CN114477208B - Amino modified SBA molecular sieve, preparation method and application thereof, and removal method of organic template in SBA molecular sieve - Google Patents

Amino modified SBA molecular sieve, preparation method and application thereof, and removal method of organic template in SBA molecular sieve Download PDF

Info

Publication number
CN114477208B
CN114477208B CN202011148447.5A CN202011148447A CN114477208B CN 114477208 B CN114477208 B CN 114477208B CN 202011148447 A CN202011148447 A CN 202011148447A CN 114477208 B CN114477208 B CN 114477208B
Authority
CN
China
Prior art keywords
molecular sieve
groups
sba
halogen
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202011148447.5A
Other languages
Chinese (zh)
Other versions
CN114477208A (en
Inventor
吴凯
任行涛
裴庆君
贾志光
杨光
刘艳惠
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Original Assignee
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Beijing Research Institute of Chemical Industry, China Petroleum and Chemical Corp filed Critical Sinopec Beijing Research Institute of Chemical Industry
Priority to CN202011148447.5A priority Critical patent/CN114477208B/en
Publication of CN114477208A publication Critical patent/CN114477208A/en
Application granted granted Critical
Publication of CN114477208B publication Critical patent/CN114477208B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
    • 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
    • B01D53/02—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 by adsorption, e.g. preparative gas chromatography
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/50—Carbon dioxide
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
    • 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
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Silicon Compounds (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention discloses an amino modified SBA molecular sieve, a preparation method and application thereof, and a removal method of an organic template agent in the SBA molecular sieve. The preparation method of the amino modified SBA molecular sieve comprises the following steps: mixing a silicon source, an organic template agent, an acid solution and water for reaction, and sequentially carrying out hydrothermal crystallization and drying treatment on the obtained mixture to obtain an SBA molecular sieve; mixing and stirring the SBA molecular sieve and a passivating agent, adding an amino modifier containing halogen for modification reaction, and drying the reaction product to obtain the amino modified SBA molecular sieve. The invention adopts the halogen-containing amino modifier, and halogen ions can exchange ions with the organic template agent due to the action of charges, so that the organic template agent is directly removed, the subsequent extraction process is omitted, the process flow is simplified, the production cost is saved, and the loss of molecular sieve products caused by one more process is avoided.

Description

Amino modified SBA molecular sieve, preparation method and application thereof, and removal method of organic template in SBA molecular sieve
Technical Field
The invention relates to an amino modified SBA molecular sieve, a preparation method and application thereof, and a removal method of an organic template agent in the SBA molecular sieve, in particular to application of the amino modified SBA molecular sieve in a gas adsorption separation process.
Background
The novel molecular sieve mesoporous materials SBA-15 and SBA-16 have larger specific surface area, regular pore size distribution, thicker pore wall and better thermal stability, and are good catalyst materials. For pure silicon SBA molecular sieves, which do not have any acidic, basic and redox centres on their own, there is only one silicon hydroxyl (Si-OH) functional group on the surface, which largely limits the use of SBA molecular sieves in certain fields.
After the mesoporous material is subjected to organic functionalization modification, the mesoporous material can have two characteristics of the mesoporous material and the modification group, and the two characteristics also have synergistic effect. This synergy may be superior to the mesoporous material and modifying groups alone. In the organic functional modified mesoporous material, inorganic components can ensure the basic structure and stability of the material, and organic group components can endow the components with unique functions on the inner surface and the outer surface.
In the prior art, the organic functional groups are generally modified to the surface of the molecular sieve or the inside of the pore canal by a post grafting method or a copolycondensation method.
The post grafting method is to fix the functional group on the mesoporous wall by condensation reaction of the organic functional group and the silicon hydroxyl on the mesoporous material pore surface to generate corresponding covalent bond. The modification method does not damage the pore channel structure of the original mesoporous material and can access more organic functional groups, but the surface functional groups of the modified mesoporous material prepared by the method are unevenly distributed, most of the functional groups are gathered in the areas, close to the pore openings, of the outer surface and the inner surface of the pore channel, and the content of the functional groups distributed in the pore channel is low.
The copolycondensation method is to directly add an organic functional group modifier into sol composed of a template agent and a silicon source for reaction. In the prepared organic functional mesoporous material, the organic groups can participate in constructing pore walls, and the functional groups can be uniformly fixed on the pore surfaces of the mesoporous material. However, the functionalized materials prepared by this method generally suffer from poor order, and the order decreases as the amount of organic groups introduced increases.
More important, there is a problem that the stencil agent is handled in the latter stage, regardless of the copolycondensation method or the post grafting method. However, the presence of amino groups does not allow removal of the templating agent by conventional calcination. In general, the template agent is removed in an extraction mode, so that on one hand, one procedure is added, the cost is increased, and on the other hand, the loss of the molecular sieve product is caused in the extraction process.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides an amino modified SBA molecular sieve, a preparation method and application thereof, and a treatment method of an organic template agent in the amino modified SBA molecular sieve. In the preparation process of the amino modified SBA molecular sieve, the halogen-containing amino modifier is adopted to modify the SBA molecular sieve, wherein halogen ions can be exchanged with an organic template, and then the organic template is directly removed. And before modification, the SBA molecular sieve is passivated by using a passivating agent, so that amino groups can enter the pore canal of the molecular sieve to coordinate with silicon hydroxyl groups in the molecular sieve, and the pore canal structure and crystallinity of the molecular sieve are not damaged.
The first aspect of the invention provides a method for preparing an amino modified SBA molecular sieve, comprising the following steps:
step A, mixing a silicon source, an organic template agent, an acid solution and water for reaction, and sequentially carrying out hydrothermal crystallization and drying treatment on the obtained mixture to obtain an SBA molecular sieve;
and B, mixing and stirring the SBA molecular sieve and a passivating agent, then adding a halogen-containing amino modifier for modification reaction, and drying a reaction product.
According to a preferred embodiment of the preparation method of the present invention, the preparation method comprises the steps of:
step A, mixing a silicon source, an organic template agent, an acid solution and water for reaction, performing hydrothermal crystallization treatment on the obtained mixture, and performing filtration, washing and drying treatment on the obtained hydrothermal crystallization product to obtain an SBA molecular sieve;
and B, SBA, mixing and stirring the molecular sieve and the passivating agent, adding the halogen-containing amino modifier for modification reaction, and filtering, washing and drying the reaction product to obtain the amino modified SBA molecular sieve.
According to some embodiments of the preparation method of the present invention, the halogen-containing amino modifier is selected from amine or amine salts containing halogen ions and amino structures.
According to a preferred embodiment of the preparation method of the present invention, the halogen ion is a chloride ion.
According to a specific embodiment of the preparation method of the present invention, the halogen-containing amino modifier is at least one of 3-chloropropionamine hydrochloride, 4-chlorobutylamine and 3-chloropropylamine.
In the invention, when amino modification is carried out on the SBA molecular sieve, amine or amine salt containing halogen ions and an amino structure is adopted as an amino modifier, and when amino groups are introduced into the pore canal of the SBA molecular sieve, the halogen ions exchange with an organic template agent in the SBA molecular sieve to remove the organic template agent. Furthermore, the halogen-containing amino modifier is adopted for modification, so that the subsequent extraction process is avoided to remove the organic template agent, the working procedure and the cost are saved, and the loss of products is avoided.
According to some embodiments of the preparation method of the present invention, an organic solvent is further added during the modification reaction.
According to a preferred embodiment of the preparation method of the present invention, the organic solvent is ethanol and/or propanol.
According to some embodiments of the preparation method of the present invention, the weight ratio of the organic solvent to the halogen-containing amino modifier is 1:3 to 3:1.
According to the specific embodiment of the preparation method, the weight ratio of the organic solvent to the halogen-containing amino modifier is 1:1.
According to some embodiments of the preparation method of the present invention, the weight ratio of the halogen-containing amino modifier to the SBA molecular sieve is 3:1 to 1:1.
According to some embodiments of the preparation method of the present invention, the modification reaction conditions include: the temperature is 50-140 ℃ and the time is 3-9 h. For example, the modification temperature is 50 ℃, 60 ℃, 70 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 140 ℃, and any value therebetween. The modification time was 3h, 4h, 6h, 7h, 9h, and any value therebetween.
According to a preferred embodiment of the preparation method of the present invention, the conditions of the modification reaction include: the temperature is 60-120 ℃ and the time is 4-8 h.
According to a preferred embodiment of the preparation method of the present invention, the conditions of the modification reaction include: the temperature is 90-100 ℃ and the time is 6-7 h.
According to some embodiments of the method of preparation of the present invention, the silicon source is selected from at least one of white carbon black, ethyl orthosilicate, and silica sol.
According to a specific embodiment of the preparation method of the invention, the silicon source is ethyl orthosilicate.
According to some embodiments of the preparation method of the present invention, the organic template is selected from nonionic triblock copolymers and/or Hexamethylenetetramine (HMTA).
According to a preferred embodiment of the preparation method of the present invention, the nonionic triblock copolymer is selected from at least one of F127, F108, P123 and P104.
According to some embodiments of the preparation method of the present invention, when the prepared SBA molecular sieve is an SBA-15 molecular sieve, the organic template is P123 and/or P104.
According to some embodiments of the preparation method of the present invention, when the prepared SBA molecular sieve is an SBA-16 molecular sieve, the organic template is at least one of F127, F108 and HMTA.
According to some embodiments of the method of preparation of the present invention, the acid solution is selected from at least one of a hydrochloric acid solution, a sulfuric acid solution, and a nitric acid solution.
According to a specific embodiment of the preparation method of the present invention, the acid solution is hydrochloric acid.
According to some embodiments of the preparation process of the present invention, the drying temperature in step a is 100-140 ℃. Such as 100 c, 110 c, 120 c, 130 c, 140 c, and any value therebetween. At this temperature, the moisture on the surface of the SBA molecular sieve can be effectively removed.
According to a preferred embodiment of the preparation process according to the invention, the drying temperature in step A is from 110 to 130 ℃.
According to some embodiments of the preparation method of the present invention, in step a, the temperature of the mixed reaction of the silicon source, the organic template, the acid solution and the water is 20 to 70 ℃. Such as 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, and any value therebetween.
According to a preferred embodiment of the preparation method of the present invention, in the step a, the temperature at which the silicon source, the organic template, the acid solution and the water are mixed is 50 to 70 ℃.
According to some embodiments of the preparation method of the present invention, the silicon source is in the form of SiO 2 Calculated as H + The solvent is calculated as H 2 O is calculated, the organic template agent is calculated as R, and the components and the mole ratio of the mixture are SiO 2 ：aH 2 O：bR：cH + Wherein a is 80 to 200, b is 0.005 to 0.030, and c is 0.10 to 0.25. For example, a is 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, and any value therebetween. b is 0.005, 0.01, 0.015, 0.02, 0.025, 0.03, and any value therebetween. c is 0.1, 0.15, 0.2, 0.25, and any value therebetween. Wherein H is 2 O is water added in the hydrothermal crystallization process in the step A, and does not comprise water in an acid solution.
According to some embodiments of the preparation method of the present invention, the hydrothermal crystallization conditions include: the temperature is 80-140 ℃ and the time is 30-90 h.
According to a preferred embodiment of the preparation method of the present invention, the conditions for hydrothermal crystallization include: the temperature is 90-120 ℃ and the time is 40-70 h.
According to a specific embodiment of the preparation method of the present invention, the temperature of the hydrothermal crystallization is 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, and any value therebetween. The hydrothermal crystallization time is 30h, 40h, 50h, 60h, 70h, 80h, 90h, and any value therebetween.
According to some embodiments of the preparation method of the present invention, the passivating agent comprises an organosilane of the general formula R a R b R c SiR d 。
According to some embodiments of the preparation methods of the present invention, R a R b R c SiR d Wherein R is a 、R b 、R c And R is d The same or different. R is R a 、R b 、R c And R is d Each independently selected from hydrogen, halogen, C 1 -C 20 Alkyl, C of (2) 1 -C 20 Alkoxy, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl and C of (2) 1 -C 20 At least one of the haloalkyl groups, R a 、R b 、R c And R is d Not both hydrogen and R a 、R b 、R c And R is d Not both halogen.
According to a preferred embodiment of the preparation process according to the invention, R a R b R c SiR d Wherein R is a 、R b 、R c And R is d Each independently selected from hydrogen, halogen, C 1 -C 20 Alkyl, C of (2) 1 -C 20 Alkoxy, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl and C of (2) 1 -C 20 Wherein R is at least one of haloalkyl groups d Is halogen, R a 、R b And R is c Not both hydrogen and R a 、R b And R is c At different timesIs halogen.
According to a preferred embodiment of the preparation method of the present invention, the passivating agent is at least one of diphenyldichlorosilane, trimethylchlorosilane and dimethyldichlorosilane.
According to some embodiments of the preparation method of the present invention, the weight ratio of the passivating agent to the SBA molecular sieve is 4:5-1:10.
According to the preferred embodiment of the preparation method, the weight ratio of the passivating agent to the SBA molecular sieve is 3:5-1:10.
According to the preferred embodiment of the preparation method, the weight ratio of the passivating agent to the SBA molecular sieve is 3:7-1:9.
According to some embodiments of the preparation method of the present invention, the conditions under which the SBA molecular sieve is mixed with the passivating agent include: the temperature is 30-90 ℃ and the time is 2-10 h.
According to a preferred embodiment of the preparation method of the present invention, the conditions under which the SBA molecular sieve and the passivating agent are mixed and stirred include: the temperature is 50-70 ℃ and the time is 4-7 h.
According to a specific embodiment of the preparation method of the present invention, the temperature at which the SBA molecular sieve and the passivating agent are mixed and stirred is 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, and any value therebetween.
According to a specific embodiment of the preparation method of the present invention, the time for mixing and stirring the SBA molecular sieve and the passivating agent is 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, and any value therebetween.
According to some embodiments of the preparation process of the present invention, the drying temperature in step B is 100 to 140 ℃. Such as 100 c, 110 c, 120 c, 130 c, 140 c, and any value therebetween.
According to a preferred embodiment of the preparation process according to the invention, the drying temperature in step B is from 110 to 130 ℃.
When the amino modified SBA molecular sieve is prepared, firstly, the passivating agent is used for passivating the silicon hydroxyl on the surface and the orifice of the molecular sieve, so that the amino group can directly enter the pore canal of the molecular sieve to coordinate with the silicon hydroxyl therein, and the pore canal structure and the crystallinity of the molecular sieve are not damaged. In addition, the SBA molecular sieve is modified by adopting the halogen-containing amino modifier, wherein halogen ions can be exchanged with the organic template agent, so that the organic template agent in the SBA molecular sieve is directly removed, the process of removing the organic template agent by subsequent extraction is avoided, the process flow is simplified, the resource cost and the labor cost are saved, and the loss of molecular sieve products caused by more than one process is avoided.
The second aspect of the invention provides an amino modified SBA molecular sieve obtained according to the preparation method.
The amino modified SBA molecular sieve obtained by the invention has the specific surface area more than 780 (m) 2 Per g), for CO 2 The adsorption quantity of the catalyst reaches more than 1.5 mmol/g. Wherein, the specific surface area is measured by an ASAP2020 full-automatic specific surface analyzer of Micromeritics company.
The amino modified SBA molecular sieve obtained by the invention not only has the thermal stability of the SBA molecular sieve, but also has the surface characteristics brought by amino groups.
The invention provides a method for removing an organic template agent from an SBA molecular sieve, which adopts amine or amine salt containing halogen ions and amino structures as a modifier to treat the SBA molecular sieve.
According to some embodiments of the method for removing an organic template of the present invention, the halogen ion is a chloride ion.
According to a preferred embodiment of the method for removing an organic templating agent according to the present invention, the amine or amine salt is at least one of 3-chloropropanamine hydrochloride, 4-chlorobutylamine and 3-chloropropanamine.
According to some embodiments of the method for removing the organic template agent, the weight ratio of the amine or the amine salt to the SBA molecular sieve is 3:1-1:1.
According to some embodiments of the method for removing an organic template of the present invention, the conditions of the treatment process include: the temperature is 50-140 ℃ and the time is 3-9 h. For example, the temperature is 50 ℃, 60 ℃, 70 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 140 ℃, or any value therebetween. The time is 3h, 4h, 6h, 7h, 9h, and any value therebetween.
According to a preferred embodiment of the method for removing an organic template according to the present invention, the conditions of the treatment process include: the temperature is 60-120 ℃ and the time is 4-8 h.
According to a preferred embodiment of the method for removing an organic template according to the present invention, the conditions of the treatment process include: the temperature is 90-100 ℃ and the time is 6-7 h.
In the invention, in the process of treating the SBA molecular sieve by adopting amine or amine salt containing halogen ions and amino structures as the modifier, the amino structures enter the pore canal of the SBA molecular sieve to coordinate and combine with silicon hydroxyl in the pore canal, and meanwhile, the halogen ions and the organic template agent in the SBA molecular sieve can be exchanged, so that the removal of the organic template agent is realized.
In a fourth aspect, the present invention provides a method for preparing the amino-modified SBA molecular sieve and an application of the amino-modified SBA molecular sieve in a gas adsorption separation process, more preferably in an acid gas adsorption separation process, especially in CO 2 Application in adsorption separation process. But is not limited thereto.
The amino modified SBA molecular sieve of the invention is used for preparing CO 2 The adsorption capacity of (C) can reach more than 1.5 mmol/g.
The invention has the beneficial effects that:
in the invention, an amino-modified SBA molecular sieve is prepared by adopting a halogen-containing amino modifier. In the preparation process, firstly, the passivating agent is used for passivating the silicon hydroxyl on the surface and the orifice of the molecular sieve, so that the amino group can directly enter the pore canal of the molecular sieve to coordinate with the silicon hydroxyl in the pore canal of the molecular sieve, and the pore canal structure and the crystallinity of the molecular sieve can not be damaged. Meanwhile, halogen ions can exchange ions with the organic template agent in the SBA molecular sieve due to the action of charges, so that the organic template agent is directly removed.
The preparation method of the invention omits the process of removing the organic template agent by adopting the extraction method, simplifies the process flow, saves the production cost and avoids the loss of molecular sieve products caused by more than one procedure.
Drawings
FIG. 1 is a small angle XRD pattern of an amino modified SBA-16 molecular sieve obtained in example 3;
FIG. 2 is a FT-IR diagram of an amino modified SBA-16 molecular sieve obtained in example 3;
FIG. 3 is a small angle XRD pattern of the amino modified SBA-15 molecular sieve obtained in example 5;
FIG. 4 is a FT-IR chart of an amino modified SBA-15 molecular sieve obtained in example 5.
Detailed Description
In order that the invention may be more readily understood, the invention will be described in detail below with reference to the following examples, which are given by way of illustration only and are not limiting of the scope of application of the invention.
The test method and the equipment used in the test are as follows:
(1) XRD test: the structure of the molecular sieve was determined by means of an X-ray diffractometer of the Philips company X-Pert series.
(2) FT-IR test: a fourier transform infrared spectrometer, thermo Nicolet Nexus, 470 from Thermo corporation, was used to determine the presence of amino groups in the molecular sieve.
(3) BET test: the specific surface area was measured using a Micromeritics ASAP2020 full-automatic specific surface analyzer.
(4)CO 2 The adsorption test method of (2) comprises the following steps: firstly, a certain amount of the to-be-detected substance is taken and dried for 1H in a vacuum drying oven at 100 ℃ to remove H adsorbed in the product 2 O, weigh m when the temperature is reduced to room temperature equilibrium 0 . Followed by 10vol% CO 2 And 90vol% N 2 Introducing the mixed gas into the object to be detected at 35 ℃, and weighing the mixture to m after the adsorption reaches equilibrium 1 . Finally regenerating in a vacuum drying oven at 100 ℃ for 30min, and adsorbing the CO 2 All released, weighed to m 2 。m 2 Is to sum m 0 The two are normally identical if they differIf the test is too large, the test is conducted again. Repeated CO after regeneration 2 Adsorption and desorption experiments were carried out 5 times, and the average value thereof was taken. CO 2 The adsorption quantity calculation formula of (2) is: c (C) CO2 ＝(m 1 -m 0 )/44m 0 。
The sources of reagents used in the invention are:
(1) F127, F108, HMTA, P104, P123 were all purchased from Sigma-Aldrich company;
(2) SW-25 was purchased from Qingdao micro-nano silica gel technology Co., ltd;
(3) White carbon black was purchased from maple new materials, inc.
Other reagents are commercially available.
The silicon source of the invention adopts SiO 2 Calculated as H + The solvent is calculated as H 2 O is calculated, and the organic template agent is calculated as R.
[ example 1 ]
Adding 3.5g of F127 and 76g of deionized water into a reactor in sequence at 60 ℃, stirring uniformly, adding 53mL of 0.1mol/L hydrochloric acid solution, continuously stirring, and slowly and dropwise adding 11g of Tetraethoxysilane (TEOS), wherein the molar ratio of the obtained reaction mixture is SiO 2 ：80H 2 O：0.005R：0.1H + . Then, the mixture is transferred into a crystallization kettle, heated to 90 ℃ and crystallized for 40 hours at constant temperature. Separating, washing and drying the crystallized mixture at 100 ℃ to obtain SBA-16 molecular sieve raw powder.
5g of SBA-16 molecular sieve raw powder and 3g of trimethylchlorosilane are stirred for 4 hours at 40 ℃, then the product is uniformly mixed with 12g of 3-chloropropionamine hydrochloride and 12g of ethanol, and stirred for 4 hours at 60 ℃, and the obtained product is filtered, washed and dried at 100 ℃ to obtain the amino modified SBA-16 molecular sieve.
BET analysis shows that the specific surface area of the obtained amino modified SBA-16 molecular sieve is 821m 2 /g。
Will contain 10vol% CO 2 And 90vol% N 2 Introducing the mixed gas of (C) into an amino modified SBA-16 molecular sieve at 35 ℃ to determine the adsorption of CO 2 The results are shown in Table 1。
[ example 2 ]
The difference from example 1 was that the batch temperature was 40 ℃, the organic templating agent was F108 in an amount of 10.9g, the water in an amount of 135g, the silicon source was white carbon black having 90 wt% silica, the acid was sulfuric acid in an amount of 5g, and the amount of 112mL. The crystallization temperature is 100 ℃ and the crystallization time is 50 hours. The drying temperature was 110 ℃.
The passivating agent is dimethyl dichlorosilane, the dosage is 2.1g, the passivating temperature is 50 ℃, and the passivating time is 5 hours. The amino modifier is 4-chlorobutylamine, the dosage is 10g, the dosage of ethanol is 10g, the modification temperature is 80 ℃, the modification time is 5h, and the rest components and the synthesis conditions are unchanged. The molar ratio of the reaction mixture obtained in this example is SiO 2 ：100H 2 O：0.01R：0.15H + 。
BET analysis shows that the specific surface area of the amino modified SBA-16 molecular sieve is 836m 2 /g。
Will contain 10vol% CO 2 And 90vol% N 2 Introducing the mixed gas of (C) into an amino modified SBA-16 molecular sieve at 35 ℃ to determine the adsorption of CO 2 The results are shown in Table 1.
[ example 3 ]
The difference from example 1 was that the feed temperature was 50 ℃, the stencil agent was HMTA, the amount was 0.15g, the amount of water was 82.5g, the silica source was silica sol (SW-25, silica content 25% by weight), the amount was 10g, the acid was nitric acid, and the amount was 83mL. The crystallization temperature is 110 ℃, and the crystallization time is 60 hours. The drying temperature was 120 ℃.
The passivating agent is diphenyl dichlorosilane, the dosage is 1.25g, the passivating temperature is 60 ℃, and the passivating time is 6 hours. The amino modifier is 3-chloropropylamine, the dosage is 7g, the dosage of ethanol is 7g, the modification temperature is 90 ℃, the modification time is 6h, and the rest components and the synthesis conditions are unchanged. The molar ratio of the reaction mixture obtained in this example is SiO 2 ：110H 2 O：0.025R：0.2H + 。
BET analysis shows that the specific surface area of the obtained amino modified SBA-16 molecular sieve is 996m 2 /g。
The small angle XRD pattern of the amino modified SBA-16 molecular sieve is shown in figure 1. The FT-IR diagram is shown in FIG. 2.
Will contain 10vol% CO 2 And 90vol% N 2 Introducing the mixed gas of (C) into an amino modified SBA-16 molecular sieve at 35 ℃ to determine the adsorption of CO 2 The results are shown in Table 1.
[ example 4 ]
Adding 9.3g of P104 and 85.5g of deionized water into a reactor in sequence at 30 ℃, uniformly stirring, adding 132mL of 0.1mol/L hydrochloric acid solution, continuously stirring, slowly and dropwise adding 11g of TEOS, wherein the molar ratio of the obtained reaction mixture is SiO 2 ：90H 2 O：0.03R：0.25H + . Transferring the mixture into a crystallization kettle, heating to 130 ℃, and crystallizing for 90 hours at constant temperature. Separating, washing and drying the mixture after crystallization reaction at 130 ℃ to obtain SBA-15 molecular sieve raw powder.
5g of SBA-15 molecular sieve raw powder and 1.67g of trimethylchlorosilane are stirred for 9 hours at 80 ℃, then the product is uniformly mixed with 12g of 3-chloropropionamine hydrochloride and 12g of ethanol, and stirred for 8 hours at 110 ℃, and the obtained product is filtered, washed and dried at 100 ℃ to obtain the amino modified SBA-15 molecular sieve.
BET analysis shows that the specific surface area of the obtained amino modified SBA-15 molecular sieve is 785m 2 /g。
Will contain 10vol% CO 2 And 90vol% N 2 Introducing the mixed gas of (C) into an amino modified SBA-15 molecular sieve at 35 ℃ to determine the adsorption of CO 2 The results are shown in Table 1.
[ example 5 ]
The difference from example 4 was that the feed temperature was 70 ℃, the templating agent was P123, the amount of water was 4.4g, the amount of water was 175.5g, the silicon source was white carbon black having 90 wt% silica, the amount was 5g, the acid was nitric acid, and the amount was 112.5mL. The crystallization temperature is 120 ℃ and the crystallization time is 70h. The drying temperature was 120 ℃. The passivating agent is dimethyl dichlorosilane, the dosage is 1g, the passivating temperature is 70 ℃, and the passivating time is 7h. The amino modifier is 4-chlorobutylamine, the dosage is 10g, the dosage of ethanol is 10g, and the modification temperature isThe modification time is 7 hours at 100 ℃, and the other components and synthesis conditions are unchanged. The molar ratio of the obtained reaction mixture is SiO 2 ：130H 2 O：0.01R：0.15H + 。
BET analysis shows that the specific surface area of the obtained amino modified SBA-15 molecular sieve is 968m 2 /g。
The small angle XRD pattern of the amino modified SBA-16 molecular sieve is shown in figure 3. The FT-IR diagram is shown in FIG. 4.
Will contain 10vol% CO 2 And 90% volN 2 Introducing the mixed gas of (C) into an amino modified SBA-15 molecular sieve at 35 ℃ to determine the adsorption of CO 2 The results are shown in Table 1.
[ example 6 ]
The difference from example 4 was that the feed temperature was 50 ℃, the templating agent was P123, the amount was 4.8g, the amount of water was 112.5g, the silica source was silica sol (SW-25, silica content 25 wt%), the amount was 10g, the acid was nitric acid, and the amount was 41.7mL. The crystallization temperature is 110 ℃ and the crystallization time is 80h. The drying temperature was 110 ℃. The passivating agent is dimethyl dichlorosilane, the dosage is 0.56g, the passivating temperature is 90 ℃, and the passivating time is 10 hours. The amino modifier is 3-chloropropylamine, the dosage is 5g, the dosage of ethanol is 5g, the modification temperature is 120 ℃, the modification time is 6h, and the rest components and the synthesis conditions are unchanged. The molar ratio of the obtained reaction mixture is SiO 2 ：150H 2 O：0.02R：0.1H + 。
BET analysis shows that the specific surface area of the obtained amino modified SBA-15 molecular sieve is 881m 2 /g。
Will contain 10vol% CO 2 And 90vol% N 2 Introducing the mixed gas of (C) into an amino modified SBA-15 molecular sieve at 35 ℃ to determine the adsorption of CO 2 The results are shown in Table 1.
Comparative example 1
Adding 3.5g of F127 and 76g of deionized water into a reactor in sequence at 60 ℃, stirring uniformly, adding 53mL of 0.1mol/L hydrochloric acid solution, continuously stirring, slowly and dropwise adding 11g of TEOS, and then adding 12g of 3-chloropropionamine hydrochloride and 12g of ethanol, wherein the molar ratio of the obtained reaction mixture is SiO 2 ：80H 2 O：0.005R：0.1H + . Transferring the mixture into a crystallization kettle, heating to 90 ℃, and crystallizing for 40 hours at constant temperature. Separating, washing and drying the reacted mixture at 100 ℃ to obtain the amino modified SBA-16 molecular sieve. The amino-modified SBA-16 molecular sieve was then dried at 100deg.C and analyzed by BET to give a product having a specific surface area of 629m 2 /g。
Will contain 10vol% CO 2 And 90vol% N 2 Introducing the mixed gas of (C) into an amino modified SBA-16 molecular sieve at 35 ℃ to determine the adsorption of CO 2 The results are shown in Table 1.
Comparative example 2
Adding 3.5g of F127 and 76g of deionized water into a reactor in sequence at 60 ℃, stirring uniformly, adding 53mL of 0.1mol/L hydrochloric acid solution, continuously stirring, slowly and dropwise adding 11g of TEOS, wherein the molar ratio of the obtained reaction mixture is SiO 2 ：80H 2 O：0.005R：0.1H + . Transferring the mixture into a crystallization kettle, heating to 90 ℃, and crystallizing for 40 hours at constant temperature. Separating, washing and drying the reacted mixture at 100 ℃ to obtain the SBA-16 molecular sieve raw powder. Mixing 5g of SBA-16 molecular sieve raw powder, 12g of 3-chloropropionamine hydrochloride and 12g of ethanol uniformly, stirring for 4 hours at 60 ℃, filtering and washing the obtained product, drying at 100 ℃, and measuring the specific surface area of the product to be 861m by BET analysis 2 /g。
Will contain 10vol% CO 2 And 90vol% N 2 Introducing the mixed gas of (C) into an amino modified SBA-16 molecular sieve at 35 ℃ to determine the adsorption of CO 2 The results are shown in Table 1.
[ comparative example 3 ]
Adding 0.7g of F127 and 66.5g of deionized water into a reactor in sequence at 60 ℃, uniformly stirring, adding 158.4mL of 0.1mol/L hydrochloric acid solution, continuously stirring, slowly and dropwise adding 11g of TEOS, wherein the molar ratio of the obtained reaction mixture is SiO 2 ：70H 2 O：0.001R：0.3H + . Transferring the mixture into a crystallization kettle, heating to 90 ℃, and keeping the temperature constantCrystallizing for 40h. Separating, washing and drying the reacted mixture at 100 deg.c to obtain the product. Taking 5g of the obtained product and 3g of trimethylchlorosilane, stirring for 4 hours at 40 ℃, then uniformly mixing the product with 12g of 3-chloropropionamine hydrochloride and 12g of ethanol, stirring for 4 hours at 60 ℃, filtering, washing and drying the obtained product at 100 ℃, and carrying out BET analysis to obtain the product with the specific surface area of 27m 2 /g。
At 35℃the product was used to determine that it contained 10vol% CO 2 And 90vol% N 2 CO adsorption by mixed gas of (2) 2 The results are shown in Table 1.
[ comparative example 4 ]
Adding 0.3g of P104 and 66.5g of deionized water into a reactor in sequence at 30 ℃, stirring uniformly, adding 158.4mL of 0.1mol/L hydrochloric acid solution, continuously stirring, slowly and dropwise adding 11g of TEOS, wherein the molar ratio of the obtained reaction mixture is SiO 2 ：70H 2 O：0.001R：0.3H + . Transferring the mixture into a crystallization kettle, heating to 130 ℃, and crystallizing for 90 hours at constant temperature. Separating, washing and drying the reacted mixture at 130 ℃ to obtain the SBA-15 molecular sieve raw powder. Mixing 5g of SBA-15 molecular sieve raw powder and 1.67g of trimethylchlorosilane at 80 ℃ for 9 hours, uniformly mixing the product with 12g of 3-chloropropionamine hydrochloride and 12g of ethanol, stirring for 8 hours at 110 ℃, filtering and washing the obtained product, drying at 100 ℃, and analyzing by BET to obtain the specific surface area of the product of 26m 2 /g。
At 35℃the product was used to determine that it contained 10vol% CO 2 And 90vol% N 2 CO adsorption by mixed gas of (2) 2 The results are shown in Table 1.
Comparative example 5
Adding 3.5g of F127 and 76g of deionized water into a reactor in sequence at 60 ℃, stirring uniformly, adding 53mL of 0.1mol/L hydrochloric acid solution, continuously stirring, slowly and dropwise adding 11g of TEOS, wherein the molar ratio of the obtained reaction mixture is SiO 2 ：80H 2 O：0.005R：0.1H + . Transferring the mixture into a crystallization kettle, heating to 90 ℃, and crystallizing for 40 hours at constant temperature. Separating, washing and drying the reacted mixture at 100 ℃ to obtain the SBA-16 molecular sieve raw powder. Mixing 5g of SBA-16 molecular sieve raw powder with 5g of trimethylchlorosilane at 40 ℃ for 4 hours, uniformly mixing the product with 12g of 3-chloropropionamine hydrochloride and 12g of ethanol, stirring for 4 hours at 60 ℃, filtering and washing the obtained product, drying at 100 ℃, and analyzing by BET to obtain the specific surface area of 741m 2 /g。
Will contain 10vol% CO 2 And 90vol% N 2 Introducing the mixed gas of (C) into an amino modified SBA-16 molecular sieve at 35 ℃ to determine the adsorption of CO 2 The results are shown in Table 1.
[ comparative example 6 ]
According to the method of example 1, except that an amino modifier without chloride ions is adopted, the steps of extracting and removing the organic template agent are added, and specifically:
adding 3.5g of F127 and 76g of deionized water into a reactor in sequence at 60 ℃, stirring uniformly, adding 53mL of 0.1mol/L hydrochloric acid solution, continuously stirring, slowly and dropwise adding 11g of TEOS, wherein the molar ratio of the obtained reaction mixture is SiO 2 ：80H 2 O：0.005R：0.1H + . Then, the mixture is transferred into a crystallization kettle, heated to 90 ℃ and crystallized for 40 hours at constant temperature. Separating, washing and drying the crystallized mixture at 100 ℃ to obtain SBA-16 molecular sieve raw powder.
5g of SBA-16 molecular sieve raw powder and 3g of trimethylchlorosilane are stirred for 4 hours at 40 ℃, then the product is uniformly mixed with 15g of 3- (phenylamino) propyl trimethoxysilane and 15g of ethanol and stirred for 4 hours at 60 ℃, then the product is uniformly mixed with 20g of methyl ether and stirred for 2 hours, and the obtained product is filtered, washed and dried at 100 ℃ to obtain the amino modified SBA-16 molecular sieve.
BET analysis shows that the specific surface area of the obtained amino modified SBA-16 molecular sieve is 746m 2 /g。
Will contain 10vol％CO 2 And 90vol% N 2 Introducing the mixed gas of (C) into an amino modified SBA-16 molecular sieve at 35 ℃ to determine the adsorption of CO 2 The results are shown in Table 1.
TABLE 1
CO 2 Adsorption quantity (mmol/g) Specific surface area (m) 2 /g)
Example 1 1.58 821
Example 2 1.58 836
Example 3 1.82 996
Example 4 1.50 785
Example 5 1.79 968
Example 6 1.60 881
Comparative example 1 0.34 629
Comparative example 2 0.75 861
Comparative example 3 0 27
Comparative example 4 0 26
Comparative example 5 0.36 641
Comparative example 6 1.38 746
As is clear from comparative examples 1-2 and example 1, the copolycondensation method was used in comparative example 1, and the amino modifier was directly added during the synthesis. The copolycondensation method has simple preparation process, amino groups are introduced into the pore canal of the molecular sieve in one step, but a large amount of organic groups also enter the pore canal of the molecular sieve, so that the diameter of the molecular sieve is increased in the synthesis process, the order of the molecular sieve is reduced, and the specific surface area of the molecular sieve is reduced. The conventional grafting method is adopted in the comparative example 2, most of the amino modifier introduced by the method is on the surface of the molecular sieve or at the openings of the molecular sieve pores, and amino groups are difficult to enter the inside of the molecular sieve pores. In contrast, the comparative examples 3 and 4 did not synthesize SBA-16 molecular sieves and SBA-15 molecular sieves because the synthesis ratio of the molecular sieves was exceeded.
As can be seen from FIGS. 1 and 3, the amino modified SBA molecular sieves prepared according to the method of the invention show characteristic diffraction peaks of SBA-16 and SBA-15 molecular sieves, which indicate that the SBA series molecular sieves are successfully synthesized, and the presence of amino groups does not affect the order of the SBA molecular sieves.
As can be seen from FIGS. 2 and 4, 465cm -1 And 1080cm -1 The symmetrical vibration peak and the asymmetrical vibration peak of Si-O-Si of SBA are positioned at 1569cm -1 Is of amino NH group 2 The vibrational peak in the pore canal with the silicon hydroxyl group indicates that the amino group exists in the interior of the pore canal of the molecular sieve, but does not exist on the surface and the pore opening of the molecular sieve.
As can be seen from Table 1, the amino-modified SBA molecular sieves prepared in examples 1-6 are specific for CO 2 Has obvious adsorption effect. Comparative example 1 is simple in preparation method, but the adsorption amount is low because the order of the molecular sieve is damaged by a large amount of organic groups. The amino-modified molecular sieve prepared in comparative example 2, although having a high specific surface area, has a limited adsorption amount because a large amount of amino groups are concentrated on the surface and pores of the molecular sieve. Comparative example 3 and comparative example 4 have an adsorption amount of 0 since the porous structure of the SBA molecular sieve is not formed. In comparative example 5, since the passivating agent is excessive, although the silicon hydroxyl groups on the surface of the SBA molecular sieve are occupied by the passivating agent, the excessive passivating agent also enters the molecular sieve pore to occupy the silicon hydroxyl groups in the pore, so that the amino group cannot enter the molecular sieve pore, thereby affecting CO 2 Adsorption amount. In comparative example 6, SBA molecular sieve was modified with an amino modifier free of halogen ions, and an extraction step was added to remove the organic template agent, but a small amount of template agent remained in the pore channels of the molecular sieve after extraction, resulting in the specific surface area and CO of the final modified SBA molecular sieve 2 The adsorption amounts of (a) are lower than those of the examples.
What has been described above is merely a preferred example of the present invention. It should be noted that other equivalent modifications and improvements will occur to those skilled in the art, and are intended to be within the scope of the present invention, as a matter of common general knowledge in the art, in light of the technical teaching provided by the present invention.

Claims (22)

1. A preparation method of an amino modified SBA molecular sieve comprises the following steps:
step A, mixing a silicon source, an organic template agent, an acid solution and water for reaction, and sequentially carrying out hydrothermal crystallization and drying treatment on the obtained mixture to obtain an SBA molecular sieve;
step B, mixing and stirring the SBA molecular sieve and a passivating agent, then adding a halogen-containing amino modifier for modification reaction, and drying a reaction product;
silicon source is SiO 2 Calculated as H + The solvent is calculated as H 2 O is calculated, the organic template agent is calculated as R, and the components and the mole ratio of the mixture are SiO 2 ：aH 2 O：bR：cH + Wherein a is 80 to 200, b is 0.005 to 0.030, and c is 0.10 to 0.25;
the weight ratio of the passivating agent to the SBA molecular sieve is 4:5-1:10.
2. The method of claim 1, wherein the halogen-containing amino modifier is selected from the group consisting of amines or amine salts containing halogen ions and amino structures.
3. The method according to claim 2, wherein the halogen ion is a chloride ion.
4. The method according to claim 3, wherein the halogen-containing amino modifier is at least one of 3-chloropropionamine hydrochloride, 4-chlorobutylamine and 3-chloropropylamine.
5. The method according to any one of claims 1 to 4, wherein an organic solvent is further added during the modification reaction.
6. The method according to claim 5, wherein the organic solvent is ethanol and/or propanol; and/or the number of the groups of groups,
the weight ratio of the organic solvent to the halogen-containing amino modifier is 1:3-3:1.
7. The method according to any one of claims 1 to 4, wherein the weight ratio of the halogen-containing amino modifier to the SBA molecular sieve is 3:1 to 1:1; and/or the number of the groups of groups,
the conditions of the modification reaction include: the temperature is 50-140 ℃ and the time is 3-9 h.
8. The method according to claim 7, wherein the conditions of the modification reaction include: the temperature is 60-120 ℃ and the time is 4-8 h.
9. The method of claim 8, wherein the modification reaction conditions include: the temperature is 90-100 ℃ and the time is 6-7 h.
10. The method according to any one of claims 1 to 4, wherein the silicon source is at least one selected from the group consisting of white carbon black, ethyl orthosilicate, and silica sol; and/or the number of the groups of groups,
the organic template agent is selected from nonionic triblock copolymer and/or hexamethylenetetramine; and/or the number of the groups of groups,
the acid solution is at least one selected from hydrochloric acid solution, sulfuric acid solution and nitric acid solution; and/or the number of the groups of groups,
the drying temperature in the step A is 100-140 ℃; and/or the number of the groups of groups,
in the step A, the temperature of the mixed reaction of the silicon source, the organic template agent, the acid solution and the water is 20-70 ℃; and/or the number of the groups of groups,
the conditions of the hydrothermal crystallization include: the temperature is 80-140 ℃ and the time is 30-90 h.
11. The method of claim 10, wherein the nonionic triblock copolymer is selected from at least one of F127, F108, P123, and P104; and/or the number of the groups of groups,
the drying temperature in the step A is 110-130 ℃; and/or the number of the groups of groups,
the conditions of the hydrothermal crystallization include: the temperature is 90-120 ℃ and the time is 40-70 h.
12. The method of any one of claims 1 to 4, wherein the passivating agent comprises an organosilane of the formula R a R b R c SiR d Wherein R is a 、R b 、R c And R is d The same or different, each independently selected from hydrogen, halogen, C 1 -C 20 Alkyl, C of (2) 1 -C 20 Alkoxy, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl and C of (2) 1 -C 20 At least one of the haloalkyl groups, R a 、R b 、R c And R is d Not both hydrogen and R a 、R b 、R c And R is d Not both halogen; and/or the number of the groups of groups,
the SBA molecular sieve and the passivating agent are mixed and stirred under the conditions that: the temperature is 30-90 ℃ and the time is 2-10 h; and/or the number of the groups of groups,
and in the step B, the drying temperature is 100-140 ℃.
13. The method of claim 12, wherein R d Is halogen, R a 、R b And R is c Not both hydrogen and R a 、R b And R is c Not both halogen; and/or the number of the groups of groups,
the weight ratio of the passivating agent to the SBA molecular sieve is 3:5-1:10; and/or the number of the groups of groups,
the SBA molecular sieve and the passivating agent are mixed and stirred under the conditions that: the temperature is 50-70 ℃ and the time is 4-7 h; and/or the number of the groups of groups,
and in the step B, the drying temperature is 110-130 ℃.
14. The method of claim 13, wherein the passivating agent is at least one of diphenyldichlorosilane, trimethylchlorosilane, and dimethyldichlorosilane; and/or the number of the groups of groups,
the weight ratio of the passivating agent to the SBA molecular sieve is 3:7-1:9.
15. An amino-modified SBA molecular sieve obtainable by a process according to any one of claims 1 to 14.
16. A method for removing organic template agent in SBA molecular sieve adopts amine or amine salt containing halogen ion and amino structure as modifier to treat SBA molecular sieve;
the halogen ion is chloride ion;
the weight ratio of the amine or the amine salt to the SBA molecular sieve is 3:1-1:1.
17. The removal method of claim 16, wherein the treatment process conditions include: the temperature is 50-140 ℃ and the time is 3-9 h.
18. The removal method as claimed in claim 17, wherein the amine or amine salt containing a halogen ion and an amino structure is at least one of 3-chloropropanamine hydrochloride, 4-chlorobutylamine and 3-chloropropanamine; and/or the number of the groups of groups,
the conditions of the treatment process include: the temperature is 60-120 ℃ and the time is 4-8 h.
19. The removal method of claim 18, wherein the treatment process conditions include: the temperature is 90-100 ℃ and the time is 6-7 h.
20. A process for the preparation of an amino-modified SBA molecular sieve according to any of claims 1 to 14 or the use of an amino-modified SBA molecular sieve according to claim 15 in a gas adsorption separation process.
21. The use according to claim 20, wherein the use is in an acid gas adsorption separation process.
22. The use according to claim 21, characterized in that the use is in CO 2 Application in adsorption separation process.
CN202011148447.5A 2020-10-23 2020-10-23 Amino modified SBA molecular sieve, preparation method and application thereof, and removal method of organic template in SBA molecular sieve Active CN114477208B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011148447.5A CN114477208B (en) 2020-10-23 2020-10-23 Amino modified SBA molecular sieve, preparation method and application thereof, and removal method of organic template in SBA molecular sieve

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011148447.5A CN114477208B (en) 2020-10-23 2020-10-23 Amino modified SBA molecular sieve, preparation method and application thereof, and removal method of organic template in SBA molecular sieve

Publications (2)

Publication Number Publication Date
CN114477208A CN114477208A (en) 2022-05-13
CN114477208B true CN114477208B (en) 2023-09-08

Family

ID=81470652

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011148447.5A Active CN114477208B (en) 2020-10-23 2020-10-23 Amino modified SBA molecular sieve, preparation method and application thereof, and removal method of organic template in SBA molecular sieve

Country Status (1)

Country Link
CN (1) CN114477208B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115974097B (en) * 2023-02-17 2023-12-19 四川轻化工大学 Molecular sieve and application thereof in reducing content of miscellaneous aldehyde in white spirit

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105170099B (en) * 2015-10-14 2017-08-11 太原理工大学 A kind of amino functional ionic liquid base adsorption catalyst and preparation method thereof
CN110627083B (en) * 2018-06-25 2022-01-04 中国石油化工股份有限公司 Preparation method and application of amino-functionalized MCM molecular sieve
CN110627081A (en) * 2018-06-25 2019-12-31 中国石油化工股份有限公司 Preparation method and application of amino functionalized SBA molecular sieve

Also Published As

Publication number Publication date
CN114477208A (en) 2022-05-13

Similar Documents

Publication Publication Date Title
CN110627090A (en) Preparation method and application of sulfydryl functionalized SBA molecular sieve
CN102745708B (en) Synthetic method of mesoporous-microporous molecular sieve by raising hydrothermal stability
CN104477933B (en) A kind of preparation method of silylating reagent molecular sieve
CN110627085B (en) Preparation method and application of sulfydryl functionalized MCM (mesoporous crystalline silica) molecular sieve
CN114477208B (en) Amino modified SBA molecular sieve, preparation method and application thereof, and removal method of organic template in SBA molecular sieve
CN110627084B (en) Preparation method of organic functional group functionalized MCM molecular sieve
CN110627081A (en) Preparation method and application of amino functionalized SBA molecular sieve
TW201406658A (en) Aluminum silicate and method for producing same
CN110627083B (en) Preparation method and application of amino-functionalized MCM molecular sieve
CN110624524A (en) Preparation method and application of amino-functionalized MCM molecular sieve
CN110627082A (en) Preparation method and application of sulfydryl functionalized MCM (mesoporous crystalline silica) molecular sieve
KR100390321B1 (en) The selective adsorption of heavy metal ions using molecular-imprinted adsorbents synthesized with low cost silica sources
CN110624597B (en) Preparation method of organic functional group functionalized MCM molecular sieve
CN110627086A (en) Preparation method of organic functional group functionalized SBA molecular sieve
CN112007690B (en) Core-shell structure titanium-silicon material, preparation method thereof and method for producing ketoxime by macromolecular ketone ammoximation reaction
CN112299437B (en) Sulfydryl functionalized SBA molecular sieve raw powder, molecular sieve, and preparation methods and applications thereof
CN114100566B (en) Amino-functional MCM molecular sieve and preparation method and application thereof
CN114477212B (en) Organic functional group modified SBA molecular sieve and preparation method and application thereof
CN114105167B (en) Sulfhydryl functional MCM-41 molecular sieve and preparation method and application thereof
CN112320813B (en) Preparation method and application of amino-functionalized SBA molecular sieve
CN114477223B (en) Preparation method and application of sulfhydryl-functionalized SBA molecular sieve
CN112299431B (en) Organic functional group functionalized SBA molecular sieve, and preparation method and application thereof
CN112299434A (en) Amino-functionalized MCM molecular sieve raw powder, molecular sieve, and preparation method and application thereof
CN112320815B (en) Preparation method and application of sulfhydryl functional MCM molecular sieve
CN114477202B (en) Organic functional group modified MCM molecular sieve and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant