CN111482158A - Preparation system of pure silicon zeolite-3 adsorbent without adhesive - Google Patents
Preparation system of pure silicon zeolite-3 adsorbent without adhesive Download PDFInfo
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- CN111482158A CN111482158A CN202010194252.8A CN202010194252A CN111482158A CN 111482158 A CN111482158 A CN 111482158A CN 202010194252 A CN202010194252 A CN 202010194252A CN 111482158 A CN111482158 A CN 111482158A
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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
- B01J20/02—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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- 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
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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
- B01J20/28002—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 physical properties
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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
- B01J20/28078—Pore diameter
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/82—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by solid-liquid treatment; by chemisorption
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
The invention provides a preparation system of pure silicon zeolite-3 adsorbent without adhesive, comprising: placing the quartz boat or ceramic boat containing the precursor binderless pure silicon zeolite-1 adsorbent particles in a quartz tube or corundum tube in a tubular high-temperature electric furnace hearth, a pipe orifice at one side of the quartz tube or the corundum tube is provided with a pipeline externally connected with an air source, the externally connected air source is connected with a gas steel cylinder, when in use, a pressure reducing valve of the gas steel cylinder releases gas to enter a humidifying device, when the water introduced into the humidifying pipe by the carrier gas through the pipeline is saturated by the water vapor of the humidifying pipe, the humidified gas enters a quartz pipe or a corundum pipe of the tubular electric furnace to be the atmosphere required to be kept for roasting the precursor binderless pure silicon silicalite-1 adsorbent, the precursor loaded by the quartz boat or the ceramic boat is transformed into the pure silicon zeolite-3 adsorbent without the adhesive due to the great shrinkage of crystal lattices at high temperature.
Description
Technical Field
The invention relates to the technical field of silicon dioxide zeolite, in particular to a preparation system of a pure silicon zeolite-3 adsorbent without an adhesive.
Background
In the prior art, a zeolite molecular sieve composed of pure silica as a framework element can be called as pure silicalite (Allsilica zeolite), and the structure of the zeolite molecular sieve has higher thermal stability and hydrothermal stability, but because the framework structure of the zeolite does not have aluminum atoms, solid acid property and strong water adsorption centers, the zeolite molecular sieve presents inert and hydrophobic and organophilic adsorption characteristics to catalytic property, so that the zeolite is particularly suitable for being used in catalyst carriers, adsorption separation of small molecular isomers, removal of organic matters in waste water and waste gas and the like.
According to incomplete statistics, 28 kinds of silicalite which are synthesized in the prior art and given structure codes by international zeolite molecular sieve association (IZA) have respective characteristic XRD spectrums and have regular open pore channels or pore cages with different sizes in the framework structure, in addition, zeolites with a plurality of structures, such as MOR (mordenite ), L T L (L zeolite) and the like are prepared by chemical dealumination to extract aluminum on a silica-alumina framework structure but keep the crystal structure completely, at present, 8 kinds of silicalite structure types commonly used in international industrial production are classified according to the pore size, the left and right of the pore size 4A is called small pore, the left and right of the pore size 5A is called medium pore, the left and right of the pore size 7A is called large pore, and the left and right of the pore size 7A are called large pore, and the 4 kinds of silicalite with different size ranges are respectively suitable for adsorption fractions of molecules with different sizesThe small-pore silicalite is suitable for adsorbing, separating and enriching small-molecular hydrocarbons, such as methane, ethane, ethylene, propane and propylene, and can also be used for removing ammonia, CO and CO2、SO2、NOx、HCN、H2S, CSO, and the like. The mesoporous silica zeolite is mainly used for adsorbing, separating or removing C4-C7 hydrocarbon, separating isomers of disubstituted aromatic hydrocarbon derivatives and the like. The large-pore silicon zeolite is mainly used for adsorbing, separating or removing hydrocarbons above C8, in particular heavy aromatic hydrocarbon derivatives or polycyclic aromatic hydrocarbons and the like.
For adsorption separation, zeolite powder is bound by a binder to form adsorbents in different shapes such as spheres, columns, hollow columns or honeycombs so as to be filled in an adsorption bed for use. In order to ensure that the adsorbent packed in the adsorbent bed is not crushed due to too high packed layer or pulverized by high velocity gas stream impact during repeated adsorption/desorption use to wear and block valves, it is necessary to provide the formed adsorbent with a certain compressive strength and a low degree of pulverization by attrition. In addition, the adsorbent contains amorphous binder which belongs to non-zeolite substances and does not have the adsorption performance of zeolite, and the addition of the amorphous binder accounting for 15-40% of the total weight of the adsorbent is usually required for ensuring that the adsorbent has the pressure resistance reaching the industrial product, so that the effective components in the adsorbent are necessarily reduced correspondingly. For the adsorption and separation engineering, the diffusion speed of adsorbed and desorbed molecules in the adsorbent is inevitably hindered by the binder in the adsorbent or the zeolite orifice is blocked by the binder to be obviously reduced, so that the efficiency of the adsorption and separation process is obviously reduced. The invention 'a hydrophobic silicon zeolite adsorbent without adhesive and its preparation method' (Chinese invention patent, application No. 94112035, X, application No. 1995.08.02) proposes that ZSM-5 type hydrophobic zeolite powder and adhesive containing silicon dioxide are mixed and formed, dried, treated in organic amine or quaternary ammonium base solution or steam under hydrothermal condition, dried and roasted to obtain the adsorbent. The invention of Chinese patent 'BEA type non-adhesive high silicon hydrophobic zeolite adsorbent and its preparation method' (application No. 201010022790.5, published Japanese 2010.06.30, published Japanese 2010.01.14) proposes that commercially available nano-type BEA zeolite powder is used as raw material, silica-rich amorphous silica-alumina gel is added to form into particles, the particles are in-situ transformed under hydrothermal condition, and then the particles are subjected to inorganic acid dealumination and water vapor hydrophobization treatment at high temperature to prepare the adsorbent.
The binder-free hydrophobic ZSM-5 type zeolite adsorbent and the BEA type hydrophobic zeolite adsorbent are prepared by respectively taking ZSM-5 zeolite powder or BEA zeolite as raw materials, adding amorphous silica-containing binder, molding, carrying out crystal transformation, and carrying out water vapor hydrophobization treatment, namely the target product and the raw material powder are the zeolite molecular sieve with the same structure type. Therefore, the effective adsorption pore diameter of the prepared adsorbent product is the same as that of the raw material powder, and the separation selectivity of the adsorbent product on organic molecules with different molecular sizes is very similar.
The Chinese invention patent 'a new structure Silicalite' (application No. 201910825855.0; application No. 2019.09.03) and the Chinese invention patent 'a new structure Silicalite synthesis process' (application No. 201910825854.6; application No. 2019.09.03) disclose the structural characteristics of a new structure zeolite powder named as Silicalite-3 (Silicalite-3) and the synthesis method and process thereof. The characteristic diffraction line of zeolite-silicalite-3 of this structure is d ═ 10.71 ± 0.1a (vs); 9.62 ± 0.1a (vs); 5.75 ± 0.05 a(s); 4.16 ± 0.02a (m); 3.70. + -. 0.01A (vs). The pore diameters of the two pore openings in the structure are respectively 4.4x5.6A and 5.1 x5.7A. The new structure Silicalite-3 (Silicalite-3) zeolite powder is prepared by calcining precursor pure Silicalite-1 (Silicalite-1) zeolite powder synthesized by hydrothermal reaction of high-purity fumed silica or tetraethoxysilane at a temperature of more than 500 ℃ in a certain atmosphere for a certain time to severely shrink the crystal lattice. Since the structural pore diameter of the zeolite with the Silicalite-3 (Silicalite-3) structure is obviously smaller than the pore diameter in the corresponding direction of the precursor Silicalite-1 (Silicalite-1), it can be expected that when an adsorbent prepared by using the Silicalite-1 (Silicalite-1) zeolite powder and a binder is used for adsorption separation of a certain organic small molecule system with similar molecular size (such as benzene disubstituted series isomer mixture, such as mixed xylene, mixed diethylbenzene, mixed dichlorobenzene, mixed xylenol and the like), if the phenomena of low adsorption separation selectivity and poor separation efficiency occur, the binder-free pure Silicalite-3 (Silicalite-3) adsorbent provided by the invention can be considered to be used instead.
Disclosure of Invention
In this summary, concepts in a simplified form are introduced that are further described in the detailed description section. This summary of the invention is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used as an aid in determining the scope of the claimed subject matter. To at least partially solve the above technical problems, the present invention provides a binder-free pure silicalite-3 adsorbent preparation system comprising: a tubular high-temperature electric furnace; a quartz tube or a corundum tube is placed in a hearth of the tubular high-temperature electric furnace, a quartz boat or a ceramic boat containing precursor binderless pure silicon zeolite-1 adsorbent particles is placed in the quartz tube or the corundum tube, a pipe orifice at one side of the quartz tube or the corundum tube is provided with a pipeline externally connected with an air source, the externally connected air source is connected with a gas steel cylinder, when the tubular high-temperature electric furnace is used, a pressure reducing valve of the gas steel cylinder releases air to enter a humidifying device, and the humidifying device is composed of a constant-temperature water tank and a humidifying tube; when the carrier gas is introduced into the water of the humidifying pipe through the pipeline, the carrier gas is saturated by the water vapor of the humidifying pipe; the humidity of the gas flowing out of the humidifying pipe can be controlled within the range of 10-50% of relative humidity by adding ice into the constant-temperature water tank or increasing the temperature of the constant-temperature water tank to a certain degree to keep constant temperature. The humidified gas enters a quartz tube or a corundum tube of the tubular electric furnace, a quartz boat or a ceramic boat is arranged in the quartz tube or the corundum tube of the tubular electric furnace, the precursor binderless pure silicon zeolite-1 adsorbent loaded by the quartz boat or the ceramic boat is heated to above 650 ℃ in the atmosphere, the time is 1-4 hours, and the binderless pure silicon zeolite-1 adsorbent is transformed into the binderless pure silicon zeolite-3 adsorbent due to the large shrinkage of crystal lattices at high temperature.
Furthermore, the electronic temperature controller for the tubular high-temperature electric furnace controls the heating temperature, and the precision is +/-1 ℃.
Further, the gas in the gas cylinder may be any one of air, nitrogen, oxygen, and carbon dioxide.
Further, synthesizing a precursor binderless pure-silicon zeolite-1 adsorbent through a hydrothermal reaction, wherein the hydrothermal reaction uses a stainless steel pressure-resistant reaction kettle which is 1000m L capacity and is covered by 4F, amorphous pure silicon dioxide is used as a binder and is prepared into granules which are placed in the stainless steel pressure-resistant reaction kettle, a template agent R is added into the reaction kettle according to the proportion, the stainless steel reaction kettle is sealed and then placed in an oven to be heated to 120 ℃ and 200 ℃ for the hydrothermal reaction time of 5-100 hours, the reaction kettle is cooled after the reaction is finished, a reaction product is taken out, filtered, washed, dried and roasted to 450 ℃ and 500 ℃ for removing the template agent R, and the binderless pure-silicon zeolite-1 adsorbent of the precursor is prepared, and the binderless pure-silicon zeolite-3 adsorbent is roasted at a high temperature by the binderless pure-silicon zeolite-1 adsorbent of the precursor.
Compared with the prior art, the invention has the technical effects that: the method is characterized in that pure silicon zeolite-1 zeolite molecular sieve powder is used as a raw material, an adsorbent formed by using amorphous pure silicon dioxide as a binder is transformed into the binder-free silicon zeolite-1 adsorbent through gas-solid phase or liquid-solid phase hydrothermal reaction in water or a mixed medium containing water and an organic guiding agent, the binder-free silicon zeolite-1 adsorbent is used as a precursor, and the precursor is roasted at high temperature under a certain atmosphere to shrink unit cells of the precursor to prepare the binder-free pure silicon zeolite-3 adsorbent. Because the adsorption pore diameter of the binderless pure silicalite-3 adsorbent is obviously smaller than that of the binderless pure silicalite-1 adsorbent, the binderless pure silicalite-3 adsorbent is expected to selectively adsorb para-isomer such as para-cresol in a mixture of mixed benzene disubstituted isomers such as mixed cresol isomers in a shape selective manner, so that the binderless pure silicalite-3 adsorbent is practically applied to a shape selective separation adsorbent with excellent properties in adsorption engineering. Meanwhile, the pure silicon zeolite-3 adsorbent without the adhesive has good oleophylic and hydrophobic adsorption properties, and can be used for adsorption separation of small molecular isomers, catalyst carriers and removal of organic matters in waste water and waste gas.
Drawings
In order that the advantages of the invention will be readily understood, a more particular description of the invention briefly described above will be rendered by reference to specific embodiments that are illustrated in the appended drawings. Understanding that these drawings depict only typical embodiments of the invention and are not therefore to be considered to be limiting of its scope, the invention will be described and explained with additional specificity and detail through the use of the accompanying drawings.
FIG. 1 is a schematic diagram of a system for preparing a binderless pure silicalite-3 adsorbent according to the present invention.
Detailed Description
Preferred embodiments of the invention are described below. It should be understood by those skilled in the art that these embodiments are only for explaining the technical principle of the invention, and do not limit the scope of the invention.
The embodiment of the invention provides a preparation system of pure silicon zeolite-3 adsorbent without adhesive, which comprises the following components: a tubular high-temperature electric furnace; a quartz tube or a corundum tube is placed in a hearth of the tubular high-temperature electric furnace, a quartz boat or a ceramic boat containing precursor binderless pure silicon zeolite-1 adsorbent particles is placed in the quartz tube or the corundum tube, a pipe orifice at one side of the quartz tube or the corundum tube is provided with a pipeline externally connected with an air source, the externally connected air source is connected with a gas steel cylinder 1, when the tubular high-temperature electric furnace is used, a pressure reducing valve 2 of the gas steel cylinder releases gas to enter a humidifying device, and the humidifying device is composed of a constant-temperature water tank 3 and a humidifying tube 4; when the carrier gas is introduced into the water of the humidifying pipe 4 through the pipeline, the carrier gas is saturated by the water vapor of the humidifying pipe 4; the humidity of the gas flowing out of the humidifying pipe 4 can be controlled within the range of 10-50% of relative humidity by adding ice into the constant-temperature water tank 3 or increasing the temperature of the constant-temperature water tank to a certain degree to keep constant temperature. The humidified gas enters a quartz tube or a corundum tube of the tubular electric furnace 6, a quartz boat or a ceramic boat 7 is arranged in the quartz tube or the corundum tube of the tubular electric furnace 6 for roasting the precursor binderless pure silicon zeolite-1 adsorbent, the precursor binderless pure silicon zeolite-1 adsorbent loaded by the quartz boat or the ceramic boat 7 is heated to above 650 ℃ in the atmosphere for 1-4 hours, and the binderless pure silicon zeolite-1 adsorbent is transformed into the binderless pure silicon zeolite-3 adsorbent due to the large shrinkage of crystal lattices at high temperature.
Specifically, the electronic temperature controller for the tubular high-temperature electric furnace controls the heating temperature, and the precision is +/-1 ℃.
Specifically, the gas in the gas cylinder may be any one of air, nitrogen, oxygen, and carbon dioxide.
Specifically, a precursor binderless pure silicon zeolite-1 adsorbent is synthesized through a hydrothermal reaction, in the process, a stainless steel pressure-resistant reaction kettle which is covered by a capacity zone of 1000m L and 4F is used for the hydrothermal reaction, amorphous pure silicon dioxide is used as a binder and is prepared into granules, a template agent R is added into the reaction kettle according to the proportion, the stainless steel reaction kettle is sealed and then placed in an oven to be heated to 120-200 ℃, the hydrothermal reaction time is 5-100 hours, after the reaction is finished, the reaction kettle is cooled, a reaction product is taken out to be filtered, washed, dried and roasted to 450-500 ℃, the template agent R is removed, and the precursor binderless pure silicon zeolite-1 adsorbent is prepared, and the precursor binderless pure silicon zeolite-1 adsorbent is roasted at a high temperature to obtain the binderless pure silicon zeolite-3 adsorbent.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. A binderless pure silicalite-3 adsorbent production system, comprising:
a tubular high-temperature electric furnace; a quartz tube or a corundum tube is placed in a hearth of the tubular high-temperature electric furnace, particles containing the precursor binderless pure silicon zeolite-1 adsorbent are placed in the quartz tube or the corundum tube, a tube orifice at one side of the quartz tube or the corundum tube is provided with a pipeline of an external gas source, the external gas source is connected with a gas steel cylinder, a pressure reducing valve of the gas steel cylinder releases gas to enter a humidifying device, the humidified gas enters the quartz tube or the corundum tube of the tubular high-temperature electric furnace, the loaded particles of the precursor binderless pure silicon zeolite-1 adsorbent are heated in the atmosphere, and the binderless pure silicon zeolite-1 adsorbent is calcined at high temperature to generate lattice shrinkage and is transformed into the binderless pure silicon zeolite-3 adsorbent.
2. The system of claim 1, wherein the humidification device is comprised of a constant temperature water tank and a humidification tube.
3. The system of claim 1, wherein the heating temperature is 120 ℃ and 200 ℃ for 5-100 h.
4. The system of claim 1, wherein the tubular high temperature electric furnace is heated with an electronic temperature controller to a precision of ± 1 ℃.
5. The system of claim 1, wherein the gas in the gas cylinder is any one of air, nitrogen, oxygen, or carbon dioxide.
6. The binderless pure silicalite-3 adsorbent production system of claim 1 wherein the relative humidity of the gas in the humidifying tubes is 10-50%.
7. The system of claim 1, wherein the atmosphere is a mixture of air and oxygen having a relative humidity of 10-40%.
8. The system of claim 1, wherein the high temperature calcination is performed at 500-850 ℃ for 1-4 hours.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1105906A (en) * | 1994-01-29 | 1995-08-02 | 复旦大学 | Hydrophobic silicon zeolite adsorbent without cohesive agent and its preparation |
| WO2004113227A1 (en) * | 2003-06-20 | 2004-12-29 | Mitsubishi Chemical Corporation | Zeolite, method for production thereof, adsorbent comprising said zeolite, heat utilization system, adsorption heat pump, heating and cooling storage system and humidity controlling air-conditioning apparatus |
| CN1806908A (en) * | 2005-10-27 | 2006-07-26 | 复旦大学 | Macroporous zeolite absorbent and preparation method thereof |
| CN101757889A (en) * | 2010-01-14 | 2010-06-30 | 上海复旭分子筛有限公司 | BEA type binder-free dewatering silica-rich zeolite adsorbent and preparation method thereof |
| CN110683556A (en) * | 2019-09-03 | 2020-01-14 | 复榆(张家港)新材料科技有限公司 | Novel structure silicon dioxide zeolite |
| CN110683555A (en) * | 2019-09-03 | 2020-01-14 | 复榆(张家港)新材料科技有限公司 | Synthesis process of new structure silicon dioxide zeolite |
-
2020
- 2020-03-19 CN CN202010194252.8A patent/CN111482158A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1105906A (en) * | 1994-01-29 | 1995-08-02 | 复旦大学 | Hydrophobic silicon zeolite adsorbent without cohesive agent and its preparation |
| WO2004113227A1 (en) * | 2003-06-20 | 2004-12-29 | Mitsubishi Chemical Corporation | Zeolite, method for production thereof, adsorbent comprising said zeolite, heat utilization system, adsorption heat pump, heating and cooling storage system and humidity controlling air-conditioning apparatus |
| CN1806908A (en) * | 2005-10-27 | 2006-07-26 | 复旦大学 | Macroporous zeolite absorbent and preparation method thereof |
| CN101757889A (en) * | 2010-01-14 | 2010-06-30 | 上海复旭分子筛有限公司 | BEA type binder-free dewatering silica-rich zeolite adsorbent and preparation method thereof |
| CN110683556A (en) * | 2019-09-03 | 2020-01-14 | 复榆(张家港)新材料科技有限公司 | Novel structure silicon dioxide zeolite |
| CN110683555A (en) * | 2019-09-03 | 2020-01-14 | 复榆(张家港)新材料科技有限公司 | Synthesis process of new structure silicon dioxide zeolite |
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Application publication date: 20200804 |