CN1241664C - Composite porous metal catalyst distillation construction member and preparing method thereof - Google Patents
Composite porous metal catalyst distillation construction member and preparing method thereof Download PDFInfo
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- CN1241664C CN1241664C CN 02156506 CN02156506A CN1241664C CN 1241664 C CN1241664 C CN 1241664C CN 02156506 CN02156506 CN 02156506 CN 02156506 A CN02156506 A CN 02156506A CN 1241664 C CN1241664 C CN 1241664C
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- catalytic distillation
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Abstract
The present invention discloses a composite porous metal catalytic distillation component and a preparing method thereof. The composite porous metal catalytic distillation component of the present invention is composed of a base, a modification layer and an active layer. The composite porous metal catalytic distillation component is characterized in that porous metal regular filler with a micropore structure is used as the base; after the surface of the base is treated, a ceramic coating layer is formed, and the ceramic coating layer is the modification layer; a catalyst active component covered above the modification layer is the active layer. The catalytic distillation component of the present invention integrates distillation filler and a catalyst into a whole. Thus, the catalytic distillation tower member can sufficiently exert catalyst efficiency, provides adequate gas-liquid contacting area, and is favorable for mass transfer between a gas phase and a liquid phase; the catalytic distillation component has good reaction and separation effect, is easy to assemble and disassemble, and is easy for industrial application.
Description
Technical field
The present invention relates to be applied to the catalytic distillation structure in the petrochemical industry, specifically, relate to structure of the catalytic distillation tower inner member in a kind of catalytic distillation technology and preparation method thereof.
Background technology
Catalytic distillation technology is a kind of new Chemical Engineering method that development in recent years is got up, and this technology collection catalytic process and still-process are one, and reaction is carried out in same tower simultaneously with the operating process that separates.This process can constantly be removed product from each reaction member separation, also can utilize reaction heat as the required heat of vaporization of still-process simultaneously.Series of advantages such as catalytic distillation technology has the conversion ratio height, selectivity is good, energy consumption is low, product purity is high, easy to operate, reduced investment are so just obtained extensive studies and development rapidly in the eighties.Catalytic distillation technology is application success in the production of methyl tertiary butyl ether(MTBE) (MTBE) at first, and has been applied to other many fields.
The key of catalytic distillation technology is the type of feed of reacting section catalyst in the catalytic distillation tower.Catalyst be filled with a lot of forms, usually can be divided into two classes: a class is catalyst and the processing and manufacturing respectively of distillation filler, be about to catalyst and directly make the particle of different shape size, and in different ways with the distillation filler combination together, fill in the catalytic distillation tower then; Another kind of is that catalyst is made of one with the distillation filler, is put in catalytic distillation tower again behind the even unified element of formation.
US4443559 discloses in a kind of tiny pocket that catalyst granules is seated on the cloth bag made from glass cloth, cover to support with the stainless steel cloth that the certain opening space is arranged, be rolled into again have the layer of steel wire net, the harness shape cylinder catalyst structure of one deck cloth bag.This member is packed in the tower, and make its spatial distribution even, liquid phase can fully be contacted with catalyst, and leave enough gas-liquid phase flow channel and contact area.In order to prevent the steam short circuit of rising, adjacent two layers member silk screen also should be staggeredly placed.This patented technology is adopted by the catalytic distillation of synthetic MTBE, has realized industrialization.This scheme makes the catalytic distillation tower conversion zone into the voidage general little particular fillers tower of packed tower, and the conversion zone above and below is still common filler or column plate.Therefore, the skewness of catalyst in bed when adopting this type of feed, the pressure drop part is excessive, and the Liquid Flow situation is relatively poor, and the design of member, makes more complicated, and specification requirement is higher, and the filler loading and unloading are also cumbersome.
CN1060228 has described a kind of catalytic rectifying tower, and column plate wherein or filler have solved the packing and the Packing Problems of catalytic rectifying tower catalyst with containing activity of such catalysts materials processing moulding.This catalytic rectifying tower can be a packed tower, also can be plate column, bubble column or its any combination, wherein be used for dumped packing or corrugated plate shape such as the Raschig ring, Bao Erhuan, wheel shape, rectangular saddle ring of packed tower, spherical, column, cellular structured packing can be with containing activity of such catalysts materials processing moulding; Sieve plate, corrugated plating, bubble cap plate, the valve plate of same plate column also can be with containing activity of such catalysts materials processing moulding.This patent has only proposed column plate or filler usefulness contains the imagination of activity of such catalysts materials processing moulding, and does not provide the specific implementation method.In fact this imagination implements very difficulty, just there is strength problem because contain activity of such catalysts material itself, and when being processed into column plate or filler various factors such as Yin Gaowen and make the catalyst activity forfeiture often, thereby do not have the effect of catalytic reaction.
CN1167009 has prepared a kind of mordenite/metal or ceramic composite, is made up of the pre-designed shape with dumped packing, structured packing, static mixer, special-shaped catalyst and integral catalyzer of mordenite molecular sieve and this molecular sieve of load and the metal or the ceramic base material of size or shape similarly and size.It has kept the characteristic of mordenite molecular sieve on catalytic performance, and can satisfy the needs of differential responses by modification; On engineering properties, can be used as catalytic distillation structure, also can be used as irregular shape catalyst by changing the metal or the shape of ceramic base material, the requirement that size satisfies different process.Yet this composite only limits to mordenite molecular sieve is compounded on metal or the ceramic base material, only effective to the reaction of modenite useful as catalysts, reaction applicatory field is more limited, and composite methods only adopted the crystallization method of immersing, and compound means are also very limited.
CN1228032 has described a kind of catalyst filling that uses in catalytic distillation technology, it is by gas deposition and/or be ejected on yarn fabric, knit goods or the flake stuffing as matrix and make with at least a active material as catalyst and/or promoter.The catalyst matrix that this patent is selected for use is yarn fabric, knit goods or flake stuffing, but these materials and be not suitable for all chemical reaction processes, if as fractional distillation filling-material, is subjected to the separation requirement restriction also may not be suitable fully.
US5235102 discloses the technology that a kind of method that adopts catalytic distillation is converted into gas phase or liquid-phase feed stream required product, wherein the catalytic distillation tower rigidity honeycomb block that adopts the rigidity honeycomb block or be coated with the catalyst activity component is as filler, the preferably ceramic honeycomb block.But the ceramic honeycomb piece that this technology is selected for use is the rigidity alveolate texture with some upright openings that are parallel to each other, and is separate between each duct, is unfavorable for the mass transfer between gas-liquid, and the usefulness of catalytic distillation can not get effective performance.In addition, this filler adopts the rigidity honeycomb block, is not easy to the coated catalysts active component.
DE29609079U1 has described a kind of catalyst that is used for exhaust-gas treatment, and this catalyst is coated with and invests on the ceramic body, the outsourcing steel bushing.Steel bushing can have side opening, also can be made up of the parts of some mechanical connections.This kind structure is easy to dismounting, and convenient test can be reclaimed noble metal and reused, and can be used for the catalyst of Any shape, comprises ball-type.But this catalyst outside is surrounded by steel bushing, and structure is too complicated, be unwell to be used as the catalytic distillation tower packing, and this structure only limits the use of in exhaust-gas treatment,
CN1235066 discloses a kind of Catalysts and its preparation method of purifying exhausted gas of motor vehicle, and this catalyst is made of metallic carrier and catalyst activity component, and metallic walls and Catalytic Layer are incorporate.The manufacture craft that CN1226463 has proposed a kind of motor vehicle vent gas purification catalysis agent and combined with metallic carrier, the catalyst that has adopted lanthanide oxide and non-noble metal oxide to form can reduce firing temperature.CN1226465 has described a kind of catalyst metal carrier that is used to handle the band alumina layer of motor-vehicle tail-gas, adopt the chromium aluminum steel sheet to make metal carrier material, its coefficient of expansion and activated alumina are approaching, and be simultaneously good with the affinity of activated alumina, can guarantee metallic carrier and catalyst strong bonded.The metal carrier catalyst of above-mentioned patent preparation only is applicable to the processing motor-vehicle tail-gas, and application is limited, and complicated process of preparation, and is impracticable.
Summary of the invention
The object of the present invention is to provide a kind of new catalytic distillation member simple, that be easy to realize of making.This new structure can be given full play to the efficient of catalyst, and enough gas-liquid contacts area are provided, and helps the mass transfer between gas-liquid two-phase, and reaction and separating effect are all good, and easy to loading and unloading, are easy to commercial Application.
Compound porous metal catalytic distillation member of the present invention is made of matrix, modified layer and active layer, it is characterized in that with the porous metals structured packing with microcellular structure be matrix, the ceramic coating that matrix is carried out forming after the surface treatment with the employing metal oxide is a modified layer, to cover the catalyst activity component that invests on the modified layer is active layer, form the catalytic distillation structure with reaction and separation of double effect of homogeneous, wherein said metal oxide is selected from aluminium oxide, silica and titanium oxide.
The porous metals structured packing of described formation matrix is made up of the porous metals corrugated plating.The porous metals corrugated plating is made by expanded metal, and wherein expanded metal satisfies following feature: have uniform microcellular structure, its aperture is 5-20 μ m, and porosity is 30-40%.The base material of the expanded metal that the present invention adopts is a stainless steel, all can be used to prepare the porous metals corrugated plating as long as satisfy the stainless steel porous material of above-mentioned feature, preferably uses complex sintered metal micro-holes material.
Described porous metals ripple thickness of slab 0.2～1.0mm, 30 °～45 ° at ripple inclination angle, the crest height of wave and the pitch of waves are 5～30mm.Constitute the porous metals structured packing by some porous metals corrugated plating combinations.Preferably whole dish type is made in described porous metals structured packing below diameter 500mm, made six below the diameter 800mm and piece together system shape, be nine or more assembly system shapes more than the 800mm.
The specific area of preferred described matrix generally should be greater than 400m
2/ m
3, can choose 400～800m
2/ m
3, voidage generally should be greater than 90%, and number of theoretical plate is greater than 4 plates/m.
For making the catalyst activity component can be effectively and cover securely and invest in the porous metals structured packing, the porous metals structured packing that makes as stated above need be carried out modification, promptly adopt metal oxide that matrix is carried out surface treatment, the ceramic coating of formation is as modified layer.Preferred described metal oxide is selected from aluminium oxide, silica or titanium oxide.
The preparation method of catalytic distillation structure of the present invention comprises: described modified layer be adopt the thermal chemical reaction method with metal oxide-coated in matrix surface, specifically may further comprise the steps:
(1) prepares a kind of water based paint, wherein be dispersed with the superfine oxide particulate;
(2) coating that step (1) is obtained is coated on the matrix, after super-dry and heat of solidification processing, forms uniform and stable ceramic coating at matrix surface;
Described active layer is to adopt liquid phase to immerse method or spraying process catalyst activity component is covered to invest on the modified layer equably to form.
The preparation method of preferred modified layer specifically may further comprise the steps:
(1) the preparation water based paint is selected ultra-fine alumina, silica or titan oxide particles for use, and grain diameter is below 10 μ m; By weight 1: 2-5 adds distilled water, stirs; Add phosphoric acid, regulator solution pH value 2-4, thus make water based paint; (2) the back oven dry is cleaned on porous metals structured packing surface; (3) with the even dip-coating of water based paint on the porous metals structured packing, and airing at room temperature; (4) the porous metals structured packing behind the airing is 100-120 ℃ of oven dry; (5) the porous metals structured packing after the oven dry is cured heat treatment 600～800 ℃ of roastings 6～12 hours, to quicken chemical reaction wherein, finally forms a kind of uniform and stable ceramic coating in the metal surface.In curing, the oxide generation thermal chemical reaction in metal surface and the coating forms compound phase, thereby coating and metallic matrix is combined securely.
Described active layer is the catalyst activity component to be covered equably invest in the porous metals structured packing that forms modified layer.The porous metals structured packing is after modification, catalyst activity component can cover equably, securely to invest on the porous metals structured packing modified layer that designs as required in advance and forms active layer by immersing method or spraying process, thereby makes compound porous metal catalytic distillation member of the present invention.
The method of formation active layer provided by the present invention can have two kinds, and a kind of is that liquid phase is immersed method, and another kind is a spraying process.
It is that the porous metals structured packing through modification is immersed in the solution that contains catalyst activity component that described liquid phase is immersed method, took out washing, drying through 24～48 hours after the crystallization, so repeatedly for several times, 400～600 ℃ of following roastings are 8～12 hours then, make the catalytic distillation structure with reaction and separation of double effect.
Described spraying process is to select suitable sprayer for use, with the solution spraying that contains catalyst activity component for preparing in the porous metals structured packing after the modification, 50～150 ℃ of dryings, 400～600 ℃ of roastings 8～20 hours, again through reducing gas such as H
2Reduce after 10～20 hours, make described catalytic distillation structure.
Described catalyst activity component can be selected from VIII family or IB family metal and composition thereof, and acid cation exchange resin also can be traditional or through the improved Y type of ion-exchange, X type, zeolite beta molecular sieve.Have as the metal of catalyst activity component according to the present invention: the mixture of element such as copper, silver, gold, rhenium, ruthenium, cobalt, rhodium, nickel, palladium, platinum and these elements.
Compound porous metal catalytic distillation member of the present invention can be applied to the chemical process of multiple applied catalysis distillation technique, selects hydrogenation, processes such as etherificate, ether decomposition, esterification, alkylation, isomerization, dehydration, hydrolysis as the cracking gas catalytic distillation.
Compound porous metal catalytic distillation member provided by the present invention has following advantage:
1) member is made of matrix, modified layer and active layer, integrate distillation filler and catalyst, both had higher separating property, have good reactivity worth again, can make the catalytic distillation process be able to efficiently successfully carry out, improve the conversion ratio and the selectivity of catalytic reaction;
2) matrix is the porous metals structured packing, has the character of metal with this catalytic distillation structure that makes, and existing good heat transfer property has enough intensity and toughness again, is convenient to processing, makes and installs;
3) ceramic coating that forms after surface treatment of matrix is as modified layer, and catalyst activity component can cover thereon attached securely, has avoided the loss of active constituent;
4) catalyst activity component evenly distributes in member, has improved the geometrical surface of catalyst, makes catalyst have higher utilization rate;
5) member shape and big I are flexible and changeable as required, but also flexible modulation of active constituent and content;
6) member has bigger voidage and specific area, and pressure drop reduces, and mass-and heat-transfer efficient greatly improves.
The specific embodiment
Embodiment 1
Select the expanded metal (Antai Science and Technology Co., Ltd provides by Iron and Steel Research Geueral Inst) of stainless steel substrate for use, it has uniform microcellular structure, and the aperture is 10-20 μ m, and porosity is 35%, and thickness of slab is 0.5mm.According to the method for preparing metal corrugated plate of routine, expanded metal is made 45 ° at ripple inclination angle, the crest height of wave and the pitch of waves are the porous metals corrugated plating of 15mm.Prepare some porous metals corrugated platings as stated above, and each sheet is assembled, adjacent two ripple intersects 90 ° during assembling, and each sheet assembling back forms φ 100 * 50mm structured packing dish.
Embodiment 2
The porous metals structured packing made from embodiment 1 is carried out surface modification as matrix to it.(1) selects the superfine alumina powder of particle diameter below 10 μ m for use, added distilled water, stir by weight 1: 3; Add phosphoric acid, the regulator solution pH value is 2.5, thereby makes water based paint; (2) the back oven dry is cleaned on porous metals structured packing surface; (3) with the even dip-coating of water based paint on the porous metals structured packing, and at room temperature dry; (4) the porous metals structured packing after drying places baking oven, in 110 ℃ of oven dry; (5) the porous metals structured packing after the oven dry is cured heat treatment 600 ℃ of roastings 8 hours, obtains forming the porous metals structured packing of modified layer.
Embodiment 3
Catalytic distillation structure proposed by the invention can be used for ethene and producing phenylethane from alkylation of benzene.To the modified porous metal structured packing that embodiment 2 makes, adopt liquid phase to immerse method load beta-molecular sieve.Get the beta-molecular sieve powder of particle diameter less than 10 μ m, added distilled water by weight 1: 2, stir, adding nitric acid regulator solution pH value again is 4, the porous metals structured packing is immersed among the solution then, takes out washing, dry, crystallization after 48 hours; With above-mentionedly immerse, wash, dry, crystallization process carries out 3 times repeatedly, 500 ℃ of following roastings are 10 hours then, make compound porous metal catalytic distillation member.The catalytic distillation structure of making is loaded in the φ 100mm catalytic distillation tower conversion zone.Catalytic distillation tower is made up of conversion zone and stripping section, the high 6m of conversion zone, the high 2m of stripping section, the random packing of stripping section filling φ 6 * 6mm stainless steel cannon ring.Operating condition is: the weight ethylene air speed is 0.28h
-1, benzene/ethylene molar ratio is 6: 1, and system pressure is 1.8MPa, and reaction temperature is 150～180 ℃.Operation with this understanding, reaction result is good, and conversion of ethylene reaches 100%, ethylbenzene selectivity average out to 98%.
Embodiment 4
Catalytic distillation structure proposed by the invention can be used for propylene and benzene alkylation preparing isopropylbenzene.Prepare catalytic distillation structure by the described method of embodiment 1-3, just expanded metal among the embodiment 1 is made crest height of wave 15mm, pitch of waves 30mm, 30 ° at ripple inclination angle, the porous metals corrugated plating of wall thickness 0.5mm is made the compound porous metal structured packing dish of φ 500 * 200mm.The catalytic distillation structure that makes is loaded in the φ 500mm catalytic distillation tower conversion zone.Catalytic distillation tower is made up of conversion zone and stripping section, the high 9m of conversion zone, and the high 3m of stripping section, (φ 500 * 200mm) for stripping section filling 250Y type metal structured packing.Operating condition is: the propylene weight air speed is 0.36h
-1, benzene alkene ratio is 6: 1, and system pressure is 0.8MPa, and reaction temperature is 140～180 ℃.Reaction with this understanding, propylene conversion reaches 100%, isopropylbenzene selectivity average out to 98%.
Embodiment 5
Catalytic distillation structure proposed by the invention can be used for the c 3 fraction catalytic distillation and selects hydrogenation and removing propine and allene (MAPD).To the modified porous metal structured packing that embodiment 2 makes, adopt spraying process supported catalyst active ingredient palladium.Press palladium content 0.5% (weight) preparation palladium bichloride or palladium nitrate aqueous solution, regulate pH value to 5.0～6.5, be sprayed on the modified matrix that is preheating to 40～60 ℃ with suitable sprayer, then 120 ℃ of dryings.The filler that carries palladium preferably is no more than 500 ℃ 350～500 ℃ of roastings, general roasting time 10 hours.Under suitable pressure and 60～120 ℃, make it to reduce 12 hours with hydrogen-containing gas then, make compound porous metal catalytic distillation member.The member that makes is packed in the φ 100mm catalytic distillation tower conversion zone.Catalytic distillation tower height 6m divides rectifying section, conversion zone and stripping section, the high 5m of rectifying section and stripping section, the random packing of filling φ 6 * 6mm stainless steel cannon ring; The high 1m of conversion zone, 20 of the metal catalytic distillation members that the φ 100 * 50mm that packs into altogether makes.Raw material feeds from the conversion zone bottom, and cat head obtains product.Feed composition is as shown in the table.
| Component | C 2 0 | C 3 0 | C 3 ＝ | C 3 ＝＝ | C 3 ≡ | C 4 | C 5 |
| Mole fraction (%) | 0.02 | 2.50 | 72.14 | 1.08 | 2.09 | 19.43 | 2.72 |
At reaction temperature 40-50 ℃, reaction pressure 1.6-1.8MPa, liquid phase feeding volume space velocity 2h
-1, hydrogen alkynes is than testing under 1.1 the condition.The result shows that this catalytic distillation structure has good reaction and separating property, and by catalytic distillation, propine and allene content are reduced to below the 3ppm in the cat head discharging, and propene yield is up to 103%.
Claims (8)
1, a kind of catalytic distillation structure, it is characterized in that, this member is made of matrix, modified layer and active layer, be matrix wherein with the porous metals structured packing, the ceramic coating that matrix is carried out forming after the surface treatment with the employing metal oxide is a modified layer, to cover the catalyst activity component that invests on the modified layer is active layer, and wherein said metal oxide is selected from aluminium oxide, silica and titanium oxide.
2,, it is characterized in that the porous metals structured packing of described its matrix of formation is made up of the porous metals corrugated plating according to the described catalytic distillation structure of claim 1.
3, according to the described catalytic distillation structure of claim 2, it is characterized in that described porous metals corrugated plating made by expanded metal, wherein expanded metal has uniform microcellular structure, and its aperture is 5-20 μ m, and porosity is 30-40%.
4, according to the described catalytic distillation structure of claim 2, it is characterized in that described porous metals ripple thickness of slab 0.2～1.0mm, 30 °～45 ° at ripple inclination angle, the crest height of wave and the pitch of waves are 5～30mm.
5, according to the described catalytic distillation structure of claim 1, it is characterized in that catalyst activity component is selected from following material: (1) VIII family or IB family metal and composition thereof, (2) acid cation exchange resin or (3) are traditional or through the improved Y type of ion-exchange, X type, zeolite beta molecular sieve.
6, the preparation method of the described catalytic distillation structure of one of claim 1-5, it is characterized in that described modified layer adopt the thermal chemical reaction method with metal oxide-coated in matrix surface, wherein said metal oxide is selected from aluminium oxide, silica and titanium oxide, may further comprise the steps: (1) prepares a kind of water based paint, wherein is dispersed with the superfine oxide particulate; (2) coating that step (1) is obtained is coated on the matrix, after super-dry and heat of solidification processing, forms uniform and stable ceramic coating at matrix surface;
Described active layer is to adopt liquid phase to immerse method or spraying process catalyst activity component is covered to invest on the modified layer equably to form.
7, according to the described preparation method of claim 6, it is characterized in that described water based paint prepares by the following method: select ultra-fine alumina, silica or titan oxide particles for use, grain diameter is below 10 μ m; By weight 1: 2-5 adds distilled water, stirs; Add phosphoric acid, regulator solution pH value 2-4, thus make water based paint.
8, according to the preparation method of the described catalytic distillation structure of claim 6, it is characterized in that described liquid phase immerses method and comprise that the matrix that will form modified layer is immersed in crystallization in the solution that contains catalyst activity component, take out back washing, dry, roasting.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02156506 CN1241664C (en) | 2002-12-16 | 2002-12-16 | Composite porous metal catalyst distillation construction member and preparing method thereof |
| US10/361,084 US7226884B2 (en) | 2002-02-07 | 2003-02-06 | Composite for catalytic distillation and its preparation |
| US11/741,395 US7642388B2 (en) | 2002-02-07 | 2007-04-27 | Composite for catalytic distillation and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02156506 CN1241664C (en) | 2002-12-16 | 2002-12-16 | Composite porous metal catalyst distillation construction member and preparing method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1507933A CN1507933A (en) | 2004-06-30 |
| CN1241664C true CN1241664C (en) | 2006-02-15 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 02156506 Expired - Lifetime CN1241664C (en) | 2002-02-07 | 2002-12-16 | Composite porous metal catalyst distillation construction member and preparing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10047880B2 (en) * | 2015-10-15 | 2018-08-14 | Praxair Technology, Inc. | Porous coatings |
| CN105597357B (en) * | 2016-02-29 | 2018-08-24 | 中石化炼化工程（集团）股份有限公司 | A kind of compound regular packing and preparation method thereof |
| CN113198535B (en) * | 2021-05-17 | 2022-05-03 | 厦门大学 | Preparation method of ceramic surface supported catalytic filler |
| CN115261064B (en) * | 2022-08-08 | 2023-11-21 | 内蒙古伊泰煤基新材料研究院有限公司 | Raw material pretreatment system and method for preparing alkyl aromatic hydrocarbon from Fischer-Tropsch light oil |
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