US1197167A - Process of concentrating nitric acid. - Google Patents

Process of concentrating nitric acid. Download PDF

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Publication number
US1197167A
US1197167A US86678114A US1914866781A US1197167A US 1197167 A US1197167 A US 1197167A US 86678114 A US86678114 A US 86678114A US 1914866781 A US1914866781 A US 1914866781A US 1197167 A US1197167 A US 1197167A
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nitric acid
acid
sulfuric
nitric
vapors
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US86678114A
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Fred C Zeisberg
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DuPont Powder Coatings USA Inc
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DuPont Powder Coatings USA Inc
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00Nitrogen; Compounds thereof
    • C01B21/20Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
    • C01B21/38Nitric acid
    • C01B21/44Concentration
    • 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
    • Y10S159/19Acid

Definitions

  • the object of my invention is to avoid the necessity of separating the different portions ofl the distillate and to provide a continuous process in which a highly ⁇ concentrated nitric acid may be obtained.
  • a further object of my invention is t provide a process of the above character in which there' is only a very small amount of decomposition of the nitric acid.
  • a further object is to bring about the con ⁇ cent'ration of nitric acid in the presence of a dehydrating agent -without the necessity of introducing any water other than that contained in the nitric acid and the dehydrating agent.
  • a still further object is to utilize the vapors of the dehydrating agent to assist in the dehydration of the nitric acid.
  • a still 1 ⁇ which has a draw-olf pipe 2 at its side for drawing off the sulfuric acid that accumulates in the still.
  • a column 3 filled with any suitable illingmaterial 3, such as pumice stone, the same being retained in place by being supported upon a perforated plate 4c located in the bottom of the column.
  • an inlet pipe 5 for mixed nitric and sulfuric acids said pipe 5 having a stop-cock 6 and being connected to4 a tank 7 which contains the supply'of mixed ynitric and sulfuric acids.
  • a condenser 9 located 1n a container 10 for circulating a current of cold water around the coil.
  • Said coil 9 has 'an outlet pipe 11 for discharging the condensed nitric acid into a receptacle 12.
  • the container 10 is provided with a valved cold water supply pipe 13 and a discharge water pipe 14.
  • a pipe l5. leads to the bottom of a tower 16 which contains any suitable filling material, and which is provided witha valved water supply pipe 17 for supplying a current of water within the tower 16, which absorbs the lower oxids of lnitrogen that-.pass out of the coil 9.
  • a water supply pipe 21 provides a supply of water for the pipes 13 and 17.
  • the still '1 is filled with sulfuric acid of any convenient strength as, for example, 80%, and is heated until the acid is boiling vigorously.
  • sulfuric acid of any convenient strength as, for example, 80%
  • a mixture of sulfuric and nitric acids is allowed yto flow downwardly from the tank 7, or said acids are separately introduced into the column 3 where the acid mixture meets the ascending vapors from the introduced at the same level in the column 3.
  • the vapors are condensed and the heat given up by the condensing vapors drives out the nitric acid, which ascends in the column freed from any water vapor, and finally passes out of the column through the pipe 8 as strong nitric acid vapor.
  • the vapors are then conducted to the coil 9 where the nitric acid vapor is condensed and from which it is collected in the receptacle 12.
  • the small amounts of lower oxids of nitrogen resulting from the unavoidable decomposition of some of the nitric acid in the distillation are absorbed by the current of water in the tower 16.
  • the weak acid solution flowing out of the tower 16 is collected in the receptacle 19.
  • the dilute sulfuric acid which collects in the still 1 flows out from the same through the pipe 2 from which it may be collected and concentrated in any suitable manner, but preferably while hot to avoid the loss of heat.
  • .product obtained is therefore of great utiltain a residual acid of any desired strength. boiling solution of sulfuric aci ity, considering its high strength.
  • the amounts of lower oxids formed were much greater, owing to the fact that the nitric acid vapors came int-o contact with super-heated portions of the still and 'were there decomposed.
  • the process is easy to control as it is a continuous one, and as it is merely necessary, in carrying out the process; to adjust the rate of flow of the incoming mixed acids.
  • no Water need be introduced in the process other than that contained in the nitric and sul- ,furic acids introduced into the column.
  • I may operate the process with a mixture of one part of 50% nitric acid and three parts of 90% sulfuric acid. Upon distilling this mixture in the apparatus above referred to, a distillate is obtained which has a total acidity of 100%.
  • the residual sulfuric acid coming from the still 1 contains 77.6% sulfuric acid and less than .1% of nitric acid.
  • the temperature of the top of the column 8 may be about 86 C. and in the still about 200o C. It is to be understood, of course, that the above proportions and temperatures may be largely varied without departing from the spirit of my invention.
  • the process which comprises passing sulfuric and nitric acids into a chamber, and driving off the nitric acid from the same by bringing into contact therewith vapors from a boiling solution of sulfuric acid, condensing the nitric acid vapors, and recovering the residual oxids of nitrogen by absorbing the same in water.
  • the process of concentrating nitric acid which comprises passing nitric acid and a dehydrating agent into a chamber and driving off the nitric acid from the same by subjecting the nitric acid therein to the action of water vapors obtained from weak nitric acid previously concentrated by the same process.
  • the process of concentrating nitric acid which comprises passing nitric acid and sulfuric acid into a chamber and driving of the nitric acid from the same by subjecting the nitric acid therein to the action of water vapors obtained from weak nitric acid previously concentrated by the same process.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)

Description

I". C. ZEISBERG.
PROCESS 0F CONCENTRATING NITRIC ACID.
APPLICATION FILED OCT. I5. 1914.
Paentedbept. 5, 1916,
I I I FRED C. ZEISBERG, OF WILMINGTON, DELAWARE, ASSIGNOR. TO E. I. DU PONT Dr: NEMOURS POWDER COMPANY, OF WILMINGTON, DELAWARE, A CORPORA- TION OF NEW JERSEY.
PROCESS OF CONCENTRATIN G NITRIC ACID.
Specification of Letters Patent.
Patented Sept. 5, 1916..
Application filed October 15, 191A. Serial No. 866,781.
To all whom it may concern Be it knownl that I, FRED C. ZEISBERG, of Wilmington, in the county of New Castle,
and in the State of Delaware, have invented to a method for the separation of nitric and sulfuric acids.
Hitherto ithas been found that when concentrating weak, nitric acid by mixing it with a dehydrating agent as, for example, sulfuric acid, and distilling thermixture, the iirst portions of the distillate contain strong nitric acid but the later portions contain a considerable amount of water so that if all of the ldistillate is recovered together, and without separating the different portions, a rather weak distillate is obtained. It has therefore been customar to obtain the latter portions of the distilfate separately from the first portions, and after mixing the same with sulfuric acid, to redistil the nitric acid mixture to obtain a more concentrated nitric acid. *l
The object of my invention is to avoid the necessity of separating the different portions ofl the distillate and to provide a continuous process in which a highly` concentrated nitric acid may be obtained. Y
A further object of my invention is t provide a process of the above character in which there' is only a very small amount of decomposition of the nitric acid.
A further object is to bring about the con` cent'ration of nitric acid in the presence of a dehydrating agent -without the necessity of introducing any water other than that contained in the nitric acid and the dehydrating agent.
A still further object is to utilize the vapors of the dehydrating agent to assist in the dehydration of the nitric acid.
While my invention is capable of embodiment in many different forms, for the purl pose of illustration I shall describe only oneform, and while it is capable of being carried out in many different forms of apparatus, I have shown only one form thereof in the accompanying drawings, in which the figure is a diagrammatic representation of an apparatus that may be used for carrying out my invention.
In the drawings I have shown a still 1` which has a draw-olf pipe 2 at its side for drawing off the sulfuric acid that accumulates in the still. At the top of the still 1. there is a column 3 filled with any suitable illingmaterial 3, such as pumice stone, the same being retained in place by being supported upon a perforated plate 4c located in the bottom of the column. At the top of the column 3 there is an inlet pipe 5 for mixed nitric and sulfuric acids, said pipe 5 having a stop-cock 6 and being connected to4 a tank 7 which contains the supply'of mixed ynitric and sulfuric acids. From the top of the column 3 appe 8 conducts the vaporized nitric acid to a condenser 9 located 1n a container 10 for circulating a current of cold water around the coil. Said coil 9 has 'an outlet pipe 11 for discharging the condensed nitric acid into a receptacle 12. The container 10 is provided with a valved cold water supply pipe 13 and a discharge water pipe 14. From the coil 9 a pipe l5. leads to the bottom of a tower 16 which contains any suitable filling material, and which is provided witha valved water supply pipe 17 for supplying a current of water within the tower 16, which absorbs the lower oxids of lnitrogen that-.pass out of the coil 9. The
water, with its dissolved oxids of nitrogen, passes out of the tower 16 by means of a -aoI pipe 18 and is collected in a receptacle 19.
Any gases which are not absorbed in the column 16 may escape out of a pipe 20 located at the top of the column 16. A water supply pipe 21 provides a supply of water for the pipes 13 and 17.
In carrying out my process, the still '1 is filled with sulfuric acid of any convenient strength as, for example, 80%, and is heated until the acid is boiling vigorously. When this occurs, a mixture of sulfuric and nitric acids is allowed yto flow downwardly from the tank 7, or said acids are separately introduced into the column 3 where the acid mixture meets the ascending vapors from the introduced at the same level in the column 3. As a result the vapors are condensed and the heat given up by the condensing vapors drives out the nitric acid, which ascends in the column freed from any water vapor, and finally passes out of the column through the pipe 8 as strong nitric acid vapor. The vapors are then conducted to the coil 9 where the nitric acid vapor is condensed and from which it is collected in the receptacle 12. The small amounts of lower oxids of nitrogen resulting from the unavoidable decomposition of some of the nitric acid in the distillation are absorbed by the current of water in the tower 16. The weak acid solution flowing out of the tower 16 is collected in the receptacle 19. The dilute sulfuric acid which collects in the still 1 flows out from the same through the pipe 2 from which it may be collected and concentrated in any suitable manner, but preferably while hot to avoid the loss of heat.
In this process practically all of the nitric acid is obtained in a highly concentrated condition. In this process only a small percentage of lower oxids of nitrogen is produced, owing to the fact that the nitric acid, upon being vaporized, immediately ascends t0 a cooler portion of the apparatus, the temperature of the column 3 being such that it may be as low as 85o C. at the top. The
.product obtained is therefore of great utiltain a residual acid of any desired strength. boiling solution of sulfuric aci ity, considering its high strength. In previous processes of obtaining nitric acid by distilling the mixture of sulfuric and nitric acids, the amounts of lower oxids formed were much greater, owing to the fact that the nitric acid vapors came int-o contact with super-heated portions of the still and 'were there decomposed. The process is easy to control as it is a continuous one, and as it is merely necessary, in carrying out the process; to adjust the rate of flow of the incoming mixed acids. Furthermore, no Water need be introduced in the process other than that contained in the nitric and sul- ,furic acids introduced into the column.
As one example of my process, I may operate the process with a mixture of one part of 50% nitric acid and three parts of 90% sulfuric acid. Upon distilling this mixture in the apparatus above referred to, a distillate is obtained which has a total acidity of 100%. The residual sulfuric acid coming from the still 1 contains 77.6% sulfuric acid and less than .1% of nitric acid. The temperature of the top of the column 8 may be about 86 C. and in the still about 200o C. It is to be understood, of course, that the above proportions and temperatures may be largely varied without departing from the spirit of my invention.
It is possible, by changing the proportions and strengths of the acids introduced, to ob- While I have described my invention above in detail, I wish it to be understood that many changes may be. made therein without departing from the spirit of my invention.
I claim:
1. The process which comprises passing nitric acid and a dehydrating agent into a chamber, and driving off the nitric acid from the same by bringing into contact therewith water vapors obtained from a boiling aqueous solution of said dehydrating agent.
2. The process which comprises passing sulfuric and nitric acids into a chamber, and driving off the nitric acid from the same by bringing into contact therewith vapors from a boiling solution of sulfuric acid, condensing the nitric acid vapors, and recovering the residual oxids of nitrogen by absorbing the same in water.
3. The process which comprises continuously passing sulfuric and nitric acids into a chamber, and driving off the nitric acid from the same by bringing into contact therewith vapors from a boiling solution of sulfuric acid, condensing the nitric acid vapors, and recovering the residual oxids of nitrogen by absorbing the same in water.
4. The process which comprises continuously passing sulfuric and nitric acids into a chamber, and driving off the nitric acid from the same by bringing into contact therewith vapors from a boiling solution of sulfuric acid, and continuously removing the diluted sulfuric acid, condensing the nitric acid vapors, and recovering the residual oxids of nitrogen by absorbing the same in water.
5. The process of concentrating nitric acid which comprises passing nitric acid and a dehydrating agent into a chamber and driving off the nitric acid from the same by subjecting the nitric acid therein to the action of water vapors obtained from weak nitric acid previously concentrated by the same process.
- 6. The process of concentrating nitric acid which comprises passing nitric acid and sulfuric acid into a chamber and driving of the nitric acid from the same by subjecting the nitric acid therein to the action of water vapors obtained from weak nitric acid previously concentrated by the same process.
7. The process which comprises passing sulfuric and nitric acids in the form of a liquid into a chamber, and driving off the nitric acid from the same by bringing into contact therewith vapors from a boiling solution of sulfuric acid.
8. The process which comprises continuously passing sulfuric and nitric acids in the form of a liquid into a chamber and driving off the nitric acid from the same by bringing into contact therewith v anors from a in testimony that I claim the foregoing I have hereunto set my hand.
FRED C. ZEISBERG.
Witnesses:
P.' G. STRICHLAND, R. H. RAWLEIGH.
US86678114A 1914-10-15 1914-10-15 Process of concentrating nitric acid. Expired - Lifetime US1197167A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2594588A (en) * 1947-06-19 1952-04-29 Hercules Powder Co Ltd Method of producing fuming nitric acid

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2594588A (en) * 1947-06-19 1952-04-29 Hercules Powder Co Ltd Method of producing fuming nitric acid

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