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    • 专利摘要:
    process to produce low hydrogen halide hydrocarbon products, and alkylated gasoline. a process for producing low hydrogen halide products comprising: a) extracting or distilling an effluent from a reactor in a first reaction having a quantity of hydrogen halide and a second fraction having a reduced amount of hydrogen halide; wherein the reactor comprises: an ionic liquid catalyst having a metal halide and a hydrogen halide or an organic halide; and b) recovering one or more product streams from the second fraction having less than 25 ppm by weight hydrogen halide. in one embodiment the ionic liquid catalyst has metal halide; and the recovery recovers propane, n-butane and alkylated gasoline having less than 25 ppm by weight hydrogen halide. in another embodiment the recovery uses a distillation column having poor resistance to hydrogen helide corrosion; and the distillation column shows no corrosion. An alkylated gasoline having less than 5 ppm by weight hydrogen halide, a high ron and low rvp is also provided.
    公开号:BR112012009303B1
    申请号:R112012009303
    申请日:2010-11-11
    公开日:2018-10-09
    发明作者:Phillips Christine；Timken Hye-Kyung；F Cleverdon Robert
    申请人:Chevron Usa Inc；
    IPC主号:
    专利说明:

    (54) Title: PROCESS TO PRODUCE HYDROCARBON PRODUCTS WITH LOW HYDROGEN HALIDE CONTENT.
    (73) Holder: CHEVRON U.S.A. INC., North American Company. Address: 6001 Bollinger Canyon Road, San Ramon, California 94583-2324, UNITED STATES OF AMERICA (US) (72) Inventor: HYE-KYUNG TIMKEN; CHRISTINE PHILLIPS; ROBERT F. CLEVERDON
    Validity Term: 20 (twenty) years from 11/11/2010, subject to legal conditions
    Issued on: 10/9/2018
    Digitally signed by:
    Liane Elizabeth Caldeira Lage
    Director of Patents, Computer Programs and Topographies of Integrated Circuits
    1/17 “PROCESS TO PRODUCE HYDROGEN HALIDE HYDROCARBON PRODUCTS” [0001] This order refers to a coded order, entitled “A PROCESS FOR RECYCLING HYDROGEN HALIDE TO A REACTOR COMPRISING AN IONIC LIQUID”, fully incorporated here .
    FIELD OF THE INVENTION [0002] This order is directed to processes for creating products with a low hydrogen halide content by extraction or distillation of a reactor effluent comprising an ionic liquid catalyst. This order is also addressed to an alkylated petrol prepared by a process of this order.
    SUMMARY OF THE INVENTION [0003] This application provides a process for manufacturing products with a low hydrogen halide content, comprising:
    a) extraction or distillation of a reactor effluent in a first fraction having a quantity of a hydrogen halide and a second fraction having a reduced amount of a hydrogen halide less than the first fraction; where the reactor comprises:
    i. ionic liquid catalyst having a metal halide, and ii. the hydrogen halide or an organic halide; and
    b) recovering one or more product streams of the second fraction having less than 25 ppm by weight of the hydrogen halide.
    [0004] This application also provides a process for manufacturing products with a low hydrogen halide content comprising:
    a) extraction or distillation of a reactor effluent in a first fraction having a quantity of a hydrogen halide and a second fraction having a reduced quantity of a hydrogen halide; wherein the reactor comprises an ionic liquid catalyst having a metal halide; and
    b) recovery of propane, n-butane and alkylated gasoline of the second fraction, all having less than 25 ppm by weight of halide.
    Petition 870180033178, of 04/24/2018, p. 6/27
    2/17 hydrogen.
    [0005] This application also provides a process for manufacturing products with a low hydrogen halide content, comprising:
    a) extraction or distillation of a reactor effluent in a first fraction having an increased amount of a hydrogen halide and a second fraction having a reduced amount of the hydrogen halide; where the reactor comprises:
    i. an ionic liquid catalyst having a metal halide, and ii. a hydrogen halide or an organic halide; and
    b) recovery of one or more product streams of the second fraction using a distillation column made with one or more metals having corrosion resistance for the hydrogen halides, and in which the distillation column does not show corrosion from the recovery.
    [0006] This order also provides alkylated gasoline with a low level of hydrogen halide, made by a process comprising:
    a) extraction or distillation of a reactor effluent in a first fraction having a quantity of a hydrogen halide and a second fraction having a reduced amount of a hydrogen halide less than the first fraction; where the reactor comprises:
    i. an ionic liquid catalyst having a metal halide, and ii. a hydrogen halide or an organic halide; and
    b) recovering an alkylated gasoline comprising less than 5 ppm by weight of hydrogen halides directly from the second fraction.
    BRIEF DESCRIPTION OF THE DRAWINGS [0007] Fig. 1 is a process flow diagram of a modality showing the removal of HCI in a hydrocarbon process stream.
    [0008] Fig. 2 is a process flow diagram of an embodiment showing the recycling of HCI and anhydrous isobutane for paraffin alkylation. DETAILED DESCRIPTION OF THE INVENTION
    Petition 870180033178, of 04/24/2018, p. 7/27
    3/17 [0009] Hydrogen halides are acids resulting from the chemical reaction of hydrogen with one of the halogen elements (fluorine, chlorine, bromine, iodine, astatin and ununséptium), which are found in Group 17 of the periodic table. Astatin is very rare, unstable and not found as the acid in substantial amounts, ununséptio has never been synthesized. Hydrogen halides can be abbreviated as HX where H represents a hydrogen atom and X represents a halogen atom (fluorine, chlorine, bromine or iodine). The boiling points of the most common hydrogen halides are listed below:
    HF 19 ° C HCI -85 Ό HBr -67 Ό Hl -35 ° C [0010] Due to their relatively low boiling points, hydrogen halides that can be separated from other hydrocarbons by distillation or extraction. It is desired that the levels of hydrogen halides are kept to a minimum in many finished products.
    [0011] In the context of this disclosure, 'an increased amount' is at least 5 ppm greater than a minimum amount. 'A reduced amount' is at least 5 ppm less than an initial amount, or at least 5 ppm less than the amount in the first fraction.
    [0012] Separation is the removal of volatile components from a liquid by evaporation. In extraction processes, the extraction step solution must be separated to allow the recovery of the separated hydrocarbons and to recycle the lighter gases. Extraction can be achieved by reducing pressure, applying heat, or using an inert gas or hydrogen gas (extraction vapor). Some processes may employ a combination of all three; that is, after the extraction, the hydrocarbon products are flared at atmospheric pressure, heated and admitted to an extraction column that is provided with a heater at the bottom (refill). The solvent vapor generated in the cooler or inert gas at the bottom of the column serves as steam extraction that increases by
    Petition 870180033178, of 04/24/2018, p. 8/27
    4/17 counter-current for the downward flow of hydrocarbon products.
    [0013] Distillation is the extraction of volatile components from a mixture by condensation and collection of vapors that are produced as the mixture is heated. Distillation is described in Section 13 of Perry's Chemical Engineer's Handbook (8 th Edition), by Don W. Green and Robert H. Perry, © 2008 McGraw-HilI, pages 13-1 to 13-79. In one embodiment, distillation is carried out on a distillation column at a pressure between 50 and 500 psig (344 and 3447kPa). In one embodiment, the bottom temperature in a distillation column is between 10 and 204 ° C (50 and 400 ° F). In one embodiment, the temperature above a distillation column is between 38 and 316 ° C (100 and 600 s F). In one embodiment, distillation is carried out with reflux. Reflux is a technique, using a reflux condenser, which allows the contents of a vessel to boil over an extended period. Distillation conditions are selected to provide a first fraction having an increased amount of hydrogen halide and the second fraction having a reduced amount of hydrogen halide. Distillation conditions are adjusted to obtain desired levels of hydrogen halide in each fraction. In one embodiment, the level of hydrogen halide in the first fraction is at least 5% by weight. In another embodiment, the level of hydrogen halide in the second fraction is less than 25 ppm by weight.
    [0014] For maximum recovery of the hydrogen halide, distillation would be more likely to be employed. If maximum recovery of hydrogen halide is not as critical, then extraction may be more desirable to reduce the cost of equipment.
    [0015] The reactor can be of any suitable design to obtain a desired hydrocarbon conversion. Examples of hydrogen conversions for which the reactor is used to include paraffin alkylation, olefin dimerization, olefin oligomerization, isomerization, aromatic alkylation and mixtures thereof. Examples of reactors include stirred tank reactors, which can be a batch reactor or a continuously stirred tank reactor (CSTR). Alternatively, a batch reactor, a semi-batch reactor, a reactor
    Petition 870180033178, of 04/24/2018, p. 9/27
    5/17 riser, a tubular reactor, a loop reactor, a continuous reactor, a static mixer, a packaged bed contactor, or any other reactor and combinations of two or more of them can be used. Specific examples of alkylation reactions include ionic liquid catalysts that are useful for paraffin alkylation are described in US 2009-0166257 A1, US 20090171134 A1, and US 2009-0171133 A1.
    [0016] In one embodiment the reactor comprises an ionic liquid catalyst having a metal halide, and a hydrogen halide or an organic halide. In another embodiment, the reactor comprises an ionic liquid catalyst having a metal halide. Examples of metal halides are AICI 3 , AIBr 3 , GaCI 3 , GaBr 3 , lnCI 3 , lnBr 3 , and mixtures thereof. In one embodiment, the hydrogen halide is anhydrous HCI. In one embodiment, the metal halide is aluminum chloride and the hydrogen halide is hydrogen chloride (HCI). In some embodiments, excess amounts of anhydrous HCI are needed to ensure the extended operation of a catalytic process.
    [0017] The effluent from the reactor comprises a level of hydrogen halide that is higher than 0 that is desired in a product stream. The hydrogen halide is derived from one or more metal halide, hydrogen halide, or organic halide that are present in the reactor.
    [0018] The one or more product streams that are recovered have an acceptable level of hydrogen halide. In some embodiments, they are less than 25 ppm by weight of the hydrogen halide. In other embodiments, they are less than 20, less than 10, less than 5, less than 2, or less than 1 ppm by weight of the hydrogen halide. In some embodiments, one or more product streams have less than 25 ppm by weight, less than 20, less than 10, less than 5, less than 2, or even less than 1 ppm by weight hydrogen halide before any optional caustic treatment. Due to the fact that one or more product streams have low amounts of hydrogen halide, little or no caustic treatment is required, which reduces process complexity and cost.
    Petition 870180033178, of 04/24/2018, p. 10/27
    6/17 [0019] The one or more product streams comprises hydrocarbon. In one embodiment, one or more product streams comprise propane, butane, an alkylated gasoline, and mixtures thereof; and they all have less than 25 ppm by weight of hydrogen halide. Other product streams may include medium distillate, airplane fuel and base oil. In other embodiments, all of one or more product streams are less than 10 ppm by weight, less than 5 ppm by weight, less than 2 ppm by weight, or less than 1 ppm by weight. Alkylated gasoline is the reaction product of butylene or propylene or ethylene or pentene with isobutane, or the reaction product of ethylene or propylene or butylene with isopentane. In some embodiments, alkylated gasoline has a high octane value and can be mixed with engine and aviation gasoline to improve the anti-knock value of the fuel.
    [0020] In one embodiment, an alkylated gasoline having less than 5 ppm by weight hydrogen halide is recovered directly from the second fraction. No further processing of alkylated gasoline is required to obtain this low level of hydrogen halide. In other embodiments, alkylated gasoline that is recovered from the second fraction has less than 2 ppm by weight or less than 1 ppm by weight hydrogen halide.
    [0021] In one embodiment, the alkylated gas recovered from the second fraction has low volatility. In an embodiment, alkylated gasoline has a Reid Vapor Pressure (RVP) of less than 2.8 psi (19.31 kPa). In other embodiments, alkylated gasoline has an RVP of 2.2 psi (15.2 kPa) or less, or less than the amount defined by the equation: RVP = -0.035 x (50 vol% boiling point, ° C) + 5.8, in psi. The graph of this equation is shown in Figure 1 in US Patent Application 12/184109, filed on July 31, 2008. To convert psi to kPa, multiply the result by 6,895.
    [0022] In one embodiment, alkylated gasoline has a high octane number. Examples of high octane numbers are 82 or greater, greater than 85, greater than 90, and greater than 95. Different methods are
    Petition 870180033178, of 04/24/2018, p. 11/27
    7/17 used to calculate fuel octane numbers or fuel mix components. The octane number of the Research method (RON) is determined using ASTM D 2699-07a. RON employs the Cooperative Fuel Research (CFR) detonation test machine. In addition, the octane number of the Research method can be calculated [RON (GC)] from the boiling range distribution data by gas chromatography. The calculation of RON (GC) is described in the publication, Anderson, P.C., Sharkey, J.M., and Walsh, R.P., “Journal Institute of Petroleum”, 58 (560), 83 (1972).
    [0023] The alkylation processes for creating alkylated gasoline with low volatility and high octane number are described in US 7,432,408 and US Patent Application 12/184109, filed on July 31, 2008.
    [0024] The ionic catalyst is composed of at least two components that form a complex. The ionic liquid catalyst comprises a first component and a second component. The first component of the catalyst may comprise a Lewis acid selected from the components as Lewis acid compounds of Group 13 metals, including aluminum halides, aluminum alkyl halide, gallium halide, and alkyl gallium halide (see International Union of Pure and Applied Chemistry (IUPAC), version 3, October 2005, for metals in Group 13 of the periodic table). Other Lewis acid compounds, in addition to those metals in Group 13, can also be used. In one embodiment the first component is aluminum halide or alkyl aluminum halide. For example, aluminum trichloride may be the first component of the liquid ionic acid catalyst.
    [0025] The second component that produces the liquid ionic acid catalyst is an organic salt or mixtures of the salts. These salts can be characterized by the general formula Q + A-, where Q + is an ammonium, phosphonium, boron, iodonium or sulfonium cation and A- is a negatively charged ion such as Cl '· Br', CIO 4 ', NO 3 ' , BF 4 ', BCI 4 , PFe, SbF 6 , AICI 4 , TaF6, CuCL, FeCI 3 , HSO 3 , RSO 3 , SO 3 CF 3 , 3 sulfurtrioxiphenyl. In a modality the second component is selected from those
    Petition 870180033178, of 04/24/2018, p. 12/27
    8/17 having quaternary ammonium halides having one or more alkyl fractions having from about 1 to about 12 carbon atoms, such as, for example, trimethylamine hydrochloride, methyltributylammonium halide, or substituted heterocyclic ammonium halide compounds, such as substituted hydrocarbyl pyridinium halide compounds, for example, 1-butylpyridinium halide, benzylpyridinium halide, or substituted hydrocarbyl imidazolium halides, such as, for example, 1-ethyl-3-methyl-imidazolium chloride.
    [0026] In one embodiment the ionic liquid catalyst is selected from the group consisting of substituted hydrocarbyl chloroaluminate, substituted hydrocarbyl imidazolium chloroaluminate, quaternary amine chloraluminate, trialkyl amine hydrogen chloride chloroaluminate, and pyridine hydrogen chloride chloroaluminate. mixtures thereof. For example, the ionic liquid catalyst can be an acidic haloaluminate acidic liquid, such as a substituted alkyl pyridinium chloroaluminate or a substituted alkyl imidazolium chloroaluminate of general formulas A and B, respectively.
    [0027] In formulas A and B; R, R 2 , and R 3 are H, methyl, ethyl, propyl, butyl, pentyl or hexyl group, X is a chloroaluminate. In formulas A and B, R, Rt, R 2 , and R 3 may or may not be the same. In one embodiment, the ionic liquid catalyst is N-butylpyridinium chloraluminate.
    [0028] In another embodiment, the ionic liquid catalyst can have the general formula RR 'R ”NH + AI 2 CÍ7', where N is a group having nitrogen, and where RR 'and R” are alkyl groups having 1 to 12 carbons, and where RR 'and R ”may or may not be the same. [0029] The presence of the first component should give the ionic liquid a Lewis or Franklin acid characteristic. Generally, the highest proportion of mol
    Petition 870180033178, of 04/24/2018, p. 13/27
    9/17 from the first component to the second component, the greater is the acidity of the ionic liquid catalyst.
    [0030] In one embodiment, the ionic liquid catalyst is mixed in the reactor with a hydrogen halide or an organic halide. The hydrogen halide or organic halide can boost the general activity and change the selectivity of the ionic liquid catalyst. The organic halide can be an alkyl halide. The alkyl halides that can be used include alkyl bromides, alkyl chlorides, alkyl iodides and mixtures thereof. A variety of alkyl halides can be used. The alkyl halide derivatives of isoparaffins or olefins that comprise the feed streams in the alkylation process are good choices. Said alkyl halides include, but are not limited to, isopentyl halides, isobutyl halides, butyl halides, propyl halides and ethyl halides. Other alkyl chlorides or halides having 1 to 8 carbon atoms can still be used. Alkyl halides can be used alone or in combination. The use of alkyl halides to promote hydrocarbon conversion by ionic liquid catalysts is taught in US7495144 and in US Patent Application 12/468750, filed on May 19, 2009.
    [0031] It is believed that the alkyl halide decomposes under hydroconversion conditions to release Bronsted acids or hydrogen halides, such as hydrochloric acid (HCl) or hydrobromic acid (HBr). These Bronsted acids or hydrogen halide promote the hydrocarbon conversion reaction. In one embodiment, the halide in the hydrogen halide or alkyl halide is the same as a halide component of the ionic liquid catalyst. In one embodiment, the alkyl halide is an alkyl chloride. A hydrogen chloride or an alkyl chloride can be used advantageously, for example, when the ionic liquid catalyst is a chloroaluminate.
    [0032] In one embodiment, at least a portion of the first fraction having an increased amount of the hydrogen halide is recycled back to the reactor. For example, the process may further comprise the recycling step of at least a portion or all of the first fraction of the reactor. When recycling halide
    Petition 870180033178, of 04/24/2018, p. 14/27
    10/17 hydrogen, less (or none) hydrogen halide or additional organic halide is required to be fed to the reactor. Alternatively, at least a portion of the first fraction having an increased amount of the hydrogen halide is treated with a caustic solid or an aqueous caustic solution. Because the first fraction has a higher concentration of hydrogen halide, it is easier and less expensive to treat than the complete effluent from the reactor, or a hydrocarbon phase that is separated from the effluent.
    [0033] In one embodiment, one or more product streams comprise one or more isoparaffins that are recycled back to the reactor. For example, the process may further comprise the step of recycling one or more isoparaffins back to the reactor. The isoparaffins can be the same as the reactants that were originally fed to the reactor. The processes for recycling isoparaffin to a reactor comprising an ionic liquid catalyst are described in US Patent Publication 20090171133. Among other factors, recycling isoparaffins to the reactor provides a more efficient process of alkylation and / or oligomerization when using an ionic liquid catalyst. The recycling of isoparaffins allows the reaction in the presence of the ionic liquid catalyst to maintain a more effective ratio of isoparaffin to olefin (W / O). Having the correct L / O is essential to minimize unwanted side reactions. You can also use a lower quality of supply while maintaining a desired I / O inside the reactor.
    [0034] In one embodiment, the effluent from the reactor is separated into a hydrocarbon phase and a catalyst phase, and extraction or distillation is carried out in the hydrocarbon phase.
    [0035] The extraction or distillation of the effluent can be carried out once or in a series of extraction or distillation steps. In one embodiment, the process comprises a single stage of extraction or distillation. Equipment and energy costs are reduced when the extraction or distillation is done only once. Modalities where extraction or distillation is done once, do not exclude processes where the portions of the first or second fraction are
    Petition 870180033178, of 04/24/2018, p. 15/27
    11/17 recycled back to the reactor.
    [0036] In one embodiment, recovery is done on the process equipment having low corrosion resistance for HCl. For example, equipment in the process can be prepared with one or more metals that have poor corrosion resistance to HCl and where the equipment in the process does not show corrosion from recovery. Examples of process equipment that can be used for recovery include separators, expression tanks, distillation columns, tubing, valves, trays, plates, random or structured packaging, coalescers, screens, filters, fractionators, partition walls, absorbents, etc. Metals that have poor corrosion resistance to HCl include aluminum, carbon steel, cast iron, stainless steel, bronze, and Durimet® alloys. In one embodiment the one or more metals having poor resistance to corrosion to the hydrogen halide comprises carbon steel, stainless steel, or a mixture thereof. These metals are less expensive and more readily available than metals that have better resistance to HCl corrosion, such as Hastelloy® alloys, Monel® alloys, Carpenter® alloys, tantalum, titanium, or cobalt based alloys. DURIMET is a registered trademark of Flowserve Corporation. HASTELLOY is a registered trademark of Haynes International, Inc. MONEL is a registered trademark of INCO family of companies. CARPENTER is a registered trademark of Carpenter Technology Corporation. Information on materials that are more or less resistant to corrosion by HCl is described in Kirk-Othmer Encyclopedia of Chemical Technology (John Wiley & Sons, Inc.), DOI: 10.1002 / 0471238961.0825041808091908.a01.pub2. Online Article Posting Date: December 17, 2004.
    [0037] Carbon steel is the steel where the main constituent of the alloy is carbon. Steel is considered to be carbon steel when no minimum content is specified or required for chromium, cobalt, collodion, molybdenum, nickel, titanium, tungsten, vanadium or zirconium, or any other element to be added to obtain a desired alloy effect; when the minimum specified for copper does not exceed 0.40 percent; or when the maximum content specified for any
    Petition 870180033178, of 04/24/2018, p. 16/27
    12/17 one of the following elements does not exceed the percentages observed: manganese 1.65, silicon 0.60 and copper 0.60.
    [0038] Stainless steel is an alloy steel with a minimum of 10.5 or 11% chromium content by mass. Stainless steel does not oxidize, corrode, or rust as easily as ordinary steel. There are different grades and surface finishes to suit the environment to which the material will be subjected in its lifetime. Stainless steel differs from carbon steel by the amount of chromium present. Carbon steel will rust when exposed to air and moisture. This iron oxide film (rust) is active and accelerates corrosion by forming more iron oxide. Stainless steels have sufficient amounts of chromium present so that a passive chromium oxide film forms which prevents further corrosion of the surface when exposed to air and moisture, and the passive film blocks corrosion from spreading into the structure. metal.
    [0039] In one embodiment the recovery uses a distillation column made with one or more metals having poor resistance to corrosion to the hydrogen halide, and the distillation column does not show corrosion from the recovery. Examples of these metals are carbon steel, stainless steel, and mixtures thereof. The evidence for when a distillation column or process equipment does not corrode is when the metal preparation is less than 10,000 / year, where 1,000 = 0.001 inch. In one embodiment, the process equipment has less than 10 thousand / year of penetration.
    [0040] The concentration of hydrogen halide in one or more product streams, the first fraction, the second fraction, or portions thereof can be measured by any methods that are accurate in the concentration range of the hydrogen halide. For gas streams, the following test methods are appropriate: (1) using a DRAEGER TUBE ™ with a pre-calibrated hydrogen halide selective probe, (2) using an online hydrogen halide measurement device, or (3) through acid / base titration with a standard caustic solution with a known concentration. DRAEGER TUBE ™ is a registered trademark of Draeger Safety Inc. For liquid currents the hydrogen halide
    Petition 870180033178, of 04/24/2018, p. 17/27
    13/17 can be measured by titration using a standard caustic solution with a known concentration.
    [0041] The following is a description of a modality of the process with respect to Figure 1:
    [0042] Reactive hydrogen chloride or organic chloride and an ionic liquid catalyst are fed to the reactor. The effluents from the reactor are passed through a separator, which separates the effluent into a hydrocarbon phase and a catalyst phase. At least a portion of the catalyst phase is recycled back to the ionic liquid catalyst being fed to the reactor. At least a portion of the hydrocarbon phase is fed into a distillation column. The distillation column distills the effluent from the reactor in a first fraction having essentially all hydrogen chloride and a second fraction that has essentially no hydrogen chloride. The second fraction is then distilled to recover the multiple product streams that are free of hydrogen chloride.
    [0043] The following is the description of a modality of the process with respect to Figure 2:
    [0044] Hydrogen chloride or organic chloride, reactive comprising one or more paraffins and one or more olefins, and an ionic liquid catalyst are fed into an alkylation reactor. The effluents from the alkylation reactor are passed through a separator, which separates the effluent into a hydrocarbon phase and a catalyst phase. At least a portion of the catalyst phase is recycled back to the ionic liquid catalyst being fed to the alkylation reactor. At least a portion of the hydrocarbon phase is fed into a distillation column. The distillation column distills the effluent from the reactor in a first fraction having essentially all hydrogen chloride and a second fraction that has essentially no hydrogen chloride. At least a portion of the first fraction is fed to the alkylation reactor. The second fraction is then distilled to recover the multiple product streams that are fed with hydrogen chloride, and an anhydrous isobutane stream that is recycled back to the alkylation reactor. The multiple product streams that are free of chloride
    Petition 870180033178, of 04/24/2018, p. 18/27
    Hydrogen 14/17 comprises methane, n-butane, and alkylated gasoline.
    [0045] For the purposes of this specification and appended claims, unless otherwise stated, all numbers expressing quantities, percentages or proportions, and other numerical values used in the specification and claims, are to be understood as being modified in all cases by the term "about". In addition, all ranges revealed here are inclusive of the extreme points and are independently combinable. Whenever a numerical range with a lower limit and an upper limit is revealed, any number that is within the range is also specifically revealed.
    [0046] Any term, abbreviation, or shorthand not defined is understood to have an ordinary meaning used by a person skilled in the art at the time the application is filed. The singular forms "um," "uma," and "o / a," include plural references expressly and unequivocally limited to one case.
    [0047] All publications, patents and patent applications cited in this application are hereby incorporated by reference in their entirety to the same extent as if the disclosure of each individual publication, patent application or patent were specifically and individually indicated as being incorporated by reference in its entirety.
    [0048] This written description uses examples to reveal the invention, including the best mode, and also allows anyone skilled in the art to create and use the invention. Many modifications of the exemplary embodiments of the invention disclosed above will readily occur to those skilled in the art. Thus, the invention should be interpreted as including all structures and methods that are within the scope of the appended claims. Unless otherwise specified, the recitation of a genre of elements, materials or other components, from which an individual component or mixture of components can be selected, is intended to include all possible gender subcombination of the listed components and mixtures thereof. EXAMPLES [0049] Example 1
    Petition 870180033178, of 04/24/2018, p. 19/27
    15/17 [0050] A sample of Nbutylpyridinium chloroaluminate ionic catalyst (C5H5NC4H9AI2CI7) was analyzed and had the following elemental composition. The ionic liquid catalyst had aluminum chloride as the metal halide.
    % by weight Al 12.4 % by weight Cl 56.5 % by weight C 24.6 % by weight H 3.2 % by weight N 3.3
    [0051] Example 2 [0052] The ionic liquid catalyst described in Example 1 was used to alkylate C3 and C4 olefins with isobutane. The alkylation was performed in a continuously stirred tank reactor (CSTR). An 8: 1 molar ratio of isobutane to the total olefin mixture was fed through a port of entry while under vigorous stirring. The ionic liquid catalyst was fed to the reactor through a second inlet port, aiming to occupy 7% vol in the reactor. A small amount of anhydrous HCI gas was added to the ionic liquid catalyst in the reactor. The average residence time of the combined feeds (mixture of isobutane / olefin and catalyst) in the reactor was about eight minutes. The outlet pressure was maintained at 200 psig (1378kPa) and the reactor temperature was maintained at 15.6 ° C (60 ° F) using external cooling. The effluents from the reactor were separated with a gravity separator in a hydrocarbon phase and an ionic liquid catalyst phase.
    [0053] The separated hydrocarbon phase was sent to a distillation column operating at 245 psig (1689kPa), 99 ° C (210 ° F) as the lower temperature and 49 ° C (120 ° F) above, with reflux. The stream above was rich in HCI, up to 15% by weight of HCI, and the remainder was mostly propane. The HCI-rich overhead current was sent back to the reactor for another use. The bottom stream was approximately HCI free, showing less than 10 ppm HCI concentration. The hydrocarbon bottom stream essentially free from
    Petition 870180033178, of 04/24/2018, p. 20/27
    16/17 HCI was sent to another distillation to generate an isobutane recycling stream as well as propane, n-butane, and alkylated gas streams. The propane, n-butane, and alkylated gasoline streams did not contain measurable HCI, showing less than 5 ppm HCI. This process scheme is desirable since HCl is concentrated only to the first distillation column, so any corrosion concern for the subsequent distillation columns are deleted. By recycling the HCI-enriched propane stream back to the reactor, the cost of HCI material and hazard handling is minimized.
    [0054] Example 3 (comparative example, reduction of HCI using caustic treatment):
    [0055] The effluent from the reactor in Example 2 was treated with 8% by weight of caustic NaOH solution in a reactor in a stirred tank under process conditions with a 3: 1 ratio of hydrocarbon to caustic solution, ambient temperature 60 s F), average residence time of 15 minutes and vigorous agitation. The resulting mixture of hydrocarbon and caustic solution was then separated by gravity in a decanter. The hydrocarbon phase was sent to a distillation column to produce propane, n-butane and alkylated gasoline streams and isobutane recycling streams. All of these streams did not contain measurable HCI, showing less than 5 ppm HCI. However, with this process, HCI is consumed and cannot be recycled back to the reactor. Yet the isobutane recycling stream is now saturated with water, thus requiring complete drying before being sent back to the reactor for reuse. These additional steps make the process operation more costly, and there are also corrosion issues for the caustic treatment equipment.
    [0056] Example 4 (HCI recycling using cascade distillation):
    [0057] The effluent from the reactor of Example 2 was sent in a series of distillation columns to separate the first hydrocarbon streams. The distillation columns operated at 38-149 ° C (100 - 300 ° F) bottom temperatures, 10-93 ° C (50 - 200 ° F) above temperatures, and 100-200 psig pressure. The chains
    Petition 870180033178, of 04/24/2018, p. 21/27
    17/17 alkylated results did not contain measurable HCI, showing less than 5 ppm HCI. The butane streams also did not contain measurable HCI, showing less than 5 ppm HCI. The isobutane recycling stream contained some HCI up to a few hundred ppm depending on operating conditions. The propane stream was enriched with more than 1000 ppm HCI. By adding another distillation column to the propane stream, HCI was enriched to more than about 15% by weight of HCI and the rest was mainly propane. This HCI-enriched stream is recycled back to the reactor. This HCI and isobutane recycling process is workable. However, all distillation columns are now exposed to HCI gas and this raises concerns for corrosion.
    Petition 870180033178, of 04/24/2018, p. 22/27
    1/4
    权利要求:
    Claims (24)
    [1]
    1. Process for producing hydrocarbon products with a low hydrogen halide content, characterized by the fact that it comprises:
    a) extraction or distillation of a reactor effluent in a first fraction having a quantity of a hydrogen halide and a second fraction having a reduced amount of a hydrogen halide less than the first fraction; wherein extraction is the removal of volatile components from the effluent by vaporization; where the reactor comprises:
    1. an ionic liquid catalyst having a metal halide, and ii. hydrogen halide or an organic halide; and
    b) recovery of one or more streams of hydrocarbon product directly from the second fraction, having less than 25 ppm by weight of the hydrogen halide.
    [2]
    2. Process according to claim 1, characterized by the fact that the reactor is used for paraffin alkylation, olefin dimerization, olefin oligomerization, isomerization, aromatic alkylation or mixtures thereof.
    [3]
    3. Process according to claim 1, characterized by the fact that the reactor comprises anhydrous HCI.
    [4]
    4. Process according to claim 1, characterized in that the one or more streams of hydrocarbon product of the second fraction have less than 10 ppm by weight of the hydrogen halide.
    [5]
    5. Process according to claim 1, characterized in that the one or more streams of hydrocarbon product of the second fraction have less than 5 ppm by weight of the hydrogen halide.
    [6]
    6. Process according to claim 1, characterized in that the one or more streams of hydrocarbon product of the second fraction have less than 1 ppm by weight of the hydrogen halide.
    [7]
    7. Process according to claim 1, characterized by the fact that the metal halide is aluminum chloride and the hydrogen halide is HCI.
    Petition 870180033178, of 04/24/2018, p. 23/27
    2/4
    [8]
    Process according to claim 1, characterized in that the one or more streams of hydrocarbon product comprise an alkylated gasoline.
    [9]
    Process according to claim 1, characterized by the fact that one or more product streams comprise one or more isoparaffins and the process further comprises recycling one or more isoparaffins back to the reactor.
    [10]
    10. Process, according to claim 1, characterized by the fact that it also comprises the step of separating the catalyst phase from the effluent before the extraction or distillation of the effluent.
    [11]
    11. Process, according to claim 1, characterized by the fact that the process comprises a simple extraction or distillation step.
    [12]
    Process according to claim 1, characterized by the fact that one or more hydrocarbon product streams comprise propane, butane, alkylated gasoline or mixtures thereof.
    [13]
    13. Process according to claim 1, characterized by the fact that one or more streams of hydrocarbon product have less than 25 ppm by weight of hydrogen halide before any optional caustic treatment.
    [14]
    14. Process according to claim 1, characterized by the fact that the metal halide is selected from the group consisting of AICI 3 , AIBr 3 , GaCI 3 , GaBr 3 , lnCI 3 , lnBr 3 and mixtures thereof.
    [15]
    15. Process according to claim 1, characterized by the fact that the ionic liquid catalyst is selected from the group consisting of substituted hydrocarbyl pyridinium chloroaluminate, substituted hydrocarbyl imidazolium chloraluminate, quaternary amine chloroaluminate, trialkyl amine chloride chloraluminate hydrogen, alkyl pyridine chloride chloroaluminate and mixtures thereof.
    [16]
    16. Process according to claim 15, characterized by the fact that the ionic liquid catalyst is N-butylpyridinium chloraluminate.
    Petition 870180033178, of 04/24/2018, p. 24/27
    3/4
    [17]
    17. Process according to claim 1, characterized by the fact that one or more streams of hydrocarbon product are recovered in the process equipment having poor resistance to corrosion to HCI and in which the process equipment does not present corrosion from of recovery.
    [18]
    18. Process for producing hydrocarbon products with a low hydrogen halide content, characterized by the fact that it comprises:
    a) extraction or distillation of a reactor effluent in a first fraction having a quantity of a hydrogen halide and a second fraction having a reduced quantity of a hydrogen halide; wherein extraction is the removal of volatile components from the effluent by vaporization; wherein the reactor comprises an ionic liquid catalyst having a metal halide; and
    b) recovery of propane, n-butane and alkylated gasoline directly from the second fraction, all having less than 25 ppm by weight of the hydrogen halide.
    [19]
    19. Process according to claim 18, characterized by the fact that propane, n-butane and alkylated gasoline all have less than 10 ppm by weight of the hydrogen halide.
    [20]
    20. Process according to claim 18, characterized by the fact that propane, n-butane and alkylated gasoline all have less than 5 ppm by weight of the hydrogen halide.
    [21]
    21. Process according to claim 18, characterized by the fact that the reactor additionally comprises a hydrogen halide or an organic halide.
    [22]
    22. Process for producing hydrocarbon products with a low hydrogen halide content, characterized by the fact that it comprises:
    a) extraction or distillation of a reactor effluent in a first fraction having an increased amount of a hydrogen halide and a second fraction having a reduced amount of a hydrogen halide less than the first fraction; wherein extraction is the removal of volatile components from the effluent by vaporization; where the reactor comprises:
    Petition 870180033178, of 04/24/2018, p. 25/27
    4/4
    i. an ionic liquid catalyst having a metal halide, and ii. hydrogen halide or an organic halide; and
    b) recovering one or more streams of hydrocarbon product directly from the second fraction, using a distillation column comprising one or more metals having poor resistance to corrosion to the hydrogen halide; and where the distillation column shows no corrosion from the recovery.
    [23]
    23. Process according to claim 22, characterized by the fact that the one or more metals having poor resistance to corrosion to the hydrogen halide comprise a carbon steel, a stainless steel or a mixture thereof.
    [24]
    24. Process according to claim 1, 18 or 22, characterized by the fact that it still comprises the step of recycling the first fraction back to the reactor.
    Petition 870180033178, of 04/24/2018, p. 26/27
    1/2
    FIGURE 1
    HCI removal
    2/2
    FIGURE 2
    Deisobutane recycling
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    同族专利:
    公开号 | 公开日
    DE112010005065T5|2012-11-08|
    US8237004B2|2012-08-07|
    US20110155632A1|2011-06-30|
    GB201205024D0|2012-05-09|
    SG182292A1|2012-08-30|
    CN102666445A|2012-09-12|
    AU2010337321A1|2012-04-12|
    CN102666445B|2013-08-28|
    AU2010337321B2|2012-10-11|
    WO2011081721A2|2011-07-07|
    WO2011081721A3|2011-09-15|
    KR101284408B1|2013-07-09|
    GB2488678B|2015-10-21|
    KR20120125475A|2012-11-15|
    GB2488678A|2012-09-05|
    WO2011081721A4|2011-11-10|
    BR112012009303A2|2016-06-07|
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    法律状态:
    2018-04-10| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|
    2018-09-04| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2018-10-09| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 11/11/2010, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US12/650,816|US8237004B2|2009-12-31|2009-12-31|Process for making products with low hydrogen halide|
    PCT/US2010/056379|WO2011081721A2|2009-12-31|2010-11-11|A process for making products with low hydrogen halide|
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