CN1332140A - Method for alkylation of aromatic hydrocarbon using solid alkylation catalyst - Google Patents
Method for alkylation of aromatic hydrocarbon using solid alkylation catalyst Download PDFInfo
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- CN1332140A CN1332140A CN00120026A CN00120026A CN1332140A CN 1332140 A CN1332140 A CN 1332140A CN 00120026 A CN00120026 A CN 00120026A CN 00120026 A CN00120026 A CN 00120026A CN 1332140 A CN1332140 A CN 1332140A
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Abstract
The present invention discloses a process of alkylating arene adopting solid catalyst. The preocess uses olefine in alkylating arene and regenerating alkylating solid catalyst. Arene containing matter with relatively lower purity is used in preparing alkylated arene and that with relatively higher purity in regenerating alkylating solid catalyst. It an other embodiment scheme, the process is combined further with paraffin dehydrogenation and arene by-product elimination. The benzene containing matter produced by the present invention is essential for alkylation process and regeneration in more economical method.
Description
The present invention relates to use solid catalyst to utilize alkene to make the aromatic hydroxy compound alkylation.
Before about 30 years, pollute rivers and lakes gradually just clearly by the development trend of household laundry detergent of branched-chain alkyl benzene sulfonate manufacturing.Address this problem the washing composition that causes producing by linear alkyl benzene sulphonic acid ester (LABS) manufacturing, have been found that the straight chained alkyl sulphonate is than the biological degradation more promptly of side chain class.
LABS is produced by linear alkylbenzene (LAB).Petrochemical industry utilizes normal olefine to make benzene alkylation produce LAB when HF exists by the linear paraffin dehydrogenation is obtained normal olefine then.This is an industry standard approach.Since nearly ten years, received publicity day by day, cause seeking a kind of with the standard method equivalence or be better than alternative method standard method, that use non-HF catalyzer at the environmental problem of HF.For example, solid alkylation catalyst is a problem very promising, that studying.
The solid alkylation catalyst method inclination is in operating under the mol ratio of higher benzene/alkene than the method for using HF.The detergent alkylation method inclination that uses HF is in benzene/olefin molar ratio being 12: 1 to 6: 1 times operations.The solid alkylation catalyst method inclination is in operating under higher benzene/olefin molar ratio, and one of reason that is generally 30: 1 to 20: 1 relevant this point is that solid alkylation catalyst is lower to the selectivity of manufacture order alkylbenzene.Therefore should increase the mol ratio of benzene/alkene, further to satisfy strict selectivity requirement.The selectivity definition is the weight ratio of monoalkylated benzenes product and all products.
Solid catalyst is inactivation along with use.The alkylation of use solid alkylation catalyst generally includes the method for regular regeneration catalyzer, and this regenerative process is undertaken by removing the gum polymers that is accumulated in catalyst surface and stops up on the response location.Therefore, for solid alkylation catalyst, catalyst life is to measure with the time that stable transformation efficiency moves between twice regeneration according to it.
Solid catalyst can perform well in the continuous alkylation process of aromatic hydrocarbons, and wherein effectively cheap catalyst regeneration process is feasible.
Be used to utilize the alkene in alkene, the particularly 6-20 carbon atom scope, make the alkylating solid catalyst of aromatic hydroxy compound, usually because by the by product of catalyzer preferentially adsorbed and inactivation.These by products are included in C
6-C
12The linear paraffin certain embodiments in polycyclic hydrocarbon that form, in the 10-20 carbon atom scope, also comprise the higher product of the needed monoalkylated benzenes of molecular weight ratio, as two-and three-alkylbenzene, and olefinic monomer.These catalyst deactivation agent or " poisonous substance " are the by-products of alkylating aromatic hydrocarbon.Utilize aromatic hydrocarbons reaction reagent flushing catalyzer, can make the desorb from the catalyzer of these deactivators at an easy rate.Therefore, can utilize aromatic hydrocarbons reaction reagent drip washing catalyzer easily, remove the poisonous substance of accumulation, make catalyzer recover active or regeneration, catalyst activity 100% is recovered from catalyst surface.
Therefore, can repeat to regenerate the method for these catalyzer, just make catalyzer recover active method in order to utilize the catalytic effect of catalyzer for a long time, must to have.Wish that also the required optional equipment of regeneration is minimum.
Therefore, seek a kind of with remove the catalyst deactivation agent or make the method continuous alkylation linked together of catalyst deactivation minimum.
In one embodiment, the present invention is the integrated processes of being produced the solid alkylation catalyst of alkylaromatic hydrocarbon, regeneration of deactivated and randomly being prevented to cause the by product of catalyst deactivation to contact with solid alkylation catalyst by paraffin and aromatic hydrocarbons.In the present invention, the effluent of the solid catalyst alkylation reactor of production alkylaromatic hydrocarbon (as the alkylaromatic hydrocarbon of washing composition level) is separated, contain aromatic hydrocarbons (as containing benzene) logistics and relative highly purified aromatic hydrocarbons (as containing benzene) logistics that contains with what produce relative low-purity, wherein the arene stream that contains of low-purity is suitable for being circulated back to solid catalyst reactor in the production, and the highly purified relatively arene stream that contains then is adapted to pass through to be equipped with and carries out the alkylation reactor regenerated decaying catalyst, that stop using.Rectifying tower provide a kind of produce relative low-purity contain arene stream, and aborning solid catalyst bed in keep the high relatively aromatic hydrocarbons (as benzene) and the economic means of the mol ratio of every mole of alkene, thereby help to postpone the inactivation of solid alkylation catalyst and prolong its life-span.The tower base stream of rectifying tower can pass through the aromatic hydrocarbons separation column, produces the highly purified relatively arene stream that contains.Although can need some funds and running cost during highly purified logistics relatively producing this, the aromatic hydrocarbons tower is not in the alkylation reactor that unnecessarily highly purified relatively logistics is circulated back in the production.Therefore, replace highly purified relatively fractionator overhead logistics, the logistics of relative low-purity is recycled in the alkylation reactor in the production as the logistics that is obtained by rectifying tower, can save some expenses naturally.On the other hand, the present invention can also remove unit associations with the adsorptivity of removing the aromatic hydrocarbons by product that forms in the paraffin certain embodiments, and adsorptivity is removed the adsorption bed of stopping using in the unit because the high purity logistics also is suitable for regenerating.
A kind of configuration of the present invention can use single tower that low-purity and the highly purified tower base stream that contains arene stream and contain charging aromatic hydrocarbons and alkylaromatic hydrocarbon are provided.In this configuration, single tower in most of the cases, wherein can contain the benzene from single tower usually with the highly purified arene stream that contains of the form extraction of clean overhead stream.The logistics that contains aromatic hydrocarbons or benzene of low-purity is usually as the inter-chamber tower Board position place extraction of side-stream at single separation column relatively.This side line is usually by the intermediate altitude place extraction of rectifying section in the separation column.The tower base stream of single tower will contain the alkyl aromatic hydrocarbons product of alkylation process, and other the heavy alkylate by-product that is produced by other paraffin circulation component in the alkylation section.
When being used for the detergent alkylation process, the present invention can use rectifying tower, to reduce the cost of recycle benzene in the alkylation reactor of producing the detergent alkylation thing.In the detergent alkylation reactor aborning, the mol ratio of benzene/alkene is high more, and benefit of the present invention is big more.This benefit is not only because rectifying is the method for separating the alkylation reactor effluent than the separation column that is adopted in the art methods more economically, and, be used for being recycled in the detergent alkylation reactor of production because the recycle stream that rectifying produces is the pure benzene logistics that contains enough pure but also within reason.Therefore, when the overhead stream of relative low-purity was enough, by using less highly purified relatively logistics, the present invention had reduced the cost of recycle benzene in alkylation reactor.
In a kind of specific form, the bottoms of benzene rectifying section is by a separation column, be common known benzene tower, this tower is removed most of remaining benzene in the alkylation reactor effluent, and produces the benzene column overhead logistics higher than the overhead stream purity of benzene rectifying tower.Certainly, the logistics of part benzene column overhead can be recycled in the detergent alkylation reactor in the production, this also within the scope of the invention, but by flow in the alkylation reactor of benzene column overhead in produce, highly purified relatively benzene hour, benefit of the present invention is maximum.
It is the size that significantly reduces the benzene tower that the present invention can reduce one of important way of the cost of recycle benzene in the alkylation reactor in producing.With the remainder of reactor effluent by before the benzene tower, it is stupid to remove part in the effluent of the alkylation reactor from produce, owing to reduce by the benzene flow of benzene tower, therefore can reduce the load of diameter, height and the reboiler of benzene tower.Although new solid catalyst alkylation can be benefited by this advantage, this advantage is for having profound significance by existing HF detergent alkylation process being changed into the solid catalyst alkylation process that solid alkylation catalyst sets up.This is owing to utilize the benzene rectifying tower to remove abundant benzene from the effluent of alkylation reactor, causes to heat up in a steamer at benzin that remaining benzene is not more than the benzene content in the HF stripping tower tower base stream in the HF alkylation process in the Tata bottoms stream.Therefore between alkylation reactor effluent and benzene tower, use the benzene rectifying tower, when catalyzer changes solid alkylation catalyst into by HF, the whole fractionating system of existing HF alkylation process can be reused, thereby can be when converting the solid catalyst alkylation to, fund input will be saved greatly.Saving in addition also is possible, and this is owing to can be easy to transform the HF stripping tower of existing HF alkylation process, used as the benzene rectifying tower in the solid alkylation process, has therefore avoided many costs of new benzene rectifying tower.
Therefore, in one embodiment, the present invention is for producing the method for alkylaromatic hydrocarbon.Under alkylation conditions, when solid alkylation catalyst existed, alkene and charging aromatic hydrocarbons alkylation section internal reaction aborning formed alkylaromatic hydrocarbon.In the alkylation section aborning, alkylation conditions is enough to make at least a portion solid alkylation catalyst to the small part inactivation.Contain outflow logistics in the production of alkylaromatic hydrocarbon and charging aromatic hydrocarbons by the alkylation section extraction in producing.Outflow logistics during at least a portion is produced is separated into the impure relatively logistics that contains charging aromatic hydrocarbons, do not contain alkylaromatic hydrocarbon, impure relatively, contain charging aromatic hydrocarbons and do not contain the logistics of alkylaromatic hydrocarbon with the purity that is higher than pure logistics, and contain charging aromatic hydrocarbons and be rich in the tower base stream of alkylaromatic hydrocarbon.Have at least the pure relatively logistics of a part to be circulated back in the alkylation section in the production.Alkylaromatic hydrocarbon is reclaimed by tower base stream.The logistics that contains charging aromatic hydrocarbons that at least a portion is impure relatively by stop using, be equipped with to the alkylation section of the solid alkylation catalyst of small part inactivation.In the alkylation section of stopping using, impure relatively logistics contacts with the solid alkylation catalyst of part inactivation, makes the solid alkylation catalyst partial regeneration, and produces the solid alkylation catalyst of partial regeneration at least in the alkylation section of stopping using.The outflow logistics of stopping using that contains charging aromatic hydrocarbons is by the alkylation section extraction of stopping using.Make it to form alkylation section in the production and the operation alkylation section in producing and make it to form inactive alkylation section by moving inactive alkylation section, the function of alkylation section in the production and that stop using is regularly changed.
US-A-5645879 people such as () Kulprathinpanja proposes to utilize alkene to make the alkylating solid catalyst of aromatic hydroxy compound, usually because the preferentially by product that is adsorbed by solid catalyst and inactivation, and can utilize aromatic hydrocarbons reaction reagent washing catalyst at an easy rate, make the desorb from the solid alkylation catalyst of these deactivators.
US-A-5276231 people such as () Kocal proposes a kind of alkylated aromatic hydrocarbons method of removing the aromatic hydrocarbons by product that forms usually in the paraffin certain embodiments, and this removes process by being adsorbed onto the aromatic hydrocarbons by product on the sorbent material and sorbent material being contacted and reproducing adsorbent with liquid benzene.
Accompanying drawing is the process flow diagram flow chart of one embodiment of this invention
The present invention is to use solid alkylation catalyst, utilize alkene to make alkylating aromatic hydrocarbon and produce the integrated processes of the solid alkylation catalyst of alkylaromatic hydrocarbon and regeneration of deactivated.Being used to implement charging of the present invention is obtained by the paraffin dehydrogenation usually.Normally used is the mixture of whole dehydrogenation reaction.Be used for implementing charging of the present invention, should making the olefin polymerization that forms in the certain embodiments minimum.Thereby charging is mainly the mixture of unreacted paraffin, side chain monoolefine and non-side chain or straight chain mono-olefins.These paraffin and monoolefine are usually at C
6-C
22In the scope, but when enforcement is of the present invention, preferably at C
8-C
16In the scope, more preferably at C
10-C
14In the scope.Monoolefine in the charging and the alkyl derivative reaction that joins benzene in the treating processes or benzene.The alkyl derivative (alkylaromatic hydrocarbon) of the benzene that is fit to comprises propyl benzene, butylbenzene and penta benzene of the benzene that methylates, ethylbenzene, diethylbenzene and triethyl-benzene, isopropyl benzene (isopropyl benzene), n-proplbenzene and the Geng Gao of toluene, dimethylbenzene and Geng Gao, but is not limited to these materials.Therefore, the alkyl derivative of benzene can have one or more alkyl groups, and each alkyl group can have 1-5 or more a plurality of carbon atoms.
The application alkylated aromatic hydrocarbons process of the present invention of extensive enforcement is to produce linear alkylbenzene (LAB).
The LAB process adds normal paraffin usually in dehydrogenation reactor.Usually do not remove the branched-chain alkene that forms in the certain embodiments, the side chain monoolefine in the charging exists with less concentration usually.Because the position to two keys does not require, therefore for the monoolefine in the charging, unsaturated any position that can appear on the monoene hydrocarbon chain.Because the alkylate of the alkyl derivative of monoolefine and benzene may not be the alkylbenzene washing composition parent that is fit to, so monoolefine in the charging and benzene reaction.Although it is 1 that the stoichiometry of alkylated reaction is only required the mol ratio of benzene and straight chain mono-olefins, but the mol ratio that adopted 1: 1 causes excessive olefin polymerization and many alkylations, forms that a large amount of dialkyl benzenes, trialkyl benzene, possible higher many alkyl are stupid, dimerizing olefins body, tripolymer etc. and unreacted benzene.In order under desired transformation efficiency, selectivity and straight chain, to carry out alkylation, advise total benzene: the monoolefine mol ratio be 5: 1 to up to 30: 1, the ratio between about 8: 1 and about 20: 1 is preferred.
Under alkylation conditions, when solid alkylation catalyst exists, benzene and straight monoene hydrocarbon reaction.These alkylation conditions comprise about 80 ℃ (176 °F) to the interior temperature of about 140 ℃ (284) scopes, and the most frequently used temperature is no more than 135 ℃ (275 °F).Because alkylation is carried out with liquid phase cracking process, pressure should be enough to keep reaction reagent and be in liquid state.Desired pressure must depend on charging and temperature, but is in usually in absolute pressure (200-1000psi (the g)) scope of 1480-7000kPa, and that the most frequently used is 2170-3550kPa (g) (300-500psi (g)).
Solid alkylation catalyst has the effect of acid usually, therefore is known as solid acid catalyst.The material that this class solid acid catalyst generally includes such as soft silica-aluminum oxide, crystal aluminosilicate material such as zeolite and molecular sieve comprise natural or artificial clay, sulfation oxide compound such as the sulfoxidation zirconium of pillared clays, traditional friedel-crafts catalysts such as aluminum chloride and zinc chloride and solid Lewis acid.Described solid alkylation catalyst discloses a kind of extrusion moulding catalyzer that contains clay and at least a polyvalent metal; The U.S. Pat 5034564 that belongs to J.A.Kocal discloses a kind of catalyzer that contains pillared clays and binding agent; Two U.S. Pat 5196574 and the US5344997 that belong to J.A.Kocal disclose a kind of fluorizated silica-alumina catalyzer; The U.S. Pat 5302732 that belongs to people such as K.Z.Steigleder has been described a kind of ultralow sodium silica-alumina catalyzer; The U.S. Pat 5491271 that belongs to people such as Marinangeli discloses application deaminizating or the tetrahedral charged clay of column.
The effluent of alkylation reaction zone preferably passes through rectifying tower.Rectifying tower obviously is different from stripping tower.Consider rectifying on the whole, the difference between rectifying tower and stripping tower is just very clear.Known trend when rectifying depends on liquid, gas phase contact, easy more evaporable component trends towards being concentrated in the gas phase more, rather than in the liquid phase.In multistage operations, liquid descends along vertical rectifying tower, by level a plurality of and rising steam counter current contact.The tower of naming a person for a particular job of introducing charging in rectifying tower is divided into two sections.Stripping section is below feed points, and rectifying section is more than feed points.In stripping section, by proposing volatile components in the liquid that descends.In rectifying section, the concentration of difficult volatiles reduces in the steam.In practice, liquid and steam logistics be in contact with one another the level can be column plate or filler.Therefore, compare with stripping tower, in rectifying tower, charging is positioned at a plurality of grades bottom, and the charging of stripping tower is positioned at a plurality of grades top.In addition, rectifying tower reduces the concentration of difficult volatiles in the steam, and stripping tower proposes volatile components from dropping liq.
Rectifying tower has about 10 to about 20 usually and separates level, and to use plate efficiency usually be about 60% sieve plate.Therefore, rectifying tower has about 15 usually to about 25 blocks of column plates, is generally 20 blocks of column plates.Be less than 15 blocks of column plates and also can use, and partly or entirely column plate all can replace with the solution-air contact medium, as Bohr's saddle ring of the conventional shape of filling at random or Raschig ring or as the regular element of filling in order.The benzene rectifying tower usually adopts and is positioned at the outside or inner reboiler of benzene rectifying tower, feed preheater or both all adopt.The benzene rectifying tower also adopts complete condenser usually, condensing steam or steam mixture, the above steam of common condensation 95 weight %, the steam that the 99.5 weight % of condensation more commonly are above.The part of condensed overhead stream is back to the top of benzene rectifying tower usually.The remainder of condensed overhead stream is circulated back in the alkylation reactor in the production.Employed part logistics in the context for the application, except as otherwise noted, otherwise the meaning of term " part " is aliquot or non-aliquot.The aliquot of logistics is the stream portions that has same composition basically with logistics.
The operational condition of benzene rectifying tower generally includes the pressure of about 50 to about 345-483kPa (g) (70psi (g)), although also can use the higher pressure up to the device design limit.The cat head of benzene rectifying tower and column bottom temperature are typically about 300 °F (149 ℃), cause the benzene rectifying tower operating under the temperature difference at the bottom of relatively little cat head and the tower.The benzene rectifying tower usually produces the tower base stream that contains abundant benzene, and the boiling point that causes tower base stream is relatively near the boiling point of overhead stream.Usually the benzene that enters rectifying tower has about 50% to about 70% with clean overhead stream outflow.
The impure relatively benzene logistics that contains reclaims the logistics that obtains as the clean overhead stream by the benzene rectifying tower, its purity with highly purified relatively, can be that to reclaim that the logistics that obtains compares be relatively low for clean overhead stream by the benzene tower.The impure relatively benzene concentration that contains the clean logistics of benzene that is obtained by the recovered overhead of benzene rectifying tower is typically about 80 to about 98 moles of %.For the overhead stream of benzene rectifying tower, its paraffin concentration is generally 2-20 mole %, be preferably 2-5 mole %, and the concentration of alkylbenzene (alkylaromatic hydrocarbon) is usually less than 100wppm.Under normal alkylation temperature, when contacting, can be sure of that the existence of paraffin does not have tangible harmful effect to solid alkylation catalyst except occupying the reactor volume of producing alkylbenzene with catalyzer.Therefore, no matter its paraffinicity, the logistics of impure relatively liquid stream such as benzene rectifying tower is to an alkylation reactor circulation part or its aliquot suitable benzene source.
The paraffin that is present in the clean overhead stream of benzene rectifying tower has 5-22 carbon atom usually.First paraffinic source of heating up in a steamer in the column overhead logistics at benzin is to follow the paraffin of the charging that contains monoolefine.These paraffin usually with charging in monoolefine have identical carbonatoms.Paraffin is also in the feed stream that contains benzene enters the overhead stream of benzene rectifying tower.The boiling point of the paraffin in the benzene feed stream is usually near the boiling point of benzene.
The mol ratio of benzene and alkylaromatic hydrocarbon is that the clean tower base stream of about 7: 1 benzene rectifying tower can pass through the benzene tower.The benzene tower utilizes 45-55 piece sieve plate usually, is typically about 50 sieve plates, can remove remaining benzene.When the benzene top of tower began to count, the tower base stream of benzene rectifying tower entered near the 30th sieve plate or the 30th sieve plate.Do not need pre-dry additional benzene can add in the benzene tower yet.The benzene tower uses reboiler and complete condenser usually, and complete condenser is used for overhead stream, to benzene column overhead withdrawing fluid.The operational condition of benzene tower comprises the pressure of about 170kPa absolute pressure (10psi (g)), the tower top temperature of about 93 ℃ (200), and the column bottom temperature of about 232 ℃ (450).The benzene tower produces clean overhead stream, and its benzene concentration preferably is higher than 99.9 moles of % usually above 95 moles of %, further preferably is higher than 99.99 moles of %.The clean overhead stream of benzene tower can also contain the paraffin than small concentration, and its concentration is usually less than 5 moles of %, preferably is lower than 0.1 mole of %, further preferably is lower than 100wppm, more preferably less than 10wppm.In the clean overhead stream of benzene tower, if any, alkylbenzene (alkylaromatic hydrocarbon) exists with the concentration that is lower than paraffin concentration usually.Therefore, according to the present invention, the purity that is reclaimed the benzene logistics obtain by the benzene column overhead reclaims the purity of the benzene logistics that obtains usually above heated up in a steamer column overhead by benzin.
The clean overhead stream of benzene tower can contain the paraffin that carbonatoms is 5-22.Be present in specific paraffin in the clean overhead stream of benzene tower depend primarily in the charging in the monoolefine charging, that contain benzene and, if adopt, the aromatic hydrocarbons by product is removed the paraffin that contains in the purge stream in the section, if any.
According to the present invention, the part of the clean overhead liquid logistics of benzene tower such as the aliquot alkylation reactor by stopping using wherein is equipped with and recovers activity or regenerated solid alkylation catalyst.Can be sure of that the purity of the benzene of the solid alkylation catalyst that is used to regenerate is an important variable, combine, guarantee that the catalyzer after the regeneration reaches acceptable alkylation activity level with regeneration temperature.Under not by any specific situation that theory fettered, can be sure of that under the higher relatively temperature that is adopted, when contacting with alkylation catalyst, the existence of paraffin has harmful effect to catalyzer in regenerative process.Therefore, can be sure of, with respect to the suitable logistics of the clean overhead liquid logistics of lower pure relatively logistics of the clean overhead liquid logistics paraffin concentration of impure relatively logistics such as benzene rectifying tower such as the benzene tower solid alkylation catalyst that is regeneration of deactivated.
Therefore in preferred embodiments, the clean overhead liquid logistics that makes the benzene tower is by carrying out the bed of regenerated solid alkylation catalyst.The effluent that carries out the regenerated reactor contains benzene, paraffin, alkylbenzene and by the heavy constituent of desorb on the catalyzer.Although this outflow logistics from inactive alkylation reactor can preferably should regeneration outflow logistics be passed through the benzene tower according to mode identical with the alkylation reactor effluent in the course of normal operation by the benzene rectifying tower.Therefore, can add not only having in the benzene tower and heat up in a steamer benzene at the bottom of the Tata, replenish benzene, and have from the benzene that carries out the regenerated alkylation reactor from benzin.
In a kind of configuration commonly used, the tower base stream of benzene tower is by the paraffin tower, generation contains the overhead liquid logistics of unreacted paraffin, the higher side line hydrocarbon product of other molecular weight that contains the tower base stream of alkylate and form in the selective alkylation section, wherein the overhead liquid logistics is circulated back to dehydrogenation section as recycle stream usually.Tower base stream enters in the treating column again, produces the cat head alkylate stream that contains the detergent alkylation product and contains olefin polymerization and the tower base stream of many alkylated benzenes (heavy alkylate).
In another embodiment, the present invention is a kind of integrated processes, this method obtains normal olefine with the linear paraffin dehydrogenation, then when solid alkylation catalyst exists, utilize normal olefine to make benzene alkylation produce alkylaromatic hydrocarbon, and the solid alkylation catalyst of regeneration of deactivated can stop the by product that causes catalyst deactivation to contact with solid alkylation catalyst in addition.
Dehydrogenation section is preferably constructed according to the mode shown in the drawings of US-A-5276231 basically.Contain the feed stream of paraffin and come the round-robin hydrogen of self-alkylation section and round-robin unreacted paraffin to converge.Form one reactant stream like this, this logistics is heated, and by a beds that is fit to that remains under the conditions such as suitable desorption temperature, pressure.Dehydrogenation catalyst is known in the dehydrogenation field, and the example given as US-A-3274287, US-A-3315007, US-A-3315008, US-A3745112 and US-A-4430517 no longer is elaborated here.The effluent of this beds or reactor effluent circulation often are cooled, partial condensation and separated, so that the effluent by the alkylation section to be provided.
The common variation of the present embodiment comprises makes the diolefine selective hydrogenation that is present in usually in the dehydrogenated product stream.Known diolefine forms in the paraffin dehydrogenation process.Optionally diene hydrogenation makes diolefine change into monoolefine, and the monoolefine desirable product that is dehydrogenation section, thereby produce optionally diene hydrogenation product stream.Optionally diene hydrogenation process has been proposed in US-A-4520214 and US-A5012021.
In the present embodiment that is used for producing the alkylated aromatic hydrocarbons compound, aromatic hydrocarbons is removed the section elimination or has obviously been reduced the aromatic hydrocarbons by product that enters into the charging in the selective alkylation section.The removal of aromatic hydrocarbons by product has reduced the deactivation rate of solid alkylation catalyst, thereby reaches the yield of higher straight chained alkyl aromatic hydroxy compound.
It is known forming the aromatic hydrocarbons by product in the paraffin dehydrogenation process.Be sure of that these aromatic hydrocarbons by products comprise alkylbenzene, naphthalene, other polynuclear aromatic hydrocarbons, C
10-C
15Alkylation polycyclic hydrocarbon, indane, tetraline in the scope and can be considered aromatization N PARAFFIN ﹠ HEAVY NORMAL PARAFFIN.Usually entering in the paraffin compound charging of dehydrogenation section has about 0.2 to about 0.7 weight %, is no more than 1 weight % usually and forms the aromatic hydrocarbons by product.Can be sure of that these by products are at great majority-if not whole words-when industrial available dehydrogenation catalyst exists, under the dehydrogenation condition that is fit to, form at least on less degree.In the process of not removing the aromatic hydrocarbons by product, the concentration that flows out aromatic hydrocarbons by product in the logistics in dehydrogenation can run up to 4-10 weight % usually, and this will cause the rapid inactivation of solid alkylation catalyst.
This embodiment of the present invention utilizes at least one aromatic hydrocarbons to remove section, removes a part of aromatic hydrocarbons by product in the dehydrogenated product stream at least.This aromatic hydrocarbons is removed section and is preferably placed between dehydrogenation section and the selective alkylation section, this be because preferably before entering the selective alkylation section selectivity remove the aromatic hydrocarbons by product.For this embodiment of the present invention, the aromatic hydrocarbons that is fit to is removed section and is comprised the fractionation by adsorption section.Wherein to remove section be the fractionation by adsorption section to aromatic hydrocarbons, and the present invention can implement in fixed bed or mobile adsorbent bed system, but fixed bed system is preferred.The stream flow that contains the aromatic hydrocarbons by product by the fractionation by adsorption section is preferably carried out with parallel mode, thereby when lost efficacy by accumulating the aromatic hydrocarbons by product thereon in an adsorbent bed or chamber, this exhaustion phase can be passed through by bypass, and does not interrupt the operation by parallel section.
The sorbent material that is fit to can be selected from has the material that basic selectivity requires and can conveniently use to the aromatic hydrocarbons by product.For example, the sorbent material of Shi Heing comprises molecular sieve, silicon-dioxide, activated carbon, gac, activated alumina, silica-alumina, clay, cellulose ethanoate, synthetic Magnesium Silicate q-agent, macropore Magnesium Silicate q-agent and/or macroporous polystyrene gel.Should be appreciated that the effect of above-mentioned sorbent material needs not to be and is equal to.The selection of sorbent material will be depended on Several Factors, comprise that sorbent material keeps the capacity of aromatic hydrocarbons by product, and sorbent material keeps the selectivity to the more deleterious aromatic hydrocarbons by product of solid alkylation catalyst, and the cost of sorbent material.Preferred sorbent material is a molecular sieve, and preferred molecular sieve is 13X zeolite (natrolite X).
Under the situation that does not have too much experiment, those skilled in the art can select suitable sorbent material operational condition.For example, the ADSORPTION IN A FIXED BED segregation section that the 13X zeolite is housed can remain under the temperature of about 20 ℃-300 ℃ (68 to about 572) usually, be preferably about 100 ℃-200 ℃ (212 °F to about 392 °F), the logistics that pressure should effectively keep containing the aromatic hydrocarbons by product under selected temperature is in liquid phase, and about 1 hour
-1To about 10 hours
-1Liquid hourly space velocity, be preferably about 1 hour
-1To about 3 hours
-1The stream flow that contains the aromatic hydrocarbons by product by the fractionation by adsorption section can be undertaken by upper reaches, dirty or radial flow mode.
Although liquid and the operation of steam two-phase can be used for multiple adsorption separation process, liquid-phase operation is preferred to the fractionation by adsorption section, and this is owing to its lower temperature requirement, and utilizes liquid-phase operation can reach higher aromatic hydrocarbons by product absorption yield.Therefore, in the process of absorption aromatic hydrocarbons by product, the temperature and pressure of fractionation by adsorption section should carry out preferably, be in liquid phase with the logistics that keeps selectivity therefrom to remove the aromatic hydrocarbons by product, however, the operational condition of fractionation by adsorption section can be optimized by those skilled in the art, and to operate in the scope of broad, this scope wishes to comprise condition and the variation thereof in the conversion zone of the present invention.Therefore, this embodiment of the present invention comprises a fractionation by adsorption section, and this fractionation by adsorption section is included in the shared reaction vessel with dehydrogenation section, selectivity diene hydrogenation section, selective alkylation section or selectivity monoolefin hydrogenation section.
After the suitable treatment time, remove adsorbed aromatic hydrocarbons by product and make adsorbent reactivation from sorbent material.Multiple adsorbent regeneration method is arranged, and can use any suitable renovation process, comprise the temperature and pressure that changes sorbent material, and utilize pure relatively logistics to handle sorbent material, to replace adsorbed aromatic hydrocarbons by product or to make it desorb as the logistics that obtains by the logistics of benzene column overhead.The flow direction of the benzene column overhead logistics by the fractionation by adsorption section can be upper reaches or radial flow, but preferred direction is dirty.The state of the benzene column overhead logistics mixture by the fractionation by adsorption section can be liquid phase and/or gas phase.
Flow out logistics and remove the section extraction by aromatic hydrocarbons, the aromatic hydrocarbons by product that wherein contains benzene, purging hydrocarbon such as pentane and in certain embodiments, produce, wherein this aromatic hydrocarbons removal Duan Zaiyu will purge with the purging hydrocarbon before containing benzene logistics contact.This effluent circulation is normal by a desorb separation column, produces the tower base stream of the weight that contains the aromatic hydrocarbons by product.If the benzene column overhead logistics that contains other charging paraffin is removed section by aromatic hydrocarbons, then these charging paraffin should be present in and flow out in the logistics, and appear at last in the tower base stream of weight of desorption tower.This be since the aromatic hydrocarbons by product have identical carbonatoms usually with paraffin, so aromatic hydrocarbons by product and paraffin the two be similar to azeotropic under identical temperature.Because paraffin may be converted to desirable alkylated aromatic hydrocarbons, the aromatic hydrocarbons by product then is not easy to be converted to desirable alkylaromatic hydrocarbon, and the two reclaims in same logistics, and therefore giving up the aromatic hydrocarbons by product by desorption tower causes having given up simultaneously paraffin.Paraffin concentration in the benzene column overhead logistics that enters aromatic hydrocarbons removal section is high more, and is many more with the paraffin that the aromatic hydrocarbons by product loses by desorption tower.Therefore, the regeneration that preferably is used for aromatic hydrocarbons removal section is pure relatively logistics, as the logistics from the clean overhead liquid of benzene tower.Rather than impure relatively logistics, as the clean overhead liquid of benzene rectifying tower, this is because the purity of this liquid is higher.Owing to this reason, pure relatively logistics such as the logistics of benzene column overhead preferably contain the paraffin that is less than 0.1 mole of %, further preferably are less than the paraffin of 100wppm, and the preferred paraffin that is less than 10wppm.
Desorption tower also produces clean overhead stream, wherein contains lighter component, i.e. benzene and purging compound such as pentane.This clean overhead stream makes the purging compound separate with benzene by separation column.When the purging compound was pentane, this segregation section was the depentanize separation column, wherein produced clean overhead stream that contains pentane and the clean tower base stream that contains benzene.Clean overhead stream is recovered and is used to purge aromatic hydrocarbons removal section, and clean tower base stream is cycled back in the solid catalyst alkylation section.In this mode, the more needed benzene of solid catalyst alkylation section are to supply with by removing section separation column in the desorption tower downstream that links with aromatic hydrocarbons, and this tower is depentanizer in afore-mentioned.
By the technical process of the preferred embodiment entire operation of understanding process more fully.With reference to the accompanying drawings, pipeline 212 adds in dehydrogenation section 210 and contains C
10-C
15The paraffin feed stream (wherein containing the circulation paraffin from pipeline 174 usually) of normal mineral wax mixture in dehydrogenation section, when hydrogen exists, is changing into a large amount of paraffin under the condition of corresponding alkene, and paraffin contacts with dehydrogenation catalyst.The product of dehydrogenation section contains monoolefine, unreacted paraffin and aromatic hydrocarbons by product, and this logistics enters the aromatic hydrocarbons by product through pipeline 214 and removes section, wherein has being used in the production to remove the bed 230 of aromatic hydrocarbons by product and the bed that is used for reproducing adsorbent 220 of stopping using.Valve 222 is opened and valve 226 is closed.The product of dehydrogenation section by pipeline 218 and 224 and open valve 222 enter bed 230 in the production, remove the aromatic hydrocarbons by product.The effluent of bed 230 flows through pipeline 232,234 and 258 and enters depentanizer 280, and valve 240 is opened and valve 250 is closed.The most of alkene and the paraffinic hydrocarbon that enter depentanizer 280 through pipeline 258 are all heavy than pentane, therefore by discharging through pipeline 27B at the bottom of the tower of depentanizer 280.Preferably, in the tower base stream in pipeline 278, C
7Following paraffin concentration is less.Hydrocarbon in the pipeline 278 with converge from the clean overhead stream that contains benzene benzene rectifying tower 150, that flow through pipeline 164.
Alkene, paraffin and benzene converge the logistics pipeline 116,122 and 286 of flowing through, enter alkylation reactor 110 through open valve 126, utilize alkene to make benzene alkylation.Reactor effluent in the production is by open valve 132 and pipeline 136.Open valve 134 and pipeline 138 converge with effluent in production effluent, off-stream case 120 that has in the production.Logistics after converging flows through pipeline 142, is heated in interchanger 130, and the pipeline 146 of flowing through further is heated in interchanger 140, and the pipeline 152 of flowing through enters benzene rectifying tower 150.Interchanger 130 is by the vapor stream of top of the tower heat supply of the benzene rectifying tower in the pipeline 144.Contain the further condensation in condenser 160 of benzene vapor stream of top of the tower in the pipeline 148 of benzene rectifying tower 150.The pipeline 154 of flowing through enters cat head receptor 170.The clean logistics of the uncooled lighter hydrocarbons of less one through pipeline 156 by receptor 170 extraction.Receptor 170 provides withdrawing fluid and is circulated back to alkylation reactor 110 in the production through pipeline 164 to benzene rectifying tower 150 through pipeline 166.
The tower base stream of benzene rectifying tower flows into benzene separation column 180 through pipeline 158.In illustrated process configuration, benzene separation column 180 is the containers that separate with benzene rectifying tower 150.The fill-in that the contains benzene pipeline 114 of flowing through enters benzene tower 180.The tower base stream of benzene tower 180 flows into product recovery system 190 commonly used through pipeline 172.Logistics by recovery system 190 extraction comprises that paraffin cycling stream 174, heavy alkylate stream 178 and alkyl aromatic hydrocarbons product flow 176.After the condensation, the clean liquid overhead stream of benzene tower 180 flows into the bed 220 of stopping using through pipeline 168, and carries out in the regenerated solid alkylation catalyst in the inflow off-stream case 120.
Therefore, the part logistics in the pipeline 168 flow into beds 220 through pipeline 268 and 228, and valve 272 is opened and valve 266 is closed.Therefore, when bed 220 is stopped using, wherein do not have flow to pass through pipeline 216, and when bed 230 is in production status, wherein do not have flow to pass through pipeline 264.Effluent flows into desorption towers 270 through pipeline 236,244 and 256, and valve 242 is opened and valve 250 is closed.Since valve 250 when closing bed 220 stop using, do not have flow to pass through pipeline 248, and since valve 238 when closing bed 230 be in production status, do not have flow to pass through pipeline 246.Desorption tower 270 produces the tower base stream 276 that contains the aromatic hydrocarbons by product, and this logistics is by extraction in the process and can be used as fuel.Desorption tower also produces the overhead stream 274 that contains benzene and pentane, and this logistics enters depentanizer 280.Depentanizer 280 produces the overhead stream 260 that contains pentane, and this logistics is imported into the bunkerage (not shown), is used to preserve the pentane resource, when stopping using with convenient bed, is used to purge adsorption bed 230.
Another part in the pipeline 168 contains the benzene logistics and flows into off-stream case 120 through pipeline 252,254 and 288.Valve 262 is opened and valve 284 is closed.Stop using and reactor 110 when being in production status when reactor 120, do not have logistics to pass through pipeline 282, also do not have logistics to pass through pipeline 124.The benzene that enters reactor 120 flush away from the alkylation catalyst causes the by product of the weight of catalyst deactivation.Therefore the effluent from off-stream case 120 contains benzene and these by products, and these by products may comprise polycyclic hydrocarbon, many alkylated aromatic hydrocarbons and olefinic monomer.By product in the effluent of off-stream case 120 tends to be concentrated in the tower base stream of benzene rectifying tower 150 and benzene tower 180, and finally is recovered in the heavy alkylate stream 178 by product recovery system 190.Substitute as flowing into a kind of of benzene rectifying tower 150.The effluent of off-stream case 120 can bypass pass through benzene rectifying tower 150, and flows directly into benzene tower 180.
The reactor 110 during the pipeline of reactor 110 and 120 upstream and downstream and valve configurations allow to produce and the function of off-stream case 120 are regularly changed.The serious inactivation of catalyzer in the reactor 110 in producing, when causing the continuation production operation unactual or uneconomical, perhaps the catalyzer in off-stream case 120 fully recover active, in the time of can implementing production or economical operation, when perhaps two kinds of situations exist simultaneously, carry out this function conversion.Open the valve 128 and 284 that is in closing condition, and close the valve 126 and 262 that is in open mode, can finish this function conversion.In a kind of analog system, the bed 230 during the pipeline of bed 220 and 230 upstream and downstream and valve configurations also allow to produce is regularly changed with the function of inactive bed 220.Bed 230 in the production becomes the bed 220 of stopping using, and the bed 220 of stopping using becomes the bed 230 in the production.
Claims (10)
1. method of producing alkylaromatic hydrocarbon, this method comprises:
A) under alkylation conditions, when solid alkylation catalyst exists, make alkene and charging aromatic hydrocarbons alkylation section internal reaction aborning, form alkylaromatic hydrocarbon, in the alkylation section aborning, alkylation conditions is enough to make at least a portion solid alkylation catalyst to the small part inactivation; And contain the outflow logistics of the production process of alkylaromatic hydrocarbon and charging aromatic hydrocarbons by the alkylation section extraction in producing;
B) the effluent stream of at least a portion production process is separated into containing charging aromatic hydrocarbons, not containing the logistics of alkylaromatic hydrocarbon of a relative low-purity; One highly purified relatively, contain charging aromatic hydrocarbons, do not contain the logistics of alkylaromatic hydrocarbon with the purity that is higher than relative low-purity logistics, and tower base stream that contains charging aromatic hydrocarbons, is rich in alkylaromatic hydrocarbon;
C) logistics of the relative low-purity of at least a portion is circulated back in the alkylation section in the production;
D) reclaim alkylaromatic hydrocarbon by tower base stream;
E) make the highly purified relatively logistics of at least a portion by stop using, be equipped with to the alkylation section of the solid alkylation catalyst of small part inactivation, make the relative highly purified logistics contact of the interior solid alkylation catalyst of inactive alkylation section with at least a portion to the small part inactivation, make solid alkylation catalyst partial regeneration at least, and in the alkylation section of stopping using, produce the solid alkylation catalyst of partial regeneration at least, contain the outflow logistics of stopping using of charging aromatic hydrocarbons by the alkylation section extraction of stopping using;
F) return the outflow logistics that at least a portion is stopped using, be used for the sepn process of step (b);
G) the alkylation section of stopping using by operation, make it to form step (a) and (c) in alkylation section in producing, and the alkylation section in the operation production, make it to form the alkylation section of stopping using in the step (e), the function of alkylation section in the production and that stop using is regularly changed.
2. the method for claim 1, one of them single tower provides highly purified relatively logistics as overhead stream, the logistics of relative low-purity is as side-stream, and tower base stream, and wherein is returned in this list tower from the outflow logistics that reaches the alkylation section in producing of stopping using.
3. the method for claim 1, effluent stream during wherein at least a portion is produced heats up in a steamer tower by case, the logistics of low-purity is the overhead stream of rectifying tower relatively, this rectifying tower provides the rectifying tower tower base stream, at least a portion rectifying tower tower base stream is by the fractionation section, this fractionation section produces highly purified relatively logistics as the fractionation overhead stream, and tower base stream is as the separation column bottoms stream.
4. the method for claim 3 is further characterized in that, at least a portion rectifying tower overhead stream is the aliquot of rectifying tower overhead stream, and the logistics of at least a portion separation column item is the aliquot of fractionation overhead stream.
5. claim 1,2,3 or 4 method are further characterized in that, the feed aromatics concentration of the logistics of low-purity is about 80 to about 98 moles of % relatively, and the feed aromatics concentration of highly purified relatively logistics is higher than about 95 moles of %.
6. claim 1,2,3 or 4 method are further characterized in that alkene is the alkene with 6-22 carbon atom, and charging aromatic hydrocarbons is the alkyl derivative of benzene and benzene.
7. claim 1,2,3 or 4 method are further characterized in that alkylation conditions comprises that the mol ratio of alkene and every mole of feed aromatic hydrocarbons is about 5: 1 to about 30: 1.
8. the method for claim 4 is further characterized in that, rectifying tower and fractionation section are included in the container separately.
9. claim 1,2 or 3 method are further characterized in that, the alkylaromatic hydrocarbon concentration of the logistics of low-purity is lower than 100wppm relatively.
10. claim 1,2,3 or 4 method, the step that further comprises is to make in dehydrogenation section and contain C
6-C
22The feed stream dehydrogenation of paraffin.And therefrom reclaim and contain paraffin, monoolefine, C
9The dehydrogenation logistics of following hydrocarbon, diolefine and aromatic hydrocarbons by product;
Make at least a portion dehydrogenated product stream by the alkylation section supply alkene in producing;
At at least one aromatic hydrocarbons by product sorbent material, in producing being housed removes in the section, under the adsorption conditions of effective selectivity absorption aromatic hydrocarbons by product, reduction aromatic hydrocarbons by-product concentration, selective removal at least a portion aromatic hydrocarbons by product reaches the level that is not higher than 2 weight % from least a portion dehydrogenated product stream;
At at least one aromatic hydrocarbons by product sorbent material, that stop using is housed to remove in the section-wherein sorbent material contains the aromatic hydrocarbons by product that is adsorbed, make the pure relatively logistics of a part by this sorbent material, thereby in the aromatic hydrocarbons by product of stopping using is removed section, at least by sorbent material top desorb aromatic hydrocarbons by product; Remove the section recovery by at least one aromatic hydrocarbons by product of stopping using and contain the discharge logistics of aromatic hydrocarbons by product, and the strippant logistics that contains aromatic hydroxy compound; And regularly change at least one aromatic hydrocarbons by product in producing and remove the function that section and aromatic hydrocarbons by product that at least one is stopped using are removed section.
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| CNB001200267A CN1176052C (en) | 2000-05-29 | 2000-05-29 | Method for alkylation of aromatic hydrocarbon using solid alkylation catalyst |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001200267A CN1176052C (en) | 2000-05-29 | 2000-05-29 | Method for alkylation of aromatic hydrocarbon using solid alkylation catalyst |
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| CN1332140A true CN1332140A (en) | 2002-01-23 |
| CN1176052C CN1176052C (en) | 2004-11-17 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101605747A (en) * | 2007-02-12 | 2009-12-16 | 环球油品公司 | Be used to make the integrated method of energy of detergent range alkylbenzene |
| CN101605745B (en) * | 2007-02-12 | 2013-03-27 | 环球油品公司 | Processes for making detergent range alkylbenzenes |
| CN101550050B (en) * | 2008-04-01 | 2013-10-23 | 环球油品公司 | Method and device for alkylating aromatic compounds by olefin by utilizing impure aromatic compound circulation |
| CN110655436A (en) * | 2018-06-28 | 2020-01-07 | 中国石油化工股份有限公司 | Solid acid alkylation method |
| CN110770197A (en) * | 2017-06-28 | 2020-02-07 | 环球油品有限责任公司 | Alkylaromatic process with removal of aromatic byproducts |
| US11370722B2 (en) | 2020-06-22 | 2022-06-28 | Nanjing Chemistry New Energy Technology Co. Ltd. | Method for producing long-chain alkylbenzene |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US7652182B2 (en) * | 2007-02-12 | 2010-01-26 | Uop Llc | Energy integrated processes including alkylation and transalkylation for making detergent range alkylbenzenes |
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2000
- 2000-05-29 CN CNB001200267A patent/CN1176052C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101605747A (en) * | 2007-02-12 | 2009-12-16 | 环球油品公司 | Be used to make the integrated method of energy of detergent range alkylbenzene |
| CN101605745B (en) * | 2007-02-12 | 2013-03-27 | 环球油品公司 | Processes for making detergent range alkylbenzenes |
| CN101605747B (en) * | 2007-02-12 | 2014-04-16 | 环球油品公司 | Energy integrated processes for making detergent range alkylbenzenes |
| CN101550050B (en) * | 2008-04-01 | 2013-10-23 | 环球油品公司 | Method and device for alkylating aromatic compounds by olefin by utilizing impure aromatic compound circulation |
| CN110770197A (en) * | 2017-06-28 | 2020-02-07 | 环球油品有限责任公司 | Alkylaromatic process with removal of aromatic byproducts |
| CN110770197B (en) * | 2017-06-28 | 2022-11-11 | 环球油品有限责任公司 | Alkylaromatic process with removal of aromatic byproducts |
| CN110655436A (en) * | 2018-06-28 | 2020-01-07 | 中国石油化工股份有限公司 | Solid acid alkylation method |
| CN110655436B (en) * | 2018-06-28 | 2022-07-15 | 中国石油化工股份有限公司 | Solid acid alkylation method |
| US11370722B2 (en) | 2020-06-22 | 2022-06-28 | Nanjing Chemistry New Energy Technology Co. Ltd. | Method for producing long-chain alkylbenzene |
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