• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A process is disclosed for the dehydration of a mixture of methanol and higher alcohols, containing 20 to 80% by weight of methanol, 1 to 60% by weight of at least a higher alcohol selected from those containing from 2 to 10 carbon atoms, 1 to 50% by weight of water and 0.1 to 10% by weight of hydrocarbons and/or of oxygen-containing organic compounds different from alcohols, which process comprises the following steps: p0 (a) feeding to a first rectification tower the mixture of methanol and higher alcohols to be dehydrated, a gaseous stream being discharged from the tower head, which contains a portion of the hydrocarbons and/or of the oxygen-containing organic compounds different from the alcohols; from a side point at a level higher than 2/3 of the tower height, a stream containing methanol and possibly ethanol being drawn; and from the tower bottom a stream being obtained with a methanol, and possibly ethanol, and having a content not larger than 10% by weight; (b) separating at least once the stream obtained from the bottom of the first column into two phases, one of which being aqueous, and the other phase being organic; (c) feeding the organic phase to a second tower of azeotropic distillation, using a liquid-vapor and liquid-liquid separation agent; at the bottom an anhydrous stream being obtained, which contains the higher alcohol(s); and from the tower head a stream being obtained, which contains methanol, possibly ethanol and/or propanol, water, and the separation agent used, which is added to the stream obtained from the bottom of the first tower; and (d) feeding the aqueous phase to a third rectification tower; from the bottom a stream being removed which contains water; and overhead a stream being recovered, which is enriched with methanol and higher alcohols, which is recycled by being added to the mixture of methanol and higher alcohols to be dehydrated before being fed to the first rectification tower.
    公开号:SU1646487A3
    申请号:SU884355542
    申请日:1988-04-01
    公开日:1991-04-30
    发明作者:Рескалли Карло；Ригги Рициеро；Скаццоги Адриано；Чанчи Флавно
    申请人:Снампрогетти С.П.А. (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to methods for the dehydration of mixtures of aliphatic alcohols, and more specifically to methods for the dehydration of mixtures of methanol with C2 and C5 alcohols, which can be used as a fuel in a mixture with gasoline.
    The purpose of the invention is to develop a new efficient method of dehydrating mixtures of methanol with C-C alcohols, which allows to obtain mixtures with a low water content, suitable as fuel additives.
    The drawing shows a flow chart for dewatering a mixture of methanol.
    With C-alcohol.
    A mixture of methanol with higher Cr – C5 alcohols to be dewatered, obtained from a mixture of carbon monoxide and hydrogen in a synthesis reactor, is fed into the system by stream 1, which, together with recycle stream 2 after heating at point 32, is fed to the first distillation column 4 as a combined flow 3.
    From the top of the column, a gas stream is released, which, after condensation at point 5, is sent to collector 6, from which gas stream 7, containing mostly hydrocarbons and / or oxygen-containing organic compounds that are not alcohols, flows out, and the remaining liquid phase 8 is returned to the top of column 4,
    From the side of this column 4, at a level higher than 2/3 of its height, point 9 is forcibly discharged an anhydrous stream containing mainly methanol and, possibly, ethanol.
    In order to avoid disrupting the functioning of the column due to the formation of foam, an antifoam solution 10 is introduced into the column.
    From the bottom of the column, a stream 11 containing methanol and, possibly, ethanol in an amount of not more than 10 wt0% is discharged, while the column operates in a mode of relatively low speed.
    After cooling at point 35, an aqueous solution 12 containing NaOH or Na2C03 is added to stream 11 in order to neutralize the acidic compounds contained in the stream, after which it is separated by cooling in phase separation
    0
    the torus 13 on the organic 14 and the aqueous 15 phase.
    Deionized water 16 is added to the organic phase 14 with simultaneous flow of the stream 24 discharged from the condenser 25 of the second azeotropic column 20 into the phase separator 17, after which the organic phase 14 is separated into the organic 18 and the aqueous 19 basics.
    After heating at point 21, the separated organic phase 18 is fed to the second column 20 of azeotropic distillation, in which cyclohexane or benzene is used as separating agent.
    From the bottom of the second column, an anhydrous stream 22 is obtained, containing mainly higher alcohols, and the stream leaving the column head
    24 contains methanol, ethanol, propanol, cyclohexane and water. As stated above, after condensation at
    25 This stream is added to the organic phase 14, to which an aqueous stream 16 can also be added before separating stream 14 at point 17.
    The aqueous phases 19 and 15 are combined at point 26, heated at point 27 and fed to the distillation column 28. From the bottom of the column 28, a stream 29 containing mainly water is discharged, and the overflow stream 30. containing mainly alcohol and water is recycled with stream 2 as an additive to the mixture of methanol with higher alcohols to be dehydrated.
    The positions 31 and 33 denote the upper condenser and reboiler of the column 28, and the positions 34 and 23 denote the reboilers of the columns 4 and 20, respectively.
    five
    0
    0
    Example 1. The process is carried out 5 according to the scheme shown in the drawing.
    The first distillation column 4 (cascade column with glass cap plates of the STAGE model, 50 mm in diameter with an adiabatic lower link, the total number of plates is 80, the feed point is 34-plate, with a hydraulic pressure equal to the atmospheric pressure outlet at the level of the 70th plate ) at a temperature of 50 ° C serves stream 3 containing the raw mixture of 1 methanol with high alcohols (MAS) and recirculating stream 2, which had the following composition (Table 1).
    Column 4 operates at atmospheric pressure in the head section, at a temperature of 59-63 ° С at the top of the column and 92-93 ° С in a cube at a flow rate of 8 6000 g / h, at an h / v ratio (the recovered liquid / distilled distillate - gas phase 200 g / g
    From collector 6, a gaseous stream 7 is discharged at a rate of 30.2 g / h, containing all the amount of C02 and d of methyl ether supplied by the feedstock, as well as a small amount of methanol (9.1 g / h) and other organic compounds (13.2 g / h) and water (0.1 g / h).
    The liquid phase 8 discharged from this point at a rate of 6000 g / h is completely returned to the column. It is mainly formed by methanol (3812.1 g / h), dimethyl ether (615.1 i / h), other organic compounds (1600.4 g / h) and a small amount of water (2.4 g / h).
    From the 70th plate, at a speed of 1685.5 g / h, anhydrous stream 9 is discharged, containing mainly all the amount of methanol and ethanol supplied, in particular, of the following composition, g / h:
    Methanol1606.0
    Ethanol50.8
    Other organic compounds (carbonyl compounds, ethers and esters,
    acids, hydrocarbons, heterocyclic compounds) 28.4 Water1.3
    (0.08 wt.%)
    Total flow 1686.5 To avoid disrupting the operation of the column due to foaming, to the level of the 55th plate, 1% by weight of aqueous silicone solution 10 is fed into the column at a rate of 3 g / h.
    To obtain such a high level of dewatering, the column operates in a relatively low rate of distillation of methanol and ethanol at the bottom: from this point, column 4 leaves stream 11, which is separated into aqueous phase 15 and organic phase 14 during subsequent cooling to 30 ° C. , at the point to the Phase separator 13 at a rate of 20 g / h, 7 wt.% of an aqueous solution of NaOH are fed to the chain 16464876
    Pure neutralization of 11 acidic compounds contained in the stream.
    Streams 11, 14 and 15 have the following composition, given in table. 2
    The stream 14 thus obtained is directed to the second column 20 of azeotropic distillation (glass column with a packing of 25 mm in diameter with an adiabatic lower unit, packing — Raschig glass rings 4x4 mm, feed point — upper phase separator, hydraulic pores equal to atmospheric pressure)
    in which cyclohexane was used as a separator for liquid and vapor phases and two liquid phases, ensuring the removal of water residues from a mixture of higher alcohols
    Column 20 operates at 79-84 ° C in the head section, at 114-118 ° C - (cubed, flow rates 18,143.1 g / h, L / D ratio (recovered liquid), remote distillate - liquid Laza) 5 , 2 g / g
    The organic phase 18 released from the separator 17 is recycled to the column, and the aqueous phase 19 ensures complete separation of the methanol and ethanol fed to the column. To simplify this operation, an additional stream 16 of deionized water in the amount of 70 g / h is sent to the Phase separator. From the bottom of the column 20 an anhydrous stream of 22 higher alcohols containing neither cyclohexane, nor methanol, nor ethanol is discharged. n-propanol and i-butanol.
    The streams associated with column 20 have the following composition, given in table. 3,
    The aqueous stream 19, combined with the same stream 15, serves in the third distillation column 28
    to extract the alcohols as the upper fraction 30, after which the water contained in the starting material used in the process is discharged as the lower fraction 29. The column 28 is formed by two 25 mm glass semi-columns equipped with an outer adiabatic lower link and filled Raschig rings (4x4 mm) to a height of 70 cm from the feed point up and down, respectively, hydraulic
    cue pressure in the column was equal to atmospheric pressure, and the coefficient def of legmacy 1.8. The temperature of the head of the column is 90-95 ° C, cubed 102-106 ° C.
    PRI mme R 2. When carrying out the process in accordance with the scheme shown in the drawing in distillation column 4 (column with glass plates of the STAGE model, diameter 50 mm, adiabatic cap, total number of plates 80, feed of raw materials at the level of The 30th plate, flow temperature 50 ° С, the withdrawal of the epaulet at the level of the 68th plate) serves stream 3, consisting of raw material 1 (a mixture of methanol and higher alcohols) and recirculating stream 2, including the components shown in Table 40
    From collector 6, the gas stream 7 is removed in an amount of 25.2 g / h, containing all carbon dioxide and dimethyl ether, which are present in the feed along with small amounts of methanol (7.9 g / h), other organic compounds ( 9.2 g / h) and water (0.2 g / h) „
    Column 4 is characterized by a temperature in the lower part of 92-93 ° C and a temperature in the head section of 58-62 °. The ratio L / v (stream 8 divided by stream 7) is about 1bOg / g.
    A stream 9 (1043.3 g / h) containing, g / h: Methanol 976.4 is removed from the food tray.
    Ethanol49.9
    Other organic compounds 25.4 Water 0.6
    Total1043.3
    In order to prevent disruptions in the implementation scheme, a water-silicone solution (in the amount of 1 wt.%, I.e. 2 g / h) is fed to the 55th plate.
    From the bottom of the column, stream 11 is removed, which, after cooling to 32 ° C, is separated into an aqueous phase 15 and an organic phase 14: 18 g / h of a 10% aqueous solution 12 is sent to the point where the stream enters the separator 13, containing Na2C03, for neutralizing acidic compounds in stream 11. Stream 11, 14 and 15 include the components shown in Table 5.
    Stream 14 is fed to the azeotropic distillation column 20 (column

    about
    five
    five
    0
    five
    on glass plates of the model STERD, diameter 40 mm, with an adiabatic cap located outside, the total number of plates is 40, feed to the head of the separator, feed is carried out at ambient temperature, head pressure is atmospheric, head temperature 78- 83 ° C, temperature in the lower part 113-119 ° C), in which with the help of benzene, used as an agent for the separation of two liquids, water is separated, which may still be present in the alcohol mixture about
    The organic phase 18 removed from separator 17 is recycled to the column, while the aqueous phase 19 is removed to remove ethanol and methanol if present. The L / D ratio (stream 18 / stream 19) is 5.6 g / g.
    To facilitate the process in the separator, an additional stream of water 16 is fed there, coming from the bottom of the column 28 in the amount of 65 g / h.
    From the bottom of column 20, an anhydrous stream of 22 higher alcohols free of benzene is removed.
    The streams in the column have the following composition, presented in Table 6 ,,
    Water streams 15 and 16 are fed to the final distillation column 28 in order to regenerate the alcohols and remove water from the bottom that was present in the feedstock used in the previous stages.
    Column 28 consists of two glass tubes (a STAGE model, a plate diameter of 40 mm, a total number of plates 45, the feed plate is the 30th, the flow temperature is the ambient temperature). Such a column operates at atmospheric pressure at the head and at a reflux ratio of 2.0 g / g, which is equivalent to a reflux rate of 251.2 g / h.
    权利要求:
    Claims (5)
    [1]
    1. A method of dehydrating a mixture of methanol with C-C alcohols containing 57-58% by weight of methanol, 15% by weight of alcohols selected from the group with 2-5 carbon atoms, 8.6-19% by weight of water and
    8.0-9.4 wt.% Hydrocarbons and / or oxygen-containing organic compounds that are not alcohols, for example ethers, carbonyl compounds, esters, acids, heterocyclic compounds, characterized in that the mixture of methanol with C-C alcohols to be dehydrated, is fed to the first distillation column, from the top of which a gas stream containing mainly hydrocarbons and / or oxygen-containing organic compounds, not alcohols, is discharged from a point in the side wall of the column Aries above 2/3 of the column height, forcibly release a stream containing mainly methanol and ethanol, and from the bottom of the column - an aqueous stream containing 0.0005-0.025% methanol, 0.46-1.5% ethanol, C-C -alcohols and organic compounds, to which an aqueous solution of NaOH or Na2C03 is added, and subjected to separation, while cooling to 30–321 ° C, into the aqueous and organic phases, the organic phase is fed to the second azeotropic distillation column, in which cyclohexane or benzene is used. separation of liquid and vapor phases and two liquid phases, from the bottom of the azeot column opnoy distillation outputting anhydrous stream comprising mainly alcohols selected from the group comprising 2-5
    , 64648710
    carbon atoms, and a stream containing methanol, ethanol, propanol, water and used separating agent is obtained from the head of this column, which is added to the stream released from the bottom of the first column, the aqueous phase consisting of the combined aqueous phases of the first two columns, is fed to the third distillation column, from the bottom of which a stream containing mainly water is withdrawn, from the top a stream enriched in methanol and C2-Cg.-cmipTa, which is added to the
    ten
    15
    20
    25
    thirty
    35
    dewatering a mixture of methanol with Cj-Cj-alcohols before feeding it to the first rectification column for recirculation.
    [2]
    2. A method according to claim 1, characterized in that an antifoaming solution is supplied through the side entrance of the first distillation column.
    [3]
    3. The method according to claim 2, characterized in that a water-silicone solution is used as an antifoam solution.
    [4]
    4. A method according to claim, characterized in that water in an amount of 5.1-5.6% by weight of this stream is added to the stream leaving the head of the second azeotropic distillation column.
    [5]
    5. A method according to claim 4, characterized in that deionized water is added.
    e Table 1
    blitz 2
     Other organic compounds include: iso-amyl alcohol, carbonyl compounds, complex ebers, simple electrolytes, acids, hydrocarbons, heterocyclic compounds 13
    164648714
    Table 5
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    同族专利:
    公开号 | 公开日
    US4874474A|1989-10-17|
    FR2613358A1|1988-10-07|
    GB2203148A|1988-10-12|
    DE3811150A1|1988-10-13|
    IT1206774B|1989-05-03|
    AU1386788A|1988-10-06|
    GB8807195D0|1988-04-27|
    DE3811150C2|1990-01-04|
    GB2203148B|1990-09-19|
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    IN148355B|1977-03-11|1981-01-24|Ici Ltd|
    EP0001681A1|1977-10-06|1979-05-02|BP Chemicals Limited|Dehydration of alcohols, preferably ethanol, using a cyclohexane entrainer|
    US4256541A|1979-05-29|1981-03-17|National Distillers And Chemical Corp.|Production of anydrous alcohol|
    FR2490629A1|1980-09-01|1982-03-26|Inst Francais Du Petrole|PROCESS FOR THE PRODUCTION OF ALCOHOL DEHYDRATES FOR USE AS A COMPONENT OF A FUEL FOR A MOTOR|
    DE3338439A1|1983-10-22|1985-05-02|Chemische Werke Hüls AG, 4370 Marl|METHOD FOR THE DISTILLATIVE WORKING UP OF WATER AND METHANOL CONTAINING HIGHER ALCOHOLS WITH 6 TO 20 C ATOMS|
    DD253814A1|1986-11-19|1988-02-03|Leuna Werke Veb|ENTWASTION OF MIXTURES OF METHANOL AND HIGHER ALCOHOLS|IT1256062B|1992-11-20|1995-11-23|Snam Progetti|PROCEDURE FOR OBTAINING METHANOL, ETHANOL, N-PROPANOL, ISOBUTANOL, USABLE ABOVE ALL IN THE PREPARATION OF HIGH-OCTANIC PRODUCTS, FROM MIXTURES CONTAINING ALCOHOLS WITH WATER AND OTHER LOW BOILING AND HIGH BOILING COMPOUNDS|
    GB9409375D0|1994-05-11|1994-06-29|Johnson Electric Sa|Noise suppressed commutator|
    IT1271310B|1994-12-21|1997-05-27|Snam Progetti|PROCEDURE FOR OBTAINING DISTINCT CURRENTS OF METHANOL AND ETHANOL, OF N-PROPANOL, OF ISOBUTANOL, USABLE IN THE SYNTHESIS OF HIGH-OCTANIC PRODUCTS, FROM MIXTURES CONTAINING ALCOHOLS WITH WATER AND OTHER LOW BOILING AND HIGH BOILING COMPOUNDS|
    US5908538A|1997-06-06|1999-06-01|Berg; Lloyd|Separation of T-amyl alcohol from 2- methyl-1 -propanol azeotropic distillation|
    US5904815A|1998-03-05|1999-05-18|Berg; Lloyd|Separation of t-amyl alcohol from n-butanol by azeotropic distillation|
    CN102381937A|2011-08-30|2012-03-21|山西华顿实业有限公司|Dehydration method for multi-carbon alcohol|
    EP3205387A1|2016-02-15|2017-08-16|Johannes August Lercher|Preparation and use of zeolitic membranes for selective removal of water|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    IT8719938A|IT1206774B|1987-04-02|1987-04-02|PROCEDURE FOR THE DEHYDRATION OF A MIXTURE OF METHANOL AND HIGHER ALCOHOLS.|
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