Study On Preparation Of Petroleum Sulfonate By Gas Phase Sulfonation With HIGEE

Petroleum sulfonate is one of the most common anionic surfactant,which has been widely used in enhancing oil recovery because of its low production cost,high surface activity,and strong oil displacement capability.At present,the preparation technologies of petroleum sulfonate mainly include liquid-phase sulfonation and gas-phase sulfonation.Gas-phase sulfonation has gradually become the mainstream sulfonation technology because no organic solvent is used and no waste acid is generated during this process.However,the traditional gas-phase sulfonation reactor,falling-film reactor(FFR),has poor performance in mass transfer and mixing.During its operating process,the organic reactant viscosity increases largely along the wall of the reactor,resulting in the mismatch between mass transfer and mixing with sulfonation reaction rate.In view of the advantages of the HIGEE reactor in enhancing mass transfer and mixing,this project proposes the use of a HIGEE reactor to intensify the gas-phase sulfonation process,regulating the performance of mass transfer and mixing to make them match with sulfonation reaction rate,finally,solving traditional gas-phase sulfonation problems(such as coking,polysulfonation and difficult continuous production,et al.).The main research contents and conclusions of this work are as follows:1)Preparation of petroleum sulfonate by gas-liquid sulfonation with HIGEE reactor.The SO3 gas generating device and the HIGEE gas-phase sulfonating device were set up.Various operating conditions such as rotation speed(N)of HIGEE reactor,feeding rate(Q of liquid-phase,sulfonation reaction temperature(T),SO3 concentration(ζ),and aging time(t)were investigated to obtain the effect law of the gas-phase sulfonation process.The optimal operating conditions were obtained:N=1800 rpm,Q=60 mL.min-1,7=60 °C,ζ=10 v%,t=60 min.Under the optimal operating conditions,the active matter content of petroleum sulfonate product and the content of unsulfonated oil can reach to 43.5%and 47.3%,respectively,and the index of the obtained product is better than that of industrial product.2)Preliminary optimization study of neutralization process of petroleum sulfonate.The effects of neutralization conditions including neutralizers,neutralization temperature(T’),stirring speed(N),and lye concentration(c)on the content of the active matter were investigated,and an optimal neutralization conditions was obtained:T’=60 0C,N’=1000 rpm,c=40 w%.In addition,while adopting ammonia and NaOH as neutralizers,the active matter contents of the obtained products are closed,therefore,both ammonia and NaOH is appropriate for the neutralization process.3)Feedstock oil and product composition analysis.Component analysis of the feedstock oil and the raw sulfonate were carried out by mass spectrum to obtain their mass spectrum distribution map,heteroatom compound types,carbon number distribution,and equivalent double bond number(DBE).The results showed that the active matter of petroleum sulfonate mainly consisted of the heteroatom-containing compound O3S1,and their abundances(DBE)were higher(≥ 4).The corresponding structures were usually alkyl benzene and alkyl naphthalene sulfonate.In unsulfonated oils,the content of compounds with DBE=4 and DBE=5 is relatively high.The results show that most of the highly unsaturated aromatics have been sulfonated,and higher unsaturation of aromatics in feedstock oil is easier to be sulfonated.In addition,most of unsulfonated oils are low-saturated naphthenes.Through the study on sulfonation process,neutralization process,and component analysis of feedstock oils and product,the optimal operating conditions of sulfonation and neutralization processes,and the components informantion of feedstock oils and sulfonated product were obtained.Which provide the basis data and guidance for process amplification and feedstock adjustment.