Pyrolytic fragmentation of sugars

Abstract

The present invention relates to a method for pyrolytic fragmentation of sugars to C1-C3 oxygenated compounds, comprising separating solids from the fragmentation product, wherein the temperature of the fragmentation product at the reactor outlet is at least 250°C and the water content is at least 40% by volume, based on all gas phase components. The present invention also relates to an apparatus for carrying out the pyrolytic fragmentation of sugars to 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; and diols such as 1,2-propanediol, 1,2-butanediol, 2,3-butanediol, 1,2-pentanediol, 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 converting 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 ablative 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.). [Prior art documents] [Patent documents]

[0009] [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] WO21 / 032590 [Non-patent literature]

[0010] [Non-Patent Document 1] “Gasification”, Higman, C., 2nd edition, 2008, p.224-225 Summary of the Invention [Problem to be solved by the invention]

[0011] 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. [Means for solving the problem]

[0012] According to one aspect of the present invention, there is provided 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; and d) separating solids from the fragmentation product; Including, the solids comprise solids selected from the 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; The temperature of the fragmentation product at the reactor outlet is at least 250°C, e.g., at least 300°C, at least 350°C, at least 400°C, or at least 450°C; and The water content is at least 40% by volume, based on all gas phase components; The method is provided.

[0013] According to another aspect of the present invention, there is provided 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; and d) separating solids from the fragmentation product; Including, the solids comprise solids selected from the 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; The temperature of the fragmentation product at the reactor outlet is at least 250°C, e.g., at least 300°C, at least 350°C, at least 400°C, or at least 450°C; and The partial pressure of water vapor is greater than 650 mbar. The method is provided.

[0014] The present inventors have sought to provide improved methods and apparatus for the pyrolytic fragmentation of sugars to C1-C3 oxygenates. Such methods and apparatus typically use a fluidized bed fragmentation reactor to pyrolytically fragment sugars to provide a fragmentation product comprising C1-C3 oxygenates.

[0015] During these investigations, the inventors observed problems in the operation of equipment downstream of the reactor. Surprisingly, the inventors discovered the presence of material adhering to the equipment. In some cases, this material led to failures or blockages in the equipment.

[0016] Having made this discovery, the inventors conducted experiments to characterize the material and determined that the material comprises solids selected from flowable heat transfer medium particles (transported from the reactor), fragments of flowable heat transfer medium particles (transported from the reactor), by-products from the pyrolysis fragmentation of the feedstock solution, and mixtures thereof.

[0017] The inventors tested various means (e.g., physical separation devices such as filters) to reduce the amount of solids carried downstream of the reactor. While such means initially helped to achieve this, the inventors also discovered that solids accumulated on such means (e.g., as a "filter cake") in increasing amounts as a function of time (reactor run time). To facilitate effective process operation, the solids were eventually removed. However, removing the solids by replacing the means required interruption of the process, resulting in significant downtime, which is inefficient. In cases where the means included a filter, the inventors also attempted to remove the solids from the filter by "back-pulsing" or "back-blowing" techniques, for example, involving passing air through the filter in the opposite direction. However, these techniques were ineffective because the solids remained attached to the filter.

[0018] With the above problems in mind, the present inventors have surprisingly found that the presence of water in an amount of at least 40% by volume, based on all gas phase components, results in improved performance of equipment downstream of the reactor. In particular, such a water content has resulted in reduced failure and / or clogging of equipment downstream of the reactor. Furthermore, in cases where a physical separation device, such as a filter, located downstream of the reactor is used, the present inventors have also surprisingly found that such a water content reduces solids buildup on the physical separation device.

[0019] Without being bound by theory, it is hypothesized that such a moisture content reduces the amount of solids carried downstream of the reactor and / or reduces the tendency for solids to form and / or reduces the tendency for solids to obstruct and / or plug equipment downstream of the reactor. Furthermore, in cases where a physical separation device, such as a filter located downstream of the reactor, is used, it is hypothesized that such a moisture content reduces the amount of solids reaching the physical separation device and / or reduces the tendency for solids to adhere to the physical separation device and / or reduces the tendency for solids to obstruct or plug the physical separation device.

[0020] 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.

[0021] The moisture content based on all gas phase components can be readily calculated by one skilled in the art using, for example, input flow data.

[0022] a) Feedstock solution The method includes providing an aqueous feedstock solution comprising sugars.

[0023] 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.

[0024] 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.

[0025] 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.

[0026] In one aspect, the feedstock solution is a liquid.

[0027] 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.

[0028] 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.

[0029] 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.

[0030] In one aspect, the saccharide is a carbohydrate that includes one or more C6 and / or C5 saccharide units.

[0031] In one aspect, the saccharide is a monosaccharide or a disaccharide.

[0032] In one aspect, the sugars are selected from sucrose, lactose, xylose, arabinose, ribose, mannose, tagatose, galactose, glucose, and fructose.

[0033] In one aspect, the feedstock solution may include sugar syrup.

[0034] In one aspect, the feedstock solution includes more than one sugar.

[0035] Each saccharide may independently be as described herein.

[0036] 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.

[0037] As will be appreciated by those skilled in the art, 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 properties of the fluidizable particles and the fluidizing gas and can be determined experimentally or calculated by one skilled in the art.

[0038] 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.

[0039] 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.

[0040] In one aspect, the reactor includes a riser.

[0041] In one aspect, the risers extend vertically.

[0042] In one aspect, the riser (eg, a lower portion of the riser) includes a fluidizing gas inlet.

[0043] In one aspect, the riser (eg, the lower portion of the rider) includes a flowable particle inlet.

[0044] In one aspect, the riser (eg, a lower portion of the riser) includes a feed inlet.

[0045] In one aspect, the flowable particle inlet is located downstream of the fluidizing gas inlet.

[0046] In one aspect, the feed solution inlet is located downstream of the flowable particle inlet.

[0047] 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.

[0048] 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.

[0049] In one aspect, a feed solution inlet is provided downstream of the single inlet for the fluidizable particles and fluidizing gas.

[0050] In one aspect, the method includes introducing flowable heat transfer medium particles into a reactor.

[0051] In one aspect, the method includes introducing flowable particles into a reactor via a flowable particle inlet.

[0052] In one aspect, the method includes introducing flowable particles into the reactor via said single inlet for the flowable particles and fluidizing gas.

[0053] In one aspect, the temperature of the flowable heat transfer medium particles in the reactor is at least 250°C, e.g., at least 300°C, at least 350°C, at least 400°C, at least 450°C, at least 500°C, at least 550°C, at least 600°C, or at least 650°C.

[0054] 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.

[0055] 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.

[0056] In one aspect, the temperature of the fluidizable heat transfer particles at the fluidizable particle inlet (or at one inlet for the fluidizable particles and fluidizing gas) is at least 250°C, e.g., at least 300°C, at least 350°C, at least 400°C, at least 450°C, at least 500°C, at least 550°C, at least 600°C, or at least 650°C.

[0057] 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.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] 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.

[0062] In one aspect, the flowable heat transfer medium particles are selected from sand, mullite, silica, glass, alumina, silica-alumina, steel, and silicon carbide.

[0063] 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.

[0064] It will also be apparent to those skilled in the art that the flow of the fluidizable heat transfer particles within the reactor can be adjusted relative to the flow of the feed solution to provide the desired amount of heat to the feed solution. Fluidizable heat transfer particles having a large heat capacity will require a lower mass flow rate than fluidizable heat transfer particles having a relatively small heat capacity.

[0065] c) introducing the feedstock solution into a reactor to pyrolytically fragment the sugars to provide a fragmentation product comprising C1-C3 oxygenates; The method includes introducing a feedstock solution into a reactor to pyrolytically fragment sugars to provide a fragmentation product comprising C1-C3 oxygenates.

[0066] The pyrolytic fragmentation of sugars is an endothermic reaction, driven primarily by the evaporation of liquid in the feed solution.

[0067] In one aspect, the temperature difference of the flowable particles between the flowable particle inlet of the fragmentation reactor (or a single inlet for the flowable particles and fluidizing gas) and the flowable particle outlet of the fragmentation reactor is in the range of from 10 to 600°C, e.g., from 50 to 250°C, or from 50 to 150°C.

[0068] 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.

[0069] 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).

[0070] Fluidizing Gas In one aspect, the method includes introducing a fluidizing gas into the reactor.

[0071] 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.

[0072] In one aspect, the method includes introducing a fluidizing gas into the reactor via a fluidizing gas inlet.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] In one aspect, in step c), the feed solution is entrained in a fluidizing gas.

[0077] In one aspect, the fluidizing gas comprises water (eg, steam).

[0078] In one aspect, the fluidizing gas consists essentially of water (eg, steam).

[0079] In one aspect, the fluidizing gas comprises water (eg, steam).

[0080] Herein, "water" and "water vapor" may be used interchangeably.

[0081] In one aspect, the water content in the fluidizing gas is at least 50% by weight, e.g., at least 60% by weight, at least 70% by weight, at least 75% by weight, at least 80% by weight, at least 85% by weight, at least 90% by weight, at least 95% by weight, or at least 99% by weight, based on the total weight of the fluidizing gas.

[0082] In one aspect, the water content in the fluidizing gas is 90 wt.% or less, such as 95 wt.% or less, 99 wt.% or less, or 99.5 wt.% or less, based on the total weight of the fluidizing gas.

[0083] In one aspect, in step c), the fluidizing gas is introduced into the reactor at a rate of at least 100 kg / h. In one aspect, in step c), the fluidizing gas is introduced into the reactor at a rate of at least 500 kg / h. In one aspect, in step c), the fluidizing gas is introduced into the reactor at a rate of at least 1000 kg / h. In one aspect, in step c), the fluidizing gas is introduced into the reactor at a rate of at least 2000 kg / h. In one aspect, in step c), the fluidizing gas is introduced into the reactor at a rate of at least 4000 kg / h. In one aspect, in step c), the fluidizing gas is introduced into the reactor at a rate of at least 5000 kg / h.

[0084] 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.

[0085] atomizing gas In one aspect, the method includes introducing an atomizing gas into a reactor.

[0086] 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.

[0087] 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.

[0088] In one aspect, the atomizing gas comprises water (eg, water vapor).

[0089] In one aspect, the atomizing gas consists essentially of water (eg, water vapor).

[0090] In one aspect, the atomizing gas comprises water (eg, water vapor).

[0091] In one aspect, the water content in the atomized gas is at least 50% by weight, e.g., at least 60% by weight, at least 70% by weight, at least 75% by weight, at least 80% by weight, at least 85% by weight, at least 90% by weight, at least 95% by weight, or at least 99% by weight, based on the total weight of the atomized gas.

[0092] In one aspect, the water content in the atomized gas is 90% by weight or less, such as 95% by weight or less, 99% by weight or less, or 99.5% by weight or less, based on the total weight of the atomized gas.

[0093] 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.

[0094] 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.

[0095] Introduced water The method includes introducing water into a reactor.

[0096] 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.

[0097] In one aspect, water is introduced into the reactor via the fluidizing gas.

[0098] In one aspect, water is introduced into the reactor via an atomizing gas.

[0099] In one aspect, the mass ratio of the total amount of sugars introduced into the reactor to the total amount of water introduced into the reactor is at least 0.1:1, e.g., at least 0.2:1, at least 0.3:1, at least 0.4:1, at least 0.45:1, at least 0.5:1, at least 0.55:1, at least 0.6:1, at least 0.65:1, at least 0.7:1, at least 0.75:1, at least 0.8:1, at least 0.85:1, at least 0.9:1, or at least 0.95:1.

[0100] In one aspect, the mass ratio of the total amount of sugars introduced into the reactor to the total amount of water introduced into the reactor is 5:1 or less, e.g., 4:1 or less, 3.5:1 or less, 3:1 or less, 2.5:1 or less, 2:1 or less, 1.5:1 or less, 1.4:1 or less, 1.3:1 or less, 1.25:1 or less, 1.2:1 or less, 1.15:1 or less, 1.1:1 or less, 1.05:1 or less, or 1:1 or less.

[0101] In one aspect, the mass ratio of the total amount of sugars introduced into the reactor to the total amount of water introduced into the reactor is from 0.2:1 to 5:1, e.g., from 0.25:1 to 4:1, from 0.25:1 to 3.5:1, from 0.25:1 to 2.2:1, from 0.3:1 to 1.8:1, from 0.4:1 to 1.75:1, from 0.55:1 to 1.5:1, from 0.6:1 to 1.3:1, from 0.65:1 to 1.2:1, from 0.7:1 to 1:1, or from 0.75:1 to 0.90:1.

[0102] In one aspect, the mass ratio of water introduced into the reactor via the feed solution to the total amount of water introduced into the reactor is at least 0.001:1, e.g., at least 0.005:1, at least 0.01:1, at least 0.02:1, at least 0.04:1, at least 0.05:1, at least 0.1:1, at least 0.15:1, at least 0.2:1, at least 0.25:1, or at least 0.3:1.

[0103] In one aspect, the weight ratio of water introduced into the reactor via the feed solution to the total amount of water introduced into the reactor is 5:1 or less, e.g., 4:1 or less, 3:1 or less, 2:1 or less, 1:1 or less, 0.8:1 or less, 0.6:1 or less, 0.55:1 or less, 0.5:1 or less, 0.45:1 or less, or 0.4:1 or less.

[0104] In one aspect, the weight ratio of water introduced into the reactor via the feed solution to the total amount of water introduced into the reactor is from 0.2:1 to 3:1, e.g., from 0.04:1 to 4:1, from 0.05:1 to 2:1, from 0.1 to 1:1, from 0.15:1 to 0.6:1, from 0.2:1 to 0.5:1, from 0.25:1 to 0.45:1, or from 0.3:1 to 0.4:1.

[0105] 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.

[0106] In one aspect, in step c), the fragmentation product is a solids-dense fragmentation product.

[0107] In one aspect, the solids-rich fragmentation product comprises C1-C3 oxygenates and solids.

[0108] In one aspect, step d) comprises separating solids from the solids-rich fragmentation product 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.

[0109] In one aspect, the solids-lean fragmentation product comprises C1-C3 oxygenates.

[0110] In one aspect, the solids-lean fragmentation product contains less solids than the solids-rich fragmentation product.

[0111] Here, the term "lean" in "lean solids" and the term "rich" in "rich solids" are relative terms.

[0112] 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.

[0113] 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.

[0114] In one aspect, the fragmentation products include glycolaldehyde.

[0115] In one aspect, the fragmentation product comprises glycolaldehyde as its major portion.

[0116] 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.

[0117] 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.

[0118] In one aspect, the fragmentation product comprises one or more of pyruvaldehyde or acetol in an amount of at least 3 wt %, such as at least 5 wt % or at least 7 wt %, based on the total weight of the fragmentation product.

[0119] 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.

[0120] 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).

[0121] In one aspect, "based on the total weight of the fragmentation product" refers to the fragmentation product after step (d) (eg, the solids-lean fragmentation product).

[0122] In one aspect, "based on the total weight of the fragmented product" refers to the fragmented product without solids.

[0123] Water content by volume % In one aspect, the moisture content is based on all gas phase components at the reactor outlet.

[0124] In one aspect, the moisture content is based on all gas phase components in the reactor.

[0125] In one aspect, the moisture content is measured (e.g., using a suitable instrument). Suitable instruments for measuring moisture content will be known to those skilled in the art.

[0126] In one aspect, the moisture content is calculated (e.g., determined theoretically). Suitable means for calculating the moisture content will be known to those skilled in the art.

[0127] As described below in "d) Separating Solids from the Fragmentation Product," in one aspect, step d) includes separating the solids from the fragmentation product using a physical separation device.

[0128] In one aspect, when a physical separation device (eg, a filter) is used, the moisture content is based on all gas phase components at the inlet of the physical separation device (eg, a filter).

[0129] In one aspect, the water content is at least 45% by volume, e.g., at least 50% by volume, at least 55% by volume, at least 60% by volume, at least 65% by volume, at least 70% by volume, at least 75% by volume, or at least 80% by volume, based on all gas phase components.

[0130] In one aspect, the water content at the reactor outlet is at least 45% by volume, e.g., at least 50% by volume, at least 55% by volume, at least 60% by volume, at least 65% by volume, at least 70% by volume, at least 75% by volume, or at least 80% by volume, based on all gas phase components at the reactor outlet.

[0131] In one aspect, the water content in the reactor is at least 45% by volume, e.g., at least 50% by volume, at least 55% by volume, at least 60% by volume, at least 65% by volume, at least 70% by volume, at least 75% by volume, or at least 80% by volume, based on all gas phase components in the reactor.

[0132] In one aspect, the moisture content at the inlet of the physical separation device (e.g., a filter) is at least 45% by volume, e.g., at least 50% by volume, at least 55% by volume, at least 60% by volume, at least 65% by volume, at least 70% by volume, at least 75% by volume, or at least 80% by volume, based on all gas phase components at the inlet of the physical separation device.

[0133] In one aspect, the water content is 99% or less by volume, eg, 95% or less, 90% or less, 85% or less, or 80% or less by volume, based on all gas phase components.

[0134] In one aspect, the water content at the reactor outlet is 99% by volume or less, e.g., 95% by volume or less, 90% by volume or less, 85% by volume or less, or 80% by volume or less, based on all gas phase components at the reactor outlet.

[0135] In one aspect, the water content in the reactor is 99% by volume or less, e.g., 95% by volume or less, 90% by volume or less, 85% by volume or less, or 80% by volume or less, based on all gas phase components in the reactor.

[0136] In one aspect, the moisture content at the inlet of the physical separation device (e.g., a filter) is 99% by volume or less, e.g., 95% by volume or less, 90% by volume or less, 85% by volume or less, or 80% by volume or less, based on all gas phase components at the inlet of the physical separation device.

[0137] In one aspect, the water content is from 45 to 99.5% by volume, e.g., from 50 to 99% by volume, from 55 to 97.5% by volume, from 60 to 92.5% by volume, from 65 to 90% by volume, from 70 to 87.5% by volume, or from 75 to 85% by volume, based on all gas phase components.

[0138] In one aspect, the water content at the reactor outlet is from 45 to 99.5 vol%, e.g., from 50 to 99 vol%, from 55 to 97.5 vol%, from 60 to 92.5 vol%, from 65 to 90 vol%, from 70 to 87.5 vol%, or from 75 to 85 vol%, based on all gas phase components at the reactor outlet.

[0139] In one aspect, the water content in the reactor is from 45 to 99.5 vol%, e.g., from 50 to 99 vol%, 55 to 97.5 vol%, 60 to 92.5 vol%, 65 to 90 vol%, 70 to 87.5 vol%, or 75 to 85 vol%, based on all gas phase components in the reactor.

[0140] In one aspect, the moisture content at the inlet of the physical separation device (e.g., filter) is from 45 to 99.5 vol%, e.g., from 50 to 99 vol%, from 55 to 97.5 vol%, from 60 to 92.5 vol%, from 65 to 90 vol%, from 70 to 87.5 vol%, or from 75 to 85 vol%, based on all gas phase components at the inlet of the physical separation device.

[0141] Voltage division In one aspect, the partial pressure of water vapor is greater than 650 mbar.

[0142] The inventors have also found that the presence of water vapor at a partial pressure above 650 mbar helps to reduce the amount of such solids that are carried downstream of the reactor and negatively impact equipment.

[0143] In one aspect, the partial pressure of water vapor is the partial pressure at the outlet of the reactor.

[0144] In one aspect, the partial pressure of the water vapor is the partial pressure within the reactor.

[0145] In one aspect, when a physical separation device (eg, a filter) is used, the partial pressure is the partial pressure at the physical separation device (eg, at the inlet thereof).

[0146] As will be appreciated by those skilled in the art, the partial pressure of a gas may be defined by the following formula: p i =x i ×p In the formula, p i is the partial pressure of a component in the gas mixture, and x i is the volume fraction of the component in the gas mixture, and p is the total pressure of the gas mixture.

[0147] In one aspect, the partial pressure is measured (e.g., using a suitable instrument). Suitable instruments for measuring partial pressure will be known to those skilled in the art.

[0148] In one aspect, the partial pressure is calculated (e.g., determined theoretically). Suitable means for calculating the partial pressure will be known to those skilled in the art.

[0149] In one aspect, the partial pressure of water vapor is at least 700 mbar, e.g., at least 750 mbar, at least 800 mbar, at least 850 mbar, at least 900 mbar, at least 950 mbar, at least 1000 mbar, at least 1050 mbar, at least 1100 mbar, at least 1150 mbar, at least 1200 mbar, at least 1250 mbar, at least 1300 mbar, at least 1350 mbar, at least 1400 mbar, at least at least 1450 mbar, at least 1500 mbar, at least 1550 mbar, at least 1600 mbar, at least 1650 mbar, at least 1700 mbar, at least 1750 mbar, at least 1800 mbar, at least 1850 mbar, at least 1900 mbar, at least 1950 mbar, at least 2000 mbar, at least 2050 mbar, at least 2100 mbar, at least 2150 mbar, or at least 2200 mbar.

[0150] In one aspect, the partial pressure of water vapor at the reactor outlet is greater than 650 mbar. In one aspect, the partial pressure of water vapor at the reactor outlet is at least 700 mbar, e.g., at least 750 mbar, at least 800 mbar, at least 850 mbar, at least 900 mbar, at least 950 mbar, at least 1000 mbar, at least 1050 mbar, at least 1100 mbar, at least 1150 mbar, at least 1200 mbar, at least 1250 mbar, at least 1300 mbar, at least 1350 mbar, or at least 1400 mbar. , at least 1450 mbar, at least 1500 mbar, at least 1550 mbar, at least 1600 mbar, at least 1650 mbar, at least 1700 mbar, at least 1750 mbar, at least 1800 mbar, at least 1850 mbar, at least 1900 mbar, at least 1950 mbar, at least 2000 mbar, at least 2050 mbar, at least 2100 mbar, at least 2150 mbar, or at least 2200 mbar.

[0151] In one aspect, the partial pressure of water vapor in the reactor is greater than 650 mbar. In one aspect, the partial pressure of water vapor in the reactor is at least 700 mbar, e.g., at least 750 mbar, at least 800 mbar, at least 850 mbar, at least 900 mbar, at least 950 mbar, at least 1000 mbar, at least 1050 mbar, at least 1100 mbar, at least 1150 mbar, at least 1200 mbar, at least 1250 mbar, at least 1300 mbar, at least 1350 mbar, at least 1400 mbar, at least 1500 mbar, at least 1600 mbar, at least 1700 mbar, at least 1800 mbar, at least 1900 mbar, at least 2000 mbar, at least 2100 mbar, at least 2200 mbar, at least 2300 mbar, at least 2400 mbar, at least 2500 mbar, at least 2600 mbar, at least 2700 mbar, at least 2800 mbar, at least 2900 mbar, at least 3000 mbar, at least 3100 mbar, at least 3200 mbar, at least 3300 mbar, at least 3400 mbar, at least 3500 mbar, at least 3600 mbar, at least 3700 mbar, at least 3800 mbar, at least 3900 mbar, at least 4000 mbar, at least 4100 mbar, at least 4200 mbar, at least 4300 mbar, at least 4400 mbar, at least 4500 mbar, at least 4600 mbar, at least 47 at least 1450 mbar, at least 1500 mbar, at least 1550 mbar, at least 1600 mbar, at least 1650 mbar, at least 1700 mbar, at least 1750 mbar, at least 1800 mbar, at least 1850 mbar, at least 1900 mbar, at least 1950 mbar, at least 2000 mbar, at least 2050 mbar, at least 2100 mbar, at least 2150 mbar, or at least 2200 mbar.

[0152] In one aspect, the partial pressure of water vapor at the inlet of the physical separation device (e.g., filter) is greater than 650 mbar. In one aspect, the partial pressure of water vapor at the inlet of the physical separation device (e.g., filter) is at least 700 mbar, e.g., at least 750 mbar, at least 800 mbar, at least 850 mbar, at least 900 mbar, at least 950 mbar, at least 1000 mbar, at least 1050 mbar, at least 1100 mbar, at least 1150 mbar, at least 1200 mbar, at least 1250 mbar, at least 1300 mbar, at least 1350 mbar, at least or at least 1400 mbar, at least 1450 mbar, at least 1500 mbar, at least 1550 mbar, at least 1600 mbar, at least 1650 mbar, at least 1700 mbar, at least 1750 mbar, at least 1800 mbar, at least 1850 mbar, at least 1900 mbar, at least 1950 mbar, at least 2000 mbar, at least 2050 mbar, at least 2100 mbar, at least 2150 mbar, or at least 2200 mbar.

[0153] In one aspect, the partial pressure of water vapor is 5000 mbar or less, e.g., 4500 mbar or less, 4000 mbar or less, 3800 mbar or less, 3600 mbar or less, 3400 mbar or less, 3200 mbar or less, 3000 mbar or less, 2800 mbar or less, 2600 mbar or less, or 2500 mbar or less.

[0154] In one aspect, the partial pressure of water vapor at the reactor outlet is 5000 mbar or less, e.g., 4500 mbar or less, 4000 mbar or less, 3800 mbar or less, 3600 mbar or less, 3400 mbar or less, 3200 mbar or less, 3000 mbar or less, 2800 mbar or less, 2600 mbar or less, or 2500 mbar or less.

[0155] In one aspect, the partial pressure of water vapor in the reactor is 5000 mbar or less, e.g., 4500 mbar or less, 4000 mbar or less, 3800 mbar or less, 3600 mbar or less, 3400 mbar or less, 3200 mbar or less, 3000 mbar or less, 2800 mbar or less, 2600 mbar or less, or 2500 mbar or less.

[0156] In one aspect, the partial pressure of water vapor at the inlet of the physical separation device (e.g., a filter) is 5000 mbar or less, e.g., 4500 mbar or less, 4000 mbar or less, 3800 mbar or less, 3600 mbar or less, 3400 mbar or less, 3200 mbar or less, 3000 mbar or less, 2800 mbar or less, 2600 mbar or less, or 2500 mbar or less.

[0157] In one aspect, the partial pressure of the water vapor is from 700 to 5000 mbar, for example from 750 to 4000 mbar, from 800 to 3500 mbar, from 1000 to 3000 mbar, from 1200 to 2800 mbar, from 1500 to 2700 mbar, or from 2000 to 2500 mbar.

[0158] In one aspect, the partial pressure of water vapor at the reactor outlet is from 700 to 5000 mbar, e.g., from 750 to 4000 mbar, from 800 to 3500 mbar, from 1000 to 3000 mbar, from 1200 to 2800 mbar, from 1500 to 2700 mbar, or from 2000 to 2500 mbar.

[0159] In one aspect, the partial pressure of water vapor in the reactor is from 700 to 5000 mbar, e.g., from 750 to 4000 mbar, from 800 to 3500 mbar, from 1000 to 3000 mbar, from 1200 to 2800 mbar, from 1500 to 2700 mbar, or from 2000 to 2500 mbar.

[0160] In one aspect, the partial pressure of water vapor at the inlet of the physical separation device (e.g., filter) is from 700 to 5000 mbar, e.g., from 750 to 4000 mbar, from 800 to 3500 mbar, from 1000 to 3000 mbar, from 1200 to 2800 mbar, from 1500 to 2700 mbar, or from 2000 to 2500 mbar.

[0161] d) Separating the solids from the fragmentation product The method includes separating solids from the fragmentation product, wherein the solids include solids selected from flowable particles, fractions of flowable particles, by-products from pyrolytic fragmentation of a feedstock solution, and mixtures thereof.

[0162] In one aspect, step d) 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.

[0163] In one aspect, step d) includes separating 99.999% by weight or less, e.g., 99.99% by weight or less, 99.9% by weight or less, 99.5% by weight or less, or 99% by weight or less of the solids from the fragmentation product, based on the total weight of the solids.

[0164] In one aspect, step d) comprises separating a major portion of the solids from the fragmentation product.

[0165] In one aspect, step d) 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.

[0166] In one aspect, step d) comprises separating substantially all of the solids from the fragmentation product.

[0167] In one aspect, step d) comprises separating the solids from the fragmentation product using a physical separation device.

[0168] In one aspect, the physical separation device is a particle separator.

[0169] In one aspect, the physical separation device is a low volume separator.

[0170] In one aspect, the physical separation device is a change of direction separator.

[0171] In one aspect, the physical separation device is a cyclone.

[0172] In one aspect, the physical separation device is a filter.

[0173] In one aspect, the filter is selected from a metal filter and a ceramic filter.

[0174] 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.

[0175] 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.

[0176] In one aspect, the filter element comprises a porous matrix.

[0177] 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.

[0178] 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.

[0179] In one aspect, the filter includes a plurality of filter elements, each of which may be independently as described herein.

[0180] In one aspect, the filter is a candle filter.

[0181] In one aspect, the filter is a bag filter.

[0182] In one aspect, step d) occurs downstream of the reactor.

[0183] In one aspect, the physical separation device is located downstream of the reactor.

[0184] In one aspect, multiple physical separation devices are used, each of which may independently be as described herein.

[0185] In one aspect, step d) comprises filtering the fragmentation product using a filter.

[0186] In one aspect, the temperature at the inlet to the filter is from 230 to 390°C, or from 270 to 390°C, or from 300 to 380°C, or from 330 to 370°C.

[0187] In one aspect, 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. Filtration efficiency can be measured using ASTM 795 ACFTD.

[0188] In one aspect, the method is suitable for industrial-scale production of C1-C3 oxygen-containing compounds.

[0189] 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.

[0190] As the flowable heat transfer medium particles are fluidized within the reactor, a certain amount of the 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.

[0191] 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.

[0192] In one aspect, the solids substantially comprise 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.

[0193] 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.

[0194] 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.

[0195] 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.

[0196] 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.

[0197] In one aspect, the pyrolytic fragmentation process is operated as a continuous process.

[0198] 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 pyrolysis 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.

[0199] 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.

[0200] 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.

[0201] 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.

[0202] 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.

[0203] 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.

[0204] 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.

[0205] 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.

[0206] 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.

[0207] 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.

[0208] 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).

[0209] 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 configured to pyrolytically fragment sugars to provide a fragmentation product comprising C1-C3 oxygenates, the fluidized bed fragmentation reactor comprising fluidizable heat transfer particles; and c) a separation device configured to separate solids from the fragmentation product, said solids comprising 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; Including, The temperature of the fragmentation product at the reactor outlet is at least 250°C, e.g., at least 300°C, at least 350°C, at least 400°C, or at least 450°C; and The water content is at least 40% by volume, based on all gas phase components; An apparatus is provided.

[0210] 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 configured to pyrolytically fragment sugars to provide a fragmentation product comprising C1-C3 oxygenates, the fluidized bed fragmentation reactor comprising fluidizable heat transfer particles; and c) a separation device configured to separate solids from the fragmentation product, said solids comprising 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; Including, The temperature of the fragmentation product at the reactor outlet is at least 250°C, e.g., at least 300°C, at least 350°C, at least 400°C, or at least 450°C; and The partial pressure of water vapor is greater than 650 mbar. An apparatus is provided.

[0211] 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.

[0212] 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]

[0213] [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 variation in pressure drop across a filter of a device according to an embodiment of the present invention. [Figure 7] Figure 7 shows a schematic diagram of a candle filter. [Figure 8] FIG. 8 shows a schematic diagram of a fragmentation reactor forming part of an apparatus according to one embodiment of the present invention. [Explanation of symbols]

[0214] 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. Inlets for feedstock and atomizing gas 9.Product outlet 10. Flowable particle outlet 11. Preheater 12. Inlets for fuel and combustion air 13. Burner chamber 14. Flowable particle preheater inlet 15. Preheater riser 16. Fluidizable particle preheater separator 17. Flowable particle preheater outlet 18.Preheater gas outlet 19. Second preheater separator for flowable particles 20. Stripper 21. Sub-fluidization gas inlet 22. Inlet for sub-preheater fluidizing gas and stripping gas O': Outlet of reactor 100.Heat exchanger 200. Physical separation devices (e.g., filters) for gas / solid filtration 300. Fragmentation Reactor 301. Fluidizing Gas 302.Feedstock solution 303. Atomizing gas 304. Inlet for feedstock and atomizing gas (feed nozzle) 305.First particle separator 306. Recycled Heat Transfer Particles 307. Approximate boundary separating concentrated and dilute phases 308.Heating device DETAILED DESCRIPTION OF THE INVENTION

[0215] 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 and has a small cross-sectional area relative to its height. This facilitates a short 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 0'. It can be seen that, in use, the fragmentation product exits the reactor 01 at the outlet 0' for further processing and / or collection.

[0216] 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.

[0217] 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.

[0218] 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.

[0219] 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.

[0220] 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.

[0221] 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.

[0222] An optional cooling section 05 is located within the fragmentation reactor 01. In the embodiment of Figure 1, the cooling section is installed between the first particle separator 03 and the outlet O' of the reactor 01.

[0223] The fragmentation product is withdrawn from the fragmentation reactor 01 via the product outlet 09.

[0224] 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.

[0225] 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.

[0226] 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.

[0227] 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 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 depends on various process parameters, such as pressure drop across the separator, flow rate, particle size, etc., as known in the art.

[0228] 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, inlets 22 for secondary fluidizing and stripping gas 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 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.

[0229] Referring to Figure 5, additional components of the apparatus of Figure 4 are shown (although not all parts 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. Those skilled in the art will understand that the apparatus may include additional components, such as one or more cooling steps or other unit operations.

[0230] In the embodiment of Figure 5, the product gas enters heat exchanger 100 over product outlet 9, 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).

[0231] 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.

[0232] 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 (Non-Patent Document 1). 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.

[0233] In use, the fragmented product exits the reactor 1 via product outlet 09 and passes through the heat exchanger 100 before passing through the separation device 200 .

[0234] The inventors surprisingly discovered the presence of a material adhering to equipment downstream of Reactor 01. In some cases, this material led to equipment failure or blockage. The inventors conducted experiments to characterize this material and determined that it contained solids selected from flowable heat transfer medium particles (transported from Reactor 01), fragments of flowable heat transfer medium particles (transported from Reactor 01), by-products from pyrolysis fragmentation of the feedstock solution, and mixtures thereof. The inventors tested various means (e.g., physical separation devices 200, such as filters) to reduce the amount of solids transported downstream of Reactor 01. While such means initially helped to achieve this, the inventors also discovered that solids accumulated on such means (e.g., as a "filter cake") in increasing amounts as a function of time (reactor operating hours). To facilitate effective process operation, the solids were eventually removed. However, removing solids by replacing the means requires interrupting the process, resulting in significant downtime, which is inefficient. In cases where the means includes a filter 200, the inventors have also attempted to remove the solids from the filter 200 by "back-pulsing" or "back-blowing" techniques, for example, which involve passing air in the opposite direction through the filter 200. However, these techniques were ineffective because the solids remained attached to the filter 200.

[0235] With the above problems in mind, the present inventors have surprisingly found that the presence of water in an amount of at least 40% by volume, based on all gas phase components, results in improved performance of equipment downstream of reactor 01. In particular, such a water content has resulted in reduced failure and / or clogging of equipment downstream of reactor 01. Furthermore, in cases where a physical separation device, such as filter 200, located downstream of reactor 01 is used, the present inventors have also surprisingly found that such a water content reduces solids buildup on physical separation device 01.

[0236] Without being bound by theory, it is hypothesized that such a moisture content reduces the amount of solids carried downstream of reactor 01 and / or reduces the tendency for solids to form and / or reduces the tendency for solids to obstruct or plug equipment downstream of reactor 01. Furthermore, in cases where a physical separation device, such as filter 200 located downstream of the reactor, is used, it is hypothesized that such a moisture content reduces the amount of solids that reach physical separation device 200 and / or reduces the tendency for solids to adhere to physical separation device 200 and / or reduces the tendency for solids to obstruct or plug physical separation device 200.

[0237] For example, in embodiments including filter 200 located downstream of reactor 01, using water vapor instead of nitrogen, e.g., as the atomizing gas via inlet 8 and / or as the fluidizing gas via inlets 6 and 21, can have a surprisingly beneficial effect on the observed filter pressure drop during operation. That is, water can be used to maintain a more uniform pressure drop across filter 23 during operation. In contrast, when nitrogen or low concentrations of water are used, the observed filter pressure drop gradually increases during operation. This beneficial effect on the observed pressure drop indicates a reduction in the amount of solids carried downstream of reactor 1 and collected on filter 200. Accordingly, the process can be run for a longer period of time before filter 200 needs to be replaced.

[0238] 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]

[0239] Example 1: Effect of moisture content on pressure drop across a filter Pyrolytic fragmentation of an aqueous feed solution 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., Figures 4 and 5). This involved introducing the feed solution into reactor 01 at position 8 at a (liquid) feed rate of 30 kg per hour. The fragmentation was carried out under the following conditions: (A) Just before the first particle separator (3), the water content was 35 to 40% by volume based on all gas phase components, and at the outlet O' of the reactor O1, the water content was 25 to 30% by volume based on all gas phase components (water vapor partial pressure of 880 to 1030 mbar). The reactor was a riser-type reactor O1 with a length of approximately 3 meters and a superficial gas velocity of approximately 6 meters per second after evaporation and fragmentation of the feed solution. The feed solution was injected into the reactor O1 through a gas-assisted internal mixing atomization nozzle (i.e., feed and atomization gas inlet O8) entering from the bottom of the riser O2 using an atomization gas flow rate of 15 kg / h of nitrogen. The optional cooling step O5 was omitted.

[0240] (B) Just before the first particle separator (3), the water content was 80 to 81% by volume, based on all gas phase components, and at the outlet O' of the reactor O1, the water content was 85 to 90% by volume, based on all gas phase components (water vapor partial pressure of 2040 mbar). The reactor was a riser-type reactor O1 with a length of approximately 3 meters and a superficial gas velocity of approximately 6 meters per second after evaporation and fragmentation of the feed solution. The feed solution was injected into the reactor O1 through a gas-assisted internal mixing atomization nozzle (i.e., feed and atomization gas inlet O8) entering from the bottom of the riser O2 using an atomization gas flow rate of 12 kg / h of steam. An optional cooling step O5 was run from 15 h on stream to 25 h on stream, and this cooled the product gas by approximately 50°C.

[0241] In case (A), nitrogen was introduced into the reactor through fluidization inlet 6 at a flow rate of 8.7 kg / h of nitrogen; through inlet 8 for the feedstock and atomizing gas (i.e., as atomizing gas added together with the feedstock solution, as described above); and through fluidizing gas inlet 21 at a flow rate of 15 kg / h of nitrogen. The total pressure measured at outlet O' of reactor O1 was approximately 2.4 bara (absolute). The temperature of the fluidizable heat transfer particles at inlet O7 was approximately 570°C, and the temperature at outlet O' of the reactor was approximately 475°C. The temperature at the inlet to filter 200 was approximately 400°C.

[0242] In case (B), water was introduced into the reactor through fluidization inlet 6 at a gas flow rate of 7 kg / h of steam; through inlet 8 for feedstock and atomizing gas (i.e., as atomizing gas added together with the feedstock solution, as described above); and through fluidizing gas inlet 21 at a flow rate of 12 kg / h of steam. The total pressure measured at outlet O' of reactor O1 was approximately 2.4 bara (absolute). The temperature of the fluidizable heat transfer particles at inlet O7 was approximately 570°C, and the temperature at outlet O' of the reactor was approximately 475°C. The temperature at the inlet to filter 200 was approximately 400°C.

[0243] In the case of (B), the mass ratio of the total amount of sugars introduced into reactor 01 to the total amount of water introduced into the reactor was 0.41:1.

[0244] The volumetric gas flow rates through the apparatus were similar in the two cases, providing the same superficial gas velocities and residence times in the different parts of the apparatus.

[0245] FIG. 6 shows the measured change in pressure drop across filter 200 during operation for cases (A) ("x" data points) and (B) ("o" data points). The water content at outlet O' of reactor O1 was calculated using flow rate data for the input stream to reactor O1. One skilled in the art can easily perform this calculation.

[0246] As can be seen from Figure 6, in case (A), the pressure drop across filter 200 steadily increased over time at a rate of approximately 0.27 mbar / h. Also evident from Figure 6, in case (B), the pressure drop across filter 200 remained approximately constant (at a rate of change of approximately 0 mbar / h). This is a significantly improved performance parameter for long-term industrial operation. The small change in measured pressure drop in case (B) at approximately 15 hours was attributed to the increase in moisture content from 80% to 81% by volume (based on all gas phase components immediately prior to the first particle separator (3)) and the relatively high gas flow rate.

[0247] The filter pressure drop is determined by a number of filtration parameters, such as the surface area of ​​the filter 200 (in this example, 3.4 m at the gas inlet surface of the filter). 2 The rate at which pressure drop increases during operation is also a function of the pressure drop across the filter 200 (was 0.01), the gas stream characteristics (e.g., flow rate and composition), and the thickness of the filter cake (including solids) deposited on the filter 200. For example, increasing the surface area of ​​the filter or decreasing the gas flow rate can reduce the rate at which pressure drop increases during operation. It will also be appreciated that the reactor can operate in other unintended modes that produce even more fragmented by-products. Those skilled in the art will know how to control the commonly known effects of filtration parameters.

[0248] This example showed that increasing the moisture content, for example, at the outlet O' of reactor O1, reduced the amount of solids carried downstream of the reactor and collected on separation device 200. Without being bound by theory, it is believed that such a moisture content may reduce the deposition rate of solids on separation device 200 and / or increase the desorption rate of solids from separation device 200. For example, the moisture content may be such that the net deposition of solids on separation device 200, i.e., deposition rate minus desorption rate, may be reduced compared to if a lower moisture content were used.

[0249] In each of (A) and (B), a solids-lean fragmented product was obtained after filtration through filter 200. The solids-lean fragmented product was essentially free of solids.

[0250] In each of (A) and (B), after filtration in filter 200, the fragmentation product (lean in solids) stream was condensed in a cooling tower using recycled condensed product liquid. The glycolaldehyde concentration of the condensed product (lean in solids) was measured by HPLC, and a mass (or carbon) balance was applied to derive the carbon-based yield of glycolaldehyde from the pyrolysis fragmentation, i.e., the percentage of carbon in the feed solution that was recovered as carbon in glycolaldehyde. For example, the glycolaldehyde concentration of the condensed product (lean in solids) can be calculated according to the following formula: Glycolaldehyde carbon yield = 100% × (2 × mc × Cc / (MwGA × DensC)) / (6 × m1 × C1 / MwGlu) During the ceremony, mc is the measured mass flow rate in kg / h leaving the condensation step; Cc is the glycolaldehyde concentration in kg / cm3 exiting the condensation step; MwGA is the molecular weight of glycolaldehyde in kg / mol; DensC is the density of the condensed product in kg / m3; m1 is the feedstock solution feed rate to reactor O1 in kg / h; C1 is the glucose concentration in wt% MwGlu is the molecular weight of glucose in kg / mol.

[0251] The carbon yield of glycolaldehyde produced in case (A) was approximately 48%. The carbon yield of glycolaldehyde produced in case (B) was approximately 53%. Those skilled in the art will know how to calculate the carbon yield of glycolaldehyde.

[0252] 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. 8, 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 particles used for the pyrolytic fragmentation of sugars. The gas distributor distributes the fluidizing gas (301) across the entire cross section of the reactor (300). In FIG. 8, 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 particles in the reactor (300). Although only one feed nozzle (304) is shown in FIG. 8, it will be understood 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).

[0253] 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, thereby increasing the upward gas flow rate. 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' carries the fragmentation product gas for downstream processing. While only one particle separator (305) is shown, it will be understood that the particle separator can be configured in various ways, and multiple particle separators can be used. For example, parallel cyclones, series cyclones, or a combination of these can be used. Surface filters can also be used.

[0254] 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 8, 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.

[0255] 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).

[0256] 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.

[0257] The apparatus of Figure 8 can be used to carry out the pyrolytic fragmentation of sugars under industrial conditions. Approximately 25,000 liters (bulk) of heat transfer particles described in Example 2 of WO 21 / 032590 (Patent Document 7) are added to the reactor (300). A 60 wt% aqueous glucose 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. Glucose gives the following yields of primarily C2-C3 oxygenated compounds on a carbon basis: 57 C% glycolaldehyde, 10 C% pyruvaldehyde, 4 C% acetol, 3 C% glyoxal, and 10 C% formaldehyde.

[0258] The water content at outlet O' of reactor (300) is approximately greater than 75% by volume, based on all gas phase components. The yield of other by-products, such as CO, CO, and acetic acid, will not significantly change this water vapor volume fraction. It will be appreciated that, for example, changing the flow rate and / or composition of the atomizing gas (303) or fluidizing gas (301) may change the resulting water vapor volume fraction at outlet O'.

[0259] 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.

[0260] 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 oxygenates, 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; and d) separating solids from the fragmentation product; Including, the solids comprise solids selected from the 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; The temperature of the fragmentation product at the reactor outlet is at least 250°C, e.g., at least 300°C, at least 350°C, at least 400°C, or at least 450°C; and The water content is at least 40% by volume, based on all gas phase components; The method.

2. 10. The method of claim 1, wherein the water content at the outlet of the reactor is at least 40% by volume, based on all gas phase components at the outlet of the reactor.

3. 3. The process according to claim 1 or 2, wherein the partial pressure of water vapor at the outlet of the reactor is greater than 650 mbar.

4. 4. The method of claim 1, wherein the water content at the outlet of the reactor is at least 60% by volume, based on all gas phase components at the outlet of the reactor.

5. The method of any one of claims 1 to 4, wherein step d) comprises separating the solids from the fragmentation product using a physical separation device.

6. The method of claim 5 , wherein the physical separation device is located downstream of the reactor.

7. 7. The method of claim 5 or 6, wherein the physical separation device is a filter, optionally the filter is selected from a bag filter and a candle filter.

8. The method of any one of claims 5 to 7, wherein the filter comprises a filter element having a filtering surface.

9. The method of any one of claims 5 to 8, wherein the moisture content is based on all gas phase components at the inlet of the physical separation device.

10. 10. The method of any one of claims 1 to 9, comprising introducing an atomizing gas into the reactor, and optionally, the atomizing gas has a water content of at least 50 wt. %, based on the total weight of the atomizing gas.

11. 11. The method according to any one of claims 1 to 10, wherein the sugar is a carbohydrate comprising one or more C6 and / or C5 saccharide units, and / or the sugar is a monosaccharide or a disaccharide, and / or the sugar is selected from sucrose, lactose, xylose, arabinose, ribose, mannose, tagatose, galactose, glucose and fructose.

12. 12. The method of any one of claims 1 to 11, wherein the total sugars content of the feed solution is from 30 to 99 wt%, such as from 40 to 90 wt%, or from 50 to 80 wt%, based on the total weight of the feed solution.

13. The method of any one of claims 1 to 12, wherein the fragmentation product comprises glycolaldehyde.

14. The method of any one of claims 1 to 13, wherein the fragmentation product comprises glycolaldehyde in an amount of at least 10% by weight, based on the total weight of the fragmentation product.

15. The process according to any one of claims 1 to 14, wherein the pressure at the outlet of the reactor is at least 0.9 bara.

16. 16. The method of any one of claims 1 to 15, 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, and optionally, the or each separation step between step c) and step d) is carried out in a reactor.

17. 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 configured to pyrolytically fragment the sugars to provide a fragmentation product comprising the C1-C3 oxygenates, the fluidized-bed fragmentation reactor comprising fluidizable heat transfer particles; and c) a separation device configured to separate solids from the fragmentation product, wherein the solids comprise 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; Including, The temperature of the fragmentation product at the reactor outlet is at least 250°C, e.g., at least 300°C, at least 350°C, at least 400°C, or at least 450°C; and The water content is at least 40% by volume, based on all gas phase components; The device.

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

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