This invention relates to a simple reactor/mixer design for the sulfuric acid alkylation process where C3, C4 and C5 olefins are reacted with isobutane to produce alkylate in the presence of Sulfuric acid catalyst. The conventional process has been practiced for a long time with mechanical propeller mixers and complex seals. The internal mixer and seals are working in a hostile environment (strong sulfuric acid which is used as catalyst for the process) which is demanding. To provide the mixing and tight emulsion one needs reasonable energy being provided to each contactor/reactor and has been cause of lot of maintenance. The process is practiced at certain temperature so as to keep the viscosity low and is not working at optimum temperature. Conventional process works at higher temperature so as to keep the viscosity reasonable for mixing. The Opex of the present conventional application together with complicated mixing device which has been known to require higher maintenance can be improved and more specifically present device of an Eductor is being suggested. The total Capital and Operating costs can be reduced by the new device of Eductor by a factor.
Additionally a new concept of recovering the C3/C4 vapors from the auto refrigeration is being introduced which additionally saves capital cost by either not having the compressor or in the case of revamps additional equipment for absorption and desorption can be introduced which reduces the cost of revamp by a large margin.
The alkylate product normally has reasonably good ROI based on the conventional process, but still the units require high investment. The HF alkylation does not require refrigeration and acid regeneration so it is marginal better in that respect but is much more hazardous due to HF acids and is not readily acceptable environmentally and still capital cost is little better.
RHT alkylation process (RHT-Alkylation) of C3/C4/C5 Olefins or mix carbon number stream with these olefins, react with Isobutane in the presence of Strong sulfuric acid as a catalyst to produce Alkylate (TMP), the reaction chemistry is similar to the conventional process, except the low cost contacting device providing optimum conditions for better product quality and low acid consumption without needing excessive maintenance. The process operates essentially at isothermal conditions. The art of the reactor mixing device together with normal refinery equipment makes it a simple operating system. The art of the invention with eductor mixing device (or equivalent as a sparger and nozzles or similar in configuration) is able to operate at low temperature with auto refrigeration at isothermal conditions. The advantages of art has been already mentioned but will be summarized in the Claims. The contacting device is unique that it can work with viscous fluids under operating conditions and without having any moving parts in the hostile environment in the reactor which makes it very cost effective. It does not have any other complex packing material which has to be changed frequently and could be problem as regards to integrity of the system. The some of the reactor with internals as packed systems have to obtain from a single source which is major drawback for any process and are installed through a manway.
The reactor effluent is taken partly after settling as alkylate/C4 mix and entrained acid. Due to the art in this embodiment utilized in the process, the unique mixing device in the reactor which is an Eductor, allows that the entrained acid can be removed from the hydrocarbon by successive Coalescing devices as manufactured by York or equivalent to remove the acid from the hydrocarbon to ppm level as has been described in Stratco articles in recent years they have been able to reduce the acid carry over to by three fold to few ppm to about <15 ppm. RHT have gone ahead and made the coalescing system to provide lower than 1 ppm level of sulfur in hydrocarbon product by changing and improving the design of Coalescers and also doing the coalescing under better conditions i.e. higher temperature. This acid free hydrocarbon is sent to conventional alkylate recovery section after heat integration. The heat integration system where hydrocarbons are heated to flash of C4's hydrocarbon from alkylate between the coalescing stages, so that one can get better coalescing at higher temperature before the second or successive stages of coalescing and separation. This location of this flash drum is an important art employed to provide an efficient acid separation at slightly elevated temperature of 40 to 300 F and heat integration so as to reduce the load on compressor and are some of the claims of this process.
The vapor from this flash drum can be sent to compressor intermediate stage or if the flash is done at higher pressure than can be condensed separately and recycled to the reactor with olefin feed and isobutane recycle after cooling with the cold alkylate. Alkylate is one of most desirable gasoline component as it is free of sulfur, aromatics and olefins Refiners are always looking at improving this alkylation process so as to reduce the acid consumption and utilities together with maintenance costs. Due to the side reactions taking place due to the impurities, during the alkylation process, acid soluble oils (conjunct Polymers; ASO) are produced which reduce the acid concentration and fresh acid make up is provided to overcome this requirement. The acid soluble oil is sent to the acid regeneration unit. The cost of acid regeneration for low acid consumption unit is about 20% of the operating cost of the alkylation unit. The RHT-Alkylation process at low temperature reduces the acid consumption and provides lower cost of acid regeneration apart from the major cost benefits of process mentioned above.
This invention describes the alkylation of C3, C4 and C5 mix streams with isobutane and claims in the embodiment that the process uses a unique mixing device in the form of Mixing Eductor, or any similar device like sparger or nozzles to mix the hydrocarbon stream with sulfuric acid to provide a much simpler and reliable process which can operate at optimum temperature at just about isothermal conditions. The mixing device is a paradigm shift from the existing technologies which either have impeller and use excessive energy or complicated packing which has to be changed every so often. The eductor does not have any mechanical moving parts in the reactor and can be scaled to 15,000 b/d in one reactor and even with field erected reactor the equipment can essentially be of any unit capacity with one train. But most of the Clients would want a shop erected reactor and also for easier mobility for the unit. This provides scale of economy by a factor compared to the existing art. As process can work at lower temperature with multiple eductors, it has multiple advantages compared to present art being practiced or being offered which will be illustrated in the claims, and is low Capex, low Opex option.
Another alternate can be provided with no C4 compression system, which can be replaced with absorption system. As regards to Eductor it does not have to come from a single source, like internals and also has low maintenance costs. The unique concept of C4 auto refrigeration vapors can be increased in pressure by Isobutane from the Deisobutanizer overhead by the use of an ejector. This can be further increased in pressure by absorbing liquid, could be Iso-Octane product, heavy Naphtha or any other solvent which will absorb this C4 vapor stream. This vapor and the absorbing liquid can be separated by conventional distillation and C4 separation. This is major breakthrough of the process and is an art of the embodiment.
It has already been published in the literature and art of alkylation of olefins with isobutane, and sulfuric acid as a catalyst under low temperature conditions (U.S. Pat. No. 5,095,168) and its benefits e.g. better product quality, low acid consumption. The present art of invention provides a low capex and opex based on the eductor patented mixing device.
As has been published in the articles that in the papers by Stratco that the sulfuric acid has been reduced by three fold by the use of coalescers in the range of 5 to 7 wppm in hydrocarbon/alkylate stream, i.e. raw mix alkylate. The present embodiment with the help of major improvements in the design of coalescer have brought the sulfuric acid to below 1 wppm in the product going to de-isobutanizer and removed the alkyl sulfates as well. The process is shown in
As explained the chemistry is being used the same as by the conventional process but major improvements are in:
An aspect of this disclosure in this patent describes the process to alkylate C3, C4 and C5 mixed olefins and isobutane stream is mixed vigorously in the presence of Sulfuric acid catalyst with novel eductor device. Internal acid piping is provided to the ejector for the motive fluid. The alkylate is produced at low temperature which has a better quality than the conventional process. The Capex and Opex are lower than any other technology and it does not have any non reliable internals and also installation of any internals in not time consuming. Essentially the process works under similar acid concentration as conventional process in the range 89 to 95% but preferably around 90 to 92% to provide the best quality product and low acid consumption, but at lower temperature than conventional process at about 20 to 50 F but preferably at 25 to 27 F in essentially isothermal conditions. The low temperature is obtained by auto refrigeration by flashing the C4 hydrocarbons. Acid to olefin molar ratio is kept around 45 to 180, preferably in the range of 45 to 60, to provide the desired alkylate reaction and quality. The Isobutane to olefin molar ratio of 6 to 15 is desired. These ratio's are very important and are controlled to provide the optimum conditions at the low Opex. To provide the good mixing all the hydrocarbon streams are mixed and sent to the eductor where motive fluid of acid mixes all the streams with acid catalyst and reactants to provide good selectivity, and undesirable reactions are minimized.
The disclosed methods and apparatuses can be understood by referring to the attached figures, which are described in detail herein. It should be understood that the pipelines are being designated when streams are being identified and that streams are intended, if not stated, when materials are mentioned. Moreover, flow control valves, temperature/pressure regulating devices, pumps, compressors, exchangers, drums and the like are understood as installed and operating in conventional relationships to the major equipment items which are shown in Figures/drawings and discussed hereinafter with reference to the continuously operating process of the this invention. All of these valves, devices, pumps, compressor and exchangers and the like, are included in the term auxiliary equipment. It is in the ability of one of the ordinary skill in the art to implement such auxiliary equipment, as needed in view of the present disclosure.
In the embodiment of this invention, following arts are being specifically practiced:
Operating the reactor at low temperature with unique reactor design where mixing is being done by the Eductor. Acid is supplied as motive fluid by an internal pipe in the reactor. The eductor provides adequate mixing so as to have reaction completed. The vapor is generated de to auto refrigeration and heat of reaction which is taken as vapor stream from the top of the reactor. The reactor effluent products which have 20 45% alkylate is taken as a side draw with entrained acid which is separated down stream.
The reactor is operated at about 1 to 10 psig pressure and 25 to 27 F temperature.
The process in this embodiment uses reactor effluent cold energy is used to condense the De-Isobutanizer overhead and, or compressor discharge after cooling the total hydrocarbon stream recycled back to the reactor. This art has already been described in the U.S. Pat. No. 4,130,593 of 1978.
The reaction of olefins with isobutane provides Tri methyl Pentanes (TMP) which is the desired reaction products. The C3 olefins provide more of di methyl Pentane (DMP) in the Alkylate and C5 provide more of C9 alkylate component giving lower octane product compared to C4 olefins. The straight chain olefins provide the slightly higher octane Alkylate from the Sulfuric acid alkylation compared to branched chain olefins, and the acid consumption for branched chain olefins is higher as well. So straight chain olefins C3, C4 and C5 are the preferred Olefin species.
In the Sulfuric Acid alkylation process, olefins and isobutane are reacted in the presence of Sulfuric acid catalyst at 20 to 60 F to form essentially TMP and some other products like Di methyl Hexanes (DMH) and DMP.
Alkylation Chemistry
Butylenes+Isobutane→TMP
Propylene+Isobutane→DMP
It should be noted that even though in C4 alkylation TMP has high concentration over 60 to 70% in the alkylate product, but other components are e.g. DMH and DMP, which are formed in the alkylation reaction.
The side reactions can be postulated as follows:
Polymerization olefin+olefin →Polymer C6, C8 and C12 etc
Cracking
In the reaction larger compounds are made which crack to make smaller compounds:
C11H24 →C6H12+C5 H12
Hydrogen Transfer reactions
This reaction takes place by transferring hydrogen to olefin to make paraffin. Essentially Isopentane is made in the reaction.
2 C4H10+C5 H10 →C8H18 +C5 H12
Esterification reaction
Sulfuric acid reacts with olefins to form small amount of di-butyl sulfate, which is unstable at high temperature and is removed in the coalescer so as to produce good quality product.
Disproportionation
This takes place by rearrangement of the hydrocarbons to form different molecules from a larger hydrocarbon molecule.
2 C10H22 →C8HIs+C12H26
The relative reaction rates of olefins influence the product quality and relative conversion rates can be postulated as follows:
n-butene >i-butene>isopentenes>n-pentenes>propylene
From above one can deduce that one needs lower space velocity for pentenes and even lower for propylene compared to butylenes. In the present embodiment the novel reactor mixing device for alkylation where mixed olefins stream and other recycle streams and excess of isobutene is fed to the eductor and is mixed by acid being recycled as the motive fluid is new concept. The mixing is done in the eductor and in the reactor where predominantly TMP mixture, and 20 to 35% of other DMH, DMP and heavy compounds e.g. nonanes are produced.
As it has already been illustrated by prior art U.S. Pat. No. 5,095,168 that working at lower temperatures around 10 to 50 F preferably at 25 to 28 F, the selectivity to TMP is better providing better octane and also lower acid consumption, the art here is being practiced under low temperature conditions. RHT-Alkylate process works at most desired temperature conditions, at isothermal conditions, which provide even better results for selectivity. RHT-Alkylate process has much better advantage on Capex and Opex compared to competitive technologies and is less complex due to essentially reactor internal being just eductor.
The above feed was used to produced alkylate and the results were very good. The Road Octane was observed to be 94.5 to 95.0 with RON clear to be 95.5 to 96.0 and MON Clear to be 93.5 to 94.0.
Based on flow sheet, the estimated total Installed cost of the unit is expected to be 40 to 45% lower than the conventional process. The Opex is expected to be 35 to 40 lower than the conventional process. The capital cost saving can be realized even higher if auto refrigeration compression is deleted and absorption of the C4's (lower molecular weight hydrocarbons) is done in heavy Naphtha, any solvents or alkylate.
Number | Date | Country | |
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60774326 | Feb 2006 | US |