Alkylation processes sulfuric acid

Although it is not the most frequently reported toxic chemical released or transferred, sulfuric acid is, by far, generated in the largest quantities. Spent sulfuric acid is primarily generated during the alkylation process. The acid is typically... 

Such reactions can take place predominantly in either the continuous or disperse phase or in both phases or mainly at the interface. Mutual solubilities, distribution coefficients, and the amount of interfadal surface are factors that determine the overall rate of conversion. Stirred tanks with power inputs of 5-10 HP/1000 gal or extraction-type equipment of various kinds are used to enhance mass transfer. Horizontal TFRs usually are impractical unless sufficiently stable emulsions can be formed, but mixing baffles at intervals are helpful if there are strong reasons for using such equipment. Multistage stirred chambers in a single shell are used for example in butene-isobutane alkylation with sulfuric acid catalyst. Other liquid-liquid processes listed in Table 17.1 are numbers 8, 27, 45, 78, and 90. 

In industrial practice, two liquid acids are employed as catalysts for isobutane/ butene alkylation, namely sulfuric acid and hydrofluoric acid [3, 19, 20]. Both processes deliver a high-quality gasoline component. The catalyst consumption in the H2S04 process is high, typically 70-100kg/t The spent sulfuric acid contains tarry hydrocarbons and water and has to be processed externally. On the other hand, corrosiveness and toxicity of HF are reasons of concern that require use of additives that lower the HF vapor pressure and minimize the amount of HF released in the case of an accident. However, in many industrialized countries, new HF alkylation processes are no longer approved by authorities. 

As has been Indicated earlier (1,2), C, olefins react to a significant, and maybe even predominant, extent before Isotutane reacts during alkylations using sulfuric acid as a catalyst. In the previous paper (3) of this series the reactions that occur when n-butene and Isobutylene were contacted with relatively small amounts of sulfuric acid In the temperature range of about -30 to -10°C were Investigated. These reactions defined as first-step reactions In the two-step alkylation process were found to be as follows ... 

Supplemental processes which can be operated in conjunction with alkylation and/or sulfuric acid production can influence the overall economics. Examples are (1) the integration of normal butane-to-isobutane isomerization with alkylation, utilizing common fractionation equipment and (2), utilizing 65% sulfuric acid extraction of isobutylene or isoamylene from olefins fed to alkylation, justified by monetary return on sale of the high purity iso-olefin as a petrochemical feedstock, which reduces quantity of alkylate produced and reduces isobutane required while producing still higher quality alkylate with sulfuric acid catalyst. 

In addition to cat cracking and coking, we did a lot of work on ultraforming. This was a hot area and we got caught up in a wide variety of pilot plants and catalysts. We also got involved in alkylation using sulfuric acid, a pretty messy process. Td have to say that over the years at Standard Oil there was literally no end to the number of projects that we handled. 

The amide group is readily hydrolyzed to acrylic acid, and this reaction is kinetically faster in base than in acid solutions (5,32,33). However, hydrolysis of N-alkyl derivatives proceeds at slower rates. The presence of an electron-with-drawing group on nitrogen not only facilitates hydrolysis but also affects the polymerization behavior of these derivatives (34,35). With concentrated sulfuric acid, acrylamide forms acrylamide sulfate salt, the intermediate of the former sulfuric acid process for producing acrylamide commercially. Further reaction of the salt with alcohols produces acrylate esters (5). In strongly alkaline anhydrous solutions a potassium salt can be formed by reaction with potassium / /-butoxide in tert-huty alcohol at room temperature (36). 

The catalysts used in the industrial alkylation processes are strong Hquid acids, either sulfuric acid [7664-93-9] (H2SO or hydrofluoric acid [7664-39-3] (HE). Other strong acids have been shown to be capable of alkylation in the laboratory but have not been used commercially. Aluminum chloride [7446-70-0] (AlCl ) is suitable for the alkylation of isobutane with ethylene (12). Super acids, such as trifluoromethanesulfonic acid [1493-13-6] also produce alkylate (13). SoHd strong acid catalysts, such as Y-type zeoHte or BE -promoted acidic ion-exchange resin, have also been investigated (14—16). 

Sulfuric Acid All lation. The H2SO4 alkylation process was developed during the late 1930s. In the late 1980s, the H2SO4 process accounted for about 50% of the motor fuel alkylate produced worldwide. 

The reduction ia tetraethyl lead for gasoline production is expected to iacrease the demand for petroleum alkylate both ia the U.S. and abroad. Alkylate producers have a choice of either a hydrofluoric acid or sulfuric acid process. Both processes are widely used. However, concerns over the safety or potential regulation of hydrofluoric acid seem likely to convince more refiners to use the sulfuric acid process for future alkylate capacity. 

Toluenesulfonic Acid. Toluene reacts readily with fuming sulfuric acid to yield toluene—sulfonic acid. By proper control of conditions, /)i7n7-toluenesulfonic acid is obtained. The primary use is for conversion, by fusion with NaOH, to i ra-cresol. The resulting high purity i7n -cresol is then alkylated with isobutylene to produce 2 (i-dii-tert-huty -para-cmso (BHT), which is used as an antioxidant in foods, gasoline, and mbber. Mixed cresols can be obtained by alkylation of phenol and by isolation from certain petroleum and coal-tar process streams. 

The Cy and Cg paraffias comprise about 90% of the alkylate Cg accounts for over 60%. Over 70% of the commercial alkylation processes employ sulfuric acid as the catalyst. Among the butylenes, 2-butene is superior to 1-butene. The C —fraction from the catalytic crackers is considered to be a superior feedstock to the alkylation unit. 

Di- and Triisobutylcncs. Diisobutylene [18923-87-0] and tnisobutylenes are prepared by heating the sulfuric acid extract of isobutylene from a separation process to about 90°C. A 90% yield containing 80% dimers and 20% trimers results. Use centers on the dimer, CgH, a mixture of 2,4,4-trimethylpentene-1 and -2. Most of the dimer-trimer mixture is added to the gasoline pool as an octane improver. The balance is used for alkylation of phenols to yield octylphenol, which in turn is ethoxylated or condensed with formaldehyde. The water-soluble ethoxylated phenols are used as surface-active agents in textiles, paints, caulks, and sealants (see Alkylphenols). 

In the sulfuric acid process, the sulfuric acid removed must be regenerated in a sulfuric acid plant which is generally not a part of the alkylation unit and may be located off-site. Spent sulfuric acid generation is substantial typically in the range of 13 to 30 pounds per barrel of alkylate. Air emissions from the alkylation process may arise from process vents and fugitive emissions. 

The principal use of the alkylation process is the production of high octane aviation and motor gasoline blending stocks by the chemical addition of C2, C3, C4, or C5 olefins or mixtures of these olefins to an iso-paraffin, usually isobutane. Alkylation of benzene with olefins to produce styrene, cumene, and detergent alkylate are petrochemical processes. The alkylation reaction can be promoted by concentrated sulfuric acid, hydrofluoric acid, aluminum chloride, or boron fluoride at low temperatures. Thermal alkylation is possible at high temperatures and very high pressures. 

In conventional alkylation operations, 98 wt. %, sulfuric acid is used as the catalyst, although some processes use HF.The spent alkylation acid, withdrawn as 88-92% acid, is not consumed in the chemical sense, but is diluted by carbonaceous material and small amounts of water. Acid reconditioning is usually completed in a separate plant. The range in makeup acid requirement and in octane quality varies with plant design, with type of feedstock, and with alkylate product rate. A wide variety of feedstocks can be processed through alkylation plants, as both low and high boiling olefins can be alkylated. 

In some cases, because of severe corrosion problems or for special process reasons, a unit must have its own separate blowdown system. A sulfuric acid alkylation process is an example. Here the discharge from safety valves which can contain acid emulsion presents two particular problems corrosion and slow disengaging of hydrocarbon from acid. 

In a widely used industrial process, the mixture of ethylene and propene that is obtained by dehydrogenation of natural gas is passed into concentrated sulfuric acid. Water is added, and the solution is heated to hydrolyze the alkyl hydrogen sulfate. The product is almost exclusively a single alcohol. Is this alcohol ethanol, 1-propanol, or 2-propanol Why is this particular one formed almost exclusively ... 

Acylation of norephedrine (56) with the acid chloride from benzoylglycolic acid leads to the amide (57), Reduction with lithium aluminum hydride serves both to reduce the amide to the amine and to remove the protecting group by reduction (58), Cyclization by means of sulfuric acid (probably via the benzylic carbonium ion) affords phenmetrazine (59), In a related process, alkylation of ephedrine itself (60) with ethylene oxide gives the diol, 61, (The secondary nature of the amine in 60 eliminates the complication of dialkylation and thus the need to go through the amide.) Cyclization as above affords phendimetra-zine (62), - Both these agents show activity related to the parent acyclic molecule that is, the agents are CNS stimulants... 

---