Separation of furfural/middle distillate streams

Abstract: A furfural-containing middle distillate stream is supported by use of a polyethylene-imine membrane which has been crosslinked with a polyisocyanate or a poly (carbonyl chloride) cross-linking agent.

Description: This invention relates to the separation of a furfural/middle distillate stream. More particularly it relates to separation of furfural from the product streams from a unit wherein furfural is used to extract undesirable components from middle distillates such as diesel oil. As is well known to those skilled in the art, middle distillates such as diesel oils, cracking stocks, and catalytic cycle oils as produced are characterized by various deficiencies including poor cetane number and burning quality. It is common to attempt to improve the quality of these hydrocarbon stocks by extracting the undesirable components which are responsible for the deficiencies. These stocks may for example be treated with furfural which may extract aromatics, olefins, and compounds of nitrogen, oxygen, and sulfur from the middle distillate oil. The treated oil is typically characterized by improved properties. Furfural treating of these charge oils is typically carried out by contacting 100 parts of deaerated charge oil (typically having an ibp (initial boiling point) of 350°F - 475°F (176 - 246°C), say 375°F (190°C) and a 50% bp (boiling point) of 500°F - 600°F (260 - 315°C), say 550°F (280°C) and an ep (end point) of 600°F - 750°F (315 - 399°C), say 650°F (343°C) and an aromatics content of 10 - 40 w%, say 30 w%) with 50 - 250 parts, say 110 parts of furfural. Contact is commonly at 70°F - 150°F (21 - 65°C), say 110°F (43°C) at 40 - 120 psig (0.45 - 0.82 MPa), say 100 psig (0.78 MPa) in a contacting operation which may be carried out in a rotating disc contactor. The raffinate (commonly containing 75 - 90 w%, say 83 w% oil and 10 - 25 w%, say 17 w% furfural and aromatics content of 5 - 25 w%, say 12 w%) is commonly recovered at 400°F - 450°F (204 - 232°C), say 430°F (221°C) and passed to a series of stripping towers and vacuum flash towers to separate refined oil and furfural. The extract stream (commonly containing 20 - 50 w%, say 30 w% oil and 50 - 80 w%, say 70 w% furfural and aromatics content of 70 - 90 w%, say 80 w%) is commonly recovered at 380°F - 450°F (193 - 232°C), say 420°F (215°C) and passed to a series of stripping towers and vacuum flash towers to separate extract and furfural. The several furfural streams recovered during these operations are further passed to a series of separation and fractionation operations wherein furfural is recovered and recycled to the contacting operation e.g. the rotating disc extractor. It will be apparent that a substantial portion of the cost of a furfural treating unit lies in the several distillation columns and associated equipment including fired heaters, heat exchangers, pumps, etc; and the cost of operation is clearly large because of the cost of heat and power associated with these operations. It is an object of this invention to provide a novel process for furfural treating of middle distillates. It is a particular object of this invention to provide a process which minimizes the need to provide distillation steps and which permits substantial savings in operating costs. Other objects will be apparent to those skilled in the art. In accordance with certain of its aspects, this invention is directed to a process which comprises passing a charge containing furfural and a middle distillate hydrocarbon into contact with, as a separation membrane, a non-porous separating polyimine layer which has been crosslinked with a polyisocyanate or with a poly (carbonyl chloride) crosslinking agent; maintaining a pressure drop across said membrane thereby forming a high pressure retentate containing increased content of middle distillate hydrocarbon and decreased content of furfural and a lower pressure permeate containing decreased content of middle distillate hydrocarbon and increased content of furfural; maintaining the pressure on the low pressure discharge side of said membrane above the vapor pressure of said permeate thereby maintaining said permeate in liquid phase; maintaining the pressure on the high pressure retentate side of said membrane above the vapor pressure of said retentate thereby maintaining said retentate in liquid phase; recovering said permeate of increased content of furfural and decreased content of middle distillate hydrocarbon from the low pressure discharge side of said membrane; and recovering said retentate of increased content of middle distillate hydrocarbon and decreased content of furfural from the high pressure side of said membrane. The charge hydrocarbon oil which may be subjected to furfural extraction and thereafter treated according to the process of this invention may be a middle distillate hydrocarbon oil characterized by the following properties: These charge oils may include diesel oils, cracking stock, catalytic cycle oils, etc. When the charge oil is a diesel oil, it may be characterized by the following properties: When the charge oil is a Vacuum Gas Oil (VGO) cracking stock, it may be characterized by the following properties: When the charge oil is a Light Cycle Gas Oil (LCGO) catalytic cycle oil, it may be characterized by the following properties: The charge hydrocarbon oil to be furfural treated may be stripped of entrained air (to minimize degradation of furfural by oxidation and to prevent formation of coke if the oil is heated to elevated temperatures). The deaerated oil (100 parts) at 70°F - 150°F (21 - 65°C), say 110°F (43°C) is passed to a contacting operation (typically a rotating disc extractor) wherein it is contacted countercurrently at 40 - 120 psig (0.45 - 0.92 MPa), say 100 psig (0.78 MPa) with furfural (110 parts) entering at 80°F - 160°F (27 - 71°C), say 120°F (48°C). Raffinate (60 - 80 parts, say 70 parts) at 80°F - 160°F (26 - 71°C), say 120°F (48°C) leaving the top of the extractor contains 75 - 90 parts, say 83 parts of oil and 10 - 25 parts, say 17 parts of furfural. Extract (20 - 40 parts, say 30 parts) at 60°F - 140°F (15 - 60°C), say 100°F (38°C) leaving the bottom of the extractor contains 20 - 50 parts, say 30 parts of oil and 50 - 80 parts, say 70 parts of furfural. It is a feature of the process of this invention that it permits treatment of each of these streams separately to permit recovery of the furfural which may be recycled to the contacting operation. The other component of each stream (i.e. the refined oil from the raffinate stream and the extract from the extract stream) may be withdrawn for further handling in the refinery. It is a feature of this invention that separation of each of the furfural-containing streams may be effected by a pressure driven process utilizing a composite structure which includes a separation layer. THE MEMBRANE ASSEMBLY The process of this invention may be carried out by use of a composite structure which in one preferred embodiment may include (i) a carrier layer which provides mechanical strength, (ii) a porous support layer, and (iii) a separating layer across which separation occurs. The composite structure of this invention includes a multi-layer assembly which in the preferred embodiment preferably includes a porous carrier layer which provides mechanical strength and support to the assembly. THE CARRIER LAYER This carrier layer, when used, is characterized by its high degree of porosity and mechanical strength. It may be fibrous or non-fibrous, woven or non-woven. In the preferred embodiment, the carrier layer may be a porous, flexible, woven fibrous polyester. A typical polyester carrier layer may be formulated of non-woven, thermally-bonded strands. THE POROUS SUPPORT LAYER The porous support layer (typically an ultrafiltration membrane) which may be used in practice of this invention is preferably formed of polyacrylonitrile polymer. Typically the polyacrylonitrile may be of thickness of 40-80 microns, say 50 microns and is preferably characterized by a pore size of less than about 500A and typically about 200A. This corresponds to a molecular weight cut-off of less than about 100,000, typically about 40,000. THE SEPARATING LAYER The separating layer which permits attainment of separation in accordance with the process of this invention includes a non-porous film or membrane, of preferably 0.2-1.5 microns, say about 0.5 microns, of a polyimine polymer, preferably of molecular weight M n of about 40,000-100,000, say about 60,000 (prior to cross-linking), which is cross-linked by urea or amide linkages. The separating layer may be prepared by cross-linking a polyimine polymer in situ. In the preferred embodiment, the polyimine polymer is crosslinked in situ. Polyimine polymers are characterized by the presence of recurring -N-R''- groups as integral parts of the main polymer chain. Typical structural formula of linear polyimines may be represented as wherein n represents the degree of polymerization or number of recurring groups in the polymer chain, and is different from 0. In the above formula, R'' may preferably be a hydrocarbon group selected from the group consisting of alkylene, aralkylene, cycloalkylene, arylene, and alkarylene, including such radicals when inertly substituted. When R'' is alkylene, it may typically be methylene, ethylene, n-propylene, iso-propylene, n-butylene, i-butylene, sec-butylene, amylene, octylene, decylene, octadecylene, etc. When R'' is aralkylene, it may typically be benzylene, betaphenylethylene, etc. When R'' is cycloalkylene, it may typically be cyclohexylene, cycloheptylene, cyclooctylene, 2-methylcycloheptylene, 3-butylcyclohexylene, 3-methylcyclohexylene, etc. When R'' is arylene, it may typically be phenylene, naphthylene, etc. When R is alkarylene, it may typically be tolylene, xylylene, etc. R'' may be inertly substituted i.e. it may bear a non-reactive substitutent such as alkyl, aryl, cycloalkyl,ether, etc. typically inertly substituted R'' groups may include 3-methoxypropylene, 2-ethoxyethylene, carboethoxymethylene, 4-methylcyclohexylene, p-methylphenylene, p-methylbenzylene, 3-ethyl-5-methylphenylene, etc. The preferred R'' groups may be phenylene or lower alkylene, i.e. C₁-C₁₀ alkylene, groups including e.g. methylene, ethylene, n-propylene, i-propylene, butylene, amylene, hexylene, octylene, decylene, etc. R'' may preferably be phenylene or ethylene -CH₂CH₂-. Illustrative polyimine polymers include those of molecular weight M n of 40,000-100,000, say 60,000. Suitable polyimines may include the following, the first listed being preferred: A. Cordova Chemical Company Corcat P-600 brand of polyethyleneimine resin membrane ( M n of 60,000) in 33 w% aqueous solution - Brookfield viscosity @ 25°C of 5000 cP (5 Pa.s) Sp.Gr & 25°C of 1.04-1.06, and pH of 10-11, having the formula wherein R is H or (CH₂CH₂N) x (containing 30% primary, 40% secondary, and 30% tertiary amines). B. Dow Chemical Co Tydex 12 brand of polyethyleneimine membrane ( M n of 50,000) in 30w% aqueous solution having the same formula as the Corcat P-600 membrane. The polyethyleneimine resin in 0.01-1w% aqueous solution, say 0.1w% concentration is deposited on the porous support layer over 1-5 minutes, say 2 minutes, drained, and then interfacially cross-linked. Interfacial cross-linking of the preformed polyimine polymer may be effected by contact with, as cross-linking agent. R''[ (NCO) a (COC1) 1-a ] b When the isocyanate cross-linking agent R'' (NCO) b is employed, the cross-linking forms urea bonds. When the carbonyl chloride cross-linking agent R'' (COC1) b is employed, the cross-linking forms amide bonds. The cross-linking agent R'' [ (NCO) a (COC1) 1-a ] b , wherein a is 0 or 1 and b is an integer greater than 1, may be a polyisocyanate when a is 1. When a is 0 , the cross-linking agent may be a poly(carbonyl chloride). Preferably a is 1 and b is 2 i.e. the preferred cross-linking agent is a diisocyanate. It will be apparent to those skilled in the art when b is 2, R'' may be for example alkylene. When b is greater than 2, e. g. 3, it is obvious that the above definition of R'' as e.g. alkylene is for convenience; and the actual hydrocarbon residue will have more than two relevant valences. The preferred polyisocyanates (i.e. monomeric compounds bearing a plurality of -NCO isocyanate groups) may include those which contain an aromatic nucleus, typically a toluene diisocyanate or a phenylene dissocyanate. In practice of this aspect of the invention, cross-linking is effected by contacting the surface of the porous layer with a 0.1w%-1.0w%, say 0.8w% solution of cross-linking agent in solvent, typically hydrocarbon such as hexane. Contact may be at 20°C-40°C, say 25°C for 15-60 seconds, say 15 seconds. Thereafter the membrane may be cured at 60°C-140°C, say 120°C for 10-20 minutes, say 15 minutes. THE COMPOSITE MEMBRANE It is a feature of this invention that it may utilize a composite membrane which comprises (i) a carrier layer characterized by mechanical strength, for supporting a porous support layer and a separating layer (ii) a porous support layer such as a polyacrylonitrile membrane of 40-80 microns, and of molecular weight cutoff of 25,000-100,000, and (iii) as a non-porous separating layer a polyimime of molecular weight M n of 40,000-100,000, which has been cross-linked with a polyisocyanate or a poly(carbonyl chloride). It is possible to utilize a spiral wound module which includes a non-porous separating layer membrane mounted on a porous support layer and a carrier layer, the assembly being typically folded and bonded or sealed along all the edges but an open edge - to form a bag-like unit which preferably has the separating layer on the outside. A cloth spacer, serving as the permeate or discharge channel is placed within the bag-like unit. The discharge channel projects from the open end of the unit. There is then placed on one face of the bag-like unit, adjacent to the separating layer, and coterminous therewith, a feed channel sheet - typically formed of a plastic net. The so-formed assembly is wrapped around a preferably cylindrical conduit which bears a plurality of perforations in the wall - preferably in a linear array which is as long as the width of the bag-like unit. The projecting portion of the discharge channel of the bag-like unit is placed over the perforations of the conduit; and the bag-like unit is wrapped around the conduit to form a spiral wound configuration. It will be apparent that, although only one feed channel is present, the single feed channel in the wound assembly will be adjacent to two faces of the membrane layer. The spiral wound configuration may be formed by wrapping the assembly around the conduit a plurality of times to form a readily handleable unit. The unit is fitted within a shell (in manner comparable to a shell-and-tube heat exchanger) provided with an inlet at one end and an outlet at the other. A baffle-like seal between the inner surface of the shell and the outer surface of the spiral-wound unit prevents fluid from bypassing the operative membrane system and insures that fluid enters the system principally at one end. The charge passes from the feed channel, into contact with the separating layer and thence therethrough, into the permeate channel and thence therealong to and through the perforations in the conduit through which it is withdrawn as net permeate. In use of the spiral wound membrane, charge liquid is permitted to pass through the plastic net which serves as a feed channel and thence into contact with the non-porous separating membranes. The liquid which does not pass through the membranes is withdrawn as retentate. The liquid which permeates the membrane passes into the volume occupied by the permeate spacer and through this permeate channel to the perforations in the cylindrical conduit through which it is withdrawn from the system. In another embodiment, it is possible to utilize the system of this invention as a tubular or hollow fibre. In this embodiment, the polyacrylonitrile porous support layer may be extruded as a fine tube with a wall thickness of typically 0.001-0.1 mm. The extruded tubes are passed through a bath of polyethyleneimine which is cross-linked and cured in situ. A bundle of these tubes is secured (with an epoxy adhesive) at each end in a header; and the fibres are cut so that they are flush with the ends of the header. This tube bundle is mounted within a shell in a typical shell-and-tube assembly. In operation, the charge liquid is admitted to the tube side and passes through the inside of the tubes and exits as retentate. During passage through the tubes, permeate passes through the non-porous separating layer and permeate is collected in the shell side. PRESSURE DRIVEN PROCESS It is a feature of the non-porous cross-linked polyimine separating layer that is found to be particularly effective when used in a pressure driven process. In a pressure driven process, the charge liquid containing a more permeable and a less permeable component is maintained in contact with a non-porous separating layer; and a pressure drop is maintained across that layer. A portion of the charge liquid dissolves into the membrane and diffuses therethrough. The permeate passes through the membrane and exits as a liquid. In practice of the process of this invention, the charge (e.g. raffinate plus furfural or extract plus furfural) at 20°C-40°C, say 25°C and 400-1000 psig (2.9 - 7.1 MPa) say 800 psig (5.7 MPa) and a charge rate of 800 - 1400, say 1200 ml/min is admitted to the high pressure side of the membrane assembly. The retentate which is recovered in liquid phase from the high pressure side of the membrane typically contains decreased content of furfural when treating a typical charge (e.g. a raffinate) containing 10-1000 parts, say 200 parts of diesel oil and 100-1000 parts, say 800 parts of furfural. Permeate, recovered in liquid phase, in this instance may contain 1-10 parts, say 1 part of diesel oil and 40-100 parts, say 99 parts of furfural. Flux may typically be 10-60 kmh (kilograms per square meter per hour), say 54 kmh. Selectivity (measured in terms of w% furfural in the permeate) may be as high as 90-99.9 w%. It is common to attain 99.9 w% selectivity. It will be apparent that the process of this invention may be employed to separate furfural from various hydrocarbon oils or from various aromatic hydrocarbons. DESCRIPTION OF SPECIFIC EMBODIMENTS Practice of the process of this invention may be apparent to those skilled in the art from the following examples wherein, as explained in this specification, all parts are parts by weight unless otherwise stated. Asterisk (*) indicates a control example. EXAMPLE I In this example which represents the best mode of carrying out the process of this invention, the carrier layer is the woven polyester backing described supra. The porous support layer is the commercially available layer of Daicel DUY-L polyacrylonitrile of molecular weight cutoff of 40,000. The polyethyleneimine PEI separating layer is fabricated from the Corcat P-600 brand of polyethyleneimine ( M n of 60,000). This 33 w% aqueous solution is diluted to 0.1 w% by addition of water. This solution is deposited on the porous support layer over 2 minutes and is then interfacially crosslinked. The assembly containing the preferred microporous polyacrylonitrile supra as porous support layer and the woven polyester backing supra as carrier layer (total area Ca 45 cm²) is contacted for 2 minutes with the dilute aqueous solution of polyethyleneimine. Excess solution is removed by holding the membrane assembly in a vertical position in air for one minute. The assembly is then contacted with a cross-linking agent (0.8 w% of 2,4-toluene diisocyanate TDI in hexane) for 15 seconds during which time cross-linking occurs. The membrane assembly is then heat cured at 120°C for 15 minutes. The membrane is mounted in a standard cell. There is admitted to the cell and to the non-porous polyethyleneimine separating layer a charge liquid containing 80% furfural and 20 w% diesel oil. This charge is typical of the extract recovered from a furfural treating unit in commercial practice. Separation is carried out at 25°C and a charge (and retentate) pressure of 800 psig (5.7 MPa). Permeate pressure is atmospheric. Selectivity is measured and reported as % Rejection which is calculated as 100x (the quantity of diesel oil in the feed minus the quantity of diesel oil in the permeate) divided by the quantity of diesel oil in the feed. Clearly a higher selectivity is desired, as this mean that the retentate desirably contains less furfural and the permeate desirably contains more furfural. Flux is measured as kilograms per square meter per hour (kmh). In these examples the selectivity is 99.9% Rejection and the Flux is 53.9 kmh. EXAMPLE II In this Example the procedure of Example I is followed except that the cross-linking agent (toluene diisocyanate TDI) is present as a 0.2 w% solution. EXAMPLES III-VI In these series of Examples, the procedure of Example I is followed except that: (i) The support is the Gemeinshaft fur Trenntechnik (GFT) brand of polyacrylonitrile. (ii) The concentration of crosslinking agent (TDI) is 0.2 w% (Example III), 0.4 w% (Example IV), 0.6 w% (Example V), and 0.8 w% (Example VI). (iii) The curing temperature is 80°C. From the above Table, it is apparent that it is possible to achieve Selectivity as high as 99.9 w% at a flux as high as 53.9 kmh. Preferred conditions include cross-linking with 0.8 w% TDI with curing at 120°C - using the Diacel polyacrylonitrile support and the polyethyleneimine separating layer. EXAMPLES VII-XVII In this series of Examples, the charge liquid contains 20 w% furfural and 80 w% diesel oil. This charge is typical of the raffinate recovered from a furfural treating unit in commercial practice. The separating mebranes of Examples VII, VIII, and IX are formed by the same procedures as is followed in Examples III, IV, and VI; and performance is determined at 5,5 16 MPa (800 psi) charge pressure. The separating membranes of Examples X - XVII are of polyethyleneimine (prepared as in Example I). Crosslinking is carried out with 0.8 w% TDI in Examples X - XIII, with 0.4 w% hexamethylene diisocyanate HDI as in Example XIV with 0.4 w% suberoyl dichloride SDC in Examples XV, with 0.8 w% isophthaloyl dichloride IPC in Example XVI, and in Example XVII with a mixture of equal parts of 0.4 w% TDI solution and 0.4 w% HDI solution in hexane. Curing is at 110°C in Example X and at 120°C in Examples XI - XVII. Charge pressure is 400 psig (2.9 MPa) in Example XIII, 600 psig (4.3 MPa) in Example XII, and 800 psig (5.7 MPa) in all other Examples. From the above Table, it is apparent that it is possible to attain Selectivity as high as 99.9%. Flux may be as high as 13.5 kmh, although with sacrifice of Selectivity. Best performance in this series of runs appears to be that of Example XVII which yields Selectivity of 99.9% at Flux of 6.9. Results comparable to the above may be attained if other middle distillates are employed i.e. the raffinate and extract streams leaving a furfural unit in which other middle distillates have been treated. It is a feature of the process of this invention that the oils which have been treated are characterized by improved cetane number; by decreased content of aromatics, olefins, oxygen compounds, sulfur compounds, nitrogen compounds, and metals.

Claims: A method for reducing the furfural content of a charge containing furfural and a middle distillate hydrocarbon characterized by bringing the charge into contact with a separation membrane comprising a non-porous separating polyimine layer crosslinked with a polyisocyanate or poly (carbonyl chloride) cross-linking agent; maintaining a pressure drop across the membrane thereby forming a high pressure retentate with an increased content of middle distillate hydrocarbon and decreased content of furfural, and a lower pressure permeate with a decreased content of middle distillate hydrocarbon and increased content of furfural; the pressure on the low pressure discharge side of the membrane being above the vapor pressure of the permeate to maintain the permeate in liquid phase; and the pressure on the high pressure rententate side of the membrane above the vapor pressure of the retentate to maintain the rententate in liquid phases. A process according to Claim 1 characterized in that the middle distillate is a diesel oil. A process according to Claim 1 characterised in that the middle distillate is a cracking stock. A process according to Claim 1 characterised in that the middle distillate is a catalytic cycle oil. A process according to any one of Claims 1 to 4 characterized in that the cross-linking agent is a toluene diisocyanate. A process according to any one of Claims 1 to 5 characterized in that the cross-linking agent is a toluene diisocyanate plus a hexamethylene diisocyanate. A process according to any one of Claims 1 to 6 characterized in that the polyimine component of the membrane is wherein R'' is an alkylene, aralkylene, cycloalkylene, arylene, or alkarylene hydrocarbon group and n is a number, and n≠0 A process according to Claim 7 characterized in that R'' is ethylene - CH₂CH₂ -.

Inventors: PASTERNAK MORDECHAI, REALE JOHN JR, PASTERNAK, MORDECHAI, REALE, JOHN, JR.
Applicants: TEXACO DEVELOPMENT CORP, TEXACO DEVELOPMENT CORPORATION
Application year: 1990
Main classification: C10G31
IPC codes: C10L1, B01D61, C10G53, C07D307, C10G29, C10G31, C10G21, B01D71