，其特征在于，包括如下步骤：
(1)制备高铜含量的Cu-SAPO分子筛，其Cu负载量为5-20wt％，优选5-15wt％；
(2)将有机胺模板剂R和水以及可选的硅源、铝源和磷源混合制得晶化液；
(3)将步骤(1)中得到的高铜含量的Cu-SAPO分子筛作为原料与步骤(2)中制得的晶化液混合并进行水热晶化，得到Cu-SAPO分子筛产品。
可选地，步骤(1)中的Cu-SAPO分子筛是使用包含铜胺络合物的模板剂合成的，或者由SAPO分子筛通过离子交换法获得。
可选地，步骤(1)中的Cu-SAPO分子筛是使用铜胺络合物作为单一模板或与有机胺模板剂R1一起作为混合模板剂，由硅源、铝源、磷源和水通过水热晶化合成的Cu-SAPO，其中硅源可以选自正硅酸乙酯、硅溶胶和白炭黑中的一种或几种；铝源可以选自异丙醇铝、拟薄水铝石、铝溶胶和氢氧化铝中的一种或几种；磷源可以选自磷酸、亚磷酸和五氧化二磷中的一种或几种；有机胺模板剂R1可以选自三乙胺、二乙胺、吗啉、四乙基氢氧化铵、丙胺、二异丙胺、N，N二异丙基乙胺、三甲胺、二乙醇胺和哌嗪中的一种或几种的混合。
可选地，步骤(1)中用于合成Cu-SAPO分子筛原料的铝源、磷源、硅源、铜胺络合物、有机胺模板剂R1和水的摩尔比例为Al2O3:P2O5:SiO2:Cu:R1:H2O＝1:0.8～1:0.3～1.0:0.1～0.8:0-3.5:40～80。
可选地，步骤(1)中的铜胺络合物包括铜-多乙烯多胺络合物，优选Cu-四乙烯五胺络合物、Cu-三乙烯四胺络合物、Cu-二乙烯三胺络合物和Cu-五乙烯六胺络合物。
可选地，步骤(1)中高铜含量的Cu-SAPO分子筛的合成在SAPO晶种的存在下进行。
可选地，步骤(2)中使用的硅源可以选自正硅酸乙酯、硅溶胶和白炭黑中的一种或几种；铝源可以选自异丙醇铝、拟薄水铝石、铝溶胶和氢氧化铝中的一种或几种；磷源可以选自磷酸、亚磷酸和五氧化二磷中的一种或几种；有机胺模板剂R可以选自三乙胺、二乙胺、吗啉、四乙基氢氧化铵、丙胺、二异丙胺、N，N二异丙基乙胺、三甲胺、二乙醇胺和哌嗪中的一种或几种的混合。
可选地，步骤(2)中使用的铝源、磷源、硅源、有机胺模板剂R和 水的摩尔比例为Al2O3:P2O5:SiO2:R:H2O＝1:0.5～2:0.01～1.5:0.5～10:15～200，优选为Al2O3:P2O5:SiO2:R:H2O＝1:0.7～1.5:0.1～1.0:1～5:30～100。
可选地，步骤(3)中高铜含量的Cu-SAPO原料的投料量为晶化液中固体氧化物质量总和的2-200wt％。
可选地，步骤(3)中进行水热晶化的温度为140-240℃，时间为0.5～72小时。更优选的晶化温度为150-200℃。
可选地，步骤(3)中制备的Cu-SAPO分子筛产品的Cu负载量与高铜含量的Cu-SAPO原料的铜含量相比下降10％以上，优选是高铜含量的Cu-SAPO原料的铜含量的10-70％。
可选地，所述Cu-SAPO分子筛包括Cu-SAPO-34分子筛，Cu-SAPO-42分子筛、Cu-SAPO-18和Cu-DNL-6(RHO)中的任一种。
在另一方面，本发明提供一种通过上述方法制备的Cu-SAPO分子筛原粉，优选Cu-SAPO-34分子筛原粉，其为菱面体状，优选粒径范围为1-2μm。
在另一方面，本发明还提供一种用于NOx选择还原脱除反应的催化剂，由根据上述方法合成的分子筛经500～800℃空气中焙烧得到。所述催化剂尤其是在氮氧化物的催化脱除反应中表现出良好的催化性能。催化剂经800℃饱和水蒸气16小时处理后仍然保持优异的催化活性。
在另一方面，本发明提供一种用于改进Cu-SAPO分子筛高温水热稳定性的方法，其特征在于，所述方法包括：将通过使用包含铜胺络合物的模板剂合成的高铜含量的Cu-SAPO分子筛与晶化液混合并进行水热晶化，其中所述晶化液是通过将有机胺模板剂R和水以及可选的硅源、铝源和磷源混合而制得的。
本发明可以产生以下有益效果中的至少一种：
(1)提供一种合成Cu-SAPO分子筛的新方法，此方法实现了具有高水热稳定性Cu-SAPO的高收率合成和Cu源的高效利用。其晶体粒度、Cu含量及硅含量和分布可以得到有效调控；
(2)所制备的分子筛可作为催化剂用于氮氧化物的催化脱除反应，并表现出良好的催化性能。催化剂经800℃水蒸气处理16小时后催化性能仍有提升或保持不变。
附图说明
图1是实施例1中合成的高铜含量Cu-SAPO-34的XRD图谱。
图2是是实施例1中合成的高铜含量Cu-SAPO-34的扫描电镜图(SEM)。
图3是实施例3产物的XRD图谱。
图4实施例5产物的扫描电镜图(SEM)。
图5是实施例3的固体29Si核磁谱图。
图6是实施例3，5，8的NH3-SCR反应评价结果。
图7是实施例5催化剂经高温水热处理前(实施例5)、后(实施例5-H)样品的NH3-SCR反应评价结果对比。
图8是实施例13样品的XRD图谱。
图9是实施例16样品的XRD图谱。
图10是实施例16产物的扫描电镜图(SEM)。
图11是对比例3样品的SEM电镜照片。
图12对比例3样品的固体29Si核磁谱图。
具体实施方式
下面结合实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。下列实施例中未注明具体条件的实验方法，通常按照常规条件或按照制造厂商所建议的条件。未做特殊说明的情况下，本申请所使用原料，均通过商业途径购买，不经特殊处理直接使用。Cu-SAPO-34分子筛原料是使用铜胺络合物作为单一模板合成或与其他有机胺一起作为混合模板剂一步合成的高铜含量Cu-SAPO-34，其Cu负载量为5-20wt％。合成方法参考文献Applied Catalysis B:Environmental 127(2012)273-280，但不限于此方法。
未做特殊说明的情况下，本申请的测试条件如下：
元素组成采用Philips公司的Magix X型X射线荧光分析仪(XRF)测定。
X射线粉末衍射物相分析(XRD)采用荷兰帕纳科(PANalytical) 公司的X’Pert PRO型X射线衍射仪，Cu靶，Kα辐射源(λ＝0.15418nm)，电压40KV，电流40mA。
采用美国Micromeritics公司ASAP 2020型物理吸附仪测定样品的比表面积和孔径分布。分析前，样品在350℃下抽真空加热预处理6h，以He为介质测量样品管自由体积。分析样品时，以氮气为吸附气体，在液氮温度(77K)下进行物理吸附和脱附测定。采用BET公式确定材料的比表面积；使用相对压力(P/P0)为0.99时的N2的吸附量计算材料的总孔容。用t-plot方法计算微孔表面积和微孔孔容。计算时，N2分子横截面积取0.162nm2。
SEM形貌分析采用Hitachi TM3000型和Hitachi SU8020型台式扫描电子显微镜。
样品的固体核磁实验在Bruker AvanceIII600(14.1Tesla)谱仪上进行。29Si MAS NMR实验采用7mm双共振探头，转速为6kHz。采用高功率质子去偶程序，采样次数为5000-6000，π/4的脉冲宽度为2.5μs，采样延迟为10s，以4，4-二甲基-4-丙磺酸钠(DSS)为化学位移参考，校正到0ppm。
实施例1：
作为铜源的含铜Cu-SAPO-34样品的合成。
各原料摩尔比例和晶化条件见表1，具体配料过程如下：
向2L合成釜中依次加入拟薄水铝石(65重量％)、水、磷酸(85重量％)、硅溶胶(31重量％)、五水合硫酸铜、四乙烯五胺(TEPA)、可选的有机模板剂R1及SAPO-34晶种，搅拌均匀，然后密封，在搅拌下升温至140-200℃，晶化5-24h。固体产物经离心分离、用去离子水洗涤样品至中性，在120℃空气中干燥后，得到待用的Cu-SAPO-34分子筛(命名为Cu-34-x，x＝a,b,c,d)。合成中加入晶种是为了降低合成的高铜Cu-SAPO-34的粒度，使其更好的参与后续的晶化，起到晶种和铜源的作用，晶种的加入也有利于提高产品收率。晶种是参考专利CN104340986B合成的纳米级SAPO-34。合成的四个高铜Cu-SAPO-34样品的XRD见图1，样品Cu-34-a的SEM见图2，粒度在300-500nm。
表1作为铜源的含铜Cu-SAPO-34的原料摩尔比例和晶化条件
Figure PCTCN2017102095-appb-000001
a晶种的投料量(wt％)＝(M晶种/(MP2O5+MAl2O3+MSiO2))*100％,产品收率＝(M产品原粉*85％/(MP2O5+MAl2O3+MSiO2)*100％
实施例2～9：高水热稳定性Cu-SAPO-34分子筛产品的制备
各原料摩尔比例和晶化条件见表2。具体配料过程如下：
首先将铝源与水混合溶解，然后依次向其中加入可选的磷源、硅源和模板剂R。向上述混合物中加入实施例1中制备的Cu-SAPO-34样品。在室温搅拌均匀后将凝胶转移到不锈钢反应釜中。反应釜放入烘箱后，升温到160-200℃反应0.5-72h，晶化结束。将固体产物离心，洗涤，在120℃空气中烘干后，得到分子筛原粉样品。样品做XRD分析，峰形呈现典型的CHA结构特征峰，实施例3的XRD衍射谱图见图3。另外，图4给出了实施例5中制备的Cu-SAPO-34分子筛的SEM照片。可以看出，所得样品的形貌为菱面体状，粒径范围为1-2μm。可见使用本发明合成方法制备样品的粒度较常规水热合成SAPO分子筛的晶体粒度偏小。这与使用含铜Cu-SAPO-34作为原料和晶种有直接关系。将样品焙烧脱除模板剂后， 测其比表面积及孔容，样品具有高的BET比表面积560.7m2g-1，及大的孔体积0.29cm3g-1，其中按照t-plot方法计算得到的微孔比表面积和微孔容积分别为542.5m2g-1和0.25cm3g-1。图5给出了实施例7样品的固体核磁29Si谱图，结果显示样品分别在90ppm出现单一的峰，归属为样品的Si(4Al)配位环境。
Figure PCTCN2017102095-appb-000002
实施例10
将实施例3、5和8的样品于650℃高温焙烧2h，除去模板剂后，用于NH3选择性还原脱除NOx反应的催化性能测试。具体实验过程和条件如下：焙烧后样品压片筛分，称取0.1g 60到80目样品与0.4g石英砂(60到80目)混合，装入固定床反应器。于600℃下通氮气活化40min，然后降温至120℃开始反应，并升温到550℃。反应原料气为：NO：500ppm，NH3：500ppm，O2：5％，H2O：5％，N2作为平衡气，气体流速300mL/min。反应尾气采用Bruker公司的Tensor 27型仪器，进行在线FTIR分析，结果见图6。可以看到，实施例3样品由于具有较低的铜含量，在低于200℃温度段活性较低，随着温度升高NO转化率逐步升高，500℃仍保持接近100％的转化率。实施例5样品铜含量提高了一些，因此提升了其低温反应活性，随着温度升高NO转化率进一步升高，350℃接近100％的转化率，温度升高到450-500℃以后，转化率略有下降，但仍保持在90％以上。实施例8样品具有更高的Cu含量，因此，其低温活性高，但偏高的Cu含量会导致高温段副反应发生，使得NO转化率在高于400℃以后略有下降。
实施例11
实施例5样品在650℃高温焙烧2h，除去模板剂后，进一步在800℃高温水热处理16小时，分别命名为样品5-H然后进行NH3选择性还原脱除NOx反应的催化性能测试。测试条件同实施例10，结果见图7。可以看到，样品在高温水处理后其SCR反应活性都得到了较好的保持，表明，用本申请所描述的方法制备的Cu-SAPO-34具有优异的高温水热稳定性，具备走向实际应用的条件。
实施例12
作为铜源的含铜Cu-SAPO-42样品的合成过程如下：
向2L合成釜中依次加入拟薄水铝石(65重量％)、水、磷酸(85重量％)、硅溶胶(31重量％)、五水合硫酸铜、四乙烯五胺(TEPA)、二乙醇胺、三甲胺(33重量％)、氢氟酸(40重量％)及SAPO-42晶种。投料配比Al2O3:P2O5:SiO2:Cu-四乙烯五胺络合物:二乙醇胺：三甲胺：氢氟酸:H2O＝1：1：1.0：0.10：3.0：0.9：0.5：50，晶种投料10重量％。搅拌均匀，然后密封， 在搅拌下升温至180℃，晶化48h。固体产物经离心分离、用去离子水洗涤样品至中性，在120℃空气中干燥后，得到待用的Cu-SAPO-42分子筛，编号Cu-42，含铜量9重量％。
实施例13-14
各原料摩尔比例和晶化条件见表3。具体配料过程如下：
首先将铝源与水混合溶解，然后依次向其中加入可选的磷源、硅源。二乙醇胺、三甲胺和氢氟酸。向上述混合物中加入实施例12中制备的Cu-SAPO-42样品。在室温搅拌均匀后将凝胶转移到不锈钢反应釜中。反应釜放入烘箱后，升温到200℃反应48h，晶化结束。将固体产物离心，洗涤，在120℃空气中烘干后，得到分子筛原粉样品。样品做XRD分析，峰形呈现典型的LTA结构特征峰，实施例13的XRD衍射谱图见图8。
表3合成原料摩尔比例、晶化条件及合成结果
Figure PCTCN2017102095-appb-000003
实施例15
作为铜源的含铜Cu-SAPO-18样品的合成过程如下：
向2L合成釜中依次加入拟薄水铝石(65重量％)、水、磷酸(85重量％)、硅溶胶(31重量％)、五水合硫酸铜、四乙烯五胺(TEPA)、N，N二异丙基乙胺及SAPO-18或者SAPO-34的晶种。投料配比Al2O3:P2O5:SiO2:Cu-四乙烯五胺络合物:N，N二异丙基乙胺:H2O＝1：1：0.15：0.10：3.0：1.9：40，晶种投料10重量％。搅拌均匀，然后密封，在搅拌下升温至160℃，晶化48h。固体产物经离心分离、用去离子水洗涤样品至中性，在120℃空气中干燥后，得到待用的Cu-SAPO-18分子筛，编号Cu-18，含铜量9重量％。
实施例16
首先将铝源与水混合溶解，然后依次向其中加入磷源、硅源和N，N二异丙基乙胺。向上述混合物中加入实施例15中制备的Cu-18样品，在室温搅拌均匀后将凝胶转移到不锈钢反应釜中。投料配比Al2O3:P2O5:SiO2:N，N二异丙基乙胺:H2O＝1.0：1.0：0.2：2：50，反应釜放入烘箱后，升温到170℃反应48h，晶化结束。将固体产物离心，洗涤，在120℃空气中烘干后，得到分子筛原粉样品。样品做XRD分析，峰形呈现典型的SAPO-18结构特征峰，实施例16的XRD衍射谱图见图9。另外，图10给出了实施例16中制备的Cu-SAPO-18分子筛的SEM照片。
对比例1-4：
各原料摩尔比例和晶化条件见表3。具体步骤如下：向100mL合成釜中依次加入拟薄水铝石(65重量％)、水、磷酸(85重量％)、硅溶胶(31重量％)、五水合硫酸铜、四乙烯五胺及二乙胺(DEA)。SAPO-34晶种添加量为反应混合物固含量的5wt％，搅拌均匀，然后密封，在搅拌下升温至170℃，晶化3天。固体产物经离心分离。用去离子水洗涤样品至中性，在120℃空气中干燥后，得到Cu-SAPO-34分子筛样品。
表4原料摩尔比例和晶化条件
Figure PCTCN2017102095-appb-000004
产品收率＝(M产品*85％/(MP2O5+MAl2O3+MSiO2)*100％
图11给出了对比例样品3的SEM电镜照片，结果显示样品的粒度在 5-10微米。图12给出了对比例样品3的29Si NMR固体核磁谱图，可以发现，除Si(4Al)信号外，样品在110ppm存在明显的信号，归属于Si(0Al)。铜胺络合物模板剂易于导致硅岛形成。从四个对比例的结果可知，对于使用铜胺络合物与其他有机胺共模板合成Cu-SAPO-34分子筛来说，减少铜胺络合物的投料量可以降低产品中的铜含量。但是，所合成产品的铜含量还同时受控于合成体系中氧化硅投料量。当氧化硅的投料量降低时，产品中的铜含量下降程度有限。氧化硅和铜胺络合物的投料量同时降低，还会导致SAPO分子筛的晶化速度减慢，收率明显下降(对比例4)。
本发明提供的方法解决了上述问题。首先预制高铜含量的Cu-SAPO分子筛原料，合成过程中投入的铜胺络合物量较高，提高晶化速度和产品收率。然后，将预制的Cu-SAPO-34原料作为铜源、部分硅磷铝原和晶种进行Cu-SAPO-34的合成。在此步合成过程中，避免了铜胺络合物与其他有机胺模板剂竞争的问题，产品硅含量及硅原子分布基本受控于选用的有机胺模板剂。Cu含量也可以在相对宽的范围内调控，实现Cu-SAPO-34的可控合成。Cu-SAPO分子筛中的硅量和配位环境改善为提高合成的Cu-SAPO-34的水热稳定性提供了可能。
对比例5
将对比例1-4得到的样品于650℃高温焙烧2h，除去模板剂后，进一步在800℃高温水热处理16小时，XRD测试显示三个样品属于CHA晶相的衍射峰消失，样品在20-25度范围内有衍射峰，形成致密相，可见其高温水热稳定性差。
应当指出，对于使本技术领域的专业技术人员，在不脱离本发明原理的前提下，能够实现对这些实施例的多种修改，而这些修改也应视为在本发明的保护范围内。

Claims (15)

  1. 一种制备Cu-SAPO分子筛的方法，其特征在于，所述方法包括以下步骤：
    (1)制备高铜含量的Cu-SAPO分子筛，其Cu负载量为5-20wt％；
    (2)将有机胺模板剂R和水以及可选的硅源、铝源和磷源混合制得晶化液；
    (3)将步骤(1)中得到的高铜含量的Cu-SAPO分子筛作为原料与步骤(2)中制得的晶化液混合并进行水热晶化，得到Cu-SAPO分子筛产品。
  2. 按照权利要求1所述的方法，其特征在于，所述步骤(1)中高铜含量的Cu-SAPO分子筛是使用包含铜胺络合物的模板剂合成的，或者由SAPO分子筛通过离子交换法获得。
  3. 按照权利要求2所述的方法，其特征在于，所述铜胺络合物包括铜-多乙烯多胺络合物，优选Cu-四乙烯五胺络合物、Cu-三乙烯四胺络合物、Cu-二乙烯三胺络合物和Cu-五乙烯六胺络合物。
  4. 按照权利要求1所述的方法，其特征在于，所述步骤(1)中高铜含量的Cu-SAPO分子筛是使用铜胺络合物作为单一模板或与有机胺模板剂R1混合为共模板剂，由硅源、铝源、磷源和水通过水热晶化合成的Cu-SAPO，所述有机胺模板剂R1选自三乙胺、二乙胺、吗啉、四乙基氢氧化铵、丙胺、二异丙胺、N，N二异丙基乙胺、三甲胺、二乙醇胺和哌嗪中的一种或几种的混合。
  5. 按照权利要求3所述的方法，其特征在于，所述步骤(1)中高铜含量的Cu-SAPO分子筛的合成在SAPO晶种的存在下进行。
  6. 按照权利要求1所述的方法，其特征在于，所述步骤(2)中使用的硅源选自正硅酸乙酯、硅溶胶和白炭黑中的一种或几种；铝源选自异丙醇铝、拟薄水铝石、铝溶胶和氢氧化铝中的一种或几种；磷源选自磷酸、亚磷酸和五氧化二磷中的一种或几种；有机胺模板剂R选自三乙胺、二乙胺、吗啉、四乙基氢氧化铵、丙胺、二异丙胺、N，N二异丙基乙胺、三甲胺、二乙醇胺和哌嗪中的一种或几种的混合。
  7. 按照权利要求1所述的方法，其特征在于，所述步骤(2)中使用的铝源、磷源、硅源、有机胺模板剂R和水的摩尔比例为Al2O3:P2O5:SiO2:R:H2O＝1:0.5～2:0.01～1.5:0.5～10:15～200，优选为Al2O3:P2O5:SiO2:R:H2O＝1:0.7～1.5:0.1～1.0:1～5:30～100。
  8. 按照权利要求1所述的方法，其特征在于，步骤(3)中所述的高铜含量的Cu-SAPO原料的投料量为配制的晶化液中固体氧化物质量总和的2-200wt％。
  9. 按照权利要求1所述的方法，其特征在于，所述步骤(3)中进行水热晶化的温度为140-240℃，时间为0.5～72小时；更优选的晶化温度为150-200℃。
  10. 按照权利要求1所述的方法，其特征在于，步骤(3)中制备的Cu-SAPO分子筛产品的Cu负载量是高铜含量的Cu-SAPO原料的铜含量的10-70％。
  11. 按照权利要求1-10中任一项所述的方法，其特征在于，所述Cu-SAPO分子筛包括Cu-SAPO-34分子筛，Cu-SAPO-42分子筛、Cu-SAPO-18和Cu-DNL-6(RHO)中的任一种。
  12. 一种Cu-SAPO分子筛原粉，其由根据权利要求1-11中任一项所述的方法合成。
  13. 根据权利要求12所述的Cu-SAPO分子筛原粉，其特征在于，所述Cu-SAPO分子筛是Cu-SAPO-34分子筛，所述Cu-SAPO-34分子筛为菱面体状，优选粒径范围为1-2μm。
  14. 一种用于NOx选择还原脱除反应的催化剂，其由根据权利要求1-11中任一项所述的方法合成的分子筛经500～800℃空气中焙烧得到。
  15. 一种用于改进Cu-SAPO分子筛高温水热稳定性的方法，其特征在于，所述方法包括：将高铜含量的Cu-SAPO分子筛与晶化液混合并进行水热晶化，其中所述晶化液是通过将有机胺模板剂R和水以及可选的硅源、铝源和磷源混合而制得的。
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113683099A (zh) * 2021-08-31 2021-11-23 大连理工大学 一种富含羟基窝的缺陷型沸石分子筛合成方法
CN114433169A (zh) * 2020-10-31 2022-05-06 中国石油化工股份有限公司 一种三联苯加氢改质催化剂、其制备方法及应用
CN114735718A (zh) * 2021-01-07 2022-07-12 国家能源投资集团有限责任公司 Sapo-34分子筛及其制备方法和应用
CN115193408A (zh) * 2022-07-15 2022-10-18 盐城工学院 一种Ag-SAPO-34@Cu-BTC复合材料及其制备和应用方法
CN115245838A (zh) * 2022-06-16 2022-10-28 天津大学 T分子筛快速合成方法及催化剂和应用
CN116060113A (zh) * 2021-10-29 2023-05-05 中国石油化工股份有限公司 一种直馏柴油加氢改质催化剂及其制备方法和应用

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112827507B (zh) * 2019-11-22 2023-08-11 中冶京诚工程技术有限公司 铜锌离子交换分子筛scr催化剂及其制备方法和应用
CN111437876B (zh) * 2020-04-21 2023-11-14 河北大学 一种Cu-SAPO-34分子筛催化剂及其制备方法与应用
CN116409800A (zh) * 2023-04-10 2023-07-11 山东宇洋汽车尾气净化装置有限公司 一种具有CHA结构的Cu-SAPO-34分子筛的制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102802791A (zh) * 2009-04-17 2012-11-28 约翰逊马西有限公司 用于还原氮氧化物、能耐受贫燃/富燃老化的小孔分子筛负载铜催化剂
CN104209141A (zh) * 2014-09-24 2014-12-17 中国科学院生态环境研究中心 一种Cu-SAPO-34分子筛催化剂、制备方法及其用途
CN104722331A (zh) * 2014-12-13 2015-06-24 济南大学 一种Cu-SAPO-44微孔分子筛的制备方法及其作为NH3-SCR催化剂的应用
CN105008048A (zh) * 2013-03-13 2015-10-28 巴斯夫公司 稳定的金属交换的sapo材料

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090196812A1 (en) * 2008-01-31 2009-08-06 Basf Catalysts Llc Catalysts, Systems and Methods Utilizing Non-Zeolitic Metal-Containing Molecular Sieves Having the CHA Crystal Structure
CA2871262C (en) * 2012-04-27 2017-08-01 Haldor Topsoe A/S Process for the direct synthesis of cu-sapo-34
CN104340985B (zh) * 2013-07-30 2017-03-29 中国科学院大连化学物理研究所 制备小晶粒sapo分子筛的方法及其产品和用途
CN103818927B (zh) * 2014-02-20 2016-05-18 无锡威孚环保催化剂有限公司 一步法合成高水热稳定性含铜cha型分子筛的方法
CN105984876B (zh) * 2015-01-30 2018-06-29 中国科学院大连化学物理研究所 一种金属改性sapo分子筛的制备方法
CN104891528A (zh) * 2015-06-12 2015-09-09 杭州回水科技股份有限公司 铜胺络合物作为模板剂固相合成Cu-SAPO-34分子筛的方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102802791A (zh) * 2009-04-17 2012-11-28 约翰逊马西有限公司 用于还原氮氧化物、能耐受贫燃/富燃老化的小孔分子筛负载铜催化剂
CN105008048A (zh) * 2013-03-13 2015-10-28 巴斯夫公司 稳定的金属交换的sapo材料
CN104209141A (zh) * 2014-09-24 2014-12-17 中国科学院生态环境研究中心 一种Cu-SAPO-34分子筛催化剂、制备方法及其用途
CN104722331A (zh) * 2014-12-13 2015-06-24 济南大学 一种Cu-SAPO-44微孔分子筛的制备方法及其作为NH3-SCR催化剂的应用

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114433169A (zh) * 2020-10-31 2022-05-06 中国石油化工股份有限公司 一种三联苯加氢改质催化剂、其制备方法及应用
CN114433169B (zh) * 2020-10-31 2023-09-01 中国石油化工股份有限公司 一种三联苯加氢改质催化剂、其制备方法及应用
CN114735718A (zh) * 2021-01-07 2022-07-12 国家能源投资集团有限责任公司 Sapo-34分子筛及其制备方法和应用
CN113683099A (zh) * 2021-08-31 2021-11-23 大连理工大学 一种富含羟基窝的缺陷型沸石分子筛合成方法
CN113683099B (zh) * 2021-08-31 2023-12-29 大连理工大学 一种富含羟基窝的缺陷型沸石分子筛合成方法
CN116060113A (zh) * 2021-10-29 2023-05-05 中国石油化工股份有限公司 一种直馏柴油加氢改质催化剂及其制备方法和应用
CN116060113B (zh) * 2021-10-29 2024-05-07 中国石油化工股份有限公司 一种直馏柴油加氢改质催化剂及其制备方法和应用
CN115245838A (zh) * 2022-06-16 2022-10-28 天津大学 T分子筛快速合成方法及催化剂和应用
CN115245838B (zh) * 2022-06-16 2023-06-27 天津大学 T分子筛快速合成方法及催化剂和应用
CN115193408A (zh) * 2022-07-15 2022-10-18 盐城工学院 一种Ag-SAPO-34@Cu-BTC复合材料及其制备和应用方法
CN115193408B (zh) * 2022-07-15 2023-05-05 盐城工学院 一种Ag-SAPO-34@Cu-BTC复合材料及其制备和应用方法

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