CN101121148B - Direct forming method of fluidized reaction catalyst containing molecular sieve - Google Patents

Direct forming method of fluidized reaction catalyst containing molecular sieve Download PDF

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CN101121148B
CN101121148B CN2006101385083A CN200610138508A CN101121148B CN 101121148 B CN101121148 B CN 101121148B CN 2006101385083 A CN2006101385083 A CN 2006101385083A CN 200610138508 A CN200610138508 A CN 200610138508A CN 101121148 B CN101121148 B CN 101121148B
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molecular sieve
catalyst
sapo
slurries
drying
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CN101121148A (en
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田鹏
许磊
刘中民
杨立新
袁翠峪
齐越
王贤高
何长青
孟霜鹤
张今令
李铭芝
吕志辉
魏迎旭
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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

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Abstract

The present invention relates to a direct forming method of a catalyst of a molecular sieve-containing fluidized reaction. The solid products after a crystallization of the molecular sieve are not separated, but a bonder and substrate components are directly added into a molecular sieve slurry, which is dried by spray after colloid milling, and a formed microsphere molecular sieve is obtain. The method omits the steps of separation, washing and drying of the crystallization products of the molecular sieve, which simplifies the operation steps and reduces pollution, at the same time, because unreacted components which consist in the slurry can be used the substrate components of the formed catalyst, which reduces the cost of raw material, and accordingly the preparation cost of the molecular sieve catalyst is greatly reduced.

Description

A kind of direct forming method of fluidized reaction catalyst that contains molecular sieve
Technical field
The present invention relates to a kind of direct forming method of fluidized reaction catalyst that contains molecular sieve, is that the slurries after the molecular sieve crystallization are not separated, and directly adds binding agent, matrix components, carries out spray-drying behind the glue mill, obtains moulding microballoon molecular sieve catalyst.
Background technology
Spray drying process is all adopted in the moulding of fluid catalyst, obtains microspherical catalyst with carrying out spray-drying behind active component, binding agent, matrix and the water making beating glue mill, and active component adopts the molecular sieve solid powder more.
Chinese patent ZL 00103386 discloses a kind of preparation method of catalytic cracking catalyst, and this method comprises molecular sieve pulp, aluminium colloidal sol, boehmite, clay and inorganic acid making beating mixed makes catalyst slurry, then spray-drying.It is characterized in that controlling the addition sequence of inorganic acid, and in catalyst slurry, add a kind of alkali silicate, can improve the solid content of slurries.Chinese patent ZL 01100019 discloses a kind of preparation method of catalytic cracking catalyst, and this method comprises molecular sieve pulp, boehmite, clay and inorganic acid making beating mixed makes catalyst slurry, then spray-drying.It is characterized in that controlling the mineral acid quantity that the boehmite peptization is added, thereby avoid the fluctuation of catalyst strength and pore volume with the viscosity of catalyst slurry.Chinese patent ZL98117896 discloses a kind of preparation method of catalytic cracking catalyst, and this method comprises molecular sieve pulp, aluminium colloidal sol, boehmite, clay and inorganic acid making beating mixed makes catalyst slurry, then spray-drying.It is characterized in that controlling the charging sequence of molecular sieve and inorganic acid, thereby improve the solid content of catalyst slurry.Chinese patent ZL 98119914 discloses a kind of preparation method of catalyst of cracking petroleum, and this method comprises molecular sieve pulp, aluminium colloidal sol, boehmite, clay and inorganic acid making beating mixed makes catalyst slurry, then spray-drying.Its feature also is to control the charging sequence of molecular sieve and inorganic acid, thereby improves the solid content of catalyst slurry.In the above-mentioned patent, all be with the charging sequence of controlling each material or to add the solid content that additive improves catalyst slurry be purpose, and its indication molecular sieve pulp is the molecular sieve pulp of molecular sieve solid powder and water making beating preparation, is not the synthetic slurries of molecular sieve itself.Chinese patent ZL 00137233 discloses a kind of preparation method of zeolite catalyst, this method comprises that rapid draing contains the aqueous dispersions of crystalline zeolite, oligomeric silica and hydroxide tetrahydroxy ammonium, the suspension and the oligomeric Ludox that form when it is characterized in that directly with synthetic zeolite are mixed with aqueous dispersions, carry out spray-drying then.Though this patent has been used the synthetic suspension that forms of zeolite, its purpose is not the direct utilization of the synthetic slurries of molecular sieve, but utilizes the template agent that exists in the slurries, the microspherical catalyst that preparation has feature structure.
Summary of the invention
The purpose of this invention is to provide a kind of direct spray drying forming method of fluidized reaction catalyst that contains molecular sieve.Slurries after the molecular sieve crystallization are not separated, but directly add binding agent, matrix components, behind glue mill, carry out spray-drying, obtain molded molecular sieve catalyst.
The step of fluid bed molecular sieve catalyst straight forming method of the present invention is:
A) in the synthetic initial gel of molecular sieve synthesized gel rubber ratio preparation, carry out crystallization under certain condition, obtain molecular sieve crystallization rear slurry;
B) the molecular sieve crystallization rear slurry that step a) is obtained takes out and carries out centrifugation on a small quantity, analyzes the composition of solid product crystal phase structure and filtrate;
C) molecular sieve pulp that obtains according to step b) is formed data, adds binding agent, matrix and water in the molecular sieve pulp that step a) obtains in proportion, is mixed with the spray-drying catalyst pulp;
D) catalyst pulp that will obtain in step c) carries out spray-drying, obtains the fluid bed microspherical catalyst.
E) microspherical catalyst that step d) is obtained is under 400-600 ℃ of condition roasting 3-6 hour, obtains removing the fluid bed microspherical catalyst of template agent.
The present invention prepares the method for microspherical catalyst, and is simple, both can make full use of unreacted useful constituent in the molecular sieve pulp, simplified the forming step of catalyst again.
Characteristics of the present invention are: the slurries after the molecular sieve crystallization are not separated, and directly in slurries, add binding agent, matrix components, behind the glue mill, carry out spray-drying, obtain molded molecular sieve catalyst, can save separation, washing and the drying course of molecular sieve crystallization product, simplify the Preparation of catalysts step, reduced pollution.Simultaneously, because the matrix that exists many unreacted components to can be used as preformed catalyst in the slurries is used, reduced consumption of raw materials, thereby reduced the preparation cost of molecular sieve catalyst greatly.
The phosphor-silicon-aluminum molecular sieve fluid bed microspherical catalyst of the present invention's preparation can be applied to methyl alcohol or dimethyl ether reaction for preparing light olefins, and reaction temperature is 300-600 ℃, and preferable reaction temperature is 400-500 ℃, and material benzenemethanol or dimethyl ether weight space velocity are 1～40h -1, C in the product 2-C 3Selectivity of light olefin can reach 90%.
Description of drawings
Fig. 1: the fluid bed microspherical catalyst SEM of preparation figure in the embodiment of the invention 6;
Fig. 2: the fluid bed microspherical catalyst SEM of preparation figure in the embodiment of the invention 7;
Fig. 3: the fluid bed microspherical catalyst SEM of preparation figure in the embodiment of the invention 8;
Fig. 4: the fluid bed microspherical catalyst SEM of preparation figure in the embodiment of the invention 9.
The specific embodiment
Below by embodiment in detail the present invention is described in detail.
Embodiment 1 (the SAPO-17 molecular sieve is synthetic)
With initial gel ratio 1.5C 6H 11NH 2: 0.1SiO 2: P 2O 5: Al 2O 3: 40H 2O (C 6H 11NH 2Be the agent of cyclohexylamine template) will measure raw material and mix in certain sequence, fully stir into gel, in the stainless steel autoclave of packing into then, 120 ℃ aging 6 hours, 200 ℃ of thermostatic crystallizations 24 hours obtain the SAPO-17 molecular sieve pulp.
The molecular sieve pulp that takes a morsel carries out centrifugation, and solid product carries out XRD analysis after washing and drying, and the result shows that synthetic product is the SAPO-17 molecular sieve.
Embodiment 2 (Preparation of Catalyst)
Get the SAPO-17 molecular sieve pulp that an amount of embodiment 1 obtains, the kaolin, Ludox, sesbania powder and the water that add respective amount more respectively, be prepared into the spray-drying slurries behind making beating, the glue mill, slurry solid content is 30%, each constituent content is (containing component in the molecular sieve pulp) in the slurries: 40% molecular sieve, 45%SiO 2, 10%Al 2O 3, 4.5%P 2O 5, 0.5% sesbania powder.Spray-drying with slurries spray drying forming under certain condition, is obtained the fluid bed microspherical catalyst.
Embodiment 3 (the SAPO-18 molecular sieve is synthetic)
With initial gel ratio 1.75N, N-diisopropylethylamine: 0.2SiO 2: 0.95P 2O 5: Al 2O 3: 50H 2O (N, N-diisopropylethylamine are the template agent) will measure raw material to be mixed in certain sequence, fully stirs into gel, and in the stainless steel autoclave of packing into then, 170 ℃ of thermostatic crystallizations 24 hours obtain the SAPO-18 molecular sieve pulp.
The molecular sieve pulp that takes a morsel carries out centrifugation, and solid product carries out XRD analysis after washing and drying, and the result shows that synthetic product is the SAPO-18 molecular sieve.
Embodiment 4 (Preparation of Catalyst)
Get the SAPO-18 molecular sieve pulp that an amount of embodiment 3 obtains, the kaolin, Ludox, sesbania powder and the water that add respective amount more respectively, be prepared into the spray-drying slurries behind making beating, the glue mill, slurry solid content is 35%, each constituent content is (containing component in the molecular sieve pulp) in the slurries: 30% molecular sieve, 40%SiO 2, 25%Al 2O 3, 4.5%P 2O 5, 0.5% sesbania powder.Spray-drying with slurries spray drying forming under certain condition, is obtained the fluid bed microspherical catalyst.
Embodiment 5 (the SAPO-34 molecular sieve is synthetic)
With initial gel ratio 3.OTEA: 0.2SiO 2: P 2O 5: Al 2O 3: 50H 2O (TEA is the agent of triethylamine template) will measure raw material to be mixed in certain sequence, fully stirs into gel, and in the stainless steel autoclave of packing into then, 200 ℃ of thermostatic crystallizations 24 hours obtain molecular sieve pulp after the crystallization.
The molecular sieve pulp that takes a morsel carries out centrifugation, and solid product carries out XRD analysis after washing and drying, and the result is as shown in table 1, and synthetic product is the SAPO-34 molecular sieve.
Table 1 embodiment 5 synthetic sample X-ray diffraction analysis results
Figure G2006101385083D00081
Embodiment 6 (Preparation of Catalyst)
Get the SAPO-34 molecular sieve pulp that an amount of embodiment 5 obtains, the kaolin, Ludox, sesbania powder and the water that add respective amount more respectively, be prepared into the spray-drying slurries behind making beating, the glue mill, slurry solid content is 30%, each constituent content is (containing component in the molecular sieve pulp) in the slurries: 40% molecular sieve, 38%SiO 2, 21%Al 2O 3, 0.5%P 2O 5, 0.5% sesbania powder.Spray-drying with slurries spray drying forming under certain condition, is obtained the fluid bed microspherical catalyst, its surface topography scanning electron microscope analysis, the result is as shown in Figure 1.
With microsphere zeolite catalyst 350 ℃ of roastings 2 hours, 450 ℃ of roastings 1 hour, 550 ℃ of roastings 4 hours obtain the SAPO-34 microsphere zeolite catalyst, are numbered FRC-01.
Embodiment 7 (Preparation of Catalyst)
Get the SAPO-34 molecular sieve pulp that an amount of embodiment 5 obtains, the kaolin, aluminium colloidal sol, sesbania powder and the water that add respective amount more respectively, be prepared into the spray-drying slurries behind making beating, the glue mill, slurry solid content is 30%, each constituent content is (containing component in the molecular sieve pulp) in the slurries: 40% molecular sieve, 23%SiO 2, 36%Al 2O 3, 0.5%P 2O 5, 0.5% sesbania powder.Spray-drying with slurries spray drying forming under certain condition, is obtained the fluid bed microspherical catalyst, its surface topography scanning electron microscope analysis, the result is as shown in Figure 2.
With microsphere zeolite catalyst 350 ℃ of roastings 2 hours, 450 ℃ of roastings 1 hour, 550 ℃ of roastings 4 hours obtain the SAPO-34 microsphere zeolite catalyst, are numbered FRC-02.
Embodiment 8 (Preparation of Catalyst)
Get the SAPO-34 molecular sieve pulp that an amount of embodiment 5 obtains, the kaolin, aluminium colloidal sol, Ludox, sesbania powder and the water that add respective amount more respectively, be prepared into the spray-drying slurries behind making beating, the glue mill, slurry solid content is 30%, each constituent content is (containing component in the molecular sieve pulp) in the slurries: 40% molecular sieve, 30%SiO 2, 29%Al 2O 3, 0.5%P 2O 5, 0.5% sesbania powder.Spray-drying with slurries spray drying forming under certain condition, is obtained the fluid bed microspherical catalyst, its surface topography scanning electron microscope analysis, the result is as shown in Figure 3.
With microsphere zeolite catalyst 350 ℃ of roastings 2 hours, 450 ℃ of roastings 1 hour, 550 ℃ of roastings 4 hours obtain the SAPO-34 microsphere zeolite catalyst, are numbered FRC-03.
Embodiment 9 (Preparation of Catalyst)
Get the SAPO-34 molecular sieve pulp that an amount of embodiment 5 obtains, the kaolin, aluminium colloidal sol, Ludox, phosphoric acid, sesbania powder and the water that add respective amount more respectively, be prepared into the spray-drying slurries behind making beating, the glue mill, slurry solid content is 30%, each constituent content is (containing component in the molecular sieve pulp) in the slurries: 40% molecular sieve, 28%SiO 2, 26%Al 2O 3, 5.5%P 2O 5, 0.5% sesbania powder.Spray-drying with slurries spray drying forming under certain condition, is obtained the fluid bed microspherical catalyst, its surface topography scanning electron microscope analysis, the result is as shown in Figure 4.
With microsphere zeolite catalyst 350 ℃ of roastings 2 hours, 450 ℃ of roastings 1 hour, 550 ℃ of roastings 4 hours obtain the SAPO-34 microsphere zeolite catalyst, are numbered FRC-04.
Embodiment 10 (evaluating catalyst)
With the FRC-01 that embodiment 6,7,8,9 obtains, FRC-02, FRC-03 and FRC-04 catalyst carry out the preparing light olefins from methanol catalytic reaction.Get 10 gram catalyst samples, in the fixed fluidized-bed reactor of packing into, be used for methanol to olefins reaction.550 ℃ of down logical nitrogen activation 1 hour, be cooled to 500 ℃ then and react.With the 60wt% methanol feeding, methyl alcohol weight space velocity 2.0h -1Product is formed the online gas chromatographic analysis of employing, and the reaction result of four kinds of catalyst is as shown in table 2.The fixed fluidized bed methanol conversion reaction result of table 2
Figure G2006101385083D00131
Figure G2006101385083D00141
Embodiment 11 (evaluating catalyst)
With the FRC-01 that embodiment 6,7,8,9 obtains, FRC-02, FRC-03 and FRC-04 catalyst carry out dimethyl ether producing light olefins catalytic reaction.Get 10 gram catalyst samples, in the fixed fluidized-bed reactor of packing into, be used for dimethyl ether system olefine reaction.550 ℃ of down logical nitrogen activation 1 hour, be cooled to 500 ℃ then and react.With the gas of dimethyl ether charging, dimethyl ether weight space velocity 2.0h -1. product is formed the online gas chromatographic analysis of employing, and the reaction result of four kinds of catalyst is as shown in table 3.
The fixed fluidized bed dimethyl ether conversion reaction result of table 3
Figure G2006101385083D00151
Embodiment 12 (the SAPO-35 molecular sieve is synthetic)
With initial gel ratio 1.5HN (CH 2) 6: 0.3SiO 2: P 2O 5: Al 2O 3: 55H 2O (HN (CH 2) 6Be time amine template agent of six methines) will measure raw material and mix in certain sequence, fully stir into gel, in the stainless steel autoclave of packing into then, 200 ℃ of thermostatic crystallizations 24 hours obtain the SAPO-35 molecular sieve pulp.
The molecular sieve pulp that takes a morsel carries out centrifugation, and solid product carries out XRD analysis after washing and drying, and the result shows that synthetic product is the SAPO-35 molecular sieve.
Embodiment 13 (Preparation of Catalyst)
Get the SAPO-35 molecular sieve pulp that an amount of embodiment 12 obtains, the kaolin, Ludox, sesbania powder and the water that add respective amount more respectively, be prepared into the spray-drying slurries behind making beating, the glue mill, slurry solid content is 30%, each constituent content is (containing component in the molecular sieve pulp) in the slurries: 30% molecular sieve, 45%SiO 2, 23%Al 2O 3, 1.5%P 2O 5, 0.5% sesbania powder.Spray-drying with slurries spray drying forming under certain condition, is obtained the fluid bed microspherical catalyst.
Embodiment 14 (the SAPO-44 molecular sieve is synthetic)
With initial gel ratio 2.5C 6H 11NH 2: 0.6SiO 2: P 2O 5: Al 2O 3: 40H 2O (C 6H 11NH 2Be the agent of cyclohexylamine template) will measure raw material and mix in certain sequence, fully stir into gel, in the stainless steel autoclave of packing into then, 200 ℃ of thermostatic crystallizations 24 hours obtain the SAPO-44 molecular sieve pulp.
The molecular sieve pulp that takes a morsel carries out centrifugation, and solid product carries out XRD analysis after washing and drying, and the result shows that synthetic product is the SAPO-44 molecular sieve.
Embodiment 15 (Preparation of Catalyst)
Get the SAPO-44 molecular sieve pulp that an amount of embodiment 14 obtains, the kaolin, aluminium colloidal sol, sesbania powder and the water that add respective amount more respectively, be prepared into the spray-drying slurries behind making beating, the glue mill, slurry solid content is 35%, each constituent content is (containing component in the molecular sieve pulp) in the slurries: 20% molecular sieve, 38%SiO 2, 40%Al 2O 3, 1.5%P 2O 5, 0.5% sesbania powder.Spray-drying with slurries spray drying forming under certain condition, is obtained the fluid bed microspherical catalyst.
Embodiment 16 (the SAPO-56 molecular sieve is synthetic)
With initial gel ratio 1.5N ', N ', N, N-tetramethyl-1,6-hexamethylene diamine: 0.75SiO 2: 1.25P 2O 5: Al 2O 3: 55H 2O (N ', N ', N, N-tetramethyl-1,6-hexamethylene diamine are the template agent) will measure raw material to be mixed in certain sequence, fully stirs into gel, and in the stainless steel autoclave of packing into then, 200 ℃ of thermostatic crystallizations 24 hours obtain the SAPO-56 molecular sieve pulp.
The molecular sieve pulp that takes a morsel carries out centrifugation, and solid product carries out XRD analysis after washing and drying, and the result shows that synthetic product is the SAPO-56 molecular sieve.
Embodiment 17 (Preparation of Catalyst)
Get the SAPO-56 molecular sieve pulp that an amount of embodiment 16 obtains, the kaolin, Ludox, phosphoric acid, sesbania powder and the water that add respective amount more respectively, be prepared into the spray-drying slurries behind making beating, the glue mill, slurry solid content is 30%, each constituent content is (containing component in the molecular sieve pulp) in the slurries: 40% molecular sieve, 32.5%SiO 2, 21.5%Al 2O 3, 5.5%P 2O 5, 0.5% sesbania powder.Spray-drying with slurries spray drying forming under certain condition, is obtained the fluid bed microspherical catalyst.

Claims (7)

1. a direct forming method of fluidized reaction catalyst that contains molecular sieve is characterized in that, directly adds binding agent, matrix components in the slurries after the molecular sieve crystallization, carries out spray-drying behind the glue mill, obtains moulding microballoon molecular sieve catalyst; The described direct raw material as preparation microballoon molecular sieve catalyst of slurries that will contain molecular sieve after the molecular sieve crystallization uses; Described molecular sieve is a phosphor-silicon-aluminum molecular sieve.
2. in accordance with the method for claim 1, it is characterized in that described phosphor-silicon-aluminum molecular sieve is SAPO-17, SAPO-18, SAPO-34, SAPO-35, SAPO-44, SAPO-56 molecular sieve.
3. in accordance with the method for claim 1, it is characterized in that molecular sieve content is 10-50% in the catalyst.
4. in accordance with the method for claim 1, it is characterized in that described binding agent is the oxide of Ludox or silicon, content is 10-80%.
5. in accordance with the method for claim 1, it is characterized in that described binding agent is the oxide of aluminium colloidal sol or aluminium, content is 10-80%.
6. in accordance with the method for claim 1, it is characterized in that described matrix is amorphous silicon aluminium oxide, indefiniteness phosphorus sieve and silica-sesquioxide, kaolin, metakaolin or carclazyte, content is 10-80%.
7. in accordance with the method for claim 1, it is characterized in that the preformed catalyst of preparation after the roasting, is used for methyl alcohol or dimethyl ether producing light olefins catalyst in 400-600 ℃ of air.
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