EP0452411A4 - Acid catalyzed process - Google Patents

Acid catalyzed process

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Publication number
EP0452411A4
EP0452411A4 EP19900902427 EP90902427A EP0452411A4 EP 0452411 A4 EP0452411 A4 EP 0452411A4 EP 19900902427 EP19900902427 EP 19900902427 EP 90902427 A EP90902427 A EP 90902427A EP 0452411 A4 EP0452411 A4 EP 0452411A4
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EP
European Patent Office
Prior art keywords
reactant
reaction product
catalyst
olefin
group
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.)
Ceased
Application number
EP19900902427
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English (en)
Other versions
EP0452411A1 (fr
Inventor
David L. King
Michael D. Cooper
Ken K. Ushiba
William A. Sanderson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Catalytica Inc
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Catalytica Inc
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Publication of EP0452411A1 publication Critical patent/EP0452411A1/fr
Publication of EP0452411A4 publication Critical patent/EP0452411A4/en
Ceased legal-status Critical Current

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    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
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    • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • C07C37/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by addition reactions, i.e. reactions involving at least one carbon-to-carbon unsaturated bond
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    • C07C407/00—Preparation of peroxy compounds
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    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
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    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • C07C45/455—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation with carboxylic acids or their derivatives
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    • C07C45/46—Friedel-Crafts reactions
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    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
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    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
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    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
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    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
    • C07C51/14—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on a carbon-to-carbon unsaturated bond in organic compounds
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
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    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/025—Sulfonic acids
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    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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    • C07C2531/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • C07C2531/08—Ion-exchange resins
    • C07C2531/10—Ion-exchange resins sulfonated
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    • C07C2531/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24
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    • C07C2531/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24
    • C07C2531/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24 of titanium, zirconium or hafnium
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • This invention relates to an improved process for the acid-catalyzed conversion of a reactant into a reaction product.
  • Reactants which may be converted into reaction products in the process of this invention include hydrocarbons and heteroatom-substituted hydrocarbons, wherein said heteroatoms may be selected from the group consisting of nitrogen, oxygen, sulfur, phosphorus and halogen atoms.
  • olefins may be isomerized, polymerized or oligomerized; olefins may be reacted with aromatics or tertiary al anes to provide alkylated products; olefins may be reacted with carboxylic acids to obtain esters; olefins may be reacted with a peroxy acid to obtain an epoxide; alcohols may be dehydrated to obtain olefins or ethers or reacted with an aromatic compound or a carboxylic acid to obtain an alkylated product or an ester, respectively; anhydrides may be reacted with an aromatic or an olefinic compound to obtain acetylated derivatives thereof; epoxides may be reacted to the corresponding glycols; aromatic compounds may be nitrated to provide nitro aromatics, etc.
  • the acidic catalyst may be used in a homogeneous or heterogeneous mode, i.e. the catalyst can be dissolved in the reactant-containing solution or the catalyst may exist in a different phase than the reactant and/or the reaction products.
  • Homogeneous acid catalysts may have certain advantages over heterogeneous acid catalysts, such as increased activity or selectivity, provided separation of the reaction products from the catalyst is easily carried out. Since such separation may be difficult, many times a heterogeneous acid catalyst is preferred, even when the activity or selectivity is less than a homogeneous catalyst in the same reaction.
  • One widely used class of heterogeneous acid catalyst is the solid polystyrene sulfonic acids.
  • the present invention provides a process for the conversion of a reactant into a reaction product in the presence of an acid catalyst which comprises contacting said reactant with an acid catalyst comprising a compound comprising one or more fluorine atoms, sulfo radicals and phosphono radicals, each such radical being bonded to the same or different carbon atom, with the proviso that at least one sulfo radical and at least one phosphono radical are bonded to such carbon atoms through the sulfur atom and the phosphorus atom, respectively.
  • These compounds are preferably non-polymeric, i.e. they have a molecular weight of about 5000 or less.
  • These acid catalysts may be represented by compounds selected from the group of compounds represented by the general formula:
  • R is an organo radical having at least one covalent carbon-fluorine bond
  • R 1 is hydrogen
  • R 2 is a hydrocarbyl radical, having up to 20 carbon atoms, e.g. a lower alkyl radical or is hydrogen
  • r is 2 or 3, preferably 3
  • y is an integer of from 1 to 3
  • x is an integer of from 1 to 3, with the proviso that the phosphorus and the sulfur are covalently bonded to a carbon atom.
  • the above fluorinated phosphonsulfonic acids may be reacted with a tetravalent metal ion according to the procedures described in U.S. Patents 4,232,146; 4,235,990; 4,235,991; 4,256,872; 4,267,308; 4,276,409; 4,276,410; 4,276,411; 4,298,723; 4,299,943; 4,373,079; 4,384,981; 4,386,013; 4,390,690; 4,429,111; and 4,435,899, which are hereby incorporated by reference, to provide a solid acid catalyst having pendant sulfonic acid groups.
  • the phosphonic acid derivative i.e. R 2 is hydrogen
  • a tetravalent metal ion is reacted with a tetravalent metal ion to yield a solid compound represented by the general formula:
  • M[(0) 2 P(0)] y R(SO r R 1 ) x ] d wherein M is the tetravalent metal and d is 2/3, 1 or 2, as y varies from 3 to 2 to 1, respectively.
  • the acid catalyst may be prepared by the sulfonation of the reaction product of a tetravalent metal ion and ((R 2 0) 2 P(0)yR7' wherein R 2 and y are as defined above, and R 7 is an organo radical having at least one covalent carbon-fluorine bond and at least one sulfonatable group, e.g.. an aryl or olefin group.
  • the acid catalyst may be prepared by sequential impregnation of the tetravalent metal ion and ((HO) 2 P(0))yR(SO r R 1 ) x onto a suitable support, e.g. a refractory inorganic oxide such as silica, and reacting the impregnated support to yield a supported M[(0) 2 P(0)] y R(SO r R 1 ) x ] d .
  • a suitable support e.g. a refractory inorganic oxide such as silica
  • the above fluorinated phosphono sulfonic acids may be prepared by reacting a first reactant represented by the general formula (R 4 0) 3 P with a second reactant represented by the general formula R 3 X Z to yield a first reaction product represented by the general formula
  • R 4 may be a lower alkyl radical having up to six carbon atoms, e.g. methyl, ethyl, n- propyl or i-propyl, and preferably i-propyl or ethyl;
  • R 3 is an organo radical having at least one covalent fluorine bond;
  • X is bromine or iodine and
  • z is an integer of 2 or 3.
  • the first reaction product may be synthesized in high yield merely by combining the first and second reactant in a sealed vessel at a temperature of from -50°C to 200°C, e.g. from 0 to 120°C, i.e. conveniently from 0°C to about 25°C.
  • Reaction time may vary from 1 to 100 hours, e.g. 48 hours. Of course, increasing the reaction temperature can lower the reaction time to 2 to 10 hours, e.g. about 3 hours.
  • the reaction can be carried out neat or in the presence of an inert solvent.
  • an ether solvent may be used.
  • diethylether is useful as a solvent for this reaction.
  • the first reaction product is recovered by methods known in the art, e.g. distillation at a reduced pressure.
  • the first reaction product may be reacted with (R 5 ) 2 S 2 0 4 , wherein R 5 is an alkali metal ion, e.g. a sodium ion, to yield a second reaction product represented by the general formula
  • reaction is conveniently carried out by combining the first reaction product and the above dithionite in a basic aqueous solution comprising, as a cosolvent, acetonitrile or the like.
  • the reaction may be effected at an elevated temperature of from 50 to 100°C, e.g. about 80°C, and a reaction time of from 1 to 20 hours, e.g. 2 to 12 hours.
  • the second reaction product may be recovered by evaporation of the excess solvent and purified by extraction with acetonitrile or a like solvent.
  • Suitable fluorinated organo radicals (R 3 ) for the above reaction scheme include alkylene radicals, both cyclic and acyclic radicals, which may be interrupted with hetero atoms such as nitrogen, oxygen and sulfur, alkenylene radicals, both cyclic and acyclic, which may also be interrupted with heteroatoms such as nitrogen, oxygen and sulfur, and arylene radicals, including heteroaryl, e.g. nitrogen, sulfur and oxygen-containing heteroarylene radicals, mono and poly arylene radicals, e.g. condensed arylene radicals having from 2 to 5 aryl rings, biphenyl, etc.
  • the above fluorinated organo radicals may comprise from one to about 100 carbon atoms, e.g.
  • radicals will comprise one or more covalently • bonded fluorine and may be perfluorinated, i.e. all of the carbon bonds, other than the sulfur or phosphorus bonds, may be filled by fluorine radicals.
  • the above fluorinated organo radicals may also be substituted with inert substituents such as halo, nitro, amino, oxy, hydroxy, carboxy, thio, etc.
  • the fluorinated organo radicals will be either halo substituted or unsubstituted, i.e. all the carbon bonds other than the bonds to the fluoro, sulfo or phosphono radicals, as required by the above general formula, will be filled by hydrogen radicals or halo radicals (other than fluoro radicals) .
  • fluorinated organo radicals are chloro or bromo-substituted or unsubstituted alkylene radicals having from 1 to 6 carbon atoms and chloro or bromo-substituted or unsubstituted arylene radicals having from 6 to 10 carbon atoms.
  • alkyleneoxyalkylene radicals wherein the alkylene moieties comprise from 2 to 4 carbon atoms.
  • lower alkylene radicals including alkyleneoxyalkylene radicals such as methylene, ethylene, propylene, butylene, methyleneoxymethylene, ethyleneoxyethylene, butyleneoxyethylene radicals, etc.
  • R-* may be CF , — CF, CHF, CFBr, - CF 2 ) 4 0(CF 27 - 2 , etc. f /
  • the second reaction product may be oxidized to yield a third reaction product having the general formula
  • H 0 2 or similar oxidizing agent may be provided in molar excess directly to the second reaction product or to an aqueous solution thereof.
  • a sufficient amount of a 30% aqueous H 2 0 2 solution may be combined with the second reaction product to provide an aqueous solution, H 2 0 2 comprising from 1.1 to 5 moles of per mole of the second reaction product, at a temperature of from 0° to 25°C and such aqueous solution allowed to react for 1 to 10 hours, e.g. about 4 to 5 hours.
  • the third reaction product is conveniently recovered by evaporation of the excess solvent.
  • (R 4 0) 2 P ( O) CFBr (S0 3 R 5 ) may be reduced to (R 4 0) 2 P(0)CHF(S0 3 R 5 ) by a reducing agent, for example metallic zinc, in a suitable inert solvent, for example tetrahydrofuran.
  • a reducing agent for example metallic zinc
  • a suitable inert solvent for example tetrahydrofuran.
  • Such reduction may be effected at an elevated temperature, e.g. about 60°C and a ratio of Zn to the bromo product of about 1 to about 2, e.g. about 1.1 and the reduced product recovered by extraction with water.
  • the third reaction product may be reacted, e.g. hydrolyzed, to yield the corresponding phosphonic acid.
  • the third reaction product may be hydrolyzed in an aqueous solution of a strong acid, e.g. concentrated hydrochloric acid, wherein said hydrolysis is effected at an elevated temperature, e.g. at reflux, in the presence of excess strong acid, e.g. from about 1.1 to 10 moles, i.e. 3 moles of strong acid per equivalent of R 4 .
  • a strong acid e.g. concentrated hydrochloric acid
  • excess strong acid e.g. from about 1.1 to 10 moles, i.e. 3 moles of strong acid per equivalent of R 4 .
  • the hydrolysis product or the fourth reaction product may be recovered by evaporation of excess solvent.
  • the fourth reaction product may be further reacted to exchange hydrogen ions for R 5 .
  • the fourth reaction product may be passed through an ion exchange column, e.g. a strong acid such as an acidified sulfonated polystyrene resin such as Amberlite 1R-120 to exchange hydrogen ions for the alkali ions.
  • a strong acid such as an acidified sulfonated polystyrene resin such as Amberlite 1R-120 to exchange hydrogen ions for the alkali ions.
  • sulfate ion contamination may be removed by reacting an aqueous solution thereof with an excess of barium ions to precipitate barium sulfate.
  • the filtrate, comprising the acid-exchanged reaction product and sodium and barium ions is then passed through the acid form of an ion exchange column, to remove such ions and a purified solution of such acid-exchanged reaction product is recovered.
  • phosphate contaminants can also be removed as an insoluble product.
  • the acid-exchanged reaction product may be converted to the corresponding phosphonylsulfonyl chloride by reaction with sufficient PCI5 to yield such phosphonylsulfonyl chloride which can be recovered by distillation.
  • Any or all of the sulfonic acid and phosphonic acid moieties of the acid-exchanged reaction product may be converted into the corresponding acid chloride by reaction with an amount of PC1 5 equivalent to from 1 to all of the acid moieties in the acid-exchanged reaction product.
  • reaction scheme utilizes a monophosphono reactant.
  • Compounds within the scope of the present invention, wherein polyphosphono functionality are desired, e.g. wherein y is 2 or 3, may be prepared by reacting supra molar amounts of (R 4 0) 3 P with R 3 X 2 wherein z is from 3 to 6 and proceeding according to the above illustrative reaction scheme.
  • An alternate method for making certain of the fluorinated phosphonosulfo compounds of the present invention comprises reacting a first reactant having the general formula
  • the first reactant may be prepared by reacting
  • CF 2 CF 2 in the presence of KF and IC1
  • the second reaction product may be treated as described above to yield the corresponding third and fourth reaction product, as well as the hydrogen ion- exchanged reaction product.
  • CF 2 may be any other fluorinated organo radical disclosed herein. That is, CF 2 may be R as defined above.
  • This reaction is effected in water or aqueous ethanol at reflux and provides a third reaction product which can be subsequently treated as described above.
  • This invention provides an improved process for converting reactants, especially organic reactants, to reaction products in the presence of an acid catalyst.
  • the improvement in said process is found in the choice of compounds which function as the acid catalyst and are defined below.
  • these compounds increase the rate of reaction, as compared to other well known acid catalysts, e.g. polystyrene sulfonic acids, (which comprises sulfonic acid groups pendant from a polystyrene polymer backbone) and are more stable with time and temperature, as compared to said polystyrene sulfonic acid catalysts.
  • the reactants utilized in the process of this invention are hydrocarbons or hydrocarbons substituted with heteroatoms such as nitrogen, oxygen, sulfur, phosphorus and halogen atoms, and especially oxygen atoms.
  • olefins may be isomerized or oligomerized or polymerized in one embodiment of the process of this invention. (Isomerization of olefins will include skeletal isomerization as well as migration of the double bond.)
  • mono olefins having from four to ten carbon atoms may be isomerized or oligomerized or polymerized to reaction products in accordance with the present invention.
  • a mixture of nonenes comprising predominantly 1-n-nonene is reacted to nonene dimer by heating at 130°C. for two hours in the presence of an acid catalyst comprising the acid catalysts disclosed herein.
  • Propylene is heated for 1 hour, or more, at a temperature of from 50 to 175°C. and a pressure of from 1 to 50 atmospheres, in the presence of any of the acid catalysts disclosed herein, to yield a mixture including as the predominant fraction monoolefins having from nine to twelve carbon atoms and useful as a polymer gasoline.
  • the olefin is contacted with the acid catalyst, described herein, in the presence of another reactant to yield reaction products of said olefin and said other reactant.
  • said second reactant may include a hydroxyl group to yield an ether or an alcohol.
  • alkanols having from one to four carbon atoms may be reacted with olefins having from two to seven carbon atoms in the presence of the acid catalysts described below to yield ethers.
  • Particularly preferred is the reaction of ethanol and isobutylene, isoamylene or propylene to yield methyl- tertiary butyl ether, methyl-tertiary amyl ether or methyl isopropyl ether, respectively.
  • Such reactions may take place at a temperature of from 15 to 100°C. and a pressure of from 1 to 10 atmospheres.
  • Olefins may also be contacted with a carboxylic acid in the process of this invention to yield esters.
  • straight chain olefins having from two to ten carbon atoms, isobutylene or cyclohexene may be reacted in the presence of carboxylic acids having from one to eight carbon atoms at a temperature within the range of 0°C. to 100°C. to yield the corresponding esters as the reaction product.
  • U.S. Patent 3,037,052 to Bortnick gives the details on this general reaction and is hereby incorporated by reference to show specific reactants and reaction conditions.
  • Particularly preferred reactions include the reaction of monoolefins having from one to eight carbon atoms, more preferably from two to four carbon atoms, with methacrylic acid, acrylic acid, acetic acid or phthalic acid to obtain the corresponding esters.
  • esters of acrylic acid and methacrylic acid are useful monomers for the preparation of acrylic plastics and rubbers.
  • the acetate esters are useful as solvents.
  • the phthalic esters are useful as plasticizers.
  • the olefin may also be reacted in the presence of an aromatic compound to provide alkylated aromatics.
  • an aromatic compound for example, propylene may be reacted with benzene to provide cumene.
  • 1-n-olefins having from six to twelve carbon atoms, may be reacted with phenol to provide alkylated phenols which may be subsequently reacted with ethylene oxide to provide nonionic surfactants such as nonophenylethyleneoxide adducts.
  • isoparaffins such as with tertiary alkanes, e.g. 1-n-butene and isobutane, to yield isoctane may be carried out in the present process.
  • the olefin may be carbonylated by reaction with carbon monoxide using known Koch chemistry.
  • olefins may be reacted in the presence of a peroxy acid compound to obtain an epoxide.
  • ethylene and propylene may be converted to ethylene oxide and propylene oxide, respectively.
  • Unsaturated oils and esters, such as soybean oil, oleic acid esters, tall oil esters may be epoxidized, similarly, in the presence of hydrogen peroxide.
  • Aromatics having from 6 carbon atoms to about 14 to about may be alkylated by alkylhalides, alcohols, ethers or esters of up to about 10 carbon atoms, e.g. from one to four carbon atoms, byuse of the acid catalysts disclosed herein. Similarly, such aromatics maybe acylated or transalkylated.
  • Alcohols having from one to eight carbon atoms, more preferably from one to four carbon atoms, are reacted, in the presence of the acid catalyst described below, to yield either ethers or olefins (by dehydration) .
  • ethers or olefins by dehydration
  • methanol or ethanol may be reacted at a temperature of from 25 to 150°C. and a pressure of from 1 to 20 At os. to yield dimethyl ether or diethylether, respectively.
  • Tertiary butanol may be dehydrated to isobutene at a temperature of from 50 to 175°C.
  • butanediol may be dehydrated to tetahydrofuran.
  • alcohols may be reacted in the presence of a second reactant to provide reaction products of said alcohol and said second reactant.
  • said second reactant may comprise a carboxylic acid group or an aromatic group to yield an ester or an alkylated aromatic, respectively.
  • anhydride Another reactant that may be used in the process of the present invention is an anhydride.
  • anhydrides such as acetic anhydride
  • acetic anhydride may be reacted with a compound having an aromatic group or an olefinic group to yield acetylated aromatics or acetylated olefins, respectively.
  • acetic anhydride may be reacted with anisole to provide p-methoxyacetophenone or with diisobutylene to provide 2,2-methyl, 6-oxo-hept-4- ene.
  • These reactions can be carried out at a temperature of from 25 to 125°C. and a pressure of from 1 to- 30 At os.
  • Aldehydes orketones may be condensed to provide the respective condensed products by means of the process of the present invention.
  • 2-ethylhexenal may be prepared by condensing two molecules of n-butyraldehyde at a temperature of from 20 to 70°C. and a pressure of from 1 to 10 Atmos.
  • methylisobutylketone may be condensed to 1-methyl, 4-methyl, 6-oxo, 9-methylnon-4-ene.
  • aldehydes and ketones, having from one to ten carbon atoms may be condensed to provide dimers thereof in the process of the present invention.
  • aldehydes and ketones may be reacted in the presence of an aromatic compound to obtain the resulting reaction products.
  • acetone may be reacted with phenol to yield bisphenol A and formaldehyde may be reacted with aniline to yield diaminodiphenylmethane.
  • Peroxides or hydroperoxides may be decomposed to the corresponding decomposition products by the process of this invention.
  • cumene hydroperoxide may be decomposed to acetone and phenol at low temperatures as compared to the non-acid catalyzed decomposition.
  • the acid catalysts of this invention are not heat sensitive.
  • Glycols may be prepared by utilizing an epoxide as the reactant in the process of the present invention.
  • ethylene oxide and propylene oxide may be converted to ethylene glycol and propylene glycol, respectively.
  • Esters may be converted, efficiently, to carboxylic acid and alcohol in the present inventive process.
  • sucrose may be hydrolyzed to fructose and glucose.
  • the present process may also be utilized to provide nitroaromatics by utilizing as a reactant a mixture of an aromatic compound, e.g. benzene or toluene, and nitric acid.
  • an aromatic compound e.g. benzene or toluene
  • nitric acid e.g. benzene or toluene
  • the reaction conditions for these reactions are well known in the art.
  • Example 1(e) containing sulfate ions, was dissolved in water and an aqueous BaCl 2 solution was added thereto with stirring, until an excess was present, i.e. until additions caused no further precipitation of BaS0 4 . After centrifugation, a supernatant was decanted, concentrated, and passed through a 4.5cm by 50 cm packed column of DOWEX M-31 (Dow Chemical Company) , a styrenesulfonic acid resin, to recover an eluate containing no detectable sulfate.
  • DOWEX M-31 DOWEX M-31
  • Ba(OH) 2 may be used in place of BaCl 2 to obtain a similarly purified solution. Moreover, if the pH of said purification was adjusted to 11 or greater, by addition of Ba(OH) 2 , the inorganic phosphate ion was reduced to a level undetectable by 31 P NMR.
  • Fumed silica having a BET surface area of 200 M 2 /gm was impregnated with an aqueous solution of ZrOCl 2 .8H 2 0, using the incipient wetness technique, and the resulting composite was dried for 12 hours at 110°C.
  • the dried composite was impregnated with an aqueous solution of (HO) 2 P(0)CF 2 S0 3 H.H 2 0 using the incipient wetness technique and the resulting composite was dried for 12 hours at 110 o C. 49.92 gms. of the supported acid catalyst having a BET surface area of 143.99 M 2 /gm and a pore volume of 99 cc/gm. was obtained.
  • Example 7(a) The procedure of Example 7(a) was repeated except that the first drying step was carried out at 80°C to yield 47.81 gms. of supported acid catalyst having a BET surface area of 173.38 M 2 /gm and a pore volume of 1.08 cc/gm.
  • This acid catalyst may be represented by the general formula:
  • the reactor effluent was weathered to remove C 4 *s and the C 5 + product was analyzed by GLC.
  • a total of 1.2 g of product were collected, and was analyzed to contain 58.3% C 8 olefin, 33.2% Cg+ (predominantly C ⁇ 2 ) , with the remainder mostly C 8 saturate.
  • the catalyst can be seen as an effective olefin oligomerization catalyst at the 80 o C. temperature, with a productivity 0.09 g product per gram catalyst-hour.
  • a catalyst was prepared by incipient wetness impregnation of an aqueous alcoholic solution of Nafion, equivalent weight 1000, depositing on Si0 2 to a weight loading of 12.8 wt %.
  • the catalyst was vacuum dried at 100°C. overnight and stored in a bottle under N 2 .
  • 2.29 g catalyst (5.0 ml) was loaded into the reactor and dry nitrogen was passed over the catalyst at ambient temperature for 12 hours.
  • Liquid isobutane was fed over the catalyst and the temperature raised to 60°C. Upon reaching temperture, the feed was changed to (wt %) isobutane, 92.2; butene-1, 5.5; isobutene, 1.6; n-heptane, 0.75.
  • a reaction product after removal of C 4 components, consisted of 0.68 g C 5 + (productivity 0.03 g/g catalyst-h) which comprised the following: 57.1 wt % C 8 olefin, 36.4 wt % C 12 olefin, and 6.2 wt % C 8 saturate.
  • the catalytic behavior is similar to that of the catalysts described in Examples 8 and 9, but the catalyst productivity is clearly lower with Nafion compared with the catalysts derived from the sulfodifluoromethylphosphonic acid.
  • a catalyst comprising 23.0 wt % zirconium sulfodifluoromethylphosphonate on a fumed silica support was prepared by sequential impregnation by incipient wetness of a solution of sulfodifluoromethylphosphonic acid followed by drying and then impregnation of zirconium oxychloride. (The procedure was similar to the procedure of Example 7(a) except for the reversal of the impregnation steps.) 2.08 g (5.3 ml) of catalyst was loaded into the fixed bed reactor and the catalyst was predried by passing dry N over the catalyst for 0.5 hour at 100°C.
  • the catalyst was cooled to ambient, a liquid isobutane feed was added to thecatalyst, and the catalyst was heated to 140°C. while maintaining a liquid phase at 610 psig.
  • The- feed was then switched to one comprising by weight %: isobutane, 93.1; trans-2-butene, 4.2; isobutene, 1.4; n-heptane, 1.4.
  • the reaction proceeded for 1.75 hours, during which time 1.75 g of a liquid product free of C 4 was collected (productivity, 0.19 g/g cat-hr) .
  • the liquid product had the following distribution, in wt./ %: C 8 saturates, 28.1; C 8 olefins, 31.0; C ⁇ 2 olefin, 35.1. Trimethylpentanes, indicative of alkylation activity, comprised 34.9% of the total C 8 saturates and 9.8 wt. % of the total product.
  • Example 9 The same catalyst and loading as was described in Example 9 was again employed, comprising 8.4 wt % of sulfodifluoromethylphosponic acid on a fumed silica support. After predrying thecatalyst at 100°C. in flowing N 2 for 1 hour, liquid isobutane was introduced to the catalyst and the temperature was raised to 130°C. The feed was then switched to one comprising the following in wt %: isobutane, 93.5; trans-2-butene, 3.7; isobutene, 1.8; n-heptane, 1.0. The reaction proceeded for 4.85 hours, during which time 1.6 g of C 4 -free product was collected (productivity 0.19 g/g cat-h) .
  • the product was analyzed as follows in wt %: C 8 saturates, 14.8; C 8 olefins, 26.6; C ⁇ 2 olefins, 51.0. Of the C saturates, 62.7 wt % were trimethyl pentanes.
  • the data shows that the catalyst prepared from sulfodifluoromethylphosphonic acid has sufficient acidity to catalyze alkylation of isobutane provided that the reaction temperature is sufficiently high.

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Abstract

L'invention concerne un procédé de conversion d'un réactif en un produit de réaction en présence d'un catalyseur acide solide comprenant un ou plusieurs atomes de fluor, des radicaux sulfo et des radicaux phosphono, chacun desdits radicaux étant lié au même atome de carbone ou à un atome de carbone différent, à condition qu'au moins un radical sulfo et au moins un radical phosphono soient liés auxdits atomes de carbone par l'atome de soufre et l'atome de phosphono respectivement. Ces composés sont de préférence non polymères, c'est-à-dire qu'ils ont une masse moléculaire d'environ 5000 au moins. On peut faire réagir les catalyseurs acides précités avec un métal tétravalent, par exemple Zr, afin de produire un catalyseur acide solide.
EP19900902427 1989-01-03 1990-01-03 Acid catalyzed process Ceased EP0452411A4 (en)

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US5241112A (en) * 1991-04-09 1993-08-31 Catalytica, Inc. Preparation of trialkylacetic acids, particularly of pivalic acid, using solid acid catalysis
US5731299A (en) * 1992-05-29 1998-03-24 The Procter & Gamble Company Phosphonosulfonate compounds, pharmaceutical compositions, and methods for treating abnormal calcium and phosphate metabolism
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US3249633A (en) * 1958-07-23 1966-05-03 Union Carbide Corp Acrylic acid ester synthesis
US4080391A (en) * 1971-08-26 1978-03-21 Mitsui Toatsu Chemicals Process for the production of alcohols
US4533651A (en) * 1982-02-17 1985-08-06 Commonwealth Scientific And Industrial Research Organization Catalysts for olefin oligomerization and isomerization

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Title
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 111, 1989, pages 1773-1776, American Chemical Society, Easton, US; D.J. BURTON et al.: "Synthesis of (Sulfodifluoromethyl)phosphonic acid" *
See also references of WO9007480A1 *

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