CN1120040C - Efficient part for catalytic distillation tower - Google Patents
Efficient part for catalytic distillation tower Download PDFInfo
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- CN1120040C CN1120040C CN 99124796 CN99124796A CN1120040C CN 1120040 C CN1120040 C CN 1120040C CN 99124796 CN99124796 CN 99124796 CN 99124796 A CN99124796 A CN 99124796A CN 1120040 C CN1120040 C CN 1120040C
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- catalyst
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- tower member
- catalytic distillation
- distillation tower
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Abstract
The present invention discloses an efficient part of a catalytic distillation tower, which comprises a catalyst and regular filler which can support the catalyst. The present invention is characterized in that the catalyst is made into particles with central pore canals; catalyst particles are connected into a string by a connecting piece; the catalyst particles are uniformly put into a gas-liquid free passage of the regular filler to form the efficient part of a catalytic distillation tower according to the present invention. The efficient part of a catalytic distillation tower of the present invention has the characteristics of uniform catalyst distribution and large bed voidage simultaneously. Thus, the present invention has the advantages of high catalyst utilization rate, large bed-layer flux, small tower diameter, small tower pressure drop and convenient tower loading, unloading and operation.
Description
The present invention relates to a kind of catalytic distillation tower member efficiently.Or rather, the present invention relates to a kind of efficient catalytic destilling tower member that is applicable to liquid-solid two-phase or gas-liquid-solid three-phase reaction system.
In a lot of fields as chemical industry, petrochemical industry and environmental protection field, exist many objects that adopt the processing of liquid-solid two-phase or gas-liquid-solid three-phase reaction system, wherein a kind of gas and/or a kind of liquid are as reaction raw materials, it or they on a kind of solid catalyst haptoreaction, generate the purpose product.
This liquid-solid two-phase or gas-liquid-solid three-phase reaction system are particularly useful for adopting catalytic distillation process to carry out.Catalytic distillation technology is a kind of new Chemical Reaction Engineering method that development in recent years is got up, and it is integrated catalytic reaction process and separated process, reacts simultaneously and the operation that separates in same catalytic distillation tower reactor.This process can constantly go up reactivity point the instant product transfer that generates and leave reaction zone, and molecular balance is moved to the direction that generates the purpose product, and reaction heat also can be used as the required heat of vaporization of still-process simultaneously.Therefore catalytic distillation technology have that reaction mass conversion ratio height, product choose, series of advantages such as product purity height, energy consumption are low, easy to operate, reduced investment.Catalytic distillation technology is application success in the production of methyl tertiary butyl ether(MTBE) (MTBE) at first, and has been applied to many other fields.
The key of catalytic distillation technology is the constituted mode of the catalytic distillation structure in the catalytic distillation tower.The constituted mode of so-called catalytic distillation structure relates to the factors such as type of feed of configuration, catalyst and the filler of catalyst used in the member and/or its configuration, filler.Constituted mode to catalytic distillation structure has launched many work, present reported packed tower and the plate column two big classes of can being divided into basically, and the document that wherein relates to the catalytic distillation structure of liquid-solid two-phase and gas-liquid-solid three-phase reaction system for example has:
United States Patent (USP) 4471154 proposes catalyst is placed on the column plate of plate column and constitutes catalytic distillation structure, and catalyst is fluidized state on column plate.The constituted mode of this member can make entire reaction district catalyst distribution even, and gas-liquid is affixed touches well the catalyst utilization height; But bed voidage is less, and operation flux is restricted, and the resistance of conversion zone is excessive.
United States Patent (USP) 4443559 proposes catalyst granules is seated in the tiny pocket of the strap 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 type cylinder catalytic distillation structure of one deck cloth bag.This member belongs to the packed tower type, and its form of the composition makes catalyst even in spatial distribution, and leaves enough gas-liquid phase flow channel and contact area.This member is adopted by the catalytic distillation of synthetic MTBE, has realized industrialization.But this scheme is contained in catalyst granules in bag class container, touches mutually between particle and the particle, makes a part of catalyst surface area be not easy to contact with reaction mass.Therefore, the utilization rate of catalyst surface has much room for improvement; In addition, this scheme is made the general little special tower configuration of packed tower of its voidage with the conversion zone of catalytic distillation tower, the above and below of conversion zone then remains common filler or column plate, thereby the design of whole catalytic distillation tower, make with regard to more complicated, specification requirement height, and the filler loading and unloading are pretty troublesome.
United States Patent (USP) 5262012 proposes catalyst is pressed the form filling of dumped packing, for example, granular catalyst is mixed in the bucket formula container upright in the tower of packing into inertia filled media such as porcelain ball, bead, hollow porous spheroid or cylinder etc., form the catalytic distillation structure in the reaction zone.This member belongs to the packed tower type.Its deficiency is, catalyst is solid, so granularity can not be too big, otherwise can not make full use of catalyst, but catalyst grain size is too little it is easy in operation and the filler layering, make catalyst and filler maldistribution, damaged the synergistic function that this member is brought into play its catalytic reaction-separated; Between the catalyst granules, that part of surface touched of catalyst granules and filler particles can not be fully used; This in addition component form also is easy to produce channel in bed, this has also hindered this member to bring into play its normal catalytic distillation function.
In addition, Chinese patent 1042664 proposes the catalytic distillation tower conversion zone is divided into several beds, each bed by sandwich type assembly a plurality of arranged verticals in parallel to each other, that form by two parallel clamping catalyst of corrugated plating to constituting, adjacent component between the bed space give over to gas phase channel, make up gas pass bed and separation tray.It is convenient that this catalytic distillation structure has catalyst loading and unloading, and reaction mass and the advantage that catalyst can directly contact can reduce the influence of diffusion couple reaction rate.But because gas-liquid two-phase passes in the conversion zone passage separately respectively, the alternate mass transfer of solution-air two be difficult for to take place, so it is unwell to gas phase and liquid phase all is gas-liquid-solid three-phase reaction system of reaction mass, though guaranteed bed enough voidages are arranged, but the distribution of catalyst in bed is also inhomogeneous, there is not that part of bed space of catalyst not to be utilized effectively, so bigger defective is also arranged when being used for the biphasic reaction system.In addition, it also exists owing to catalyst granules touches the shortcoming that the catalyst granules surface is not fully utilized mutually.
In sum, catalytic distillation tower member of the prior art-no matter be packed tower type or plate column type-all exist shortcoming separately, they are difficult to satisfy simultaneously the requirement of following two aspects, promptly can make in the catalytic distillation tower conversion zone bed voidage very big, make liquid-solid two-phase or the abundant mass transfer of gas-liquid-solid three-phase, reduce pressure drop, catalyst always is evenly distributed in the whole bed, thus the utilization ratio that contacts, improves catalyst between the surface area that makes full use of catalyst granules and the reaction mass.
Therefore purpose of the present invention provides a kind of efficient catalytic destilling tower member, and it has overcome the defective of catalytic distillation tower member well known in the prior art, can make the conversion zone bed have very big voidage, and catalyst is evenly distributed in the whole bed.
Comprise a kind of catalyst and a kind of energy supporting catalyst and carry out the structured packing of mass transfer by efficient catalytic destilling tower member of the present invention, it is characterized in that, catalyst is made particle with central duct, pass the central duct of each catalyst granules with a kind of connector, so that they connect bunchiness, constitute catalyst granules and connect string location; Catalyst granules is connected the gas-liquid clear passage that structured packing was put into and be fixed on to string location, form catalytic distillation tower member; The catalytic distillation tower member of Gou Chenging should satisfy the requirement of its separative efficiency 〉=0.5 theoretical plate/rice mensuration tower like this;
Accompanying drawing 1 is the configuration schematic diagram commonly used by the catalyst granules that uses in the catalytic distillation tower member of the present invention;
Accompanying drawing 2 is for connecting the common form schematic diagram of string location by the catalyst granules that uses in the catalytic distillation tower member of the present invention;
But accompanying drawing 3 is configuration and catalyst arrangement mode schematic diagram therein by the structured packing of a kind of preferred supporting catalyst that uses in the catalytic distillation tower member of the present invention;
Accompanying drawing 4 is the schematic diagram of the tower member that forms by catalytic distillation tower member of the present invention unit with by the plate column member unit.
Within the scope of the present invention, any catalyst that can be used for liquid-solid two-phase or gas-liquid-solid reaction all can be used as by the catalyst in the tower member of the present invention, but it must be made the particle with central duct, preferably has the particle of special-shaped outer surface. The purpose of making the particle of special-shaped outer surface is in order to increase catalyst granules and gas-and/or area of contacting of liquid material as far as possible. Referring to Fig. 1, common catalyst granules comprises trifolium-shaped with central duct, circular ring type, column type, ball-type, cuboid, square build, polyhedral, circular platform type etc., preferably has trifolium-shaped or the cylinder type of special-shaped outer surface. The size of catalyst granules is decided with the catalyst granules configuration of specifically selecting, and makes its density 〉=1g/cm as long as satisfy3Get final product, be preferably the particle size of φ 3-10mm.
That the catalyst granules connector that adopts among the present invention can be rigidity or have certain flexible, such as making silk with elongated strip, rod, bar, rope etc. by the bar of the wire of different size such as stainless steel wire, the thin rod of pottery or other applicable material such as plastics, fiber and other composite, rope etc. It connects bunchiness by the central duct on the catalyst granules with catalyst granules, forms catalyst granules and connects string location; Such catalyst granules connects string location can have configuration shown in Figure 2, such as the configuration of single string, two strings, many strings, spiral helicine, polyhedral, polygonal and ring-type etc.
By of the present invention, can supporting catalyst and the structured packing of carrying out mass transfer comprise structured packing any configuration, that satisfy following condition, promptly can provide after catalyst granules connects string location 〉=separative efficiency of 0.5 theoretical plate/rice mensuration tower height as long as it can above-mentioned catalyst granules connects in the free space that string location firmly and equably be bearing in the gas-liquid channel that structured packing provides and has supported.Used term " supporting " means and above-mentioned catalyst granules is connected ground, string location location hangs, supports or be stacked in the gas-liquid clear passage that structured packing provides, make its position relative fixed, in gas-liquid channel, remarkable displacement can not be arranged, constitute the catalytic distillation tower member unit like this.The loadings of catalyst and bed voidage will depend on the factors such as separative efficiency of concrete reaction system, catalyst system therefor kind and performance and structured packing.For the system of liquid-solid two-phase mass transfer and reaction, bed voidage can hang down a bit relatively, for example 〉=60%; For the system of gas-liquid-solid three-phase mass transfer and reaction, then require bed voidage bigger, for example 〉=80%; The filling branch rate of catalyst can be asked for by simple experiment in the bed, promptly progressively increase the filling branch rate of catalyst, no longer cause up to the catalytic distillation system till the corresponding increase of conversion ratio of reaction raw materials, the amount that slightly increases by a site catalyst in practicality is as standby surplus.For liquid-solid two phase systems, the filling branch rate of catalyst is generally 15-70% in the bed, and for gas-liquid-solid three-phase system, the filling branch rate of catalyst is generally 5-50% in the bed.
Can be divided into a plurality of tower member layers by tower member of the present invention, every layer of tower member layer can be made up of one or more above-mentioned tower members unit, specifically according to tower diameter size and the convenient principle decision of making and loading and unloading.But adjacent two layers both adjacent layer stacks and puts, and available again other device as gas/liquid are collected redistributor and separated and place the formation conversion zone.The position relation of adjacent two layers tower member layer is to make the cross section dislocation as far as possible in the horizontal direction of two-layer gas-liquid clear passage.Said conversion zone bed be meant constitute by the tower member unit that has comprised catalyst in the conversion zone, have the reaction and a that part of bed of separation function simultaneously.
According to the present invention, filler or measure by distillation test by the number of theoretical plate that catalyst connects the conversion zone bed that series unit and structured packing constitute.System to be measured is put into destilling tower, and destilling tower mainly is made up of body of the tower, tower still reboiler and overhead condenser.Measure and to select binary systems such as benzene-toluene, benzene-carbon tetrachloride for use with system.When measuring beginning, the system that at first will measure usefulness once drops in the tower still, regulate the heat that adds of reboiler, under normal pressure, operated about one and a half hours in the infinite reflux mode, after treating that vapour one liquid two-phase reaches balance, measure the vapour-liquid phase composition of cat head and tower still, (Mai Kaibo-Di Lifa) or shortcut method (Fenske equation) are calculated the theoretical cam curve of trying to achieve system to be measured to adopt diagram method then, divided by system to be measured (filler or bed) highly, quotient is every meter number of theoretical plate of this filler or bed again.
But accompanying drawing 3 illustrative by supporting catalyst that uses in the catalytic distillation tower member of the present invention and the preferred embodiment and the arrangement mode of catalyst in this structured packing that carry out the structured packing of mass transfer, wherein structured packing is a stainless steel calendering corrugated plating, and the crest height of wave of corrugated plating is 4-100mm; The pitch of waves is 4-150mm; Ripple direction and vertical axis have one 0-45 °, the inclination angle of preferred 15-30; Catalyst granules is connected the formation that string location is made two strings, and be bearing within the trough along the ripple direction, they both can be positioned in each trough, also can place a catalyst granules every one or more troughs and connect string location; As Fig. 3 (a, b) shown in, supported the corrugated platings that catalyst granules connects string location and be arranged in parallel like this by numerous, constitute the similar cellular catalytic distillation tower member of its cross section unit.For less tower, such tower member unit promptly can be used as a tower member layer, shown in Fig. 4 a; For bigger tower, shape shown in Fig. 4 b can be made in such tower member unit, by adjacent shop, a plurality of this unit sign indicating number, constitute a tower member layer; Adjacent stacked or at interval stacked by one or more such tower member layers again, constitute catalytic distillation tower member, as Fig. 4 (c, d, e) shown in.
The conversion zone that is used for tower by catalytic distillation tower member of the present invention, in the tower other section as stripping section and optionally the filler in the rectifying section can use conventional fillers, comprise dumped packing and structured packing, preferred use with conversion zone in used identical structured packing, as long as satisfied 〉=1 theoretical plate/rice mensuration tower of its separative efficiency.Can guarantee that by catalytic distillation tower member of the present invention catalyst is evenly distributed in the bed space of catalytic distillation tower conversion zone, loadings and loading density can be regulated, can fully contact with reaction mass, catalyst utilization ratio height, loading amount is less, saves catalyst amount, reduces tower diameter, saves investment; In addition, its bed voidage is big, can sufficient mass transfer take place and separate, the material flux is big, and bed resistance is less, can obviously improve disposal ability, be applicable to the catalytic distillation process of liquid-solid two-phase and gas-liquid-solid three-phase reaction system simultaneously, good product quality, operating flexibility is big; Has easily advantage such as filling and replacing of tower member and catalyst in addition.
Following examples are used for explaining in more detail the present invention, but this and do not mean that any restriction to the scope of the invention.After learning the disclosure of the present patent application, those of ordinary skills can make technical solution of the present invention and changing or improvement, but these changes and improvements all do not exceed the scope of the flesh and blood of the present invention of appended claim qualification.
Embodiment
Use is made sources of ethylene by the following oil refinery dry gas of forming
Adopt catalytic distillation process to make it and benzene carry out alkylation to prepare ethylbenzene, adopt FX-02 type beta-zeolite alkylation catalyst, reaction temperature 140-160 ℃, pressure 1.6MPa.Designed productive capacity is predefined for 100,000 tons of ethylbenzene/years, requires conversion of ethylene 〉=95%, the selectivity of ethylbenzene 〉=95%.When adopting by catalytic distillation tower member of the present invention, use 12.5 tons of catalyst, 12 meters of catalytic bed floor heights, be divided into 3 sections, with supporting member (the peak height 11.7mm of TJ250 type corrugated plate regular packing as catalyst, the pitch of waves is 15mm, 42.5 ° at inclination angle), each tower member floor height 200mm, catalyst is made the particle of the φ 4 * 4mm cylinder type with central duct, as connector catalyst is connected into two serial type catalyst granules with stainless steel wire and connect string location, such catalyst granules of each trough internal support connects string location.In such a way, the tower that only to need a tower diameter be φ 2800mm just can satisfy production requirement, bed pressure drop≤0.2MPa.
| Component | H 2 | ?CO 2 | ?N 2+O 2 | ?CH 4 | C 2H 6 | ?C 2H 4 | C 3H 8 | ?C 3H 6 | ?C 4H 10 | ?C 4H 8 |
| Mole % | 15.3 | ?3.7 | ?13.2 | ?31.4 | 15.8 | ?17.4 | 0.9 | ?1.4 | ?0.7 | ?0.17 |
When other condition is identical, the catalytic distillation tower member that constitutes if adopt accumulation catalyst granules in bulk-distillation filler in corrugated plate regular packing-wherein catalyst the is made for column type particle of φ 4 * 4mm, the distillation filler is the stainless steel θ type calendering ring of φ 4mm, be seated in the clear passage of corrugated plate regular packing after both mixtures are even, the tower that then to need a tower diameter be φ 4200mm could satisfy production requirement, and bed pressure drop is bigger, is difficult to make Δ P≤0.2MPa.
Claims (10)
1. catalytic distillation tower member, comprise a kind of catalyst and a kind of energy supporting catalyst and carry out the structured packing of mass transfer, it is characterized in that, catalyst is made particle with central duct, pass the central duct of each catalyst granules with a kind of connector, so that they connect bunchiness, constitute catalyst particles and connect string location; Catalyst granules is connected the gas-liquid clear passage that string location is put into structured packing, form catalytic distillation tower member; The catalytic distillation tower member of Gou Chenging should satisfy its separative efficiency 〉=0.5 theoretical plate/rice mensuration tower like this.
2. by the tower member of claim 1, it is characterized in that the density of said catalyst granules is 〉=1g/cm
3
3. according to the tower member of claim 1, it is characterized in that said catalyst granules with central duct is trifolium-shaped, circular ring type, cylinder type, ball-type, rectangular build, upright build, multiaspect build or the circular platform type particle with central duct.
4. by the tower member of claim 3, it is characterized in that said catalyst granules with central duct is cylinder type and trifolium-shaped particle.
5. by the tower member of claim 1, it is characterized in that, said connector be rigidity or have certain flexible.
6. by the tower member of claim 5, it is characterized in that connector is made by the elongated strip silk, rod, bar, the rope that are selected from metal, pottery, plastics, fiber and other composite.
7. by the tower member of claim 1, it is characterized in that, catalyst granules is connected the configuration that string location is made single string, two strings, many strings, spiral helicine, polyhedral, polygonal or ring-type.
8. by the tower member of claim 1, it is characterized in that, can supporting catalyst and the structured packing of carrying out mass transfer be the metal corrugated plate structured packing, its crest height of wave is 4-100mm, the pitch of waves is 4-150mm, ripple direction and vertical axis are one 0-45 ° inclination angle.
9. by the tower member of claim 8, it is characterized in that said metal corrugated plate structured packing is a stainless steel calendering corrugated plate regular packing, its crest height of wave is 11.7mm, and the pitch of waves is 15mm, and ripple direction and vertical axis are 42.5 ° of inclination angles.
10. each the application of tower member in catalytic distillation tower among the claim 1-9 is characterized in that, for liquid-solid biphasic reaction system, the catalyst filling branch rate in the conversion zone bed is 15-70%, bed voidage 〉=60%; For gas-liquid-solid three-phase reaction system, the catalyst filling rate in the conversion zone bed is 5-50%, and bed voidage is 〉=80%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99124796 CN1120040C (en) | 1999-12-10 | 1999-12-10 | Efficient part for catalytic distillation tower |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99124796 CN1120040C (en) | 1999-12-10 | 1999-12-10 | Efficient part for catalytic distillation tower |
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| Publication Number | Publication Date |
|---|---|
| CN1299703A CN1299703A (en) | 2001-06-20 |
| CN1120040C true CN1120040C (en) | 2003-09-03 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 99124796 Expired - Fee Related CN1120040C (en) | 1999-12-10 | 1999-12-10 | Efficient part for catalytic distillation tower |
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| CN (1) | CN1120040C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107812392A (en) * | 2016-09-13 | 2018-03-20 | 河北新欣园能源股份有限公司 | Methyl tertiary butyl ether(MTBE) catalytic rectifying tower filling-material structure and fill method |
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1999
- 1999-12-10 CN CN 99124796 patent/CN1120040C/en not_active Expired - Fee Related
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| CN1299703A (en) | 2001-06-20 |
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