DE4104333A1 - Conversion of raw material in mixed phase reaction distn. - Google Patents

Abstract

In the mixed phase reaction distn. by conversion of raw material and distn. of the prods. in a mixed phase reaction distn. column, (i) the pre-heated raw material is fed into column contg. rectification zone in upper part, mixed phase reaction zone in middle part, and stripping zone in lower part, where mixed phase reaction zone has (a) in upper part a sealed lid, at the bottom a perforated plate or grid to carry catalyst, and wire mesh covering the perforated plate or grid, so that catalyst is charged between lid and perforated plate or grid, (b) at least one catalyst bed, a catalyst flow pipe between each two adjacent catalyst beds, a catalyst inlet at upper part of uppermost catalyst bed, and a catalyst bed, and a catalyst outlet at lower part of lowest catalyst bed, (c) at least one side pipe for introduction of non-preheated raw material, arranged between each adjacent pair of beds, and (d) a vapour passage on one side of the mixed phase reaction zone, and at least one liq. passage at the other side of mixed phase reaction zone, (ii) the conversion is carried out by allowing raw material entering mixed phase reaction zone at a definite pressure to flow downwards from upper part of the reaction zone through at least one catalyst bed, (iii) the vapour phase stream is distilled in rectification zone, with vapour phase stream formed in reaction zone and in stripping zone and rising through vapour phase passage in mixed phase reaction zone, into rectification zone, (iv) the liq. phase stream is distilled in stripping zone, with a part of liq. phase stream being formed in mixed phase reaction zone and sinking directly to upper plate of the stripping zone and another part of the liq. phase stream coming from rectification zone and sinking to upper plate of stripping zone through liq. passage in mixed phase reaction zone, (v) vapour stream, contg. mainly unconverted reactants, is released from column head, and (vi) the liq. stream, contg. mainly prod., is withdrawn from bottom of column.

Description

The invention relates to a method for mixed-phase reaction distillation. This procedure is different from both the process in which the reaction and the distillation ge be carried out as well as by the catalytic De Nursing method, in which the implementation and the distillery tion alternately performed in the same device.

The invention also relates to a device for implementation of the procedure.

The invention is particularly suitable for producing MTBE and is also suitable for making other petrochemical products net.

It is known that in the usual manufacturing processes the Reaction of the fed as starting material reaction part recipient and the separation of the products separated into reaction apparatus and in distillation columns. Sol These methods have the following disadvantages: too many procedures steps, high investment costs for the devices, Waste of heat of reaction and need for an additional cooling system to absorb the heat of reaction, so that the Reaction temperature is kept constant. If this procedure must be used for reversible reactions, sol chen process the reaction-distillation process because of limited conversion of the equilibrium reaction twice or be repeated more often for an acceptable conversion of the Reactants is achieved.

For simplifying the above-mentioned method and for Exploiting the heat of reaction during the reaction destilla tion process is developed catalytic distillation Service. In the catalytic distillation, the reaction of the starting material and the distillation of the products in the the same catalytic distillation column carried out; the Products are distilled out once they have been made are. As a result, the reaction equilibrium is disturbed where  improved by the implementation to the completeness and the Conversion of the starting material is increased. In addition, the Heat of reaction by evaporation of the as starting material set reactants are added. Consequently, can not only kept the reaction temperature constant, but also the energy consumption of the process to a great extent vermin be changed.

A typical catalytic distillation column contains three Zo NEN: the rectification zone in the upper part, the catalytic reaction zone in the middle part and the wiper zone in the lower part the column. It is clear that in this column the liquid phase current and the gas phase current according to the countercurrent principle pass through the catalytic reaction zone and in this Zone simultaneously a reaction and a distillation out are set. When the particle size of the catalyst is too small is, however, the flow resistance of the catalyst bed too large, so that the liquid phase flow and the gas phase flow can not simultaneously flow through the reaction zone which leads to a continuation of the reaction lations procedure is very difficult.

There are several methods for filling catalysts ent been wound to solve the above-mentioned problems. According to the teaching of US-PS 34 34 534 catalyst is in Flüs filled with liquid reflux tubes, which as additional Reacti onsbehälter attached to distillation trays. After this Procedures are the amounts in which the catalyst is in the Reflux is filled, limited. US-PS 44 71 154 suggests the use of catalyst capsules in which the catalyst in a textile fabric or in a tissue crossed stainless steel wires used for liquids permeable, but for catalyst particles, the have a rectangular or other shape, impermeable is included, and these capsules on the distillati onsoils in the distillation column to distribute. The off gangue penetrates into the capsules and reacts with the in the catalyst contained in the capsules, while it is over the De still bottoms flows. Also in this method, the men  ge, in which the catalyst is filled, limited, and it promotes the reaction of the reactants because of the cons the capsules against penetration or diffusion of the Reactants and the products are not. Likewise is in the US-PS 42 15 011 a method of using cata disclosed in which the catalyst twice in Schich made of a textile fabric and a fabric of intersecting Wrapped in stainless steel wires and the capsules are then introduced into the catalytic reaction zone be filled, which is between the capsules pores or channels so that liquid and steam after the Gegenstromprin zip can flow through this catalyst bed. In the US-PS 48 47 430 is proposed a reaction distillation apply at least two superimposed and contains non-contiguous fixed catalyst beds, wherein Passages provided for a vapor phase are between the fixed beds at least one distribution floor and at least two floors are available for redistribution of liquid and Liquid phase materials react with the catalyst while they flow down through the catalyst beds, and on the distillation trays for the heat and mass transfer to care. The disadvantages of the process are the complicated ones Construction of the column, the limited amount in which the cata- is filled, which is due to the room, the between the beds through the distribution and distillation soils and the lower efficiency of the Um which is due to the fact that the concentration the reactant and the contact time of the reaction Mixing the supplied starting material with the liquid Materials that are already present in the reactor, are reduced.

As described above, the usual methods, in which the reaction of the reactants and the De still be carried out separately, the following Disadvantages: high investment and maintenance costs, complicated Operating procedure, waste of heat of reaction and necessary speed of an additional cooling system. Although at the katalyti the distillation process, the reaction of the reaction part  and distillation of the products in the same batch tion and the heat of reaction exploited who can, is the construction of the catalytic distillation zone complicated, is the amount in which the catalyst is filled can, low, has the catalytic distillation column a high altitude and the operation is awkward.

The invention has for its object to provide a method for To provide mixed phase reaction distillation, the Vor parts of a simple technical process and a higher one Catalyst efficiency has, where in the mixed phase Reaction distillation column for carrying out the Verfah is determined, the catalyst as bulk or loose in the at least one catalyst bed of the mixed phase reaction zone should be filled, it should be possible that the Catalyst directly into the at least one catalyst bed filled and removed from it, being between the neigh catalyst beds in the mixed-phase reaction zone of Column no distillation tray and no distribution tray should be ordered and the construction of the column is very simple should be and reduces the investment costs for the column should be.

The invention relates to a method for mixed-phase reaction distillation and the apparatus therefor. In this process, the reaction is carried out in a mixed phase reaction distillation column by passing the feedstock under pressure through the at least one catalyst bed, wherein the preheated feedstock is introduced into the mixed phase reaction distillation column and from the top of the at least one catalyst bed of the mixed phase reaction zone is allowed to flow down through the at least one catalyst bed under pressure; the liquid phase products generated in the reaction zone flow into the stripper zone for distillation, and the vapor phase stream produced in the at least one bed, which is mixed with the rising vapor phase stream from the stripper zone, rises into the rectification zone via the vapor passageway disposed in the reaction zone and the liquid phase stream distilled from the rectification zone is lowered into the scraper zone via the liquid passage disposed in the mixed phase reaction zone (see Fig. 1) or the preheated feedstock is first introduced into the at least one catalyst bed of the lower mixed phase reaction zone and passing through the at least one catalyst bed of this range down, the liquid phase generated therein stream for distilling directly into the Abstreiferzone drops and the vapor phase stream, which is mixed with the ascending vapor phase stream from the Abstreiferzone , via the vapor passage, which is arranged in the lower mixed-phase reaction region, rises in the middle distillation zone; the vapor phase stream distilled from the middle distillation zone to continue the reaction into the upper mixing phase reaction zone increases by passing through outer conduits and a heat exchanger, and the liquid phase stream from the middle distillation zone via the liquid passage passing in the lower mixed phase reactor. Reaction area is arranged, downwards on the uppermost bottom of the Abstrei ferzone flows; the vapor phase stream generated in the upper mixed phase reaction region rises above the vapor passage located in the upper mixed phase reaction region into the recirculation zone and the liquid phase stream generated in the upper reaction region is forced into the middle distillation region by an outer pump and conduits ( see Fig. 2) or wherein the vapor phase stream produced by the reactions in the mixed phase reaction zone which is mixed with the vapor phase stream from the stripper zone, through the vapor passage disposed in the mixed phase reaction zone, enters a catalytic reaction distillation zone rises, then through the vapor passages of the catalytic reaction Destilla tion zone rises in the rectification and the reacted from the Rek tifizierzone distilled liquid phase stream in the catalyst beds of the catalytic reaction distillation zone responds (see Fig. 3).

According to the inventive method flows only the Ausgangsma material through the at least one catalyst bed of Mischpha sen reaction zone, and in the mixed-phase reaction zo  ne is neither a distillation tray nor a distribution tray available. Compared to the state of the art are in the frame the invention, the amount in which the catalyst in the column can be filled, as well as the degree of utilization of the cata- significantly improved, the process steps reduced and also the investment and maintenance costs to a high degree reduced.

The invention will be described below with reference to FIGS added drawings explained.

Fig. 1 is a schematic drawing of the mixed phase reac tion distillation column according to an embodiment of the invention.

Fig. 2 is a schematic drawing of the mixed phase reac tion distillation column according to another embodiment of the invention, which is preferred when a high conversion of the reactants is required.

Fig. 3 is a schematic drawing of the mixed phase reac tion distillation column according to another embodiment of the invention, which is also particularly preferred when ei ne high conversion of the reactants is required.

Fig. 4 is a schematic cross-sectional view of the mixed phase reaction zone in the mixed phase reaction distillation columns.

As shown in Fig. 1, the process is carried out in which the starting material is reacted in a Mischpha sen reaction distillation column according to the invention or reacted and the products distilled in the column who the. The method comprises the following steps, in which:

• i) the preheated starting material is introduced into the column which contains a rectification zone I in the upper part, a mixed-phase reaction zone II in the middle part and a stripping zone III in the lower part, the mixed-phase reaction zone II
  • a) on the upper part a sealed lid ( 51 ), at the bottom of a perforated plate or a grid ( 2 ) for supporting the catalyst and the perforated plate or the grid ( 2 ) covering wire mesh, wherein the catalyst as a bulk material between the sealed lid ( 51 ) and the perforated plate or grid ( 2 ) is filled,
  • b) at least one catalyst bed ( 1 ), at least one catalyst flow tube ( 7 ) between every two adjacent catalyst beds, a catalyst inlet ( 5 ) located at the uppermost part of the uppermost catalyst bed and a catalyst outlet ( 6 ), which is arranged at the lowest part of the lowest catalyst bed,
  • c) at least one side line (9 a, 9 b) for introducing non-preheated raw material, the Benach between each disclosed pair of beds is arranged,
  • d) at least one vapor passage ( 3 ) arranged on one side in the mixed-phase reaction zone II and at least one fluid passage ( 4 ) arranged on the other side in the mixed-phase reaction zone II,
• ii) the reaction is carried out by allowing the starting material entering the reaction zone II to flow down through the at least one catalyst bed ( 1 ) at a certain pressure from the top of the reaction zone II,
• iii) the vapor phase stream is distilled in the rectification zone I, the vapor phase stream formed in the reaction zone II and coming from the stripper zone III rising above the vapor passage ( 3 ) arranged in the reaction zone II into the reclaiming zone I,
• iv) the liquid phase stream in the stripper zone III is Destil profiled, wherein a portion of the liquid phase stream comes from the mixed-phase reaction zone II and falls directly to the uppermost bottom of Abstreiferzone III and another part of the liquid phase stream from the rectification zone I comes and on in the Reaction zone II arranged liquid passage ( 4 ) on the uppermost bottom of the Abstreiferzone drops,
• v) the vapor stream, which is mainly the unconverted Reactant contains, from the top of the mixed phase reac tion distillation column is discharged and
• vi) the liquid stream, the ent holds, from the bottom of the mixed-phase reaction distillation lonne is taken.

According to the invention, the upper part of the mixed-phase reaction zone II is a sealed lid ( 51 ); the starting material is introduced into the mixed-phase reaction zone II via the feedstock inlet ( 8 ) and allowed to flow down through the at least one catalyst bed ( 1 ) at a certain pressure. The liquid phase stream coming from the reaction zone sinks directly into the stripper zone III, and the vapor phase rises above the vapor passage ( 3 ), which is located on one side of the at least one catalyst bed ( 1 ) in the reaction zone II, into the rectification zone I.

According to the method of the invention, the reaction temperature is set by controlling the operating pressure so that it is below the boiling point of the starting material. In the case that the concentration of the reactants in the starting material is higher, the catalyst in the reaction zone II is divided into at least two or more catalyst beds because of the possible release of the large amount of heat of reaction during the reaction. Between the catalyst beds there is neither a distillation bottom nor a bottom for redistribution. The catalyst in each of the catalyst beds is connected by a plurality of flow tubes ( 7 ) in order for the catalyst beds to form a contiguous catalyst bed. As between the adjacent catalyst beds neither a Ver distribution soil still a distillation bottom is arranged, more catalyst can be filled in the column of the invention who than in a normal catalytic distillation column according to the prior art.

As shown in Fig. 1, between each pair of Benach disclosed catalyst beds at least one side line ((9 a,) 9 b) arranged for the insertion of non-pre-heated raw material to, wherein the non-preheated raw material is introduced into the spaces between the catalyst beds to absorb the heat of reaction and further to adjust the amounts of evaporation of the starting material and the reaction temperature.

The upper end of the liquid passage ( 4 ) is connected to the lowest floor ( 12 ) of the rectification zone (I) having a weir to maintain a certain liquid level on that floor ( 12 ) and to ensure that the liquid phase stream is fully contained the liquid passage ( 4 ) is introduced, and the lower end of the liquid passage ( 4 ) is below the level of a weir ( 52 ) disposed on the opposite side of the uppermost floor ( 11 ) in the Abstrei ferzone III to prevent in that the vapor phase stream enters the fluid passage ( 4 ). The vapor phase stream from the stripper zone III enters via the uppermost bottom ( 11 ) of the stripper zone III in the vapor passage ( 3 ), and the vapor phase in the vapor passage ( 3 ) enters the Rek tifizierzone.

According to the inventive method, the catalyst as bulk material or loose inside the at least one cata- torbett ( 1 ) is filled. The starting material can therefore come into contact with the catalyst effectively, whereby the reaction can be promoted. Further, the catalyst can be filled via the catalyst inlet ( 5 ) into the at least one catalyst bed ( 1 ) and the deactivated catalyst can be removed from the catalyst outlet ( 6 ). As a result, the filling and the removal of the catalyst can be greatly simplified, and the investment costs are greatly reduced.

According to another embodiment of the invention Ver The preheated starting material flows from the bottom of the Mixed-phase reaction zone II through the at least one Kataly  satorbett up, the gebil increases in the reaction zone II vapor phase stream directly to the bottom floor of the recti fizierzone and the liquid phase coming from zone II sinks senstrom on the liquid passage of the zone II on the top bottom of the wiper zone III.

In the application of the method according to the invention for the manufacture methyl tert-butyl ether (MTBE) by reacting an iso Butene-containing hydrocarbon mixture with methanol in counter The catalyst is made of sulfonated resin Isobutene in the range of about 90 to about 95 Mas Se%, and the remaining hydrocarbon mixture contains about 1 to about 5 mass% isobutene and can be used as starting material for an alkylation can be used.

The mixed-phase reaction distillation column for carrying out the method is shown in FIG . This column ent holds in the upper part of a rectification zone I, in the middle part of a mixed phase reaction zone II and in the lower part of a stripping zone III, one at the top of the rectification zone I arranged line ( 13 ) for discharging the vapor stream, the main neuter not contains converted reactants, and arranged at the bottom of Abstreiferzone III conduit 18 for withdrawing the liquid stream containing mainly the products, wherein the reaction zone II

• a) on the upper part a sealed lid ( 51 ), at the bottom of a perforated plate or a grid ( 2 ) for supporting the catalyst and the perforated plate or the grid ( 2 ) covering wire mesh, wherein the catalyst as a bulk material between the sealed lid ( 51 ) and the perforated plate or grid ( 2 ) is filled,
• b) at least one catalyst bed ( 1 ), at least one catalyst flow tube ( 7 ) between every two adjacent catalyst beds, a catalyst inlet ( 5 ) located at the uppermost part of the uppermost catalyst bed and a catalyst outlet ( 6 ), which is arranged at the lowest part of the lowest catalyst bed,
• c) at least one side line (9 a, 9 b) for introducing non-preheated raw material, the Benach between each disclosed pair of beds is arranged,
• d) at least one vapor passage ( 3 ), which is arranged on one side in the mixed-phase reaction zone II, and at least one liquid passage ( 4 ).

According to the preferred embodiment of the invention, the mixed-phase reaction zone II may contain two mixed-phase reaction areas. The unreacted reactants in the first mixed phase reaction region continue to revert in the second reaction region. As a result, the overall conversion of the reactants of an equilibrium reaction can be further increased. This process is carried out in a mixed phase reaction distillation column as shown in Fig. 2, and comprises the following steps, in which:

• i) the preheated starting material is introduced into the column, which contains a rectification zone I in the upper part, a mixed-phase reaction zone II in the middle part and a wiping zone III in the lower part, the mixed-phase reaction zone II
  • a) a lower mixed-phase reaction zone IIa, a middle distillation zone IIb and an upper mixed-phase reaction zone IIc,
  • b) a sealed lid ( 55 ) on the upper part and a perforated plate or grid ( 25 ) for supporting the catalyst at the Bo the lower mixed-phase reaction area IIa, wherein the perforated plate or the grid ( 25 ) is covered with a wire mesh; at least one catalyst bed in the lower mixed phase reaction zone IIa and at least one catalyst flow pipe ( 7 ) disposed between the adjacent catalyst beds, a catalyst inlet ( 5 ) located at the uppermost part of the uppermost catalyst bed, a catalyst outlet ( 6 ) which is arranged at the lowest part of the lowest catalyst bed, and at least one side pipe ( 9 a, 9 b) for introducing non-preheated starting material which is arranged between the adjacent catalyst beds,
  • c) at least one distribution tray in the middle distillation zone IIb, one liquid phase inlet on one side and a vapor phase outlet on the other side of the topmost part of the zone IIb,
  • d) a sealed lid ( 51 ) on the upper part and a perforated plate or a grid ( 2 ) for supporting the catalyst at the bottom of the upper mixed-phase reaction region IIc, wherein the hole plate or the grid ( 2 ) is covered with a wire mesh, a Catalyst bed in the upper mixed phase reaction zone IIc and a catalyst inlet ( 27 ) located at the top, and a catalyst outlet ( 28 ) located at the bottom of the catalyst bed of the zone IIc,
  • e) at least one vapor passage ( 3 ) and at least one fluid passage ( 4 ), which are arranged in the lower mixed-phase reac tion area IIa; a vapor phase outlet ( 30 ) disposed on one side and a liquid phase inlet ( 34 ) disposed on the other side of the uppermost portion of the middle distillation region IIb; at least one liquid passage ( 24 ) and at least one vapor passage ( 23 ) arranged in the upper mixed-phase reaction region IIc, a partition wall ( 29 ) arranged between the upper mixed-phase reaction region IIc and the middle distillation region IIb, a raw material inlet ( 26 ) located at the upper part of the upper mixed-phase reaction zone IIc, and a liquid-phase outlet ( 32 ) disposed above the partition wall ( 29 ) of the upper mixed-phase reaction zone IIc;
• contains
• ii) the reaction is carried out by the starting material under a certain pressure from the top of the at least one Catalyst bed of the lower mixed-phase reaction zone IIa down through the at least one catalyst bed is allowed to flow
• iii) the liquid phase stream coming from the lower mixed-phase reaction zone IIa enters the stripper zone III directly and the liquid phase stream coming from the middle distillation zone IIb sinks into the stripper zone III via the liquid passage ( 4 ) in the lower mixed-phase reaction zone IIa, during the vapor phase stream coming from the lower mixed phase reaction region IIa, which is mixed with the vapor phase stream separated in the stripper zone III, via the vapor passage ( 3 ) located in the lower mixed phase reaction zone IIa, into the middle distillation zone IIb increases,
• iv) coming from the middle distillation zone IIb Vapor phase flow discharged from the top of this area IIb and this drained vapor phase current through heat Exchange between the drained vapor phase stream and not preheated starting material in a proportion of about 20 to about 50% by mass is liquefied,
• v) the partially liquefied vapor phase stream in step iv) into the top of the upper mixed phase reaction zone IIc introduced and for further transformation of the not umgewan after a certain pressure down through the at least one catalyst bed of the area IIc flows through,
• vi) coming from the upper mixed-phase reaction region IIc de vapor phase stream from the bottom of the catalyst bed flows out and via the vapor passage ( 23 ) in the Rektifizierzo ne I increases, the coming of the same area IIc liq sigphasenstrom via a pump ( 33 ) the Flüssigphasenauslaß ( 32 ), which is arranged at the lower part of this range, ent taken and in circulation via the pump ( 33 ) and arranged on the upper part of the distillation section IIb liq sigphaseneinlaß ( 34 ) in the uppermost distillation tray of the middle distillation zone IIb is attributed
• vii) the vapor phase stream entering the rectification zone I is distilled in this zone I and the liquid phase stream after the distillation flows via the liquid passage ( 24 ) located in the upper mixed phase reaction zone IIc onto the dividing wall ( 29 ) and over the pump ( 33 ) and via the liquid phase inlet ( 34 ) on the top Destil lationsboden the middle distillation zone IIb is introduced
• viii) the vapor stream, which is mainly the unconverted Contains reactants, is discharged from the top of the column and
• ix) the liquid stream, which mainly ent holds, is removed from the bottom of the column.

According to this process of the invention, only one catalyst bed ( 22 ) is present in the upper mixing phase reaction zone IIc, and a partition wall ( 29 ) is arranged between the upper mixed-phase reaction zone IIc and the middle distillation zone IIb. A catalyst inlet ( 27 ) is at the uppermost part and a catalyst outlet ( 28 ) is located at the bottom of the catalyst bed ( 22 ) in the region IIc. The catalyst is filled as bulk material or loosely in the catalyst bed ( 22 ). Fresh catalyst is introduced via the catalyst inlet ( 27 ), and spent, deactivated catalyst is removed from the catalyst outlet ( 28 ). In the middle distillation zone IIb, at least one distillation tray is arranged to separate the product and the untransformed reactants therein. Also in the lower mixed-phase reaction region IIa, the catalyst is good as bulk or loose in the at least one catalyst bed ( 1 ) is filled. Fresh catalyst is introduced via the catalyst inlet ( 5 ) in the at least one catalyst bed ( 1 ), and ver used, deactivated catalyst is removed via the cata- torauslaß ( 6 ) from the at least one catalyst bed ( 1 ) ent.

After this process according to the invention, the coming of the Be IIb vapor phase stream from the line ( 30 ) is abge and exchanged in a heat exchanger ( 31 ) with not vorer heated starting material heat and then on the Lei device ( 26 ) from the top forth again introduced into region IIc and allowed to flow downward under pressure through bed ( 22 ) of region IIc. The starting material is introduced after the heat exchange via the line ( 8 ) in the at least one Ka talysatorbett ( 1 ) in the area IIa.

According to this inventive method is not vorer overheated starting material via the side line (9 a, 9 b) introduced into the space between the catalyst beds to the amount of evaporation to control the starting material and the reaction temperature in the range IIa.

According to another embodiment of this inventive method, the starting material enters the bottom of the mixing phase reaction areas (IIa, IIc) and flows under a certain pressure through the at least one catalyst bed of the mixed-phase reaction areas (IIa, IIc) up through, wherein the after the reaction, liquid phase stream generated by the liquid passage ( 4 ) disposed in the mixed-phase lower reaction region IIa enters the stripper zone III or via the liquid passage ( 24 ) located in the upper mixed-phase reaction region IIc, the pump (FIG. 33 ) and the line ( 34 ) enters the middle distillation zone IIb and wherein the vapor phase stream produced in the region IIa or in the region IIc directly into the middle ren distillation region IIb or the rectification zone I increases.

The vapor stream discharged from the top of the column is condensed in a cooler ( 14 ) and enters a reflux vessel ( 15 ), at least a portion of the liquid in the vessel ( 15 ) being recycled as reflux to the top of the column and the remaining liquid in the vessel ( 15 ) is taken from it via a line ( 17 ). Similarly, the liquid phase is removed from the column bottom via a line ( 18 ), wherein at least a portion of the liquid phase in the distillate bubble or the reboiler ( 19 ) is evaporated and then returned via a line ( 20 ) in the column bottom, while the residual liquid via a line ( 21 ) is removed from the colon ne.

In the application of this method according to the invention for making methyl tert-butyl ether (MTBE), the conversion of the reactants in a single column can be more than 99.0%. For example, in the case of the reaction of the isobutene-containing C ₄ fraction with methanol, the conversion of isobutene is more than 99.5% by mass, ie, the residual C ₄ fraction contains less than 0.5% by mass of isobutene. This residual C ₄ fraction can be used as starting material for the preparation of high purity butadiene or high purity butene-1.

According to another preferred embodiment of the invention, the mixed-phase reaction zone II contains a mixed-phase reac tion zone IId and a catalytic reaction distillation zone IIe, wherein the starting material is first passed through the at least one catalyst bed of zone IId and reacted. The unconverted in the zone IId reactants who introduced into the catalytic reaction distillation zone IIe and further reacted. As a result, the conversion of the reactants of an equilibrium reaction can be increased to more than 99.0%. This process is carried out by reacting the starting material in a mixed-phase reaction distillation column as shown in FIG. 3 and distilling the products, and comprises the following steps, in which:

• i) the preheated starting material is introduced into the mixed-phase reaction distillation column which contains a rectification zone I, a catalytic reaction zone IIe, a mixed-phase reaction zone IId and a stripper zone III, the zone IIe
  • a) superposed catalyst beds ( 35 , 48 , 37 ), at least one catalyst flow tube ( 39 ) disposed between the disclosed catalyst beds, a catalyst inlet ( 36 ) disposed at the uppermost portion of the uppermost catalyst bed ( 35 ) and a catalyst outlet ( 38 ) disposed at the lowermost portion of the lowermost catalyst bed ( 37 ), and
  • b) at least one distillation tray (40) of the adjacent catalyst beds is arranged between each pair (41 each said distillation tray (40) in its center a return tube), and a sealing liquid tank (42),
  • c) each catalyst bed having at least one vapor passage ( 43 ) and each vapor passage ( 43 ) having a height of from about 100 to about 300 mm, preferably from about 150 to about 200 mm, higher than the surface area of the catalyst bed; Mixed phase reaction zone IId
    • a) at the top of a sealed lid ( 5 ), at the bottom of a perforated plate or a grid ( 2 ) for supporting the catalyst and the perforated plate or the grid ( 2 ) covering wire mesh, wherein the catalyst as a bulk material between the sealed lid ( 5 ) and the perforated plate or grid ( 2 ) is filled,
    • b) at least one catalyst bed ( 1 ), at least one catalyst flow tube ( 7 ) between each two adjacent catalyst beds, a catalyst inlet ( 5 ) located at the uppermost part of the uppermost catalyst bed, and a catalyst outlet ( 6 ), which is located at the lowest part of the lowest catalyst bed,
    • c) at least one side line (9 a, 9 b) for introducing non-preheated raw material, the Benach between each disclosed pair of beds is arranged,
    • d) at least one vapor passage ( 3 ) containing on one side, and at least one fluid passage ( 4 ) located on the other side in the mixed-phase reaction zone IId,
• ii) the reaction is carried out by allowing the starting material that has passed into the column to flow down through the at least one catalyst bed ( 1 ) at a certain pressure from the top of the mixed-phase reaction zone IId,
• iii) the vapor phase stream produced after the reaction in step ii) is mixed with the vapor phase stream coming from the stripper zone III and increases into the catalytic reaction zone IIe for further reaction via the vapor passage ( 3 ), while the liquid phase stream after the reaction in step ii ) flows directly into the stripper zone III,
• iv) the vapor phase stream in the catalytic reaction zone IIe flows upward through the vapor passages ( 43 ) and the bottommost distillation tray ( 47 ) in the rectification zone I through each of the catalyst beds ( 35 , 48 , 37 ) and enters the rectification zone I,
• v) coming from the rectifying I liquid phase stream (on the bottom 47) for further reaction in the uppermost Kata lysatorbett (35) of the catalytic reaction zone IIe occurs, the liquid phase stream after the reaction to the Destillationsbo to (40) occurs, and (in this soil 40 ) With the ascend the vapor phase exchanges heat and material, then on the return flow pipe ( 41 ) and the barrier liquid tank ( 42 ), which are arranged in the middle of this floor ( 40 ) lysatorbett on the next Kata and arranged under this catalyst bed distillation bottom decreases to alternately continue the reaction and distillation, and finally the liquid phase stream in the lowermost catalyst bed of the catalytic reaction zone IIe flows past the liquid passage ( 4 ) disposed in the mixed-phase reaction zone IId to the uppermost bottom of the scraper zone III,
• vi) the vapor stream containing mainly the unconverted reactants, is discharged from the top of the column via a conduit ( 13 ) and
• vii) the liquid stream, which mainly ent holds the products is removed from the bottom of the column via line ( 18 ).

After this process according to the invention, the catalyst as bulk material or loosely in the catalyst beds of the catalytic reaction zone IIe and the mixed-phase reaction zone IId is filled. Fresh catalyst is introduced into the catalyst beds via the catalyst inlets ( 5 , 36 ), and spent, deactivated catalyst is removed from the catalyst beds via catalyst outlets ( 6 , 38 ). The amount of Kata lysators and the number of catalyst beds of the catalyst reaction zone IIe depend on the requirements of the conversion.

During the reaction and distillation (reaction distillation) in the catalytic reaction zone IIe, the liquid level becomes each of the overlying catalyst beds by selection suitable operating conditions at a height of about 50 to kept about 200 mm. The liquid phase can therefore in any the catalyst beds of zone IIe are evenly distributed.

It should be understood that the facilities of Zone IIe any others in the art may be.

In this process, the facilities of mixed phase Re action zone IId and the route of the starting material similar to those of the preceding methods. It is advantageous that min at least part of the upper part of the rectification zone I abge let vapor phase stream and then condensed to zone I. is returned and at least part of the ground from the Abstreiferzone III withdrawn liquid phase stream evaporated and then returned to zone III.

When this method of producing MTBE by reacting the isobutene-containing C ₄ fraction with methanol is used, the conversion of isobutene is higher than 99.0 mass%, ie, the residual C ₄ fraction after the reaction contains less than 0.5 Mass%, and the remaining C ₄ fraction can be used as starting material for producing high-purity butene-1 or as starting material for producing high-purity butadiene by the process of oxydehydrogenation.

The inventive method can except for the production of MTBE also for making other ethers by reacting tert-olefins with alcohols; of ethylbenzene by reacting Ethylene with benzene; of alcohols by reacting olefins with water and esters by reacting acids with Alko be applied.

When the process of the invention is used to produce MTBE, the reaction conditions are as follows: operating pressure in the range of about 0.4 to about 2.0 MPa, preferably in the range of about 0.5 to 1.2 MPa, reaction temperature in Range of about 30 to about 120 ° C, preferably in the range of about 40 to about 90 ° C, LHSV (hourly liquid space velocity) in the range of about 0.5 to about 15 h ^-1 , preferably in the range of about 1.0 to about 10 h ^-1 .

It is advantageous that in the invention, only the off by the at least one catalyst bed of the Mixed phase reaction zone or mixed phase reaction flows through it. Unlike the ordinary katalyti distillation, which is separated off in the rectification zone Liquid phase flow through the fluid passage directly into the Wiper zone and does not flow through the catalyst beds in the mixed-phase reaction zone or in the mixed-phase Reakti onsbereich through. If F is the amount of the starting material and R is the amount of reflux of the column is according to ei in a conventional catalytic distillation process R + F the Amount of liquid passing through the catalyst beds below flows half of the supply line, and the exploitation degree of the catalyst is only F / (R + F), while according to the Invention the amount of material by the at least ei a catalyst bed flows through, only equal to the amount F of Starting material is.

The utilization rate of the catalyst is therefore according to the Er higher than in the usual distillation process.

On the other hand, the vapor phase currents that increase in the mix phase reaction zone and are generated in the stripper zone, through the vapor passage directly into the rectification zone, thereby the resistance problems are solved by that in the counter current passing the ascending vapor phase Stromes and the sinking liquid phase current through the Ka be caused so that the invention Procedures for the implementation of the implementation and the Destilla tion is more advantageous.  

The process of the invention is characterized by the following examples with reference to making MTBE by Um Isobutene with methanol in the presence of a cata- sector of sulfonated resin explained in more detail.

Examples 1 to 4

The process according to the invention is used to prepare MTBE by reacting an isobutene-containing C ₄ fraction with methanol in a mixed-phase reaction distillation column, as shown in FIG. 1. The mixed-phase reaction distillation columns used in Examples 1 and 2 are relatively small and have a diameter of 25 mm and a height of 2 m. The amount of catalyst charged to each of the columns is 290 ml (dry), and the starting material is a C ₄ -hydrocarbon fraction containing 40% by mass of isobutene. The columns used in examples 3 and 4 are a pi lot with a diameter of 100 mm and a height of 7 m. The amount of catalyst charged to each of the columns is 1.5 liters (dry), and the starting material is a C ₄ hydrocarbon fraction containing 36.4 mass% of isobutene. In all of these examples a sulfonated s-type resin catalyst having a particle size in the range of about 0.3 to about 1.3 mm is used. The operating conditions and the results are shown in Table 1.

As shown in Table 1, after the reaction according to the process of the invention, under the reaction conditions of a pressure of 0.8 MPa and a space velocity of 4 to 8 h ^-1, more than 90 mass% of the iso contained in the C ₄ fraction butens converted. The vapor stream discharged from the top of the column contains less than 4% by weight of isobutene and less than 100 ppm of MTBE and can be used as the starting material for alkylation. The withdrawn from the bottom of the column liquid stream contains more than 98% by mass of MTBE.

Examples 5 to 7

The process of the present invention is used to prepare MTB by reacting a C ₄ hydrocarbon fraction containing 36.4% by weight of isobutene with methanol in a mixed-phase reaction distillation column as shown in FIG. 2. The column has a diameter of 100 mm and a height of 9 m. The total amount of the s-type sulfonated resin catalyst having larger pores filled in the column is 4.8 liters (dry). Under the reaction conditions of a pressure of 0.9 MPa, a reaction temperature of 40 to 80 ° C and an hourly liquid space velocity (LHSV) of 6.2 to 7.0 h ^-1 in the lower mixed phase reaction region and a pressure of 0 , 9 MPa, a reaction temperature of 77 to 82 ° C and an hourly liquid Raumgeschwindig speed (LHSV) of 2.3 to 2.6 h ^-1 in the upper Mischphasen- Reacti onsbereich be more than 99% by mass of the C in the _4th Fraction containing isobutene converted into MTBE. The head-off vapor stream, which can be used as a raw material for producing high-purity butene or as a starting material for producing high-purity butadiene by the oxydehydrogenation process, contains less than 0.5 mass% isobutene and less than 100 ppm MTBE. The stream of liquid taken from the soil contains more than 98% by weight of MTBE. The results are shown in Table 2.

Examples 8 and 9

The process of this invention is used to prepare MTB by reacting a C ₄ hydrocarbon fraction containing 36.6% by weight of isobutene with methanol in a mixed-phase reaction distillation column as shown in FIG. 3. The column has a diameter of 100 mm and a height of 12 m. The amount of catalyst charged into the column is 6.3 l (dry). The operating conditions and the results are shown in Table 3.

As shown in Table 3, the conversion of the isobutene contained in the starting material is under the reaction conditions of a pressure of 0.95 to 0.96 MPa, a temperature of 40 to 81 ° C and a total hourly liquid space velocity (LHSV). from 1.8 to 1.85 h ^-1 more than 99% by mass. The vapor phase stream removed from the head, which can be used as a raw material for producing high quality butene-1 or as a starting material for producing high purity butadiene, contains less than 0.5 mass% of isobutene. The liquid phase stream withdrawn from the soil contains more than 98.0% by weight of MTBE.

Comparison between the invention and the prior art:
The differences between the structure of the devices according to the invention and the structure of known devices are described as follows:

1. Are pre-reactors available? Devices according to the invention In Fig. 1 apparatus shown No In Fig. 2 apparatus shown No In Fig. 3 apparatus shown No Device according to US-PS 43 36 407 No Device according to US-PS 48 47 430 Yes

2. Type of catalyst beds in the columns Devices according to the invention In Fig. 1 apparatus shown A fixed catalyst bed, wherein the catalyst is filled as bulk material in the bed In Fig. 2 apparatus shown Two fixed catalyst beds, wherein the catalyst is filled as bulk material in the beds In Fig. 3 apparatus shown More than two or a plurality of zones of fixed catalyst beds, wherein the catalyst is filled as bulk material in the beds and wherein the zones of the fixed catalyst beds form a coherent catalyst bed, that the individual beds are connected using a connecting tube Device according to US-PS 43 36 407 More than two or a plurality of catalyst beds, wherein the catalyst is first wrapped in a packing of glass fabric and then arranged regularly in the reaction zone Device according to US-PS 48 47 430 More than two or a plurality of non-adjacent beds, wherein the catalyst is introduced as bulk material in each of the catalyst beds

3. Method for filling and removing the catalyst Devices according to the invention (Fig. 1, Fig. 2 and Fig. 3) The fresh catalyst is introduced into the catalyst beds via the catalyst inlet located in the uppermost part of the uppermost catalyst bed, and the spent, deactivated catalyst is taken directly from the catalyst outlet located in the lowermost part of the lowermost catalyst bed. The filling and removal of the catalyst is very simple. Device according to US-PS 43 36 407 The catalyst is first wrapped in a glass cloth packing, and then the packed catalyst packing of workers entering the column is placed in the column; the reacted catalyst is removed by workers entering the column. The filling and removal of the catalyst is very complicated. Device according to US-PS 48 47 430 Since the more than two or the plurality of catalyst beds are non-contiguous fixed beds, each of these catalyst beds should be equipped with a catalyst inlet for introducing fresh catalyst and a catalyst outlet for removing spent, deactivated catalyst. The filling and removal of the catalyst is complicated.

4. Are there any distillation trays between the adjacent catalyst beds? In Fig. 1 apparatus shown No In Fig. 2 apparatus shown No In Fig. 3 shown device @ Upper part of the reaction zone Yes Lower part of the reaction zone No Device according to US-PS 43 36 407 Yes Device according to US-PS 48 47 430 Yes

5. According to the methods of the invention and US-PS 48 47 430 the reactants enter directly with the catalyst Contact. According to the method of US-PS 43 36 407 penetrate the Reactants through the glass fabric and come then in contact with the catalyst.

The test results obtained by the method according to the invention and obtained by the known methods are in Table 4.  

Table 1

Producing MTBE according to the method and apparatus shown in FIG

Table 2

Producing MTBE according to the method and apparatus shown in FIG

Table 3

Producing MTBE according to the method and apparatus shown in FIG

Table 4

Claims (20)

1. A process for mixed-phase reaction distillation by imple tion of the starting material and distillation of the products in a mixed-phase reaction distillation column, characterized in that

• i) the preheated starting material is introduced into the column, which contains a rectification zone in the upper part, a mixed-phase reaction zone in the middle part and a stripping zone in the lower part, the mixed-phase reaction zone
  • a) at the top of a sealed lid, at the bottom of a hole plate or grid for carrying the catalyst and a perforated plate or grid for carrying the catalyst bedec Kendes wire mesh, the catalyst as bulk material between the lid and the perforated plate or the grid for Carrying the catalyst is filled,
  • b) at least one catalyst bed, at least one catalyst flow tube between each two adjacent catalyst beds, a catalyst inlet disposed at the uppermost portion of the uppermost catalyst bed, and a catalyst outlet disposed at the lowermost portion of the lowermost catalyst bed;
  • c) at least one side conduit for introducing non-preheated starting material disposed between each adjacent pair of beds,
  • d) at least one vapor passage disposed on one side of the mixed phase reaction zone and at least one fluid passage disposed on the other side of the mixed phase reaction zone;
• having,
• ii) the reaction is carried out by allowing the starting material entering the mixed phase reaction zone to flow down through the at least one catalyst bed under a certain pressure from the top of the reaction zone,
• iii) the vapor phase stream is distilled in the rectification zone, wherein the vapor phase stream is generated in the reaction zone and in the stripper zone and rises above the vapor passage arranged in the mixed phase reaction zone into the rectification zone,
• iv) the liquid phase stream is distilled in the stripper zone, wherein a portion of the liquid phase stream is generated in the Mischpha sen reaction zone and directly to the top Bo the Abstreiferzone drops and another part of the liquid phase stream comes from the rectification zone and on the in the mixed phases Reaction zone arranged liquid passage on the top bottom of the Abstreiferzone drops,
• v) the vapor stream, which mainly contains the unconverted reactants, is discharged from the top of the column and
• vi) the liquid stream, which mainly ent holds the products, is removed from the bottom of the column.

2. The method according to claim 1, characterized in that Control of the operating pressure is ensured that the Umset tion takes place below the boiling point of the starting material.   3. The method according to claim 1, characterized in that fer ner the reaction temperature and the evaporation amount of the off controlled by non-preheated Off material via the side pipe for non-preheated Starting material in the catalyst beds of the mixed phase Reak tion zone is introduced. 4. The method according to claim 1, characterized in that the upper end of the fluid passage with the lowest bottom connected to the rectification zone, which has a weir to to maintain a certain liquid level on this soil obtain and ensure that the entire liquid phase stream flows into the liquid passage. 5. The method according to claim 1, characterized in that the lower end of the fluid passage below the level of a Weirs lies on the opposite side of the uppermost Floor of the wiper zone is arranged to a specific Maintain and ensure barrier fluid height that the entire vapor phase flow into the vapor passage flows. 6. The method according to claim 1, characterized in that the Catalyst as bulk material in the at least one catalyst bed is filled. 7. The method according to claim 1, characterized in that zwi At least one catalyst is present in the adjacent catalyst beds sator flow tube is arranged to fresh catalyst over to fill the catalyst inlet into the catalyst beds and spent, deactivated catalyst over the catalyst remove outlet from the catalyst beds. 8. The method according to claim 1, characterized in that the Wire mesh made of intersecting wires made of stainless steel or another metal used for the liquid phase stream and permeable to the vapor phase flow, but for the catalyst impermeable torteilchen is formed.   9. The method according to claim 1, characterized in that the preheated starting material enters the column and from Bottom of the mixed phase reaction zone through the at least one Catalyst bed flows upwards, wherein in the mixed phase Reaction zone generated vapor phase stream directly into the rectifi zierzone rises and the separated in the Abstreiferzone steam phase current over that in the mixed phase reaction zone angeord Neten vapor passage in the rectification zone increases and the Flüs sigprodukte from the mixed-phase reaction zone and in the Rectification zone separated liquid products over in the Reaction zone arranged fluid passage in the Abstrei sink. 10. The method according to claim 9, characterized in that the uppermost part of the uppermost catalyst bed a weir angeord is net to prevent that produced in the reaction zone te liquid phase stream enters the vapor passage. 11. A process for mixed-phase reaction distillation by imple mentation of the starting material and distillation of the products in a mixed-phase reaction distillation column, characterized in that

• i) the preheated starting material is introduced into the column, which contains a rectification zone in the upper part, a mixed-phase reaction zone in the middle part and a stripping zone in the lower part, the mixed-phase reaction zone
  • a) a mixed-phase lower reaction region, a middle distillation region and an upper mixed-phase reaction region,
  • b) a sealed lid on the top and a perforated plate or grid for supporting the catalyst at the bottom of the lower mixing phase reaction area and a wire mesh covering the perforated plate or grid; at least one catalyst bed in the lower mixed phase reaction region and at least one catalyst flow tube disposed between the adjacent catalyst beds, a catalyst inlet disposed at the uppermost portion of the uppermost catalyst bed, a catalyst outlet disposed at the lowermost portion of the lowermost catalyst bed is and at least one side line for introducing non-preheated starting material, which is arranged between the adjacent catalyst beds,
  • c) at least one liquid phase inlet on one side and a vapor phase outlet on the other side of the uppermost part of the middle distillation zone,
  • d) a sealed lid on the top and a perforated plate or grid for supporting the catalyst at the bottom of the upper mixed phase reaction zone, a catalyst bed in the upper mixed phase reaction zone and a catalyst inlet located at the top and a catalyst outlet located at the bottom of the Catalyst bed of the upper mixed-phase reaction region is arranged to
  • e) at least one vapor passage and at least one fluid passage arranged in the lower mixed phase reaction region both reaching the middle distillation region; a vapor phase outlet disposed on one side and a liquid phase inlet disposed on the other side of the uppermost portion of the middle distillation region; at least one liquid passage and at least one vapor passage disposed in the upper mixed phase reaction region, a partition wall disposed between the upper mixed phase reaction region and the middle distillation region, a raw material inlet located at the top, and a liquid phase outlet is arranged above the dividing wall between the upper mixed-phase reaction region and the distillation region,
• contains
• ii) the reaction is carried out by allowing the starting material to flow down through the at least one catalyst bed at a certain pressure from the top of the lower mixed phase reaction zone,
• iii) it is ensured that the liquid products generated in the lower mixed phase re-action region enter directly into the Abstrei ferzone and the liquid separated in the middle distillation section liquid phase via the liquid passage in the lower mixed-phase reaction area in the Abstreiferzone drops, while in the lower Mixed phase reaction region generated vapor phase stream, which is mixed with the separated in the stripper zone vapor phase stream, through the vapor passage, which is arranged in the lower mixed-phase reaction region, in the middle distillation zone increases,
• iv) the vapor phase stream separated in the middle distillation zone is discharged from the top of that zone and this vapor phase removed is liquefied by heat exchange with non-preheated raw material in an amount of from about 20 to about 50% by weight,
• v) the vapor phase stream which has been partially liquefied in step iv) is introduced into the top of the upper mixed-phase reaction zone and passes through the catalyst bed of this region at a certain pressure for further reaction of this partially liquefied vapor phase stream,
• vi) the vapor phase stream generated in the upper mixed phase reaction area flows out of the bottom of the catalyst bed of said region and increases richly into the rectification zone via the vapor passage in that region, the liquid phase stream generated in the same region being pumped from the liquid phase outlet is arranged at the lower part of this area, is taken off and recirculated in the circulation via the pump and via the liquid arranged at the upper part of the distillation area into the topmost distillation bottom of the central distillation zone.
• vii) the vapor phase stream entering the rectification zone is distilled in that zone and the liquid phase stream produced after distillation flows over the liquid passage located in the upper mixed phase reaction zone onto the dividing wall and via the pump and via the liquid phase inlet to the uppermost one Distillation bottom of the middle distillation zone is introduced
• viii) the vapor stream containing mainly unconverted reactants is discharged from the top of the column and
• ix) the liquid stream which mainly contains the product is taken from the bottom of the column.

12. The method according to claim 11, characterized in that Further, the reaction temperature and the evaporation amount of the Starting material to be controlled by not preheated Feedstock via the side pipe into the catalyst bed the lower mixed phase reaction region. 13. The method according to claim 11, characterized in that the catalyst as bulk material in the interior of Katalysatorbet filled in the mixed-phase reaction zone, wherein fri filled catalyst over the catalyst inlets and spent, deactivated catalyst over the catalyst outlets is removed. 14. The method according to claim 11, characterized in that the lower part of the liquid passage of the upper mixed phase Reaction area a weir is arranged to prevent that generated in the upper mixed phase reaction area Vapor phase flow enters the fluid passage. 15. The method according to claim 11, characterized in that the Starting material in the mixed-phase reaction areas of their Soils enter and under a certain pressure to the top through the at least one catalyst bed of the mixed-phase Reak flows through tion regions, wherein in the lower mixing phase reaction region generated liquid phase current over the in the lower mixed phase reaction area arranged liquid passage in the Abstreiferzone occurs in the obe The mixed phase reaction region produced liquid phase stream above that in the upper mixed phase reaction region fluid passage, the pump and the liquid phase let enter into the middle distillation area and the in separately generated in these areas vapor phase stream directly into  the middle distillation zone or in the rectification zone increases. 16. A process for mixed-phase reaction distillation by imple mentation of the starting material and distillation of the products in a mixed-phase reaction distillation column, characterized in that

• i) the preheated starting material is introduced into the column which contains a rectification zone, a catalysis reaction zone, a mixed phase reaction zone and a stripper zone, the catalysis reaction zone
  • a) one overlying catalyst beds, at least one Kata lysator flow tube, which is arranged between the adjacent catalyst beds, a catalyst inlet disposed at the uppermost part of the uppermost catalyst bed, and egg NEN catalyst outlet, which is arranged at the bottom of the lowest Ka talysatorbetts , and
  • b) at least one distillation tray disposed between each pair of adjacent catalyst beds, each de stilleration tray having at its center a return tube and a barrier fluid tray,
  • c) wherein each catalyst bed has at least one vapor passage and each vapor passage has a height which is about 100 to about 300 mm, preferably about 150 to about 200 mm, higher than the upper surface of the catalyst bed, and wherein the mixed phase reaction zone
    • a) at the top of a sealed lid, at the bottom of a hole plate or grid for carrying the catalyst and a perforated plate or grid for carrying the catalyst bedec Kendes wire mesh, the catalyst as bulk material between the lid and the perforated plate or the grid for Carrying the catalyst is filled,
    • b) at least one catalyst bed, at least one catalyst flow tube between each two adjacent catalyst beds, a catalyst inlet disposed at the uppermost portion of the uppermost catalyst bed, and a catalyst outlet disposed at the lowermost portion of the lowermost catalyst bed;
    • c) at least one side conduit for introducing non-preheated starting material disposed between each adjacent pair of beds,
    • d) at least one vapor passage disposed on one side of the mixed phase reaction zone and at least one fluid passage disposed on the other side of the mixed phase reaction zone;
• contains
• ii) the reaction is carried out by allowing the starting material entering the column to flow down through the at least one catalyst bed at a certain pressure from the top of the mixed-phase reaction zone,
• iii) it is ensured that the vapor phase stream produced after the reaction in step ii) is mixed with the vapor phase stream separated in the stripping zone and increases into the catalytic reaction zone for further reaction via the vapor passage arranged in the mixed-phase reaction zone during the after-treatment the liquid phase stream generated in step ii) flows directly into the stripper zone,
• iv) the vapor phase stream in the catalytic reaction distillation zone passes through the vapor passages and the distillation beds located between each pair of adjacent beds through each of the catalyst beds and enters the rectification zone,
• v) the liquid phase stream produced in the rectification zone enters the uppermost catalyst bed of the catalysis reaction zone for further reaction, the liquid phase stream flows to the bottom of the catalyst bed and the liquid phase stream passes on to the bottom and the upflowing vapor phase stream exchanges heat and material, then via the reflux tube and the barrier liquid trough, which are located in the center of this floor, sinks to the next catalyst bed to continue the sequence of reaction and distillation, and finally the liquid in the bottommost catalyst bed of the catalysis reaction zone above that in the mixed phase sen reaction zone arranged liquid passage on the top bottom of the Abstreiferzone flows,
• vi) the vapor stream, which mainly contains the unconverted reactants, is discharged from the top of the column and
• vii) the liquid stream which mainly contains the products is taken from the bottom of the column.

17. The method according to claim 16, characterized in that the Reaction conditions are controlled so that on each of Catalyst beds of the catalytic reaction zone a liquid standing with a height of about 50 to about 200 mm, thereby ensuring that the liquid phase in each Catalyst bed evenly distributed. 18. The method according to claim 16, characterized in that the catalyst is introduced as bulk material into the catalyst beds is filled with fresh catalyst over the Katalysatorein Runs filled in the catalyst beds and deactivated Catalyst over the catalyst outlets from the catalyst beds is removed. 19. Application of the method according to claim 1, 11 or 16 to Preparation of ethers by reacting tert-olefins with Al koholen; of ethylbenzene by reacting ethylene with benzene; of alcohols by reacting olefins with water and of Esters by reacting acids with alcohols. 20. Use according to claim 19 for producing MTBE under the conditions of an operating pressure in the range of about 0.4 to about 2.0 MPa, preferably in the range of about 0.5 to 1.2 MPa, a reaction temperature in the range of about 40 to about 90 ° C and an hourly liquid space velocity in the range of about 0.5 to about 15 h ^-1 , preferably in the range of about 1.0 to about 10 h ^-1 .