CN105435822A - 用于乙烯氧氯化为1.2-二氯乙烷的催化剂 - Google Patents
用于乙烯氧氯化为1.2-二氯乙烷的催化剂 Download PDFInfo
- Publication number
- CN105435822A CN105435822A CN201510920118.0A CN201510920118A CN105435822A CN 105435822 A CN105435822 A CN 105435822A CN 201510920118 A CN201510920118 A CN 201510920118A CN 105435822 A CN105435822 A CN 105435822A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- particle
- earth metal
- content
- circuit cylinder
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 239000005977 Ethylene Substances 0.000 title claims abstract description 11
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 title abstract 2
- 239000011148 porous material Substances 0.000 claims abstract description 21
- 238000009826 distribution Methods 0.000 claims abstract description 14
- 239000008187 granular material Substances 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims description 44
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 29
- 229910001593 boehmite Inorganic materials 0.000 claims description 17
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 239000007800 oxidant agent Substances 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 7
- 150000001342 alkaline earth metals Chemical group 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 7
- 150000002910 rare earth metals Chemical class 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910001510 metal chloride Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- GSQKXUNYYCYYKT-UHFFFAOYSA-N cyclo-trialuminium Chemical compound [Al]1[Al]=[Al]1 GSQKXUNYYCYYKT-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 1
- 229940063655 aluminum stearate Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000008450 motivation Effects 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000007115 recruitment Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000011800 void material Substances 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/31—Density
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/122—Halides of copper
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/15—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination
- C07C17/152—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons
- C07C17/156—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons of unsaturated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C19/00—Acyclic saturated compounds containing halogen atoms
- C07C19/01—Acyclic saturated compounds containing halogen atoms containing chlorine
- C07C19/043—Chloroethanes
- C07C19/045—Dichloroethanes
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/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
- B01J35/64—Pore diameter
- B01J35/651—50-500 nm
-
- 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
- B01J35/64—Pore diameter
- B01J35/653—500-1000 nm
-
- 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
- B01J35/64—Pore diameter
- B01J35/657—Pore diameter larger than 1000 nm
-
- 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
- B01J35/66—Pore distribution
-
- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
一种用于乙烯氧氯化为1.2-二氯乙烷的催化剂，该催化剂为具有一定几何构型和孔体积分布的中空颗粒，其中颗粒中大孔占总孔体积的至少20％，大孔分布曲线最大值处的孔径为高于800且至多1500nm。
Description
本申请是以下申请的分案申请：“2009年12月17日”，申请号为“200911000016.8”；发明名称：“用于乙烯氧氯化为1.2-二氯乙烷的催化剂”。
技术领域
本发明涉及一种用于固定床中乙烯氧氯化(oxychlorinationofethylene)为1.2-二氯乙烷(DCE)的颗粒形式的催化剂，该颗粒为具有特定孔体积分布的中空几何构型，并且本发明涉及用于所述催化剂的中空载体。
背景技术
众所周知，乙烯氧氯化为二氯乙烷可以在流化床或固定床中进行。前种情况下，反应器中温度分布更均一，而在固定床中，虽然反应参数比较容易控制，但由于催化剂颗粒之间以及颗粒与反应气体之间热交换效率低，局部的热点温度会对产物选择性和催化剂寿命产生不利的影响。
催化剂通常采用中空圆柱状颗粒，由于它的S/V比(几何表面积和体积的比例)高于球体和实心圆柱，可以通过催化反应床获得更有效的热交换和较低的压降，所以比较容易控制沿着反应床的温度，增加工业反应器生产能力。
尽管具有以上优点，但是应仔细设计中空圆柱状颗粒，否则其他的缺点便会凸显出来。
例如，如果中空圆柱状颗粒的外径和内径的比例(De/Di)大于一定值，颗粒容易破碎，催化剂堆密度降低，由于催化剂活性相的总含量较低从而导致催化床单位体积的转化率降低。
圆柱体的De或者长度增加过多且保持De/Di不变会引起反应器管内催化剂装载的不均一，可能使颗粒破碎而导致压降增加。
EP1053789A1公开了一种圆柱形催化剂，其De为4-7mm，Di为2.0-2.8mm，高度为6.1-6.9mm。
该催化剂优于USP4740644所述的长度比外径短的圆柱体催化剂和长度大于外径的圆柱体催化剂(USP5166120)。
后一个所引用的US专利中催化剂的总孔体积为0.6-1.0ml/g，所有的孔径都大于4nm，孔径为8-20nm的孔占孔体积的至少80％，其他孔的孔径为大于20且至多200nm。该催化剂与孔体积中主要孔的孔径小于8nm的催化剂相比，具有较高的活性。
依照EP1053789的考虑，USP5166120公开的催化剂，缺点在于床层空隙率太高，这意味着床层中催化材料的含量较低，导致较低的DCE比生产率(specificproductivity)(gDCE/g催化剂.h)并伴随着装载步骤中催化剂颗粒的破裂所引起高的压降。
US4,414,156公开了用于乙烯氧氯化的催化剂，所述催化剂装载于双峰氧化铝上，所述氧化铝具有两个孔体积尺寸分布，一个为15-25μm，第二个为具有1000-1200μm的高得多的峰值尺寸，其中所述第一孔体积尺寸提供主要的益处。该文献还表明体积分布中催化剂大孔范围在约80μm以下非常关键，在该范围内发生大部分的氧氯化反应。由该文献表5的结果可见，其中不存在直径小于7μm的小孔的氧化铝球体的表面积为其中直径小于7μm的小孔占主导的氧化铝球体的表面积的二分之一至三分之一。该文献由此得到的结论是在1000-1200μm范围的大孔的表面积应非常小，因此具有该范围大孔的催化剂的量也应该非常少，因为该范围内的催化活性并不显著。本领域技术人员基于US4,414,156的公开显然不会有动机去提高一个不存在的催化剂的催化活性。
发明内容
本发明的目的在于提供一种固定床乙烯氧氯化为DCE的中空颗粒形式的催化剂，包括负载在中空圆柱形γ氧化铝颗粒上的氯化铜和选自碱金属、碱土金属和稀土金属的金属氯化物，该催化剂在选择性和转化率上具有令人满意的性能，并且与其他具有相同几何参数(形状和大小)和组成的催化剂相比，该催化剂具有较高的DCE(gDCE/g催化剂.h)比生产率。
具体实施方式
从本发明下面的描述中可以明显的看到达到了其他目的。
本发明的催化剂是具有一定几何构型的中空颗粒，包括负载在中空圆柱形氧化铝颗粒上的氯化铜和至少一种或多种选自碱金属、碱土金属和稀土金属的金属氯化物，其特征在于颗粒中大孔体积(macroporevolume)分数为总孔体积的至少20％且至多40％，大孔体积分布曲线最大值处的孔径为从800nm到至多1500nm，堆密度(bulkdensity)优选为0.80g/ml-0.65g/ml，更优选为从0.7g/ml到小于0.78g/ml。
与已知的具有相似几何构型(形状和大小)和组成的颗粒状催化剂相比，本发明的催化剂具有单位时间内单位质量催化剂上较高的DCE产率，且其大孔分布曲线最大值处的大孔孔径高于已知催化剂相应的孔径。这意味着本发明的催化剂的活性(转化率和活性)高于已知催化剂。
用于制备本发明催化剂的勃姆石的d50为至少100μm且至多170μm，且小于100μm的颗粒分数低于50wt％。
例如，SASOLAG(德国)生产的PuralSCC150商业勃姆石可用于本发明。
由相对质量筛分法测定的该勃姆石的颗粒大小分布(wt％)如下：
d50(平均值)为130μm，d90(平均值)为209μm。粒径小于100μm的颗粒体积占30％，粒径小于250μm的颗粒体积占98％。
上述勃姆石经压制成型后制得的中空圆柱形颗粒在650℃，700℃和800℃焙烧后转化为γ氧化铝，并具有以下性质：
-经上述温度焙烧后的表面积(BET)分别为239，208和183m2/g；
-孔体积(BET)为0.41-0.43ml/g；
-总孔体积＝0.48-0.52ml/g(由颗粒密度(PD)和真密度(RD)的倒数之差计算得出，＝1/PD-1/RD)；
-大孔体积＝0.1ml/g(压汞法(Hgporosimetry))；
-大孔体积分布曲线最大值处孔径(MPS)＝1068nm。
当勃姆石的d50大于150μm时可以得到高达1600nm的大孔孔径，由该勃姆石制得的催化剂具有优良的性能和足够的机械性能(轴向和径向抗冲击性)。
用于制备本发明催化剂的勃姆石可以通过已知的方法获得，将铝溶于经由齐格勒醇改性的己醇中：将得到的勃姆石浆料喷雾干燥。
表1列出了由勃姆石PuralSCC150中空颗粒制得的中空圆柱形γ氧化铝颗粒的性质，该氧化铝颗粒外径(De)约为5mm，内径(De)为2.5mm，高约为5mm；此外还列出了与勃姆石PuralSCC150制得的γ氧化铝颗粒具有相同的大小和形状的、由SASOLPuralSB1制得的γ氧化铝颗粒，其d50(平均值)为43μm，d90(平均值)为119μm，粒径小于100μm的颗粒体积占83.9％，粒径小于250μm颗粒体积占100％。
表1
将勃姆石粉末与润滑剂，如含量为3-6wt％硬脂酸铝，混合后压制成型得颗粒。
成型颗粒在大约600-800℃下焙烧，由勃姆石转化为γ氧化铝后，然后浸渍金属氯化物水溶液-催化剂成分。优选在溶液体积等于或小于氧化铝颗粒的总孔体积下浸渍。
催化剂中氯化物的含量，以金属计为3-12wt％Cu，1-4wt％碱金属，0.05-2wt％碱土金属，0.1-3wt％稀土金属。
优选Cu含量为4-10wt％，碱金属是钾和/或铯，含量为0.5-3wt％，碱土金属是镁，含量为0.05-2wt％，稀土金属是铈，含量为0.5-3wt％。
中空颗粒中至少有一个与颗粒轴向相平行的贯通孔。当颗粒形状为圆柱形时，De直径4-6mm，Di直径1-3mm，高度为4-7mm。
通常采用横截面为三叶草形的丸粒，每片叶具有平行于颗粒轴向的贯通孔。
表2列出本发明催化剂颗粒的主要性质，表3是实施例催化剂的催化性能测试的数据。
图1和2分别为本发明涉及的催化剂(图1，实施例1中的催化剂)和现有技术中的催化剂(图2，对比例1中的催化剂)的大孔体积分布图(压汞法)。纵坐标中，左边表示的是累计孔体积，右边表示的是孔体积增加量(对数值)与孔径的变化量的比值(log.dPV/dPD，PV代表孔体积，PD代表孔径)。
可根据已知方法在固定床中采用本发明的催化剂由乙烯氧氯化制1.2-二氯乙烷，以空气或氧气作为氧化剂，反应温度200-300℃，空气为氧化剂时，总的进料摩尔比C2H4/HCl/O2是1∶1.99∶0.51，氧气做氧化剂时，C2H4/HCl/O2摩尔比是1∶0.71∶0.18。
当以氧气作为氧化剂时，反应在串联的三个反应器中进行时优选的HCl/C2H4，O2/C2H4，和HCl/O2摩尔比分别是0.15-0.50，0.04-0.1和3.20-5.8，其中第三个反应器装载有由本发明所述的催化剂颗粒形成的或者包括所述催化剂的固定床。
测试
大孔孔体积由压汞法测量：微孔和中孔的孔体积由BET氮气吸附-脱附法测量。
堆密度(也称为表观堆密度)由ASTM方法D4164-82测量。
以下实施例用来阐述本发明，但本发明不止局限于这些范围。
实施例1
由勃姆石PuralSCC150粉末和6wt％三硬酯酸铝混合后的压制成型的圆柱体经700℃焙烧得到400gDe＝5mm，Di＝2.5mm和高＝5mm的氧化铝中空圆柱体，其(BET)比表面积为208m2/g，总孔体积为0.51ml/g。将上述氧化铝置于可旋转的5升反应罐中，室温至50℃下，用200ml含有以下物质的水溶液进行浸渍：
CuCl2*2H2O＝110.8g
KCl＝7.9g
MgCl2*6H2O＝2.1g
HCl37wt％＝8.0ml
余量＝溶液加至200ml的去离子水
浸渍后的颗粒按下述程序于烘箱中干燥＝60℃1小时，80℃2小时，100℃3小时，150℃16小时。
表2列出了实施例1催化剂颗粒的性质，以及对比例1和2的催化剂颗粒的性质。
催化剂性能结果在表3列出。
对比例1
由勃姆石PuralSB1粉末和4wt％三硬酯酸铝混合后压缩成型制得的粗圆柱形颗粒经煅烧得到300g与实施例1具有相同尺寸和形状的氧化铝中空圆柱体，然后置于可旋转的5升反应罐中，室温下，用150ml含有以下物质的水溶液浸渍：
CuCl2*2H2O＝83.1g
KCl＝5.9g
MgCl2*6H2O＝1.5g
HCl37wt％＝6.0ml
余量＝溶液加至150ml的去离子水
浸渍后的颗粒干燥条件如实施例1。
表3列出了和实施例1相同的反应条件下的催化测试结果。
对比例2
使用两种与实施例1的催化剂尺寸和形状相似、组成相近的商业催化剂，反应条件与实施例1相同。
表3列出测试结果。
表2
(*)M.P.S＝大孔体积分布曲线最大值处孔径
大孔＝孔径为大于50nm且至多10.000nm的孔。
(**)床层空隙分数＝1-表观堆密度/颗粒密度。
表3
催化剂性能
(*)总的进料：C2H4＝30.4体积％，O2＝2.7体积％，HCl＝9.5体积％，N2＝57.4体积％。
Claims (9)
1.用于乙烯氧氯化为1,2-二氯乙烷的催化剂，该催化剂为中空圆柱颗粒，并且其由氯化铜和至少一种或多种选自碱金属、碱土金属和稀土金属的金属氯化物组成，以金属计的含量为3-12wt%的铜，1-4wt%的碱金属，0.05-2wt%的碱土金属，和0.1-3wt%的稀土金属，所述的氯化物负载在γ氧化铝中空圆柱颗粒上，其特征在于该催化剂颗粒中大孔体积分数为总孔体积的20％-40％，且大孔体积分布曲线最大值处的孔径为至少800nm且至多1500nm；其中所述γ氧化铝中空圆柱颗粒由勃姆石中空圆柱颗粒在600℃-800℃下焙烧制备得到，所述γ氧化铝中空圆柱颗粒的大孔体积占总孔体积的20%-40%，其中大孔体积分布曲线最大值处的孔径为800-1600nm，并且所述勃姆石中空圆柱颗粒由具有以下孔径分布的勃姆石得到：
并且，d50平均值为130μm，d90平均值为209μm。
2.根据权利要求1所述的催化剂，其中大孔体积分数为总孔体积的20％-30％，且大孔体积分布曲线最大值处的孔径为1000-1300nm。
3.根据权利要求1或2所述的催化剂，催化剂的堆密度为0.65-0.80g/ml。
4.根据权利要求1-3任一项所述的催化剂，其中铜的含量为4-10wt%，碱金属是钾和/或铯，碱土金属是镁，并且稀土金属是铈。
5.根据权利要求1-4任一项所述的催化剂，其中钾和/或铯的含量为0.5-3wt%，镁含量为0.1-2wt%，并且铈含量为0.5-2wt%。
6.根据权利要求1-5任一项所述的催化剂，其中催化剂为外径4-6mm，内径1-3mm和高度为4-7mm的中空圆柱体形式。
7.根据权利要求1-5任一项所述的催化剂，其具有三叶草形的圆柱横截面，每片叶具有平行于颗粒轴向的贯通孔，并且每片叶到其它叶的轴线是等距的。
8.用于将乙烯氧氯化为1,2-二氯乙烷的方法，其在由权利要求1-7所述的催化剂颗粒形成或包含所述催化剂颗粒的固定床中，以空气或氧气作为氧化剂在200-300℃温度下进行，当以空气为氧化剂时，HCl/C2H4/O2摩尔比是1:1.99:0.51，以氧气为氧化剂时，HCl/C2H4/O2摩尔比是1:0.70:1.79。
9.根据权利要求8所述的方法，其以氧气作为氧化剂，并在串联的三个反应器中进行，其中第三个反应器装载有由权利要求1-7所述的催化剂颗粒所形成或包含所述催化剂颗粒的固定床，并且其中HCl/C2H4，O2/C2H4和HCl/O2的摩尔比分别是0.15-0.50，0.04-0.10和3.20-5.8。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP08172023.7A EP2198958B1 (en) | 2008-12-17 | 2008-12-17 | Catalysts for oxychlorination of ethylene to 1.2-dichloroethane |
| EP08172023.7 | 2008-12-17 | ||
| CN200911000016A CN101786007A (zh) | 2008-12-17 | 2009-12-17 | 用于乙烯氧氯化为1.2-二氯乙烷的催化剂 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200911000016A Division CN101786007A (zh) | 2008-12-17 | 2009-12-17 | 用于乙烯氧氯化为1.2-二氯乙烷的催化剂 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105435822A true CN105435822A (zh) | 2016-03-30 |
| CN105435822B CN105435822B (zh) | 2019-07-30 |
Family
ID=40351685
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200911000016A Pending CN101786007A (zh) | 2008-12-17 | 2009-12-17 | 用于乙烯氧氯化为1.2-二氯乙烷的催化剂 |
| CN201510920118.0A Active CN105435822B (zh) | 2008-12-17 | 2009-12-17 | 用于乙烯氧氯化为1.2-二氯乙烷的催化剂 |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200911000016A Pending CN101786007A (zh) | 2008-12-17 | 2009-12-17 | 用于乙烯氧氯化为1.2-二氯乙烷的催化剂 |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20100152505A1 (zh) |
| EP (1) | EP2198958B1 (zh) |
| JP (1) | JP2010142803A (zh) |
| KR (1) | KR20100070293A (zh) |
| CN (2) | CN101786007A (zh) |
| BR (1) | BRPI0905195B1 (zh) |
| TW (1) | TW201028211A (zh) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6215514B2 (ja) * | 2011-02-21 | 2017-10-18 | 東ソー株式会社 | オキシ塩素化触媒 |
| JP5817435B2 (ja) * | 2011-10-25 | 2015-11-18 | 東ソー株式会社 | オキシ塩素化触媒の製造法 |
| JP2014117673A (ja) * | 2012-12-18 | 2014-06-30 | Tosoh Corp | オキシ塩素化触媒およびそれを用いた１，２−ジクロロエタンの製造方法 |
| JP6056457B2 (ja) * | 2012-12-25 | 2017-01-11 | 東ソー株式会社 | １，２−ジクロロエタンの製造方法 |
| JP6194809B2 (ja) * | 2014-02-05 | 2017-09-13 | 東ソー株式会社 | １，２−ジクロロエタンの製造方法 |
| CN104016822B (zh) * | 2014-06-25 | 2015-11-04 | 厦门中科易工化学科技有限公司 | 一种乙烷制备乙烯或二氯乙烷的方法 |
| WO2017015487A1 (en) | 2015-07-22 | 2017-01-26 | Basf Corporation | High geometric surface area catalysts for vinyl acetate monomer production |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4414136A (en) | 1982-04-02 | 1983-11-08 | Conoco Inc. | Catalysts for ethylene oxychlorination |
| DE3522474A1 (de) | 1985-06-22 | 1987-01-02 | Basf Ag | Verfahren zur herstellung von 1,2-dichlorethan durch oxichlorierung von ethylen an kupfer enthaltenden traegerkatalysatoren |
| DE4018512A1 (de) | 1990-06-09 | 1991-12-12 | Wacker Chemie Gmbh | Zylindrisch geformter katalysator und dessen verwendung bei der oxichlorierung von ethylen |
| US5861353A (en) * | 1992-10-06 | 1999-01-19 | Montecatini Tecnologie S.R.L. | Catalyst in granular form for 1,2-dichloroethane synthesis |
| IT1282267B1 (it) * | 1995-03-14 | 1998-03-16 | Montecatini Tecnologie Srl | Catalizzatori e supporti per catalizzatori ottenuti per pastigliatura |
| DE69918672T2 (de) * | 1999-05-21 | 2005-07-21 | Evc Technology Ag | Katalysator und Oxychlorinierungsverfahren unter Verwendung derselben |
| US6795215B1 (en) * | 2000-05-23 | 2004-09-21 | Silverbrook Research Pty Ltd | Print engine/controller and printhead interface chip incorporating the engine/controller |
| TWI255736B (en) * | 2002-02-05 | 2006-06-01 | Basf Ag | A catalyst composition for the oxychlorination of ethylene and its use |
| CN1164363C (zh) * | 2002-03-21 | 2004-09-01 | 中国石油化工股份有限公司 | 一种氧氯化反应催化剂及其制备方法和应用 |
| RU2009120540A (ru) * | 2006-11-01 | 2010-12-10 | Дау Глобал Текнолоджиз Инк. (Us) | Формованные пористые элементы из альфа-оксида алюминия и способы их получения |
-
2008
- 2008-12-17 EP EP08172023.7A patent/EP2198958B1/en not_active Not-in-force
-
2009
- 2009-11-23 US US12/623,743 patent/US20100152505A1/en not_active Abandoned
- 2009-12-09 TW TW098142037A patent/TW201028211A/zh unknown
- 2009-12-10 KR KR1020090122607A patent/KR20100070293A/ko not_active Application Discontinuation
- 2009-12-16 BR BRPI0905195-3A patent/BRPI0905195B1/pt not_active IP Right Cessation
- 2009-12-16 JP JP2009285538A patent/JP2010142803A/ja active Pending
- 2009-12-17 CN CN200911000016A patent/CN101786007A/zh active Pending
- 2009-12-17 CN CN201510920118.0A patent/CN105435822B/zh active Active
Also Published As
| Publication number | Publication date |
|---|---|
| BRPI0905195A2 (pt) | 2011-03-22 |
| TW201028211A (en) | 2010-08-01 |
| EP2198958A1 (en) | 2010-06-23 |
| US20100152505A1 (en) | 2010-06-17 |
| KR20100070293A (ko) | 2010-06-25 |
| JP2010142803A (ja) | 2010-07-01 |
| CN105435822B (zh) | 2019-07-30 |
| EP2198958B1 (en) | 2017-11-08 |
| CN101786007A (zh) | 2010-07-28 |
| EP2198958A8 (en) | 2010-11-17 |
| BRPI0905195B1 (pt) | 2017-07-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105435822A (zh) | 用于乙烯氧氯化为1.2-二氯乙烷的催化剂 | |
| CN101786025B (zh) | 用于乙烯固定床氧氯化为1,2-二氯乙烷的催化剂 | |
| EP1478458B1 (en) | Catalyst carriers | |
| CN1198688C (zh) | 成形催化剂 | |
| EP3222347B1 (en) | Catalyst for oxidative dehydrogenation reaction and method for producing same | |
| CN1327963C (zh) | 一种适用作选择性放热反应的催化剂载体的中空颗粒 | |
| CN104174420B (zh) | 一种用于合成气甲烷化的碳化硅基整体催化剂及制备方法 | |
| JP4638975B2 (ja) | 触媒およびそれを用いたオキシ塩素化法 | |
| KR20220122784A (ko) | 복합체 | |
| CN108671934A (zh) | 一种高机械强度的加氢精制催化剂的制备方法 | |
| CN106622195A (zh) | 一种α-氧化铝载体及其制备方法和应用 | |
| TW201217048A (en) | Catalyst system | |
| KR102035471B1 (ko) | 선택도가 우수한 탈수소 촉매의 제조방법 | |
| CN113694944B (zh) | 一种裂解汽油用钯系选择加氢催化剂及其制备方法与应用 | |
| RU2431524C1 (ru) | Катализатор, способ его приготовления и способ фторирования галогенированных углеводородов | |
| CN112439399B (zh) | 一种α-氧化铝载体及制备方法和银催化剂与应用 | |
| KR102571531B1 (ko) | 압출 성형에 의한 co2 직접 수소화 촉매의 제조방법 및 이에 따라 제조된 co2 직접 수소화 촉매 | |
| WO2022030515A1 (ja) | アルミナ担体 | |
| CN115703973A (zh) | 重整生成油脱氯剂及其制备方法和应用 | |
| CN113694944A (zh) | 一种裂解汽油用钯系选择加氢催化剂及其制备方法与应用 | |
| CN114433044A (zh) | 一种α-氧化铝载体及其制备方法 | |
| CN116120961A (zh) | 一种液相脱氯剂及其制备方法和应用 | |
| CN117563594A (zh) | 一种成型的羟基丙酮催化剂及其制备方法和应用 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |