CN1033800C - 二氧化钛挤压物 - Google Patents
二氧化钛挤压物 Download PDFInfo
- Publication number
- CN1033800C CN1033800C CN90101299A CN90101299A CN1033800C CN 1033800 C CN1033800 C CN 1033800C CN 90101299 A CN90101299 A CN 90101299A CN 90101299 A CN90101299 A CN 90101299A CN 1033800 C CN1033800 C CN 1033800C
- Authority
- CN
- China
- Prior art keywords
- mixture
- weight
- ammonia
- alkanolamine
- titanium dioxide
- 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.)
- Expired - Lifetime
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims description 122
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 21
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 13
- 239000004408 titanium dioxide Substances 0.000 claims description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 229910021536 Zeolite Inorganic materials 0.000 claims description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 7
- 239000010457 zeolite Substances 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 3
- 229960001866 silicon dioxide Drugs 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 13
- 229930195733 hydrocarbon Natural products 0.000 abstract description 6
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 6
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000007789 gas Substances 0.000 abstract description 4
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 239000000969 carrier Substances 0.000 abstract 1
- 238000004898 kneading Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 229920000034 Plastomer Polymers 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 7
- -1 clearly Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920000867 polyelectrolyte Polymers 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 230000009183 running Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 239000003979 granulating agent Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- ZWRUINPWMLAQRD-UHFFFAOYSA-N n-Nonyl alcohol Natural products CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 1
- MWKFXSUHUHTGQN-UHFFFAOYSA-N n-decyl alcohol Natural products CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 1
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N n-hexyl alcohol Natural products CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S264/00—Plastic and nonmetallic article shaping or treating: processes
- Y10S264/19—Inorganic fiber
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
- Glanulating (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Materials For Medical Uses (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
本发明涉及制备可成型捏合体的方法,包括将颗粒二氧化钛与水和链烷醇胺或氨或可释放氨的化合物混合并捏合,得到含固体物总量为50-85%(重量)的混合物,以混合物中固体物总量计,链烷醇胺或氨的用量为0.5-20%;涉及所得可成型捏合体;涉及由该捏合体制备二氧化钛挤压物的方法;以及该二氧化钛挤压物在加氢转化、氢化、烃合成反应或废气净化方法中作为催化剂载体的应用。
Description
本发明涉及二氧化钛挤压物的制备方法,涉及用于制做二氧化钛挤压物的可成型塑性体的制备方法,涉及用于制做二氧化钛挤压物的可成型塑性体,涉及焙烧二氧化钛挤压物的制备方法及其应用。
二氧化钛是一种已知的材料,它通常在各种化学方法中被用作为催化剂载体或催化剂。应当指出,在现有技术中所描述的含有二氧化钛的催化剂体系都是以二氧化钛粉末为基础的,这就使得该体系不能直接适应于工业应用。为了把二氧化钛制成更适于工业应用的形式,DE-C-3217751最近公开了通过使用某种造粒剂(例如多无链烷醇和特别是粉末状石墨)使热解生产的二氧化钛造粒以生产二氧化钛丸粒的方法。
然而,迄今不可能用常规的挤压设备象挤压其它载体材料(例如氧化铝)一样挤压二氧化钛以得到强度适宜的产物,由于二氧化钛是令人感兴趣的载体材料,特别是在其不含粘合材料时,因此有必要研究这种非常难以成型的材料是否可经挤压方法制成其强度足以具有工业意义的二氧化钛挤压物。
已经发现,在制备其后可由基获得二氧化钛挤压物的塑性体时,采用一种链烷醇胺或氨水或可释放氨的化合物,可制备出适宜的二氧化钛挤压物。
因此,本发明涉及制备可成型塑性体的方法,包括将颗粒二氧化钛与水和链烷醇胺或氨水或可释放氨的化合物混合并搅拌,得到含固体的物总量为50-85%(重量)的混合物,以混合物中固体物总量计,链烷醇胺或氨的用量为0.5-20%(重量)。
本发明还涉及制备二氧化钛挤压物的方法,包括将颗粒二氧钛与水和链烷醇胺或氨水或可释放氨的化合物混合并搅拌,得到含固体物总量为50-85%(重量)的混合物,以混合物中固体物总量计,链烷醇胺或氨水的用量为0.5-20%(重量),然后挤压该混合物。
本发明还涉及焙烧二氧化钛挤压物的制备方法,包括将可成型塑性体挤压成二氧化钛挤压物,干燥和焙烧该二氧化钛挤压物至最终温度300°-1000℃。本发明还涉及由该方法得到的焙烧二氧化钛挤压物。
用于本发明的二氧化钛既可以是金红石属性的,也可以是锐钛矿属性的。也可适宜地采用两种二氧化钛的混合物。在有必要或建议使用含有金红石和锐钛矿两者的情况下,很明显,较好的金红石/锐钛矿应用比在某种程度上取决于所涉及的具体应用。通常,采用的比例可为0.66∶1-100∶1。当目的在于合成气转化反应时,金红石/锐钛矿之比以至少为2∶1为宜。适宜的二氧化钛源实例包括市场可供的p25(Degussa),低表面积二氧化钛(锐钛矿和金红石的混合物)和由锐钛矿构成的高表面积材料。此外,在本发明中还可以使用各种热解生产的二氧化钛制备可成型塑性体和相应的挤压物。
为获得可挤压成型的混合物,二氧化钛,链烷醇胺或氨或可释放氨的组分(以氨表示)和水的混合物的固体物总量一般为50-85%(重量),较好为55-80%(重量),更好为60-75%(重量)。
链烷醇胺或氨水或可释放氨的组分(以氨表示)的用量为0.5-20%(重量),较好为2-15%(重量),更好为3-10%(重量)。上述含量以固体物总重量为基础计算。
在制备可成型塑性体和由其产生的挤压物时,可以使用除NH4OH外的可释放氨的化合物和链烷醇胺。本发明中定义的可释放氨的化合物是在分解时,例如在热作用下,能释放NH3气体的化合物。
适于本发明方法中使用的链烷醇胺包括一、二和三链烷醇胺。较好的是一链烷醇胺,例如含有2-10个碳原子的乙醇胺,丙醇胺,己醇胺,壬醇胺和癸醇胺。其它适用的链烷醇胺包括二乙醇胺和三乙醇胺。优选的是使用一乙醇胺。如果需要,也可采用链烷醇胺的混合物或含有氨和一种或多种链烷醇胺的混合物。
为改善挤压机中流动性,待挤压的塑性体中也可含有聚电解质,例如Naleo7879(可由Nalco获得)。可向其中加入聚电解质的塑性体可容易地经Bonnot挤压的金属模板挤压。可以制备圆柱形挤出物,也可制备其它形状的挤出物,例如USP4028227所述。二氧化钛挤压物的表面积根据用于制备可成型塑性体的初始二氧化钛,可为40-300m2/g。
已经发现,所制备的二氧化钛挤压物的表面积在某种程度上取决于初始粉末材料的表面积。当使用较低表面积的粉末时,得到的挤压物具有很相似的表面积。但当使用较高表面积的粉末时,可使挤压物具有显著低的表面积,例如低30-50%,但比使用低表面粉末为初始原料所得要足够大。
尽管不是非这样做才有利,但仍可向待挤压的组合物中加入其它氧化物,例如二氧化硅和/或二氧化锆。待挤压组合物中其它氧化物的量可高达50%,但优选的是其量不超过20%(重量)。已经发现。过多量其它氧化物的存在对所得挤压物的强度有不利影响。
还可将其它物料例如结晶(金属)硅酸盐(特别是沸石,如沸石Y)掺加到待挤压的塑性体中,以获得具有可观强度的含沸石二氧化钛挤压物。
挤压成型后,含二氧化钛的挤压物进行干燥和通常的焙烧处理。干燥宜在温和的温度条件下对挤压物进行热处理,例如在不超过150℃下脱除挤压物中残留的水分。采用约120℃的干燥温度可以取得良好的效果。
对挤压物的焙烧通常在300°-1000℃温度下进行,较好的温度范围是450°-750℃,更好为475°-725℃。
二氧化钛挤压物可被适宜地用作下述工艺方法中常用催化剂的载体,所述工艺方法包括加氢转化,例如对重质烃油的加氢脱金属和加氢脱硫;对可氢化的组分或烃馏分如煤油和各种循环油的加氢处理;烃的合成反应;烯属不饱和化合物与有机氢化过氧化物的环氧化反应;烯属不饱和化合物生产相应链烷醇的水合反应;和废气的净化,特别是脱除氮氧化物。
烃合成反应的实例包括目的在于由一氧化碳和氢生产(长链)烃类的费-托(Fischer-TroPsch)法合成反应。具体讲,载有适宜费-托金属(例如VIII族金属铁、镍或钴)并根据需要含有一种或多种助剂(例如锆或铼)的二氧化钛挤压物适用于重质链烷烃合成步骤,这是由甲烷生产作为重质链烷烃合成的初始材料的合成气,进而生产中间馏分的综合工艺方法中的一个步骤,其中得到的重质链烷烃经催化转化,得到所需的中间馏分。
下面用实施例对本发明加以描述。
实例1
制备具有下列组成的混合物:
二氧化钛(ex Degussa) 74.5g
水(软化水) 32.5g
一乙醇胺(MEA) 2.6g
总量 109.6g
将MEA和水加到二氧化钛中,混合物搅拌30分钟。用实验室挤压机挤压得到的混合物。挤出物(1.5mm)于120℃干燥2小时,于500℃焙烧2小时。
得到的二氧化钛具有下列性能:
BET表面积 52m2/g
平均孔径 32nm
孔隙体积 0.29ml/g
实例2
使用含200g二氧化钛粉末、80g水和8g MEA的混合物重复实例1的实验。混合物搅拌45分钟,然后挤压,干燥和焙烧(如实例1所述)。得到的二氧化钛具有下列性能:
BET表面积 51m2/g
平均孔径 39nm
孔隙体积 0.36ml/g
整体碎裂强度 0.59Mpa
实例3
使用150g二氧化钛粉末、30g水和30g氨(25%),重复实例1的实验。混合物搅拌20分针。然后加入两份10g水,继续混合25分钟。混合物如实例1所述经挤压、干燥和焙烧。得到的二氧化钛具有下列性能:
BET表面积 47m2/g
平均孔径 27nm
孔隙体积 0.30ml/g
整体碎裂强度 0.62KPa实例4
制备具有下列组成的混合物:
二氧化钛(ex TIL) 228g
水 110g
MEA 5g
总量 343g
将混合物搅拌45分钟,然后如实例1所述进行挤压、干燥和焙烧。得到的二氧化钛具有下列性能:
BET表面积 82m2/g
平均孔径 37nm
孔隙体积 0.36ml/g
整体碎裂强度 0.25MPa
实例5
向114g二氧化钛(ex TIL)和107g二氧化硅(excrossfield)的混合物中加入5g MEA和150g水。在其后的45分钟内,以小批量加入60g水。将所得混合物挤压、干燥并于700℃焙烧2小时.得到的二氧化钛-二氧化硅具有下列性能:
BET表面积 192m2/g
平均孔径 22nm
孔隙体积 0.76ml/g
整体碎裂强度 0.33MPa
实例6
由150g二氧化钛(ex Degussa)、7.5g MEA和50g水制成混合物,向该混合物中加入111g二氧化硅/氧化铝摩尔比为40的沸石Y和50g水。15分钟后再加入15g水。均匀挤压出所得混合物。挤出物于120℃干燥,于500℃焙烧2小时。得到的二氧化钛-沸石Y具有下列性能:
BET表面积 246m2/g
平均孔径 32nm
孔隙体积 0.33ml/g
整体碎裂强度 0.90KPa
实例7
将实例6制备的挤出物(1.6mm)浸渍于H2ptCl6溶液,该溶液的配制使得在400℃用氢还原后二氧化钛上的pt含量为0.8%(重量)。
将上述制备的催化剂用于氢化实验。氢化实验是采用加氢处理过的每100g含有273毫摩尔单芳族化合物的轻质循环油进行的。该油的90%(重量)沸点达到351℃,含有112ppmw硫和7.6ppmw氮。实验在压力为50巴、温度最高为340℃下进行。结果发现,单芳族化合物的含量降至约70毫摩尔/100g。
Claims (9)
1.一种制备二氧化钛挤压物的方法,包括将颗粒二氧化钛与水和链烷醇胺或氨水或可释放氨气的化合物混合并搅拌,得到含固体物总量为50-85%(重量)的混合物,以混合物中固体物总量计,链烷醇胺或氨的用量为0.5-20%(重量),然后挤压该混合物,得到挤压物。
2.权利要求1的方法,其中混合物中固体物总量为55-80%(重量),更好为60-75%(重量)。
3.权利要求1或2的方法,其中使用锐钛矿和/或金红石作为二氧化钛源。
4.权利要求1或2的方法,其中链烷醇胺或氨的用量为2-15%(重量),更好为3-10%(重量)。
5.权利要求1或2的方法,其中使用2-10个碳原子的一、二或三链烷醇胺。
6.权利要求5的方法,其中使用一乙醇胺。
7.权利要求1或2的方法,其中混合物中含有至多50%(重量)二氧化硅和/或二氧化锆和/或沸石,以沸石Y为好。
8.权利要求1或2的方法,其中还包括干燥和焙烧所述二氧化钛挤压物至最终温度300-1000℃。
9.权利要求8的方法,其中焙烧在450-750℃,更好在475-725℃下进行。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB898906726A GB8906726D0 (en) | 1989-03-23 | 1989-03-23 | Titania extrudates |
GB8906726.8 | 1989-03-23 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1045763A CN1045763A (zh) | 1990-10-03 |
CN1033800C true CN1033800C (zh) | 1997-01-15 |
Family
ID=10653905
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN90101299A Expired - Lifetime CN1033800C (zh) | 1989-03-23 | 1990-03-19 | 二氧化钛挤压物 |
Country Status (22)
Country | Link |
---|---|
US (1) | US5106549A (zh) |
EP (1) | EP0389041B2 (zh) |
JP (1) | JP3159698B2 (zh) |
CN (1) | CN1033800C (zh) |
AT (1) | ATE96053T1 (zh) |
AU (1) | AU627004B2 (zh) |
BR (1) | BR9001319A (zh) |
CA (1) | CA2012663C (zh) |
DE (1) | DE69003978T3 (zh) |
DK (1) | DK0389041T3 (zh) |
DZ (1) | DZ1406A1 (zh) |
ES (1) | ES2045751T5 (zh) |
GB (1) | GB8906726D0 (zh) |
GR (1) | GR3026117T3 (zh) |
IE (1) | IE63314B1 (zh) |
IN (1) | IN176762B (zh) |
MY (1) | MY105590A (zh) |
NO (1) | NO301068B1 (zh) |
NZ (1) | NZ233026A (zh) |
RU (1) | RU2007216C1 (zh) |
SA (1) | SA90100159B1 (zh) |
ZA (1) | ZA902169B (zh) |
Families Citing this family (50)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4012479A1 (de) * | 1990-04-19 | 1991-10-24 | Degussa | Titandioxidpresslinge, verfahren zu ihrer herstellung sowie ihre verwendung |
GB9108656D0 (en) * | 1991-04-23 | 1991-06-12 | Shell Int Research | Process for the preparation of a catalyst or catalyst precursor |
US5342563A (en) * | 1991-11-22 | 1994-08-30 | The Lubrizol Corporation | Methods of preparing sintered shapes and green bodies used therein |
DE4242227A1 (de) * | 1992-12-15 | 1994-06-16 | Heraeus Quarzglas | Katalysatorträger und Verfahren für seine Herstellung |
CN1048192C (zh) * | 1995-03-16 | 2000-01-12 | 中国石化齐鲁石油化工公司 | 一种用于从石油和天然气加工过程中产生的硫化氢中回收硫磺的二氧化钛催化剂 |
EP0768110B1 (en) | 1995-10-09 | 2002-02-20 | Shell Internationale Researchmaatschappij B.V. | Catalyst and process for converting nitrogen oxide compounds |
DE19843845A1 (de) | 1998-09-24 | 2000-03-30 | Degussa | Formkörper, bestehend aus pyrogenem Mischoxid und deren Verwendung |
JP3775179B2 (ja) * | 1999-08-05 | 2006-05-17 | 住友化学株式会社 | 担持酸化ルテニウム触媒の製造方法及び塩素の製造方法 |
CA2342566A1 (en) | 2000-03-31 | 2001-09-30 | Hironobu Koike | Process for producing titanium oxide |
US20020013216A1 (en) | 2000-05-30 | 2002-01-31 | Broekhoven Emanuel Hermanus Van | Novel alkylation catalyst and its use in alkylation |
EP1286769B1 (en) * | 2000-05-30 | 2004-09-29 | Akzo Nobel N.V. | Use of a catalyst for the alkylation of hydrocarbons |
US20040054199A1 (en) | 2002-09-17 | 2004-03-18 | Basf Aktiengesellschaft | Process for epoxidation and catalyst to be used therein |
DE10320635A1 (de) | 2003-05-08 | 2004-11-18 | Basf Ag | Verfahren zur Herstellung von Propylenoxid |
DE10320634A1 (de) | 2003-05-08 | 2004-11-18 | Basf Ag | Verfahren zur Umsetzung einer organischen Verbindung mit einem Hydroperoxid |
JP4052210B2 (ja) * | 2003-09-04 | 2008-02-27 | ソニー株式会社 | セラミック構造体の製造方法 |
US7343747B2 (en) | 2005-02-23 | 2008-03-18 | Basf Aktiengesellschaft | Metal-organic framework materials for gaseous hydrocarbon storage |
DE102005060364A1 (de) | 2005-12-16 | 2007-06-21 | Basf Ag | Sauer funktionalisierte metallorganische Gerüstmaterialien |
US20090092818A1 (en) | 2006-04-18 | 2009-04-09 | Basf Se | Organometallic aluminum fumarate backbone material |
DE102006020852A1 (de) | 2006-05-04 | 2007-11-15 | Robert Bosch Gmbh | Gasdruckbehälter für gasbetriebene Kraftfahrzeuge |
DE102006058800A1 (de) * | 2006-12-13 | 2008-06-19 | Wacker Chemie Ag | Verfahren zur Herstellung von Katalysatoren und deren Verwendung für die Gasphasenoxidation von Olefinen |
US7825204B2 (en) * | 2006-12-19 | 2010-11-02 | Lyondell Chemical Technology, L.P. | Inorganic oxide extrudates |
DE102006061587A1 (de) | 2006-12-27 | 2008-07-03 | Basf Se | Verwendung poröser metallorganischer Gerüstmaterialien zur farblichen Kennzeichung von Filtern |
EP2155390B1 (de) | 2007-04-24 | 2012-10-17 | Basf Se | Metallorganische gerüstmaterialien mit hexagonal-trigonaler struktur basierend auf aluminium, eisen oder chrom, sowie einer dicarbonsäure |
WO2009007267A1 (en) | 2007-07-10 | 2009-01-15 | Basf Se | Process for the separation of unbranched hydrocarbons from their branched isomers |
US7824473B2 (en) | 2007-07-27 | 2010-11-02 | Northwestern University | Metal-organic framework materials based on icosahedral boranes and carboranes |
EP2387459A2 (de) | 2009-01-14 | 2011-11-23 | Basf Se | Vakuumisolationseinheiten mit gettermaterialien |
JP2012520756A (ja) | 2009-03-20 | 2012-09-10 | ビーエーエスエフ ソシエタス・ヨーロピア | アミンを含浸した有機金属骨格材料を用いた酸性ガスの分離方法 |
EP2230288B1 (de) | 2009-03-20 | 2016-05-25 | Basf Se | Metallorganische gerüstmaterialien in kälte/wärmemaschinen |
BR112012012910A2 (pt) | 2009-11-30 | 2017-03-01 | Basf Se | material de estrutura metalorgânica porosa, corpo moldado, processo para preparar um material de estrutura, e, uso de u m material de estrutura ou de um corpo moldado. |
DE102010062374A1 (de) | 2009-12-04 | 2011-06-09 | Basf Se | Verfahren zur Herstellung von Homo- oder Copolymeren |
CN103635255A (zh) | 2011-04-21 | 2014-03-12 | 巴斯夫欧洲公司 | 含有多孔芳族骨架(paf)材料的成型体 |
TWI460004B (zh) * | 2012-07-13 | 2014-11-11 | China Steel Corp | 選擇性觸媒還原反應的板狀觸媒與其製造方法 |
CN104797548A (zh) | 2012-09-19 | 2015-07-22 | 巴斯夫欧洲公司 | 乙炔桥联连接剂及其制备的金属有机框架(mof) |
WO2014118054A1 (en) | 2013-01-31 | 2014-08-07 | Basf Se | Stable spherical, porous metal-organic framework shaped bodies for gas storage and gas separation |
KR20150112988A (ko) | 2013-01-31 | 2015-10-07 | 바스프 에스이 | 고 패킹 밀도 및 조정가능한 기공 부피를 갖는 금속-유기 골격 압출물 |
US9561995B2 (en) | 2013-09-23 | 2017-02-07 | Basf Se | Process for the recovery of components forming a metal-organic framework material |
JP6796492B2 (ja) | 2014-02-21 | 2020-12-09 | ハンツマン・ピー・アンド・エイ・ジャーマニー・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング | TiO2ベースの触媒前駆体材料、その製造、およびその使用 |
EP2985075A1 (en) | 2014-08-15 | 2016-02-17 | Basf Se | Shaped body made of a porous material |
WO2016075100A1 (en) | 2014-11-11 | 2016-05-19 | Basf Se | Storage vessel comprising layers of a shaped body of a porous solid separated by a seal |
EP3218641A1 (en) | 2014-11-11 | 2017-09-20 | Basf Se | A storage vessel comprising a one-piece shaped body of a porous solid |
WO2016116406A1 (de) | 2015-01-21 | 2016-07-28 | Basf Se | Gasdruckbehälter enthaltend ein gas, ein latentwärmespeichermaterial und einen porösen feststoff |
WO2016135133A1 (en) | 2015-02-27 | 2016-09-01 | Basf Se | A vehicle comprising a storage system and a combustion engine, the storage system comprising a container and at least one storage vessel |
EP3093549A1 (en) | 2015-05-11 | 2016-11-16 | Basf Se | Vehicle comprising an internal combustion engine, at least one storage vessel and a cooling chamber and/or an air condition unit |
EP3093550A1 (en) | 2015-05-11 | 2016-11-16 | Basf Se | Storage vessel comprising at least one shaped body of a porous solid |
EP3130834A1 (en) | 2015-08-13 | 2017-02-15 | Basf Se | A vehicle comprising a storage system and a combustion engine, the storage system comprising a container and at least two storage vessels |
EP3130835A1 (en) | 2015-08-13 | 2017-02-15 | Basf Se | A vehicle comprising a storage system and a combustion engine, the storage system comprising a container and at least one storage vessel surrounded by a housing |
WO2017089410A1 (en) | 2015-11-27 | 2017-06-01 | Basf Se | Ultrafast high space-time-yield synthesis of metal-organic frameworks |
US11452967B2 (en) | 2017-07-17 | 2022-09-27 | Zymergen Inc. | Metal-organic framework materials |
EP3653800A1 (en) | 2018-11-15 | 2020-05-20 | Basf Se | Generation of drinking water from air by means of a box, comprising at least one sorption material |
JP7333558B2 (ja) * | 2019-09-11 | 2023-08-25 | 国立大学法人東京工業大学 | 固体ルイス酸触媒成形体 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3652749A (en) * | 1970-01-26 | 1972-03-28 | Universal Oil Prod Co | Continuous drawing of fibers from a mixture containing an inorgani oxide sol covered by a protective fluid |
US4010233A (en) * | 1970-11-06 | 1977-03-01 | Bayer Aktiengesellschaft | Production of inorganic fibers |
GB1426365A (en) * | 1973-06-04 | 1976-02-25 | British Steel Corp | Catalxst carrier |
FR2481145A1 (fr) * | 1980-04-23 | 1981-10-30 | Rhone Poulenc Ind | Procede de fabrication de catalyseurs ou de supports de catalyseurs faconnes a base d'oxyde de titane et leurs applications a la catalyse claus |
CA1206392A (en) * | 1983-04-29 | 1986-06-24 | William H. Morrison, Jr. | Tio.sub.2 slurries containing alkanolamines |
GB8607596D0 (en) * | 1986-03-26 | 1986-04-30 | Ici Plc | Dispersible composition of ceramic |
-
1989
- 1989-03-23 GB GB898906726A patent/GB8906726D0/en active Pending
-
1990
- 1990-02-07 US US07/476,216 patent/US5106549A/en not_active Expired - Lifetime
- 1990-03-14 ES ES90200611T patent/ES2045751T5/es not_active Expired - Lifetime
- 1990-03-14 AT AT90200611T patent/ATE96053T1/de not_active IP Right Cessation
- 1990-03-14 DE DE69003978T patent/DE69003978T3/de not_active Expired - Fee Related
- 1990-03-14 EP EP90200611A patent/EP0389041B2/en not_active Expired - Lifetime
- 1990-03-14 DK DK90200611.3T patent/DK0389041T3/da active
- 1990-03-19 CN CN90101299A patent/CN1033800C/zh not_active Expired - Lifetime
- 1990-03-20 JP JP06851090A patent/JP3159698B2/ja not_active Expired - Fee Related
- 1990-03-21 BR BR909001319A patent/BR9001319A/pt not_active IP Right Cessation
- 1990-03-21 RU SU904743435A patent/RU2007216C1/ru not_active IP Right Cessation
- 1990-03-21 NO NO901297A patent/NO301068B1/no not_active IP Right Cessation
- 1990-03-21 AU AU52117/90A patent/AU627004B2/en not_active Ceased
- 1990-03-21 NZ NZ233026A patent/NZ233026A/xx unknown
- 1990-03-21 IE IE104290A patent/IE63314B1/en not_active IP Right Cessation
- 1990-03-21 ZA ZA902169A patent/ZA902169B/xx unknown
- 1990-03-21 CA CA002012663A patent/CA2012663C/en not_active Expired - Lifetime
- 1990-03-21 MY MYPI90000440A patent/MY105590A/en unknown
- 1990-03-21 IN IN210MA1990 patent/IN176762B/en unknown
- 1990-03-21 DZ DZ900054A patent/DZ1406A1/fr active
- 1990-04-11 SA SA90100159A patent/SA90100159B1/ar unknown
-
1998
- 1998-02-12 GR GR980400289T patent/GR3026117T3/el unknown
Also Published As
Publication number | Publication date |
---|---|
ES2045751T5 (es) | 1998-02-16 |
BR9001319A (pt) | 1991-04-02 |
MY105590A (en) | 1994-11-30 |
NO301068B1 (no) | 1997-09-08 |
IN176762B (zh) | 1996-09-07 |
SA90100159B1 (ar) | 2002-03-04 |
GR3026117T3 (en) | 1998-05-29 |
NO901297D0 (no) | 1990-03-21 |
CA2012663A1 (en) | 1990-09-23 |
DZ1406A1 (fr) | 2004-09-13 |
DE69003978D1 (de) | 1993-11-25 |
NO901297L (no) | 1990-09-24 |
ATE96053T1 (de) | 1993-11-15 |
AU627004B2 (en) | 1992-08-13 |
EP0389041B1 (en) | 1993-10-20 |
EP0389041B2 (en) | 1997-12-17 |
DK0389041T3 (da) | 1993-11-15 |
ES2045751T3 (es) | 1994-01-16 |
EP0389041A1 (en) | 1990-09-26 |
CA2012663C (en) | 2000-04-18 |
RU2007216C1 (ru) | 1994-02-15 |
ZA902169B (en) | 1990-12-28 |
JPH02284650A (ja) | 1990-11-22 |
JP3159698B2 (ja) | 2001-04-23 |
GB8906726D0 (en) | 1989-05-10 |
CN1045763A (zh) | 1990-10-03 |
DE69003978T2 (de) | 1994-02-10 |
NZ233026A (en) | 1991-08-27 |
US5106549A (en) | 1992-04-21 |
DE69003978T3 (de) | 1998-04-02 |
IE63314B1 (en) | 1995-04-05 |
IE901042L (en) | 1990-09-23 |
AU5211790A (en) | 1990-09-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1033800C (zh) | 二氧化钛挤压物 | |
CN1020625C (zh) | 烃转化方法及催化剂 | |
CN1021738C (zh) | 烃转化催化剂 | |
CN1035063A (zh) | 用于处理废气的催化剂与处理废气的方法 | |
CN1448480A (zh) | 一种异构脱蜡催化剂及其制备方法 | |
CN1086308C (zh) | 用铜基催化剂将硫化合物直接氧化成硫的方法 | |
US9314781B2 (en) | Catalyst for selective paraffin isomerization and preparation method and use thereof | |
CN1016319B (zh) | 镍/氧化铝催化剂的制备 | |
CN1123713A (zh) | 处理含硫化合物气体用催化剂及应用和处理气体的方法 | |
CN1054015A (zh) | 处理气体排放物用的催化剂与处理这些气体排放物的方法 | |
CN1211461C (zh) | 一种加氢处理催化剂的制备方法 | |
CN1185325C (zh) | 烃类的异构化方法、用于该方法的固体酸催化剂和异构化装置 | |
CN1211464C (zh) | 重质原料油加氢处理催化剂及其制备方法 | |
CN1206038C (zh) | 一种含氟-铝物料及其制备方法 | |
CN100337741C (zh) | 一种活性氧化铝催化剂及其制备方法和应用 | |
CN1044816C (zh) | 用于精制石油蜡的加氢精制催化剂 | |
CN1362479A (zh) | 含zsm分子筛的催化剂及其制备方法 | |
CN1047326C (zh) | 一种铂铼重整催化剂 | |
CN1251797C (zh) | 一种加氢处理催化剂的制备方法 | |
CN113546671B (zh) | 含有超大孔硅胶的轻汽油裂解增产丙烯催化剂及其制备方法和应用 | |
JPS6312659B2 (zh) | ||
CN1142016C (zh) | 苯甲酸加氢制六氢苯甲酸的催化剂 | |
JP3303533B2 (ja) | 炭化水素油の水素化処理用触媒とその製造方法 | |
CN1302092C (zh) | 一种加氢处理催化剂的制备方法 | |
CN105642369A (zh) | 一种降低NOx排放的氧化铝载体成型处理方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C15 | Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993) | ||
OR01 | Other related matters |