Lurgi Eurofuel a new Alkylation Process

Dr. Henning Buchold, Dr. Holger Dropsch, Dr. Jrgen Eberhardt Lurgi l.Gas.Chemie, Frankfurt, Germany

Abstract
Basis of this process is a new zeolite catalyst developed by TU Mnchen and Sdchemie. The catalyst is suspended in liquid isobutane. The reaction takes place in a new developed reaction system. The reactor is a reaction column, where the trays are functioning as reactor. Rising isobutane vapour and the boiling liquid on the trays are supporting the mixing of the reaction components. This secures the best possible dilution of the reactants. Reaction mixture is isobutane and butene which is fed to each reaction tray via separate ports. After the reaction the mixture is transported to a separation column where isobutane, alkylate and the high boiling fraction including catalyst are separated. The catalyst is sent back to the reaction column. The regeneration of the catalyst takes place in a new developed kind of hydrocracking process where the high boiling components are converted into valuable products. This new regeneration is a cooperation with the university in Stuttgart. This moderate regeneration method allows to high recycling rates of the catalyst.

Introduction
Worldwide the demand for unleaded gasoline is growing. Several countries are banning or have already banned the lead as additive. The substitutes of lead, aromatics and MTBE are still under discussion. Aromatics must be reduced and the usage of MTBE is limited. Therefore the only octane-buster left for safe use are high octane aliphatic components. A additional demand of alkylates will come from the oncoming specifications for road transport fuels being introduced in 2005. Also the political pressure from local governments or the European parliament to reduce the CO2-emissions which comes from the ratification of the Kyoto protocol will force refineries to look to an alternative fuel production. Alkylate is an ideal blendstock for production of high octane fuel. It has negligible amounts of toxics and ozone precursors. It has high RON and MON values. In addition blending more alkylate into gasoline helps lower the benzene, aromatics, and sulfur levels trough dilution and can also help replace the octane lost due to reduction of aromatics. Alkylation offers several key advantages to refiners including the highest average quality of all components available to the gasoline pool, increased amounts of gasoline per volume of crude oil and high heats of combustion. The alkylation process entails contacting light olefins propylene, butylenes, and amyleneswith isobutane in the presence of a strong acid catalyst to form an alkylate product, consisted of branched paraffins having a low RVP and high octane number. Commercial alkylation plants use either sulfuric acid (H2SO4) or hydrogen fluoride (HF) as catalysts. Although H2SO4 alkylation generally is viewed as less hazardous than HF processing, it requires handling large quantities of acid and typically requires off site acid regeneration. Transporting and handling large volumes of spent H2SO4 has significant potential risks.

The ultimate goal is, of course, to replace the existing alkylation technology by a completely new process which relies on a nontoxic, non-corrosive, easy-to-handle and environmentally friendly catalyst. In this context, much attention has been paid in recent years not only to true solid acids such as zeolites or heteropolyacids, but also to more traditional liquid or gaseous acids artificially solidified on suitable carriers. A broad range of solid or solidified acids has been tested as potential catalysts in the isobutane/alkene alkylation, so far without commercial success. This presentation shows the results of a catalyst which can be produced commercially and his application in a new reaction system.

Alkylation Chemistry
To run an alkylation process several parameters must be reconsidered. The alkylation reaction is not always the preferred reaction path. Some others are competing and it is important to find the right environment to lead the reaction to the right way
1. initiation + H-Z (Z = zeolite)
H3C H H

ZCH
+

CH3 CH3 H3C C

ZCH3

CH3 H3C

2. propagation
CH3 C H3C
+

ZCH3

CH3 H3C H3C H3C

CH3 CH
+

ZCH3 CH3

(and isomers) 3. product formation

ZCH3

CH3 H3C H CH3 CH3 H3C

H3C

H3C CH3

CH3

CH3

(and isomers)

Figure 1 Concerted Mechanism The main reaction is the alkylation catalyzed through Broensted acid sites. The reaction takes place between butene and isobutane and the ideal product is an isooctane. The olefin reacts with t-C4H9+ (a key intermediate cation) to produce C7 to C9 cations. Hydride transfer to this cations produces C7 to C9 isoparaffins (or alkylate). The produced isoparaffins are dimethylpentanes, dimethylhexanes (DMH), trimehtylpentanes (TMP) and various C9 isoparaffins. Products of these reactions are alkylates with very high octane numbers. The formation of relatively heavy cations, such as C12-C20 cations, occurs by polymerization-type reactions. These cations then fragment to produce C5-C9 cations and olefins. Subsequent hydride and proton transfer results in the formation of C5-C9 alkylate with a lower octane number. The heavy cations formed as byproduct of the alkylation reaction are important precursors for catalyst deactivation by coking.

The formed heavy cations can also be converted by hydride transfer to heavy isoparaffins. These isoparaffins can be partly used as alkylate with a lower octane number. Resulting from the knowledge of this reaction mechanism is one condition for the reaction system. Indispensable for such a reaction is a high dilution of butene in isobutane. Ideal would be a infinitesimal dilution. Here the process engineer is challenged to find the right reactor to fulfill a maximum of these conditions Important is the conversion of butene to the right products. The conversion rate of butene at the most alkylation processes is one hundred percent. This is also important to avoid losses of butene because this would also lead to an additional gas separation. The catalyst chosen for the process describe here shows also a complete conversion of fed butenes. As soon as butenes are observed in the reactor product, the alkylation activity of the catalyst is exhausted and no further alkylation products are formed in this catalytic cycle. Therefore the catalyst must be removed in time and the catalyst must be regenerated. This process has a very good selectivity towards the desired alkylation product. The product consists not only of C8 alkanes it has also:

C5 C7: Cracked products C9+ : Heavy products

C8 100 80 60 40 20 0 0

C5-C7

C9+

Selectivity (wt %)

Time

Figure 2 Product Selectivity During the reaction period mostly octane is produced but also the lower boiling products and partly the higher boiling products can be used in the octane pool. The product selectivity and also the product yield is relative constant during the reaction time because the condition of the catalyst is nearly the same. Regenerated catalyst is added to the system and a reversibly deactivated catalyst is removed.

The octane yield shows a high concentration on 2,3,3- and 2,3,4-trimethylpentane.

Trimethylpentanes

Dimethylhexanes

Selectivity in C8 fraction (wt %)

100 80 60 40 20 0 0

Time
Figure 3 Product Yield

Reaction System
A reaction like the alkylation reaction imposes high demands to the process engineer. The high dilution of butene and the limited reaction time because of the high coking rate of the catalyst is calling for a special reaction system. Additional a fine dispersion of the catalyst in isobutane must be realized. Therefore the most easiest solution a fixed bed reactor could not be used in this special case. Since years different groups are working to replace the liquid acid with a solid catalyst but until now no process is commercially proven. Different reaction systems are used, even mixtures between a liquid acid and solids. In the Haldor Topsoe process the liquid acid is supported on a solid substrate. The acid must be replaced on the solid periodically mamking a liquid-acid handling system necessary. The UOP process has a solid catalyst with a moving bed reaction system derived from the FCC reaction system. Akzo/ABB Lumus are using the solid catalyst in a ebulated bed reactor coming from the upgrading of heavy residues. Lurgi has looked for a new way to carry out this reaction. One of the major points have been also reduced investment costs. After discussions of several possibilities we decided to use a distillation system. In this distillation the trays are the reactor steps and the catalyst is not fixed on the trays but transported as suspension in the reaction mixture. High advantage of this system is the dilution of butene through a fine distribution of the catalyst and a specially designed system to feed butene to the reaction mixture. Resulting is a very effective distribution of butene. Additional a high efficient mixing of the reaction mixture takes place. The reaction takes place on the trays. The reaction mixture of butene and isobutane is fed to these trays via separate feed llines. The diluent is isobutane which is vaporized in the bottom of the column. The rising vapor mixes the catalyst suspension and brings the necessary turbulence to the reaction mixture. The vapor is condensed and cooled in the overhead cooler and is refluxed back as diluent to the trays.

The reactor-column is operated under total reflux. The temperature profile of the reaction column is controlled by the volume of isobutane withdrawn at the columns bottoms. The olefin/paraffin ratio in the feed to the tray is 1:7. The system comes to a overall dilution coefficient of about 1 : 12. The following figure shows the overall reaction system with the reactor and the separation column.

Alkylation

Flow Sheet

Figure 4 Flow Sheet The reaction temperature is approximately 75 oC and has a small variation along the reaction trays. The reaction pressure is corresponding to the temperature.

Separation System
The second column is the separation column. The mixture of the remaining isobutane, reaction products and catalyst is sent to the feed tray. Below the feed tray the column is equipped with special trays. These trays are a special construction for suspensions with solids. The bottom product contains the remaining catalyst and the high boiling components. In the upper part of the column isobutane and alkylate are separated. Because the distillates are containig no solids normal distillation trays can be used. The overhead product isobutane- is condensed. The isobutane is alkylate free. The isobutane is used to dilute the catalyst mixture. Isobutane consumption is compensated by feeding fresh isobutane and the catalyst/isobutane mixture is sent to the top tray of the reaction column. Tthe catalyst/isobutane mixture is circulated between reaction and separation column. The product alkylate is withdrawn from a side draw. The alkylate consist of a mixture from C5 to C10 hydrocarbons. The necessary heat for the column comes from a steam reboiler.

The column is running with a small over pressure to keep the overhead and bottom temperature of the column in a save range for the catalyst.

Regeneration of Catalyst
The regeneration of the catalyst has two different steps. One is washing with isobutane and hydrogen. The second step is a kind of hydrocracking. The first step is carried our more often then the second step. More details cannot made public at this moment because of patent reasons.

Development Steps
After having fixed the idea of the reaction system the process was simulated with Aspen Plus to obtain to the mass flows and the optimal temperature and pressure conditions. This results were screened with calculations about residence and reaction time. As second step a cold model was developed to follow up the mixing and back-mixing in the reactor and to avoid sedimentation of catalyst. The first tests of the reactions trays have not been very successful. But after new calculations and constructions the optimal designed tray has been found.

Figure 5 Reactor With these special trays a suspension with a high weightfraction of suspended catalyst in isobutane can be established. This is the basic condition for the successful reactor design . After the successful test of the cold flow system a pilot plant for the real test system is under construction. The diameter of the reaction trays are the minimum size for the later up-scale to a commercial unit. It is planned to run the pilot reaction column at first with pure components . Within a short period after receiving the necessary test result- a test series in a refinery with the original feed is planned.

After completion of the on-site testing period the process will be ready for commercialization. The maximum planned reactor diameter for this solution is between 2500 and 3000 mm. The investment for this new reaction system is much lower compared to conventional alkylations and is therefore a high economic solution.