KR101652605B1 - Apparatus and method for regenerating catalyst - Google Patents

Abstract

The present invention relates to a catalyst regeneration apparatus for regenerating a catalyst for regenerating a metal carbonyl by forming a carbon monoxide zone in a catalyst regeneration apparatus composed of a combustion zone, a chlorination zone and a drying zone, According to the present invention, it is possible to improve the process yield of the catalyst regeneration reaction and reduce the unit cost.

Description

TECHNICAL FIELD [0001] The present invention relates to a catalyst regeneration apparatus,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst regeneration apparatus and method, and more particularly, to a catalyst regeneration apparatus and method for regenerating spent catalyst in contact conversion for converting a hydrocarbon into a useful hydrocarbon product so that it can be reused in a hydrocarbon conversion reaction .

A number of hydrocarbon conversion processes can be used to alter the structure or properties of the hydrocarbon stream. Generally, such processes include isomerization from straight chain paraffins or olefinic hydrocarbons to more branched chain hydrocarbons, dehydrogenation for the preparation of olefins or aromatics, dehydrocyclization for the preparation of aromatic and automotive fuels, Alkylation, transalkylation, and the like for the manufacture of daily commodities and automotive fuels.

Propylene can be obtained by dehydrogenation of propane through a catalytic dehydrogenation reaction. However, the reaction is a strong endothermic reaction and requires high temperature to proceed the reaction at a satisfactory rate. As the catalytic reaction progresses at a high temperature, a side reaction therewith involves pyrolysis and coke formation reaction, and the degree of such side reaction is a key factor determining the selectivity and activity of the catalyst. One of the side reactions, the coke formation reaction, covers the active material on the catalyst with coke, thereby blocking the contact with the reactants, thereby lowering the overall reaction conversion rate. Further, as the production of coke proceeds, the inlet of the pores existing in the catalyst is blocked to dampen the active substance present in the pores, thereby promptly promoting deactivation. Thus, when the accumulation of coke deposits causes inactivation in the next stage of the dehydrogenation reactor, a catalyst regenerator is connected to regenerate the catalyst to regain the activity of the catalyst to remove coke deposits.

The catalyst regeneration apparatus in mobile phase mode generally comprises a reaction zone which may comprise a series of three or four reactors and a reaction zone comprising any number of stages, generally the combustion stage, the subsequent chlorination stage, Is used.

Referring to FIG. 1, domestic patent publication No. 2014-0012165 discloses a continuous catalyst regenerator 10 for regenerating catalyst particles, having a combustion zone 18 and a halogenation zone 40, A combustion zone chamber (24) configured to contact the gas and burn coke deposits on the catalyst particles; A passage configured to direct the catalyst particles from the combustion zone to the halogenation zone; And a halogenated zone inlet (46) configured to supply a chlorinated gas (48) and a second oxygen containing gas (50) to the halogenated zone, the halogenated zone contacting the catalyst particles with a chlorinated gas and a second oxygen containing gas, And the catalyst particles are chlorinated to redisperse the platinum group metal to form regenerated catalyst particles.

In the conventional catalyst regenerating apparatus, the catalyst is moved in addition to the catalyst formed by the catalytic reaction, and a coke is formed while being connected with a metal material such as cobalt, nickel, copper, iron, chromium and the like. In order to solve this problem, a sulfur-containing compound such as hydrogen sulfide, dimethyl sulfide (DMS) and dimethyl disulfide (DMDS) is conventionally added together. The sulfur-containing compound scavenges newly formed coke precursors to inhibit coke formation and reduce cracking. However, some of these sulfur-containing compounds have the problem of reducing the activity of the catalyst and increasing the cost by igniting the active site of the catalyst.

SUMMARY OF THE INVENTION It is an object of the present invention to overcome the problems of the prior art described above and it is an object of the present invention to provide a method and an apparatus for removing carbon monoxide from an exhaust gas by adding carbon monoxide (CO) to an existing combustion zone, The present invention provides a catalyst regeneration apparatus and method which can reduce the amount of sulfur-containing compounds used to remove substances, improve the fairness of the catalyst regeneration reaction, and reduce the unit load.

Another object of the present invention is to improve the efficiency and stability of the catalyst regeneration process by variously designing the shape and gas flow of the catalyst regenerator by adding a carbon monoxide zone to the catalyst regenerator.

According to one aspect of the present invention for achieving the above object,

A device for regenerating a catalyst comprising: at least one feed gas inlet tube and a discharge tube for discharging the regenerated catalyst, the catalyst being configured to continuously pass the combustion zone, the chlorination zone and the drying zone to the mobile phase, And a carbon monoxide zone for removing the metal substance by reacting carbon monoxide with the metal material to form a metal carbonyl.

According to another aspect of the present invention, there is provided a method for producing a catalyst, comprising: burning a coke deposit on spent catalyst particles using a combustion gas; A method for regenerating a catalyst for regenerating a catalyst comprising: chlorinating catalyst particles and drying the chlorinated catalyst to form regenerated catalyst particles, the method comprising: reacting carbon monoxide with a metal material accumulated as the catalyst is moved And forming a metal carbonyl to remove the metal material.

According to the catalyst regenerating apparatus according to various embodiments of the present invention, it is possible to reduce the amount of the sulfur-containing compound used for removing the metal materials (Co, Ni, Cu, Fe, Cr, etc.) Improve fairness and reduce unit cost.

According to the present invention, besides the coke formed by the catalytic reaction, the coke produced when the catalyst moves can be reduced, and the regenerator type and the gas flow can be designed by adding the carbon monoxide zone.

1 is a schematic view of a conventional catalyst regeneration apparatus.
2 is a schematic diagram of an apparatus for regenerating a catalyst according to an exemplary embodiment of the present invention.
3 is a schematic diagram of an apparatus for regenerating catalyst particles according to another exemplary embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in more detail with reference to the accompanying drawings. The embodiments of the present invention are shown by way of example and are not limited to the features of the accompanying drawings. In the following, similar components will be described using similar reference numerals.

As used herein, the term " zone " refers to a specific area within a catalyst regenerator device that includes one or more devices or sub-zones, and the body of the catalyst regenerator device in the present invention may include one or more zones And may include sub-zones.

2 is a schematic diagram of an apparatus for regenerating a catalyst according to an exemplary embodiment of the present invention. Referring to FIG. 2, a catalyst regeneration apparatus according to an embodiment of the present invention includes at least one feed gas inlet pipe 12, 22, 31, 42 and a catalyst exhaust conduit 50 for discharging the regenerated catalyst, The carbon monoxide is removed by continuously passing through the combustion zone Z1, the chlorination zone Z2 and the drying zone Z3 as the mobile phase, and by reacting the metal substances accumulated with the catalyst and the carbon monoxide by moving the catalyst, Zone (CO).

The carbon monoxide zones 40 and 40 'include a carbon monoxide injection conduit 42 for injecting carbon monoxide and a discharge means (not shown) for discharging the produced metal carbonyl compound.

In the catalyst regenerating apparatus of the present invention, the amount of the coke produced by the catalyst other than the coke formed by the catalytic reaction can be reduced. For example, by adding a carbon monoxide zone (CO) to a coke produced by connecting a metal such as Fe, Co, Ni, Cr or Cu while the catalyst moves, metal carbonyl is reacted with carbon monoxide So that the metal forming the coke is removed beforehand in the carbon monoxide zone 40, 40 '. In the carbon monoxide zones 40 and 40 ', metallic substances such as cobalt, nickel, iron and chromium are carbon monoxide supplied through the conduit 43 to form cobalt carbonyl (Co (CO) ₄ , Co (CO) _3), nickel carbonyl (Ni (CO) _4), iron carbonyl (Fe (CO) _5), chromium carbonyl (Cr (CO) _6), carbon monoxide zone (CO metals to form a) zone Can be removed in advance.

Ni + 4CO? Ni (CO) ₄

Co + 4CO ⇒ Co (CO) ₄

Cr + 6CO? Cr (CO) ₆

Fe + 5CO? Fe (CO) ₅

The metals such as Ni (CO) ₄ , Co (CO) ₄ , Cr (CO) ₆ and Fe (CO) ₅ produced in the carbon monoxide zones 40, 40 ' And there is a CO adsorption filter at this outlet, so that CO is maintained at a constant concentration.

The catalyst regenerating apparatus of the present invention may further include a release input device 1 integrally formed at the upper end of the combustion zone. Such a termination injector is formed integrally with the combustion zone 10, 10 'and removes catalyst residues and contaminants from the spent catalyst.

In the catalyst regeneration apparatus of the present invention, the combustion zone 10, 10 ', the carbon monoxide zone 40, 40' and the chlorination zone 20, 20 'are formed in an annular disc shape, and the catalyst bed is formed of two coaxial cylindrical walls Lt; RTI ID = 0.0 > a < / RTI > The oxygen-containing gas supplied to the combustion zones 10 and 10 'flows through the inlet conduit 12 of one wall and passes through the combustion zones 10 and 10' (13).

In the catalyst regeneration apparatus of the present invention, the combustion zones 10 and 10 ', the chlorination zones 20 and 20' and the carbon monoxide zones 40 and 40 'are provided with means 11 and 21 for expanding the horizontal cross- , 41). The cross sectional area expanding means 11, 21 and 41 have a porous plate structure and the size of the pores formed in the porous plate should be such that the reaction gas can easily pass therethrough and the passage of catalyst particles can be suppressed . The holes of the perforated plate may be in the form of a circle, a square, a rectangle, a triangle, a narrow horizontal or vertical slot, or the like.

In the combustion zone Z1, one or more conduits 12 for introducing an inert gas into the combustion zones 10, 10 'for transporting the catalyst are connected between the release device 1 and the combustion zones 10, 10' And at least one combustion gas discharge pipe 13 for discharging gas from the combustion zone 10, 10 'is connected to the opposite lower end of the combustion zone. In the combustion zones 10 and 10 ', the gas circulation is the same as the catalyst flow from the upper part to the lower part, so that the problem caused by the clogging of the catalyst during the regeneration of the catalyst can be prevented in advance.

After combustion, a catalyst having a lower content of carbon-containing material is passed down the conduit to the carbon monoxide zone 40, 40 'and then downwardly to the chlorination zone 20, 20'. Then flows into the drying zone 30 and exits the body via the catalyst exhaust conduit 50.

If the chlorination zone is in the axial direction, it is advantageous that the chlorination gas is introduced into the lower portion of the chlorination zone 20, 20 'to flow countercurrently to the catalyst. In the chlorination zone 20, 20 ', the chlorinated gas is introduced through at least one conduit 22, which is located at the bottom of the chlorination zone, and the gas exiting the chlorination zone passes through the conduit between the combustion zones 10, 10' Is discharged through a chlorination gas discharge pipe 14 formed in the upper part of the combustion zone so that the circulation of the gas in the chlorination zone 20, 20 'is made from the lower part to the upper part.

The chlorination zone 20, 20 'is supplied with at least one chlorinated gas, at least one oxygen-containing gas, or water. The chlorinated gas may be chlorine, HCl, or chlorinated hydrocarbons (e.g., carbon tetrachloride) containing less than 12 carbon atoms and 1 to 6 chlorine atoms or any chlorinated gas known to release chlorine in such a regeneration process.

In the chlorination zone 20, 20 ', the catalyst is contacted with the chlorinated gas introduced through the introduced conduit 22 and also with the gas from the drying zone 30, recharging the charged oxygen, Lt; / RTI > of water.

In addition, the catalyst regenerating apparatus according to an embodiment of the present invention may further include a triangular-pyramid type auxiliary plate 35 for allowing regenerated catalyst particles to be discharged smoothly without stagnation at the lower end of the drying zone. This triangular-pyramid assist plate 35 helps the regenerated catalyst particles to be gradually dispersed and discharged without being exhausted to the catalyst exhaust conduit 50 at once.

The drying zone 30 may include one or more gas cooling means, one or more gas treatment means for removing impurities, one or more gas drying means and one or more gas compression means.

3 shows a catalyst regeneration apparatus of another embodiment of the present invention.

3, a combustion zone Z1, a chlorination zone Z2, a carbon monoxide zone CO, and a drying zone Z3 are provided in the same manner as the apparatus shown in FIG. 2 in the catalyst regeneration apparatus of another embodiment of the present invention. The apparatus also includes a conduit 12 configured to supply a hot oxygen-containing gas to the combustion zone Z1. Further, in the combustion zone Z1, the catalyst particles are contacted with an oxygen-containing gas to burn coke deposits on the catalyst particles. The apparatus further comprises a passage configured to direct the catalyst particles from the combustion zone (Z1) to the chlorination zone (Z2). Structurally, the apparatus comprises a conduit 22 configured to supply a chlorination gas and an oxygen-containing gas to the chlorination zone Z2. In addition, the apparatus is provided with a chlorination zone (Z2) configured to contact the catalyst particles with a chlorinated gas and an oxygen-containing gas, and to form regenerated catalyst particles by chlorinating the catalyst particles to redisperse the platinum group metals. In the catalyst regeneration apparatus of another embodiment of the present invention, the carbon monoxide zone C0 may be provided between the chlorination zone Z2 and the drying zone Z3.

In another embodiment, instead of adding a carbon monoxide zone (CO) in the catalyst regenerator, a carbon monoxide zone may be added in the chamber for the catalyst reduction prior to the catalyst regeneration process.

Further, the catalyst regenerating apparatus of the present invention can bypass the carbon monoxide zone and replace the combustion zone or the chlorination zone when the amount of the coke increases or the catalyst sintering increases.

Another aspect of the present invention relates to a catalyst regeneration method. The method of the present invention comprises the steps of burning coke deposits on spent catalyst particles using a combustion gas; A method for regenerating a catalyst for regenerating a catalyst comprising: chlorinating catalyst particles and drying the chlorinated catalyst to form regenerated catalyst particles, the method comprising: reacting carbon monoxide with a metal material accumulated as the catalyst is moved And removing the metal material by forming a metal carbonyl. In the method of the present invention, the combustion step, the chlorination step and the drying step are not sequentially carried out, and instead, the chlorination step, the carbon monoxide reaction step, the chlorination step and the drying step may be sequentially carried out. Alternatively, the chlorination step, the chlorination step, the carbon monoxide reaction step, and the drying step may be carried out sequentially.

Referring again to FIG. 2, a stream containing spent catalyst particles containing coke deposits is provided to the catalyst inlet 2. In order to maintain or restore the catalytic activity of the spent catalyst particles, the spent catalyst particles must be regenerated, i.e. almost all of the coke must be removed from the spent catalyst particles.

 The removal of the coke from the spent catalyst particles is carried out by combustion in the combustion zone 10, 10 'of the catalyst regenerator. As shown, the combustion zone Z1 includes a first combustion zone 10 and a second combustion zone 10 '. A stream of spent catalyst particles is first introduced into the combustion zone 10, 10 'to burn the coke on the spent catalyst particles. At this time, in order to control combustion of the coke in the combustion zone 10, 10 ', the combustion gas and the oxygen content of the environment in the combustion zone are strictly controlled.

The spent catalyst particles can be regarded as catalyst particles since they exit the combustion zone 10, 10 'after coke combustion. The catalyst particles pass downward from the combustion zone 10, 10 'to the carbon monoxide zone CO. In the carbon monoxide zone, a metal material immersed in the catalyst is converted into metal carbonyl by reacting with carbon monoxide supplied through the conduit 41, and then discharged to the outside of the system.

The catalyst particles from which the metal material has been removed pass through the carbon monoxide zones 40, 40 'and down through the catalyst regenerator to the chlorination zones 20, 20'. Chlorinated gas is fed into the chlorination zone 20, 20 'through at least one inlet 22. The chlorinated gas includes chlorinated gas such as chlorine and oxygen containing gas such as air or water. 2, a single inlet 22 is illustrated as feeding a combined stream of chlorinated gas and oxygen-containing gas to the chlorination zone 20, 20 ', although a separate inlet may be used as a separate May be provided for transport.

The presence of chlorinated gas and oxygen-containing gas in the chlorination zone 20, 20 'is supplied for chlorination of the catalyst particles. Chlorination is essential because the platinum group metals in the catalyst particles experience aggregation at high temperatures encountered during processing. The aggregated platinum group metal on the catalyst particles is redispersed for better catalytic activity than the chlorination reaction.

The catalyst particles after chlorination can be regarded as chlorinated catalyst particles. The chlorinated catalyst particles are led from the chlorination zone 20, 20 'to the drying zone 30 in the catalyst regenerator. The heated dry gas is supplied to the drying zone (30) through at least one inlet pipe (31). The dry gas may comprise an oxygen containing gas such as an inert gas, chlorinated gas and / or air. In the drying zone 30, the drying gas is vented through the catalyst particles to remove water due to the upstream reaction. 2, a single inlet pipe 31 shows an exemplary embodiment for feeding a combined stream of different gases to the drying zone 30, but a separate inlet is provided for separate transport of the various gases .

In one embodiment of the present invention, the drying zone 30 is in fluid communication with the chlorination zone 20, 20 'so that the gas required for the chlorination zone 20, 20' flows through the drying zone 30 into the inlet 31 Lt; RTI ID = 0.0 > chlorination < / RTI > The gas from the chlorination zones 20 and 20 'can be removed from the catalyst regenerator through the chlorination gas discharge pipe 14 via conduits formed between the combustion zones 10 and 10'.

As shown in FIG. 2, the regenerated catalyst particles may exit the catalyst regenerator through the catalyst exhaust conduit 50 after passing through the drying zone 30 and may be fed back to the catalyst reforming system or other catalyst system, And may be recycled to the spent catalyst particle stream being fed to the combustion zone 10, 10 '.

While the foregoing detailed description of the invention has been provided for specific embodiments, it should be understood that there are many variations. It is also to be understood that the exemplary embodiments or exemplary embodiments are merely examples, and are not intended to limit the scope, applicability or configuration of the invention in any way. Rather, the foregoing detailed description will provide those skilled in the art with a convenient guidance for implementing the exemplary embodiments of the invention, and without departing from the scope of the invention and its legal equivalents as set forth in the appended claims, It is to be understood that various changes may be made in the function and construction of the elements described in the foregoing description.

1: Termination input device
20, 20 ': combustion zone
30, 30 ': Carbon monoxide (CO) zone
40, 40 ': chlorination zone
50: Drying area

Claims (12)

A device for regenerating a catalyst comprising: at least one feed gas inlet tube and a discharge tube for discharging the regenerated catalyst, the catalyst being configured to continuously pass the combustion zone, the chlorination zone and the drying zone to the mobile phase, Further comprising a carbon monoxide zone for removing metallic material by reacting carbon monoxide with a metallic material to form a metal carbonyl.
The apparatus of claim 1, wherein the carbon monoxide zone is formed between a combustion zone and a chlorination zone.
The apparatus of claim 1, wherein the carbon monoxide zone is formed between the chlorination zone and the drying zone.
The catalyst regeneration apparatus according to claim 1, wherein the catalyst regenerating apparatus further comprises a release-charging device for removing catalyst residues and contaminants from the spent catalyst integrally formed at the upper end of the combustion zone. 2. The catalyst regeneration apparatus according to claim 1, wherein the carbon monoxide zone includes a carbon monoxide injection conduit for injecting carbon monoxide and a discharging means for discharging the produced metal carbonyl compound.
2. The catalyst regeneration apparatus according to claim 1, wherein the combustion zone, the carbon monoxide zone and the chlorination zone are formed in an annular disc shape, and the catalyst bed is configured to move in an annular space defined by two coaxial cylindrical walls. .
2. The method of claim 1, wherein a chlorine gas discharge conduit is formed between the combustion zones in the catalyst regenerator, the gas discharge gas conduit starting from a chlorination zone and discharging gas discharged from the chlorination zone, the outlet of the chlorination gas discharge conduit being formed on the combustion zone .
The apparatus according to claim 1, wherein the catalyst regenerating apparatus comprises at least one conduit for injecting an oxygen-containing gas into the combustion zone at one side of the combustion zone, and at least one conduit for exhausting gas from the combustion zone, Opposition
And the gas circulation is arranged in a diagonal direction from the upper part to the lower part in the combustion zone.
The method of claim 1, wherein the chlorination zone is connected to at least one conduit for introducing chlorinated gas to the chlorination zone and to at least one conduit for exhausting gas from the chlorination zone formed at the top of the combustion zone, Direction of the catalyst.
The catalyst regenerating apparatus according to claim 1, wherein the catalyst regenerating apparatus further comprises a triangular-pyramidal auxiliary plate for allowing the regenerated catalyst particles to be discharged smoothly without stagnation at the lower end of the drying zone.
Burning the coke deposit on the spent catalyst particles using a combustion gas; A method for regenerating a catalyst for regenerating a catalyst comprising: chlorinating catalyst particles and drying the chlorinated catalyst to form regenerated catalyst particles, the method comprising: reacting carbon monoxide with a metal material accumulated as the catalyst is moved And forming a metal carbonyl to remove the metal material.
12. The method of claim 11, wherein the step of removing the metal material by the carbon monoxide is performed before or after the chlorination step.

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