US3703473A - Sequestering agents for metal ion contamination of alkyl-aromatic hydrocarbons - Google Patents
Sequestering agents for metal ion contamination of alkyl-aromatic hydrocarbons Download PDFInfo
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- US3703473A US3703473A US64619A US3703473DA US3703473A US 3703473 A US3703473 A US 3703473A US 64619 A US64619 A US 64619A US 3703473D A US3703473D A US 3703473DA US 3703473 A US3703473 A US 3703473A
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- xylene
- halogenation
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- phosphorous
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/152—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by forming adducts or complexes
Definitions
- This invention relates to a combination of sequestering agents for metal-ion-contaminated, alkyl-aromatic hydrocarbons, and additionally relates to a process for sequestering such contamination and to compositions resulting therefrom.
- the present invention is directed to a sequestering agent for metal ion contaminants contained in an alkyl-aromatic hydrocarbon, which sequestering agent comprises a mixture of phosphorous halide with organic phosphate, i.e., aryl phosphate, alkyl phosphate, or their mixtures, where the halogen in the phosphorous halide has atomic weight between about 35-80.
- sequestering agent comprises a mixture of phosphorous halide with organic phosphate, i.e., aryl phosphate, alkyl phosphate, or their mixtures, where the halogen in the phosphorous halide has atomic weight between about 35-80.
- One aspect of the invention is a composition
- a composition comprising a metal-ion-contaminated, alkyharomatic hydrocarbon, a phosphorous halide, and an organic phosphate, where the hydrocarbon contains a sequestering amount of the phosphorous halide plus organic phosphate.
- Another aspect of this invention is the method of sequestering metal ion contamination in an alkyl-aromatic hydrocarbon which comprises mixing such hydrocarbon with a sequestering amount of an organic phosphate and phosphorous halide.
- a still further aspect of the invention is directed to a method of halogenating alkyl-aromatic hydrocarbon contaminated with metal ions, which method comprises chemically reacting, under catalytic influence, the hydrocarbon with chlorine or bromine in the presence of phosphorous halide and an organic phosphate.
- the suppression of side chain cleavage of alkyl groups from the aromatic nucleus is usually referred to hereinafter as the suppression of either chlorinolysis, for such cleavage during chlorination, or of brominolysis, for cleavage during bromination.
- the halogen of the phosphorous halide as Well as the halogen for reaction with the alkyl-aromatic hydrocarbon, has atomic weight between about 35-80, i.e., chlorine and/ or bromine.
- the term halogen in the specification is employed for convenience to refer to chlorine and/or bromine, and the term halogenation to conveniently refer to reacting chlorine and/or bromine.
- phosphorous halide sequestering agent is meant to include phosphorous trichloride, phosphorous pentachloride, phosphorous bromide, phosphorous pentabromide, and their mixtures.
- these agents are preferably used in their commercially available, essentially anhydrous form since addition with solvents such as water can retard the initiation of halogenation.
- Phosphorous trichloride is the preferred phosphorous halide for economy as well as efiiciency.
- Organic phosphate as emyployed in the specification and claims is intended to refer broadly to compounds of the structure:
- R R and R are selected from the group conchlorophenyl, 2bromophenyl, and Z-chloronaphthyl radicals, hydroxyalkyl radicals, e.g., 2 hydroxyethyl, dihydroxypropyl, and trihydroxyoctyl radicals.
- An aryl phosphate is intended to refer broadly to the structure set forth above wherein at least two of the R groups are aryl, hydroxyaryl, haloaryl, or their mixtures.
- an alkyl phosphate is intended to refer broadly to the above structure wherein at least two of the R groups are alkyl, hydroxyalkyl, or their mixtures.
- alkyl-aromatic hydrocarbon is meant to include hydrocarbons having an aromatic ring which contains one or more methyl, ethyl, propyl, isopropyl, vinyl, propenyl, chloroor bromomethyl, chloroor bromoethyl, or like radical, also referred to herein as side chains; generally such side chains are lower alkyl, i.e., have 8 carbon atoms or less.
- the hydrocarbons can, in addition to having partial side chain halogenation, have partial to complete ring halogenation (needing suppression of further ring halogenation and/or side chain cleavage) such as a,m'-2-trichloro-p-xylene and a,ot'2,4,5,6 hexachloro-m-xylene.
- alkyl-aromatic hydrocarbons are: ortho-, meta-, and para-xylene, toluene, durene, rnesitylene, e'thylbenzene, diethylbenzene, triethylbenzene, diiso propylbenzene, and cymene.
- all of these substances are also referred to herein simply as hydrocarbons or as hydrocarbon compounds.
- xylene is used herein for convenience to refer to any of the three structurally different types of xylene as well as to any mixture of two or more of such types.
- alkyl-arotnatic hydrocarbons are those which are halogen-free, or have partial halogenation but are capable of further side chain halogenation.
- This latter group consists of compounds possessing some side chain halogenation, with partial (or without any) ring halogenation, compounds that are partly ring halogenated but are free from side chain halogenation, for example 4,6-dibromo-rn-xylene, and compounds which are exhaustively ring halogenated.
- These latter compounds can have some side chain halogenation, e.g., a 2,3,5,6-heptachloro-pxylene.
- those which are halogen free, and those which have some side chain halogenation but no ring halogens such as a,a-dichloro-p-xylene generally become contaminated by contact with dust, dirt, or metallic containers or feed lines and accumulate minute amounts of metal ion contamination, i.e., typically between about 0.125 ppm. or more of contaminants, but usually less than about 0.01 weight percent.
- the partly ring halogenated materials having some, or having no side chain halogens are usually prepared in the presence of contamination to catalyze ring halogenation. However, such a reaction usually yields a mixture, and upon separation of one or more reaction products from the mixture these products become substantially isolated from the catalyst.
- a sufficient amount of phosphorous halide plus organic phosphate is used to prepare a composition containing from about 0.01 to about 5 weight percent of phosphorous, based on the weight of the hydrocarbon.
- sequestered compositions should usually have enough of the sequestering agents for the composition to contain at least about 0.01 weight percent of phosphorous; generally, it is uneconomical to prepare compositions having sequestering agents in such amounts that the composition contains more than about 5 weight percent of phosphorous.
- halogen-free material such as rn-xylene, and those having some side chain halogenation but no ring halogens, both of which usually have less than about 0.01 weight percent contamination
- ring halogenated compounds often contain about 5 weight percent or more of contaminants, only side chain cleavage is the deleterious reaction to be suppressed.
- these compounds like halogen-free materials, advantageously contain, for economy, a combination of sequestering agents such that from about 0.01 to about 3 Weight percent of phosphorous is present in the compound.
- Partly ring halogenated substances possessing little or no side chain halogenation and which, through separation from a reaction mixture, typically have less than about 0.1 weight percent of contamination, are advantageously admixed, for economy, with a combination of sequestering agents so that from about 0.01 to about 4 weight percent of phosphorous is contained in such substances.
- sequestering agents so that from about 0.01 to about 4 weight percent of phosphorous is contained in such substances.
- those substances wherein up to about 5 weight percent of phosphorous is contained therein are most often the unpurified mixtures of partially ring halogenated hydrocarbons.
- the sequestering agents are employed to provide a molar proportion of phosphorous halide to organic phosphate between about 10:1 and about 1:10.
- a combination of sequestering agents having a molar proportion of phosphorous halide organic phosphate of greater than about 10:1 usually will not provide sufiicient organic phosphate to obtain enhanced suppression of ring halogenation, compared to the use of phosphorous halide alone.
- a combination of sequestering agents containing a molar proportion of phosphorous halide to organic phosphate of less than about 1:10 can be uneconomical.
- the sequestering agents are used to provide a molar proportion of phosphorous halide to organic phosphate of between about 5:1 to about 2:1.
- Halogenation of these hydrocarbon compounds is typically carried out in a steel reactor or one formed from iron or other conventional material, and these are lined, e.g., with a glass liner, to prevent any contaminating contact between the metal reactor and the reaction medium.
- the reactor is equipped, typically, with agitation means, halogen inlet means, hydrocarbon inlet, temperature control means, and product outlet. If desired, several reactors can be sequentially arranged particularly in the prep aration of hydrocarbons containing more than one halogen per side chain, with essentially only the first halogen being chemically reacted with each side chain in the initial reactor.
- a liquid reaction medium free from solid portions of alkyl-aromatic hydrocarbon is advantageous to promote the rate of halogenation
- reactions are usually carried out at a temperature above the melting point of the hydrocarbon at the pressure of the reaction.
- a liquid dispersant can be used in sufficient amount to prepare a liquid reaction medium, and the solid hydrocarbon dispersed therein.
- the halogenation generally is carried out at temperatures within the range from about 10 to about 350 C. Although halogenation can be exothermic, reaction temperatures are generally maintained above about 10 C. to promote reaction rates, and advantageously to further enhance reaction rates are maintained above about 40 C. For economy, halogenation temperatures are advantageously not in excess of about 350 C.
- Low halogenation temperatures i.e., about 10 to about C.
- This initial use of low temperatures retards deleterious side reactiions, e.g., condensation of xylene forming diphenylmethane derivatives, although initial temperatures as high as about C. can be employed when halogenating xylene, without uneconomical formation of side reaction products, when continuous, careful control is exercised over reactant feed rates and the reaction temperature.
- reaction temperatures can be increased to promote the rate of halogenation without enhancing the rate of side reactions.
- reaction temperature can be elevated to between about 170-250 C.
- elevated temperatures e.g., above about 150 C., can nevertheless be employed at the'outset without'promoting deleterious condensation side reactions.
- a',2,4,5,6h6Xachloro-m-xylene can be efiectively chlorinated to a,a,a',a', 2,4,5,6 octachloro-m-xylene at a temperature between about 215-235 C. with concomitant suppression of chlorinolysis.
- reactors can be used for sequential chlorination from the initial p-xylene.
- Such reactors can be separately main tained at different temperatures, i.e., a low temperature reactor can be used for initial chlorination of p-xylene with about 0.5-3 moles of chlorine to thus prepare a substantial amount of a,a-dichloro-p-xylene, and so on.
- gaseous halogens are employed for a part to all of the halogenation (as opposed to employing essentially all solid or liquid halogenating agent, e.g., sulphuryl chloride or liquid bromide)
- a pressure above atmospheric is advantageously used to promote the solubility of the gaseous halogen in the reaction mixture.
- gaseous chlorine is preferred for economy and advantageously the reaction is carried out at a pressure between about 3 to about 45 p.s.i.g. Pressures below about 3 p.s.i.g. do not generally promote rapid solubility of the gaseous chlorine in the reaction medium whereas pressures above about 45 p.s.i.g. are usually not economical.
- the gaseous chlorine can be diluted with an inert gas such as nitrogen, e.g., to assist in controlling the rate of chlorination.
- Catalysis of the halogenation is essential and can be initiated by any conventional free radical initiator such as an actinic light source, thermal initiation, or by the addition of a conventional free radical initiating chemical such as benzoyl peroxide.
- a visible light source is used with any sequestrant.
- a source can be a mercury vapor lamp which can be maintained in a cooled immersion well, fluorescent lamps either white, blue, black or clear, or unfrosted incandescent lamps.
- such hydrocarbon can be dispersed in suitable liquid dispersant, i.e., one which is unreactive to the halogen, such as carbon tetrachloride, benzene, or acetic acid.
- suitable liquid dispersant i.e., one which is unreactive to the halogen, such as carbon tetrachloride, benzene, or acetic acid.
- the resulting reaction medium can be preponderantly liquid dispersant, e.g., up to 95 volume percent or more carbon tetrachloride solvent can be used to dissolve a balance of a,a',2,3, 5,6-hexachloro-p-xylene.
- any vaporized diluent can be condensed and recycled back to the reaction medium, or some to all of this vapor loss can be made up by a fresh feed of diluent to the reaction medium.
- the halogenation is normally carried out to completion as determined by evolution of the desired amount of hydrogen halide.
- the product desired will dictate the amount of halogen to be added in view of the fact that essentially the stoichiometric amount or a slight excess is normally used.
- a substantial excess of halogen may be advantageous in certain instances where a highly halogenated material is desired, as in the chlorination of p-xylene to O6,d,a,ot',0t',Ot'-heXaCh1OIO-P-XylI16.
- sequestering agents which fume from the reaction medium can be replaced by feeding fresh sequestrant to such medium.
- removal of virtually all sequestrant from the reaction product can generally be accomplished by crystallizing out halogenated product and decanting the sequestering agents with the mother liquor.
- the phosphorus halide sequestrant can be removed from the halogenated product by extraction with a suitable solvent such as water and the reaction product then isolated through distillation, preferably at reduced pressure for efiiciency, to remove the organic phosphate.
- solution A is filtered p-xylene containing, after filtration, about 0.1 p.p.m. iron.
- Solution B is a more highly iron contaminated solution prepared by dissolving ferric chloride into distilled p-xylene, with agitation, and allowing the solution to stand for two days followed by filtering to remove insolubles.
- Solution B contains 20 p.p.m. iron.
- the iron content of these solutions is determined by the thiocyanate test method described in Colorimetric Determinations of Traces of Metals, by E. B. 'Sandel-l, vol. III, 1950, page 363. Ring chlorination, production of dichloro-p-xylene, and production of hexachloro-p-xylene, all expressed in mole or weight percent of respective product, are determined by analysis of each product by total area vapor phase chromotography.
- Example 1 A reaction mixture containing about 3.1 p.p.m. iron is prepared from 84.9 parts of solution A mixed with 15.1 parts of solution B and the resulting mixture is nominated as portion C.
- a second reaction mixture, designated as portion D and containing about 3.2 p.p.m. iron is made from 83.9 parts of solution A mixed with 16.1 parts of solution B.
- a third reaction mixture containing about 5.1 p.p.m. iron is prepared from 74.9 parts of solution A mixed with 25.1 parts of solution B, and the mixture thus prepared is designated portion E, and a third reaction mixture containing about 7.1 parts p.p.m. iron is prepared from 64.8 parts of solution A mixed with 35.2 parts of solution B and the resulting mixture is separated into two aliquot portions F and G.
- sequestering agents are admixed with all portions C, D, E, F and G as shown in the tables below. Each portion is then separately treated at atmospheric pressure by first heating to a temperature of and then chlorinating, while catalyzed by a 22-watt fluorescent lamp, by passing gaseous chlorine into the reaction mixture until 1.8 moles of chlorine are reacted per mole of p-xylene, as measured by the amount of hydrogen chloride evolved.
- Dichloro-p-xylene product determinations are run on the reaction mixtures C, D, and E and the determinations are set forth in Table 1 below.
- portions F and G are further chlorinated by passing gaseous chlorine into the reaction mixture,
- Chlorine addition is terminated when the presence of a,u,a,u,a'-pentachloro-p-xylene is virtually eliminated from the reaction mixture, as determined by monitoring the reaction mixture with vapor phase chromotography.
- reaction products consist essentially of u-monochloro-, 0t,Ol.-dlChlO- ro-, and a,a,a-trichloro-p-xylene.
- the 79 weight percent hexachloro-p-xylene obtained with the triphenyl phosphate sequestering agent is the maximum amount obtainable calculated from the analysis of the C portion after 1.8 moles of chlorine are reacted.
- vapor phase chromotography analysis already shows the presence of 4 weight percent ring chlorinated product and 17 weight percent of xylene condensation product. Thus further chlorination is terminated since the maximum achievable yield of 79 weight percent hexachloro-p-xylene is undesirable.
- the sequestrant combination provides an excellent increase in hexachloro-pxylene yield compared with the use of phosphorous trichloride sequestrant alone.
- the increase of 4.9 weight percent of hexachloro-p-xylene for the sequestrant combination compared to the phosphorous trichloride alone, is especially desirable since it is an increase achieved at a level of reaction, i.e., above the 90 percent conversion level, where even a lesser increase has been impossible, or economically impractical, to obtain. Now, however, this nearly complete conversion, to the exhaustively chlorinated p-xylene is economically and simply achieved.
- Example 2 A p-xylene having readily visible particles of ferric oxide is analyzed for iron content according to the abovementioned method and found to contain 25 p.p.m. iron. To a part portion of this p-xylene is admixed 0.00 727 mole of phosphorous trichloride and 0.00215 mole of triphenyl phosphate. The resulting mixture is chlorinated in the manner of Example 1.
- a composition consisting essentially of a metal ion contaminated alkyl-aromatic hydrocarbon, and a sequestering amount of a synergistic combination of a phosphorous halide and an organic phosphate, said synergistic com-bination containing a molar proportion of phosphorous halide to organic phosphate between about 10:1 and about 1:10, wherein said organic phosphate is selected from the group consisting of aryl phosphates, alkyl phosphates, and their mixtures, and the halogen in said phosphorous halide has atomic weight between about 35-80.
- composition of claim 1 wherein the sequestering amount of said phosphorous halide together with said organic phosphate provide a composition containing from about 0.01 to about 5 weight percent of phosphorus, based on the weight of said hydrocarbon.
- composition of claim 1 wherein said organic phosphate is triphenyl phosphate and said phosphorous halide is selected from the group consisting of phosphorous trich-loride and phosphorous pentachloride.
- composition of claim 1 wherein the contaminated alkyl-aromatic hydrocarbon together with said phosphorous halide and organic phosphate, are about 5-995 volume percent of a liquid reaction medium, and the balance of said liquid reaction medium is a liquid dispersant selected from the group consisting of benzene, carbon tetrachloride, acetic acid, and their mixtures.
- organic phosphate is triphenyl phosphate and said phosphorous halide is selected from the group consisting of phosphorous trichloride and phosphorous pentachloride.
- alkyl-aromatic hydrocarbon is selected from the group consisting of toluene, xylene, and their mixtures.
- alkyl-aromatic hydrocarbon contains less than about 5 weight percent of References Cited UNITED STATES PATENTS 4/1961 Miller 260651 R 8/1961 Miller 260651 R 10 3,230,268 1/ 1966 Kobayashi 260651 R 3,350,467 10/ 1967 Lasco 260-651 R MAYER WEINBLATI, Primary Examiner 5 IRWIN GLUCK, Assistant Examiner US. Cl. XJR.
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US56134066A | 1966-06-29 | 1966-06-29 | |
US6461970A | 1970-08-17 | 1970-08-17 |
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US3703473A true US3703473A (en) | 1972-11-21 |
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US64619A Expired - Lifetime US3703473A (en) | 1966-06-29 | 1970-08-17 | Sequestering agents for metal ion contamination of alkyl-aromatic hydrocarbons |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3919054A (en) * | 1971-12-14 | 1975-11-11 | Albright & Wilson | Distillation of chloroxylenes |
US4056454A (en) * | 1975-08-09 | 1977-11-01 | Dynamit Nobel Aktiengesellschaft | Process for the preparation of α,α,αα',α'-pentachloro-o-xylene |
US4165431A (en) * | 1977-03-05 | 1979-08-21 | Bayer Aktiengesellschaft | Chlorination of polyolefins in the presence of complex formers |
US5271863A (en) * | 1992-02-26 | 1993-12-21 | Betz Laboratories, Inc. | Compositions for extracting iron species from liquid hydrocarbon systems |
CN112079685A (en) * | 2020-08-31 | 2020-12-15 | 中盐常州化工股份有限公司 | Method for reducing byproduct chlorotoluene in benzyl chloride production process |
-
1970
- 1970-08-17 US US64619A patent/US3703473A/en not_active Expired - Lifetime
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3919054A (en) * | 1971-12-14 | 1975-11-11 | Albright & Wilson | Distillation of chloroxylenes |
US4056454A (en) * | 1975-08-09 | 1977-11-01 | Dynamit Nobel Aktiengesellschaft | Process for the preparation of α,α,αα',α'-pentachloro-o-xylene |
US4165431A (en) * | 1977-03-05 | 1979-08-21 | Bayer Aktiengesellschaft | Chlorination of polyolefins in the presence of complex formers |
US5271863A (en) * | 1992-02-26 | 1993-12-21 | Betz Laboratories, Inc. | Compositions for extracting iron species from liquid hydrocarbon systems |
CN112079685A (en) * | 2020-08-31 | 2020-12-15 | 中盐常州化工股份有限公司 | Method for reducing byproduct chlorotoluene in benzyl chloride production process |
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