Process of coupling aldehydes

Abstract

A process for coupling aldehydes is disclosed. This process involves supplying an aldehyde-containing stream and a catalyst stream containing a homogeneous catalyst in an alcohol solution to a reactor. The aldehyde stream is mixed with the homogeneous catalyst in the alcohol solution. Freun molecules precipitate from the solution in the reactor. The liquid stream containing the homogeneous catalyst in the alcohol solution is recovered from the reactor. The liquid stream containing the homogeneous catalyst in the alcohol solution is recycled back into the reactor and coupled with a new feed of the aldehyde stream.

Description

[Technical Field]

[0001] (Priority statement) This application claims priority to U.S. Patent Application No. 18 / 453,220, filed on 21 August 2023, which is incorporated herein by reference in its entirety.

[0002] (Field of Invention) This field relates to processes for coupling aldehydes. In particular, this field may relate to processes for coupling aldehydes and recycling the catalytic flow used for aldehyde coupling. [Background technology]

[0003] As global demand for fuel increases, there is growing interest in producing fuel from sources other than crude oil and blending its components. These sources, often referred to as bio-renewable sources, include, but are not limited to, vegetable oils such as corn, rapeseed, canola, and soybean; microbial oils such as algal oil; animal fats such as non-edible animal fats; fish oil; and various waste flows such as yellow and brown grease and sewage sludge. A common characteristic of these sources is that they are composed of glycerides and free fatty acids (FFAs). Both triglycerides and FFAs contain aliphatic carbon chains with 8 to 24 carbon atoms. The aliphatic carbon chains in triglycerides or FFAs can be fully saturated, or monovalent, divalent, or polyunsaturated.

[0004] As concern for sustainability grows, the need for sustainable aviation fuel (SAF) is increasing because SAF emits fewer greenhouse gases (GHGs) compared to petrochemically supplied fuels. Government subsidies and mandates for the production of carbon-neutral jet fuels are driving increased support and demand for SAF worldwide. In recent years, much research has been conducted to find effective and efficient means of producing SAF. As the demand for SAF increases globally, there is growing interest in alternative sources of supply for SAF production.

[0005] Light olefins have traditionally been produced by steam cracking or catalytic cracking processes. Light olefins serve as feedstocks for the production of numerous chemicals. However, using petroleum sources as feedstocks results in GHG emissions. Researchers and refineries are seeking alternative feedstocks for these processes. The search for alternative materials for producing light olefins has led to the use of oxygenates. Oxygenates can provide non-petroleum-based routes for producing olefins and other hydrocarbons. However, a consistent supply of oxygenates is needed to meet the demand for light olefins.

[0006] Azolium compounds, such as thiazolium salts, imidazolium salts, and triazolium salts, are known to be used as catalysts for aldehyde coupling reactions, including benzoin condensation. Alkanes are examples of coupling products in aldehyde coupling reactions, which can be converted into other products, including fuels. However, these azolium compounds are difficult to recover, making their industrial use as catalysts challenging. For this reason, azolium compounds are used as supported catalysts on organic or inorganic supports. However, these azolium compound supported catalysts have problems such as insufficient yield, rapid decline in catalytic activity, and poor recyclability.

[0007] The anticipated stagnation in the growth of high-fructose corn syrup could lead to a future situation of sugar stranding. It is desirable to have effective pathways for converting these sugars into hydroxymethfurfural (HMF), which can be processed to produce sustainable aviation fuel that meets fuel standards, and other chemicals such as olefins. [Overview of the project]

[0008] A process for coupling aldehydes is disclosed. In this process, an aldehyde-containing stream is brought into contact with a catalytic stream of a catalyst in an alcohol solution. The coupling reaction produces a withdrawn Freun system molecule. The liquid stream of the catalyst in the alcohol solution is also withdrawn from the reactor. This process recycles the used catalyst by returning it to the reactor and coupling a new feedstock of aldehydes. It is demonstrated that the recycled catalyst for the coupling reaction produces a comparable yield compared to a new catalyst. Furthermore, the Freun system molecule can be processed to produce SAF or olefins. [Brief explanation of the drawing]

[0009] [Figure 1] This is a simplified process flow diagram of an aldehyde coupling process according to an exemplary embodiment of the present disclosure. [Figure 2] This is a graph plotting the yield (%) of 5,5'-di(hydroxymethyl)froin (DHMF) against time (minutes) according to another exemplary embodiment of the present disclosure. [Figure 3] This is a graph plotting the change in DHMF yield (%) versus the water content of the solvent used, according to yet another exemplary embodiment of the present disclosure. [Figure 4] This is a graph plotted to show the change in yield (%) of DHMF with respect to the molar ratio of aldehyde to catalyst at different water concentrations in an alcohol as a solvent, according to yet another exemplary embodiment of the present disclosure. [Figure 5] This is a graph plotted to show the change in DHMF yield (%) with respect to the molar ratio of aldehyde to catalyst for different catalysts, according to yet another exemplary embodiment of the present disclosure. [Figure 6] This is a graph plotted to show the change in DHMF yield (%) for novel and recycled catalysts according to yet another exemplary embodiment of the present disclosure. [Figure 7] This is a graph plotted to show the change in C10 yield (%) with respect to the hydrodeoxygenation (HDO) time of Freun, according to yet another exemplary embodiment of the present disclosure. [Figure 8] This is a graph plotted to show the change in C10 yield (%) with respect to hydrogen pressure, according to yet another exemplary embodiment of the present disclosure. [Figure 9] This is a graph plotted to show the change in C10 yield (%) with respect to the weight ratio of Freun:catalyst according to yet another exemplary embodiment of the present disclosure. [Figure 10] This is a graph plotted to show the change in C10 yield (%) with temperature according to yet another exemplary embodiment of the present disclosure. [Modes for carrying out the invention]

[0010] definition The term "column" means one or more distillation columns (singular or plural) for separating one or more components of different volatilities. Unless otherwise indicated, each column includes a condenser at the top of the column to condense and reflux a portion of the overhead stream returning to the top of the column, and a reboiler at the bottom of the column to vaporize a portion of the bottoms stream and return it to the bottom of the column. The feed to the column may be preheated. The top pressure is the pressure of the overhead vapor at the vapor outlet of the column. The bottom temperature is the liquid bottoms outlet temperature. The overhead line and the bottoms line refer to the net line from the column downstream of any reflux or reboiling to the column. A stripper column omits the reboiler at the bottom of the column and may instead provide the heating requirements and the driving force for separation from a fluidizing inert medium such as steam. A stripping column typically feeds the upper trays and withdraws the main product from the bottom. <......

[0011] As used herein, the term "component-rich stream" means that the rich stream exiting the vessel has a higher concentration of components than the feed to the vessel.

[0012] As used herein, the term "True Boiling Point" (TBP) means a test method for determining the boiling point of a substance, which test method is capable of obtaining analytical data, produces liquefied gas, distillation fractions, and residual oil of standardized quality, and the graph of temperature versus mass % distilled is generated using 15 theoretical stages in a column with a reflux ratio of 5:1 and is corresponding to ASTM D-2892 for determining the yield of the above fractions by both mass and volume.

[0013] As used herein, the term "T10" means the temperature at which 10 mass percent of a sample boils, using ASTM D-86 or TBP.

[0014] As used herein, the term "initial boiling point" (IBP) means, in some cases, the temperature at which a sample begins to boil, using ASTM D2887, ASTM D-86, or TBP.

[0015] As used herein, the term “end point” (EP) means, in some cases, the temperature at which the sample has completely evaporated, using ASTM D2887, ASTM D-86, or TBP.

[0016] As used herein, the term “jet fuel range material” means hydrocarbons that boil within the “recycle cut-off point” range, including IBP at 85°C (185°F) to 135°C (275°F), or T5 at 110°C (230°F) to 160°C (320°F), and T95 at 295°C (563°F) to 315°C (599°F), using the TBP distillation method. Hydrocarbons exceeding the “recycle cut-off point”

[0017] As used herein, the term “separator” means a vessel having an inlet and at least a top vapor outlet and a bottom liquid outlet, and which may also have an aqueous outlet from the boot. A flash drum is a type of separator that can be downstream-communicated with a separator that can operate at higher pressures.

[0018] When used herein, "C x The term should be understood to refer to a molecule having a number of carbon atoms represented by the subscript "x". Similarly, "C x The term "-" refers to a molecule containing x or fewer carbon atoms, preferably x and less. x The term "+" refers to a molecule having x or more (more than or equal to x), preferably x and more (x and more) carbon atoms.

[0019] As used herein, the term "carbon number" refers to the number of carbon atoms per hydrocarbon molecule, and typically per paraffin molecule.

[0020] As used herein, the term “alcohol” refers to at least a monohydroxysubstituted alkane. Typical alcohols are alkanes in which one or more hydroxyl groups are substituted on a hydrogen atom (C1-C2). 12 ) Contains an alkyl moiety. Examples of alcohols include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, s-butanol, t-butanol, n-pentanol, i-pentanol, hexanol, cyclohexanol, heptanol, octanol, nonanol, decanol, etc. The carbon atom chain in the alcohol may be linear, branched, or cyclic. The alcohol may be monohydroxy, dihydroxy, trihydroxy, etc.

[0021] As used herein, the term “jet fuel” means hydrocarbons that boil at a T10 of 190°C (374°F) to 215°C (419°F) and an endpoint of 290°C (554°F) to 310°C (590°F). The term “green jet fuel” means jet fuel containing hydrocarbons that are not of fossil fuel origin.

[0022] As used herein, the abbreviation "LHSV" means liquid spacetime velocity, which is defined as the volumetric flow rate of the liquid per hour divided by the catalyst volume, where the liquid volume and catalyst volume are in the same volumetric unit.

[0023] As used herein, the terms “main” or “major” mean more than 50%, preferably more than 75%, and more preferably more than 90%.

[0024] Detailed explanation As sustainability concerns grow, the need for SAF is increasing because it produces fewer GHG emissions compared to petrochemically supplied fuels. Furthermore, the stagnation of high-fructose corn syrup growth could lead to a future sugar stagnation. This disclosure demonstrates the chemical and technoeconomic feasibility of a process for coupling aldehydes, including the conversion of sugars to SAF and olefins via HMF.

[0025] This disclosure includes a novel process for coupling aldehydes. The disclosed process is unique because it demonstrates a novel reuse process for a homogeneous catalyst used in benzoin condensation to produce acyloins. Successful reuse of homogeneous catalysts is not seen in the prior art. Recycling of homogeneous catalysts is crucial for achieving economically viable processes. Since this process discloses the reuse of homogeneous catalysts, the catalyst is cost-effective in contrast to consumables.

[0026] This disclosure provides a process for coupling aldehydes in an aldehyde-containing stream. The aldehyde in this process is sometimes specifically called flualdehyde. The aldehyde stream can be obtained from biological resources or biomass. According to this disclosure, the aldehyde stream can be obtained from lignocellulosic biomass such as maize stalks and leaves, bagasse, wheat straw, rice straw, and wood.

[0027] This process involves coupling aldehydes obtained from biomass with C 10 ~C 22 The disclosure provides alkanes. The disclosed process uses renewable biomass resources to reduce reliance on petroleum-based liquid fuels, 10 ~C 22 This includes generating an alkane, which can be processed to produce a jet fuel that meets SAF requirements, or converted to a desired olefin.

[0028] As shown in FIG. 1, the process 101 for coupling aldehydes includes a reactor 120 for coupling aldehydes, an HDO reactor 140, and a processing unit 160. An aldehyde-containing stream 112 and a catalyst stream 102 containing a catalyst in an alcohol solution are sent to the reactor 120. The alcohol solution of the catalyst stream 102 may contain one or more alcohols selected from methanol, ethanol, propanol, butanol, ethanolamine, phenol, and cresol. Further, the alcohol solution of the catalyst stream 102 may contain one or more alcohols from C1 to C 20 alcohols and aromatic alcohols. According to an exemplary embodiment of the present disclosure, the reactor 120 is a benzoin condensation reactor. As described in detail below, a recycle stream 132 is also sent to the reactor 120.

[0029] In one aspect, the catalyst in the catalyst stream 102 is a homogeneous catalyst. The catalyst may include an N-heterocyclic carbene catalyst. In an exemplary embodiment, the catalyst is selected from 1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene (TPT), 1,3-di-mesityl-butyl-imidazolin-2-ylidene, and 1,3-dialkylimidazolin-2-ylidene.

[0030] The aldehyde-containing stream 112 can be taken from any suitable source 110. In an exemplary embodiment, the source of the aldehyde-containing stream 112 is a dehydration unit 110. The aldehyde-containing stream 112 may contain at least two aldehydes that may be different from each other. In an aspect of the present disclosure, the biomass-derived hydrocarbon stream in line 106 may be dehydrated in the dehydration unit 110 in the aldehyde source to provide the aldehyde-containing stream 112. In an embodiment, the biomass-derived hydrocarbon stream in line 106 may contain C5-C6 sugars. In another embodiment, the biomass-derived hydrocarbon stream in line 106 may contain one or more of cellulose, fructose, and glucose.

[0031] In an aspect of the present disclosure, the aldehyde-containing stream in line 112 has the formula (I):

[0032] [ka] (In the formula, R1, R2, and R3 are hydrogen, C1~C 20 The formula (I) contains one or more aldehydes having alkyl groups, aromatic groups, heteroatoms, and oxygenated groups including alcohols, ethers, carbonyl groups, esters, and hydroxyls (where X is selected from the group including heteroatoms, oxygen, sulfur, and nitrogen). R1, R2, and R3 in formula (I) may all be the same. Furthermore, any two of R1, R2, and R3 in formula (I) may be the same. Furthermore, R1, R2, and R3 in formula (I) may each be different from one another.

[0033] In the embodiment, the aldehyde-containing stream in line 112 contains furfural. In the exemplary embodiment, the aldehyde-containing stream in line 112 may contain 2-hydroxymethylfurfural (HMF).

[0034] According to exemplary embodiments of the present disclosure, the recycled liquid flow in line 132 is combined with the catalyst flow in line 102 to provide a combined feed flow in line 104, which is then sent to reactor 120. In another embodiment, the catalyst flow in line 102 and the recycled liquid flow in line 132 may be sent separately to reactor 120.

[0035] In reactor 120, the aldehyde-containing stream in line 112 is mixed with the catalyst in the alcohol solution, causing an aldehyde coupling reaction to occur. An aldehyde coupling reaction is a coupling reaction between two aldehyde molecules. Aldehyde coupling reactions are sometimes referred to simply as "coupling reactions." Aldehyde coupling reactions can include self-condensation (self-coupling) and cross-condensation (cross-coupling). The coupling reaction between two aromatic aldehydes (such as benzaldehyde) is generally called "benzoin condensation." However, the aldehyde coupling reactions in this disclosure are not limited to benzoin condensation.

[0036] After mixing, Freun system molecules are formed, which precipitate from the mixture in reactor 120. The precipitation of Freun system molecules occurs spontaneously in reactor 120 without the addition of any solvent or agent for precipitation. Furthermore, since the precipitation of Freun system molecules occurs in reactor 120, according to this process 101, no separate container for precipitation is required. After the coupling reaction is complete, the coupling reaction effluent is withdrawn from reactor 120 through line 122. The coupling reaction effluent in line 122 can be sent to separator 130 to separate the precipitated Freun system molecules. The Freun system molecules are collected and withdrawn from separator 130 into the coupling reaction product stream in line 134. In exemplary embodiments, the Freun system molecules can be collected via centrifuge 130 to remove the liquid from the Freun molecules. After the collection and separation of the Freun system molecules in separator 130, a liquid stream remains. The liquid stream contains a catalyst in an alcohol solution. The catalyst remaining in this liquid stream can be referred to as the spent catalyst after the coupling reaction in reactor 120. The liquid stream containing the catalyst is recovered in an alcohol solution and withdrawn from separator 130 via line 132.

[0037] According to this disclosure, a liquid stream containing a catalyst in an alcohol solution in line 132 can be directly recycled to reactor 120 to continuously catalyze the coupling of a newly supplied aldehyde-containing stream in line 112. The disclosed aldehyde coupling process is unique compared to typical or conventional processes. Therefore, unlike conventional processes, the successful recycling or reuse of the spent catalyst after the coupling reaction is demonstrated. Conventional processes typically rely on the separation and further processing of the catalyst for further use. This also demonstrates the successful use of recycled catalysts in coupling reactions. The inventors have found that after the coupling reaction, the catalyst stream can be successfully recycled to couple the aldehyde-containing stream in the reactor and produce Freunine molecules in comparable yields compared to coupling reactions in the presence of new, unrecycled catalyst. Catalyst recycling is crucial for achieving an economically viable process. The inventors then disclose an economical process for producing Freunine molecules, which generates valuable alkanes from a biomass-derived aldehyde stream. The alkanes can be processed to produce SAF or olefins.

[0038] Upon returning to reactor 120, the liquid stream containing the catalyst in the alcohol solution in line 132 is recycled to reactor 120 via line 104, along with a fresh supply of catalyst supplied to the alcohol solution in line 102. The precipitated Freun system molecules in the coupling reaction product stream in line 134 are withdrawn from separator 130 for further processing to produce alkanes. According to this disclosure, the Freun system molecules in the coupling reaction product stream in line 134 are given by formula (II):

[0039] [ka] (In the formula, R1, R2, and R3 are hydrogen, C1~C 20The formula (I) may contain one or more compounds having an alkyl group, an aromatic group, a heteroatom, and an oxygenating group including alcohols, ethers, carbonyls, esters, and hydroxyls (where X is selected from the group including heteroatoms, oxygen, sulfur, and nitrogen). R1, R2, and R3 in formula (I) may all be the same. Furthermore, any two of R1, R2, and R3 in formula (I) may be the same. Furthermore, R1, R2, and R3 in formula (I) may be different from each other. In an exemplary embodiment, the Freun system molecules in the coupling reaction product stream in line 134 may include di(hydroxymethyl)furoin (DHMF), specifically one or both of 5,5'-di(hydroxymethyl)furoin and Freunin.

[0040] Freuncione molecules in the coupling reaction product stream in line 134 are converted into valuable alkanes by hydrogenation deoxygenation of the Freuncione molecules. The total number of carbon atoms in the Freuncione molecules may be equal to the sum of the two aldehydes used in the coupling reaction. The Freuncione molecules in the coupling reaction product stream in line 134 are sent to HDO reactor 140 for hydrogenation deoxygenation of the coupling product in the presence of an HDO catalyst. The HDO catalyst in HDO reactor 140 is sometimes referred to as a hydrogenation catalyst. The Freuncione molecules in the coupling reaction product stream in line 134 can be subjected to hydrogenation in HDO reactor 140. The hydrogen gas stream in line 144 is also sent to HDO reactor 140.

[0041] Hydrogen treatment may include hydrocracking of the feedstock in the HDO reactor 140. Hydrogen treatment removes contaminants from the feedstock and product stream, while hydrocracking produces lighter, usable products. Primary hydrogen treatment reactions may include the removal of sulfur and nitrogen, as well as olefin saturation. The products of these reactions are hydrocarbons free of the corresponding contaminants, in addition to H2S and NH3. Other treatment reactions may include the removal of oxygen, metals, and halides, as well as aromatic saturation. The reactions are typically carried out under high pressure and high temperature in a hydrogen atmosphere.

[0042] The HDO reactor 140 may comprise one or more HDO catalyst beds and one or more reaction vessels. The HDO catalyst in the HDO reactor 140 may include nickel or nickel / molybdenum, or any other catalyst known in the art, dispersed on a high surface area support. Other catalysts include one or more noble metals dispersed on a high surface area support. Non-limiting examples of noble metals include platinum and / or palladium dispersed on gamma-alumina. The reaction conditions in the HDO reactor 140 are a relatively low pressure of 3447 kPa (500 psia) to 6895 kPa (1000 psia), a temperature of 200°C (392°F) to 400°C (752°F), and 0.5 hr. -1 ~10 hours -1 This may include LHSV. In another embodiment, the reaction conditions in the HDO reactor 140 are a relatively low pressure of 3447 kPa (500 psia) to 6895 kPa (1000 psia), a temperature of 288°C (550°F) to 345°C (653°F), and 1 hr -1 ~4 hours -1 This may include the liquid spacetime velocity.

[0043] In the HDO reactor 140, Freun system molecules in the coupling reaction product stream in line 134 are deoxygenated to form water and hydrocarbons. The reaction products from the deoxygenation reaction include both deoxygenated liquid and gaseous components. The HDO reaction product stream is withdrawn in line 142 and sent to the HDO separation section 150, where the deoxygenated liquid stream in line 154 is separated from the gaseous stream in line 152. The deoxygenated liquid stream in line 154 contains a hydrocarbon fraction mainly consisting of paraffins, probably having a predominant concentration of paraffins in the range of 10 to 18 carbon atoms. The gaseous stream in line 152 contains hydrogen, carbon dioxide, carbon monoxide, water vapor, propane, and light hydrocarbons. The deoxygenated liquid stream in line 154 is sometimes referred to as the HDO reactor outflow stream in line 154. In an exemplary embodiment, the deoxygenated liquid stream in line 154 is C 12 ~C 22It may contain alkanes. In another exemplary embodiment, the deoxygenated liquid flow in line 154 is C 10 ~C 12 It may contain alkanes. The deoxygenated liquid stream in line 154 can be processed in processing unit 160 to convert the alkanes into the desired product.

[0044] In one embodiment, the deoxygenated liquid flow in line 154 can be processed to produce liquid jet fuel (SAF). In an exemplary embodiment, the processing unit 160 is a hydrogen isomerization unit 160. Hydrogen isomerization is used to improve the low-temperature fluidity of the resulting jet fuel. Hydrogen isomerization, or hydrogen dewaxing, is a hydrogenation process that improves the low-temperature fluidity of hydrocarbons by increasing alkyl branching on the hydrocarbon skeleton in the presence of hydrogen and a hydrogen isomerization catalyst.

[0045] In the hydrogen isomerization unit 160, the deoxygenated liquid flow in line 154 is brought into contact with a hydrogen isomerization catalyst in a hydrogen isomerization reactor under hydrogen isomerization conditions to hydrogen isomerize the straight-chain paraffin into a branched paraffin. The hydrogen isomerization unit 160 may include one or more reactors, strip columns, and fractionation columns.

[0046] Hydrogen isomerization (including dewaxing) of straight-chain hydrocarbons in a hydrogen isomerization reactor can be achieved on one or more beds of hydrogen isomerization catalyst, and the hydrogen isomerization reactor 160 can operate in parallel flow mode. Both fixed-bed trickle bed downflow mode and fixed-bed liquid-filled upflow mode are preferred.

[0047] Suitable hydrogen isomerization catalysts may include metals from Group VIII of the periodic table (IUPAC 8-10) and supporting materials. Suitable Group VIII metals include platinum and palladium, which may be used alone or in combination. Hydrogen isomerization catalysts may also contain non-precious metals that are less susceptible to sulfur deactivation in a sour environment. Suitable non-precious metals include nickel (Ni), molybdenum (Mo), cobalt (Co), tungsten (W), manganese (Mn), copper (Cu), zinc (Zn), or ruthenium (Ru). Mixtures of metal hydrides such as Co / Mo, Ni / Mo, and Ni / W may also be used. The amount of metal hydride(s) may range from 0.1 to 5% by weight based on the catalyst weight. Methods for supporting the metal on the supporting material include, for example, impregnation and heating of the supporting material with a metal salt of the hydrogenation component. Catalyst supporting materials containing metal hydrides may also be sulfurized before use.

[0048] The support material may be amorphous or crystalline. Suitable support materials include amorphous alumina, amorphous silica-alumina, ferrielite, ALPO-31, SAPO-11, SAPO-31, SAPO-37, SAPO-41, SM-3, MgAPSO-31, FU-9, NU-10, NU-23, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, ZSM-57, MeAPO-11, MeAPO-31, MeAPO-41, MgAPSO-11, Examples include MgAPSO-31, MgAPSO-41, MgAPSO-46, ELAPO-11, ELAPO-31, ELAPO-41, ELAPSO-11, ELAPSO-31, ELAPSO-41, laumontite, cancrinite, ofletite, hydrogen-type stilbite, magnesium or calcium-type mordenite, and magnesium or calcium-type parsate, each of which may be used alone or in combination. ALPO-31 is described in U.S. Patent No. 4,310,440. SAPO-11, SAPO-31, SAPO-37, and SAPO-41 are described in U.S. Patent No. 4,440,871. SM-3 is described in U.S. Patents No. 4,943,424, 5,087,347, 5,158,665, and 5,208,005. MgAPSO is MeAPSO, which is an acronym for metal aluminumsilicophosphate molecular sieve, where metal Me is magnesium (Mg). Preferred MgAPSO-31 catalysts include MgAPSO-31. MeAPSO is described in U.S. Patent No. 4,793,984, and MgAPSO is described in U.S. Patent No. 4,758,419. MgAPSO-31 is preferred MgAPSO, where 31 means MgAPSO having structural type 31.As taught in U.S. Patents 4,795,623 and 4,924,027, many natural zeolites, such as ferrielites, which initially have reduced pore sizes, can be converted to forms suitable for olefin skeleton isomerization by ammonium ion exchange and calcination, thereby removing associated alkali metals or alkaline earth metals to substantially produce hydrogen forms. Further catalysts and conditions for skeleton isomerization are disclosed in U.S. Patents 5,510,306, 5,082,956 and 5,741,759. Hydrogen isomerization catalysts may also include modifiers selected from the group consisting of lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, terbium, and mixtures thereof, as described in U.S. Patents 5,716,897 and 5,851,949. Other suitable support materials include ZSM-22, ZSM-23, and ZSM-35, which are described for use in dewaxing in U.S. Patent No. 5,246,566 and in the paper entitled "New Molecular Sieve Process for Lube Dewaxing by Wax Isomerization," Microporous Materials 439-449 (1994) by SJ Miller. U.S. Patents No. 5,444,032 and No. 5,608,968 teach suitable bifunctional catalysts composed of amorphous silica-alumina gel and one or more metals belonging to Group VIIIA, which are effective in the hydrogen isomerization of long-chain normal paraffins containing more than 15 carbon atoms. U.S. Patents 5,981,419 and 5,908,134 teach a suitable bifunctional catalyst comprising (a) a porous crystalline material having the same structure as a beta zeolite selected from borosilicate (BOR-B) and boroaluminosilicate (Al-BOR-B) with an SiO2:Al2O3 ratio higher than 300:1, and (b) one or more metals belonging to Group VIIIA selected from platinum and palladium, in an amount ranging from 0.05 to 5% by weight. V. Calemma et al., App. Catal. A: Gen., 190 (2000), 207 teach a further suitable catalyst.Alumina or silica may be added to the carrier material.

[0049] In exemplary embodiments, DI-200, available from UOP LLC (Des Plaines, Illinois), may be a suitable hydrogen isomerization catalyst.

[0050] Hydrogen isomerization conditions generally include temperatures of 150°C (302°F) to 450°C (842°F) and pressures of 1724 kPa (abs) (250 psia) to 13.8 MPa (abs) (2000 psia). In another embodiment, hydrogen isomerization conditions include temperatures of 300°C (572°F) to 360°C (680°F) and pressures of 3102 kPa (abs) (450 psia) to 6895 kPa (abs) (1000 psia).

[0051] The hydrogen isomerization flow from the hydrogen isomerization reactor is a branched paraffin-rich flow. The term "branched paraffin-rich" means that the effluent flow has a higher concentration of branched paraffins than the flow entering the hydrogen isomerization reactor, preferably containing more than 50% by mass of branched paraffins of the total paraffin content. The hydrogen isomerization flow is expected to contain 80, 90, or 95% by mass of branched paraffins of the total paraffin content. The optimal amount of residual linear paraffins may depend on the selectivity of the hydrogen isomerization catalyst, but is typically 1 to 7% by weight.

[0052] The hydrogen isomerized stream can be sent to a hydrogen isomerized strip column to separate the hydrogen isomerized liquid stream from the hydrogen isomerized vapor stream. The hydrogen isomerized vapor stream containing light gases is removed. The hydrogen isomerized liquid stream is sent to a product distillation column to fractionally distill the hydrogen isomerized liquid stream and provide a jet fuel stream. The jet fuel stream thus produced has a T5 of 115°C (239°F) to 130°C (266°F) and a T90 of 240°C (464°F) to 270°C (518°F). The inventors have confirmed that the jet fuel stream thus produced meets the ASTM D7566 jet fuel standard. The produced jet fuel stream can be extracted from unit 160 in line 162.

[0053] According to another embodiment of the present disclosure, the deoxygenated liquid stream in line 154 may be treated to produce olefins for the production of linear alkylbenzene benzene (LAB). In an alternative embodiment, the processing unit 160 is a dehydrogenation unit 160. The dehydrogenation unit 160 may comprise one or more reactors, columns, adsorption separation zones, and extraction zones.

[0054] Alkylbenzenes (phenyl alkanes) are prepared by alkylation of benzene. Alkylbenzenes have many applications, the most notable being the production of alkylbenzene sulfonates for use in laundry detergents and similar products. The performance of alkylbenzene sulfonates in detergent compositions is influenced by the properties of the alkyl group, such as its length and stereochemistry, particularly its branching.

[0055] Linear alkylbenzene sulfonates (LABS) are produced from linear alkylbenzenes (LAB). A typical process for producing LAB involves dehydrogenating a linear paraffin to a linear olefin, and then alkylating the benzene with the linear olefin in the presence of a catalyst such as hydrofluoric acid or a solid acidic catalyst.

[0056] Any suitable catalyst can be used in the dehydrogenation process. Many types of dehydrogenation catalysts are known, as exemplified by U.S. Patents 3,274,287, 3,315,007, 3,315,008, 3,745,112, and 4,430,517. Often, the dehydrogenation catalyst is a platinum group metal-containing catalyst. One preferred catalyst is a layered composition comprising an inner core and an outer layer bonded to the inner core, wherein the outer layer contains a refractory inorganic oxide in which at least one platinum group (groups 8-10 of the periodic table) metal and at least one accelerator metal are uniformly dispersed thereon, and at least one reforming metal is dispersed on the catalyst composition.

[0057] Dehydrogenation can be carried out in the liquid phase or in a gas-liquid mixture, but is preferably carried out in the gas phase. Typical dehydrogenation conditions include temperatures of 400°C (752°F) to 900°C (1652°F), preferably 420°C (788°F) to 550°C (1022°F). Generally, for linear paraffins, the lower the molecular mass, the higher the temperature required for the equivalent conversion. The pressure is generally 1 kPa(g) (0.15 psi(g)) to 1000 kPa(g) (145 psi(g)), preferably 100 kPa(g) (14.5 psi(g)) to 400 kPa(g) (58.0 psi(g)), and the LHSV is 0.1 to 100 hr. -1 That is the case.

[0058] The deoxygenated liquid stream in line 154 is sent to a dehydrogenation section to convert the paraffin in the deoxygenated liquid stream into an olefin-containing stream. In an exemplary embodiment, the olefin-containing stream from the dehydrogenation section contains olefins having 8 to 16 carbon atoms. The olefin-containing stream is then sent to a selective hydrogenation section to convert the diolefins into monoolefins. Hydrogen is supplied to the selective hydrogenation section. The olefin-containing stream is then sent from the selective hydrogenation section to an adsorbent separation zone to remove aromatic byproducts by adsorption, providing an adsorption effluent stream which is then sent to a downstream alkylation reactor.

[0059] The sorption separation zone may include a fixed bed or a moving or fluid adsorption bed system, but a fixed bed system is preferred. The adsorbent may be installed in one or more containers in a direct or parallel flow. The flow of the feed material containing aromatic by-products through the sorption separation zone is preferably carried out in parallel so that one or more sorption beds can be regenerated while one or more beds are removing aromatic by-products.

[0060] Suitable adsorbents can be selected from materials that exhibit the primary requirement of selectivity for aromatic by-products and are otherwise convenient to use. Suitable adsorbents include, for example, molecular sieves, silica, activated carbon, activated charcoal, activated alumina, silica-alumina, clay, cellulose acetate, synthetic magnesium silicate, macroporous magnesium silicate, and / or macroporous polystyrene gel.

[0061] Alkylbenzene (phenyl-alkane) is prepared by alkylating benzene in an alkylation reactor. In the alkylation reactor, the adsorbed effluent, with a reduced concentration of aromatic by-products, is mixed with the benzene stream. The sorbed effluent contains unsorbed components, including paraffin and olefins. In the alkylation reactor, benzene is alkylated with a branched olefin in the presence of a suitable catalyst, such as hydrofluoric acid or a solid acidic catalyst. The alkylation reactor effluent is sent to the alkylbenzene purification section. From the alkylbenzene purification section, a purified alkylbenzene product stream is obtained. The alkylbenzene product stream is withdrawn from the dehydrogenation unit 160 at line 162.

[0062] Any of the lines, conduits, units, devices, containers, surrounding environments, zones, or similar entities described above may comprise one or more monitoring components, including sensors, measuring devices, data acquisition devices, or data transmission devices. Signals, process, or state measurements and data from the monitoring components can be used to monitor conditions within, around, and on process equipment. Signals, measurements, and / or data generated or recorded by the monitoring components may be collected, processed, and / or transmitted via one or more networks or connections, which may be private or public, general or specific, direct or indirect, wired or wireless, encrypted or unencrypted, and / or a combination thereof. This specification is not intended to limit us in this respect.

[0063] Signals, measurements, and / or data generated or recorded by monitoring components may be transmitted to one or more computing devices or systems. A computing device or system may include at least one processor and memory for storing computer-readable instructions that, when executed by at least one processor, cause one or more computing devices to perform a process that may include one or more steps. For example, one or more computing devices may be configured to receive data from one or more monitoring components relating to at least one component of equipment associated with a process. One or more computing devices or systems may be configured to analyze the data. Based on the analysis of the data, one or more computing devices or systems may be configured to determine one or more recommended adjustments to one or more parameters of one or more processes described herein. One or more computing devices or systems may be configured to transmit encrypted or unencrypted data containing one or more recommended adjustments to one or more parameters of one or more processes described herein.

[0064] The following examples are for illustrative purposes only. These examples illustrate in detail how the processes disclosed herein and claimed below can be carried out, and are not intended to limit the scope of the processes disclosed herein to the embodiments shown in the examples. These examples are not intended to limit the scope of the processes disclosed herein as described in the claims. [Examples]

[0065] Example 1 Synthesis of 2,5-dihydroxymethylfroin In a nitrogenous environment, 0.725 g of HMF was added to a vial containing 0.0612 g of TPT, followed by the addition of 1.5 mL of methanol solvent. The reaction mixture was stirred at 60°C for 1 hour. As the product DHMF formed, it precipitated from the reaction mixture. After removing the solvent, the product was analyzed by 1H NMR spectroscopy and showed a yield of 99%.

[0066] This procedure was repeated using different solvents. The yield of DHMF was compared for each solvent, as well as for the water content of each solvent. The results are summarized in the table below.

[0067] [Table 1]

[0068] As shown in the table, methanol yielded the highest yield of DHMF. Variables such as time, temperature, feed:catalyst ratio, water content, solvent, and catalyst were investigated for different solvents. The results are shown in Figures 2 to 7. The operating conditions in Figures 2 to 5 were: HMF:catalyst molar ratio of 17 to 24, solvent 1.5 g, time 1 hour, stirring speed of 200 rpm, and temperature 60°C.

[0069] Figure 2 is a graph plotted to show DHMF yield (%) versus time (minutes) for three different solvents: methanol, toluene, and tetrahydrofuran (THF). Results for the no-solvent condition are also shown. As shown in Figure 2, methanol yielded the highest DHMF yield.

[0070] Figure 3 is a graph plotted to show the DHMF yield (%) versus the water content of the solvent.

[0071] Figure 4 is a graph plotted to show the DHMF yield (%) versus the HMF:catalyst molar ratio for different water concentrations (90 ppm and 60 ppm) in methanol as a solvent.

[0072] Figure 5 is a graph plotted to show the DHMF yield (%) versus HMF:catalyst molar ratio for two different catalysts, TPT and 1,3-bis(2,4,6-trimethylphenyl)-1,3-dihydro-2H-imidazole-2-ylidene (IMes) in methanol as the solvent. Both catalysts contain an N-heterocyclic carbene. As shown in Figure 5, TPT in methanol solvent yielded a higher DHMF yield compared to IMes.

[0073] Example 2 Froin's synthesis In a nitrogenous environment, 0.725 g of furfural was added to a vial containing 0.0612 g of TPT, followed by the addition of 1.5 mL of methanol. The reaction mixture was stirred at 60°C for 1 hour. The solvent was removed, and the product was analyzed by 1H NMR spectroscopy. A product with 99% yield was observed.

[0074] Example 3 Synthesis of dimers from furfural and 5-hydroxymethylfurfural In a nitrogenous environment, 0.725 g of furfural was added to a vial containing 0.0612 g of TPT, followed by the addition of 1.5 mL of methanol. The reaction mixture was stirred at 60°C for 1 hour. After removing the solvent, the products were analyzed by 1H NMR spectroscopy, showing a 99% yield for three products. The three products were identified as DHMF in a 1:3:1 ratio, a heterodimer of furfural and HMF, and Freuin.

[0075] Example 4 Reuse of NHC catalyst In a nitrogenous environment, 0.725 g of HMF was added to a vial containing 0.0612 g of TPT, followed by the addition of 1.5 mL of methanol. The reaction mixture was stirred at 60°C for 1 hour. As the product, DHMF, formed, it precipitated from the reaction mixture. After the reaction was complete, the product was collected by centrifugation. The remaining liquid contained the catalyst. Fresh HMF was added to the liquid layer containing the catalyst, and the experimental procedure was repeated. By 1H NMR spectroscopy, 99% of DHMF was obtained from the reaction. The results are shown in Figure 6. As shown in Figure 6, the recycled catalyst yielded a comparable yield of DHMF compared to the fresh catalyst.

[0076] Example 5 Freund's Hydrogen Deoxygenation In a nitrogenous environment, 1 g of Freun was loaded into a 75 mL autoclave along with 7.3 g of pentadecane and 0.3 g of pre-sulfurized HYT-6319 catalyst available from UOP LLC (Des Plaines, IL). The autoclave was then filled with 500 psig to 1250 psig of hydrogen and heated to 200 to 285°C for 1 to 24 hours. Analysis of the liquid product by GC revealed a C yield of over 40 mol%. 10 The presence of hydrocarbons was confirmed. The results are shown in Figures 7 to 10.

[0077] Figure 7 is a graph plotted to show the C10 yield % (mol%) versus time (h).

[0078] Figure 8 is a graph plotted to show the C10 yield % (mol%) versus hydrogen pressure (psig).

[0079] Figure 9 is a graph plotted to show the C10 yield % (mol%) versus the Freuin:catalyst weight ratio for reaction times of 24 hours or 6 hours.

[0080] Figure 10 is a graph plotted to show the C10 yield % (mol%) versus temperature (°C).

[0081] Example 6 Freund's continuous hydrogenation deoxygenation 5% by weight of Froin in the cresol feed was passed over 20 cc of pre-sulfurized HYT-6319 catalyst in a fixed bed at a temperature of 285–310°C at 20 cc / h, 750 psig, 293 sccm of H2, and an H2 / feed ratio of 5000 scfb. After 15 hours on-stream, n-decane was observed in a 25 mol% C yield.

[0082] Specific Embodiments The following will be explained in conjunction with specific embodiments, but it should be understood that this explanation is intended to illustrate the scope of the preceding explanation and the attached claims, and is not intended to limit them.

[0083] A first embodiment of the present disclosure is a process for coupling an aldehyde, comprising: charging an aldehyde-containing stream and a catalyst-containing stream in an alcohol solution into a reactor; contacting the aldehyde-containing stream with the catalyst in the alcohol solution; precipitating Freun-type molecules in the reactor; and recovering the liquid stream containing the catalyst in the alcohol solution from the reactor. Embodiments of the present disclosure are any or all of the embodiments described in the preceding paragraphs up to the first embodiment of this paragraph, wherein the liquid stream containing the catalyst in the alcohol solution is recycled back into the reactor and coupled to a new feed of the aldehyde-containing stream. Embodiments of the present disclosure are characterized in that the aldehyde-containing stream is of formula (I):

[0084] [ka] One or all of the embodiments described in the preceding paragraph to the first embodiment of this paragraph, comprising one or more aldehydes having (wherein R1, R2, and R3 are selected from the group comprising hydrogen, C1-C20 alkyl chains, aromatic groups, heteroatoms, and oxygenating groups comprising alcohols, ethers, carbonyls, esters, and hydroxyl groups, and X is selected from the group comprising heteroatoms, oxygen, sulfur, and nitrogen). Embodiments of the present disclosure are one or all of the embodiments described in the preceding paragraph to the first embodiment of this paragraph, wherein the aldehyde-containing stream comprises furfural. Embodiments of the present disclosure are one or all of the embodiments described in the preceding paragraph to the first embodiment of this paragraph, wherein the Freun system molecule is hydrogenated and deoxygenated to produce a liquid fuel. Embodiments of the present disclosure are any or all of the embodiments from the earlier embodiments of this paragraph to the first embodiment of this paragraph, wherein the Freuin system molecule is hydrogenated and then dehydrogenated to produce a product comprising an olefin having 8 to 16 carbon atoms. Embodiments of the present disclosure are any or all of the embodiments from the earlier embodiments of this paragraph to the first embodiment of this paragraph, wherein the homogeneous catalyst is an N-heterocyclic carbene catalyst. Embodiments of the present disclosure are any or all of the embodiments from the earlier embodiments of this paragraph to the first embodiment of this paragraph, wherein the catalyst is selected from TPT, 1,3-di-mesityl-butyl-imidazoline-2-ylidene, and 1,3-dialkylimidazoline-2-ylidene. Embodiments of the present disclosure are wherein the Freuin system molecule is of formula (II):

[0085] [ka] One or all of the embodiments described in the preceding paragraph to the first embodiment of this paragraph comprises one or more compounds having (wherein R1, R2, and R3 are selected from the group comprising hydrogen, C1-C20 alkyl groups, aromatic groups, heteroatoms, and oxygenating groups comprising alcohols, ethers, carbonyls, esters, and hydroxyl groups, and X is selected from the group comprising heteroatoms, oxygen, sulfur, and nitrogen). Embodiments of the present disclosure are one or all of the embodiments described in the preceding paragraph to the first embodiment of this paragraph, wherein the Freun system molecule is 5,5'-di(hydroxymethyl)Freun. Embodiments of the present disclosure are one or all of the embodiments described in the preceding paragraph to the first embodiment of this paragraph, wherein the reactor is a benzoin condensation reactor. Embodiments of the present disclosure are any or all of the embodiments described in the preceding paragraphs to the first embodiment described in this paragraph, wherein the alcohol solution comprises one or more alcohols selected from methanol, ethanol, propanol, butanol, ethanolamine, phenol, and cresol.

[0086] A second embodiment of the present disclosure is a process for coupling an aldehyde, comprising: charging an aldehyde-containing stream and a catalyst-containing stream in an alcohol solution into a reactor; contacting the aldehyde-containing stream with the catalyst in the alcohol solution; precipitating Freun-type molecules from the solution; recovering the liquid stream containing the catalyst in the alcohol solution from the reactor; and recycling the liquid stream back into the reactor to couple a new feed of the aldehyde-containing stream. The process includes the following: Embodiments of the present disclosure involve the aldehyde-containing stream being of formula (I):

[0087] [ka] One or all of the embodiments from the earlier embodiments of this paragraph to the second embodiments of this paragraph, comprising one or more aldehydes having (wherein R1, R2, and R3 are selected from the group comprising hydrogen, C1-C20 alkyl chains, aromatic groups, heteroatoms, and oxygenating groups comprising alcohols, ethers, carbonyls, esters, and hydroxyl groups, and X is selected from the group comprising heteroatoms, oxygen, sulfur, and nitrogen). Embodiments of the present disclosure are one or all of the embodiments from the earlier embodiments of this paragraph to the second embodiments of this paragraph, which hydrogenate and deoxygenate the Freuin system molecule to produce a liquid fuel. Embodiments of the present disclosure are one or all of the embodiments from the earlier embodiments of this paragraph to the second embodiments of this paragraph, which hydrogenate and deoxygenate the Freuin system molecule and then dehydrogenate it to produce a product comprising a long-chain linear olefin having 8-16 carbon atoms. Embodiments of the present disclosure are any or all of the embodiments from the earlier embodiments of this paragraph to the second embodiments of this paragraph, wherein the homogeneous catalyst is an N-heterocyclic carbene catalyst. Embodiments of the present disclosure are any or all of the embodiments from the earlier embodiments of this paragraph to the second embodiments of this paragraph, wherein the catalyst is selected from TPT, 1,3-di-mesityl-butyl-imidazoline-2-ylidene, and 1,3-dialkylimidazoline-2-ylidene.

[0088] A third embodiment of the present disclosure is a process for coupling an aldehyde, comprising: charging an aldehyde-containing stream and a catalyst-containing stream in an alcohol solution into a reactor; mixing the aldehyde-containing stream with the catalyst in the alcohol solution to precipitate Freun-type molecules from the solution; and recovering the liquid stream containing the catalyst in the alcohol solution from the reactor.

[0089] Without further detail, it is expected that those skilled in the art will be able to utilize the Disclosure to the fullest extent without departing from the spirit and scope of the Disclosure, readily identify its essential characteristics, and make various changes and modifications to adapt it to various uses and conditions. Accordingly, the prior preferred specific embodiments should be interpreted as merely illustrative examples and not in any way limiting the remainder of the Disclosure, but are intended to cover various modifications and equivalent configurations that fall within the scope of the appended claims.

[0090] In the above, all temperatures are given in degrees Celsius, and all parts and percentages are based on weight unless otherwise indicated.

Claims

1. This is a process that couples aldehydes. The process involves charging the reactor with an aldehyde-containing stream and a catalytic stream containing a catalyst in an alcohol solution, The aldehyde-containing stream is brought into contact with the catalyst in the alcohol solution, Precipitating Freuin-type molecules in the aforementioned reactor, The liquid stream containing the catalyst in the alcohol solution is recovered from the reactor. A process that includes this.

2. The process according to claim 1, wherein the liquid stream containing the catalyst in the alcohol solution is recycled to the reactor.

3. The aldehyde-containing stream is given by formula (I): 【Chemistry 1】 (In the formula, R1, R2, and R3 are selected from the group comprising hydrogen, C1-C20 alkyl chains, aromatic groups, heteroatoms, and oxygenated groups including alcohols, ethers, carbonyls, esters, and hydroxyls. The process according to claim 1, wherein X comprises one or more aldehydes having (selected from the group including heteroatoms, oxygen, sulfur, and nitrogen).

4. The process according to claim 1, wherein the aldehyde-containing stream contains furfural.

5. The process according to claim 1, wherein the Freuyn-type molecules are hydrogenated and deoxygenated to produce a liquid fuel.

6. The process according to claim 1, wherein the Freuin-type molecule is hydrogenated and deoxygenated, and then dehydrogenated to produce a product containing an olefin having 8 to 16 carbon atoms.

7. The process according to claim 1, wherein the homogeneous catalyst system is an N-heterocyclic carbene catalyst.

8. The process according to claim 7, wherein the catalyst is selected from TPT, 1,3-dimesityl-butylimidazoline-2-ylidene, and 1,3-dialkylimidazoline-2-ylidene.

9. The aforementioned Freuyn system molecule is given by formula (II): 【Chemistry 2】 (In the formula, R1, R2, and R3 are selected from the group comprising hydrogen, C1-C20 alkyl groups, aromatic groups, heteroatoms, and oxygenated groups including alcohols, ethers, carbonyl groups, esters, and hydroxyl groups. The process according to claim 1, comprising one or more compounds having (X is selected from the group including oxygen, sulfur, and nitrogen).

10. The process according to claim 1, wherein the froin molecule comprises 5,5'-di(hydroxymethyl)froin.

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