US3714033A

US3714033A - Process for the separation of aromatic hydrocarbons from a mixed hydrocarbon feedstock

Info

Publication number: US3714033A
Application number: US00180996A
Authority: US
Inventors: G Somekh; D Kubek; A Kosseim
Original assignee: Union Carbide Corp
Current assignee: Katalistiks International Inc
Priority date: 1971-09-16
Filing date: 1971-09-16
Publication date: 1973-01-30
Anticipated expiration: 1990-01-30
Also published as: NL172337B; DE2245502A1; NL7212549A; DE2245502B2; FR2155945B1; BR7206399D0; AR229226A1; NL172337C; IT967517B; JPS4836124A; FR2155945A1; GB1410773A; BE788871A; JPS5320016B2; CA982156A

Abstract

A CONTINUOUS SOLVENT EXTRACTION-STEAM DISTILLATION PROCESS FOR THE RECOVERY OF AROMATIC HYDROCARBONS HAVING BOILING POINTS IN THE RANGE OF ABOUT 80% C. TO ABOUT 175* C. FROM A FEEDSTOCK CONTAINING ALIPHATIC HYDROCARBONS AND SAID AROMATIC HYDROCARBONS COMPRISING THE FOLLOWING STEPS: (A) CONTACTING THE FEEDSTOCK IN AN EXTRACTION ZONE WITH A MIXTURE OF WATER AND A SOLVENT, SAID SOLVENT BEING A WATER-MISCIBLE ORGANIC LIQUID HAVING A BOILING POINT OF AT LEAST ABOUT 200* C. AND HAVING A DECOMPOSITION TEMPERATURE OF AT LEAST ABOUT 225* C., AND WITH REFLUX HYDROCARBONS TO PROVIDE AN EXTRACT COMPRISING AROMATIC HYDROCARBONS, REFLUX ALIPHATIC HYDROCARBONS, SOLVENT, AND WATER AND A RAFFINATE COMPRISING ESSENTIALLY ALIPHATIC HYDROCARBONS; (B) CONTACTING THE EXTRACT WITH STEAM IN I DISTILLATION ZONE TO PROVIDE AN OVERHEAD DISTILLATE COMPRISING A REFLUX HYDROCARBONS PHASE AND A WATER PHASE, A SIDE CUT DISTILLATE COMPRISING AN AROMATIC HYDROCARBONS PHASE AND A WATER PHASE, AND BOTTOMS COMPRISING A MIXTURE OF SOLVENT AND WATER; (C) DIVIDING THE WATER PHASE OF THE OVERHEAD DISTILLATE INTO FIRST AND SECOND STREAMS; (D) CONTACTING THE RAFFINATE WITH THE FIRST STREAM TO PROVIDE AN ALIPHATIC HYDROCARBONS PHASE AND A WATER PHASE; (E) CONTACTING THE SECOND STREAM WITH AN AROMATIC HYDROCARBONS STREAM CONTAINING AT LEAST 95 PERCENT AROMATIC HYDROCARBONS, THE AMOUNT OF SAID STREAM BEING IN THE RANGE OF ABOUT 0.1 PERCENT TO ABOUT 5 PERCENT BY WEIGHT OF THE TOTAL AROMATIC HYDROCARBONS IN THE FEEDSTOCK, TO FORM AN AROMATIC HYDRFOCARBONS PHASE AND A WATER PHASE; (F) CONTACTING THE AROMATIC HYDROCARBONS PHASE OF THE SIDE-CUT DISTILLATE WITH THE WATER PHASE OF (E) TO FORM AN AROMATIC HYDROCARBONS PHASE AND A WATER PHASE; (G) CONTACTING THE WATER PHASE OF STEP (D) WITH AN AROMATIC HYDROCARBONS STREAM CONTAINING AT LEAST 95 PERCENT AROMATIC HYDROCARBONS, THE AMOUNT OF SAID STREAM BEING IN THE RANGE OF ABOUT 0.1 PERCENT TO ABOUT 5 PERCENT BY WEIGHT OF THE TOTAL AROMATIC HYDROCARBONS IN THE FEEDSTOCK TO FORM AN AROMATIC HYDROCARBONS PHASE AND A WATER PHASE; (H) RECYCLING THE WATER PHASES OF STEPS (F) AND (G) TO THE DISTILLATION ZONE WHERE SAID WATER PHASES ARE ESSENTIALLY CONVERTED TO STEAM; (I) RECYCLING THE REFLUX HYDROCARBONS PHASE OF THE OVERHEAD DISTILLATE AND THE BOTTOMS OF STEP (B) TO THE EXTRACTION ZONE TO PROVIDE REFLUX HYDROCARBONS AND MIXTURE OF WATER AND SOLVENT, RESPECTIVELY, FOR STEP (A); AND (J) RECOVERING THE AROMATIC HYDROCARBONS PHASE OF STEP (F) AND THE ALIPHATIC HYDROCARBONS PHASE OF STEP (D).

D R A W I N G

Description

Jan. 30, 1973 a. s. SOMEKH T L 3,714,033

PROCESS FOR THE SEPARATION OF AROMATIC HYDRQCARBONS. FROM A MIXED HYDROCARBQN FEEDSTOCK Filed Sept. 16, 1971 United States Patent US. Cl. 208321 22 Claims ABSTRACT OF THE DISCLOSURE A continuous solvent extraction-steam distillation process for the recovery of aromatic hydrocarbons having boiling points in the range of about 80 C. to about 175 C. from a feedstock containing aliphatic hydrocarbons and said aromatic hydrocarbons comprising the following steps:

(a) Contacting the feedstock in an extraction zone with a mixture of water and a solvent, said solvent being a water-miscible organic liquid having a boiling point of at least about 200 C. and having a decomposition temperature of at least about 225 C., and With reflux hydrocarbons to provide an extract comprising aromatic hydrocarbons, reflux aliphatic hydrocarbons, solvent, and water and a rafiinate comprising essentially aliphatic hydrocarbons;

(b) Contacting the extract with steam in a distillation zone to provide an overhead distillate comprising a reflux hydrocarbons phase and a water phase, a side out distillate comprising an aromatic hydrocarbons phase and a water phase, and bottoms comprising a mixture of solvent and water;

(c) Dividing the water phase of the overhead distillate into first and second streams;

(d) Contacting the raflinate with the first stream to provide an aliphatic hydrocarbons phase and a water phase;

(e) Contacting the second stream with an aromatic hydrocarbons stream containing at least 95 percent aromatic hydrocarbons, the amount of said stream being in the range of about 0.1 percent to about 5 percent by weight of the total aromatic hydrocarbons in the feedstock, to form an aromatic hydrocarbons phase and a water phase;

(f) Contacting the aromatic hydrocarbons phase of the side-cut distillate with the Water phase of (e) to form an aromatic hydrocarbons phase and a water phase;

(g) Contacting the water phase of step (d) with an aromatic hydrocarbons stream containing at least 95 percent aromatic hydrocarbons, the amount of said stream being in the range of about 0.1 percent to about 5 percent by weight of the total aromatic hydrocarbons in the feedstock to form an aromatic hydrocarbons phase and a water phase;

(h) Recycling the water phases of steps (f) and (g) to the distillation zone where said water phases are essentially converted to steam;

(i) Recycling the reflux hydrocarbons phase of the overhead distillate and the bottoms of step (b) to the extraction zone to provide reflux hydrocarbons and mixture of water and solvent, respectively, for step (a); and

(j) Recovering the aromatic hydrocarbons phase of step (f) and the aliphatic hydrocarbons phase of step (d).

FIELD OF THE INVENTION This invention relates to an improvement in a process for the separation of aromatic hydrocarbons from a mixed ice hydrocarbon feedstock and, more particularly, to the recovery of high purity aromatic hydrocarbons in high yields while making eflicient use of process components.

DESCRIPTION OF THE PRIOR ART With the advent of the benzene-toluene-C aromatics fraction (known and hereinafter referred to as BTX) as the principal raw material in the manufacture of petro chemicals, outstripping ethylene in this regard, and the increased demand for aromatics as a component in gasoline to increase its octane rating and thus reduce or eliminate the need for lead, which has been under fire as a pollutant, aromatics separation processes availed of in the past have come under close scrutiny with an eye toward improving process economics.

Improved process economics can be translated into, among other things, the use of less apparatus, the lowering of heating requirements, and the more effective use of process components as aids in the separation process.

Various processes have been used for aromatics separations, e.g., (1) a process using an extraction column which sends a glycol solvent/water solution, BTX and reflux to a two step distillation column. The resulting BTX is then redistilled to remove water and entrained glycol; (2) a similar process using two distillation columns, BTX and water being distilled in the second column; (3) another similar process using two distillation columns, in the second column of which BTX and glycol are distilled.

Generally, these processes use two separate water circuits. One circuit is the stripping water circuit for removing aromatics from the glycol in the stripper and the other is a water wash circuit. Both water streams are revaporized in these processes. The make-up of the water wash circuit is such that the water first washes raflinate and then is distilled. Unfortunately, distillation does not remove all dissolved and entrained aliphatics from the water and yet it is then used to wash glycol from the aromatics product resulting in decreased product purity. In the stripping water circuit, stripping water from the reflux decanter also contains some aliphatics. Finally, the use of two or more distillation columns is the rule rather than the exception in this type of system.

In one improvement over the foregoing, revaporization is avoided in the water wash circuit; however, a water rectifier is necessary in the stripping water circuit and in another improvement, the water rectifier is avoided, but various untreated water streams are combined to recover the glycol. Although an attempt is made in both improvements to displace aliphatics with aromatics in the process Water, it is apparent that aliphatics are necessarily present in the final product thus reducing purity.

In sum, all of the processes mentioned heretofore, while viable commercially, have not succeeded in optimizing process economics together with purity.

SUMMARY OF THE INVENTION An object of this invention, therefore, is to provide an improvement in a process for the separation of aromatic hydrocarbons from a mixed hydrocarbon feedstock in which a solvent-water composition is utilized whereby aromatics are recovered in high purity using a minimum of apparatus and heat and making more effective use of process components.

Other objects and advantages will become apparent hereinafter.

According to the present invention, high purity aromatic hydrocarbons are effectively recovered using minimal apparatus and heat by a continuous solvent extraction-steam distillation process for the recovery of aromatic hydrocarbons having boiling points in the range of about C. to about C. from a feedstock containing aliphatic hydrocarbons and said aromatic hydrocarbons comprising the following steps:

(a) contacting the feedstock in an extraction zone with a mixture of water and a solvent, said solvent being a water-miscible organic liquid having a boiling point of at least about 200 C. and having a decomposition temperature of at least about 225 C., and with reflux hydrocarbons to provide an extract comprising aromatic hydrocarbons, reflux aliphatic hydrocarbons, solvent, and water and a raffinate comprising essentially aliphatic hydrocarbons;

dividing the water phase of the overhead distillate into first and second streams;

(d) contacting the ratfinate with the first stream to provide an aliphatic hydrocarbons phase and a water phase;

(e) contacting the second stream with an aromatic hydrocarbons stream containing at least 95 percent aromatic hydrocarbons, the amount of said stream being in the range of about 0.1 percent to about percent by weight of the total aromatic hydrocarbons in the feedstock to form an aromatic hydrocarbons phase and a water phase;

BRIEF DESCRIPTION OF THE DRAWING The sole figure is a schematic flow diagram of an illustrative embodiment of the present invention.

DESCRIPTTON OF THE PREFERRED EMBODIMENT As noted above, there is an industrial need for BTX, which is available in high proportion, e.g., greater than 30 percent by weight, in a wide variety of hydrocarbon feedstocks such as reformed gasolines; coke oven light oils; cracked gasolines; and dripolenes, which, after hydrogenation, can contain as much as 70 to 98 percent BTX. These feedstocks also contain both aliphatic and cycloaliphatic hydrocarbons (herein referred to collectively as aliphatic hydrocarbons). Since the individual hydrocarbon compounds which make up these feedstocks are well known, they will not be discussed extensively; however, it can be pointed out that the major components of the feedstocks used herein are hydrocarbons with boiling points ranging from 25 C. to 175 C. including straightchain and branched-chain paraffins and naphthenes, such as n-heptane, isooctane, and methyl cyclohexane, and aromatics such as BTX.

The BTX fraction can include benzene, toluene, the C aromatics including ortho-xylene, meta-xylene, paraxylene, and ethyl benzene, and C aromatics, which, if

present at all, appear in the smallest proportion in relation to the other components.

The solvents used in subject process are, as described above, water-miscible organic liquids (at process temperatures) having a boiling point of at least about 200 C. and having a decomposition temperature of at least about 225 C. The term water-miscible includes those solvents which are completely miscible over a wide range of temperatures and those solvents which have a high partial miscibility at room temperature since the latter are usually completely miscible at process temperatures. The solvents are also polar and are generally comprised of carbon, hydrogen and oxygen with some exceptions. Examples of solvents which may be used in the process of this invention are dipropylene glycol, tripropylene glycol, dibutylene glycol, tributylene glycol, ethylene glycol, diethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, sulfolane, N- methyl pyrrolidone, triethylene glycol, tetraethylene glycol, ethylene glycol diethyl ether, propylene glycol monoethyl ether, pentaethylene glycol, hexamethylene glycol, and mixtures thereof. The preferred group of solvents is the polyalkylene glycols and the preferred solvent is tetraethylene glycol.

Additional solvents, which may be used alone or together, or with the aforementioned solvents are amides such as formamide, acetamide, dimethylformamide, diethylformamide, and dimethylacetamide; amines such as diethylenetriamine and triethylenetetramine; alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine; nitriles such as beta,beta -oxydipropionitrile and beta,beta -thiodipropionitrile; phenol and the cresols; the methyl sulfolanes; sulfoxides such as dimethyl sulfoxide and diethyl sulfoxide; lactones such as gammapropiolactone and gamma-butyrolactone.

The apparatus used in the process both for the main extraction and the distillation is conventional, e.g., an extraction column of the multistage reciprocating type containing a plurality of perforated plates centrally mounted on a vertical shaft driven by a motor in an oscillatory manner can be used as well as columns containing pumps with settling zones, sieve trays with upcomers, or even a hollow tube while the distillation can be conducted in a packed bubble plate fractionating column. Counter-current flows are utilized in both extraction and distillation columns.

Heat exchangers, decanters, reservoir and solvent regenerator are also conventional as well as various extractors other than the main extractor. These other extractors are preferably single stage mixer-settlers, but can be any of the well known types.

The solvent is used as an aqueous solution thereof containing water in an amount of about 1 percent to about 8 percent by weight based on the weight of the solvent and preferably containing water in an amount of about 2 percent to about 5 percent by weight. This aque ous solution is referred to hereafter in some instances as a solvent-water mixture.

Generally, to accomplish the extraction, the ratio of solvent (exclusive of water) to feedstock in the extractor is in the range of about 4 to about 8 parts by weight of solvent to one part by weight of feedstock. This broad range can be expanded upon where nonpreferred solvents are used. A broad range of about 3 to about 12 parts by weight of solvent to one part by weight of feedstock and a preferred range of about 5 parts to about 7 parts of solvent per part of feedstock can be used successfully for the solvent of preference and other like solvents. In final analysis, however, the ratio is selected by the technician based on experience with the particular feedstock and depends in part upon whether high recovery or high purity is being emphasized, although the instant process will improve purity in any case.

The reflux to the extraction zone is generally made up of about 20 percent to about 50 percent by weight aliphatics having from to 7 carbon atoms and about 50 percent to about 80 percent by weight aromatics, both based on the total weight of the reflux. The ratio of reflux to feedstock in the extraction zone is, generally, maintained in the range of about 0.5 to about 1.5 parts by weight of reflux to one part by weight of feedstock and preferably about 0.5 to about 1.0 part by weight of reflux to one part by weight of feedstock, but, again, is selected by the technician just as the ratio of solvent to feedstock. The reflux aliphatics pass into the extract rather than being taken overhead with the raflinate and are recycled to the extractor from the reflux decanter as will be seen hereinafter.

The temperature in the extraction zone is maintained in the range of about 100 C. to about 200 C. and is preferably in the range of about 125 C. to about 150 C., especially for the solvent preference.

The pressure in the extraction zone is maintained in the range of about 75 p.s.i.g. to about 20 p.s.i.g. As is well known in the art, however, one selected pressure is not maintained throughout the extraction zone, but, rather, a high pressure within the stated range is present at the bottom of the zone and a low pressure again within the stated range is present at the top of the zone with an intermediate pressure in the middle of the zone. The pressures in the zone depend on the design of the equipment and the temperature, both of which are adjusted to maintain the pressure within the stated range.

The temperature at the top of the distillation zone, which, in terms of the apparatus used, may be referred to as a distillation column or stripper, is at the boiling point of the mixture of aromatics present in the zone while the temperature at the bottom of the stripper is generally in the range of about 135 C. to about 200 C.

The pressure at the top of the stripper, an upper flash zone in this case, is in the range of about 20 p.s.i.g. to about 35 p.s.i.g. In a lower flash zone just beneath the upper flash zone and connected thereto, the pressure is in the range of about p.s.i.g. to about p.s.i.g. and is about 10 or 15 p.s.i.g. lower than the pressure in the upper flash zone. The pressure in the rest of the distillation zone is maintained in the range of about 15 p.s.i.g. to about p.s.i.g. with some variation throughout the zone.

The steam brought into the bottom of the distillation zone enters at a temperature of about 100 C. to about 150 C. and is under a pressure of about 15 p.s.i.g. to about 25 p.s.i.g. The total water present in the distillation column is essentially in vapor form and is generally in the range of about 0.1 part to about 0.5 part by weight of water to one part by weight of aromatics in the zone and preferably in the range of about 0.1 part to about 0.3 part by weight of water to one part by weight of aromatics. The water used for the steam may be called stripping water. A small amount of water is present in liquid form in the distillation zone dissolved in the solvent.

Referring to the drawing:

The feedstock is introduced through line 1 into heat exchanger 2 where it is preheated to a temperature in the range of about 50 C. to about 100 C. It then continues through line 1 to enter extractor 3 at about the middle tray thereof. An aqueous solvent solution having a temperature in the range of about 125 C. to about 175 C. enters at the top tray of extractor 3 through line 4 and percolates down the column removing aromatics from the feedstock.

The rafi'lnate, essentially free of aromatics, leaves the top of the column through heat exchanger 2 where it is used to preheat the feedstock and is cooled in turn to a temperature in the range of 75 C. to about 125 C. The ratfinate comprises about 95 percent to about 98 percent by weight aliphatics, about 1 percent to about 3 percent by weight dissolved and entrained solvent, and about 0 percent to about 3 percent by weight aromatics. The raifinate then passes through cooler 6 where it is further cooled to about 25 C. to about 50 C. and proceeds along line 5 to decanter 7 where it separates into two phases, an aliphatic hydrocarbons phase and a solvent phase, the solvent being contaminated with aliphatics.

It should be noted that the phase is named after its main component, which is present in the phase in an amount of at least 50 percent by weight and, in most cases, in an amount of at least percent by weight.

The aliphatic hydrocarbons phase, which can still be referred to as the raflinate, now contains about 96 percent to about 99 percent by weight aliphatics, about 0 percent to about 1 percent by weight dissolved and entrained solvent, and about 0 percent to about 3 percent by weight aromatics. The solvent phase, on the other hand. contains about 90 percent to about 96 percent by weight solvent, about 2 percent to about 5 percent by weight water, and about 2 percent to about 4 percent by weight aliphatics.

The raflinate continues overhead through line 5 into raffinate extractor 8, which can be a single stage mixersettler or other conventional type of extractor.

The solvent phase passes through line 10 to join line 12 referred to hereinafter or it can be optionally recycled to the top of extractor 3 along line 20 (connection to extractor not shown).

The raflinate is washed with a portion of the water phase from reflux decanter 29 and separated in raflinate extractor 8 into an aliphatic hydrocarbons phase (still called the rafl'inate) which is essentially free of solvent and water and contains about 97 percent to about 100 percent by weight aliphatics and about 0 percent to about 3 percent by weight aromatics, and a water phase as bottoms which contains about 75 percent to about 90 percent by weight water, about 10 percent to about 25 percent by weight solvent, and about 0.1 percent to about 1 percent by weight aliphatics.

Part of this water phase can optionally be recirculated through extractor 8 via line 11, line 9 and line 5 as shown. This recirculation is conventional with a mixersettler arrangement, but may not be advantageous with other types of extractors. As noted, the water phase still contains, along with the water and solvent, a small amount of aliphatics. All or the balance of the water phase is, therefore, directed from line 11 along line 12 to extractor 13, which can again be a single-stage mixer-settler.

Feeding into line 12 via line 50 is an aromatics slipstream, which at its source (see line 14) is an essentially pure stream of aromatics, i.e., having a purity of a least percent by weight, or in other words, at least 95 percent by weight of the slipstream is aromatic hydrocarbons. The purity of the slipstream is preferably about 98 percent and for optimum performance, i.e., to obtain the highest purity product, about 99 percent. It is called a slipstream or sidestream because the amount of aromatics fed into the water phase passing through line 12 is very small. The amount of slipstream aromatic hydrocarbons used in the process is in the range of about 0.1 percent to about 5 percent by weight of the aromatic hydrocarbons in the feedstock and is preferably in the range of about 0.5 percent to about 2.0 percent by weight of such aromatic hydrocarbons. The slipstream washes the water in extractor 13 to remove the small amount of aliphatics, which is so detrimental to the efficiency of the process. This aromatics slipstream can be recycled along line 15 through extractor 13 to further wash the water phase where a mixer-settler extractor is used and it is then, preferably, sent along line 16 to line 1 where it is reintroduced into the feedstock and passes into the system once more. The water, which is essentially devoid of aliphatics, but contains solvent, then passes as bottoms from extractor 13 through line 17 and into water reservoir 51 via line 37.

Returning to extractor 3, it has been noted above that the aqueous solvent percolates down the column carrying with it the aromatics. In the lower half of extractor 3, the solvent solution of aromatics comes into countercurrent contact with a reflux liquid, which enters extractor 3 below the bottom tray along line 18. The reflux percolates up the lower half of extractor 3 progressively dissolving in and purifying the solvent solution of aromatics. The solution which is formed, i.e., the extract, comprises about 5 percent to about 10 percent by weight feedstock aromatics, about 2 percent to about 5 percent by weight water, about 75 percent to about 85 percent by weight solvent, about 4 percent to about 8 percent by Weight reflux aromatics, and about 3 percent to about 6 percent by weight reflux aliphatics, all based on the total weight of the extract.

The extract leaves the bottom of extractor 3 through line 19 and passes through heat exchanger 22 where it is cooled to a temperature in the range of about 100 C. to about 125 C. The extract proceeds along line 19 and enters stripper 23, the distillation zone, at upper flash chamber 24, which, as noted heretofore, is at a lower pressure than the extractor. Part of the extract flashes on entering the flash chamber and is taken overhead through line 18 in vapor form. Another part of the extract passes as a liquid into lower flash chamber 21, which is operated at an even lower pressure and further flashing occurs. These flashed vapors join the fractionated vapors and pass through line 30 to join the vapors passing through line 18. The balance of the extract (at least about 80 percent by weight) percolates down the column into the fractionation zone where it comes into countercurrent contact with the stripping vapors, i.e., steam, and more vapors are generated. A part of the vapor rises to the top of the column and mixes with the flashed vapors in flash chamber 21 as noted. The overhead distillate comprises about 40 to about 75 percent by weight aromatics, about 20 to about 40 percent aliphatics, about 2 percent to about 10 percent by weight water, and about percent to about percent by weight solvent, all based on the total weight of the overhead distillate.

After the aqueous solvent descends about halfway down the column, it becomes essentially free of aliphatics. At this point, a vapor side-stream distillate is removed through line 26. The side-stream distillate is comprised of about 65 to about 90 percent by weight aromatics, about to about 30 percent by weight water, and about 1 percent to about 10 percent by weight of solvent, based on the total weight of the side-stream distillate.

The bulk of the solvent and water solution, an amount equal to over 99 percent by weight of the solvent and water entering stripper 23 through line 19, leaves the bottom of stripper 23 through line 4. A portion of this solution is diverted into reboiler 28 and returns as a vapor to a point below the bottom tray of stripper 23 to provide most of the strippers heating requirements. The balance of the water and solvent solution is recycled to the top tray of extractor 3 through line 4. Recycled stripping water containing some dissolved solvent enters stripper 23 through line 27 from water reservoir 51 after essentially all of it is converted in heat exchanger 22 to steam.

Returning to the overhead distillate mentioned heretofore, such overhead distillate is a combination of flashed vapors and fractionated vapors having the aforementioned composition. This overhead distillate is also known as a reflux distillate. The vapor is first condensed and cooled to between about 38 C. and 94 C. in reflux condenser 25. The condensate then passes into reflux decanter 29 where a reflux hydrocarbons phase is decanted from a water phase. The reflux hydrocarbons phase comprises about 20 to 50 percent by weight aliphatics having from 5 to 7 carbon atoms, and about 50 to about 80 percent by weight aromatics and is recycled as reflux through line 18 to extractor 3 as previously described.

The water phase contains about 95 to about 99 percent by weight water, about 0 to about 5 percent by weight solvent, and about 0.1 to about 0.5 percent by weight aliphatics. It passes through line 31 and is split in two streams,

lines

32 and 33, a raflinate wash stream and an aromatics Wash stream, respectively. These washes can take place as shown by splitting the stream or the entire stream can be used to Wash the raflinate first and then the aromatics providing that the water is treated with an aromatics slipstream before the aromatics Wash.

As noted heretofore, the side-stream distillate is withdrawn in vapor form from stripper 23 through line 26 and condensed in aromatics condenser 34 and further cooled to a temperature in the range of about 25 C. to about 50 C. in cooler 35, which can be a heat exchanger or other type of cooling device. The condensate then passes into aromatics decanter 36 where an aromatic hydrocarbons phase containing about 99.8 to about 99.9 percent by weight aromatics, and about 0.1 to about 0.2 percent by Weight solvent and a Water phase containing about percent to about 98 percent by weight water, about 2 percent to about 10 percent by weight solvent, and about 0.1 percent to about 0.5 percent by Weight aromatics are formed. The water phase passes through line 37 to Water reservoir 51. Optionally, all or part of the Water phase can be directed through valved line 38 to join line 32 for use as raflinate wash.

The aromatic hydrocarbons phase proceeds from decanter 36 through line 26 along which an aromatics slipstream is taken through line 14 to Wash water coming from reflux decanter 29 along line 33. As noted, this slipstream can be in the range of about 0.10 percent to about 5.0 percent of the total aromatics in the feedstock and is preferably in the range of about 0.50 percent to about 2.0 percent of the total aromatics in the feedstock. These percentages are by weight.

In practice, the weight of the total aromatics is determined by analysis of a sample portion of the feedstock. Aromatics added, e.g., as slipstream, during the process cycle are included in the determination.

The slipstream can, alternatively, be obtained from another source such as the overhead product of a benzene fractionating column, which is not shown in the drawing, or from a source completely removed from the system. As long as the slipstream has the previously noted high aromatics content, it will be satisfactory in this process.

The combined streams of lines 33 and 14 proceed into wash extractor 39, which can be a single stage mixersettler or other form of extractor. Where a mixer-settler is used, it is advantageous to use an aromatics recycle which passes along line 42 and joins lines 33 and 14 returning to wash extractor 39. The slipstream, now containing a small amount of aliphatics, passes overhead from wash extractor 39 into line 42 and along line 50 to join lines 12 and 15 and proceeds into wash extractor 13 as discussed previously.

Reflux water, now essentially free of aliphatics, is withdrawn from wash extractor 39 and proceeds along line 43, which joins line 26, and passes into aromatics extractor 44, which can be a single stage mixer-settler or other type of extractor. This reflux water, along with water recycled from the settling zone in the case of a mixer-settler via line 45, which joins line 43, and process makeup water from line 46 (source not shown) contacts the aromatic product proceeding along line 26 into aromatics extractor 44 and recovers essentially all of the small amount of solvent remaining in the aromatics. This water with solvent then proceeds along line 47 to join line 17, which joins line 37 and enters water reservoir 51. High purity aromatic product is withdrawn from the process through line 26.

A feature of the invention is the removal of certain impurities, which may include some aliphatics of a type which can build up in the system and affect it in a deleterious manner. This is accomplished by taking a small purge of the water circuit. To accomplish this purge, water is withdrawn from any of the decanters and discarded periodically or continuously. One such purge can be accomplished through line 48. It is found that only a small proportion of the solvent is lost by such a purge; however, this solvent can be recovered if desired. The water purge stream can be in the range of about 0.25 percent to about 2.0 percent by weight of the total water in the system and is preferably in the range of about 0.5 percent to about 1.0 percent by weight of the water in the system.

The total water in the system can be determined easily because the amount of water introduced can be controlled. Allowances must be made for water losses through leakage, entrainment and upsets, however.

Solvent can be recovered from this purge by directing the water through line 49 to join line 53 and enter solvent regenerator 52 where the solvent is separated from low boiling and high boiling impurities by steam distillation under vacuum. The solvent is recovered and recycled along line 54 to extractor 3 (connection not shown) and the Water and impurities discarded.

It will be noted that in the preferred embodiment of subject process the slipstream taken through line 14 is first used to wash the water phase from reflux decanter 29 (i.e., one stream) and then the water phases from raflinate decanter 7 (optional) and raflinate extractor 8. This procedure can be varied so that a different slipstream from a different source is used for each wash or, as previously mentioned, a single slipstream is used to wash one water phase where stream 31 is not split, but is first used to wash raflinate.

In the preferred embodiment, it was stated heretofore that the slipstream picks up some aliphatics in extractor 39 before proceeding to extractor 13. It should be pointed out that the purity of this slipstream containing the small amount of aliphatics is only reduced by about one percent and that it still has a purity of at least about 95 percent by weight and preferably about 9 8 percent so that the definition of the slipstream with respect to purity is fulfilled.

What is claimed is:

1. A continuous solvent extraction-steam distillation process for the recovery of aromatic hydrocarbons having boiling points in the range of about 80 C. to about 175 C. from a feedstock containing aliphatic hydrocarbons and said aromatic hydrocarbons comprising the following steps:

(b) contacting the extract with steam in a distillation zone to provide an overhead distillate comprising a reflux hydrocarbons phase and a water phase, a side cut distillate comprising an aromatic hydrocarbons phase and a water phase, and bottoms comprising a mixture of solvent and water;

(e) contacting the second stream with an aromatic hydrocarbons stream containing at least 95 percent aromatic hydrocarbons, the amount of said stream being in the range of about 0.1 percent to about percent by weight of the total aromatic hydrocarbons in the feedstock, to form an aromatic hydrocarbons phase and a water phase;

(g) contacting the water phase of step (d) with an aromatic hydrocarbons stream containing at least percent aromatic hydrocarbons, the amount of said stream being in the range of about 0.1 percent to about 5 percent by weight of the total aromatic hydrocarbons in the feedstock, to form an aromatic hydrocarbons phase and a water phase;

2. The process of claim 1 wherein the reflux aliphatic hydrocarbons contain from 5 to 7 carbon atoms.

3. The process of claim 2 wherein the temperature in the extraction zone is in the range of about C. to about 200 C., the pressure in the extraction zone is in the range of about 75 p.s.i.g. to about 200 p.s.i.g., the temperature in the distillation zone is in the range of about 100 C. to about 200 C., and the pressure in the distillation zone is in the range of about 10 p.s.i.g. to about 35 p.s.i.g.

4. The process of claim 3 wherein:

(i) the ratio of solvent to feedstock in the extraction zone is in the range of about 3 to about 12 parts by weight of solvent to one part by weight of feedstock;

(ii) the amount of water in the extraction zone is about 1 percent to about 8 percent by weight based on the weight of the solvent in said zone;

(iii) the ratio of reflux to feedstock in the extraction zone is in the range of about 0.5 to about 1.5 parts by weight of reflux to one part by weight of feedstock; and

(iv) the ratio of water to aromatic hydrocarbons in the distillation zone is in the range of about 0.1 to about 0.5 part by weight of water to one part by weight of aromatic hydrocarbons in said zone.

5. The process of claim 4 wherein the solvent is a polyalkylene glycol.

6. The process of claim 5 wherein the solvent is tetraethylene glycol.

7. The process defined in claim 4 comprising the following additional steps:

(k) after step (a) and prior to step (d), separating the raflinate into an aliphatic hydrocarbons phase and a solvent phase; and

(1) recycling the solvent phase of step (k) to the extraction zone.

8. The process defined in claim 4 comprising the following additional step:

(m) prior to step (k), removing water from the water phases of steps (f) and (g) in an amount in the range of about 0.25 percent to about 2.0 percent by weight of the total water used in the process.

9. The process defined in claim 7 comprising the following step:

(11) recycling the aromatic hydrocarbons phase of steps (e) and (g) to the extraction zone.

10. A continuous solvent extraction-steam distillation process for the recovery of aromatic hydrocarbons having boiling points in the range of about 80 C. to about C. from a feedstock containing aliphatic hydrocarbons and said aromatic hydrocarbons comprising the following steps:

(a) contacting the feedstock in an extraction zone with a mixture of water in a solvent, said solvent being a water-miscible organic liquid having a boiling point of at least about 200 C. and having a decomposition temperature of at least about 225 C., and with reflux hydrocarbons to provide an extract comprising aromatic hydrocarbons, reflux aliphatic hydrocarbons, solvent, and water and a raflinate comprising essentially aliphatic hydrocarbons;

(c) contacting the raflinate with the water phase of the overhead distillate to provide an aliphatic hydrocarbons phase and a water phase;

(d) contacting the water phase of step (c) with an aromatic hydrocarbons stream containing at least 95 percent aromatic hydrocarbons, the amount of said stream being in the range of about 0.1 percent to about percent by weight of the total aromatic hydrocarbons in the feedstock, to form an aromatic hydrocarbons phase and a water phase;

(e) contacting the aromatic hydrocarbons phase of the side-cut distillate with the water phase of (d) to form an aromatic hydrocarbons phase and a water phase;

(f) recycling the water phase of step (e) to the distillation zone where said water phase is essentially converted to steam;

(g) recycling the reflux hydrocarbons phase of the overhead distillate and the bottoms of step (b) to the extraction zone to provide reflux hydrocarbons and mixture of water and solvent, respectively, for step (a); and

(h) recovering the aromatic hydrocarbons phase of step (e) and the aliphatic hydrocarbons phase of step (c).

11. The process of claim wherein the reflux aliphatic hydrocarbons contain from 5 to 7 carbon atoms.

12. The process of claim 11 wherein the temperature in the extraction zone is in the range of about 100 C. to about 200 C., the pressure in the extraction zone is in the range of about 75 p.s.i.g. to about 200 p.s.i.g., the temperature in the distillation zone is in the range of about 100 C. to about 200 C., and the pressure in the distillation zone is in the range of about 10 p.s.i.g. to about 35 p.s.1.g.

13. The process of claim 12 wherein:

(i) the ratio of solvent to feedstock in the extraction zone is in the range of of about 3 to about 12 parts by weight of solvent to one part by weight of feedstock;

(iii) the ratio of reflux to feedstock in the extraction 12 zone is in the range of about 0.5 to about 1.5 parts by weight of reflux to one part by weight of feedstock; and

14. The process of claim 13 wherein the solvent is a polyalkylene glycol.

15. The process of claim 14 wherein the solvent is tetraethylene glycol.

16. The process defined in claim 13 comprising the following additional steps:

(i) after step (a) and prior to step (c), separating the raflinate into an aliphatic hydrocarbons phase and a solvent phase; and

(j) recycling the solvent phase of step (i) to the extraction zone.

17. The process defined in claim 13 comprising the following additional step:

(k) prior to step (t), removing water from the water phase of step (d) in an amount in the range of about 0.25 percent to about 2.0 percent by weight of the total water used in the process.

18. The process defined in claim 16 comprising the following additional step:

(1) recycling the aromatic hydrocarbons phase of step (d) to the extraction zone.

19. The process defined in claim 1 wherein the aromatic hydrocarbons stream contains about 98 percent by weight aromatic hydrocarbons.

20. The process defined in claim 6 wherein the aromatic hydrocarbons stream contains about 99 percent by weight aromatic hydrocarbons.

21. The process defined in claim 10 wherein the aromatic hydrocarbons stream contains about 98 percent by weight aromatic hydrocarbons.

22. The process defined in claim 15 wherein the aromatic hydrocarbons stream contains about 99 percent by weight aromatic hydrocarbons.

References Cited UNITED STATES PATENTS 3,179,708 4/ 1965 Penisten 208-321 3,173,966 3/1965 Jones et al. 208-321 3,436,435 4/1969 VanTassell 208-321 3,642,614 2/ 1972 VanTassell 208-321 DELBERT E. GANTZ, Primary Examiner C. E. SPRESSER, JR., Assistant Examiner US. Cl. X.R.