CN111054302A - Preparation method of porous desulfurized zeolite particles - Google Patents
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- 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
- B01J20/165—Natural alumino-silicates, e.g. zeolites
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- 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
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
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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
- 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
- B01J20/3007—Moulding, shaping or extruding
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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
- 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
- B01J20/3028—Granulating, agglomerating or aggregating
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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
- 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
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3204—Inorganic carriers, supports or substrates
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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
- 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
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3214—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the method for obtaining this coating or impregnating
- B01J20/3223—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the method for obtaining this coating or impregnating by means of an adhesive agent
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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
- 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
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3214—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the method for obtaining this coating or impregnating
- B01J20/3225—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the method for obtaining this coating or impregnating involving a post-treatment of the coated or impregnated product
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
- C10L3/103—Sulfur containing contaminants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/106—Silica or silicates
- B01D2253/108—Zeolites
Abstract
The invention discloses a preparation method of porous desulfurized zeolite particles, which comprises the following steps: a first mixture made from zeolite powder, a shaping additive, foam particles; a second mixture prepared from the first mixture, a glue and water; and extruding and granulating the second mixture, and soaking the second mixture in a metal salt solution for high-temperature sintering. The method for preparing the desulfurized zeolite particles has the advantages of simple process, low production cost, environmental friendliness, large specific surface area, high activity, good stability, good desulfurization effect and the like.
Description
FIELD
The invention relates to the field of preparation of desulfurized zeolite particles, in particular to preparation of porous desulfurized zeolite particles.
Background
China is a big country with coal as a main energy source, and the coal resource is rich and the petroleum and the natural gas are in short supply. The characteristics of resources occurrence in China determine that the energy problem in China must be mainly coal, but the problem of environmental pollution caused by coal burning is increasingly prominent while coal resources are developed and utilized, and the sustainable development of the economic society in China is severely restricted.
The adoption of the desulfurization technology can economically and effectively control the emission of sulfur dioxide, which becomes one of the important factors influencing the project construction and normal production of the coal-fired power plant. Therefore, the research and development of the high-efficiency flue gas desulfurization technology suitable for the national conditions of China have very important significance for solving the problem of environmental pollution caused by sulfur dioxide discharged by coal-fired power plants. Wet desulfurization or dry desulfurization, and the formed sulfate, such as calcium sulfate and magnesium sulfate, causes secondary pollution and resource waste.
The adsorption desulfurization is a novel method with broad prospect, has the advantages of low equipment investment, high desulfurization rate, no hydrogen consumption, low price of an adsorbent, simplicity, convenience, rapidness, economy and the like, and becomes a technology with prospect for solving the problem of deep desulfurization of gasoline and diesel.
The desulfurized zeolite is a special adsorbent with reasonable pore structure and moderate specific surface area, and can be repeatedly regenerated in the actual application process. At present, the types of the desulfurized zeolite particles are not many, and the desulfurized zeolite particles can be further divided into columnar particles, spherical particles and the like from the aspect of appearance, and all the desulfurized zeolite particles have solid structures.
At present, the solid particle product directly formed has poor desulfurization effect in the molten steel smelting process due to the defects of coarse porosity, poor adsorption capacity, large wind resistance and the like.
SUMMARY
The present disclosure relates to a method for preparing porous desulfurized zeolite particles comprising:
a first mixture made from zeolite powder, a shaping additive, foam particles;
a second mixture prepared from the first mixture, a glue and water; and
the second mixture is extruded and granulated, and is impregnated in a metal salt solution and then sintered at a high temperature.
Detailed description of the invention
In the following description, certain specific details are included to provide a thorough understanding of various disclosed embodiments. One skilled in the relevant art will recognize, however, that the embodiments can be practiced without one or more of the specific details, or with other methods, components, materials, and so forth.
Unless otherwise required by the disclosure, throughout the specification and the appended claims, the words "comprise", "comprising", and "have" are to be construed in an open, inclusive sense, i.e., "including but not limited to".
Reference throughout the specification to "one embodiment," "an embodiment," "in another embodiment," or "in certain embodiments" means that a particular reference element, structure, or characteristic described in connection with the embodiment is included in at least one embodiment. Thus, the appearances of the phrases "in one embodiment" or "in an embodiment" or "in another embodiment" or "in certain embodiments" in various places throughout this specification are not necessarily all referring to the same embodiment, and furthermore, particular elements, structures, or features may be combined in any suitable manner in one or more embodiments.
Definition of
In the present disclosure, the term "zeolite powder" is a water-rich aluminosilicate of Na, Ca, Ba, with Al as the main component2O3、SiO2Has the function of adsorption.
In the present disclosure, the term "forming additive" is an aid to obtain a certain shape and size from a loose granular or powdery raw material.
In the present disclosure, the term "adhesive" is also called "adhesive" and refers to a non-metal medium material for tightly connecting an object with another object.
In the present disclosure, the term "surface chemical modification" refers to the change of the structure and state of a substance surface by chemical means.
In this disclosure, the term "activation" is the burning off of the pore former in the material by calcination.
Detailed Description
The present disclosure relates to a method for preparing porous desulfurized zeolite particles comprising:
a first mixture made from zeolite powder, a shaping additive, foam particles;
a second mixture prepared from the first mixture, a glue and water; and
the second mixture is extruded and granulated, and is impregnated in a metal salt solution and then sintered at a high temperature.
The size of the pore channel of the zeolite particles is one of the important factors influencing the adsorption performance, and the adjustment of the pore diameter of the zeolite powder can be realized through the treatment of the foam particles, so that the selectivity of the zeolite particles to adsorbates and the diffusion mass transfer capacity are improved.
In certain embodiments, wherein the first mixture is made from 50 to 60 parts by weight zeolite powder, 30 to 40 parts by weight shape forming additive, 5 to 15 parts by weight foam particles.
In certain embodiments, the zeolite powder is selected from modified natural zeolites.
In certain embodiments, the zeolite powder has a particle size of 50 to 80 μm.
In certain embodiments, the shaping additive is selected from the group consisting of methylcellulose, hydroxypropyl methylcellulose, hydroxyethyl cellulose carboxymethyl cellulose, polycellulose, glass fiber, or mixtures thereof.
In certain embodiments, the foam particles are selected from polystyrene foam particles, polypropylene foam particles, polyurethane foam particles, or mixtures thereof.
In certain embodiments, the foam particles have a particle size of 1 to 3 mm.
In certain embodiments, the mixing time of the first mixture is 30 to 50 min.
In certain embodiments, the particle size of the first mixture is from 50 to 150 μm.
In certain embodiments, wherein the second mixture is prepared from 60 to 80 parts by weight of the first mixture, 15 to 25 parts by weight of the adhesive, and 5 to 15 parts by weight of water.
In certain embodiments, the adhesive is selected from the group consisting of silicates, aluminates, bentonite, attapulgite, or mixtures thereof.
In certain embodiments, the first mixture, binder, and water are mixed by a mixer to provide the second mixture.
In certain embodiments, the mixing time is 30 to 50 min.
In certain embodiments, the mixing temperature is from 20 to 40 ℃.
In certain embodiments, the mixer speed is from 60 to 100 r/min.
In certain embodiments, the second mixture is added to a forming machine for extrusion granulation and formed using a hollow structure die to form porous desulfurized zeolite particles.
In certain embodiments, the magnesium salt is selected from magnesium nitrate or magnesium carbonate.
In certain embodiments, the sodium salt is selected from sodium nitrate or sodium carbonate.
In certain embodiments, the potassium salt is selected from potassium nitrate or potassium carbonate.
In certain embodiments, the manganese salt is selected from manganese nitrate or manganese carbonate.
In certain embodiments, the hollow particles are also dried.
In certain embodiments, the drying time is 60 to 120 min.
In certain embodiments, the drying temperature is from 150 to 200 ℃.
In certain embodiments, a post-drying activation process is also included.
The dried material is placed in a roasting furnace to be calcined to form an activated product, and the pore-forming agent is burnt off to form a porous hollow structure.
In certain embodiments, the activation process is performed under an inert gas atmosphere.
In certain embodiments, the activation temperature is 450 to 550 ℃.
In certain embodiments, the activation time is from 2 to 4 hours.
Wherein, because the foam particles are flammable, the combustion temperature for removing the filler is reduced, thereby reducing the production cost of the zeolite particles.
In certain embodiments, the hollow particles are soaked in magnesium, sodium, potassium, or manganese salts such that the magnesium, sodium, potassium, or manganese salts are adsorbed on the outer surface of the hollow particles, and then sintered at high temperature to form metal oxides having an eggshell structure.
In certain embodiments, the porous desulfurized zeolite particles have an outer diameter of from 3 to 9mm and an inner diameter of from 1 to 6 mm.
Wherein the adsorptive desulfurization performance of the zeolite particles on the adsorbate is improved by increasing the number of pores of the zeolite particles.
Example 1
The embodiment discloses porous desulfurized zeolite particles, which are prepared by extruding and granulating a second mixture, wherein the first mixture is prepared from the following components in parts by weight: 50 parts of zeolite powder, 30 parts of forming additive and 5 parts of foam particles; the second mixture is prepared from the following components in parts by weight: 60 parts of the first mixture, 15 parts of a glue and 5 parts of water.
The preparation method comprises the following steps:
(1) mixing zeolite powder, molding additive and foam particles for 30 min;
(2) mixing the mixture, the adhesive and water at 20 ℃ for 30min by a mixer, wherein the rotating speed of the mixer is 60r/min, so as to obtain a second mixture;
(3) adding the mixture into a forming machine for extrusion granulation, and forming by adopting a hollow structure die to form hollow particles;
(4) the hollow particles were dried at 150 ℃ for 60 min.
(5) And (3) carrying out activation treatment on the hollow particles, wherein the activation treatment is preferably carried out in an inert gas atmosphere, wherein the activation temperature is 450 ℃, and the activation time is 2 h.
(6) Soaking the hollow particles in magnesium salt, sodium salt, potassium salt and manganese salt, and sintering at high temperature to obtain porous desulfurized zeolite particles with eggshell structure.
Example 2
The embodiment discloses porous desulfurized zeolite particles, which are prepared by extruding and granulating a second mixture, wherein the first mixture is prepared from the following components in parts by weight: 52 parts of zeolite powder, 32 parts of forming additive and 7 parts of foam particles; the second mixture is prepared from the following components in parts by weight: 62 parts of the first mixture, 17 parts of a glue, 7 parts of water.
The preparation method comprises the following steps:
(1) mixing zeolite powder, molding additive and foam particles for 30 min;
(2) mixing the mixture, the adhesive and water at 20 ℃ for 30min by a mixer, wherein the rotating speed of the mixer is 60r/min, so as to obtain a second mixture;
(3) adding the mixture into a forming machine for extrusion granulation, and forming by adopting a hollow structure die to form hollow particles;
(4) the hollow particles were dried at 150 ℃ for 60 min.
(5) And (3) carrying out activation treatment on the hollow particles, wherein the activation treatment is preferably carried out in an inert gas atmosphere, wherein the activation temperature is 450 ℃, and the activation time is 2 h.
(6) Soaking the hollow particles in magnesium salt, sodium salt, potassium salt and manganese salt, and sintering at high temperature to obtain porous desulfurized zeolite particles with eggshell structure.
Example 3
The embodiment discloses porous desulfurized zeolite particles, which are prepared by extruding and granulating a second mixture, wherein the first mixture is prepared from the following components in parts by weight: 54 parts of zeolite powder, 34 parts of forming additive and 9 parts of foam particles; the second mixture is prepared from the following components in parts by weight: 68 parts of the first mixture, 19 parts of a glue, 9 parts of water.
The preparation method comprises the following steps:
(1) mixing zeolite powder, molding additive and foam particles for 30 min;
(2) mixing the mixture, the adhesive and water at 20 ℃ for 30min by a mixer, wherein the rotating speed of the mixer is 60r/min, so as to obtain a second mixture;
(3) adding the mixture into a forming machine for extrusion granulation, and forming by adopting a hollow structure die to form hollow particles;
(4) the hollow particles were dried at 150 ℃ for 60 min.
(5) And (3) carrying out activation treatment on the hollow particles, wherein the activation treatment is preferably carried out in an inert gas atmosphere, wherein the activation temperature is 450 ℃, and the activation time is 2 h.
(6) Soaking the hollow particles in magnesium salt, sodium salt, potassium salt and manganese salt, and sintering at high temperature to obtain porous desulfurized zeolite particles with eggshell structure.
Example 4
The embodiment discloses porous desulfurized zeolite particles, which are prepared by extruding and granulating a second mixture, wherein the first mixture is prepared from the following components in parts by weight: 56 parts of zeolite powder, 36 parts of forming additive and 11 parts of foam particles; the second mixture is prepared from the following components in parts by weight: 72 parts of the first mixture, 21 parts of a glue, 11 parts of water.
The preparation method comprises the following steps:
(1) mixing zeolite powder, molding additive and foam particles for 30 min;
(2) mixing the mixture, the adhesive and water at 20 ℃ for 30min by a mixer, wherein the rotating speed of the mixer is 60r/min, so as to obtain a second mixture;
(3) adding the mixture into a forming machine for extrusion granulation, and forming by adopting a hollow structure die to form hollow particles;
(4) the hollow particles were dried at 150 ℃ for 60 min.
(5) And (3) carrying out activation treatment on the hollow particles, wherein the activation treatment is preferably carried out in an inert gas atmosphere, wherein the activation temperature is 450 ℃, and the activation time is 2 h.
(6) Soaking the hollow particles in magnesium salt, sodium salt, potassium salt and manganese salt, and sintering at high temperature to obtain porous desulfurized zeolite particles with eggshell structure.
Example 5
The embodiment discloses porous desulfurized zeolite particles, which are prepared by extruding and granulating a second mixture, wherein the first mixture is prepared from the following components in parts by weight: 58 parts of zeolite powder, 38 parts of forming additive and 13 parts of foam particles; the second mixture is prepared from the following components in parts by weight: 76 parts of the first mixture, 23 parts of a glue, 13 parts of water.
The preparation method comprises the following steps:
(1) mixing zeolite powder, forming additive and foam particles for 30-50 min;
(2) mixing the mixture, the adhesive and water at 20 ℃ for 30min by a mixer, wherein the rotating speed of the mixer is 60r/min, so as to obtain a second mixture;
(3) adding the mixture into a forming machine for extrusion granulation, and forming by adopting a hollow structure die to form hollow particles;
(4) the hollow particles were dried at 150 ℃ for 60 min.
(5) And (3) carrying out activation treatment on the hollow particles, wherein the activation treatment is preferably carried out in an inert gas atmosphere, wherein the activation temperature is 450 ℃, and the activation time is 2 h.
(6) Soaking the hollow particles in magnesium salt, sodium salt, potassium salt and manganese salt, and sintering at high temperature to obtain porous desulfurized zeolite particles with eggshell structure.
Example 6
The embodiment discloses porous desulfurized zeolite particles, which are prepared by extruding and granulating a second mixture, wherein the first mixture is prepared from the following components in parts by weight: 60 parts of zeolite powder, 40 parts of forming additive and 15 parts of foam particles; the second mixture is prepared from the following components in parts by weight: 80 parts of the first mixture, 25 parts of a glue, 15 parts of water.
The preparation method comprises the following steps:
(1) mixing zeolite powder, molding additive and foam particles for 30 min;
(2) mixing the mixture, the adhesive and water at 20 ℃ for 30min by a mixer, wherein the rotating speed of the mixer is 60r/min, so as to obtain a second mixture;
(3) adding the mixture into a forming machine for extrusion granulation, and forming by adopting a hollow structure die to form hollow particles;
(4) the hollow particles were dried at 150 ℃ for 60 min.
(5) And (3) carrying out activation treatment on the hollow particles, wherein the activation treatment is preferably carried out in an inert gas atmosphere, wherein the activation temperature is 450 ℃, and the activation time is 2 h.
(6) Soaking the hollow particles in magnesium salt, sodium salt, potassium salt and manganese salt, and sintering at high temperature to obtain porous desulfurized zeolite particles with eggshell structure.
Example 7
The hollow particles obtained in step (6) "of example 3 were immersed in magnesium salt, sodium salt, potassium salt, or manganese salt, and subjected to high-temperature sintering treatment to form porous desulfurized zeolite particles having an eggshell structure. "deleted" and other preparation conditions were unchanged.
The porous desulfurized zeolite particles prepared in examples 1 to 6 above were subjected to the BET specific surface area test, and the specific surface area, pore size, and pore volume parameters of the samples are shown in Table 1.
And (3) testing adsorption desulfurization performance:
the adsorption desulfurization effect of the porous desulfurization zeolite particles prepared in examples 1 to 7 was tested by a normal-temperature static adsorption experiment, and the specific operation steps were as follows: dissolving the phenprobucol in n-octane, and diluting to prepare 500ppm simulation oil. And (3) putting 10mL of simulated oil into a conical flask, adding 0.05g of porous desulfurized zeolite particles, adsorbing for 24 hours, filtering a liquid-phase product through a filter membrane, and analyzing the sulfur content by using gas chromatography.
The adsorptive desulfurization amounts of the porous desulfurization zeolite particles obtained in examples 1 to 7 are shown in Table 2.
To sum up: with the increase of the amount of the pore-forming agent-foam particles, the specific surface area, the pore volume and the size of the pore channel of the prepared porous desulfurized zeolite particles tend to increase first and then decrease; meanwhile, the hollow particles are soaked in magnesium salt, sodium salt and potassium salt to form an eggshell structure, so that the specific surface area, the pore volume and the pore channel size of the porous desulfurized zeolite particles can be effectively improved, and the sample has more excellent adsorption performance along with the increase of the specific surface area, the pore volume and the pore channel size. The porous hollow zeolite particles prepared by the method have better adsorption desulfurization capability.
TABLE 1
| Examples | Specific surface area/(m)2/g) | Pore volume/(cm)3/g) | Average pore diameter/nm |
| Example 1 | 420 | 0.56 | 7.8 |
| Example 2 | 456 | 0.76 | 16.9 |
| Example 3 | 580 | 0.89 | 22 |
| Example 4 | 525 | 0.77 | 19 |
| Example 5 | 486 | 0.50 | 17.3 |
| Example 6 | 412 | 0.46 | 14.6 |
| Example 7 | 386 | 0.12 | 5.2 |
TABLE 2
From the foregoing it will be appreciated that, although specific embodiments of the disclosure have been described herein for purposes of illustration, various modifications or improvements may be made by those skilled in the art without departing from the spirit and scope of the disclosure, and that such modifications or improvements are intended to be within the scope of the appended claims.
Claims (10)
1. A method of preparing porous desulfurized zeolite particles comprising:
a first mixture made from zeolite powder, a shaping additive, foam particles;
a second mixture prepared from the first mixture, a glue and water; and
the second mixture is extruded and granulated, and is impregnated in a metal salt solution and then sintered at a high temperature.
2. The method of claim 1, wherein the first mixture is prepared from 50 to 60 parts by weight of zeolite powder, 30 to 40 parts by weight of a shaping additive, and 5 to 15 parts by weight of foam particles.
3. A method of preparing porous desulphurised zeolite particles according to claim 1 or claim 2 wherein:
the zeolite powder is selected from modified natural zeolite, and preferably the particle size of the zeolite powder is 50-80 μm;
the forming additive is selected from methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose carboxymethyl cellulose, multi-polymeric cellulose, glass fiber or a mixture thereof;
the foam particles are selected from polystyrene foam particles, polypropylene foam particles, polyurethane foam particles or mixtures thereof, preferably the foam particles have a particle size of 1 to 3 mm.
4. A method of preparing porous desulphurised zeolite particles according to any one of claims 1 to 3 wherein the first mixture is mixed for a period of 30 to 50min and the first mixture has a particle size of 50 to 150 μm.
5. The method of claim 4, wherein the second mixture is prepared from 60 to 80 parts by weight of the first mixture, 15 to 25 parts by weight of the binder, and 5 to 15 parts by weight of water.
6. A process for preparing porous desulphurised zeolite particles according to claim 4 or 5 comprising: and mixing the first mixture, the adhesive and water by a mixer to obtain the second mixture, wherein the mixing time is preferably 30 to 50min, the mixing temperature is 20 to 40 ℃, and the rotating speed of the mixer is 60 to 100 r/min.
7. A process for preparing a porous desulphurised zeolite particle according to any one of claims 4 to 6 wherein:
adding the second mixture into a forming machine for extrusion granulation, and forming by adopting a hollow structure die to form hollow particles; and
and soaking the hollow particles in magnesium salt, sodium salt, potassium salt and manganese salt to form metal oxide with an eggshell structure on the outer layer of the porous zeolite particles, and finally obtaining the porous desulfurized zeolite particles.
8. The method of claim 7, wherein the hollow particles are further dried, preferably for a period of 60 to 120min at a temperature of 150 to 200 ℃.
9. The method of claim 7 or 8, further comprising an activation process after drying, preferably the activation process is performed under an inert gas atmosphere, more preferably the activation temperature is 450 to 550 ℃, more preferably the activation time is 2 to 4 hours.
10. The method for producing a porous desulfurized zeolite granule according to any one of claims 1 to 9, wherein said porous desulfurized zeolite granule has an outer diameter of 3 to 9mm and an inner diameter of 1 to 3 mm.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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