US2176883A - Stabilization of hydrocarbon - Google Patents
Stabilization of hydrocarbon Download PDFInfo
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- US2176883A US2176883A US2176883DA US2176883A US 2176883 A US2176883 A US 2176883A US 2176883D A US2176883D A US 2176883DA US 2176883 A US2176883 A US 2176883A
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- US
- United States
- Prior art keywords
- hexahydroxy
- spiro
- bis
- indane
- alkyl
- Prior art date
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- 150000002430 hydrocarbons Chemical class 0.000 title description 48
- 239000004215 Carbon black (E152) Substances 0.000 title description 40
- 238000011105 stabilization Methods 0.000 title description 12
- 239000000446 fuel Substances 0.000 description 68
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 66
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 48
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 42
- 229920000591 gum Polymers 0.000 description 36
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 36
- 125000000217 alkyl group Chemical group 0.000 description 34
- 239000000203 mixture Substances 0.000 description 34
- 239000003502 gasoline Substances 0.000 description 30
- 238000009833 condensation Methods 0.000 description 28
- 230000005494 condensation Effects 0.000 description 28
- 238000000034 method Methods 0.000 description 28
- 238000003860 storage Methods 0.000 description 26
- 235000011054 acetic acid Nutrition 0.000 description 24
- 239000007788 liquid Substances 0.000 description 24
- 235000011167 hydrochloric acid Nutrition 0.000 description 22
- 230000002401 inhibitory effect Effects 0.000 description 22
- 239000003381 stabilizer Substances 0.000 description 22
- 150000002576 ketones Chemical class 0.000 description 18
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 18
- -1 alkyl hexahydroxy indane compound Chemical class 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000002845 discoloration Methods 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 238000005755 formation reaction Methods 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 12
- 239000007859 condensation product Substances 0.000 description 12
- 238000006482 condensation reaction Methods 0.000 description 12
- 239000003208 petroleum Substances 0.000 description 12
- 239000002253 acid Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- 238000005336 cracking Methods 0.000 description 10
- 239000003112 inhibitor Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K Aluminium chloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000000975 dye Substances 0.000 description 8
- 150000008442 polyphenolic compounds Polymers 0.000 description 8
- 239000001117 sulphuric acid Substances 0.000 description 8
- 235000011149 sulphuric acid Nutrition 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- AESFGSJWSUZRGW-UHFFFAOYSA-N (3,4-diacetyloxyphenyl) acetate Chemical compound CC(=O)OC1=CC=C(OC(C)=O)C(OC(C)=O)=C1 AESFGSJWSUZRGW-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N Indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 4
- MTZWHHIREPJPTG-UHFFFAOYSA-N Phorone Chemical compound CC(C)=CC(=O)C=C(C)C MTZWHHIREPJPTG-UHFFFAOYSA-N 0.000 description 4
- WQGWDDDVZFFDIG-UHFFFAOYSA-N Pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 4
- MRMOZBOQVYRSEM-UHFFFAOYSA-N Tetraethyllead Chemical compound CC[Pb](CC)(CC)CC MRMOZBOQVYRSEM-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 239000012429 reaction media Substances 0.000 description 4
- 239000012262 resinous product Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- OZXIZRZFGJZWBF-UHFFFAOYSA-N 1,3,5-trimethyl-2-(2,4,6-trimethylphenoxy)benzene Chemical compound CC1=CC(C)=CC(C)=C1OC1=C(C)C=C(C)C=C1C OZXIZRZFGJZWBF-UHFFFAOYSA-N 0.000 description 2
- CPKMDVJBOZHSNZ-UHFFFAOYSA-N C(C)(=O)O.OC1=C(O)C=CC(=C1)O Chemical compound C(C)(=O)O.OC1=C(O)C=CC(=C1)O CPKMDVJBOZHSNZ-UHFFFAOYSA-N 0.000 description 2
- 229940108066 Coal Tar Drugs 0.000 description 2
- GGNQRNBDZQJCCN-UHFFFAOYSA-N Hydroxyquinol Chemical compound OC1=CC=C(O)C(O)=C1 GGNQRNBDZQJCCN-UHFFFAOYSA-N 0.000 description 2
- WCYWZMWISLQXQU-UHFFFAOYSA-N Methyl radical Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 2
- 229940079877 Pyrogallol Drugs 0.000 description 2
- LZKPUVULVAMJGR-UHFFFAOYSA-N acetic acid;benzene-1,4-diol Chemical compound CC(O)=O.OC1=CC=C(O)C=C1 LZKPUVULVAMJGR-UHFFFAOYSA-N 0.000 description 2
- WJGAPUXHSQQWQF-UHFFFAOYSA-N acetic acid;hydrochloride Chemical compound Cl.CC(O)=O WJGAPUXHSQQWQF-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 239000006079 antiknock agent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000011280 coal tar Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
Definitions
- the present invention relates, in general, to the eral, gasolines containing benzol, motor benzols,
- heavy motor fuels such as used in Diesel engines and the like, white or medicinal oil, coal tar distillates and the like, is not limited thereto, but may be practiced whenever it is desirable to stabilize the liquid hydrocarbons or their equivalents, and
- the invention is especially valuable in the stabilization of gasoline derived from the cracking of petroleum.
- gasolines contain unsaturated compounds which are capable of oxidation on exposure to air to form various products, some of which are of a gummy or resinous character. While the presence of unsaturants is 5 the primary cause for many gasolines discoloring and forming gummy products, difierences in structure other than the degree of saturation do cause oxidation of the gasoline.
- the present invention has for an object the stabilization of liquid hydrocarbons which because of various factors, whatever they may be, exhibit a tendency to discolor and form resinous and gummy products which prevent the hydrocarbon from functioning efiiciently for its intended purpose.
- Another object is to stabilize such hydrocarbons for use as a motor fuel.
- Still another object is to prepare a liquid hydrocarbon which contains a dye and which isstabilized against discoloration inthe presence of sunlight or its equivalent.
- Still another object is to stabilize hydrocarbon motor fuels containing a dye and/or an antilmock agent
- One suitable tetra alkyl hexahydroxy indane compound suitable for carrying out the present invention is 3, 3, 3', 3' tetramethyl, 4, 6, 7, 4', 6', '7' hexahydroxy, 1, 1' spiro-bis-indane; which has been named in accordance with the nomenclature system of Chemical Abstracts of the American Chemical Society.
- the motor there is incorporated in the motor.
- fuel a small amount of the condensationproduct of a poly hydroxy phenol or derivatives thereof with a ketone, as for example, acetone.
- the poly hydroxy phenols areexemplifie'd by hydroxyhydroquinone, or by hydroxyhydroquinone triacetate.
- pyrogallol is condensed with acetone, the following hexahydroxy spiro-bis-indane compounds are formed:
- - ketone e. g., homologues of phorone
- a weak acid such as acetic acid cc
- a strong mineral acid such as 32% hydrochloric acid cc
- the mixture is heated for about one (1) hour at a temperature of about 50 C. until a complete solution is formed.
- the mixture is then allowed to stand from several hours until about five (5) days.
- the reaction time may be lowered by carrying out the reaction at an elevated temperature, reaction being apparently complete after six (6) hours at 75 C., while five (5) days in the cold may be necessary.
- the condensation is allowed to occur and the products of reaction separated from the solution by filtration
- the solid condensation product is purified; and when in its purified state, melts at about 266 to 267 C.
- the purification is effected by washing or crystallizing from suitable solvents such as acetic acid or alcohol.
- One of the features of the above process of condensation is the production of the condensation product in a reaction medium wherein the liquors from the condensation reaction, after separation of the condensation products, are re'-used as a medium for further condensation reactions, upon fresh additions of the reacting constituents, such as a phenol and a ketone.
- the condensation is carried out in an .acid medium comprising a strong inorganic acid and a weak organic acid, other solvent mediums may be employed. It is desirable, although not absolutely necessary, to add an additional strong acid after several cycles of condensation. As stated above, it is preferred to add the strong mineral acid, such as hydrochloric acid, every other cycle, although obviously this will be governed somewhat by the character of the initial starting reaction medium. Tests can be made as to the strength of the acetic acid-hydrochloric acid condensation medium, and it may be brought up to strength as is necessary, whether this be every other cycle, or every third cycle, or otherwise.
- the batch given above is illustrative of suitable batches. It is highly desirable to keep the ratio of the poly hydroxy phenol or its alkyl ether to the ketone approximately as above specified, as any substantial change in the ratio produces a lower yield or a loss of ketone.
- the acetic acid or any other suitable medium examples of which are hereinafter given, must be present in a relatively large proportion to act as a solvent for the by-products which are tarryand must necessarily be kept in solution. It is also desirable to keep the hydrochloric acid concentration, or other condensing agents used, ashereinafter specified, substantially constant, or nearly so.
- condensation can be effected by using other condensation mediums.
- the acetic acid may be eliminated and the reaction product later purified by washing in acetic acid or alcohol.
- Other solvents besides acetic acid may be used.
- Sulphuric acid or aluminum chloride may replace the hydrochloric acid, or the hydrochloric acid may be generated in situ by a mixture of salt and sulphuric acid.
- the yield is greater because of the unconverted phenol, such as hydroxy hydroquinone acetate, or similar compound, which is always present, remaining constant throughout 'all ten (10) cycles.
- the use of a plurality of cycles has the advantage that all the polyhydric phenol added after the first cycle enters into the condensation reaction.
- the process of preparing the above or similar phenol. ketone condensation products is fiexible, and is not in any feature limited to the conditions set forth.
- the same products may be obtained by omitting the acetic acid from the batch, by using other quantities of the reagents by substituting other solvents forthe acetic acid, or by using other well known condensing agents in place of hydrochloric acid, as for example, sulphuric acid, aluminum chloride, and a mixture of salt and sulphuric acid, and the like.
- the compound produced by the above condensation reaction may be designated as a hexahydroxy derivative of alkyl spiro-bis-indane, and more specifically, 3,3,3',3' tetramethyl, 4,6,7,4',6',7' hexahydroxy, 1,1 spiro-bis-indane.
- hexahydroxy derivatives of alkyl spiro-bisindane produced by reacting a poly hydroxy phenol or its alkyl other with a ketone, such as acetone or methyl ethyl ketone, are in general white or light-colored solids melting usually at high temperatures. acetone, and moderately soluble in alcohol and chloroform, and slightly soluble in gasoline and the like.
- a tetra-alkyl hexahydroxy spiro-bis-indane compound produced by the above method, or by any other method may be incorporated in a small amount in a liquid hydrocarbon and functions to inhibit discoloration and the formation of gummy and resinous products. It is particularly adapted to so function when added to motor fuels. It is sufiiciently soluble therein to be added directly, and may be incorporated in the motor fuel in amounts ranging from 0.0005 to .01 per cent based on the weight of the motor fuel. In practice, the amount of inhibitor present may be rated in terms of grams per gallon of motor fuel to be stabilized. This usually varies between 0.025 to 0.3 gm. per gallon of fuel treated.
- the spiro-bis-indane may be dissolved in a solvent exemplified by acetone or alcohol, and said solvent containing the indane added to the motor fuel.
- a solvent exemplified by acetone or alcohol for example, 1 part by weight, of the inhibitor may be dissolved in 3 parts, by weight, of acetone, or 10 parts, by weight, of alcohol. If the inhibitor is dissolved in acetone (3 parts by weight), then to a gallon of gasoline, there should be added from 0.1 gm. to
- the amount of tetraalkyl hexahydroxy spiro-bis-indane added to the motor fuel may be varied from that specified in the illustrative example above set forth.
- the amount of inhibiting agent which is added to the motor fuel will depend upon many factors including the nature of the hydrocarbon fuel, the temperature thereof and the condition of storage It will be understood that in any case the compound is used in a comparatively small quantity, and when used in comparatively small amounts of the order of those above pointed out, it is substantially less than would deposit gum.
- the 3,3,3',3' tetramethyl and 4,6,7,4',6,7' hexahydroxy, 1,1 spiro-bis indane, and the other spiro-bis-indanes herein referred to are exemplary of suitable tetraalkyl hexahydroxy compounds which may be used as a stabilizer for the motor fuel.
- Other alkyl radicals, saturated'or unsaturated, may be substituted for the methyl radical. 1
- the mixed aim l radicals be the methyl and ethyl radicala'othez' equivalent alkyl radicals may be introduced into the rings, said-alkyl radicals being saturated or unsaturated Motor fuels treated in accordance with the present invention not only test up well on the copper dish andinduction period tests, but st and storage successfully, without going off color 1mder drastic exposure to light and regardless of the presence of other chemicals, such as lead tetraethyl and organic dyes.
- Transformer oil which is used in the electrical industry, may be treated with the present stabilizer.
- the present invention is applicable to the stabilization of'hydrocarbon fuels having an aromatic base or an aliphatic base.
- hydroxy spiro-bis -in danes are added to the hydrocarbon, and in some cases it may be advantageous to employ mixtures of different hydroxy spiro-bis-indanes.
- Any of the alkyl hydroxy spiro indanes herein set forth may be mixed together and added to the hydrocarbon. More specifically, there may be added to the hydrocarbon a mixture of different alkyl hexahydroxy spiro-bis-indanes. Y For example, there may be added to the hydrocarbon a mixture of tetra-methyl hexahydroxy spiro-bisindane and tetramethyl ethyl hexahydroxy spirobis-indane.
- a liquid hydrocarbon of a type normally tending to discolor and form gum during storage containing a small amount of a tetra alkyl hexahydroxy spiro-bis-indane.
- a liquid hydrocarbon of a type normally tending to discolor and form gum during storage containing as astabilizing agent a small amount of a tetra alkyl hexahydroxy spiro-bis-indane.
- a liquid hydrocarbon of a type normally tending to discolor and form gum during storage containing as a stabilizing agent a small amount of a tetramethyl hexahydroxy spiro-bis-indane.
- a liquid hydrocarbon of a type normally tending to discolor and form gum during storage containing as a stabilizing agent a small amount of 3,3-,3',3 tetramethyl, 4,6,'7,4',6','I hexahydroxy 1,1 spiro-bis-indane.
- a new composition of matter comprising a hydrocarbon fuel of a type normally tending to discolor and form gum during storage and as a stabilizer, a small amount of a tetra alkyl hexahydroxy spiro-bis-indane.
- a new composition of matter comprising a hydrocarbon fuel of a type normally tending to discolor and form gum during storage and as a stabilizer, a small amount of a tetramethyl hexahydroxy spiro-bis-indane.
- a new composition of matter comprising a hydrocarbonmotor fuel of a type normally tending to discolor and form gum during storage containing a small amount of 3,3,3,3 tetramethyl,
- a new composition of matter comprising a hydrocarbon-motor fuel of a type normally tending to discolor and form gum during storage, andas a stabilizer 0.0005 to 0.01 per cent of 3,3,3',3' tetramethyl, 4,6,'1,4',6',7' hexahydroxy 1,1 spiro-bis-indane.
- a mixed motor fuel of a type normally tending to discolor and. form gum during storage including gasoline and petroleum and containing as a stabilizer a small quantity of tetra alkyl hexahydroxy spiro-bis-indane.
- a liquid hydrocarbon of a type normally tending to discolor and form gum during storage containing a small amount of a mixture of alkyl hexahydroxy spiro-bisindanes.
Description
Patented @ct. 24,1939 v um I) STATEVS PATENT OFFICE' STABILIZATION F HYDROCARBON COMPOUNDS Charles Harold Fisher, Pittsburgh, Pa., assignor to The Pennsylvania Coal Products 00., Petrolia, Pa., a corporation of Pennsylvania No Drawing. Application January 8, 1936, Serial No. 58,220. Renewed March 16, 1939 i, 23 Claims.
The present invention relates, in general, to the eral, gasolines containing benzol, motor benzols,
10 heavy motor fuels such as used in Diesel engines and the like, white or medicinal oil, coal tar distillates and the like, is not limited thereto, but may be practiced whenever it is desirable to stabilize the liquid hydrocarbons or their equivalents, and
especially in connection with motor fuels which exhibit a tendency to discolor and/or form gum,
' sludge and/or resinous products. The invention is especially valuable in the stabilization of gasoline derived from the cracking of petroleum.
: Many of the present day gasolines contain unsaturated compounds which are capable of oxidation on exposure to air to form various products, some of which are of a gummy or resinous character. While the presence of unsaturants is 5 the primary cause for many gasolines discoloring and forming gummy products, difierences in structure other than the degree of saturation do cause oxidation of the gasoline.
Many of the motor fuels, including gasoline, have chemicals added thereto for various pur- D poses including coloration and the prevention of knocking. For example, various dyes are added to gasoline to color the same and tetra ethyl lead is added as an anti-knock agent. Such chemicals increase the difiiculties attendant to the proper stabilization of the gasoline.
The present invention has for an object the stabilization of liquid hydrocarbons which because of various factors, whatever they may be, exhibit a tendency to discolor and form resinous and gummy products which prevent the hydrocarbon from functioning efiiciently for its intended purpose.
Another object is to stabilize such hydrocarbons for use as a motor fuel.
Still another object is to prepare a liquid hydrocarbon which contains a dye and which isstabilized against discoloration inthe presence of sunlight or its equivalent.
Still another object is to stabilize hydrocarbon motor fuels containing a dye and/or an antilmock agent,
The above objects and other objects, as will hereinafter appear, are accomplished by incorporating in the liquid hydrocarbon or the motor fuel, a small percentage of an alkyl hexahydroxy spiro-bis-indane compound, and more specifically, a tetra alkyl hexahydroxy indane compound, although other hexahydroxy spirobis-indanes having a greater number of alkyl radicals may be used.
One suitable tetra alkyl hexahydroxy indane compound suitable for carrying out the present invention is 3, 3, 3', 3' tetramethyl, 4, 6, 7, 4', 6', '7' hexahydroxy, 1, 1' spiro-bis-indane; which has been named in accordance with the nomenclature system of Chemical Abstracts of the American Chemical Society.
In one specific form of the invention, there is incorporated in the motor. fuel a small amount of the condensationproduct of a poly hydroxy phenol or derivatives thereof with a ketone, as for example, acetone. The poly hydroxy phenols areexemplifie'd by hydroxyhydroquinone, or by hydroxyhydroquinone triacetate. The condense: tion product of the hydroquinone acetate and acetone results in the formation of tetra alkyl hexahydroxy spiro-bis-indane. When pyrogallol is condensed with acetone, the following hexahydroxy spiro-bis-indane compounds are formed:
3' tetramethyl, 4, 5, 6, 4, 5, 6 hexahydroxy, l, l Spiro-bismdane,
and
3, s, 3', a tetramethyl, 5, a, 1, 5', 6, 7' hexahydroxy, '1, 1' s ire-bis. lndane.
- ketone (e. g., homologues of phorone,
A mixture is made of Hydroxy-hydroquinone triacetate A ketone, such as acetone (0.11 mole) gin 6.4]
A weak acid, such as acetic acid cc A strong mineral acid, such as 32% hydrochloric acid cc The mixture is heated for about one (1) hour at a temperature of about 50 C. until a complete solution is formed. The mixture is then allowed to stand from several hours until about five (5) days. The time that the mixture is allowed to stand'will depend on a number of factors, including the temperature at which the condensation reaction is carried out. The reaction time may be lowered by carrying out the reaction at an elevated temperature, reaction being apparently complete after six (6) hours at 75 C., while five (5) days in the cold may be necessary.
By the above procedure, the condensation is allowed to occur and the products of reaction separated from the solution by filtration The solid condensation product is purified; and when in its purified state, melts at about 266 to 267 C. The purification is effected by washing or crystallizing from suitable solvents such as acetic acid or alcohol.
The filtrate is again charged with new quantities of Hydroxy hydroquinone triacetate gm 1'7 Acetone -i gm 6.4
and the condensation reactions are repeated. To the liquor from the above condensation, additional raw materials, as above, are again added, together with an additional amount of concentrated hydrochloric acid. It will be sufiicient to add about 3 cc. or 4 cc. of hydrochloric acid to about 45 cc. of. the filtrate.
This procedure is repeated for ten (10) cycles, and preferably every other cycle an addition of a suitable amount of hydrochloric acid is made. After ten (10) runs, the liquor is very much contaminated with by-products, and, therefore, is discarded, or may be treated to recover by known methods the acetic acid present, and the ketone condensation products (such as homologues of.
mesityl oxide and phorone present).
One of the features of the above process of condensation is the production of the condensation product in a reaction medium wherein the liquors from the condensation reaction, after separation of the condensation products, are re'-used as a medium for further condensation reactions, upon fresh additions of the reacting constituents, such as a phenol and a ketone. While preferably the condensation is carried out in an .acid medium comprising a strong inorganic acid and a weak organic acid, other solvent mediums may be employed. It is desirable, although not absolutely necessary, to add an additional strong acid after several cycles of condensation. As stated above, it is preferred to add the strong mineral acid, such as hydrochloric acid, every other cycle, although obviously this will be governed somewhat by the character of the initial starting reaction medium. Tests can be made as to the strength of the acetic acid-hydrochloric acid condensation medium, and it may be brought up to strength as is necessary, whether this be every other cycle, or every third cycle, or otherwise.
In the above example, it has been stated that the condensation liquor is used as a medium for further condensation, but that after ten (10) runs the liquor is discarded, as it is contaminated with by-products. Here again, the figure of ten (10) runs is given as illustrative and this may be considerably varied. Tests will show when the condensation liquid should be discarded.
The batch given above is illustrative of suitable batches. It is highly desirable to keep the ratio of the poly hydroxy phenol or its alkyl ether to the ketone approximately as above specified, as any substantial change in the ratio produces a lower yield or a loss of ketone. The acetic acid or any other suitable medium, examples of which are hereinafter given, must be present in a relatively large proportion to act as a solvent for the by-products which are tarryand must necessarily be kept in solution. It is also desirable to keep the hydrochloric acid concentration, or other condensing agents used, ashereinafter specified, substantially constant, or nearly so.
While the use of acetic and hydrochloric acids, as given in the above example, are most satisfactory, condensation can be effected by using other condensation mediums. For example, the acetic acid may be eliminated and the reaction product later purified by washing in acetic acid or alcohol. Other solvents besides acetic acid may be used. Sulphuric acid or aluminum chloride may replace the hydrochloric acid, or the hydrochloric acid may be generated in situ by a mixture of salt and sulphuric acid.
It is desired to point out that the re-use of liquors in the cycle process disclosed results in a saving of acetic acid. Further, it is highly desirable to use thecyclic process and to re-use the liquors, since .the recovery of the acetic acid from the liquors proved to be exceedingly difficult, and, further, the re-use of the liquors reduces the cost of the hydrochloric acid consumed in the process.
Additionally, the yield is greater because of the unconverted phenol, such as hydroxy hydroquinone acetate, or similar compound, which is always present, remaining constant throughout 'all ten (10) cycles. The use of a plurality of cycles has the advantage that all the polyhydric phenol added after the first cycle enters into the condensation reaction.
' In general, it may be stated that the process of preparing the above or similar phenol. ketone condensation products, is fiexible, and is not in any feature limited to the conditions set forth. As stated, the same products may be obtained by omitting the acetic acid from the batch, by using other quantities of the reagents by substituting other solvents forthe acetic acid, or by using other well known condensing agents in place of hydrochloric acid, as for example, sulphuric acid, aluminum chloride, and a mixture of salt and sulphuric acid, and the like.
rThe' above process introduces economies in operation and results in relatively high yields.
The compound produced by the above condensation reaction may be designated as a hexahydroxy derivative of alkyl spiro-bis-indane, and more specifically, 3,3,3',3' tetramethyl, 4,6,7,4',6',7' hexahydroxy, 1,1 spiro-bis-indane.
The hexahydroxy derivatives of alkyl spiro-bisindane produced by reacting a poly hydroxy phenol or its alkyl other with a ketone, such as acetone or methyl ethyl ketone, are in general white or light-colored solids melting usually at high temperatures. acetone, and moderately soluble in alcohol and chloroform, and slightly soluble in gasoline and the like.
It is desired to point out that the tetramethyl The products are soluble in ease of oxidation in certain types of gasoline.
This is very important. The condensation of phenols with ketones having molecular weights greater than acetone, producesspiro-bis-lfidane compounds having larger or heavier alkyl groups than the methyl group, than would be present if the condensation had been effected with acetone. It has been found, in general, that the spiro-bis-indane compounds containing larger or heavier groups have increased solubility in organic materials, such as gasoline, and are less soluble in water, thus lessening the tendency of the spiro-bis-indane to be removed by water.
A tetra-alkyl hexahydroxy spiro-bis-indane compound produced by the above method, or by any other method, may be incorporated in a small amount in a liquid hydrocarbon and functions to inhibit discoloration and the formation of gummy and resinous products. It is particularly adapted to so function when added to motor fuels. It is sufiiciently soluble therein to be added directly, and may be incorporated in the motor fuel in amounts ranging from 0.0005 to .01 per cent based on the weight of the motor fuel. In practice, the amount of inhibitor present may be rated in terms of grams per gallon of motor fuel to be stabilized. This usually varies between 0.025 to 0.3 gm. per gallon of fuel treated. In one form of the invention the spiro-bis-indane may be dissolved in a solvent exemplified by acetone or alcohol, and said solvent containing the indane added to the motor fuel. For example, 1 part by weight, of the inhibitor may be dissolved in 3 parts, by weight, of acetone, or 10 parts, by weight, of alcohol. If the inhibitor is dissolved in acetone (3 parts by weight), then to a gallon of gasoline, there should be added from 0.1 gm. to
1.2 gms. of this mixture. If the inhibitor is dissolved in 10 parts of alcohol then 0.27 gm. to 3.3 gms, of the alcohol mixture should be added to a gallon of gasoline.
It '.is desired to point out that the herein disclosed tetra-alkyl hexahydroxy splro-bis-indane is only slightly soluble in water, and, therefore, its use is decidedly advantageous over those inhibitors which are'soluble to a large extent in water.
It is to be understood that the amount of tetraalkyl hexahydroxy spiro-bis-indane added to the motor fuel may be varied from that specified in the illustrative example above set forth. In practice, the amount of inhibiting agent which is added to the motor fuel, will depend upon many factors including the nature of the hydrocarbon fuel, the temperature thereof and the condition of storage It will be understood that in any case the compound is used in a comparatively small quantity, and when used in comparatively small amounts of the order of those above pointed out, it is substantially less than would deposit gum.
The 3,3,3',3' tetramethyl and 4,6,7,4',6,7' hexahydroxy, 1,1 spiro-bis indane, and the other spiro-bis-indanes herein referred to are exemplary of suitable tetraalkyl hexahydroxy compounds which may be used as a stabilizer for the motor fuel. Other alkyl radicals, saturated'or unsaturated, may be substituted for the methyl radical. 1
It is desired to point out that during the condensation process, it is possible to form several isomers. l
While it has been' found particularly desirable thatthe mixed aim l radicals be the methyl and ethyl radicala'othez' equivalent alkyl radicals may be introduced into the rings, said-alkyl radicals being saturated or unsaturated Motor fuels treated in accordance with the present invention not only test up well on the copper dish andinduction period tests, but st and storage successfully, without going off color 1mder drastic exposure to light and regardless of the presence of other chemicals, such as lead tetraethyl and organic dyes.
Transformer oil, which is used in the electrical industry, may be treated with the present stabilizer.
The present invention is applicable to the stabilization of'hydrocarbon fuels having an aromatic base or an aliphatic base.
The 3,3,3'.3 tetramethyl, 4,6,7,4',6',7 hexahydroxy 1,1' spiro-bis-indane may be represented structurally as follows:
0H, OH; OH 0 4 Ax 5 6 2 H1 H0 1 l/OH H CH;
Usually, only one of the hydroxy spiro-bis -in danes is added to the hydrocarbon, and in some cases it may be advantageous to employ mixtures of different hydroxy spiro-bis-indanes. Any of the alkyl hydroxy spiro indanes herein set forth may be mixed together and added to the hydrocarbon. More specifically, there may be added to the hydrocarbon a mixture of different alkyl hexahydroxy spiro-bis-indanes. Y For example, there may be added to the hydrocarbon a mixture of tetra-methyl hexahydroxy spiro-bisindane and tetramethyl ethyl hexahydroxy spirobis-indane.
I claim: v
1. A liquid hydrocarbon of a type normally tending to discolor and form gum during storage containing a small amount of a tetra alkyl hexahydroxy spiro-bis-indane.
2. A liquid hydrocarbon of a type normally tending to discolor and form gum during storage containing as astabilizing agent a small amount of a tetra alkyl hexahydroxy spiro-bis-indane.
3. A liquid hydrocarbon of a type normally tending to discolor and form gum during storage containing as a stabilizing agent a small amount of a tetramethyl hexahydroxy spiro-bis-indane.
4. Gasoline derived from the cracking of petroleum and containing as a stabilizing agent a small amount of t'etr'a alkyl hexahydroxy spirobis-indane.
5. Gasoline derived from the cracking of petroleum and containing as a stabilizing agent a small amount of tetramethyl hexahydroxy spiro-.
, 9. Gasoline derived from the cracking of petroleum and containing as a stabilizing agent 0.0005
to 0.01 per cent of a tetramethyl hexahydroxy spiro-bis-indane.
10. A liquid hydrocarbon of a type normally tending to discolor and form gum during storage containing as a stabilizing agent a small amount of 3,3-,3',3 tetramethyl, 4,6,'7,4',6','I hexahydroxy 1,1 spiro-bis-indane.
11. Gasoline derived from the cracking of petroleum containing a small amount of 3,3,3',3 tetramethyl, 4,6,'7,4',6',7 hexahydrox'y 1,1 spirobis-indane. 7
12. A new composition of matter comprising a hydrocarbon fuel of a type normally tending to discolor and form gum during storage and as a stabilizer, a small amount of a tetra alkyl hexahydroxy spiro-bis-indane. I
13. A new composition of matter comprising a hydrocarbon fuel of a type normally tending to discolor and form gum during storage and as a stabilizer, a small amount of a tetramethyl hexahydroxy spiro-bis-indane.
14. A new composition of matter comprising a hydrocarbonmotor fuel of a type normally tending to discolor and form gum during storage containing a small amount of 3,3,3,3 tetramethyl,
4,6,'7,4,6',7' hexahydroxy 1,1 spiro-bis-indane.
15. A new composition of matter comprising a hydrocarbon-motor fuel of a type normally tending to discolor and form gum during storage, andas a stabilizer 0.0005 to 0.01 per cent of 3,3,3',3' tetramethyl, 4,6,'1,4',6',7' hexahydroxy 1,1 spiro-bis-indane.
16. A mixed motor fuel of a type normally tending to discolor and. form gum during storage including gasoline and petroleum and containing as a stabilizer a small quantity of tetra alkyl hexahydroxy spiro-bis-indane.
17. The process of inhibiting discoloration and/or formation of gum in a motor fuel comprising adding to the motor fuel a small quantity of tetra alkyl hexahydroxy spiro-bis-indane.
18. The process of inhibiting discoloration and/or formation of gum in a motor fuel comprising adding to the motor fuel a small quantity of tetramethyl hexahydroxy spiro-bis-indane.
19. The process of inhibiting discoloration and/ or formation of gum in a motor fuel comprising adding to the motor fuel a small quantity of 3,3,3',3' tetramethyl, 4,6,7,4,6,'7' hexahydroxy, 1,1 spiro-bis-indane.
20. The process of inhibiting discoloration and/or formation of gum in a motor fuel comprising adding to the motor fuel a small quantity of alkyl hexahydroxy spiro-bis-indane.
21. A liquid hydrocarbon of a type normally tending to discolor and form gum during storage containing a small amount of alkyl hexahydroxy spiro-bis-indane.
22. The process of inhibiting discoloration and/or formation of gum in a motor fuel comprising adding to the motor fuel a small quantity of a mixture of alkyl hexahydroxy spiro-bis-indanes.
23. A liquid hydrocarbon of a type normally tending to discolor and form gum during storage containing a small amount of a mixture of alkyl hexahydroxy spiro-bisindanes.
CHARLES HAROLD FISHER.
Publications (1)
Publication Number | Publication Date |
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US2176883A true US2176883A (en) | 1939-10-24 |
Family
ID=3430750
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US2176883D Expired - Lifetime US2176883A (en) | Stabilization of hydrocarbon |
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US (1) | US2176883A (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2462609A (en) * | 1945-01-18 | 1949-02-22 | Pennsylvania Ind Chemical Corp | Indene resin stabilized with an alkyl polyhydroxy spiro indane |
US2462608A (en) * | 1945-01-18 | 1949-02-22 | Pennsylvania Ind Chemical Corp | Coumarone-indene resin stabilized with an alkyl polyhydroxy spiro indane |
US2801928A (en) * | 1953-11-25 | 1957-08-06 | Universal Oil Prod Co | Stabilization of fatty materials |
US2810651A (en) * | 1954-12-28 | 1957-10-22 | Universal Oil Prod Co | Stabilization of organic compounds |
US2818450A (en) * | 1956-10-04 | 1957-12-31 | Universal Oil Prod Co | Spirohydrindenes for resolution of hydrocarbon mixtures containing relatively straight chain aliphatic components |
-
0
- US US2176883D patent/US2176883A/en not_active Expired - Lifetime
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2462609A (en) * | 1945-01-18 | 1949-02-22 | Pennsylvania Ind Chemical Corp | Indene resin stabilized with an alkyl polyhydroxy spiro indane |
US2462608A (en) * | 1945-01-18 | 1949-02-22 | Pennsylvania Ind Chemical Corp | Coumarone-indene resin stabilized with an alkyl polyhydroxy spiro indane |
US2801928A (en) * | 1953-11-25 | 1957-08-06 | Universal Oil Prod Co | Stabilization of fatty materials |
US2810651A (en) * | 1954-12-28 | 1957-10-22 | Universal Oil Prod Co | Stabilization of organic compounds |
US2818450A (en) * | 1956-10-04 | 1957-12-31 | Universal Oil Prod Co | Spirohydrindenes for resolution of hydrocarbon mixtures containing relatively straight chain aliphatic components |
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