WO2008019591A1 - A directly shaping method of a fluid reaction catalyst containing molecular sieve - Google Patents

A directly shaping method of a fluid reaction catalyst containing molecular sieve Download PDF

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Publication number
WO2008019591A1
WO2008019591A1 PCT/CN2007/002373 CN2007002373W WO2008019591A1 WO 2008019591 A1 WO2008019591 A1 WO 2008019591A1 CN 2007002373 W CN2007002373 W CN 2007002373W WO 2008019591 A1 WO2008019591 A1 WO 2008019591A1
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molecular sieve
catalyst
slurry
sapo
spray drying
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French (fr)
Inventor
Peng Tian
Lei Xu
Zhongmin Liu
Lixin Yang
Cuiyu Yuan
Yue Qi
Xiangao Wang
Changqing He
Shuanghe Meng
Jinling Zhang
Mingzhi Li
Zhihui Lv
Yingxu Wei
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0036—Grinding
    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0045—Drying a slurry, e.g. spray drying
    • 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
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles

Definitions

  • the invention relates to a direct molding method of a fluidized reaction catalyst containing molecular sieves.
  • the method comprises the steps of: separating the slurry after crystallization of the molecular sieve without directly separating the binder, the matrix component, and performing spray drying after being rubberized to obtain a molding.
  • Microsphere molecular sieve catalyst Background technique
  • the fluidized bed catalyst is formed by spray drying, and the active component, the binder, the matrix and the water are beaten and then spray-dried to obtain a microsphere catalyst, and the active component is used as a molecular sieve solid powder.
  • Chinese Patent No. ZL 00103386 discloses a method for preparing a catalytic cracking catalyst which comprises mixing a molecular sieve slurry, an aluminum sol, a pseudoboehmite, a clay and a mineral acid to form a catalyst slurry, followed by spray drying. It is characterized in that the order of addition of the inorganic acid is controlled, and an alkali metal silicate is added to the catalyst slurry to increase the solid content of the slurry.
  • Chinese Patent ZL 01100019 discloses a process for preparing a catalytic cracking catalyst which comprises mixing a molecular sieve slurry, pseudoboehmite, clay and mineral acid to form a catalyst slurry, followed by spray drying.
  • Chinese Patent ZL 98117896 discloses a process for preparing a catalytic cracking catalyst which comprises mixing a molecular sieve slurry, an aluminum sol, a pseudoboehmite, a clay and a mineral acid to form a catalyst slurry, followed by spray drying. It is characterized by controlling the order of addition of the molecular sieve and the inorganic acid to thereby extract the solid content of the catalyst slurry.
  • Citride ZL 98119914 discloses a process for preparing a petroleum cracking catalyst which comprises mixing a molecular sieve slurry, an aluminum sol, a pseudoboehmite, a clay and a mineral acid to form a catalyst slurry, followed by spray drying. It is also characterized by controlling the order of addition of the molecular sieve and the mineral acid, thereby increasing the solids content of the catalyst slurry.
  • the purpose is to control the feeding sequence of each material or to add an additive to increase the solid content of the catalyst slurry
  • the molecular sieve slurry referred to is a molecular sieve slurry prepared by molecular sieve solid powder and water beating, which is not a slurry of molecular sieve synthesis itself.
  • Chinese Patent No. ZL 00137233 discloses a process for preparing a zeolite catalyst which comprises rapidly drying an aqueous dispersion containing crystalline zeolite, oligomeric silica and tetrahydroxyammonium hydroxide, characterized by directly forming a suspension formed during synthesis of the zeolite.
  • the slurry after crystallization of the molecular sieve is not separated, but the binder and the matrix component are directly added, and after being subjected to rubber grinding, spray drying is carried out to obtain a shaped molecular sieve catalyst.
  • the molecular sieve is a phosphosilica molecular sieve such as SAPO-17, SAPO-18, SAPO-34, SAPO-35, SAPO-44, or SAPO-56 molecular sieve.
  • the binder may be an oxide of silica sol or silicon, or an oxide of aluminum sol or aluminum, etc.
  • the substrate may be amorphous silicon aluminum oxide, amorphous phosphorus silicon aluminum oxide, kaolin , metakaolin or clay.
  • the molecular sieve has a weight percentage of 10-50%, preferably 20-40%.
  • the binder is present in an amount of from 10 to 80% by weight, preferably from 15 to 50% by weight; the basis weight of the substrate is from 10 to 80%, preferably from 20 to 60%.
  • the molecular sieve-containing fluidization reaction catalyst direct molding method of the present invention comprises the following steps: a) preparing a synthetic initial gel according to a molecular sieve synthesis gel ratio, and performing crystallization under certain conditions to obtain a slurry after crystallization of the molecular sieve ;
  • step b) crystallization of the molecular sieve obtained in step a), taking a small amount of the slurry for centrifugation, analyzing the crystal structure of the solid product and the composition of the filtrate;
  • step c) according to the molecular sieve liquid composition data obtained in the step b), the binder, the matrix and the water are added in proportion to the molecular sieve slurry obtained in the step a) to prepare a catalyst slurry for spray drying; d) will be in the step c)
  • the catalyst slurry obtained in the above was spray-dried to obtain a fluidized bed microsphere catalyst.
  • the microsphere catalyst obtained in the step d) is calcined at 400-600 ° C for 3-6 hours to obtain a fluidized bed microsphere catalyst from which the template is removed.
  • the method for preparing a microsphere catalyst of the invention is simple and easy, and can fully utilize the unreacted useful components in the molecular sieve slurry and simplify the molding step of the catalyst.
  • the invention is characterized in that: the slurry after crystallization of the molecular sieve is not separated, and the binder and the matrix component are directly added to the slurry, and the mixture is subjected to spray drying to obtain a shaped molecular sieve catalyst, thereby omitting the molecular sieve crystallization.
  • the separation, washing and drying of the product simplifies the catalyst preparation step and reduces contamination.
  • the raw material consumption is reduced, The preparation cost of the molecular sieve catalyst is greatly reduced.
  • the phosphorus silica gel molecular sieve fluidized bed microsphere catalyst prepared by the invention can be applied to the reaction of methanol or dimethyl ether to produce low carbon olefins, the reaction temperature is 300-600 ° C, the preferred reaction temperature is 400-500 ⁇ , the raw material methanol or two Methyl ether weight space is ⁇ ! ! The C 2 -C 3 lower olefin selectivity in the product can reach 90%.
  • Figure 1 SEM image of a fluidized bed microsphere catalyst prepared in Example 6 of the present invention
  • Figure 2 SEM image of a fluidized bed microsphere catalyst prepared in Example 7 of the present invention
  • Figure 3 SEM image of a fluidized bed microsphere catalyst prepared in Example 8 of the present invention.
  • Figure 4 SEM image of a fluidized bed microsphere catalyst prepared in Example 9 of the present invention. detailed description
  • the initial gel ratio is 1.5 C 6 H U H 2 : 0.1 SiO 2 : P 2 0 5 : A1 2 0 3 : 40H 2 O
  • Example 2 An appropriate amount of the SAPO-17 molecular sieve slurry obtained in Example 1 was added, and corresponding amounts of kaolin, silica sol, phthalocyanine powder and water were separately added, and the slurry for spray drying was prepared by beating and gluing, and the slurry solid content was 30%.
  • the weight percentage of each component in the slurry is: 40% molecular sieve, 45% Si0 2 , 10 Al 2 O 3 , 4.5 % P 2 0 5 , 0.5 % field Cyanine powder.
  • the spray drying slurry was spray-dried under certain conditions to obtain a fluidized bed microsphere catalyst.
  • Example 3 Synthesis of SAPO-18 molecular sieve
  • the initial gel ratio was 1.75 N, N-diisopropylethylamine: 0.2 SiO 2 : 0.95 P 2 O 5 : A1 2 0 3 : 50H 2 O (N, N-diiso 1 ⁇ 4 base B
  • the metering material of the amine as a template was mixed, thoroughly stirred into a gel, and then placed in a stainless steel autoclave, and crystallized at 170 ° C for 24 hours to obtain a molecular sieve slurry.
  • the slurry solid content is 35 %.
  • the weight percentage of each component in the slurry (containing the components in the molecular sieve slurry) is: 30% molecular sieve, 40% Si0 2 , 25 % A1 2 0 3 , 4.5% P 2 0 5 , 0.5 % Tian Jing powder.
  • the spray drying slurry was spray-dried under certain conditions to obtain a fluidized bed microsphere catalyst.
  • the initial gel ratio is 3.0 ⁇ : 0.2 SiO 2 : ⁇ 2 0 5 : ⁇ 1 2 0 3 : 50 ⁇ 2 ⁇ ( ⁇ is a triethylamine templating agent), the metering materials are mixed, and thoroughly stirred into a gel. Then, it was placed in a stainless steel autoclave and crystallized at 200 Torr for 24 hours to obtain a crystallized molecular sieve slurry.
  • the SAPO-34 molecular sieve slurry obtained in Example 5 Take appropriate amount of the SAPO-34 molecular sieve slurry obtained in Example 5, and then add the corresponding amount of glutinous clay, silica sol, phthalocyanine powder and water, and prepare a spray-drying slurry after beating and rubber grinding.
  • the solid content of the slurry is 30. %.
  • the weight percentage of each component in the slurry (containing the components in the molecular sieve slurry) is: 40% molecular sieve, 38% Si0 2 , 21 % A1 2 0 3 , 0.5 % P 2 O 5 , 0.5 % Tian Jing powder.
  • the spray drying slurry was spray-dried under certain conditions to obtain a fluidized bed microsphere catalyst, and the surface morphology thereof was analyzed by scanning electron microscopy. The results are shown in Fig. 1.
  • the molecular sieve microsphere catalyst was calcined at 350 ° C for 2 hours, calcined at 450 ° C for 1 hour, and calcined at 550 ° C for 4 hours to obtain a SAPO-34 molecular sieve microsphere catalyst, numbered FRC-01.
  • Example 7 (catalyst preparation)
  • the weight percentage of each component in the slurry is: 40% molecular sieve, 23% Si0 2 , 36% A1 2 0 3 , 0.5 % P 2 O 5 , 0.5 % Tian Jing powder.
  • the spray drying slurry was spray-dried under certain conditions to obtain a fluidized bed microsphere catalyst, and the surface morphology thereof was analyzed by scanning electron microscopy. The results are shown in Fig. 2.
  • the molecular sieve microsphere catalyst was calcined at 350 ° C for 2 hours, calcined at 450 ° C for 1 hour, and calcined at 550 ° C for 4 hours to obtain a SAPO-34 molecular sieve microsphere catalyst, numbered FRC-02.
  • Example 8 (catalyst preparation)
  • the SAPO-34 molecular sieve slurry obtained in Example 5 Take appropriate amount of the SAPO-34 molecular sieve slurry obtained in Example 5, and then add the corresponding amount of glutinous earth, aluminum sol, silica sol, phthalocyanine powder and water, and prepare a spray-drying slurry by paddle and rubber grinding.
  • the slurry is solid. The content is 30%.
  • the weight percentage of each component in the slurry (containing the components in the molecular sieve slurry) is: 40% molecular sieve, 30% SiO 2 , 29% A1 2 0 3 , 0.5 % P 2 O 5 , 0.5 % Tian Jing powder.
  • the spray drying slurry was spray-dried under certain conditions to obtain a fluidized bed microsphere catalyst, and the surface morphology was analyzed by scanning electron microscopy. The results are shown in Fig. 3. .
  • the molecular sieve microsphere catalyst was calcined at 350 ° C for 2 hours, calcined at 450 ° C for 1 hour, and calcined at 550 Torr for 4 hours to obtain a SAPO-34 molecular sieve microsphere catalyst, numbered FRC-03.
  • Example 9 (catalyst preparation)
  • the appropriate amount of the SAPO-34 molecular sieve slurry obtained in Example 5 is added, and the corresponding amount of kaolin, aluminum sol, silica sol, phosphoric acid, phthalocyanine powder and water are respectively added, and the slurry for spray drying is prepared by beating and grinding, and the solid content of the slurry is prepared. It is 30%.
  • the weight percentage of each component in the slurry (containing the components in the molecular sieve slurry) is: 40% molecular sieve, 28% Si0 2 , 26% A1 2 0 3 , 5.5 % P 2 0 5 , 0.5 % Tian Jing powder.
  • the spray drying slurry was spray-dried under certain conditions to obtain a fluidized bed microsphere catalyst, and the surface morphology thereof was analyzed by scanning electron microscopy. The results are shown in Fig. 4.
  • the molecular sieve microsphere catalyst was calcined at 350 Torr for 2 hours, calcined at 450 ° C for 1 hour, and calcined at 550 Torr for 4 hours to obtain a SAPO-34 molecular sieve microsphere catalyst, numbered FRC-04.
  • Example 10 (catalyst evaluation)
  • the FRC-01, FRC-02, FRC-03 and FRC-04 catalysts obtained in Examples 6, 7, 8, and 9 were subjected to a methanol-based low-carbon olefin catalytic reaction.
  • a 10 gram sample of the catalyst was taken and charged to a fixed fluidized bed reactor for methanol to olefins.
  • the reaction was carried out by a nitrogen gas activation at 550 Torr for 1 hour and then cooling to 500 °C. Feeding with 60 wt% methanol, methanol weight space velocity S. Oh.
  • the composition of the reaction product was analyzed by on-line gas chromatography, and the results of the four catalysts are shown in Table 4.
  • the FRC-01, FRC-02, FRC-03 and FRC-04 catalysts obtained in Examples 6, 7, 8, and 9 were subjected to catalytic reaction of a dimethyl ether low olefin.
  • a 10 g sample of the catalyst was taken and charged to a fixed fluidized bed reactor for the dimethyl ether to olefin reaction.
  • the reaction was carried out by a nitrogen gas activation at 550 Torr for 1 hour and then cooling to 50 CTC.
  • the dimethyl ether gas feed, dimethyl ether weight space velocity S.Oh ⁇ reaction product composition was analyzed by on-line gas chromatography, and the results of the four catalysts are shown in Table 5.
  • the initial gel ratio is 1.5HN(CH 2 )6: 0.3SiO 2 : P 2 O 5 : A1 2 0 3 : 55H 2 0
  • HN(CH 2 ) 6 is a hexamethylene nitrile template
  • Example 14 An appropriate amount of the SAPO-35 molecular sieve slurry obtained in Example 12 was added, and then a corresponding amount of kaolin, silica sol, phthalocyanine powder and water were separately added, and the slurry for spray drying was prepared by beating and gluing, and the slurry solid content was 30%.
  • the weight percentage of each component in the slurry is: 30% molecular sieve, 45 % Si0 2 , 23 % A1 2 0 3 , 1.5 % P 2 0 5 , 0.5 % Tian Jing powder.
  • the spray drying slurry was spray-dried under certain conditions to obtain a fluidized bed microsphere catalyst.
  • Example 14 Synthesis of SAPO ⁇ 44 molecular sieve
  • the initial gel ratio is 2.5 C 6 H n NH 2 : 0.6 SiO 2 : P 2 0 5 : A1 2 0 3 : 40H 2 O (C 6 H
  • TrustNH 2 is a cyclohexylamine templating agent
  • the metering materials were mixed, thoroughly stirred into a gel, and then placed in a stainless steel autoclave, and crystallized at 200 ° C for 24 hours to obtain a molecular sieve slurry. A small amount of molecular sieve slurry was taken for centrifugation, and the solid product was washed and dried for XRD analysis. The results are shown in Table 7, and the synthesized product was SAPO-44 molecular sieve. Table 7 Example 14 Synthetic sample X-ray diffraction analysis results
  • Example 16 An appropriate amount of the SAPO-44 molecular sieve slurry obtained in Example 14 was added, and a corresponding amount of kaolin, aluminum sol, phthalocyanine powder and water were separately added, and the slurry for spray drying was prepared by beating and gluing, and the slurry solid content was 35%.
  • the weight percentage of each component in the slurry is: 20% zeolite, 38% Si0 2, 40% ⁇ 1 2 ⁇ 3, 1.5% P 2 0 5, 0.5% Tian Jing powder.
  • the spray drying slurry was spray-dried under certain conditions to obtain a fluidized bed microsphere catalyst.
  • Example 16 Synthesis of SAPO-56 molecular sieve
  • the initial gel ratio was 1.5 N', N', N, N-tetramethyl-1,6-hexanediamine: 0.75 SiO 2 : 1.25P 2 0 5 : A1 2 0 3 : 553 ⁇ 40 ( Mixing of N, N, N, N-tetramethyl-1,6-hexanediamine as a template The mixture was stirred into a gel, and then placed in a stainless steel autoclave, and crystallized at 200 ° C for 24 hours to obtain a molecular sieve slurry.
  • the appropriate amount of the SAPO-56 molecular sieve slurry obtained in Example 16 was added, and the corresponding amount of kaolin, silica sol, phosphoric acid, phthalocyanine powder and water were respectively added, and the slurry for spray drying was prepared by beating and grinding, and the solid content of the slurry was 30%. .
  • the weight percentage of each component in the slurry is: 40% molecular sieve, 32.5 Si0 2 , 21.5% A1 2 0 3 , 5.5% P 2 0 5 , 0.5 % Tian Jing powder.
  • the spray drying slurry was spray-dried under certain conditions to obtain a fluidized bed microsphere catalyst.

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Description

一种含分子筛的流化反应催化剂直接成型方法
技术领域
本发明涉及一种含分子筛的流化反应催化剂直接成型方法， 该方法是将分子筛晶 化后的浆液不进行分离， 直接加入粘结剂、 基质组分， 经胶磨后进行喷雾干燥， 得到 成型微球分子筛催化剂。 背景技术
流化床催化剂的成型均采用喷雾干燥方法， 将活性组分、粘结剂、基质和水打浆 胶磨后进行喷雾干燥得到微球催化剂， 活性组分多釆用分子筛固体粉末。
中国专利 ZL 00103386公开了一种催化裂化催化剂的制备方法， 该方法包括将分 子筛桨液； 铝溶胶、 拟薄水铝石、 粘土以及无机酸打装混合均匀制成催化剂浆液， 然 后喷雾干燥。 其特征在于控制无机酸的加入顺序， 并在催化剂浆液中加入一种碱金属 硅酸盐， 可以提高浆液的固含量。 中国专利 ZL 01100019公开了一种催化裂化催化剂 的制备方法， 该方法包括将分子筛浆液、 拟薄水铝石、 粘土以及无机酸打浆混合均匀 制成催化剂浆液， 然后喷雾干燥。 其特征在于以催化剂桨液的粘度控制拟薄水铝石胶 溶所加入的无机酸量， 从而避免催化剂强度和孔体积的波动。 中国专利 ZL 98117896 公开了一种催化裂化催化剂的制备方法， 该方法包括将分子筛浆液、 铝溶胶、 拟薄水 铝石、 粘土以及无机酸打浆混合均匀制成催化剂浆液， 然后喷雾干燥。 其特征在于控 制分子筛和无机酸的加料顺序，从而提髙催化剂浆液的固含量。中国专利 ZL 98119914 公开了一种石油裂化催化剂的制备方法， 该方法包括将分子筛浆液、 铝溶胶、 拟薄水 铝石、 粘土以及无机酸打浆混合均匀制成催化剂浆液， 然后喷雾干燥。 其特征也在于 控制分子筛和无机酸的加料顺序， 从而提高催化剂浆液的固含量。 上述专利中， 均是 以控制各物料的加料顺序或加入添加剂来提高催化剂浆液的固含量为目的， 而且其所 指分子筛浆液为分子筛固体粉末与水打浆制备的分子筛浆液， 不是分子筛合成本身的 浆液。 中国专利 ZL 00137233公开了一种沸石催化剂的制备方法， 该方法包括快速干 燥含有结晶沸石、 低聚二氧化硅和氢氧化四羟基铵的水质分散液， 其特征在于直接将 合成沸石时形成的悬浮液与低聚硅溶胶混合制备水质分散液， 然后进行喷雾干燥。 虽 然该专利使用了沸石合成形成的悬浮液， 但其目的不是分子筛合成浆液的直接利用， 07 002373 而是利用浆液中存在的模板剂， 制备具有特征结构的微球催化剂。 发明内容
本发明的目的是提供一种含分子筛的流化反应催化剂直接喷雾干燥成型方法。该 方法是将分子筛晶化后的浆液不进行分离， 而是直接加入粘结剂、 基质组分， 经胶磨 后进行喷雾干燥， 得到成型分子筛催化剂。
在本发明方法中，所述分子筛为磷硅铝分子筛，如 SAPO-17, SAPO-18, SAPO-34, SAPO-35, SAPO-44, 或 SAPO-56分子筛。
对本发明方法中所用的粘结剂和基质。 具体而言， 所述粘结剂可为硅溶胶或硅的 氧化物， 或铝溶胶或铝的氧化物等， 所述基质可为无定型硅铝氧化物、 无定性磷硅铝 氧化物、 高岭土、 偏高岭土或白土等。
在釆用本发明方法制得的催化剂中， 分子筛的重量百分含量为 10-50%， 优选为 20-40%。 粘结剂的重量百分含量为 10-80%, 优选为 15-50% ; 基质的重量百分含量为 10-80%, 优选为 20-60%。
具体而言， 本发明的含分子筛的流化反应催化剂直接成型方法包括如下步骤： a) 按分子筛合成凝胶比例配制合成初始凝胶，在一定条件下进行晶化，得到 分子筛晶化后桨液；
b) 将步骤 a)得到的分子筛晶化后浆液取出少量进行离心分离， 分析固体产 物晶相结构和滤液的组成；
c) 根据步骤 b)得到的分子筛 液组成数据， 在步骤 a)得到的分子筛浆液中 按比例补加粘结剂、 基质和水， 配制成喷雾干燥用催化剂浆料； d) 将在步骤 c)中得到的催化剂浆料进行喷雾干燥，得到流化床微球催化剂。 . e)将步骤 d)得到的微球催化剂在 400-600'C条件下焙烧 3-6小 时， 得到 去除模板剂的流化床微球催化剂。
本发明制备微球催化剂的方法， 简单易行， 既可以充分利用分子筛浆液中未反应 的有用组分， 又简化了催化剂的成型步骤。
本发明的特点是： 将分子筛晶化后的浆液不进行分离， 而直接在浆液中加入粘结 剂、 基质组分， 经胶磨后进行喷雾干燥， 得到成型分子筛催化剂， 可以省去分子筛晶 化产物的分离、 洗涤和烘干过程， 简化了催化剂的制备步骤， 降低了污染。 同时， 由 于浆液中存在许多未反应组分可以作为成型催化剂的基质使用， 降低了原料消耗， 从 而大大降低分子筛催化剂的制备成本。
本发明制备的磷硅铝分子筛流化床微球催化剂可以应用于甲醇或二甲醚制低碳 烯烃反应， 反应温度为 300-600°C， 较佳反应温度为 400-500Ό , 原料甲醇或二甲醚重 量空速为 〜^！！ 产物中 C2-C3低碳烯烃选择性可以达到 90%。 附图说明
图 1 : 本发明实施例 6中制备的流化床微球催化剂 SEM图;
图 2: 本发明实施例 7中制备的流化床微球催化剂 SEM图;
图 3: 本发明实施例 8中制备的流化床微球催化剂 SEM图;
图 4: 本发明实施例 9中制备的流化床微球催化剂 SEM图。 具体实施方式
下面通过实施例详述本发明。
实施例 1 ( SAPO-17分子筛合成）
以摩尔计， 将初始凝胶比例为 1.5C6HU H2 : 0.1SiO2 : P205 : A1203 : 40H2O
(C6H„NH2为环己胺模板剂)的计量原料混合， 充分搅拌成凝胶， 然后装入不锈钢高压 釜中， 于 120°C老化 6小时， 然后于 200°C恒温晶化 24小时， 得到分子筛浆液。
取少量分子筛浆液进行离心分离， 固体产物经洗涤烘干后进行 XRD分析， 结果 如表 1所示， 合成产物为 SAPO-17分子筛。
表 1 实施例 1合成样品 X射线衍射分析结果
2Θ D(A) 100x1/1。
7.57 11.67 100
9.62 9.18 39
13.24 6.64 84
15.30 5.76 47
16.44 5.34 32
19.45 4.53 42
20.35 4.33 98 21.20 4.16 52
23.13 3.79 37
23.65 3.73 35
25.19 3.51 32
26.78 3.30 42
27.26 ' 3.21 16
28.59 3.11 19
31.05 2.84 36
31.63 2.77 53
33.36 2.64 20
实施例 2 (催化剂制备）
取适量实施例 1得到的 SAPO-17分子筛浆液， 再分别加入相应量的高岭土、 硅 溶胶、 田菁粉和水， 打浆、胶磨后制备成喷雾干燥用浆液， 浆液固含量为 30%。 以干 基计， 浆液中各组分（含分子筛浆液中组分） 的重量百分含量为： 40%分子筛， 45% Si02， 10 Al2O3, 4.5 %P205, 0.5 %田菁粉。 将喷雾干燥用浆液在一定条件下喷雾干 燥成型， 得到流化床微球催化剂。 实施例 3 (SAPO- 18分子筛合成）
以摩尔计，将初始凝胶比例为 1.75N, N-二异丙基乙胺： 0.2SiO2: 0.95P2O5: A1203: 50H2O (N， N-二异 ¼基乙胺为模板剂)的计量原料混合， 充分搅拌成凝胶， 然后装入不 锈钢高压釜中， 于 170°C恒温晶化 24小时， 得到分子筛浆液。
取少量分子筛浆液进行离心分离， 固体产物经洗涤烘干后进行 XRD分析， 结果 如表 2所示， 合成产物为 SAPO-18分子筛。 表 2实施例 3合成样品 X射线衍射分析结果
2Θ D(A) IOOXI/IQ
9.48 9.33 100
10.51 8.43 12
12.82 6.92 11
14.75 6.02 9
15.94 5.55 41
16.95 5.24 52
19.57 4.55 21
20.51 4.33 28
21.23 4.19 26
23.90 . 3.74 22
26.22 3.41 24
27.75 3.23 16
30.33 2.97 18
30.93 2.90 25 实施例 4 (催化剂制备）
取适量实施例 3得到的 SAPO-18分子筛浆液， 再分别加入相应量的髙岭土、 硅 溶胶、 田菁粉和水， 打浆、 胶磨后制备成喷雾干燥用桨液， 浆液固含量为 35%。 以干 基计， 浆液中各组分（含分子筛浆液中组分） 的重量百分含量为： 30%分子筛， 40% Si02, 25 %A1203, 4.5%P205, 0.5 %田菁粉。 将喷雾干燥用浆液在一定条件下喷雾干 燥成型， 得到流化床微球催化剂。 实施例 5 (SAPO-34分子筛合成）
以摩尔计， 将初始凝胶比例为 3.0ΊΈΑ: 0.2SiO2: Ρ205: Α1203 : 50Η2Ο(ΤΈΑ为三 乙胺模板剂)的计量原料混合， 充分搅泮成凝胶， 然后装入不锈钢高压釜中， 于 200Ό 恒温晶化 24小时， 得到晶化后分子筛浆液。
取少量分子筛浆液进行离心分离， 固体产物经洗涤烘干后进行 XRD分析， 结果 如表 3所示， 合成产物为 SAPO-34分子筛。 表 3 实施例 5合成样品 X射线衍射分析结果
2Θ D(A) 100x1/1。
9.51 9.30 100.00
12.84 6.89 16.54
14.05 6.30 4.56
16.01 5.54 41.62
17.96 4.94 9.26
20.57 4.32 66.58
23.09 3.85 5.39
25.18 3.54 12.97
25.86 3.45 14.13
30.54 2.93 17.10
31.22 2.86 13.65 实施例 6 (催化剂制备）
取适量实施例 5得到的 SAPO-34分子筛浆液， 再分别加入相应量的髙岭土、 硅 溶胶、 田菁粉和水， 打浆、 胶磨后制备成喷雾干燥用浆液， 桨液固含量为 30%。 以干 基计， 浆液中各组分 （含分子筛浆液中组分） 的重量百分含量为： 40%分子筛， 38% Si02， 21 %A1203, 0.5 %P2O5, 0.5 %田菁粉。 将喷雾干燥用浆液在一定条件下喷雾干 燥成型， 得到流化床微球催化剂， 其表面形貌用扫描电镜分析， 结果如图 1所示。
将分子筛微球催化剂在 350°C焙烧 2小时， 450Ό焙烧 1小时， 550°C焙烧 4小时， 得到 SAPO-34分子筛微球催化剂， 编号为 FRC-01。 实施例 7 (催化剂制备）
取适量实施例 5得到的 SAPO-34分子筛浆液， 再分别加入相应量的高岭土、 铝 溶胶、 田菁粉和水， 打浆、 胶磨后制备成喷雾干燥用浆液， 浆液固含量为 30%。 以干 基计， 浆液中各组分 （含分子筛浆液中组分） 的重量百分含量为： 40%分子筛， 23% Si02, 36%A1203， 0.5 %P2O5, 0.5 %田菁粉。 将喷雾干燥用浆液在一定条件下喷雾干 燥成型， 得到流化床微球催化剂， 其表面形貌用扫描电镜分析， 结果如图 2所示。 将分子筛微球催化剂在 350°C焙烧 2小时， 450°C焙烧 1小时， 550°C焙烧 4小时， 得到 SAPO-34分子筛微球催化剂， 编号为 FRC-02。 实施例 8 (催化剂制备）
取适量实施例 5得到的 SAPO-34分子筛浆液， 再分别加入相应量的髙岭土、 铝 溶胶、 硅溶胶、 田菁粉和水， 打桨、 胶磨后制备成喷雾干燥用浆液， 浆液固含量为 30 %。 以干基计， 浆液中各组分 （含分子筛浆液中组分） 的重量百分含量为： 40%分子 筛， 30%SiO2， 29%A1203, 0.5 %P2O5, 0.5 %田菁粉。 将喷雾干燥用浆液在一定条件 下喷雾干燥成型， 得到流化床微球催化剂， 其表面形貌用扫描电镜分析， 结果如图 3 所示。 .
将分子筛微球催化剂在 350°C焙烧 2小时， 450Ό焙烧 1小时， 550Ό焙烧 4小时， 得到 SAPO-34分子筛微球催化剂， 编号为 FRC-03。 实施例 9 (催化剂制备）
取适量实施例 5得到的 SAPO-34分子筛浆液， 再分别加入相应量的高岭土、 铝 溶胶、 硅溶胶、 磷酸、 田菁粉和水， 打浆、 胶磨后制备成喷雾干燥用浆液， 浆液固含 量为 30%。 以干基计， 浆液中各组分 （含分子筛浆液中组分） 的重量百分含量为： 40 %分子筛， 28 %Si02， 26%A1203， 5.5 %P205, 0.5 %田菁粉。 将喷雾干燥用浆液在一 定条件下喷雾干燥成型， 得到流化床微球催化剂， 其表面形貌用扫描电镜分析， 结果 如图 4所示。
将分子筛微球催化剂在 350Ό焙烧 2小时， 450°C焙烧 1小时， 550Ό焙烧 4小时， 得到 SAPO-34分子筛微球催化剂， 编号为 FRC-04。 实施例 10 (催化剂评价）
将实施例 6、 7、 8、 9得到的 FRC-01 , FRC-02, FRC-03和 FRC-04催化剂进行 甲醇制低碳烯烃催化反应。取 10克催化剂样品， 装入固定流化床反应器中， 用于甲醇 制烯烃反应。 在 550Ό下通氮气活化 1小时， 然后降温至 500°C进行反应。 以 60wt% 甲醇进料， 甲醇重量空速 S.Oh 。反应产物组成采用在线气相色谱分析， 四种催化剂的 反应结果如表 4所示。 表 4 固定流化床甲醇转化反应结果
催化剂编号 FRC-01 FRC-02 FRC-03 FRC-04
- 进料时间 （min) 30 30 30 30
甲醇转化率(％) 100 100 100 100
CH4 2.18 2.69 2.63 2.91
C2H4 54.80 55.17 54.59 56.18
C2H6 0.54 0.8 0.65 0.64
C3¾ 34.81 34.56 34.05 33.29
C3H8 1.00 0.97 0.8 0.69
C4 + 5.37 4.74 5.36 5.16
C5 + 1.30 1.07 1.92 1.13
∑c2 =-c3 = 89.61 89.73 88.64 89.47 实施例 11 (催化剂评价〉
将实施例 6、 7、 8、 9得到的 FRC-01 , FRC-02, FRC-03和 FRC-04催化剂进行 二甲醚制低碳烯烃催化反应。取 10克催化剂样品， 装入固定流化床反应器中， 用于二 甲醚制烯烃反应。在 550Ό下通氮气活化 1小时， 然后降温至 50CTC进行反应。 以二甲 醚气体进料， 二甲醚重量空速 S.Oh^ 反应产物组成采用在线气相色谱分析， 四种催化 剂的反应结果如表 5所示。 表 5 固定流化床二甲醚转化反应结果
催化剂编号 FRC-01 FRC-02 FRC-03 FRC-04 进料时间 （min) 30 30 30 30 二甲醚转化率(％) 100 100 100 100
CH4 2.86 2.71 2.83 2.63
C2H4 55.20 56.23 55.94 55.89
C2H6 0.68 0.72 0.74 0.58
C3H6 33.07 33.57 33.64 34.31
C3H8 0.76 0.90 1.00 0.63
C4+ 6.15 4.84 4.81 4.67 C5 1.28 1.03 1.04 1.29
∑C2 =-C3 = 88.27 89.80 89.58 90.20 实施例 12 ( SAPO- 35分子筛合成）
以摩尔计，将初始凝胶比例为 1.5HN(CH2)6: 0.3SiO2: P2O5: A1203: 55H20(HN(CH2)6 为六次甲基次胺模板剂)的计量原料混合，充分搅拌成凝胶，然后装入不锈钢髙压釜中， 于 200°C恒温晶化 24小时， 得到分子筛浆液。
取少量分子筛浆液进行离心分离， 固体产物经洗涤烘干后进行 XRD分析， 结果 如表 6所示， 合成产物为 SAPO-35分子筛。
表 6实施例 12合成样品 X射线衍射分析结果
2Θ D(A) ΙΟΟχΙ/Ιο
8.52 10.36 14
10.84 8.17 42
13.20 6.72 33
15.77 5.64 8
17.19 5.14 55
17.67 5.01 8
20.92 4.27 34
21.72 4.11 100
23.07 3.87 19
24.82 3.61 9
26.73 3.36 21
28.31 3.13 33
28.95 3.10 12
32.01 2.81 52
34.37 2.64 8 实施例 13 (催化剂制备）
取适量实施例 12得到的 SAPO-35分子筛浆液， 再分别加入相应量的高岭土、 硅 溶胶、 田菁粉和水， 打浆、 胶磨后制备成喷雾干燥用浆液， 浆液固含量为 30%。 以干 基计， 桨液中各组分 （含分子筛浆液中组分） 的重量百分含量为： 30%分子筛， 45 % Si02， 23 %A1203， 1.5 %P205, 0.5 %田菁粉。 将喷雾干燥用浆液在一定条件下喷雾干 燥成型， 得到流化床微球催化剂。 实施例 14 (SAPO~44分子筛合成）
以摩尔计， 将初始凝胶比例为 2.5C6HnNH2 : 0.6SiO2 : P205 : A1203 : 40H2O (C6H„NH2为环己胺模板剂)的计量原料混合， 充分搅拌成凝胶， 然后装入不锈钢高压 釜中， 于 200Ό恒温晶化 24小时， 得到分子筛浆液。 取少量分子筛浆液进行离心分离， 固体产物经洗涤烘干后进行 XRD分析， 结果 如表 7所示， 合成产物为 SAPO-44分子筛。 表 7实施例 14合成样品 X射线衍射分析结果
2Θ D(A) 100xI/Io
9.38 9.42 81
12.93 6.84 20
16.05 5.52 57
17.21 5.15 7
18.93 4.68 13
20.70 4.29 100
21.64 4.10 34
23.03 3.86 15
24.30 3.66 92
26.14 3.41 22
27.88 3.20 10
29.97 2.98 25
30.83 2.90 47
35.43 2.53 15 实施例 15 (催化剂制备）
取适量实施例 14得到的 SAPO-44分子筛浆液， 再分别加入相应量的高岭土、 铝 溶胶、 田菁粉和水， 打浆、 胶磨后制备成喷雾干燥用浆液， 浆液固含量为 35 %。 以干 基计， 浆液中各组分（含分子筛浆液中组分） 的重量百分含量为： 20%分子筛， 38% Si02， 40%Α12Ο3, 1.5 %P205, 0.5 %田菁粉。 将喷雾干燥用浆液在一定条件下喷雾干 燥成型， 得到流化床微球催化剂。 实施例 16 (SAPO-56分子筛合成）
以摩尔计， 将初始凝胶比例为 1.5N',N',N,N-四甲基 -1,6-己二胺： 0.75SiO2 : 1.25P205: A1203: 55¾0(N，,N，,N,N-四甲基 -1,6-己二胺为模板剂)的计量原料混合， 充 分搅拌成凝胶， 然后装入不锈钢髙压釜中， 于 200°C恒温晶化 24小时， 得到分子筛漿 液。
取少量分子筛浆液进行离心分离， 固体产物经洗涤烘干后进行 XRD分析， 结果 如表 8所示， 合成产物为 SAPO-56分子筛。。 表 8实施例 16合成样品 X射线衍射分析结果
2Θ D(A) ΙΟΟχΙ/Ιο
7.40 11.93 18
8.62 10.22 65
11.54 7.68 59
12.84 6.91 36
15.51 5.69 38
17.34 5.10 52
17.72 4.98 68
20.21 4.37 74
21.65 4.07 100
23.46 3.77 36
25.86 3.47 36
27.78 3.24 67
30.31 2.97 43
31.30 2.88 38
33.41 2.65 29
34.46 2.63 22 实施例 17 (催化剂制备）
取适量实施例 16得到的 SAPO-56分子筛浆液， 再分别加入相应量的高岭土、 硅 溶胶、磷酸、 田菁粉和水， 打浆、胶磨后制备成喷雾干燥用浆液， 浆液固含量为 30%。 以干基计， 浆液中各组分（含分子筛桨液中组分） 的重量百分含量为： 40%分子筛， 32.5 Si02, 21.5%A1203, 5.5%P205, 0.5 %田菁粉。 将喷雾干燥用浆液在一定条件下 喷雾干燥成型， 得到流化床微球催化剂。

Claims

权 利 要 求
1.一种含分子筛的流化反应催化剂直接成型方法， 其特征在于， 在分子筛晶化 后的浆液中直接加入粘结剂、 基质组分， 经胶磨后进行喷雾干燥， 得到成型微球分子 筛催化剂。
2. 按照权利要求 1所述的方法， 其特征在于， 所述分子筛为磷硅铝分子筛。
3. 按照权利要求 2所述的方法， 其特征在于， 所述磷硅铝分子筛为 SAPO-17， SAPO-18, SAPO-34, SAPO-35, SAPO-44, 或 SAPO-56分子筛。
4. 按照权利要求 1 所述的方法， 其特征在于， 催化剂中分子筛的重量百分含量 为 10-50%。
5. 按照权利要求 1 所述的方法， 其特征在于， 所述粘结剂为硅溶胶或硅的氧化 物， 催化剂中 Si02的重量百分含量为 10-80%。
6. 按照权利要求 1 所述的方法， 其特征在于， 所述粘结剂为铝溶胶或铝的氧化 物， 催化剂中 A1203的重量百分含量为 10-80%。
7. 按照权利要求 1 所述的方法， 其特征在于， 所述基质为无定型硅铝氧化物、 无定型磷硅铝氧化物、高岭土、偏高岭土或白土，其在催化剂中的重量百分含量为 10-80 %。
8. 按照权利要求 1-7中任何一项所述的方法制备的成型催化剂经 400-600Ό空气 中焙烧后在甲醇或二甲醚制低碳烯烃中的应用。
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