US3228754A - Circulating concentrating evaporation for caustic regeneration - Google Patents

Circulating concentrating evaporation for caustic regeneration Download PDF

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US3228754A
US3228754A US23206762A US3228754A US 3228754 A US3228754 A US 3228754A US 23206762 A US23206762 A US 23206762A US 3228754 A US3228754 A US 3228754A
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caustic
solution
line
head
evaporator
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William K Robbins
James O Scott
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ExxonMobil Research and Engineering Co
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ExxonMobil Research and Engineering Co
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D1/00Evaporating
    • B01D1/0082Regulation; Control
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S159/00Concentrating evaporators
    • Y10S159/33Two liquids, one a heat carrier
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S159/00Concentrating evaporators
    • Y10S159/34Caustic

Description

1966 w. K. ROBBINS ETAL 3,228,754

CIRCULATING CONCENTRATING EVAPORATION FOR CAUSTIC REGENERATION Original Filed July 28. 1961 ACID-FREE CATALYTIC HEATING oIL TEMP. 30

CONTROL MERCAPTANS 8 WATER 04 i I I28 I I SCRUBBER N8 k STEAM I \I-SEPARATOR I ORGANIC I25 ACID [9-0 I20 I I CATALYTIC I HEATING oIL I22 I LEVEL H2 l CONTROL 46 EVAPORATORV L 'I I02 0 Il6 I32 I CONDENSATE II4 I60 SEPARATOR IOGI- I08 44 I52 MAKE-UP P 7 NAOH NAOH BLEED F I G I INVENTORS.

WILLIAM K. ROBBINS,

BY JAMES I SCOTT fl' hw ATTORNEY.

United States l atent O 3,228,754 CIRCULATING CQNCENTRATING EVAPORATION FOR CAUSTIC REGENERATION William K. Robbins and James 0. Scott, Baytown, Tex., assignors, by mesne assignments, to Esso Research and Engineering Company, Elizabeth, N.J., a corporation of Delaware Original application July 28, 1961, Ser. No. 127,527. Divided and this application Oct. 22, 1962, Ser. No. 232,067

1 Claim. (Cl. 23276) This application is a division of copending application Serial No. 127,527, filed July 28, 1961.

The present invention relates to the reconcentration and regeneration of solutions of alkali metal hydroxides which have been used to remove organic acids and mercaptans from flowing hydrocarbon streams. More particularly, the present invention relates to a method and means for concurrently concentrating the caustic solution while utilizing the steam evolved during concentration to strip mercaptans from the solution. In its more specific aspect, the present invention relates to a means and method of regenerating a sodium hydroxide solution which contains dissolved organic acids by concentrating and removing mercaptans from said solution in a first stage and recovering organic acids from said solution in a second stage.

Hydrocarbon streams boiling between about 100 F. and about 800 F. and containing mercaptans and organic acids (including phenols and carboxylic acids) are unsuitable for commercial use because of the corrosivity of the dissolved contaminants. As a consequence of this corrosivity, the product streams must be treated either to remove or to neutralize the effect of these contaminants. One method of removing the contaminants is by contacting the hydrocarbon stream with a concentrated solution of the hydroxide of an alkali metal hydroxide such as sodium, potassium or lithium. The use of these hydroxides is effective in removing the mercaptans, phenols, carboxylic acids and other acidic contaminants from the flowing stream, but are expensive both in the cost of the treating solution as Well as in the costs of disposing of the waste liquid after the caustic solution has become spent. By the practice of the present invention, the effective life of such a caustic solution may be extended to a period of several times that experienced in the manner hitherto utilized. Further, by the practice of the present invention, it has been found that although the caustic solutions which are used in the practice of the present invention are highly viscous, concentrations of the caustic to the desired gravity may be accomplished at atmospheric pressure. Hitherto it has been considered necessary in reconstituting these highly viscous solutions to use a vacuum evaporation system in order to minimize effects of slugging and bubbling within the evaporator. It has further been found by the practice of the present invention, that the steam evolved during the reconcentration or evaporation step may be utilized to strip mercaptans from the solution, thereby obviating the preliminary removal of mercaptans before reconstitution.

During the contacting of the flowing hydrocarbon stream with the caustic solution, the Water which normally occurs in the flowing hydrocarbon stream is also removed along with the contaminants sought to be absorbed by the caustic scrubbing solution. The natural result of the absorbing of this moisture is a constant dilution of the scrubbing caustic. If the caustic solution is maintained at a gravity above 42 Baum, the organic acids extracted from the hydrocarbon stream may be separated into a supernatant layer by cooling the caustic to a temperature of about 100 F, to 150 F, but when the caustic strength falls below 42 Baum, particularly 3,228,754 Patented Jan. 11, 1966 where the caustic strength is below 40 Baume, the organic acids are completely soluble in the caustic and will not form the separate layer. Therefore, they cannot be decanted from the caustic tank and an organic acid buildup occurs which causes the caustic to become unusable and spent in a relatively short time. They caustic strength is therefore preferably maintained within a range of about 42 to 50 Baum.

The present invention prevents the buildup of organic acids by reconstituting the caustic solution to the desired gravity. Moreover, the practice of the present invention prevents a buildup of mercaptans within the caustic solution which also would result in an untimely deactivation of the caustic solution.

The practice of the present invention may be more particularly understood by a reference to the appended drawings wherein:

FIG. 1 is a general schematic diagram of the scrubbing system; 7

FIG. 2 is a representation of a particular feed nozzle into the evaporator;

FIG. 3 is a plan view of the nozzle taken on lines 3-3 of FIG. 2; and

FIG. 4 is a sectional elevation of the nozzle taken on line 4-4 of FIG. 3.

Referring more particularly to FIG. 1, the practice of the present invention relates to the treatment of catalytic heating oil, for example, which is introduced into a scrubber by way of line 102 and is discharged after contacting with the caustic solution by way of line 104. A scrubbing caustic solution, such as sodium hydroxide, is introduced into the scrubbing tower by way of line 106 and is passed downwardly through the tower in contact with the flowing hydrocarbon stream to be discharged at the bottom of the tower by way of line 108. During the passage through the scrubbing tower, the caustic solution absorbs the mercaptans, phenols, carboxylic acids, other aromatic and parafiinic acids, and water, which are present in the catalytic heating oil feed stock. Therefore, the caustic solution passed by way of line 108 is contaminated with the absorbed acidic and sulfur-containing compounds as well as being diluted to a gravity somewhat below the optimum.

The solution is then charged by way of line 108 into an evaporator 110 and is passed into the shell 112 of the evaporator in a distributed form by means of a baflle 114 which is arranged above the inlet so that the material charged into the evaporator impinges upon the bathe and is well distributed. The distributed caustic feed is then passed through a series of tubes 116 and is discharged by way of line 118. During passage through tubes 116, the caustic is heated to a temperature of 215 F. to 300 F. by means of steam which is introduced by Way of line 120 controlled by valve 122 and passes through the steam jacket within the shell 112 to be discharged by way of line 124 as condensate. The caustic soda is maintained within the evaporator at a temperature of about 215 F. to 300 F. for a time period sufiicient to evaporate enough water to concentrate the solution from the operating gravity of about 40 to 43 Baum to a gravity of about 45 Baum or higher, preferably about 44 to 48 Baum. Also, the time period should be sufiicient to allow the mercaptans to be stripped from the caustic solution and carried into the vapor phase with the evolved steam.

The total effiuent, liquid, gas and vapor, from the evaporator 110 is passed by way of line 118 into a first separator 126 wherein the vaporous steam and gaseous mercaptans are allowed to pass overhead by way of vapor outlet 128 through condenser 130 for disposal. The liquid is passed from the separator by way of standpipe .tion inlet means. recirculation inlet means having a cross-sectional area 132 and line 134 into pump 136, and is discharged from pump 136 by way of line 138, valve 140, and cooler 142 into a second separator 144, from whence an organic acid supernatant layer is withdrawn by way of upper liquid phase outlet 146 and a reconstituted and regenerated caustic soda solution is discharged by way of lower liquid phase outlet 148 for recycle by way of line 150 into line 106 and into the scrubber 100. The caustic may be discharged intermittently or continuously by way of the caustic bleed line 152, while makeup caustic of 45 to 50 Baum or higher is introduced in offsetting amounts through line 154.

Returning now to the evaporator system proper, it is seen that a line 156 interconnects the discharge line 134 from the first separator and the evaporator 110. This line 156 recirculates a portion of the caustic to the evaporator to assure a complete concentration of the caustic and removal of the mercaptan. The evaporator 110 is provided with an inlet 158 for this recycle stream, and the inlet 158 is further provided with an orifice plate or choke plate 160 which provides sufficient pressure drop to prevent the passage of a portion of the feed which is in troduced by way of line 108 into the line 156 to bypass the evaporation system. The orifice should be about 1% to of the area of the return conduit. It should be understood that the recycle stream being recharged into the evaporator 110 may be provided with suitable pumping means if necessary to provide sufiicient head for the recirculation rate desired. Preferably, however, the recycle is accomplished by relying on the pressure head differential which may be obtained by mounting the separator 126 at a slightly higher elevation than the evaporator 110, and allowing the evolved steam within the tubes 116 to provide a vapor lift for the solution into the separator 126. Thus, the evaporation system can be seen to comprise in combination a vertical-tube heat exchanger having a shell with an upper head and a lower head, and a plurality of vertically disposed tubes enclosed within the shell which communicate with the upper head and lower head. Outlet means are provided in the upper head, and inlet means for the feed are provided in the bottom of the lower head, with baffie means within and depending from the lower head positioned in confronting relationship with the feed inlet means. A recirculation inlet is provided in the side of the lower head. Separating means are provided for separating vapor and liquid which are discharged from the exchanger, having a vapor outlet and a standpipe, with overhead conduit means being employed to connect the outlet means with the separating means, and with return conduit means being employed for connecting the standpipe with the recircula- A choke orifice is provided in the 1% to 5% of the area of the return conduit, and means communicating with the standpipe are also provided for withdrawing a portion of the liquid from the separator.

Referring now to FIG. 2, a particular form of injection nozzle is disclosed which obviates the necessity of using a choke plate such as the plate 160 shown in FIG. 1. In the modification of FIG. 2, a feed nozzle 200 is shown within an evaporator 210 which is generally similar to that shown in FIG. 1. The recycle inlet 220 shown in FIG. 2 is free of obstruction, and need not be provided with a choke plate. This is accomplished by mounting the feed nozzle 200 at a position at least as high as the bottom of the recycle inlet pipe, but preferably above this position, and in forming the feed nozzle with a generally hemispherical upper surface with discharge passages extending radially therethrough so that the feed stream will be directed above the inlet 220.

The structure of the nozzle 200 may better be understood by referring to FIGS. 3 and 4 wherein there is disclosed a plan view and a sectional elevational view of the nozzle. In particular, referring to FIG. 4, the nozzle 200 is seen to communicate with the feed pipe 240 which contains the charge stream. Radial passages 250 are formed in the head of the nozzle for directing the feed stream in a direction above the horizontal plane defined by the lower portion of the nozzle indicated by the numeral 260. Therefore, with the nozzle mounted above the recycle pipe, the vector forces imparted to the feed stream will prevent the fresh feed stock from entering the recycle nozzle.

By the practice of the present invention, caustic consumption has been reduced over 50%. In the practice of caustic scrubbing of a catalytic heating oil stream without regeneration, an average life span of a caustic solution charged had been established at about five days.

-By utilizing the present invention, the life span of the Catalytic heating oil (30,000 bbls./day) was passed through a caustic scrubber in contact with a total charge of 1,000,000 lbs. of 50 Baum sodium hydroxide solution (circulated at a rate of 2% to 5% by volumedilution from water in feed decreasing the Baum gravity). The caustic was recirculated until the specific gravity reached 40 Baum, at which time the caustic was discarded and a new caustic charge of 50 Baum specific gravity was injected into the system. Under these conditions, the caustic consumption of 50 Baum sodium hydroxide was about 2,000 bbls. or 520,000 lbs/month.

Example II Utilizing the evaporator system as described in FIG. 1, the catalytic heating oil (30,000 bbls./day) was passed in contact with a total charge of 1,000,000 lbs. of caustic soda which was circulated at 2% to 5% by volume. The caustic soda solution was reconstituted as set forth in the discussion of the aforesaid figure with mercaptans and organic acids being removed in accordance with the invention.

By utilizing the practice of the present invention, the caustic consumption is about 800 to 900 bbls./month of 50 Baum caustic or slightly less than 235,000 lbs./ month, less than 50% of the caustic consumption heretofore experienced. Also, during the operation of the evaporator system, 95,000 lbs. of marketable organic steam consumption on a monthly basis is about 7,000 to 12,000 lbs/hr. (estimatedaverage is 8,000 lbs/hr.) of steam, which results in a high, attractive economic advantage based on the saving of caustic solution. An added advantage is the lessening of spent caustic solution which must be disposed of.

The nature and practice of the present invention having been set forth in detail, including a preferred manner and best mode of practicing the invention, what is desired to be protected by Letters Patent should be determined only by the appended claim and should not be limited by the specific examples hereinabove given.

We claim:

An evaporation system comprising, in combination,

a vertical-tube heat exchanger comprising a shell, means for circulating a heating fluid through said shell, an upper head, a lower head, a plurality of vertically disposed tubes enclosed within said shell and communicating with said upper head and said lower head, outlet means in said upper head, feed in et means .in the bottom of said lower head, bafile means within and depending from said lower head and positioned in confronting relationship with said feed inlet means, recirculation inlet means communicating with the side of said lower head,

separating means for separating vapor and liquid discharged from said exchanger and having a vapor outlet and a standpipe,

overhead conduit means connecting said outlet means with said separating means,

return conduit means connecting said standpipe with said recirculation inlet means,

a choke orifice in said recirculation inlet means, said choke orifice having a cross-sectional area from 1% to 5% of the area of said return conduit means,

separator means having an inlet, an upper liquid phase outlet, and a lower liquid phase outlet,

conduit means connecting said standpipe with said separator means,

cooling means in said conduit means intermediate said standpipe and said separator means,

and pump means for circulating fluid from said standpipe to said separator means and through said cooling means.

References Cited by the Examiner UNITED STATES PATENTS 6/1911 Guillaume 196-100 2/1917 Trump 23-273 11/1922 Webre 159-27 8/ 1931 Lichtenthaeler 159-27 11/1931 Kermer 159-27 1/1934 Burnham 159-27 6/1939 Bonotto 202-237 XR 1/ 1949 Beckel 202-204 XR 10/1949 Baumann 159-28 2/1953 Toulmin 23-274 XR 1/1963 Sumiya 23-274 XR FOREIGN PATENTS 5/1949 Canada. 3/ 1960 Germany. 7/1949 Great Britain.

NORMAN YUDKOFF, Primary Examiner.

US23206762 1961-07-28 1962-10-22 Circulating concentrating evaporation for caustic regeneration Expired - Lifetime US3228754A (en)

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US127527A US3216796A (en) 1961-07-28 1961-07-28 Caustic regeneration
US23206762 US3228754A (en) 1961-07-28 1962-10-22 Circulating concentrating evaporation for caustic regeneration

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3380889A (en) * 1966-03-30 1968-04-30 Westinghouse Electric Corp Boric acid removal process and apparatus
EP2397204B1 (en) * 2010-06-21 2016-06-08 Neste Oyj Feed section of a separation column

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US996081A (en) * 1908-07-09 1911-06-27 Emile Guillaume Process and apparatus for the rectification of crude petroleum and other volatile liquids.
US1216187A (en) * 1916-03-24 1917-02-13 Solvay Process Co Process of recovering salts from admixtures thereof in solution.
US1436739A (en) * 1919-03-03 1922-11-28 Alfred L Webre Evaporator
US1819517A (en) * 1927-10-22 1931-08-18 Frank E Lichtenthaeler Heating system for liquids
US1831121A (en) * 1930-01-23 1931-11-10 Buffalo Foundry & Machine Comp Evaporating apparatus
US1943106A (en) * 1931-07-06 1934-01-09 Clifford L Burnham Evaporator
US2163303A (en) * 1935-08-09 1939-06-20 Extractol Process Ltd Process for separating solvent from oil in miscella and like mixtures
US2460117A (en) * 1945-04-18 1949-01-25 Arthur C Beckel Still and decanter for the recovery of products from alcoholic solutions of oleaginous materials
CA456952A (en) * 1949-05-24 Standard Oil Development Company Refining of mineral oils
GB626522A (en) * 1941-03-15 1949-07-15 Standard Oil Dev Co Refining of mineral oils
US2485689A (en) * 1943-10-18 1949-10-25 Arnold W Baumann Milk evaporator
US2628485A (en) * 1949-10-19 1953-02-17 Ohio Commw Eng Co Method and apparatus for dehydration
DE957472C (en) * 1954-09-20 1960-03-17 Ruetgerswerke Ag Method and device for the partial or complete evaporation of liquids which are not soluble in each other in every ratio
US3075578A (en) * 1959-07-27 1963-01-29 Sumiya Shinzo Multiple vacuum effect evaporator

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA456952A (en) * 1949-05-24 Standard Oil Development Company Refining of mineral oils
US996081A (en) * 1908-07-09 1911-06-27 Emile Guillaume Process and apparatus for the rectification of crude petroleum and other volatile liquids.
US1216187A (en) * 1916-03-24 1917-02-13 Solvay Process Co Process of recovering salts from admixtures thereof in solution.
US1436739A (en) * 1919-03-03 1922-11-28 Alfred L Webre Evaporator
US1819517A (en) * 1927-10-22 1931-08-18 Frank E Lichtenthaeler Heating system for liquids
US1831121A (en) * 1930-01-23 1931-11-10 Buffalo Foundry & Machine Comp Evaporating apparatus
US1943106A (en) * 1931-07-06 1934-01-09 Clifford L Burnham Evaporator
US2163303A (en) * 1935-08-09 1939-06-20 Extractol Process Ltd Process for separating solvent from oil in miscella and like mixtures
GB626522A (en) * 1941-03-15 1949-07-15 Standard Oil Dev Co Refining of mineral oils
US2485689A (en) * 1943-10-18 1949-10-25 Arnold W Baumann Milk evaporator
US2460117A (en) * 1945-04-18 1949-01-25 Arthur C Beckel Still and decanter for the recovery of products from alcoholic solutions of oleaginous materials
US2628485A (en) * 1949-10-19 1953-02-17 Ohio Commw Eng Co Method and apparatus for dehydration
DE957472C (en) * 1954-09-20 1960-03-17 Ruetgerswerke Ag Method and device for the partial or complete evaporation of liquids which are not soluble in each other in every ratio
US3075578A (en) * 1959-07-27 1963-01-29 Sumiya Shinzo Multiple vacuum effect evaporator

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3380889A (en) * 1966-03-30 1968-04-30 Westinghouse Electric Corp Boric acid removal process and apparatus
EP2397204B1 (en) * 2010-06-21 2016-06-08 Neste Oyj Feed section of a separation column

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