CN110980750A - 一种介孔硅酸镁的制备方法及其应用 - Google Patents
一种介孔硅酸镁的制备方法及其应用 Download PDFInfo
- Publication number
- CN110980750A CN110980750A CN201911349783.3A CN201911349783A CN110980750A CN 110980750 A CN110980750 A CN 110980750A CN 201911349783 A CN201911349783 A CN 201911349783A CN 110980750 A CN110980750 A CN 110980750A
- Authority
- CN
- China
- Prior art keywords
- silicate
- magnesium silicate
- magnesium
- mesoporous
- preparation
- 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.)
- Granted
Links
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000000391 magnesium silicate Substances 0.000 title claims abstract description 32
- 229910052919 magnesium silicate Inorganic materials 0.000 title claims abstract description 32
- 235000019792 magnesium silicate Nutrition 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 18
- 230000003197 catalytic effect Effects 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 10
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000004115 Sodium Silicate Substances 0.000 claims description 15
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 15
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 11
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 239000011259 mixed solution Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 abstract description 38
- 230000007062 hydrolysis Effects 0.000 abstract description 11
- 239000011148 porous material Substances 0.000 abstract description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 15
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 229910052749 magnesium Inorganic materials 0.000 description 8
- 238000009826 distribution Methods 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 238000003795 desorption Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000004763 sulfides Chemical group 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/22—Magnesium silicates
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
-
- 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
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28064—Surface area, e.g. B.E.T specific surface area being in the range 500-1000 m2/g
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/204—Alkaline earth metals
- B01D2255/2047—Magnesium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/308—Carbonoxysulfide COS
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Biomedical Technology (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
本发明公开了一种介孔硅酸镁的制备方法及其应用,其以镁盐和硅酸盐为原料,经过溶解、过滤、混合搅拌等处理步骤,调节pH值至8‑14,并将所得混合碱液在60‑110℃加热搅拌1‑8 h,经过洗涤、干燥后得到大比表面积的介孔硅酸镁。该方法采用无模板剂合成方法,大大降低了制备成本,同时所制备的硅酸镁具有较大的比表面积,良好的孔道结构和丰富的表面羟基,在羰基硫催化水解过程中展示出优异的催化活性。
Description
技术领域
本发明属于无机功能材料制备技术领域,具体涉及一种介孔硅酸镁的制备方法及其应用。
背景技术
全球经济迅猛增长,对能源的需求与日俱增。然而,能源的低效率使用造成严重的污染,环境问题愈加严重。大气中的污染物严重影响空气质量和威胁人类健康。有毒害的含硫化物是造成大气污染的重要原因。羰基硫(COS)是硫化物的典型代表,但其化学性质不活泼,在脱除上比较困难。
目前,工业上脱除COS的方法主要有加氢转化法、吸收法、氧化转化法、光解法、水解法。水解反应(COS+H2O→CO2+H2S)是工业上应用最为广泛的反应之一。γ-Al2O3是最常见的中低温COS水解催化剂载体,其本身具有一定的活性。进一步负载碱性组分后可明显增强碱性中心,进一步提高水解活性。但以γ-Al2O3为载体的催化剂稳定性一般,并且当原料气的含量高时,其转化率较低。活性炭因具有丰富的微孔结构和良好的电子传导性等特点,也被作为载体应用到COS水解反应中。但硫化物及硫酸盐的沉积易导致催化剂中毒,影响其寿命。专利CN106861665A公布了一种在γ-Al2O3上负载草酸钾的水解催化剂,所公布的催化剂具有优良的催化水解性能,但催化剂载体γ-Al2O3的制备需要多种模板剂,制备成本高,过程繁琐。专利CN101703928A公布了一种活性炭载体的水解催化剂,其制备过程简单,水解催化活性良好,但其抗硫酸盐性能较差,催化寿命较短。
基于上述问题,我们提出一种无模板制备大比表面介孔硅酸镁的制备方法。将镁盐和硅酸盐经过简单的溶解、过滤、混合搅拌处理后调节pH值至8-14,再进行简单热处理和洗涤后得到大比表面积的介孔硅酸镁。所制备的硅酸镁不仅比表面积大,且具有良好的孔道结构和丰富的表面羟基,可展示出优异的催化活性。
发明内容
本发明提供了一种介孔硅酸镁的制备方法及其应用,通过在无模板剂的合成条件下制备大比表面积的介孔硅酸镁,且具有丰富的表面羟基。所制备的介孔硅酸镁可应用于催化COS水解领域,在无需负载其他活性组分的条件下便可达到较高的催化转化率。
为实现上述目的,本发明采用如下技术方案:
以镁盐和硅酸盐为原料,经过溶解、过滤、混合搅拌,再通过碱液调节至一定的pH值,然后进行热处理、洗涤、干燥后得到介孔硅酸镁,可用于有机硫催化水解反应。
进一步地,所述的镁盐为氯化镁、硝酸镁、硫酸镁中的一种,所述的硅酸盐为硅酸钠,所用的碱液为氢氧化钠溶液或氢氧化钾溶液中的一种,镁盐和硅酸盐的摩尔比为0.5-2。
进一步地,所述的溶解过程是将可溶性镁盐和硅酸钠溶于水搅拌溶解,搅拌速率为500-800 rpm。
进一步地,所述的pH调节过程是通过逐滴滴加碱溶液的方式,将pH值调节至8-14。
进一步地,所述热处理的温度为60-110 ℃,热处理的时间为1-8 h。
进一步地,所述洗涤过程为用大量热去离子水洗涤至pH值为7。
所述的硅酸镁在COS催化水解反应中的应用,具体以COS和N2为原料气体,并通入水蒸气进行COS催化水解反应。原料气体流速为20 mL/min,反应温度为30~170 ℃,升温速率为3℃/min,反应中水蒸气温度为40℃。
本发明的优势在于:
1. 本发明制备的大比表面积硅酸镁,采用无模板法合成,与传统水热法和模板法相比,该方法制备工艺简单,制备过程无需模板即可得到大比表面积和介孔结构,成本更低,有利于大规模生产。
2. 本发明制备的介孔硅酸镁,可应用于COS水解,无需负载其他活性组分,而达到较高的催化转化率。
附图说明
图1为介孔硅酸镁的物理吸附的吸脱附曲线;
图2为介孔硅酸镁的孔径分布图。
具体实施方式
以下结合实施例进一步阐述本发明,但本发明的保护范围不限于下述实施例。为进一步说明本发明的实验操作及其实验结果,本部分结合发明的实施例进行更为详细的描述。
实施例1
称取6 g硫酸镁溶于17 ml去离子水中搅拌溶解,过滤并取其澄清液,得到硫酸镁溶液。称取5 g硅酸钠溶于13 ml去离子水中搅拌溶解,过滤并取其澄清液,得到硅酸钠溶液。将配制好的硅酸钠溶液逐滴加入配制好的硫酸镁溶液中。逐滴加入30 wt% 的氢氧化钠溶液,至体系pH为8。将得到的混合体系移入烧瓶中并于90 ℃油浴锅中保持3小时,混合体系冷却后用大量热水洗涤并过滤。得到的产物于烘箱120℃干燥24小时。产物记为硅酸镁-1,该催化剂的比表面积为361 m2/g。
实施例2
称取7 g硫酸镁溶于17 ml去离子水中搅拌溶解,过滤并取其澄清液,得到硫酸镁溶液。称取5 g硅酸钠溶于13 ml去离子水中搅拌溶解,过滤并取其澄清液,得到硅酸钠溶液。将配制好的硅酸钠溶液逐滴加入配制好的硫酸镁溶液中。逐滴加入30 wt% 的氢氧化钠溶液,至体系pH为13。将得到的混合体系移入烧瓶中并于120℃油浴锅中保持5小时,混合体系冷却后用大量热水洗涤并过滤。得到的产物于烘箱120 ℃干燥24小时。产物记为硅酸镁-2,该催化剂的比表面积为535 m2/g。
实施例3
称取10 g硫酸镁溶于17 ml去离子水中搅拌溶解,过滤并取其澄清液,得到硫酸镁溶液。称取5 g硅酸钠溶于13 ml去离子水中搅拌溶解,过滤并取其澄清液,得到硅酸钠溶液。将配制好的硅酸钠溶液逐滴加入配制好的硫酸镁溶液中。逐滴加入30 wt% 的氢氧化钾溶液,至体系pH为14。将得到的混合体系移入烧瓶中并于100 ℃油浴锅中保持5小时,混合体系冷却后用大量热水洗涤并过滤。得到的产物于烘箱120℃干燥24小时。产物记为硅酸镁-3,该催化剂的比表面积为599 m2/g。
实施例4
称取12 g硫酸镁溶于17 ml去离子水中搅拌溶解,过滤并取其澄清液,得到硫酸镁溶液。称取5 g硅酸钠溶于13 ml去离子水中搅拌溶解,过滤并取其澄清液,得到硅酸钠溶液。将配制好的硅酸钠溶液逐滴加入配制好的硫酸镁溶液中。逐滴加入30 wt% 的氢氧化钾溶液,至体系pH为9。将得到的混合体系移入烧瓶中并于90℃油浴锅中保持3小时,混合体系冷却后用大量热水洗涤并过滤。得到的产物于烘箱120 ℃干燥24小时。产物记为硅酸镁-4,该催化剂的比表面积为356 m2/g。
参比例1
采用商业γ-Al2O3脱硫催化剂(国药集团化学试剂有限公司),动态平衡水吸附量≥25%(100% RH,20 ℃),堆积密度≤0.96 g/ml,抗压强度≥50 N,记为催化剂A。
参比例2
采用商业分子筛SBA-15(南京吉仓纳米科技有限公司),记为催化剂B。
表征分析:
N2物理吸附:采用美国Micrometric公司的TriStarⅡ 3020分析仪在液氮温度(-196℃)下进行测定样品比表面积和孔尺寸,样品先在180℃下脱气6 h,用BET(Brunauer-Emmett-Teller )法计算样品的比表面积,孔径分布曲线根据BJH(Barrett-Joyner-Halenda)法求出。
如图1所示,为本发明实例1~4的硅酸镁样品的N2物理吸脱附曲线。从N2物理吸脱附曲线中可以看出,硅酸镁-1的曲线均呈现I型吸脱附曲线,说明样品中微孔和大孔所占的比例较大,介孔含量相对较小。硅酸镁2~4样品的曲线均呈现IV型吸脱附曲线以及H2型滞后环,说明样品中均存在介孔结构。
如图2所示,为本发明实施例1~4的硅酸镁样品的孔径分布图。孔径分布图主要显示了样品介孔的分布情况。从孔径分布图中可以看出样品均含有丰富的介孔,孔径分布主要集中在3-4 nm。
COS水解催化性能测试:
催化性能测试条件:催化剂质量为0.2 g,原料气浓度为110 mg/cm3 COS/N2,原料气浓度为20 ml/min-1,反应管内径为5 mm,反应物中的水蒸气温度为40℃,活性以COS的转化率(%)表示。测试结果由表1所示。
表1为本发明实施例 1~4,对比例A和B的催化水解COS反应的COS转化率表。
由表中数据可以看出,无模板法制备的大比表面积硅酸镁具有优异的COS催化效率。其中硅酸镁-2的COS转化率要明显高于其它硅酸镁材料和对比催化剂,硅酸镁-2在70℃时COS的转化率便可达到45.8%,在130℃时COS的转化率便可达到100%。且随着温度的进一步升高其活性保持不变。与对比样γ-Al2O3和SBA-15催化剂相比,硅酸镁-2在COS水解反应中的具有明显的催化性能优势,尤其在低温反应区域。
以上所述的具体实施方式,对本发明的目的、技术方案和有益效果进行了进一步详细说明,所应理解的是,以上所述仅为本发明的具体实施方式而已,并不用于限定本发明的保护范围,凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (7)
1.一种介孔硅酸镁的制备方法,其特征在于:所述制备方法包括以下步骤:以镁盐和硅酸盐为原料,经过溶解、过滤、混合搅拌后得到混合溶液,再使用碱液调节pH值,然后进行热处理、洗涤、干燥后得到介孔硅酸镁。
2.根据权利要求1所述的介孔硅酸镁的制备方法,其特征在于:所述镁盐为氯化镁、硝酸镁、硫酸镁中的一种,所述硅酸盐为硅酸钠,所述镁盐与硅酸盐的摩尔比为0.5-2,所用碱液为氢氧化钠溶液或氢氧化钾溶液。
3.根据权利要求1所述的介孔硅酸镁的制备方法,其特征在于:所述的溶解过程是以水为溶剂,并将镁盐和硅酸盐溶于水后剧烈搅拌溶解,溶解搅拌速度为500~800 rpm。
4.根据权利要求1所述的介孔硅酸镁的制备方法,其特征在于:所述调节pH值是通过逐滴滴加碱液的方式进行调整,pH值为8-14。
5.根据权利要求1所述的介孔硅酸镁的制备方法,其特征在于:所述热处理的温度为60-110℃,热处理的时间为1-8 h。
6.根据权利要求1所述的介孔硅酸镁的制备方法,其特征在于:所述洗涤过程是用热去离子水进行多次洗涤,洗至pH值为7。
7.一种如权利要求1-6任一项所述介孔硅酸镁的制备方法制得的介孔硅酸镁在COS催化水解反应中的应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201911349783.3A CN110980750B (zh) | 2019-12-24 | 2019-12-24 | 一种介孔硅酸镁的制备方法及其应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201911349783.3A CN110980750B (zh) | 2019-12-24 | 2019-12-24 | 一种介孔硅酸镁的制备方法及其应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN110980750A true CN110980750A (zh) | 2020-04-10 |
CN110980750B CN110980750B (zh) | 2022-10-21 |
Family
ID=70076401
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201911349783.3A Active CN110980750B (zh) | 2019-12-24 | 2019-12-24 | 一种介孔硅酸镁的制备方法及其应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN110980750B (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113511657A (zh) * | 2021-05-21 | 2021-10-19 | 镁力新生生物科技有限公司 | 一种高比表面积硅酸镁纳米粉体、制备方法及应用 |
CN113694878A (zh) * | 2021-08-27 | 2021-11-26 | 浙江皇马科技股份有限公司 | 一种硅酸镁吸附剂的制备方法及应用 |
CN114849673A (zh) * | 2022-05-31 | 2022-08-05 | 浙江皇马科技股份有限公司 | 一种制备高比表面积硅酸镁吸附剂的方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0169828A2 (fr) * | 1984-07-25 | 1986-01-29 | Labofina S.A. | Procédé pour enlever le sulfure de carbonyle des charges d'hydrocarbures liquides oléfiniques |
EP0190480A1 (en) * | 1985-02-05 | 1986-08-13 | The Dow Chemical Company | Magnesium silicate compositions, process for their preparation and alkylation process employing same |
WO2010023249A1 (de) * | 2008-09-01 | 2010-03-04 | Basf Se | Adsorbermaterial und verfahren zur entschwefelung von kohlenwasserstoffhaltigen gasen |
CN106237975A (zh) * | 2016-08-09 | 2016-12-21 | 北京化工大学 | 一种高比表面大孔容硅酸镁吸附材料及其制备方法和应用 |
CN107500303A (zh) * | 2017-08-14 | 2017-12-22 | 曲阜师范大学 | 一种介孔硅酸镁微球及其水热‑热转化制备方法 |
CN110479251A (zh) * | 2019-08-15 | 2019-11-22 | 鲁西催化剂有限公司 | 一种大孔-介孔负载型钯催化剂及其制备方法和应用 |
-
2019
- 2019-12-24 CN CN201911349783.3A patent/CN110980750B/zh active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0169828A2 (fr) * | 1984-07-25 | 1986-01-29 | Labofina S.A. | Procédé pour enlever le sulfure de carbonyle des charges d'hydrocarbures liquides oléfiniques |
EP0190480A1 (en) * | 1985-02-05 | 1986-08-13 | The Dow Chemical Company | Magnesium silicate compositions, process for their preparation and alkylation process employing same |
WO2010023249A1 (de) * | 2008-09-01 | 2010-03-04 | Basf Se | Adsorbermaterial und verfahren zur entschwefelung von kohlenwasserstoffhaltigen gasen |
CN106237975A (zh) * | 2016-08-09 | 2016-12-21 | 北京化工大学 | 一种高比表面大孔容硅酸镁吸附材料及其制备方法和应用 |
CN107500303A (zh) * | 2017-08-14 | 2017-12-22 | 曲阜师范大学 | 一种介孔硅酸镁微球及其水热‑热转化制备方法 |
CN110479251A (zh) * | 2019-08-15 | 2019-11-22 | 鲁西催化剂有限公司 | 一种大孔-介孔负载型钯催化剂及其制备方法和应用 |
Non-Patent Citations (2)
Title |
---|
KATABATHINI NARASIMHARAOA ET AL.: ""Effect of Si precursor on structural and catalytic properties of nanosize magnesium silicates"", 《APPLIED CATALYSIS A-GENERAL》 * |
冯凌等: ""共沉淀法合成三硅酸镁及其微观分析"", 《北京科技大学学报》 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113511657A (zh) * | 2021-05-21 | 2021-10-19 | 镁力新生生物科技有限公司 | 一种高比表面积硅酸镁纳米粉体、制备方法及应用 |
CN113694878A (zh) * | 2021-08-27 | 2021-11-26 | 浙江皇马科技股份有限公司 | 一种硅酸镁吸附剂的制备方法及应用 |
CN114849673A (zh) * | 2022-05-31 | 2022-08-05 | 浙江皇马科技股份有限公司 | 一种制备高比表面积硅酸镁吸附剂的方法 |
Also Published As
Publication number | Publication date |
---|---|
CN110980750B (zh) | 2022-10-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN110980750B (zh) | 一种介孔硅酸镁的制备方法及其应用 | |
CN111790350B (zh) | 一种氮掺杂炭材料的制备方法及其在脱除含硫气体中的应用 | |
CN114308042B (zh) | 一种凹凸棒石基有序微孔沸石催化剂及其制备方法与应用 | |
CN112371173B (zh) | 一种应用于间硝基苯磺酸加氢的铂炭催化剂及其制备方法 | |
KR20210024148A (ko) | 다공질 탄소의 제조 방법 및 이 제조 방법에 의해 제조된 다공질 탄소를 포함하는 전극 및 촉매 담체 | |
CN114887654B (zh) | 分子筛基纳米炭包覆的负载型高级氧化催化剂及制备方法 | |
CN113772656B (zh) | 一种金属盐辅助制备多孔碳材料的方法及其应用 | |
CN114029048B (zh) | 一种多孔碳包裹的氧化钨催化剂的制备方法及应用 | |
CN111468118A (zh) | 碳包覆过渡金属的纳米复合材料及其制备方法和应用 | |
CN107473218B (zh) | 官能团定向分布的有序分级孔碳材料及其制备方法和在烟气脱硫中的应用 | |
CN111804293A (zh) | 一种多孔氧化铝负载过渡金属的制备方法及其在脱除cos中的应用 | |
CN109248689B (zh) | 一种大孔氧化物催化剂 | |
CN114522691B (zh) | 一种用于有机硫催化水解的复合金属氧化物的制备方法 | |
CN111135857A (zh) | 还原型催化剂的制备方法及其用途 | |
CN114160181B (zh) | 一种用于脱除有机硫的核壳催化剂及其制备方法和应用 | |
CN107473219B (zh) | 有序分级孔碳材料的烟气脱硫再生方法 | |
CN114433055B (zh) | 一种具有高度开放多级孔结构的碳催化剂及其制备方法和应用 | |
CN111468154A (zh) | 碳包覆过渡金属的纳米复合材料及其制备方法和应用 | |
CN112473721A (zh) | 一种PdAg/NH2-MCM-41催化剂及其制备方法和应用 | |
CN111977663A (zh) | 一种多级孔道结构沸石分子筛及其制备方法和应用 | |
CN116196936B (zh) | 一种甲醇蒸汽重整制氢球形微介孔复合材料催化剂及其制备方法与应用 | |
CN114479096A (zh) | 一种双配体金属有机骨架材料及其制备方法与应用 | |
CN112264022A (zh) | 蜂窝状有机硫水解催化剂及其制备方法和应用 | |
CN110694659A (zh) | 一种分层多孔氮掺杂碳材料及其制备方法和应用 | |
CN114073945B (zh) | 一种复合氧化铝催化剂及其制备方法和应用 |
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 |