Pyrolytic fragmentation of sugars

Abstract

The present invention relates to a method for pyrolytic fragmentation of sugars into C1-C3 oxygenated compounds, comprising cooling the fragmentation product downstream of a reactor to a cooling temperature of 230°C to 390°C, and then separating solids from the fragmentation product cooled to the cooling temperature. The present invention also relates to an apparatus for carrying out the pyrolytic fragmentation of sugars into C1-C3 oxygenated compounds. The method and apparatus are suitable for industrial-scale production.

Description

[Technical Field]

[0001] The present invention relates to a method for pyrolytic fragmentation of sugars into C1-C3 oxygenates. The present invention also relates to an apparatus for pyrolytic fragmentation of sugars into C1-C3 oxygenates. The method and apparatus are suitable for industrial-scale production. [Background technology]

[0002] Biomass is particularly important as a raw material due to its potential to supplement and possibly replace petroleum as a feedstock for the production of commercial chemicals. In recent years, various technologies for utilizing biomass have been explored. Carbohydrates represent a large proportion of biomass, and various strategies are being established for their effective use as feedstocks for the production of commercial chemicals. These strategies include various fragmentation-based processes, pyrolysis, and catalytic reactions such as hydrocracking, conversion reactions via retro-aldol chemistry, and various processes using acid-catalyzed dehydration processes.

[0003] Examples of chemicals produced from biomass include small alcohols such as ethanol, propanol, and butanol; monomers such as ethylene glycol, ethylene, propylene, butadiene, isoprene, furandicarboxylic acid, succinic acid, lactic acid and lactide, acrylic acid, epichlorohydrin, and vinyl glycolic acid; diols such as 1,2-propanediol, 1,2-butanediol, 2,3-butanediol, 1,2-pentanediol, and 1,2-hexanediol; and sorbitol, glycerol, glycolaldehyde, pyruvaldehyde, and levulinic acid. Other products include synthetic natural gas, syngas, and biofuels.

[0004] In the field of pyrolysis, efforts have focused on using feedstocks based on solid biomass and other lignocellulosic materials for the production of these chemicals.

[0005] Some efforts have been devoted to using sugars as feedstocks to produce food browning materials that are rich in glycolaldehyde (also called hydroxyacetaldehyde) as the primary browning agent.

[0006] Fluidized bed reactors containing heat transfer particles are used to process a variety of feedstocks. They can be operated in a range of different fluidization modes. The preferred mode is selected depending on the feedstock used and the target chemical to be obtained, and as such, there are many different reactor configurations for fluidized bed reactors.

[0007] Several reactor configurations have been considered for the conversion of biomass to bio-oil by pyrolysis, including dense-phase (i.e., bubbling fluidized bed) and dilute-phase (i.e., riser) reactors, as well as radically different types of reactors such as ablation pyrolysis reactors.

[0008] Examples of prior art that disclose the use of a fluidized bed reactor include US Pat. No. 5,397,582 (Underwood), US Pat. No. 7,094,932 (Majerski), WO 2014 / 131764, WO 2012 / 115754, US Pat. No. 5,302,280 (Lomas), and WO 2017 / 216311 (Larsen et al.).

[0009] There remains a need for improved methods and apparatus for the pyrolytic fragmentation of sugars to C1-C3 oxygenates, particularly suitable for industrial-scale production. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] US5,397,582 [Patent Document 2] US7,094,932 [Patent Document 3] WO2014 / 131764 [Patent Document 4] WO2012 / 115754 [Patent Document 5] US$5,302,280 [Patent Document 6] WO2017 / 216311 [Patent Document 7] WO2021 / 032590A1 [Non-patent literature]

[0011] [Non-Patent Document 1] Gasification, Higman, C., 2nd edition, 2008, p.224-225 Summary of the Invention

[0012] According to one aspect of the present invention, there is provided a method for the pyrolytic fragmentation of sugars into C1-C3 oxygenated compounds, comprising the steps of: a) providing an aqueous feedstock solution comprising said sugars; b) providing a fluidized bed fragmentation reactor for pyrolytic fragmentation of said sugars, comprising fluidizable heat transfer medium particles; c) introducing the feedstock solution into the reactor to pyrolytically fragment the sugars to produce a fragmentation product containing the C1-C3 oxygen-containing compounds, wherein the temperature of the fragmentation product at the outlet of the reactor is at least 400°C; d) cooling the fragmentation product downstream of the reactor to a cooling temperature of 230°C to 390°C; and e) separating solids from the fragmentation product cooled to the cooling temperature, wherein the solids include solids selected from flowable heat transfer medium particles, fragments of the flowable heat transfer medium particles, by-products from pyrolysis fragmentation of the feedstock solution, and mixtures thereof; A method is provided which includes:

[0013] Surprisingly, the inventors have found that by cooling the fragmentation product to the cooling temperature downstream of the reactor, the process achieves good product yields of C1-C3 oxygenates while improving efficiency and design. In particular, rather than, for example, including a cooling step within the reactor, the downstream cooling step allows the cooling step and the reactor physical unit operations to be located at different locations. In this manner, the reactor can be designed without the need to accommodate the cooling step physical unit operation, which reduces design and installation complexity and improves space efficiency and ease of handling. Regarding installation complexity, the cooling step physical unit operation can be located closer to the ground surface than the reactor and can be installed independently of the reactor. Regarding space efficiency and ease of handling, the reactor can be designed without the need to accommodate the cooling step physical unit operation, resulting in a more compact and lighter reactor. Furthermore, for example, the reactor can be installed once (i.e., in a modular manner) and then the cooling step physical unit operation can be connected to the reactor. Cooling to cooling temperatures downstream of the reactor unexpectedly provided these benefits along with good product yields of C1-C3.

[0014] The above advantages are particularly beneficial in the context of industrial production processes where large capital expenditures (CAPEX) and operating expenditures (OPEX) can be used to build and maintain process equipment and where product yield is a primary consideration.

[0015] In the context of the present invention, the terms "downstream" and "upstream" refer to the direction in which components flow. For example, if components flow from a location where a feed solution is introduced to an outlet of a reactor, the outlet of the reactor is downstream of the location where the feed solution is introduced into the reactor.

[0016] a) Feedstock solution The method includes providing an aqueous feedstock solution comprising sugars.

[0017] In one aspect, the total sugars content in the feed solution is at least 30 wt %, e.g., at least 35 wt %, at least 40 wt %, at least 45 wt %, at least 50 wt %, at least 55 wt %, at least 60 wt %, at least 65 wt %, at least 70 wt %, at least 75 wt %, at least 80 wt %, at least 85 wt %, at least 90 wt %, or at least 95 wt %, based on the total weight of the feed solution.

[0018] In one aspect, the total sugars content in the feed solution is 99.9 wt.% or less, e.g., 99.5 wt.% or less, 99 wt.% or less, 95 wt.% or less, 85 wt.% or less, or 80 wt.% or less, based on the total weight of the feed solution.

[0019] In one aspect, the total sugars content in the feed solution is from 30 to 99 wt %, for example, from 40 to 90 wt %, or from 50 to 80 wt %, based on the total weight of the feed solution.

[0020] In one aspect, the feedstock solution is a liquid.

[0021] In one aspect, the water content in the feed solution is at least 20 wt.%, e.g., at least 25 wt.%, at least 30 wt.%, at least 35 wt.%, at least 40 wt.%, at least 45 wt.%, at least 50 wt.%, based on the total weight of the feed solution.

[0022] In one aspect, the water content in the feed solution is 70 wt.% or less, e.g., 65 wt.% or less, 60 wt.% or less, 55 wt.% or less, 50 wt.% or less, or 45 wt.% or less, based on the total weight of the feed solution.

[0023] In one aspect, the total sugars content in the aqueous feed solution is from 20 to 70 wt %, for example, from 25 to 60 wt %, or from 30 to 50 wt %, based on the total weight of the feed solution.

[0024] In one aspect, the saccharide is a carbohydrate that includes one or more C6 and / or C5 saccharide units.

[0025] In one aspect, the saccharide is a monosaccharide or a disaccharide.

[0026] In one aspect, the sugars are selected from sucrose, lactose, xylose, arabinose, ribose, mannose, tagatose, galactose, glucose, and fructose.

[0027] In one aspect, the feedstock solution may include sugar syrup.

[0028] In one aspect, the feedstock solution includes more than one sugar.

[0029] Each saccharide may independently be as described herein.

[0030] b) providing a fluidized bed fragmentation reactor for pyrolytic fragmentation of sugars, the reactor comprising fluidizable heat transfer medium particles; The method includes providing a fluidized bed fragmentation reactor for pyrolytic fragmentation of said sugars, the fluidized bed fragmentation reactor comprising fluidizable heat transfer medium particles.

[0031] As those skilled in the art will appreciate, a fluidized bed reactor is a reactor containing a bed of particles that can be fluidized (e.g., by a fluidizing gas that can be introduced into the bottom of the reactor). The velocity and physical properties of the fluidizing gas, combined with the physical properties of the fluidizable particles, can control the fluidization state of the fluidizable particles within the bed. Dense / turbulent / bubble beds have a superficial velocity of the fluidizing gas within the reactor of 0.01 to 2 m / s. High velocity beds (also called riser / transport reactors) can have a superficial velocity of the fluidizing gas within the reactor of 3 to 22 m / s. However, the exact velocity range depends on the physical characteristics of the fluidizable particles and the fluidizing gas and can be determined experimentally or calculated by one skilled in the art.

[0032] In one aspect, the fluidized bed fragmentation reactor operates in a bubbling fluidization regime, a slugging fluidization regime, a turbulent fluidization regime, a fast fluidization regime, and / or a pneumatic transport regime.

[0033] In one aspect, the fluidized bed fragmentation reactor operates in a fast fluidization mode. Such a reactor is also referred to as a "riser reactor." Therefore, in one aspect, the reactor is a riser reactor.

[0034] In one aspect, the reactor includes a riser.

[0035] In one aspect, the risers extend vertically.

[0036] In one aspect, the riser (eg, a lower portion of the riser) includes a fluidizing gas inlet.

[0037] In one aspect, the riser (eg, the lower portion of the rider) includes a flowable particle inlet.

[0038] In one aspect, the riser (eg, a lower portion of the riser) includes a feed inlet.

[0039] In one aspect, the flowable particle inlet is located downstream of the fluidizing gas inlet.

[0040] In one aspect, the feed solution inlet is located downstream of the flowable particle inlet.

[0041] In one aspect, the fluidizable heat transfer particles form a dense phase fluidized bed in the region between the fluidizable particle inlet and the feed solution inlet.

[0042] In one aspect, the riser (e.g., the lower portion of the riser) includes a single inlet for the fluidizable particles and the fluidizing gas. In this manner, the fluidizable heat transfer particles and the fluidizing gas can be introduced into the reactor through a common inlet, e.g., sequentially or simultaneously.

[0043] In one aspect, a feed solution inlet is provided downstream of the single inlet for the fluidizable particles and fluidizing gas.

[0044] In one aspect, the method includes introducing flowable heat transfer medium particles into a reactor.

[0045] In one aspect, the method includes introducing flowable heat transfer medium particles into the reactor through a flowable particle inlet.

[0046] In one aspect, the method includes introducing fluidizable heat transfer medium particles into the reactor through said single inlet for the fluidizable particles and fluidizing gas.

[0047] In one aspect, the temperature of the flowable heat transfer medium particles within the reactor is at least 400°C, such as at least 450°C, at least 500°C, at least 550°C, at least 600°C, or at least 650°C.

[0048] In one aspect, the temperature of the flowable heat transfer medium particles in the reactor is 800°C or less, such as 700°C or less or 650°C or less.

[0049] In one aspect, the temperature of the flowable heat transfer medium particles in the reactor is from 400 to 800°C, for example, from 500 to 800°C, from 450 to 650°C, or from 550 to 650°C.

[0050] In one aspect, the temperature of the fluidizable heat transfer particles at the fluidizable particle inlet (or said single inlet for the fluidizable particles and fluidizing gas) is at least 400°C, e.g., at least 450°C, at least 500°C, at least 550°C, at least 600°C, or at least 650°C.

[0051] In one aspect, the temperature of the fluidizable heat transfer particles at the fluidizable particle inlet (or the single inlet for the fluidizable particles and fluidizing gas) is 800°C or less, e.g., 700°C or less, or 650°C or less.

[0052] In one aspect, the temperature of the fluidizable heat transfer particles at the fluidizable particle inlet (or the single inlet for the fluidizable particles and fluidizing gas) is from 400 to 800°C, e.g., from 500 to 800°C, from 450 to 650°C, or from 550 to 650°C.

[0053] In one aspect, the pressure at the outlet of the reactor is at least 0.9 bara, such as at least 1 bara, at least 1.2 bara, at least 1.4 bara, at least 1.6 bara, at least 1.7 bara, at least 1.8 bara, at least 2 bara, or at least 2.2 bara.

[0054] In one aspect, the pressure at the reactor outlet is 8 bara or less, such as 6 bara or less, 5 bara or less, 4 bara or less, 3.5 bara or less, 3 bara or less, 2.9 bara or less, or 2.8 bara or less.

[0055] In one aspect, the pressure at the reactor outlet is from 0.9 to 8 bara, e.g., from 1 to 6 bara, from 1.1 to 5 bara, from 1.2 to 4 bara, from 1.5 to 3 bara, from 1.6 to 2.9 bara, from 1.7 to 2.8 bara, from 1.8 to 2.8 bara, from 2 to 2.8 bara, or from 2.2 to 2.8 bara.

[0056] In one aspect, the flowable heat transfer medium particles are selected from sand, mullite, silica, glass, alumina, silica-alumina, steel, and silicon carbide.

[0057] In one aspect, the average particle size of the flowable heat transfer medium particles is 20 to 400 μm, for example, 20 to 300 μm, or 20 to 200 μm. The particle size distribution can be measured by laser diffraction spectroscopy, microscopy, or electrical zone sensing. The average particle size can then be calculated from the particle size distribution. The average particle size can be the Sauter mean particle size. It will be apparent to those skilled in the art that other average particle sizes are also contemplated.

[0058] It will also be apparent to those skilled in the art that the flow of the flowable heat carrier particles within the reactor may be adjusted relative to the flow of the feed solution to provide the desired amount of heat to the feed solution. Flowable particles with a high heat capacity may require a lower mass flow rate than flowable particles with a relatively low heat capacity.

[0059] c) introducing a feedstock solution into the reactor to pyrolytically fragment the sugars to produce a fragmentation product comprising C1-C3 oxygenates, wherein the temperature of the fragmentation product at the reactor outlet is at least 400°C; The method includes introducing a feedstock solution into a reactor to pyrolytically fragment sugars to produce a fragmentation product comprising C1-C3 oxygenates, wherein the temperature of the fragmentation product at an outlet of the reactor is at least 400°C.

[0060] The pyrolytic fragmentation of sugars is an endothermic reaction, primarily due to the evaporation of liquid in the feed solution and the reaction enthalpy of pyrolytic fragmentation of sugars to oxygenates.

[0061] In one aspect, the temperature of the fragmentation product at the reactor outlet is at least 420°C, such as at least 430°C, at least 440°C, at least 450°C, at least 460°C, or at least 470°C.

[0062] In one aspect, the temperature of the fragmented product at the reactor outlet is 550°C or less, eg, 530°C or less, 520°C or less, 510°C or less, 500°C or less, or 490°C or less.

[0063] In one aspect, the temperature of the fragmentation product at the reactor outlet is from 400 to 600°C, for example, from 420 to 550°C, from 450 to 510°C, from 460 to 500°C, or from 470 to 490°C.

[0064] In one aspect, in step c), the feedstock solution is introduced into the reactor at a rate of at least 1000 kg / h (kilograms per hour). In one aspect, in step c), the feedstock solution is introduced into the reactor at a rate of at least 2000 kg / h. In one aspect, in step c), the feedstock solution is introduced into the reactor at a rate of at least 5000 kg / h. In one aspect, in step c), the feedstock solution is introduced into the reactor at a rate of at least 10000 kg / h. In one aspect, in step c), the feedstock solution is introduced into the reactor at a rate of at least 15000 kg / h. In one aspect, in step c), the feedstock solution is introduced into the reactor at a rate of at least 20000 kg / h.

[0065] There is no upper limit to the rate at which the feedstock solution is introduced into the reactor in step c). In one embodiment, the feedstock solution is introduced into the reactor at a rate of 1,000,000 kg / h or less in step c). In one embodiment, the feedstock solution is introduced into the reactor at a rate of 100,000 kg / h or less in step c).

[0066] Fluidizing Gas In one aspect, the method includes introducing a fluidizing gas into the reactor.

[0067] It will be apparent to those skilled in the art that the fluidizing gas causes the fluidizable heat transfer particles to flow in the reactor.

[0068] In one aspect, the method includes introducing a fluidizing gas into the reactor via a fluidizing gas inlet.

[0069] In one aspect, the method includes introducing a fluidizing gas into the reactor through a single inlet for the fluidizable particles and the fluidizing gas.

[0070] When the feedstock solution contacts the fluidizable heat transfer particles in the reactor, a vaporization zone is formed, where the liquid evaporates and gaseous products are generated through the fragmentation of sugars. As a result, the superficial velocity of the gaseous products increases, thereby entraining the fluidizable heat transfer particles. Thus, downstream of the feedstock solution inlet, the fluidizable heat transfer particles and the feedstock solution form a high velocity bed above the vaporization zone.

[0071] In one aspect, step c) includes introducing the feedstock solution and a fluidizing gas into a reactor to pyrolytically fragment the sugars to provide a fragmentation product.

[0072] In one aspect, in step c), the feed solution is entrained in a fluidizing gas.

[0073] In one aspect, the fluidizing gas comprises water (eg, steam).

[0074] In one aspect, the fluidizing gas consists essentially of water (eg, steam).

[0075] In one aspect, the fluidizing gas comprises water (eg, steam).

[0076] Herein, "water" and "water vapor" may be used interchangeably.

[0077] In one embodiment, in step c), the fluidizing gas is introduced into the reactor at a rate of at least 100 kg / h. In one embodiment, in step c), the fluidizing gas is introduced into the reactor at a rate of at least 500 kg / h. In one embodiment, in step c), the fluidizing gas is introduced into the reactor at a rate of at least 1000 kg / h. In one embodiment, in step c), the fluidizing gas is introduced into the reactor at a rate of at least 2000 kg / h. In one embodiment, in step c), the fluidizing gas is introduced into the reactor at a rate of at least 4000 kg / h. In one embodiment, in step c), the fluidizing gas is introduced into the reactor at a rate of at least 5000 kg / h.

[0078] There is no need to set an upper limit to the rate at which the fluidizing gas is introduced into the reactor in step c). In one aspect, in step c), the fluidizing gas is introduced into the reactor at a rate of 50,000 kg / h or less. In another aspect, in step c), the fluidizing gas is introduced into the reactor at a rate of 20,000 kg / h or less.

[0079] atomizing gas In one aspect, the method includes introducing an atomizing gas into a reactor.

[0080] It will be apparent to those skilled in the art that atomizing gases are used to atomize the feed solution introduced into the reactor, the term atomizing meaning breaking a liquid into small droplets.

[0081] In one aspect, an atomizing gas and a feedstock solution are introduced into a reactor such that the feedstock solution is atomized by the atomizing gas.

[0082] In one aspect, the atomizing gas comprises water (eg, water vapor).

[0083] In one aspect, the atomizing gas consists essentially of water (eg, water vapor).

[0084] In one aspect, the atomizing gas comprises water (eg, water vapor).

[0085] In one aspect, in step c), the atomizing gas is introduced into the reactor at a rate of at least 50 kg / h. In one aspect, in step c), the atomizing gas is introduced into the reactor at a rate of at least 100 kg / h. In one aspect, in step c), the atomizing gas is introduced into the reactor at a rate of at least 200 kg / h. In one aspect, in step c), the atomizing gas is introduced into the reactor at a rate of at least 500 kg / h. In one aspect, in step c), the atomizing gas is introduced into the reactor at a rate of at least 800 kg / h. In one aspect, in step c), the atomizing gas is introduced into the reactor at a rate of at least 1000 kg / h. In one aspect, in step c), the atomizing gas is introduced into the reactor at a rate of at least 1200 kg / h.

[0086] There is no need to set an upper limit to the rate at which the atomizing gas is introduced into the reactor in step c). In one aspect, in step c), the atomizing gas is introduced into the reactor at a rate of 20,000 kg / h or less. In another aspect, in step c), the atomizing gas is introduced into the reactor at a rate of 10,000 kg / h or less.

[0087] Water introduced The method includes introducing water into a reactor.

[0088] Water may be introduced in either gas (steam) or liquid form, or both. Water may be introduced in a variety of different ways and by one or more of a variety of means, such as via the feed solution and / or via the fluidizing gas and / or via the atomizing gas.

[0089] In one aspect, water is introduced into the reactor via an atomizing gas.

[0090] In one aspect, water is introduced into the reactor via the feed solution.

[0091] fragmentation products The fragmentation product comprises C1-C3 oxygenates resulting from the pyrolytic fragmentation of the feedstock solution. The fragmentation product provided in step (c) is a crude product. The fragmentation product provided in step (c) comprises solids.

[0092] In one aspect, in step c), the fragmentation product is a solids-dense fragmentation product.

[0093] In one aspect, the solids-rich fragmentation product comprises C1-C3 oxygenates and solids.

[0094] In one aspect, step e) comprises separating solids from the solids-rich fragmentation product cooled to the cooling temperature to provide a solids-lean fragmentation product, wherein the solids comprise solids selected from flowable heat transfer medium particles, fractions of flowable heat transfer medium particles, by-products from pyrolytic fragmentation of the feedstock solution, and mixtures thereof.

[0095] In one aspect, the solids-lean fragmentation product comprises C1-C3 oxygenates.

[0096] In one aspect, the solids-lean fragmentation product contains less solids than the solids-rich fragmentation product.

[0097] The terms "lean" in "thin solids" and "thick" in "thick solids" are relative terms.

[0098] In one aspect, the C1-C3 oxygenates include one, more than one, or all of formaldehyde (C1), glycolaldehyde (C2), glyoxal (C2), pyruvaldehyde (C3), and acetol (C3). For most applications, the C2 and C3 oxygenates are the most valuable.

[0099] In one aspect, the fragmentation product comprises a mixture of two or more C1-C3 oxygenates, which may be referred to interchangeably as a C1-C3 oxygenate mixture, a C1-C3 oxygenate product, or C1-C3 oxygenates.

[0100] In one aspect, the fragmentation products include glycolaldehyde.

[0101] In one aspect, the fragmentation product comprises glycolaldehyde as its major portion.

[0102] In one aspect, the fragmentation product comprises glycolaldehyde in an amount of at least 10 wt %, e.g., at least 20 wt %, at least 30 wt %, at least 40 wt %, at least 50 wt %, at least 60 wt %, or at least 70 wt %, based on the total weight of the fragmentation product.

[0103] In one aspect, the fragmentation product comprises one or more of glycolaldehyde or glyoxal in an amount of at least 10 wt%, e.g., at least 20 wt%, at least 30 wt%, at least 40 wt%, at least 50 wt%, at least 60 wt%, at least 70 wt%, or at least 80 wt%, based on the total weight of the fragmentation product.

[0104] In one aspect, the fragmentation product comprises one or more of pyruvaldehyde or acetol in an amount of at least 3 wt %, e.g., at least 5 wt %, or at least 7 wt %, based on the total weight of the fragmentation product.

[0105] In one aspect, the total amount of C1-C3 oxygenates in the fragmentation product is 99 wt. % or less, such as 95 wt. % or less, or 90 wt. % or less, based on the total weight of the fragmentation product.

[0106] In one aspect, "based on the total weight of the fragmentation product" refers to the fragmentation product (eg, the solids-enriched fragmentation product) that is provided in step (c).

[0107] In one aspect, "based on the total weight of the fragmented product" refers to the fragmented product after step (e) (eg, the solids-lean fragmented product).

[0108] In one aspect, "based on the total weight of the fragmented product" refers to the fragmented product without solids.

[0109] d) cooling the fragmentation product downstream of the reactor to a cooling temperature. The method includes cooling the fragmentation product downstream of the reactor to a cooling temperature of from 230°C to 390°C.

[0110] "Cooling temperature" corresponds to the average temperature of the fragmentation product after the cooling step d).

[0111] In one aspect, the cooling temperature is from 250 to 390°C.

[0112] In one aspect, the cooling temperature is from 260 to 385°C.

[0113] In one aspect, the cooling temperature is from 270 to 380°C.

[0114] In one aspect, the cooling temperature is from 300 to 375°C.

[0115] In one aspect, the cooling temperature is from 330 to 370°C.

[0116] In one aspect, step d) comprises indirectly cooling the fragmentation product to a cooling temperature.

[0117] In one aspect, step d) comprises cooling the fragmentation product to a cooling temperature using a cooling device.

[0118] In one aspect, the cooling device is a heat exchanger.

[0119] In one aspect, the cooling device is an indirect heat exchanger.

[0120] In one aspect, step d) is the first step of cooling the fragmentation product.

[0121] In one aspect, no step of cooling the fragmentation product is performed in the reactor.

[0122] In one aspect, no step of cooling the fragmentation product is performed prior to step d).

[0123] In one aspect, step d) is performed at a lower level (relative to sea level) than where the reactor will be located.

[0124] In one aspect, the cooling device (eg, heat exchanger) is located at a lower point (relative to sea level) than where the reactor is located.

[0125] In one aspect, the lowest surface of the cooling device (eg, heat exchanger) is located lower (relative to sea level) than the lowest surface of the reactor.

[0126] In one aspect, no cooling step is performed in the reactor.

[0127] e) separating solids from the fragmentation product cooled to the cooling temperature, wherein the solids comprise solids selected from flowable heat transfer medium particles, fractions of flowable heat transfer medium particles, by-products from pyrolysis fractionation of the feedstock solution, and mixtures thereof. The method includes separating solids from the fragmentation product cooled to a cooling temperature, wherein the solids include solids selected from flowable heat transfer medium particles, fragments of flowable heat transfer medium particles, by-products from pyrolytic fragmentation of the feedstock solution, and mixtures thereof.

[0128] In one aspect, step e) comprises separating at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt%, at least 90 wt%, at least 95 wt%, or at least 99 wt%, based on the total weight of the solids, from the fragmentation product that has been cooled to the cooling temperature.

[0129] In one aspect, step e) includes separating 99.999% or less by weight, e.g., 99.99% or less, 99.9% or less, 99.5% or less, or 99% or less by weight of solids from the fragmentation product that has been cooled to the cooling temperature, based on the total weight of solids.

[0130] In one aspect, step e) comprises separating substantially all of the solids from the fragmented product that has been cooled to a cooling temperature.

[0131] In one aspect, step e) comprises separating solids from the fragmented product that has been cooled to a cooling temperature using a physical separation device.

[0132] In one aspect, the physical separation device is a particle separator.

[0133] In one aspect, the physical separation device is a low volume separator.

[0134] In one aspect, the physical separation device is a change of direction separator.

[0135] In one aspect, the physical separation device is a cyclone.

[0136] In one aspect, the physical separation device is a filter.

[0137] In one aspect, the filter is selected from a metal filter and a ceramic filter.

[0138] In one aspect, the filter includes a filter element, which can be thought of as a material through which a fragmentation product containing solids (filtration media) is filtered to separate the solids from the fragmentation product.

[0139] In one aspect, the filter element includes a filtration surface. The filtration surface can also be referred to as a filtration region. The filtration surface can be considered the outer surface of the filter element. The filtration surface can be considered the interface through which a fragmentation product containing solids enters the filter element during use. The filtration surface can be used to separate the solids from the fragmentation product. In this way, the solids can collect on the filtration surface during use.

[0140] In one aspect, the filter element comprises a porous matrix.

[0141] In one aspect, the porous matrix is ​​selected from a porous fibrous matrix; a porous mesh matrix; a porous matrix comprising sintered spheres; a porous metal matrix (e.g., a sintered porous metal matrix); a porous ceramic matrix; and combinations thereof.

[0142] In one aspect, the porous matrix is ​​a porous fibrous matrix. In one aspect, the porous fibrous matrix is ​​a porous fibrous metal matrix. In one aspect, the porous fibrous matrix is ​​a sintered porous fibrous metal matrix.

[0143] In one aspect, the filter includes a plurality of filter elements, each of which may be independently as described herein.

[0144] In one aspect, the filter is a candle filter.

[0145] In one aspect, the filter is a bag filter.

[0146] In one aspect, the filter has an efficiency of at least 99.9% for particles having a size of at least 50 micrometers, eg, at least 30 micrometers, at least 20 micrometers, or at least 10 micrometers.

[0147] In one aspect, multiple types of physical separation devices are used, each of which may be independently as described herein.

[0148] Residence time In one aspect, the average residence time of the fragmentation product between step d) and step e) is 50 seconds or less, e.g., 45 seconds or less, 40 seconds or less, 35 seconds or less, 30 seconds or less, 25 seconds or less, or 20 seconds or less.

[0149] In one aspect, the average residence time of the fragmentation product between step d) and step e) is at least 0.1 seconds, e.g., at least 1 second, at least 3 seconds, at least 5 seconds, at least 8 seconds, at least 10 seconds, at least 12 seconds, or at least 15 seconds.

[0150] In one aspect, the average residence time of the fragmentation product between step d) and step e) is from 0.1 to 50 seconds, such as from 1 to 40 seconds, or from 2 to 20 seconds.

[0151] "Between step d) and step e)" means between the end of step d) and the start of step e). If a cooling device is used in step d), "between step d) and step e)" means between the time the fragmentation product leaves the cooling device and step e). If a separation device is used in step e), "between step d) and step e)" means between step d) and the time the fragmentation product enters the separation device. If a cooling device is used in step d) and a separation device is used in step e), "between step d) and step e)" means between the time the fragmentation product leaves the cooling device and the time the fragmentation product enters the separation device.

[0152] In one aspect, the average residence time of the fragmentation product in step e) is from 5 to 50 seconds, e.g., from 8 to 30 seconds, from 10 to 25 seconds, from 14 to 22 seconds, from 15 to 20 seconds, or from 16 to 17 seconds.

[0153] "In step e)" refers to the duration of the separation process in step e). If a physical separation device is used in step e), "in step e)" refers to the period from when the fragmentation product enters the physical separation device to when the fragmentation product exits the physical separation device. For example, if a filter is used in step e), "in step e)" refers to the period from when the fragmentation product enters the filter to when the fragmentation product exits the filter.

[0154] Sky tower speed In one aspect, when a filter is used in step e), the superficial velocity of the fragmentation product at the filtration surface of the filter is from 0.1 to 3 cm / sec, e.g., from 0.15 to 2.5 cm / sec, from 0.2 to 2 cm / sec, from 0.25 to 1.5 cm / sec, from 0.3 to 1 cm / sec, from 0.3 to 0.75 cm / sec, from 0.35 to 0.6 cm / sec, or from 0.4 to 0.5 cm / sec.

[0155] Those skilled in the art will know how to calculate surface filtration rate.

[0156] solids The solids include solids selected from flowable heat transfer medium particles, fragments of flowable heat transfer medium particles, by-products from pyrolytic fragmentation of the feedstock solution, and mixtures thereof.

[0157] As the flowable heat transfer medium particles are fluidized within the reactor, some amount of particles may be transported out of the reactor, for example, through the reactor outlet. Particle fragments may be formed by wear or breakage of the particles, for example, by mechanical interactions between the particles themselves and / or between the particles and the reactor.

[0158] The by-products may be viscous and / or sticky. If not removed, they may adhere to the filter (if present) and / or equipment downstream of the reactor. For example, if a filter is used, the by-products may form a sticky filter cake that grows over time, eventually requiring removal of the filter cake.

[0159] In one aspect, the solids comprise solids selected from flowable heat transfer medium particles, fragments of flowable heat transfer medium particles, by-products from pyrolytic fragmentation of a feedstock solution, and mixtures thereof.

[0160] In one aspect, the solids consist essentially of solids selected from flowable heat transfer medium particles, fragments of flowable heat transfer medium particles, by-products from pyrolytic fragmentation of a feedstock solution, and mixtures thereof.

[0161] In one aspect, the solids comprise solids selected from flowable heat transfer medium particles, fragments of flowable heat transfer medium particles, by-products from pyrolytic fragmentation of a feedstock solution, and mixtures thereof.

[0162] In one aspect, the method is suitable for processing sugars in amounts greater than 1,000 tons per year per fragmentation reactor, e.g., greater than 5,000 tons per year per fragmentation reactor, greater than 10,000 tons per year per fragmentation reactor, greater than 50,000 tons per year per fragmentation reactor, greater than 100,000 tons per year per fragmentation reactor, or greater than 1,000,000 tons per year per fragmentation reactor, on a dry sugars basis.

[0163] In one aspect, the method is suitable for processing sugars in amounts of up to 10,000,000 tonnes per year per fragmentation reactor, e.g., up to 5,000,000 tonnes per year per fragmentation reactor, or up to 2,000,000 tonnes per year per fragmentation reactor, on a dry sugars basis.

[0164] In one aspect, the pyrolytic fragmentation process is operated as a continuous process.

[0165] Further process steps In one aspect, the method includes one or more further separation steps between steps c) and d), wherein the or each separation between steps c) and d) includes separating solids from the fragmentation product, the solids comprising solids selected from flowable heat transfer medium particles, fragments of flowable heat transfer medium particles, by-products from the pyrolytic fragmentation of the feedstock solution, and mixtures thereof. In one aspect, the or each separation between steps c) and d) is carried out in a reactor.

[0166] In one aspect, the or each separation step between step c) and step d) comprises separating at least 50 wt%, at least 60 wt%, at least 70 wt%, at least 80 wt%, at least 90 wt%, at least 95 wt%, or at least 99 wt% of the solids from the fragmentation product, based on the total weight of the solids.

[0167] In one aspect, the or each separation step between step c) and step d) comprises separating 99.9 wt. % or less, e.g., 99.5 wt. % or less, 99 wt. % or less, 95 wt. % or less, 90 wt. % or less, or 80 wt. % or less of the solids from the fragmentation product, based on the total weight of the solids.

[0168] In one aspect, the method includes a main separation and / or a side separation between steps c) and d). In one aspect, the main separation and / or the side separation is carried out in a reactor.

[0169] In one aspect, the primary separation comprises separating solids from the fragmentation product, wherein the solids comprise solids selected from flowable heat transfer medium particles, fractions of flowable heat transfer medium particles, by-products from the pyrolytic fragmentation of the feedstock solution, and mixtures thereof.

[0170] In one aspect, the primary separation comprises separating at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or at least 99% by weight of the solids from the fragmentation product, based on the total weight of the solids.

[0171] In one aspect, the primary separation includes separating 99.9 wt. % or less, e.g., 99.5 wt. % or less, 99 wt. % or less, 95 wt. % or less, 90 wt. % or less, or 80 wt. % or less of the solids from the fragmentation product, based on the total weight of the solids.

[0172] In one aspect, the secondary separation comprises separating solids from the fragmentation product, wherein the solids comprise solids selected from flowable heat transfer medium particles, fractions of flowable heat transfer medium particles, by-products from pyrolytic fragmentation of the feedstock solution, and mixtures thereof.

[0173] In one aspect, the secondary separation includes separating at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or at least 99% by weight of the solids from the fragmentation product, based on the total weight of the solids.

[0174] In one aspect, the secondary separation includes separating 99.9 wt. % or less, e.g., 99.5 wt. % or less, 99 wt. % or less, 95 wt. % or less, 90 wt. % or less, or 80 wt. % or less of the solids from the fragmentation product, based on the total weight of the solids.

[0175] The one or more further separation steps between step c) and step d) may help to reduce the amount of solids in the fragmentation product before step d), thus consuming less energy in cooling the heat carrier particles in step d).

[0176] The method according to the invention may provide a fragmentation product that is subjected to one or more further process steps. For example, following step d), the fragmentation product may be further processed by one or more of chemical conversion (e.g., conversion to other products, e.g., via a hydrogenation reactor), purification (e.g., purification to reduce the presence of impurities), and separation (e.g., separation to provide a specific oxygenate or a specific mixture of oxygenates).

[0177] According to another aspect of the present invention, there is provided an apparatus for pyrolytic fragmentation of sugars into C1-C3 oxygen-containing compounds, comprising: a) an aqueous feedstock solution containing sugars; b) a fluidized-bed fragmentation reactor comprising fluidizable heat transfer particles configured to pyrolytically fragment sugars to provide a fragmentation product comprising C1-C3 oxygenates, wherein the temperature of the fragmentation product at an outlet of the reactor is at least 400°C; c) means for cooling the fragmentation product downstream of said reactor to a cooling temperature of from 230°C to 390°C; and d) a separation device configured to separate solids from the fragmentation product cooled to the cooling temperature, wherein the solids comprise solids selected from flowable heat transfer medium particles, fragments of flowable heat transfer medium particles, by-products from pyrolytic fragmentation of a feedstock solution, and mixtures thereof; An apparatus is provided, comprising:

[0178] According to another aspect of the present invention, there is provided an apparatus for pyrolytic fragmentation of sugars into C1-C3 oxygen-containing compounds, comprising: a) a fluidized bed fragmentation reactor configured to pyrolytically fragment sugars, thereby providing a fragmentation product comprising C1-C3 oxygenates; and b) means for cooling the fragmentation product downstream of the reactor to a cooling temperature; Including, the means for cooling the fragmentation product is located at a lower level (relative to sea level) than the reactor; The apparatus is provided.

[0179] In one aspect, the reactor and cooling means are in the form of separate physical structures.

[0180] According to another aspect of the present invention, there is provided an apparatus for pyrolytic fragmentation of sugars into C1-C3 oxygen-containing compounds, comprising: a) a fluidized bed fragmentation reactor configured to pyrolytically fragment sugars, thereby providing a fragmentation product comprising C1-C3 oxygenates; and b) means for cooling the fragmentation product downstream of the reactor to a cooling temperature; An apparatus is provided, comprising:

[0181] In one aspect, the cooling means is a cooling device, which may be as defined herein.

[0182] Any aspect of the invention may include one or more features of any other aspect of the invention. Features of any aspect of the invention may be those described herein with respect to any other aspect of the invention. For example, an apparatus according to the invention may be characterized by any feature of a method according to the invention, and vice versa.

[0183] Aspects of the present invention will now be described, by way of example only, with reference to the accompanying drawings, which illustrate exemplary aspects of the invention only and therefore should not be considered as limiting its scope, since the invention is susceptible to other alternative aspects. [Brief explanation of the drawings]

[0184] [Figure 1] FIG. 1 shows a cross-sectional side view of a fragmentation reactor forming part of an apparatus according to one embodiment of the present invention. [Figure 2] FIG. 2 shows a top view of the fragmentation reactor of FIG. [Figure 3] FIG. 3 shows a cross-sectional side view of a preheater forming part of an apparatus according to one embodiment of the invention. [Figure 4] FIG. 4 shows a cross-sectional side view of an apparatus according to one embodiment of the present invention (although not all components of the apparatus are shown), where the apparatus includes a fragmentation reactor in fluid communication with a preheater. [Figure 5] FIG. 5 shows a block diagram of an apparatus according to one embodiment of the present invention (although not all components of the apparatus are shown). [Figure 6] FIG. 6 shows the temperature profile of the flowable particle inlet, reactor outlet, and filter for one example. [Figure 7] FIG. 7 shows the carbon yield for glycolaldehyde carbon recovery and for (total) C1-C3 oxygenates carbon recovery as a function of filtration temperature. [Figure 8] FIG. 8 is a schematic diagram of a candle filter. [Figure 9]FIG. 9 shows a schematic diagram of a fragmentation reactor forming part of an apparatus according to one embodiment of the present invention. [Explanation of symbols]

[0185] 1. Fragmentation Reactor 2.Fragmentation riser 3.First particle separator 4.Second particle separator 5. Cooling section 6. Main fluidizing gas inlet 7. Flowable particle inlet 8. Feedstock and atomizing gas inlet 9.Product outlet 10. Flowable particle outlet 11. Preheater 12. Fuel and combustion air inlet 13. Burner chamber 14. Flowable particle inlet to preheater 15. Preheater riser 16. Separator for preheater of flowable particles 17. Flowable particle outlet from preheater 18.Preheater gas outlet 19. Secondary separator for preheater of flowable particles 20. Stripper 21. Sub-fluidization gas inlet 22. Sub-preheater fluidizing and stripping gas inlet O': Reactor outlet 100.Heat exchanger 200. Physical separation devices (e.g., filters) for gas / solid separation 300. Fragmentation Reactor 301. Fluidizing Gas 302.Feedstock solution 303. Atomizing gas 304. Feedstock and atomizing gas inlet (feed nozzle) 305.First particle separator 306. Recycled Heat Transfer Particles 307. Approximate boundary separating concentrated and dilute phases 308.Heating device 309. Cooling step 310. Separation step DETAILED DESCRIPTION OF THE INVENTION

[0186] As shown in Figures 1 and 4, the fragmentation reactor 01 is vertically elongated. A riser 02 is provided within the fragmentation reactor, which is elongated with a small cross-sectional area relative to its height. This facilitates shortening the residence time of the fluidizable heat transfer medium particles within the riser 02. A fluidizing gas inlet 06 is provided at the bottom of the riser 02. The main fluidizing gas inlet 06 is adapted to supply fluidizing gas to the riser 02. A fluidizable heat transfer medium particle inlet 07 is also provided at the bottom of the riser 02. The reactor 01 further includes an outlet O'.

[0187] The fluidizing gas helps promote the movement of the fluidizable heat transfer medium particles from the fluidizable heat transfer medium particle inlet 07 to the feed inlet 08 and toward the top of the riser 02. Additionally, the fluidizing gas can be used to precondition the fluidizable heat transfer medium particles before they contact the feed solution.

[0188] Inlets 8 for the feedstock and atomizing gas are located in the riser 02 above the particle and fluidizing gas inlets 06, 07, respectively. The feedstock inlet 08 allows the feedstock solution to be fed into the riser 02. As shown in Figure 1, the feedstock inlet 08 is located at the bottom of the riser 02, although its location may vary depending on the process requirements.

[0189] Once the feedstock solution and flowable particles have interacted in the riser 02, they are separated in a first particle separator 03 upon exiting the riser. In some embodiments, the first particle separator 03 is adapted to rapidly separate the flowable particles from the fragmentation product (including C1-C3 oxygenates) since such rapid separation is highly advantageous to the process. Therefore, the particle separator 03 can be of a short residence time type.

[0190] 1 and 2, the first particle separator 03 includes an outlet pipe that changes the upward direction of the outlet flow from the riser 02 by approximately 180° to a downward flow direction within the fragmentation reactor 01 but outside the riser 02. This is referred to in the sense of the present invention as a turning particle separator.

[0191] In the embodiment of Figure 4, the first particle separator 03 induces gas particle separation and directs the outlet flow of riser gas and solids into the reactor 1 tangential to the wall of the reactor 01, thereby effecting separation. A portion of the particles collect at the bottom of the fragmentation reactor 01 after exiting the first particle separator 03.

[0192] The above-described features of the riser 02, the feed inlet 06 location, and the short residence time first particle separator 03 provide the potential for very short contact times between the flowable particles and the feed solution, although this of course also depends on the process parameters, such as volumetric flow rate and specific dimensions, to be adapted to the process requirements.

[0193] An optional cooling section 05 is located within the fragmentation reactor 01. In the embodiment of Figure 1, the cooling section is between the first particle separator 03 and the outlet O' of the reactor 01.

[0194] The fragmentation product is withdrawn from the fragmentation reactor 01 via the product outlet 09.

[0195] In the embodiment shown in Figures 1 and 4, an optional further second particle separator 04 is provided to separate a further portion of the flowable particles from the product stream before the fragmented product is withdrawn.

[0196] A second particle separator 04, such as a cyclone, may provide higher separation efficiency than the direction separator 03 alone. The gas outlet of the cyclone 04 is connected to the product outlet 09, and particles from the particle outlet of the cyclone 04 are conveyed to the bottom of the fragmentation reactor 01, where the flowable particles are maintained in a fluidized state by the use of fluidizing gas supplied via the secondary fluidizing gas inlet 21. Distribution of the fluidizing gas across the horizontal cross section of the vessel 1 is ensured, for example, using a sparger. At the bottom of the fragmentation reactor 01, a particle outlet 10 allows spent flowable particles from the fragmentation reactor 01 to be withdrawn and conveyed elsewhere, for example, for preheating in another reactor. Stripping of the product gas (fragmentation product) immediately before or after the flowable particle outlet 10 in Figures 1-4 is also envisioned but not shown in the drawings.

[0197] Figure 2 is a top view of the fragmentation reactor of Figure 1. As shown, the riser 02 is located at the center of the horizontal cross section of the fragmentation reactor 01. Also shown are a number of outlet pipes forming a first particle separator 03, as well as a second particle separator 04 located off-center in the fragmentation reactor 01.

[0198] 3 and 4 show a preheater 11 for preheating the flowable particles exiting the fragmentation reactor 01. A preheater particle inlet 14 is in fluid communication with the flowable particle outlet 10, and a flowable particle preheater outlet 17 is in fluid communication with the flowable particle inlet 07. The preheater 11 also includes a riser-type fluidized bed and a preheater riser 15 with a burner chamber 13 disposed in fluid communication with a lower portion of the preheater riser 15. A fuel and combustion air inlet 12 allows fuel and combustion air to be supplied to the burner chamber 13, which provides heat to the preheater riser 15 during operation. The flowable particle preheater inlet 14 is located at the bottom of the preheater riser 15 and allows the flowable particles exiting the fragmentation reactor 01 to enter the preheater riser 15 where they are fluidized in an upward flow by the hot gases provided while being heated by the burner chamber 13. The connection between the burner chamber 13 and the flowable particle preheater inlet 14 is carefully designed to reduce or prevent shedding of the flowable particles from the riser 15 into the burner chamber 13. This design can take many different forms. For example, in Figures 3 and 4, this is shown by the constriction between 13 and 15, which provides increased gas velocity to prevent or reduce particle shedding. After preheating, the flowable particles are separated from the combustion gases and returned to the fragmentation reactor 01. 3, preheater particle separator 16 is a cyclone that allows gas to exit preheater 11 via preheater gas outlet 18, while separated flowable particles exit preheater 11 via flowable particle preheater outlet 17, which is connected to the flowable particle outlet of the cyclone of preheater 11. It will be understood that the degree of separation in the particle separator will depend on various process parameters, such as pressure drop across the separator, flow rate, particle size, etc., as known in the art.

[0199] In the embodiment of FIG. 4, the preheater primary particle separator 16 is similar to the primary particle separator 03 of the fragmentation reactor. The embodiment of FIG. 4 also includes a secondary cyclone-type particle separator 19. Both particle separators 16, 19 deliver flowable particles to the bottom of the preheater 11. At the lowest point of the preheater 11 is a section 20 for stripping excess oxygen from the flowable particles. In the embodiment of FIG. 4, secondary fluidizing and stripping gas inlets 22 for the preheater 11 and section 20 are distributed across the cross section, for example, using spargers or other methods. Additional fluidizing gas inlets may be present in the preheater 11 in FIG. 4 but are not shown. Stripping of the product gas (fragmentation product) immediately before or after the flowable particle outlet 10 in FIGS. 1-4 is also contemplated but not shown in the drawings.

[0200] Referring to Figure 5, additional components of the apparatus of Figure 4 are shown (although not all components of the apparatus are shown). This apparatus includes the components of Figure 4. In other embodiments, the apparatus includes the fragmentation reactor of Figure 1 instead of that shown in Figure 4. The apparatus may further include a cooling device, such as heat exchanger 100, to cool the product gas (fragmentation product). The apparatus also includes physical separation device 200 (described below). In the embodiment of Figure 5, heat exchanger 100 is located downstream of reactor 1, and physical separation device 200 is located downstream of heat exchanger 100. It will be apparent to one of skill in the art that the apparatus may include other components, such as one or more additional cooling steps or other unit operations.

[0201] In the embodiment of Figure 5, the product gas enters heat exchanger 100 over product outlet 09, then enters physical separation device 200, and then enters further downstream equipment. In the embodiment of Figure 5, physical separation device 200 is a filter, specifically a candle filter, where the filter element provided by the candles of the candle filter comprises a porous matrix of metal fibers. More specifically, the metal fibers comprise a nickel-chromium-molybdenum alloy (Alloy 59).

[0202] FIG. 8 shows a schematic diagram of a candle filter. The candle filter includes a housing having a solids / fragmentation product inlet, a solids outlet, and a fragmentation product / gas outlet. The fragmentation product containing solids is introduced through the inlet, the separated solids are introduced through the solids outlet, and the fragmentation product from which the solids have been separated is introduced through the fragmentation product / gas outlet. A plurality of candles are disposed within the housing. Each candle includes a filter element for separating solids from the fragmentation product. Each filter element includes a filtering surface (or filtering area). The filtering surface can be considered the interface through which the fragmentation product containing solids enters the filter element during use. The filtering surface is the outer surface of the filter element. During use, the fragmentation product enters each filter element through the filtering surface, and the solids are then separated from the fragmentation product by each filter element. The separated solids are removed from the housing through the solids outlet. The solids outlet may be equipped with a valve system (not shown) to prevent gas leakage and for removal of collected solids.

[0203] In other embodiments, other physical separation devices and other filters are contemplated. For example, candle filters are used in conjunction with "Gasification" (Higman, C., 2002). nd edition, 2008, pp. 224-225. The function and operation of candle filters are known to those skilled in the art and therefore will not be described in further detail here.

[0204] In some embodiments (e.g., the embodiment of FIG. 5 ), the step of cooling the fragmentation product using heat exchanger 100 is the first step of cooling the fragmentation product. In some embodiments, the step of cooling the fragmentation product does not occur in reactor 01. In some embodiments, the step of cooling the fragmentation product does not occur before the step of cooling the fragmentation product using heat exchanger 100.

[0205] In this particular embodiment, before passing over the product outlet 09, the fragmented product passes through a first particle separator 03 and a second particle separator 04, as previously described. These particle separators 03, 04 reduce the amount of heat transfer particles in the fragmented product.

[0206] Separation device 200 separates solids from the fragmentation product, wherein the solids include solids selected from fluidizable heat transfer medium particles, fractions of fluidizable heat transfer medium particles, by-products from pyrolysis fragmentation of the feedstock solution (the latter described below), and mixtures thereof. In this particular embodiment, the solids consist essentially of solids selected from fluidizable heat transfer medium particles, fractions of fluidizable heat transfer medium particles, by-products from pyrolysis fragmentation of the feedstock solution, and mixtures thereof. By separating the solids from the fragmentation product, these solids have a reduced impact on equipment downstream of reactor 1. In use, the fragmentation product exits reactor 1 via product outlet 09 and passes through heat exchanger 100 before passing through separation device 200.

[0207] The heat exchanger 100 is installed at ground level, while the reactor 01 is installed above ground level.

[0208] As will be apparent to those skilled in the art, water may be introduced into the reactor by a variety of means, such as via the feed solution, the fluidizing gas, and / or the atomizing gas, although it will be understood that the fluidizing gas and / or the atomizing gas may comprise an inert gas, such as N, CO, CO, CH, or mixtures thereof. [Example]

[0209] Example 1 Pyrolytic fragmentation of an aqueous feed solution (glucose syrup) containing approximately 60 wt. % glucose and 40 wt. % water (based on the total weight of the feed solution) was carried out in an apparatus according to one embodiment of the present invention (i.e., the apparatus of FIG. 4, except that the optional cooling step 05 was omitted). The aqueous feed solution was fed into the reactor at a rate of 15 kg / h.

[0210] The fragmentation reactor 1 was operated under approximately 2.5 bara (absolute pressure) (at the reactor outlet 0') with an inlet 07 heat transfer medium temperature of approximately 580°C and a reactor outlet 0' temperature of approximately 475°C. Over the approximately 15-hour reactor 01 run time, the filter 200 temperature (e.g., the temperature at the inlet of the filter 200) was gradually reduced from approximately 400°C to 340°C by increasing the cooling rate of the indirectly cooled heat exchanger 100 located between the reactor 01 and the filter 200. Figure 6 shows the temperature profile during this 15-hour run. The feed solution was injected into the reactor 1 through a gas-assisted internal mixing atomization nozzle (i.e., feed and atomization gas inlet 08) entering from the bottom of the riser 02 using an atomizing gas flow of 15 kg / h nitrogen, 7 kg / h steam via 6, and 12 kg / h steam added via inlet 21.

[0211] The average gas residence time (average residence time of the fragmentation product) in the filter 200 was approximately 16 to 17 seconds (although one skilled in the art will appreciate that this time will vary depending on temperature). The superficial velocity (i.e., the superficial velocity at the filtering surface of the filter) was 0.42 to 0.46 cm / s.

[0212] Referring to Figure 8, in use, the fragmented product containing solids flows into a candle filter, where the fragmented product containing solids is distributed on the candle and flows through the filter element of the candle. The fragmented product enters the filter element of the candle through the filtering surface of the candle. The fragmented product containing solids flows through the filtering surface of the candle at an average superficial velocity that can be calculated by the following formula: U=Q / Area In the formula, Q is expressed in units of m 3 / s and Area is in m 2 is the area of ​​the filtering surface. Those skilled in the art will know how to calculate the actual gas flow rate and correct it according to pressure and temperature. The filter element of the candle can be made from a variety of materials and can have different porosities as shown at A, B or C on the right hand side of Figure 8. The filtration rate U at the filtering surface is nearly independent of the type of material.

[0213] A solids-lean fragmented product was obtained after filtration through filter 200. The solids-lean fragmented product was substantially free of solids.

[0214] After filtration through filter 200, the fragmentation product (lean in solids) stream was condensed. The glycolaldehyde concentration of the fragmentation product (lean in solids) was measured by HPLC at various times during the 15-hour run. Similarly, the C1-C3 oxygenate concentration of the fragmentation product (lean in solids) was also measured by HPLC at various times during the 15-hour run. The yield of C1-C3 oxygenates (i.e., total C1-C3 oxygenates) was determined. Using water as an inert reference, the carbon-based yield and recovery of glycolaldehyde were calculated for each filtration temperature. The glycolaldehyde recovery or yield is the percentage of carbon in the feed solution that was recovered as carbon in glycolaldehyde. The same calculation was performed for all C1-C3 oxygenates. Figure 7 shows the carbon yield or recovery of glycolaldehyde and C1-C3 oxygenates (total C1-C3 oxygenates) as a function of filtration temperature. It was observed that the glycolaldehyde yield increased significantly as the filter temperature was lowered, from less than 40% to approximately 50%, and the C1-C3 oxygenate yield also increased significantly as the filter temperature was lowered, from approximately 65% ​​to approximately 78%.

[0215] Therefore, the inventors have surprisingly found that the yield of C1-C3 oxygenates (e.g., glycolaldehyde) depends on the filtration temperature, which is preferably below 370°C, more preferably below 350°C.

[0216] Therefore, the inventors surprisingly found that by cooling the fragmentation product to a cooling temperature downstream of the reactor 01, the method provides improved efficiency and design while achieving a good product yield of C1-C3 oxygenates (e.g., glycolaldehyde). In particular, thanks to the downstream cooling step rather than, for example, cooling within the reactor, the cooling heat exchanger 100 and the reactor 01 can be located at different positions relative to each other. In this way, the reactor 01 can be designed without the need to accommodate the cooling heat exchanger 100, which reduces design and installation complexity and improves space efficiency and ease of handling. Regarding reduced installation complexity, the cooling heat exchanger 100 can be located closer to ground level than the reactor 01 and can be installed independently of the reactor 01. Regarding space efficiency and ease of handling, because the reactor 01 can be designed without the need to accommodate the cooling heat exchanger 100, the reactor 01 can be more compact and have a lower mass. Further, for example, the cooling heat exchanger 100 can be connected to the reactor 01 after the reactor 01 is installed (i.e., in a modular fashion). Cooling to cooling temperatures downstream of the reactor 01 unintentionally provides these benefits as well as good product yields of C1-C3 oxygenates.

[0217] The above advantages are particularly beneficial in the context of industrial production where large capital expenditures (CAPEX) and operating expenditures (OPEX) can be used to build and maintain process equipment and where product yield is a primary consideration.

[0218] Example 2 This example illustrates another aspect of conducting the pyrolytic fragmentation of sugars in an industrial setting according to the present invention. Referring to FIG. 9, the apparatus and method utilize a fluidized-bed fragmentation reactor (300). Within the reactor (300), a fluidizing gas (301) is added to the bottom of the reactor (300) by a gas distributor (not shown in detail) for fluidizing the heat transfer carrier particles used in the pyrolytic fragmentation of sugars. The gas distributor distributes the fluidizing gas (301) across the entire cross section of the reactor (300). In FIG. 9, the gas distributor is a gas sparger with a downward direction (although other directions, such as upward, horizontal, or anything in between, are also possible). Liquid sugars feedstock (302) is mixed with atomizing gas (303) in a feed nozzle (304) to provide a fine spray of droplets before contacting the heat transfer carrier particles in the reactor (300). Although only one feed nozzle (304) is shown in FIG. 9, it will be appreciated that multiple feed nozzles can be used and positioned at different locations within the reactor (300) to provide better distribution of the feed (302) throughout the reactor (300).

[0219] The liquid sugars feedstock (302) contacted with the heat transfer particles is cracked within the reactor, resulting in a gas-phase C1-C3 oxygenate-rich fragmentation product. Cracking and feedwater evaporation increase the gas volumetric flow rate, thereby increasing the upward gas velocity. The gas flows upward and into a cyclone (305) (first particle separator). Within the cyclone (305), most (e.g., at least 95% by weight) of the entrained heat transfer particles are separated and recycled (306) to the lower portion of the reactor (300). The outlet of reactor O' conveys the fragmentation product for downstream processing. It will be appreciated that the particle separator (305) can be configured in various ways, and multiple particle separators can be used. For example, parallel cyclones, cyclones in series, or a combination of these can be used. Surface filters can also be used.

[0220] The lower section of reactor (300) operates in a dense-type fluidized bed with a superficial gas velocity of approximately less than 2 m / s (meters per second). The upper section of reactor 300 operates in a lean-type phase with a superficial gas velocity of approximately greater than 3 m / s. The boundary between the operating modes (rich or lean) is not sharp and may depend on the physical properties of the gas and solids, such as density, gas viscosity, and particle size and shape. The increase in gas flow rate from the cracking process may also depend on the feed concentration and product yield. In Figure 9, the approximate boundary separating the dense and lean phases is indicated by curve (307). Curve (307) also indicates the approximate location of the upper surface of the dense fluidized bed of heat transfer particles.

[0221] Within the dense fluidized bed of heat transfer particles, an indirect heating device (308) is arranged to provide the energy required for the pyrolysis fragmentation step and to account for heat and product gas losses. The heating device (308) can be a resistive electric heating rod or other type of indirect heating method. The dense mode of fluidization ensures good mixing and transport of the heat transfer particles in the reactor (300).

[0222] The heating device (308) may also be located external to the reactor (300), and additional means may be provided for the transfer of heat transfer medium particles between the reactor (300) and the heating device (308), this configuration not shown.

[0223] As shown in FIG. 9, downstream of the outlet O' of the reactor (300) there is a cooling step (309) and a subsequent solids separation step (310).

[0224] The apparatus of Figure 9 can be used to carry out the pyrolytic fragmentation of sugars under industrial conditions. Approximately 25,000 liters (bulk) of heat transfer particles, as described in Example 2 of WO 2021 / 032590 A1, are added to the reactor (300). A 60 wt% glucose aqueous solution (302) is fed to the reactor (300) at a rate of 23,000 kg / h (kilograms per hour). Steam as the atomizing gas (303) is fed to the reactor (300) at a rate of 1,380 kg / h. Steam as the fluidizing gas (301) is fed to the reactor (300) at a rate of 5,741 kg / h. The cooling step (309) involves cooling the fragmentation product to a cooling temperature of 230°C to 390°C. The separation step (310) comprises separating solids from the fragmentation product cooled to a cooling temperature, wherein the solids comprise solids selected from flowable heat transfer medium particles, fractions of flowable heat transfer medium particles, by-products from the pyrolysis fragmentation of the feedstock solution, and mixtures thereof. The following yields of predominantly C2-C3 oxygenates on a carbon basis from glucose are obtained: 57 C% glycolaldehyde, 10 C% pyruvaldehyde, 4 C% acetol, 3 C% glyoxal, and 10 C% formaldehyde.

[0225] The product gas flow rate at outlet O' of reactor (300) is approximately 24,380 Nm3 / h (Nm3 refers to standard cubic meters at a temperature of 0°C and a pressure of 1 absolute atmosphere). The yield of other by-products, such as CO, CO2, and acetic acid, will not significantly alter this flow rate. It will be understood that, for example, changing the flow rate and / or composition of the atomizing gas (303) or the fluidizing gas (301) can alter the resulting gas flow rate at outlet O'. The temperature of the process gas at outlet O' of reactor (300) is approximately 525°C, and cooling this gas to a cooling temperature of 300°C results in a required cooling load of approximately 3.7 MW (megawatts). The reactor (300) is operated at a pressure of approximately 2.1 absolute atmospheres just before the gas inlet to the particle separator (305).

[0226] It will be apparent to those skilled in the art that the present invention can be scaled up as desired. The present invention is suitable for industrial scale production.

[0227] Various modifications and variations of this invention, which will be apparent to those skilled in the art, can be introduced without departing from the scope of the invention. Although the invention has been described in connection with specific preferred embodiments, it should be understood that the invention as claimed should not be unduly limited to such specific embodiments. Indeed, various modifications of the above-described modes for carrying out the invention which are obvious to those skilled in the art are intended to be within the scope of the claims.

Claims

1. 1. A method for pyrolytic fragmentation of sugars into C1-C3 oxygenated compounds, comprising the steps of: a) providing an aqueous feedstock solution comprising said sugars; b) providing a fluidized bed fragmentation reactor for pyrolytic fragmentation of said sugars, comprising fluidizable heat transfer medium particles; c) introducing the feedstock solution into the reactor to pyrolytically fragment the sugars to provide a fragmentation product comprising the C1-C3 oxygenates, wherein the temperature of the fragmentation product at an outlet of the reactor is at least 400°C; d) cooling the fragmentation product downstream of the reactor to a cooling temperature of 230°C to 390°C; and e) separating solids from the fragmentation product cooled to the cooling temperature, wherein the solids include solids selected from the flowable heat transfer medium particles, fragments of the flowable heat transfer medium particles, by-products from the pyrolysis fragmentation of the feedstock solution, and mixtures thereof; The method comprising:

2. 2. The method of claim 1, wherein step d) comprises indirectly cooling the fragmentation product to the cooling temperature, and optionally, step d) comprises cooling the fragmentation product to the cooling temperature using a cooling device, and optionally, the cooling device is a heat exchanger.

3. 3. The method of claim 1 or 2, wherein step d) is the first step of cooling the fragmentation product, and optionally, the step of cooling the fragmentation product is not performed in the reactor, and optionally, the step of cooling the fragmentation product is not performed before step d).

4. The method of any one of claims 1 to 3, wherein the cooling temperature is from 260 to 385°C, for example from 270 to 380°C, from 300 to 375°C, or from 330 to 370°C.

5. 5. The method according to claim 1, wherein the average residence time of the fragmentation product between step d) and step e) is 50 seconds or less.

6. 6. The method according to any one of claims 1 to 5, wherein the average residence time of the fragmentation product in step e) is from 8 seconds to 34 seconds.

7. The method of any one of claims 1 to 6, wherein step e) comprises separating the solids from the fragmentation product using a physical separation device.

8. 8. The method of claim 7, wherein the physical separation device is a filter, and optionally the filter has an efficiency of at least 99.9% for particles having a size of at least 50 micrometers, e.g., at least 30 micrometers, at least 20 micrometers, or at least 10 micrometers, and optionally the filter is selected from a bag filter and a candle filter.

9. 9. The method of claim 8, wherein the filter comprises a filter element having a filtering surface, wherein the superficial velocity of the fragmentation product at the filtering surface is from 0.1 to 3 cm / s.

10. 10. The method according to any one of claims 1 to 9, wherein the sugars are carbohydrates comprising one or more C6 and / or C5 saccharide units, and / or the sugars are monosaccharides or disaccharides, optionally selected from sucrose, lactose, xylose, arabinose, ribose, mannose, tagatose, galactose, glucose, and fructose, and / or the total sugar content in the feed solution is from 30 to 99% by weight, such as from 40 to 90% by weight, or from 50 to 80% by weight, based on the total weight of the feed solution.

11. 11. The method of any one of claims 1 to 10, wherein the fragmentation product comprises glycolaldehyde; optionally, the fragmentation product comprises one, more than one, or all of formaldehyde, glycolaldehyde, glyoxal, pyruvaldehyde, and acetol; and optionally, the fragmentation product comprises glycolaldehyde in an amount of at least 10% by weight, based on the total weight of the fragmentation product.

12. 12. The method according to any one of claims 1 to 11, wherein step d) is carried out at a level below the level at which the reactor is placed.

13. 13. The process according to any one of claims 1 to 12, wherein the pressure at the outlet of the reactor is at least 1.5 bara.

14. The method of any one of claims 1 to 13, wherein the fragmentation reactor comprises a riser.

15. 15. The method of claim 1, further comprising one or more further separation steps between step c) and step d), wherein the or each separation step between step c) and step d) comprises separating solids from the fragmentation product, and the solids comprise solids selected from flowable heat transfer medium particles, fragments of the flowable heat transfer medium particles, by-products from the pyrolysis fragmentation of the feedstock solution, and mixtures thereof, and the or each separation step between step c) and step d) comprises separating at least 50 wt. % of solids from the fragmentation product, based on the total weight of the solids.

16. 1. An apparatus for pyrolytic fragmentation of sugars into C1-C3 oxygenated compounds, comprising: a) an aqueous feedstock solution comprising said sugars; b) a fluidized-bed fragmentation reactor comprising fluidizable heat transfer particles configured to pyrolytically fragment sugars to provide a fragmentation product comprising C1-C3 oxygenates, wherein the temperature of the fragmentation product at an outlet of the reactor is at least 400°C; c) means for cooling the fragmentation product downstream of the reactor to a cooling temperature of from 230°C to 390°C; and d) a separation device configured to separate solids from the fragmentation product cooled to the cooling temperature, the solids comprising solids selected from the flowable heat transfer medium particles, fragments of the flowable heat transfer medium particles, by-products from the pyrolytic fragmentation of the feedstock solution, and mixtures thereof; 1. An apparatus comprising:

17. Device according to claim 16, characterized by the features according to any one of claims 2 to 15.

18. 1. An apparatus for pyrolytic fragmentation of sugars into C1-C3 oxygenated compounds, comprising: a) a fluidized bed fragmentation reactor configured to pyrolytically fragment the sugars to provide a fragmentation product comprising the C1 to C3 oxygenates; and b) means for cooling the fragmentation product downstream of the reactor; Including, The apparatus wherein the means for cooling the fragmentation product is located at a position lower than the position at which the fluidized bed fragmentation reactor is located.

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