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  • 权利要求
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    • 专利摘要:
    1499646 Removing acetylenic compounds from hydrocarbons SNAMPROGETTI SpA 6 July 1976 [8 July 1975] 28110/76 Heading C5E Acetylenic compounds are removed from hydrocarbon mixtures containing them by contacting the mixtures with an organic acid in the presence of an acidic ion-exchange resin, the acidic groups of which have been substantially totally exchanged with both mercuric ions and alkali metal or alkaline earth metal ions, the acetylenes forming an addition compound with the organic acid. The esters formed may be removed by rectification. The preferred acid is acetic acid. The process may be carried out at 20-120‹ C. in the liquid or gaseous phases. The process may be used to purify ethylene, propylene, butadiene or mixtures thereof.
    公开号:SU751320A3
    申请号:SU762379564
    申请日:1976-07-08
    公开日:1980-07-23
    发明作者:Фарачи Рокко；Рескалли Карло；Катини Стефано
    申请人:Снам Прогетти С.П.А. (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to methods for the separation of acetylene hydrocarbons from inorganic and organic hydrocarbon mixtures.
    The method of extraction of acetylene hydrocarbons can be used in the purification of hydrocarbon streams, as well as in the preparation of valuable products based on acetylene compounds of high purity.
    A known method of separating acetylene and / or vinylacetylene by passing a hydrocarbon mixture through a column filled with crushed rubber. The process proceeds at elevated temperature, and the isolated product contains 90-95% acetylene [1].
    The main disadvantages of this method are the limited use, inconvenience in using the carrier - fragmented rubber, insufficient purity of the final target products. 25
    Closest to the proposed technical essence is a method for the separation of acetylene hydrocarbons from their mixtures - with hydrocarbons of varying degrees of saturation using a chemical absorber when heated. According to the known method, the feedstock is treated at a temperature of 50-120 ° C with an acidic aqueous solution of formaldehyde containing mercuric sulfate [2] ·
    The disadvantages of this method include the impossibility of separating acetylene compounds from complex mixtures with olefins, and without any loss of olefin fraction, as well as the use of an acid catalyst having a short service life, which complicates the separation process.
    • -g · ·
    The aim of the invention is to increase the degree of allocation of acetylene hydrocarbons.
    _ The goal is achieved by the described method for the separation of acetylene hydrocarbons from their mixtures with hydrocarbons of varying degrees of saturation by passing the initial mixture when heated through an organic acid-treated ion-exchange resin based on divinylbenzene, the acid sulfo groups of which are completely exchanged for mercury ions and alkali or alkaline earth metal ions, followed by rectification of the resulting mixture.
    The process is preferably carried out in a liquid or gas phase.
    The preferred process temperature is 20-120 ° C.
    Rectification of the resulting mixture is preferably carried out with the removal of the resulting vinyl esters and / or heme-diesters.
    The difference of the proposed method is that a neutral catalyst is used for separation, having a long service life of ion-exchange resins based on divinylbenzene, the sulfo groups of which are completely exchanged for metal ions. ''The ion exchange resins used in this method are of the acid type and contain sulfo. SOgH groups, preferably resins based on polystyrene, polydivinylbenzene or polyphenols, as well as mixtures thereof. Resins containing carboxyl- 4- py-COOH based on polyacrylates can also be used.
    Typically, divalent mercury ions can be incorporated into the resin in the form of mercury salts, more preferably in the form of divalent nitrate, mercury or divalent nitrate, mercury. The content of divalent mercury 'ions should be slightly lower than the total cationic capacity of the resin. Acidic groups of resins that have not been neutralized by divalent mercury ions. they are neutralized by sodium ions or alkaline or alkaline-earth / · metal ions, which are added to the resin in the form of salts containing these ions, but oxide hydrates can also be used for this purpose. Soder-. The burning of bivalent mercury ions in the resin should be higher than the content of Me p * ions. 40
    An aqueous solution is used to neutralize the resin, and after completion of the treatment, the resin is degraded, for example * by washing with anhydrous methanol. After this, the resin should be washed with acid, which will be used in the process. Acid must be anhydrous.
    The addition reaction is carried out in a wide range of temperatures and pressures. The process is conducted in the temperature range of 20 - 120 ° C, preferably 50 to 80 ° C. The pressure is chosen so that the hydrocarbon streams in the liquid or in the vapor phase are at a temperature corresponding to the reaction temperature, taking into account whether it is desirable to process the stream in the liquid or vapor phase. If acetylene is present in ethylene, the esterification reaction with acid (glacial) is carried out at a temperature close to the point of vinyl acetate.
    When carrying out the process in phase, the propagation velocity in the space (v / vh, volume / volume <hour) is expressed as the volume of feed per catalyst volume per hour, and during the reaction it is preferable, but not necessary, equal to 7.5-30 (l / l- h).
    The process is carried out in the presence of a small excess of acid compared to the stoichiometric amount based on acetylene present in the stream that is being treated, after which the resin is thoroughly soaked in acid.
    EXAMPLE 1 150 g of Amberlite-15 'divinylbenzene resin containing acidic sulfo group (-S0 3 H), added to 600 ml of a 3% aqueous solution of mercuric hydrate (based on weight). The mixture is stirred for 1 h, then washed with distilled water and treated with 1300 ml of a 5% solution of sodium bicarbonate in distilled water, then stirred for another 1 h. The reaction mixture is filtered in vacuo and the resin is washed successively with water, anhydrous methanol, and then glacial acetic acid until methanol is completely removed. 120 g of the resin thus treated are placed in a jacketed reactor and kept in glacial acetic acid.
    The gas to be purified is passed through the reactor, maintaining a temperature of 55-75 ^ 0. The feed gas contains 98.07 mol.% Ethylene and 1.93 mol.% Acetylene.
    Based on the content of acetylene, which was determined in the purified gas at the outlet of the reactor, counts per hour were carried out after 9 removal of vinyl acetate by cooling for 10 hours. The calculated conversion values are given in table L.
    Table. 1 'vinegar. at i boil
    Temperature C
    55 66 75 V / v * h, l / l <h Acetylene conversion,’Q.Ό v / v -h, l / l4 Acetylene conversion,% v / vh l / l> h h Acetylene Conversion.% 7.5 100.0 7.5 100.0 7.5 100.0 fifteen 100.0 fifteen 100.0 20 100.0 20 99.6 20 99.7 thirty 100.0 thirty 97.9 thirty 98.2 40 99,2
    Example 2. To 600 ml of a 3% aqueous solution of mercury acetate, 150 g of Amberlit-15 resin, 'which contains acid groups, are added, then stirred for 1 h, washed with softened water and treated with 1300 ml of a 5% solution of calcium acetate in softened water with stirring 65 '751320 for 1 h. The mixture is filtered off in vacuo and the resin washed with water, then with anhydrous methanol and glacial acetic acid to remove methanol. 120 g of the resin thus treated are placed in a jacketed reactor · and wetted with anhydrous glacial acetic acid. Gas is passed through the reactor, changing the speed (in volumes per volume per hour) of its supply. The process is carried out at a temperature of 20 ° C in one case and about 120 With in another.
    The composition of the gas entering the reactor: ethylene 98.7 mol.%, Acetylene 1.93 mol.%. Analogously to example 1, the conversion values are given in table 2.
    Temperature, ° С ' 20 120 v / v-h, l / l-h Acetylene conversion,% v / vh, l / l-h Acetylene conversion,% 7.5 100.0 7.5 100.0 fifteen 100.0 20 100.0 20 99.6 thirty 100.0
    Example 3. Analogously to example 1 serves a gaseous stream containing, mol.%: Ethane 19.5, ethylene 19.5, propane 19.5, 1-butene 19.5, 1,3-butadiene 19.5, acetylene 0, 5, propyne 0.5,
    1-butine 0.5, 2-butine 0.5, vinylacetylene 0.5.
    The process is carried out at a temperature of 75 9 C and ν / ν-h equal to 20 l / l <h.
    The conversion value is 100% for all acetylene compounds.
    Then the flow is directed for rectification into a column with 50 plates, operating under the following conditions: pressure in the head part 5 atm, reflux number 2, temperature of the lower part 50 ^ C.
    The product withdrawn from the head contains less than 10 ppm acetic acid and the following are introduced: ether ester.
    PRI me R 4. Similarly, 1 is introduced at v / v · h 30 l / l> h at a temperature of 65 ° C gaseous stream containing, mol. %: ethane 5, ethylene 91, nitrogen 2, acetylene 2. Ethylene is obtained with a conversion of 100%.
    The effluent is then directed to a distillation column containing 30 plates, operating under a pressure of 15 atm, reflux ratio 2i, sludge temperature minus 10 ° C. The prov reprimand and tem35 product obtained from the head part contains less than 10 ppm. acetic acid and vinyl acetate.
    PRI me R 5. into the reactor as in example 1, is introduced, at v / vh equal to 30 l / l-h, under pressure, allowing to maintain the reactants in a liquid state, at a temperature of 65 ° C, a gas stream containing, supposedly '. %: propane 5, propylene 91, nitrogen 2, propine 2. Get propylene with a conversion of 100%.
    The flow is then directed to a distillation column with 50 plates operating under the following conditions: head pressure 8 atm, bottom temperature .. {60 4 C, reflux number 2.
    The product obtained from the head contains less than 10 ppm. acetic acid and propylene acetate.
    PRI me R 6. Analogously to example 1, a gaseous stream containing, mol.%: Butadiene 49.0, 1-butene 49, is introduced into the reactor at v / vh equal to 20 l / l-h and a temperature of 75 ° C. propyne 0.5.1-butyn 0.5, vinylacetylene 0.5, diacetylene 0.5.
    The gas leaving the reagent after cooling is analyzed for 10 hours with sampling at an hourly interval, with 100% conversion being obtained for all samples. Then, the flow is directed to a distillation column with 30 arrows, the column operates under the following conditions: pressure in the head part 5 atm, reflux number 2, temperature of the lower part 60 ° С.
    The product that is discharged through the head of the column contains less than 10 ppm. acetic acid and injectable esters.
    权利要求:
    Claims (4)
    [1]
    The process is preferably carried out in the liquid or gas phase. The preferred process temperature is 20 -. The rectification of the resulting mixture is preferably carried out with the removal of the resulting vinyl esters and / or heme diesters. The difference of the proposed method lies in the fact that for isolation, a neutral catalyst with a long service life of ion-exchange resins based on divinylbenzene is used, the sulfo groups of which are completely exchanged for metal ions. H, preferably polystyrene, polydivinylbenzene or polyphenol resins, and mixtures thereof. Polyacrylate-based carboxyl groups can also be used. As a rule, divalent mercury ions can be introduced into the resin in the form of salt, preferably in the form of divalent nitrate. Mercury or two-bicarbonate, mercury. The content of ions of divalent mercury should be 6fJTb slightly below the total cationic capacity of the resin. Acidic resin groups that have not been neutralized by divalent mercury ions are neutralized by sodium ions or alkali or alkaline earth metal ions, which are added to the resin in the form of salts containing these ions, but you can also use oxide hydrates for this purpose. The content of divalent mercury ions in the resin should be higher than the content of ions Me. To neutralize the resin using an aqueous solution, after the treatment is completed, the resin is de-citrated, for example, by washing with anhydrous methanol. After that, the resin should be washed with acid, which will be used in the process. The acid must be necessarily anhydrous. The addition reaction is carried out in wide ranges of temperatures and pressures. The process is conducted in the temperature range of 20-120s, preferably 50-80 ° C. The pressure is chosen so that the hydrocarbon streams in the liquid or in the vapor phase are at a temperature corresponding to the reaction temperature, taking into account whether it is desirable to treat the stream in the liquid or vapor phase. In the case of acetylene in these7; In this case, the esterification reaction with acetic acid (ice) is carried out at a temperature close to the boiling point of vinyl acetate. When the process is carried out in the gas phase, the rate of propagation in a pro-1 space (v / vh, volume / volume-hour) is expressed by the volume of raw material per volume of catalyst per hour, and during the reaction it is preferable, but not necessarily, 7.5-30 (l / lh) The process is carried out in the presence of a slight excess of acid compared with the stoichiometric amount based on the acetylene present in the stream to be treated, after which the resin is thoroughly soaked in acid. Example 1. 150 g of amberlite-15, divinylbenzene-based resins containing acidic sulfo groups (-S O-jH) are added to 600 ml of a 3% aqueous solution of divalent mercury hydrate (based on weight). The mixture is stirred for 1 h, then washed with distilled water and treated with 1300 ml of 5% sodium bicarbonate solution in distilled water, and then stirred for another 1 h. The reaction mixture is filtered under vacuum and the resin is washed with water, anhydrous methanol, and then glacial acetic acid until methanol is completely removed. 120 g of the resin thus treated are placed in a jacketed reactor and kept in glacial acetic acid. The gas to be purified is passed through the reactor, maintaining the temperature between 5 and 5-75 C. The feed gas contains 98.07 mol% of ethylene and 1.93 mol% of acetylene. In terms of the content of acetylene, which was determined in the purified gas at the outlet of the reactor, after the removal of vinyl acetate by cooling for 10 hours, readings per hour were carried out. The calculated conversion values are shown in Table 1. tbl and tsl 1 Temperature, C Example 2. To 600 ml of a 3% aqueous solution of mercury acetate are added 150 g of Amberlite-15 resin, which contains acid groups, and then stirred for 1 h, washed with softened water and treated with 1300 ml of a 5% calcium acetate solution in softened water with stirring for 1 hour. The mixture is filtered under vacuum and the resin is washed with water, then anhydrous methanol and glacial acetic acid to a distance of methanol. 120 g of the resin thus treated are placed in a jacketed reactor and moistened with aqueous glacial acetic acid. The gas is passed through the reactor, changing the speed (in volumes per volume per hour) of its supply. The process is carried out at a temperature in one case and about 120 s in the other. The composition of the gas entering the reactor: ethylene is 98.7 mol.%, Acetylene is 1.93 mol. In the same way as in example 1, the conversion values given in table 2 are obtained. Table 2 Temperature, C Example 3. Analogously to example 1, a gaseous stream is supplied, containing, mol%: ethane 19.5, ethylene 19.5, propane 19.5, 1-butene 19.5, 1,3-buta diene 19.5, acetylene 0.5, propine 0.5 1-butine 0.5, 2-butine 0.5, vinyl acetylene 0.5. The process is carried out at a temperature and v / Vh equal to 20 l / LC. The conversion value is 100% for all acetylene compounds. The stream is then sent for rectification to a column with 50 plates, operating under the following conditions: head pressure 5 atm, reflux number 2, temperature of the bottom part. The product withdrawn from the head contains less than 10 ppm of acetic acid and is introduced into the re: actor esters. EXAMPLE 4. Similarly, Example 1 is introduced at V / V.h 30 l / l.h and temperature is gaseous IJOTOK, containing, say. %: ethane 5, ethylene 91, nitrogen 2, acetylene 2. Get ethylene with a conversion of 100%. The effluent is then directed to a distillation column containing 30 plates, operating under a pressure of 15 atm. The reflux number 2 is a temperature of minus minus. The product obtained from the top contains less than 10 ppm of acetic acid and vinyl acetate. Example5. As in Example 1, the reactor is introduced, at v / vh, equal to 30 l / lh, under pressure to keep the reactants in a liquid state, at a temperature the gas stream containing .Mo3f. % propane 5, propylene 91, nitrogen 2, propyne 2. Get propylene with a conversion of 100%. The stream is then sent to a distillation column with 50 plates, operating under the following conditions: pressure in the main part of 8 atm, temperature in the bottom part, reflux number 2. The product obtained from the head contains less than 10 h / mph. acetic acid and propylene acetate. EXAMPLE 6 Analogously to Example 1, a gaseous stream containing, mol.%: Butadiente 49.0, 1-butene 49, propyne O is introduced into the reactor at v / vh equal to 20 l / lh. , 5,1-butyne 0.5, vinylacetylene 0.5, diacetylene 0.5. The gas leaving the reaction after cooling is analyzed for 10 hours with sampling every 1 hour, and 100% conversion is obtained for all samples. The stream is then sent to a distillation column with 30 trays, the column is operated under the following conditions: head pressure 5 atm, reflux number 2, temperature of the bottom part. The product that is discharged through the top of the column contains less than 10 ppm of acetic acid and the esters to be injected. 1. Method for separating acetylene hydrocarbons from their mixtures with hydrocarbons of different degrees of saturation using a chemical absorber when heated, which also means that an ion-exchange resin treated with an organic acid is used as a chemical absorber. on the basis of divinylbenzene, acidic sulfo groups of which are completely exchanged for mercury ions and alkali or alkali-alkali metal ions, and the treated mixture is subjected to rectification .
    [2]
    2. Method POP.1, O1 is distinguished by the fact that the process is carried out in the liquid or gas phase.
    [3]
    3. The way popp. 1 and 2, characterized in that the process is carried out at a temperature of 20-120 C.
    1 751320 8
    4. The method according to PP.1,2 and Z, from-1. USSR author's certificate
    [4]
    characterized by the fact that number 89358 / class. C 07 S 7/12, published
    rectification of the resulting mixture Uda-1956. vinyl esters formed
    and / or heme diesters. USSR author's certificate
    Sources of information, j No. 263589, cl. C 07 S 7/00, published
    taken into account in the examination of 1968 (prototype).
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    同族专利:
    公开号 | 公开日
    FR2317256B1|1980-04-25|
    RO74131A|1981-11-24|
    LU75312A1|1977-02-24|
    DD127302A5|1977-09-14|
    HU178719B|1982-06-28|
    DE2630783B2|1979-05-31|
    SE7607853L|1977-01-09|
    TR18997A|1978-02-10|
    CS194770B2|1979-12-31|
    SE425385B|1982-09-27|
    ES449922A1|1977-07-01|
    CA1086330A|1980-09-23|
    BR7605717A|1977-08-23|
    AR221029A1|1980-12-30|
    ATA498776A|1978-01-15|
    MX144146A|1981-09-02|
    NO762205L|1977-01-11|
    DK303876A|1977-01-09|
    GB1499646A|1978-02-01|
    ZA763798B|1977-05-25|
    EG12199A|1978-06-30|
    DE2630783A1|1977-01-13|
    IN144603B|1978-05-20|
    PH13775A|1980-09-23|
    AU1543776A|1978-01-05|
    IE43389B1|1981-02-11|
    DD130572A5|1978-04-12|
    AU500172B2|1979-05-10|
    CH626267A5|1981-11-13|
    IT1039740B|1979-12-10|
    NL7607525A|1977-01-11|
    AT345263B|1978-09-11|
    JPS602287B2|1985-01-21|
    NO145572B|1982-01-11|
    DE2630783C3|1980-02-14|
    PT65331B|1978-01-06|
    US4066713A|1978-01-03|
    FR2317256A1|1977-02-04|
    BE843917A|1977-01-10|
    NO145572C|1982-04-21|
    IE43389L|1977-01-08|
    YU164576A|1982-05-31|
    PL108187B1|1980-03-31|
    PT65331A|1976-08-01|
    JPS5212117A|1977-01-29|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    NL123614C|1962-04-25|1900-01-01|
    US3287402A|1964-05-25|1966-11-22|Mobil Oil Corp|Synthesis of vinyl esters in the presence of a crystalline aluminosilicate catalyst|DE3127751A1|1981-07-14|1983-02-03|EC Erdölchemie GmbH, 5000 Köln|METHOD FOR HYDROGENATING HYDROCARBONS|
    GB9314514D0|1993-07-13|1993-08-25|Ici Plc|Hydrocarbon processing|
    US5952523A|1997-07-24|1999-09-14|Praxair Technology, Inc.|Method for producing vinyl acetate|
    DE10113381A1|2001-02-13|2002-08-14|Oxeno Olefinchemie Gmbh|Process for the preparation of high purity diisobutene|
    US8742194B2|2012-05-21|2014-06-03|CM Global Systems, LLC|Hydrocarbon-containing mixture and method and system for making the same|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    IT25171/75A|IT1039740B|1975-07-08|1975-07-08|PROCEDURE FOR THE ADDITION OF ORGANIC ACIDS TO ACETYLNIC COMPOUNDS CONTAINED IN CORRENET I HYDROCAR BURIC INORGANIC OR ORGANIC|
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