US2042412A - Process for the preparation of inhibitors - Google Patents

Process for the preparation of inhibitors Download PDF

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Publication number
US2042412A
US2042412A US14544A US1454435A US2042412A US 2042412 A US2042412 A US 2042412A US 14544 A US14544 A US 14544A US 1454435 A US1454435 A US 1454435A US 2042412 A US2042412 A US 2042412A
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US
United States
Prior art keywords
acid
ammonia
inhibitor
extract
oil
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US14544A
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English (en)
Inventor
Jan D Ruys
Russell L Kittle
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Shell Development Co
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Shell Development Co
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Filing date
Publication date
Application filed by Shell Development Co filed Critical Shell Development Co
Priority to US14544A priority Critical patent/US2042412A/en
Priority to GB8283/36A priority patent/GB459420A/en
Priority to DEN39302D priority patent/DE652959C/de
Priority to FR804516D priority patent/FR804516A/fr
Application granted granted Critical
Publication of US2042412A publication Critical patent/US2042412A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
    • C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors

Definitions

  • This invention relates to agents for the prevention of the corrosion which occurs upon the surface of metals when removing undesirable films as in the pickling of steel.
  • Fig. II is a diagrammatic iiow sheet of appa- ⁇ ratus suitable for carrying out the process.
  • acid sludge resulting from the treatment of petroleum distillates is first neutralized with ammonia preferably in a saturated solution of ammonium sulfate.
  • the sulfuric acid in the acid sludge is neutralized producing ammonium sulfate.
  • Certain organic sulfates present in the acid sludge are also acted upon by the ammonia forming ammonium sulfate and releasing organic oily material. This latter material together with other oil originally present in the acid sludge collects on the surface of the aqueous liquid from which it is removed.
  • this separated oily material resulting from the neutralization of acid sludge as recovered oil.
  • the recovered oil is heated to a sufficiently high temperature so that its iluidity is sufficiently increased to facilitate further treatment. Thereafter an aqueous solution of ammonia is added to the recovered oil to produce free ammonia in the container in such amounts that a small excess of ammonia exists in the mixture. After sufficient time has elapsed the liquid will separate into two layers. The aqueous layer of ammonia extract is drained off to a second container. The effect of this ammonia treatment is to extract certain organic material which we have called acid oil. The remaining oily material in the container is next treated with sulfuric acid fand preferably ammonium sulfate. This treatment extracts basic compounds from the oily material.
  • ammonia, sulfuric acid and ammonia sulfate as treating agents but the process may be executed equally well with other alkalis, acids and alkaline salts respectively.
  • the basic compounds extracted from the oil are mostly nitrogen compounds and will be referred to hereafter as nitrogen bases.
  • nitrogen bases The basic compounds extracted from the oil are mostly nitrogen compounds and will be referred to hereafter as nitrogen bases.
  • ammonia extract containing acid oil and an acid extract containing nitrogen bases The two extracts are next mixed one with the other.
  • the acid oil and nitrogen bases become released from their carriers and combine with one another forming a layer which we have called acid oil nitrogen base.
  • This product is removed and diluted with water resulting in further stratification of the material.
  • the upper layer called inhibitor solution is separated from the other liquor called residual acid oil nitrogen base.
  • Ammonium sulfate either as a solid salt or as concentrated aqueous solution is added to the inhibitor solution and has the effect of concentrat- (9) and (9a).
  • the finished product is removed from the surface of the tank.
  • This product is soluble in sulfuric acid, possesses no disagreeable smell and has good inhibiting properties.
  • the inhibi-i tor solution could be used directly as such, however, its inhibiting qualities will be proportional, to the concentration of the finished inhibitor in solution.
  • a required amount of recovered oil produced by neutralizing acid sludge with ammonia is introduced into the first agitator (I) from pipe (2) controlled by valve (3). Water is then run into the agitator (I) from pipe (4) controlled by valve (5). Thereafter, amounts of ammonia gas are passed into the agitator through pipe (6) which extends to the bottom of said agitator (I). The ammonia ow is controlled by a valve (40). The ammonia gas entering stirs the mixture so that a mechanical stirrer can be dispensed with. During the addition of ammonia gas the contents of the agitator are circulated by pump (8) through lines (9) and (9a).
  • ammonia gas and water instead of using ammonia gas and water, we may, of course, use an aqueous ammonia solution of desired concentration. After sufficient ammonia has been passed in so that the resulting mixture is slightly ammoniacal, the ammonia valve is closed. After a short period a layer of ammonia extract will gravitate to the bottom of the agitator (I). This extract is pumped from the first agitator (I) to the second agitator ('l) by means of pump (8) and line (9) controlled by Valve (I0). After the ammonia extract has been drawn off the valve (I0) is closed.
  • the ammonia extract and the acid extract are next mixed in the second agitator (1) by means of a stirrer (I6).
  • the acid oil of the ammonia extract combines with some of the nitrogen bases of the sulfuric acid extract forming a layer of acid oil nitrogen base material on a layer of nitrogen bases dissolved in a sulfuric acid and ammonium sulfate solution.
  • This latter we have called nitrogen base solution.
  • the nitrogen base solution is withdrawn from the second agitator (1) to'storage tank (I1) by means of pipe (I8) by opening valve (I 0). This nitrogen base solution can be used as a source of nitrogen bases by subsequent treating.
  • the stirrer (29) is next operated to cause the contents to be thoroughly mixed. After sufficient time ler settling has elapsed the inhibitor rises to the top of the remaining liquor, which liquor consists of ammonium sulfate solution. This ammonium sulfate solution is then drawn off to a storage tank (30) by pipe (3
  • the ammonium sulfate solution in tank (30) can be mixed with sulfuric acid in the necessary proportions for introducing into the first agitator (I) by pumping the same in controlled amounts into line (I I) by means of pump (36) and line (31).
  • the proportion of ammonium sulfate to sulfuric acid can be controlled by regulation of valves (38) and (39).
  • Rodine No. 110 which has the following analysis:
  • Total H2804 66 B.v used 4840 lbs. Acid concentration of bath 7% HzSO4 Inhibitor used- 4,550 ce 9.60 lbs. Steel pickled 66.07 long tons Amount of inhibitor used per long ton of steel treated .145 lb.
  • the recovered oil was obtained by neutralizing acid sludge (resulting from the treatment of pressure distillate, a cracked petroleum product) with ammonia.
  • the recovered oil at a temperature of approximately 80 C. was mixed with approximately one-seventh its volume of water at the same temperature tov which 2% of its weight of gaseous ammonia was added during the mixing of the liquids. After mixing and settling the ammonia extract was separated from the oil.
  • Process for the manufacture of steel pickling inhibitor from petroleum acid sludge comprising neutralizing the. acid content of said sludge, adding alkali to the oily layer produced, removing the resulting alkaline extract, adding acid and alkaline salt to the remaining oil, removing the acid extract produced, mixing said alkaline extract with said acid extract, removing the resulting acid oil nitrogen base, hydrolyzing said acid oil nitrogen base whereby a layer of inhibitor solution is produced, thereafter separating inhibitor from said solution by means of a suitable salt.
  • Process for the manufacture of steel pickling inhibitor from petroleum acid sludge comprising neutralizing the acid content of said sludge, adding ammonia to the oily layer produced, removing the resulting ammonia extract, adding sulfuric acid and ammonium sulfate to the remaining oil, removing the acid extract produced, mixing said ammonia extract with said acid extract, removing the resulting acid oil nitrogen base, hydrolyzing said acid oil nitrogen base whereby a layer of inhibitor solution is produced, thereafter separating inhibitor from said solution by means of ammonium sulfate.
  • Process for the manufacture of steel pickling inhibitor from petroleum acid sludge comprising neutralizing the acid content of said sludge, adding ammonia to the oil layer produced, removing the resulting ammonia extract, adding sulfuric acid and ammonium sulfate to the remaining oil, removing the acid extract produced, mixing said ammonia etxract with said acid extract, removing the resulting acid oil nitrogen base, hydrolyzing said acid oil nitrogen base whereby a layer of inhibitor solution is produced, thereafter separating inhibitor from said solution.
  • Process for the manufacture of steel pickling inhibitor from petroleum acid sludge comprising neutralizing the acid content of said sludge with ammonia, separating the oily material produced, adding ammonia to said o'ly material whereby an ammonia extract is produced, separating the ammonia extract from the remaining oil, adding sulfuric acid to the remaining oil, whereby an acid extract is produced, separating the acid extract from the remaining residual oil, adding said acid extract to said ammonia extract whereby a layer of acid oil nitrogen base material is produced, removing the acid oil nitrogen base material, hydrolyzing the same whereby a layer of inhibitor solution is formed, removing the inhibitor solution and separating inhibitor therefrom by the addition of a concentrated ammonium sulfate solution.
  • Process for the manufacture of steel pickling inhibitor from petroleum acid sludge comprising neutralizing the acid content of said sludge with ammonia, removing the resulting oily layer, adding ammonia to this oily layer, removing the resulting ammonia extract, adding ammonium sulfate and sulfuric acid in the proportion of six parts ammonium sulfate to one part sulfuric acid to the remaining oil, removing the resulting acid extract, adding the acid extract to the ammonia extract whereby a layer of acid oil nitrogen base material is produced, hydrolyzing said acid oil nitrogen base material whereby a layer of inhibitor solution is produced, thereafter separating inhibitor from said solution.
  • the herein described pickling inhibitor obtained by neutralizing the acid content of petroleum acid sludge with ammonia, separating the oily material produced, adding ammonia to said oily material, removing the resulting ammonia extract, adding sulfuric acid to the remaining oil, removing the acid extract produced, mixing said ammonia extract with said acid extract, removing the resulting acid oil nitrogen base, hydrolyzing said acid oil nitrogen base whereby a layer of inhibitor solution is produced, and separating said inhibitor from said solution by the addition of ammonium sulfate.
  • Process for the manufacture of steel pickling inhibitor from petroleum acid sludge comprising substantially neutralizing the acid content of said sludge. adding a base to the oily layer produced removing the tract, adding acid and a salt of the alkali earth metals including ammonium, removing the acid extract produced, mixing said basic extract with said acid extract, removing the resulting acid oil nitrogen base, hydrolyzing said acid oil nitrogen base whereby a layer of inhibitor solution is produced and thereafter'separating inhibitor from said solution by means of a'suitable salt.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Treatment Of Sludge (AREA)
  • Extraction Or Liquid Replacement (AREA)
US14544A 1935-04-03 1935-04-03 Process for the preparation of inhibitors Expired - Lifetime US2042412A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US14544A US2042412A (en) 1935-04-03 1935-04-03 Process for the preparation of inhibitors
GB8283/36A GB459420A (en) 1935-04-03 1936-03-19 A process for the preparation of steel picklings inhibitors
DEN39302D DE652959C (de) 1935-04-03 1936-03-26 Verfahren zur Gewinnung eines organische Stickstoffbasen enthaltenden Erzeugnisses aus Saeureschlamm
FR804516D FR804516A (fr) 1935-04-03 1936-04-02 Procédé de préparation d'un agent d'inhibition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US14544A US2042412A (en) 1935-04-03 1935-04-03 Process for the preparation of inhibitors

Publications (1)

Publication Number Publication Date
US2042412A true US2042412A (en) 1936-05-26

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US14544A Expired - Lifetime US2042412A (en) 1935-04-03 1935-04-03 Process for the preparation of inhibitors

Country Status (4)

Country Link
US (1) US2042412A (fr)
DE (1) DE652959C (fr)
FR (1) FR804516A (fr)
GB (1) GB459420A (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2421040A (en) * 1942-06-18 1947-05-27 Alox Corp Process of obtaining polar-type corrosion-inhibiting agents soluble in petroleum lubricating oils
US4835924A (en) * 1986-12-17 1989-06-06 Tate Acess Floors Self-gridding flooring system

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2421040A (en) * 1942-06-18 1947-05-27 Alox Corp Process of obtaining polar-type corrosion-inhibiting agents soluble in petroleum lubricating oils
US4835924A (en) * 1986-12-17 1989-06-06 Tate Acess Floors Self-gridding flooring system

Also Published As

Publication number Publication date
GB459420A (en) 1937-01-07
FR804516A (fr) 1936-10-26
DE652959C (de) 1937-11-11

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