Steam treatment of waste

Abstract

The present invention relates to a method for treating waste using superheated steam in an apparatus comprising: a treatment vessel comprising a treatment zone, wherein at least one steam inlet is located at one end of the treatment zone and at least one steam outlet is located at an opposite end of the treatment zone; The method includes: a. introducing the waste into the treatment zone at a temperature of less than 50°C; b. Processing steps including: i. supplying superheated steam at a temperature of 300°C to 800°C to the treatment zone through at least one of the steam inlets; and ii. removing the vapor and any gaseous reaction products through at least one said vapor outlet; and c. a removing step comprising removing any remaining solid product from the treatment vessel after the treatment step; wherein any additional heat added to the treatment zone during the treatment step, apart from the superheated steam, increases the temperature of the treatment zone by 100°C or less.

Description

[Technical Field]

[0001] The present invention relates to a method for decomposing and hydrolyzing waste materials using steam to produce a variety of useful products. [Background technology]

[0002] The effective disposal of waste, especially plastic and municipal waste, generated by industrial, commercial, and domestic activities is a major challenge for modern society. Some of the most common methods of waste disposal include landfilling and incineration. However, both of these methods result in environmental pollution and mean that the useful chemicals contained in the waste cannot be recycled.

[0003] Recently, pyrolysis processes have been used to treat waste. Pyrolysis involves the thermal decomposition of materials at high temperatures under an inert atmosphere. The pyrolysis process helps reduce the volume of the waste. However, pyrolysis has the disadvantage that high temperatures are required to treat the waste, which can complicate the treatment of mixed waste. Furthermore, the high temperatures used in pyrolysis processes result in the loss or decomposition of volatile components during the process. The end product of a pyrolysis process is typically pyrolysis oil, which is a tar-like substance from which useful chemicals are difficult to separate.

[0004] Steam reforming is a method for producing synthesis gas (hydrogen and carbon monoxide) by the reaction of hydrocarbons with water. Typically, methane is used as the feedstock for this reaction, the primary purpose of which is to produce hydrogen. Steam reforming has recently been applied to waste materials (see, for example, U.S. Patent No. 20110204294A1), but this process requires high temperatures and does not allow for the separation and reuse of volatile components from the waste material.

[0005] There remains a need in the art for improved waste treatment processes that accommodate a variety of wastes, that can be processed at moderate temperatures, and that separate and recycle volatile components from the wastes. Additionally, there is a need for waste treatment processes that prevent carbon from being released back into the atmosphere as carbon dioxide, while at the same time producing a carbonaceous material as a product that aids in carbon sequestration. Summary of the Invention

[0006] The present inventors have developed a steam reforming process that helps address the practical problems noted above.

[0007] Accordingly, in a first aspect, the present invention provides a method for treating waste using superheated steam in an apparatus comprising: The apparatus includes: a treatment vessel including a treatment zone having at least one steam inlet located at one end of the treatment zone and at least one steam outlet located at an opposite end of the treatment zone; The method includes: an input step comprising inputting said waste into a treatment zone at a temperature of less than 50°C; Processing steps including: i. supplying superheated steam at a temperature of 300 to 800°C to the treatment zone through at least one of the steam inlets; and ii. removing the vapor and any gaseous reaction products through at least one said vapor outlet; and a removing step comprising removing any remaining solid product from the processing vessel after the processing step; wherein any additional heat added to the treatment zone during the treatment step, apart from superheated steam, increases the temperature of the treatment zone by 100°C or less.

[0008] The method for treating waste according to the present invention has many advantages.

[0009] First, the method according to the present invention allows for the recycling of a variety of carbon-based materials, and in particular, the process can be used with mixed waste, meaning that there is no need to sort or clean the waste before reprocessing, as is the case with other waste treatment methods. This means that the method according to the present invention is simpler than existing waste reprocessing methods and does not require the use of expensive sorting equipment. The method according to the present invention can also handle large amounts of chemically inert materials (such as sand, brick chips, silica, and glass).

[0010] Second, the method according to the invention is compatible with problematic materials such as tires and polyvinyl chloride (PVC) and does not result in the generation of chlorine gas or other gaseous chlorine compounds or require the addition of additional ingredients such as lime to absorb harmful substances.

[0011] Third, the process allows for the separation of valuable volatile chemicals from the waste and their subsequent recondensation from the vapor in at least one of the vapor outlets, allowing for the effective recycling of valuable chemical components such as triethyl citrate, a plasticizer found in tires and other plastic materials.

[0012] Fourth, the energy required to run the process can in most cases be obtained by burning some of the gas or solid products produced, which means that the process is self-sustaining and that no additional fuel is required to operate the process.

[0013] Fifth, the method can also be used to treat e-waste. After the reaction, the solid product of the reaction can be treated to remove any carbonaceous material and glass fibers to obtain a concentrate consisting of metals, ceramics, and semiconductors. This concentrate can then be separated to obtain the precious metals contained in the e-waste.

[0014] Sixth, the solid product can be used for carbon sequestration, which means permanent removal of carbon from the atmosphere.

[0015] In yet another aspect, the present invention provides a method for treating waste using superheated steam in an apparatus comprising: a treatment vessel including a treatment zone having at least one steam inlet located at one end of the treatment zone and at least one steam outlet located at an opposite end of the treatment zone; The method includes: an input step comprising inputting the waste into the treatment zone at a temperature of less than 50°C; Processing steps including: i. supplying superheated steam at a temperature of 300 to 800°C to the treatment zone through at least one of the steam inlets; and ii. removing steam and any gaseous reaction products through at least one of said steam outlets to create a temperature gradient across said treatment zone; and A removing step comprising removing any remaining solid product from the processing vessel after the processing step.

[0016] Generally, the temperature gradient is formed between at least one of the steam inlets and at least one of the steam outlets.

[0017] In a further aspect, the present invention provides a solid product obtainable by the process according to the invention.

[0018] In a further aspect, the present invention provides a gaseous reaction product obtainable by the process according to the invention.

[0019] For purposes of this invention, the "treatment zone" is defined as the section of the treatment vessel between the at least one steam inlet and the at least one steam outlet. Generally, the treatment zone is the area where steam contacts the waste.

[0020] In the definition of this invention, the term "opposite end of the treatment zone" is intended to refer to the other end of the treatment zone, wherein the at least one steam inlet and the at least one steam outlet define the boundary of the treatment zone by their positions within the treatment vessel.

[0021] For purposes of this invention, a "continuous process" is defined as a process in which the waste is continuously fed to the treatment zone and the product is continuously removed.

[0022] By "mixed waste" we refer to any combination of different wastes. Generally, the wastes come from agricultural, industrial, commercial and domestic activities and are solid wastes, solid slurries or solid-containing wastes. Generally, the term "mixed waste" refers to non-gaseous wastes.

[0023] Without wishing to be bound by any theory, under some definitions the method according to the present invention is not a pyrolysis process.

[0024] The term "pyrolysis process" may refer to a process in which the waste is decomposed by heat and reacts only with the components of the waste itself, without the addition of additional reactants. In contrast, without wishing to be bound by any theory, the method according to the present invention may involve steam hydrolysis, which is a reaction between the components of the waste and steam, in which the decomposition of the waste is primarily due to the action of H, rather than solely due to the action of heat. + ions and OH - This is thought to be achieved by ions.

[0025] In this application, the term "recycle" is used to encompass both the recovery of components from waste and / or the subsequent reuse of the recovered components.

[0026] Without wishing to be bound by any theory, the method according to the present invention is optionally not a fluidized bed process.

[0027] heating In the method according to the invention, the heat energy in the treatment zone is obtained from the superheated steam.

[0028] Generally, the method according to the invention is expected to be operated at normal ambient temperatures, for example from about -10°C (a cold British winter) to about 50°C (a very hot tropical summer). Optionally, the temperature of the environment (indoor or outdoor) containing the apparatus is from about -10°C to about 50°C, for example, the method may be carried out at normal British outdoor temperatures (about 0°C to about 30°C), or, if the method is carried out indoors, at room temperature (about 25°C). Generally, the apparatus during the loading step is expected to be at a temperature of from about -10°C to about 50°C.

[0029] The term "additional heat added to the treatment zone" refers to any heating of the treatment zone other than superheated steam, although this term is not intended to encompass any heating required to warm the environment in which the method is carried out to ambient temperature (about -10°C to about 50°C), such as central heating in a room.

[0030] Preferably, any additional heat applied to the treatment zone during the treatment step increases the temperature of the treatment zone by no more than 100° C. Preferably, the additional heat applied to the treatment zone during the treatment step increases the temperature of the treatment zone by no more than 70° C., more preferably no more than 50° C., more preferably no more than 20° C., more preferably no more than 10° C.

[0031] Without being bound by any theory, if the temperature of the steam at at least one steam inlet is 400°C, this may mean that additional superheat is used to raise the temperature of the treatment zone to 500°C or less, preferably 470°C or less, more preferably 450°C or less, more preferably 420°C or less, more preferably 410°C or less, where the temperature is the temperature of the steam at any point in the treatment zone at any time during the treatment step, or the temperature of a probe at any point in the treatment zone at any time during the treatment step.

[0032] Alternatively, the degree of additional heating may be measured using the following method: - carrying out the method with additional heating and measuring the temperature of a temperature probe in the treatment zone at the point where the waste is treated; - carrying out the same method without additional heating and measuring the temperature of a temperature probe in the treatment zone at the point where the waste is treated; wherein the temperature is measured at the same location in the treatment zone, and wherein the temperature is measured in both methods at the same time after the start of the treatment step (the treatment step being the time that a portion of the waste resides in the treatment zone). Without being bound by any theory, it is preferred that the measurement be performed after the treatment zone has reached steady state.

[0033] Preferably, when the temperature of the superheated steam at the at least one steam inlet is 300 to 800°C, the maximum temperature inside the treatment vessel is 300 to 900°C.

[0034] Most preferably, no additional heating other than superheated steam is applied to the treatment zone during the treatment step, in which case all of the thermal energy supplied to the treatment zone is from superheated steam.

[0035] Steam inlet temperature In the method according to the invention, the superheated steam is supplied to the treatment zone through at least one of the steam inlets at a temperature of 300 to 800°C (wherein the temperature of the steam is measured at the at least one of the steam inlets).

[0036] At higher temperatures, for example, above about 650°C, the superheated steam reacts with carbon in the solid product to produce hydrogen and carbon monoxide. Thus, processes in which the superheated steam at at least one of the inlets is above about 650°C can be used to produce hydrogen gas. Preferably, in processes used to produce hydrogen gas, the superheated steam at at least one of the inlets is between 750°C and 800°C. The temperature of the superheated steam is measured directly at the at least one steam inlet using any conventional means known in the art, such as a thermocouple or thermometer.

[0037] Preferably, the method according to the invention utilizes said superheated steam at a milder temperature.

[0038] Without being bound by any theory, processes carried out at lower temperatures produce solid waste and are less energy intensive.

[0039] Preferably, the temperature of the superheated steam at at least one of the inlets is 400 to 600°C, more preferably 400 to 550°C, and most preferably 400 to 500°C.

[0040] Optionally, the method according to the present invention comprises said charging step, said treating step, and said removing step, wherein the temperature of said superheated steam at said at least one steam inlet is constant throughout said treating step.

[0041] Preferably, during the treatment step, a temperature gradient is established throughout the treatment zone between the superheated steam at the at least one steam inlet and the steam at the at least one steam outlet. This is particularly important in continuous systems where the waste material flows continuously through the treatment zone. Preferably, the temperature difference between the superheated steam at the at least one steam inlet and the steam at the at least one steam outlet is at least 10°C, more preferably at least 50°C, more preferably at least 100°C. The temperature of the superheated steam at the at least one steam inlet is measured directly at the at least one steam inlet using any conventional means known in the art, such as a thermocouple or thermometer. The temperature of the steam at the at least one steam outlet is measured directly at the at least one steam outlet using any conventional means known in the art, such as a thermocouple or thermometer.

[0042] The steam generation method used in the present invention is not particularly limited. The steam may be generated by any form of steam generating device; for example, the steam may be generated by a boiler or may be derived from a waste steam source such as a power plant, a steel mill, or other industrial steam source. Without being bound by any theory, for small-scale batch reactions, the steam is likely to be obtained from a small-scale boiler, while for large-scale continuous systems, the steam may be obtained from an industrial source.

[0043] The steam from the steam generator is heated in a superheater before being supplied to the treatment vessel through at least one inlet. Again, the type of superheater used is not particularly limited. Optionally, the superheater may include a heat exchanger, a conduction heater, or a radiant heater.

[0044] Optionally, the apparatus further comprises a heat exchanger, and the method further comprises feeding the steam from at least one of the steam outlets through the heat exchanger to recover residual heat from the steam.

[0045] continuous process Preferably, the method according to the present invention is a continuous process.

[0046] Preferably, during the treatment step, the waste is caused to flow in one direction through the treatment zone and the steam is caused to flow in the opposite direction through the treatment zone.

[0047] Without being bound by any theory, flowing the waste in one direction through the treatment zone and the steam in the opposite direction through the treatment zone creates a system in which a temperature gradient is formed in the treatment zone, and as the waste enters a particular temperature zone, chemical components that evaporate at that temperature evaporate and then travel through the treatment zone to at least one of the steam outlets. This means that fragile and volatile chemicals evaporate as soon as they reach the temperature zone where they evaporate, and are not exposed to high temperatures in the treatment zone that could lead to decomposition of these fragile chemical moieties.

[0048] Flowing the waste material in one direction through the treatment zone and the steam in the opposite direction through the treatment zone can be considered a countercurrent system in which the two reactants (i.e., waste material and steam) flow in opposite directions.

[0049] Preferably, the treatment vessel used in the above-described continuous process is a tubular treatment vessel. Optionally, the apparatus further comprises an auger feed configured to feed the waste into the treatment zone and a paddle agitator configured to move and agitate the waste within the treatment zone during the treatment step. Optionally, the feeding step comprises feeding the waste into the tubular treatment vessel and moving the waste into the treatment zone using the auger feed, and the treatment step further comprises moving the waste through the treatment zone using the paddle agitator.

[0050] Batch Processing The method according to the present invention may be a batch process.

[0051] Without wishing to be bound by any theory, batch processing is believed to be particularly effective when small amounts of waste need to be processed, for example when extracting specific chemicals from specific types of waste, such as triethyl citrate from tire waste or PVC.

[0052] In batch processing, the superheated steam takes time to permeate the waste, meaning that the waste is gradually heated to the temperature of the superheated steam at the at least one inlet, and the chemicals produced are removed as the temperature increases.

[0053] Furthermore, the method according to the invention can be used to generate new (de novo) chemicals that are useful in fields such as the pharmaceutical industry. Without being bound by any theory, it is believed that these chemicals are synthesized in the treatment zone as a result of the combination of radicals generated from the waste.

[0054] When the method of the present invention relates to batch processing, the volume of the processing vessel is preferably about 0.001 to 0.75 m 3 , preferably about 0.01 to 0.5 m 3 is.

[0055] waste The waste material used in the method of the present invention is not particularly limited. Generally, it is assumed that the waste material is solid or liquid waste material. Without being bound by any theory, the term waste material in the present invention generally excludes gaseous waste material, but foam or other liquid or solid material mixtures containing gas are not excluded from this definition.

[0056] Preferably, the waste is a solid, a solid slurry, or a solid-containing waste. Generally, the waste is derived from industrial, commercial, and domestic activities.

[0057] Optionally, the waste is organic waste, which refers to waste streams containing large amounts of carbon-based compounds found in natural, industrial, terrestrial, and aquatic environments. Examples of organic waste include waste containing plastics and biological materials (such as plant and animal waste).

[0058] Optionally, the waste is mixed waste, which is a combination of different types of waste, for example, the waste may be municipal waste, which is a combination of different waste collected from households and may include items such as food waste, plastics, textiles, electronic waste, medical waste, etc.

[0059] The waste may be selected from the group consisting of municipal waste, agricultural waste, forestry waste, electronic waste, plastic waste, scrap tires and tire-related waste, or combinations thereof.

[0060] Optionally, the waste is organic waste or industrial waste. Preferably, the waste is household organic waste, industrial waste, or farm waste.

[0061] Agricultural waste is generally defined as any material or object previously used in agriculture or horticulture. Agricultural waste may be selected from straw, bagasse (sugarcane pulp), processing residues (such as from apple pressing or sugar beets), hay, silage, manure, empty pesticide containers, plastic silage wrap, surplus milk, peat, or a mixture of one or more of these components. Some agricultural waste may include waste from the marine environment, including seaweed such as Sargassum.

[0062] Forestry waste is generally defined as waste generated from forestry activities. Forestry waste may be selected from the group of waste wood, wood chips, sawdust, empty pesticide and fertilizer containers, or a mixture of one or more of these components.

[0063] E-waste is generally defined as discarded electrical or electronic equipment. The term e-waste can refer to post-consumer e-waste or waste generated during the production of electronic devices. These devices can be obtained from individual consumers or commercial or business establishments. E-waste may be selected from the group of refrigerators, freezers, cooling units, computers, communication equipment, mobile phones, home appliances, solar panels, televisions, monitors, screens, LED light bulbs, vending machines, or a mixture of one or more of these items. In particular, e-waste may include discarded solar panels, where the cost of separation by traditional methods is considered prohibitive for recycling.

[0064] Optionally, the waste is plastic waste. Optionally, the waste is mixed plastic waste. Preferably, the plastic waste comprises polyethylene terephthalate (PET), polyethylene (such as high-density polyethylene or low-density polyethylene), polyvinyl chloride (PVC), polypropylene (PP), polystyrene, polyurethane, polyester, polyamide, and acrylate polymers. More preferably, the plastic waste comprises or consists of polyethylene or polyvinyl chloride (PVC) or a mixture of these two materials.

[0065] Optionally, the waste material is glass fiber, such as resin-impregnated glass fiber, which may be present in articles such as boats, wind turbine blades, and automobile parts (e.g., body panels). In this case, the process according to the invention may remove the resin material, leaving behind a loose mat of glass fiber.

[0066] Optionally, the waste material is scrap tires or tire-related waste material.

[0067] Optionally, the waste may be hazardous waste.

[0068] Optionally, the particle size of the waste is reduced from an average particle size to a smaller average particle size before being added to the processing vessel. The particle size of the waste may be reduced by shredding, crushing, pelletizing, pulverizing, or grinding the waste. Optionally, the waste is shredded before being added to the processing vessel. For example, the waste may be shredded using an industrial shredder such as the ZR2400H available from Untha Shredding Technology in the UK.

[0069] Optionally, the waste material has a mean (median) cross-sectional area of ​​10 cm before being added to the treatment vessel. 3 Less than 5cm, preferably 3 The following is the result.

[0070] Optionally, at least 80% v / v of the waste prior to being added to the treatment vessel in step (a) has a particle size of less than 37.5 mm as determined by sieve analysis using a British Standard test sieve shaker (Endecotts Ltd., London, UK).

[0071] A sieve shaker test may optionally be performed as follows. -Use sieve openings of 5, 6.7, 13.2, 20 and 37.5 mm, with a sieve diameter of approximately 70 cm and a vertical sieve spacing of approximately 15 cm; - 30 kg of sample is processed and the test sieve shaker is operated for 20 minutes; The particle size distribution can also be expressed as the cumulative sieve distribution for particle diameter.

[0072] Preferably, the waste is substantially free of lime (calcium oxide and / or calcium hydroxide), and no lime is added to the treatment vessel during the treatment step. Without being bound by any theory, it is believed that no lime needs to be added to the waste because any chloride present in the waste is converted to HCl as a result of the method according to the invention.

[0073] Generally, no additional catalyst is required for the operation of the present invention, and therefore preferably no additional catalyst is added to the waste prior to or during the treatment step.

[0074] pressure The process according to the invention is preferably carried out at nominal atmospheric pressure to avoid the need for pressure sealing of the process vessel. Nominal atmospheric pressure may range from 50 to 200 kPa, and is preferably 80 to 120 kPa, more preferably about 100 kPa. Without being bound by any theory, nominal atmospheric pressure is generally close to or equal to ambient atmospheric pressure.

[0075] To remove air from the process vessel, the process vessel may be purged with steam prior to the reaction.

[0076] Duration of the process The duration of the treatment step according to the present invention is not particularly limited, and without being bound by any theory, it is believed that the duration of the treatment is related to the cross-sectional area of ​​the waste being treated, the type of waste being treated, the volume of waste in the treatment zone, and the volume of superheated steam applied to the treatment zone.

[0077] In certain embodiments, the duration of the treatment step is from 1 to 20 minutes, preferably from 1 to 10 minutes, and more preferably from 1 to 5 minutes. The duration of the treatment step is defined as the total time that a portion of the waste material spends in the treatment zone. This is sometimes referred to as the residence time of the waste material in the treatment zone.

[0078] tire In a preferred embodiment, the present invention relates to a method for treating waste tires, i.e., the waste is waste tires and / or tire-related waste. Tire-related waste refers to any tire-derived waste or tire manufacturing-derived waste. Generally, tire-related waste refers to rubber waste of natural or synthetic origin and may include tire sections, tire treads, tire inners, and inner tubes.

[0079] Waste tires are considered hazardous waste and were banned from UK landfills in 2006. They are inherently flammable and can harm people and the environment by releasing chemicals and harmful gases when burned. Piles of waste tires can also provide habitat for pests that threaten human health.

[0080] Triethyl citrate is used as a plasticizer in polyvinyl chloride and tires (which are often made from or contain butadiene rubber). Traditional energy recovery processes, such as pyrolysis, used to process waste tires cannot recover triethyl citrate from waste tires, meaning that this high-value plasticizer is simply lost and cannot be recycled.

[0081] This invention allows for the recycling of triethyl citrate from used tires, which can then be used as a plasticizer in new tires and PVC materials.

[0082] The present invention may also enable the recycling of triethyl citrate from plastic materials containing triethyl citrate other than tires.

[0083] The method according to the present invention may also allow for the recycling or recovery of other additives or plasticizers added to tires or plastics from used plastics or tires, which may be in addition to or instead of recycling triethyl citrate.

[0084] Thus, the method according to the invention comprises: - condensing vapor from said at least one vapor outlet to obtain a liquid reaction product; - separating the oily product from the liquid reaction product; and Optionally, purifying the oily product to obtain a product containing at least 80% triethyl citrate. It may further include.

[0085] The process according to the invention may also lead to the production of a solid reaction product which freezes / crystallizes from the liquid reaction product. The solid material may then be separated from the liquid reaction product, for example by filtration.

[0086] The method for separating the oily reaction product from the liquid reaction product is not particularly limited. Optionally, the separation step may involve evaporation of the aqueous component, for example, by heating the aqueous reaction product at a temperature of about 100° C. Alternatively, the oily product may be separated from the aqueous component of the liquid reaction product by passing the mixture through a molecular sieve.

[0087] The methods for treating tires (and recycling triethyl citrate) described above may also be applicable to waste containing PVC and polyethylene.

[0088] Preferably, the method according to the present invention is a method for treating waste using superheated steam in an apparatus, wherein the waste is waste tires and / or tire-related waste, waste PVC or waste polyethylene; The apparatus includes: a treatment vessel including a treatment zone having at least one steam inlet located at one end of the treatment zone and at least one steam outlet located at an opposite end of the treatment zone; The method includes: a. introducing said waste material into said treatment zone at a temperature of less than 50°C; b. Processing steps including: i. supplying superheated steam at a temperature of 300 to 800°C to the treatment zone through at least one of the steam inlets; and ii. removing steam and any gaseous reaction products through at least one said steam outlet; c. a removing step comprising removing any remaining solid product from the processing vessel after the processing step; and d. condensing the vapor from the at least one vapor outlet to obtain a liquid reaction product; e. separating the oily product from the liquid reaction product; f. Optionally, purifying the oily product to obtain a product containing at least 80% triethyl citrate. Here, any additional heat added to the treatment zone during the treatment step, apart from superheated steam, increases the temperature of the treatment zone by 100°C or less.

[0089] The above method may be more generally applicable to additives or plasticizers other than triethyl citrate that are added to plastic tires.

[0090] Preferably, the method according to the present invention is a method for treating waste using superheated steam in an apparatus, wherein the waste is waste tires and / or tire-related waste, The apparatus includes: a treatment vessel including a treatment zone having at least one steam inlet located at one end of the treatment zone and at least one steam outlet located at an opposite end of the treatment zone; The method includes: a. introducing said waste material into said treatment zone at a temperature of less than 50°C; b. Processing steps including: i. supplying superheated steam at a temperature of 300 to 800°C to the treatment zone through at least one of the steam inlets; and ii. removing steam and any gaseous reaction products through at least one said steam outlet; c. a removing step comprising removing any remaining solid product from the processing vessel after the processing step; and d. condensing the vapor from the at least one vapor outlet to obtain a liquid reaction product; e. separating the oily product from the liquid reaction product; f. Optionally, purifying the oily product to obtain a product containing at least 80% triethyl citrate. Here, any additional heat added to the treatment zone during the treatment step, apart from superheated steam, increases the temperature of the treatment zone by 100°C or less.

[0091] Electronic waste disposal In a further preferred embodiment, the present invention relates to a method for the treatment of electronic waste, i.e. the present invention relates to said method according to the invention, wherein said waste is electronic waste.

[0092] Electronic waste may be considered hazardous due to the large amounts of hazardous materials such as lead, cadmium, beryllium, or brominated flame retardants. Electronic waste also poses challenges in terms of recycling circuit boards, which contain precious metals such as gold, silver, and platinum, as well as base metals such as copper, iron, and aluminum, which are particularly difficult to recycle. Due to the difficulty of initial separation of the various components, it is estimated that only 10% to 20% of electronic waste is currently recycled.

[0093] The method according to the present invention allows for the efficient processing of electronic waste, treating it to convert metal concentrates (along with any ceramic components and / or semiconductors) into a solid material from which they can be easily removed.

[0094] Thus, in the method according to the invention, the waste can be electronic waste, and the method further comprises treating the solid product from step (c) to remove any carbonaceous material and glass fibers to obtain a concentrate of metals, ceramics, and / or semiconductors. Optionally, the solid product from step (c) is treated in a cyclone or with a jet of gas (e.g., air or an inert gas such as N2) to remove any carbonaceous material and fiberglass, in order to obtain a concentrate of metals, ceramics, and / or semiconductors. Optionally, the solid product from step (c) is treated with water to cool the solid product and remove the carbonaceous material.

[0095] Preferably, high temperatures, for example above 650°C, are used when processing e-waste, which, as mentioned above, causes the carbon in the solid product to react with water vapor to produce hydrogen and carbon monoxide, leaving behind a mixture of metals that can then be purified and reused.

[0096] When the solid product is treated in a cyclone, heavy metal particles can be recovered while lighter carbonaceous and glass fiber particles remain in the air. Customised cyclones may be available from Sicca Dania A / S, Denmark.

[0097] The metal concentrates, ceramics, and / or semiconductors can be reprocessed using standard methods known in the art.

[0098] Preferably, the method according to the invention is a method for treating waste using superheated steam in an apparatus, wherein the waste is electronic waste; The apparatus includes: a treatment vessel including a treatment zone having at least one steam inlet located at one end of the treatment zone and at least one steam outlet located at an opposite end of the treatment zone; The method includes: a. introducing said waste into a treatment zone at a temperature of less than 50°C; b. Processing steps including: i. supplying superheated steam at a temperature of 300 to 800°C to the treatment zone through at least one of the steam inlets; and ii. removing the vapor and any gaseous reaction products through at least one said vapor outlet; and c. a removing step comprising removing any remaining solid product from the processing vessel after the processing step; d. treating the solid product from step (c) to remove any carbonaceous material and glass fibers to obtain a concentrate of metals and / or ceramics; Here, any additional heat added to the treatment zone during the treatment step, apart from superheated steam, increases the temperature of the treatment zone by no more than 100°C.

[0099] solid product The process according to the invention results in the production of a solid product. The particular type of solid product obtained is not particularly limited and is generally related to the waste material used and the conditions during the treatment step.

[0100] Generally, the solid reaction product is a solid comprising elemental carbon. Optionally, the solid product has an elemental carbon content of at least 40% w / w. Optionally, the solid product has an elemental carbon content of at least 50% w / w, or at least 60% w / w, or at least 70% w / w. The elemental carbon content may be between 40% w / w and 90% w / w, or between 50% w / w and 80% w / w, or between 60% w / w and 70% w / w.

[0101] The present invention also relates to the solid product obtainable by the process according to the invention.

[0102] As mentioned above, this solid product may contain high levels of elemental carbon and has a variety of uses.

[0103] The solid product may be used as a solid fuel roughly equivalent to high-quality coal. It may be used to provide energy for industrial processes, or for industrial energy generation, or as a charcoal replacement in domestic environments. Alternatively, this material may be used in other well-established coal-based technologies, including hydrogen production and "coal-to-oil technologies." The solid product may also be used as a coke replacement in the steel industry.

[0104] If the waste does not contain toxic contaminants, the solid product may also be used to amend soil, which can benefit from the addition of elemental carbon. This significantly improves soil condition and helps retain moisture and nutrients. Furthermore, all of the minerals from the waste, such as potassium, phosphate, and magnesium, are retained in the solid product, reducing the amount of new fertilizer needed when adding this material to the soil.

[0105] liquid product The method according to the present invention can be used to remove volatile components from the waste. The method according to the present invention can also be used to synthesize new chemicals that can be condensed from the vapor in at least one of the vapor outlets. These products can be easily processed into raw materials for the production of a wide variety of chemicals and plastics.

[0106] In order to retain these products, it is necessary to separate them from the vapors obtained at the outlet of the reaction vessel, and therefore the method according to the invention may further comprise the step of condensing the vapors from at least one of the vapor outlets to obtain liquid reaction products.

[0107] Preferably, the method according to the invention is a method for treating waste using superheated steam in an apparatus comprising: a treatment vessel including a treatment zone having at least one steam inlet located at one end of the treatment zone and at least one steam outlet located at an opposite end of the treatment zone; The method includes: b. introducing said waste into a treatment zone at a temperature of less than 50°C; c. Processing steps including: i. supplying superheated steam at a temperature of 300 to 800°C to the treatment zone through at least one of the steam inlets; and ii. removing steam and any gaseous reaction products through at least one said steam outlet; d. a removing step comprising removing any remaining solid product from the processing vessel after the processing step; and e. optionally, condensing said vapor from at least one said vapor outlet to obtain a liquid reaction product; Here, any additional heat added to the treatment zone during the treatment step, apart from superheated steam, increases the temperature of the treatment zone by no more than 100°C.

[0108] The present invention also relates to a liquid reaction product obtainable by the process according to the invention.

[0109] The liquid product obtainable from the method according to the invention may contain phenolic acids, sugars and short-chain organics. In particular, the process according to the invention leads to the production of high levels of cyclic compounds, which can optionally be converted to nitrophenols by reaction with nitric acid.

[0110] The liquid reaction product may also contain dissolved and / or dispersed solids. The liquid reaction product may contain no dispersed and / or dissolved solids.

[0111] The liquid reaction product may include components that crystallize or solidify from the liquid over time and / or cooling to provide additional solid material that can be separated from the liquid product using known methods, such as filtration, etc. Either or both of this solid product and the remaining liquid may be the desired product.

[0112] The liquid reaction products can be separated into individual chemicals using industrial HPLC or other methods known to those skilled in the art.

[0113] Gaseous Products The present invention may also result in the production of gaseous reaction products, which may be separated from the vapor by condensing the vapor using known techniques such as pressure swing adsorption, vacuum swing adsorption, temperature swing adsorption, or by using membranes to purify the gas of interest.

[0114] The present invention also relates to the gaseous reaction products obtainable by the process of the invention.

[0115] The present invention also relates to a product obtained from the process of the present invention, which is a mixture of vapor obtained at said vapor outlet and said gaseous reaction product.

[0116] Device The invention also relates to an apparatus for carrying out the above-mentioned method.

[0117] Generally, the device includes: a treatment vessel having a treatment zone, - Boiler for generating steam; a superheater including a heat exchanger, a conduction heater, or a radiant heater for superheating the steam from the boiler; a line connecting the superheater and the steam inlet; wherein at least one steam inlet and at least one steam outlet are located at opposite ends of the treatment zone.

[0118] Preferably, the treatment vessel is a tubular treatment vessel.

[0119] Preferably, the apparatus further comprises an insulating jacket at least partially surrounding the tubular treatment vessel.

[0120] Preferably, the device comprises: a tubular treatment vessel having a treatment zone, - Boiler for generating steam; a superheater including a heat exchanger, a conduction heater, or a radiant heater for superheating the steam from the boiler; a line connecting the superheater and the steam inlet; an insulating jacket at least partially surrounding the tubular treatment vessel; wherein at least one steam inlet and at least one steam outlet are located at opposite ends of the treatment zone.

[0121] Preferably, the apparatus refers to an apparatus for use in a continuous process.

[0122] Optionally, the apparatus further comprises: a waste delivery system for delivering waste to said tubular treatment vessel; - means for conveying said waste through said treatment zone;

[0123] Optionally, the waste delivery system comprises an auger feed, a gravity drive system, a conveyor system, or a fluidized bed system. Preferably, the waste delivery system includes an auger feed for delivering waste to the tubular treatment vessel.

[0124] Optionally, the means for conveying the waste material through the treatment zone comprises an auger feed, a conveyor system, a ribbon mixer, or a horizontal paddle agitator. Preferably, the means for conveying the waste material through the treatment zone comprises a paddle agitator.

[0125] Optionally, the apparatus includes a treatment vessel, wherein the treatment vessel is a tubular treatment vessel. The tubular treatment vessel is equipped with a central shaft paddle agitator held in place by bearings and driven by a motor at one end of the reaction vessel. Optionally, the reaction vessel also includes a feed system consisting of a feed vessel with a central shaft auger feed, held in place by bearings and driven by a motor at one end. At the opposite end, the feed vessel is connected to the reaction vessel. The feed system also includes a hopper suitable for distributing the waste to the feed vessel. The treatment vessel also includes at least one steam inlet on one side of the treatment zone and at least one steam outlet on the opposite side of the treatment zone. The apparatus further includes a boiler for generating steam, which is connected by a transfer line to a superheater including a heat exchanger, a conduction heater, or a radiant heater for superheating the steam from the boiler. The apparatus further includes a transfer line connecting the superheater to the at least one steam inlet.

[0126] Optionally, the apparatus may also include a mechanism for condensing any liquid products from the vapor discharged from the vapor outlet.

[0127] Optionally, the apparatus may further comprise a quenching system, such as a water quench spray device, for quenching / cooling the solid product after it is removed from the treatment zone by the paddle agitator.

[0128] Optionally, the apparatus may further comprise a trap system for removing the solid product from the treatment vessel. DETAILED DESCRIPTION OF THE INVENTION

[0129] Particularly preferred embodiments include:

[0130] 1. A method for treating waste using superheated steam in an apparatus comprising: a treatment vessel including a treatment zone, wherein at least one steam inlet is located at one end of the treatment zone and at least one steam outlet is located at an opposite end of the treatment zone; The method includes: a. introducing the waste material into the treatment zone at a temperature of less than 50°C; b. Processing steps including: i. supplying superheated steam at a temperature of 300 to 800°C to the treatment zone through at least one of the steam inlets; and ii. removing the vapor and any gaseous reaction products through at least one said vapor outlet; and c. a removing step comprising removing any remaining solid product from the processing vessel after the processing step. wherein any additional heat added to the treatment zone during the treatment step, apart from superheated steam, increases the temperature of the treatment zone by no more than 100°C; and wherein the method is a continuous process in which the waste flows in one direction through the treatment zone and the steam flows in the opposite direction through the treatment zone during the treatment step.

[0131] Preferably, the temperature of the superheated steam at at least one of the inlets is 400 to 550°C.

[0132] Preferably, the processing vessel is a tubular processing vessel and the apparatus further comprises: an auger feed configured to deliver the waste to the treatment zone; and a paddle agitator configured to move and agitate said waste material through said treatment zone during said treatment step; - the loading step includes loading the waste into the tubular treatment vessel and moving it to the treatment zone using an auger feed; and The treating step further comprises using the paddle agitator to move the waste through the treatment zone.

[0133] In a further particularly preferred embodiment, the present invention relates to a method for treating waste using superheated steam in an apparatus comprising: a treatment vessel including a treatment zone, wherein at least one steam inlet is located at one end of the treatment zone and at least one steam outlet is located at an opposite end of the treatment zone; The method includes: a. introducing the waste material into the treatment zone at a temperature of less than 50°C; b. Processing steps including: i. supplying superheated steam at a temperature of 300 to 800°C to the treatment zone through at least one of the steam inlets; and ii. removing the vapor and any gaseous reaction products through at least one said vapor outlet; and c. a removing step comprising removing any remaining solid product from the processing vessel after the processing step. wherein any additional heat added to the treatment zone during the treatment step, apart from superheated steam, increases the temperature of the treatment zone by no more than 100°C; wherein the waste material is scrap tires and / or tire-related waste material, and wherein the method further comprises: o condensing said vapor from at least one said vapor outlet to obtain a liquid reaction product; o separating oily products from said liquid reaction products; Optionally, purifying the oily product to obtain a product containing at least 80% triethyl citrate.

[0134] Preferably, the temperature of the superheated steam at at least one of the inlets is 400 to 550°C. [Brief explanation of the drawings]

[0135] Embodiments of the present invention will now be described, by way of example only, with reference to the accompanying drawings, in which: [Figure 1] FIG. 1 is a diagram of an apparatus suitable for carrying out the steam reforming process in batch mode. [Figure 2] FIG. 2 is a diagram of an apparatus suitable for carrying out the steam reforming process in a continuous mode. Detailed Description of the Invention

[0136] The present invention will now be described in detail with reference to preferred embodiments and other optional features.

[0137] Unless otherwise defined, all technical and scientific terms used herein have meanings consistent with the understanding of one of ordinary skill in the art. Although any methods and materials similar or equivalent to those described herein can indeed be used in testing the present invention, the preferred materials and methods are described herein. In the detailed description of the invention and in the claims of this application, the following terms will be used in accordance with the definitions set forth below. Unless otherwise specified, the use of terms such as "a," "an," etc., means one or more.

[0138] While the present invention will be described in conjunction with the exemplary embodiments set forth below, many equivalent modifications and variations will become apparent to those skilled in the art from this disclosure. Accordingly, the exemplary embodiments described herein are considered to be illustrative and not limiting. Various changes may be made without departing from the scope of the invention, as defined by the claims. All references mentioned herein are incorporated herein by reference.

[0139] All compatible combinations of the embodiments described herein are expressly disclosed herein as if each combination were expressly disclosed individually. Furthermore, as used herein, "and / or" shall be interpreted as a specific disclosure of each of two specified features, with or without the other.

[0140] Unless the context otherwise requires, the feature descriptions and definitions set forth herein are not limited to any particular aspect or embodiment, but apply equally to all aspects and embodiments described where appropriate.

[0141] When values ​​are listed as a "maximum" or a "minimum," it is understood that any of these values ​​can be independently combined to create a range.

[0142] Unless otherwise indicated, the values ​​provided are generally recorded at room temperature, i.e. in the range of 20-30°C, for example 20°C.

[0143] Where non-SI units are provided, it is understood that these can be readily converted to SI units by one of ordinary skill in the art.

[0144] Unless otherwise specified, percentage figures refer to percentages determined on a weight-to-weight basis (w / w).

[0145] The use of headings herein is intended to aid the reader in understanding the invention and does not imply any limitations on the invention defined by the claims.

[0146] Figure 1 shows a typical configuration of a batch system according to the present invention. The apparatus in Figure 1 comprises a process vessel (reaction vessel) 1 with a steam inlet on one side of the process vessel and a steam outlet on the other side. The steam inlet is connected to a steam generator 4 (e.g., a boiler or waste steam source) and a superheater 3 for generating superheated steam. The steam outlet is connected to a heat exchanger 1.

[0147] To use the apparatus, waste material is introduced into the reaction vessel. Steam at 100°C is generated in the steam generator and then superheated in the superheater to a temperature of 300-800°C. The superheated steam is then supplied to the treatment vessel through the steam inlet and flows through the waste material. The steam is removed at the steam outlet and passed through a heat exchanger where it is cooled with liquid water (or cooled using other cooling methods known in the art) and liquid products are condensed from the mixture of steam and volatile reactants.

[0148] Figure 2 shows a typical configuration of a continuous system according to the present invention. The apparatus of Figure 2 includes a treatment vessel 22 having a central shaft paddle agitator 18 held in place by bearings 16 and driven by a motor 15 at one end of the reaction vessel. The reaction vessel also includes a feed system 21 consisting of a feed vessel with a central shaft auger feed 14 held in place by bearings 16 and driven at one end by motor 15. At the opposite end, the feed vessel is connected to the reaction vessel. The feed system also incorporates a hopper 13 suitable for distributing the waste material to the feed vessel.

[0149] The treatment vessel also has a steam inlet 23 on one side of the treatment zone and a steam outlet 24 on the opposite side of the treatment zone. The steam inlet is connected to a steam generator 11 (e.g., a boiler or waste steam source) and a superheater 12 for producing superheated steam.

[0150] The treatment vessel may also include a drive auger system 17 for conveying waste to the treatment zone prior to the vapor outlet 24. The treatment vessel may also incorporate a quench system 20, such as a quench water sprayer, for quenching / cooling the solid product at the end of the reaction, and a trap system 19 for collecting the solid product.

[0151] To use the apparatus, waste is loaded into the hopper. The hopper distributes the waste to the feed vessel, and the auger feed in the feed vessel transports the waste to the treatment vessel. In the treatment vessel, the waste is conveyed through the treatment vessel by the paddle agitator and removed at the end of the treatment vessel using a trap system. Steam is generated in the steam generator and then superheated in the superheater. The steam is then supplied to the steam inlet and travels counter-current to the waste flow through the treatment vessel until it is removed at the steam outlet at the end of the treatment zone. [Example]

[0152] Device

[0153] reaction vessel The reactor was a custom-made stainless steel cylindrical vessel, 200 mm long and 100 mm in diameter, sealed at both ends with end plates and equipped with a 10 mm steam inlet and a 15 mm steam outlet at each end, surrounded by approximately 25 mm thick ceramic fiber insulation and secured with a lightweight aluminum jacket.

[0154] steam generator The steam generator was custom-built using 1.2 mm thick copper plate, with a 3 kW electric heating element and a nominal water capacity of 4 L, with the water level maintained using an all-stainless steel ball valve connected to the water mains. The evaporation rate was controlled using an SCR-based phase angle power controller that could linearly adjust the actual heater power from zero to 3 kW.

[0155] Steam superheater The steam superheater was custom-built using 10 mm standard copper tubing wound to a 1.5 m length of 80 mm diameter. Two ceramic 500 W radiant heaters were mounted 25 mm away from the copper coil, facing each other across the coil. The entire unit was completely enclosed in a 0.5 mm thick insulated stainless steel cylindrical vessel, externally insulated with ceramic fiber insulation secured by a lightweight aluminum jacket. The temperature of the copper tubing immediately downstream of the heat transfer zone was monitored using a K-type thermocouple connected to a programmable PID temperature controller and display, the output of which was used to regulate the power supplied to the radiant heating element in burst mode via a solid-state relay, regulating the steam outlet temperature to the programmed value.

[0156] Hydrolysis method 100 g of sample was placed in the reaction vessel of the apparatus shown in FIG.

[0157] The steam generator was powered on. When the temperature of the steam entering the superheater reached 100° C., the superheater was powered on. The superheated steam was PID controlled and set to 450° C. (measured at the outlet of the superheater, which was connected to the inlet leading to the reaction chamber).

[0158] The temperature of the vapor outlet of the reactor vessel was monitored as it steadily increased until it reached 350° C. For the sample tested in this section, it took approximately 40 minutes to reach a temperature of 350° C.

[0159] The steam / biogas mixture was then condensed in a water-cooled heat exchanger and collected. 2 L of condensate was obtained. The biogas burned with a blue flame, indicating the presence of hydrogen.

[0160] The reaction vessel was left to cool for 2 hours and then opened, leaving the solid product as a residue in the chamber.

[0161] A 100 mL sample of the condensate was used for GC-MS and LC-MS analysis.

[0162] Example 1 - LC-MS analysis of polyethylene 100 g of polyethylene obtained from post-consumer polytunnel polyethylene was subjected to the hydrolysis process described above at a steam inlet temperature of 500° C. The aqueous fraction was condensed and then prepared for analysis using the following procedure.

[0163] Sample preparation The sample was diluted 100 times by adding 10 μL of the liquid to 990 μL of 10% MeOH (MeOH, VWR, LC-MS grade).

[0164] Chromatographic separation and detection LC-MS analysis was performed using an Agilent QTOF 6545 equipped with a Jetstream ESI spray source connected to an Agilent 1260 Infinity II quaternary pump HPLC equipped with a 1260 autosampler, column oven compartment, and variable wavelength detector (VWD). The MS was operated in either positive or negative ionization mode with separate injections at a gas temperature of 250 °C, 12 L / min of drying gas, and 45 psi (3.10 bar) of nebulizer gas. The sheath gas temperature and flow rate were set to 350 °C and 12 L / min, respectively. The MS was calibrated using a reference calibrant introduced from a separate ESI reference sprayer. The VCap, fragmentor, and skimmer were set to 3500, 125, and 45 V, respectively. The MS was operated in all-ion mode with three collision energy scan segments at 0, 20, and 40 eV. Chromatographic separation of 5 μL sample injections was performed on an InfinityLab Poroshell 120 EC-C18 (3.0 × 50 mm, 2.7 tm) column using HO (Merck, LC-MS grade) containing 0.1% by volume formic acid (FA, Fluka) and methanol (MeOH, VWR, HiPerSolv) containing 0.1% by volume FA as mobile phases A and B, respectively. The column was operated starting with 5% mobile phase B at a flow rate of 0.4 mL / min at 50 °C, as shown in Table A.

[0165] [Table A]

[0166] The VWD was set to detect at a wavelength of 320 nm and a frequency of 2 Hz. Data processing was automated in Qual 10 with molecular feature extraction set to the 20 most intense compounds for [M+H], [MH], and [M+HCOO] ions. Results were searched against the Metlin database (containing entries for 80,0S8 compounds) with a forward score of 2S and a reverse score of 70, and a mass tolerance within 5 ppm of the reference library match.

[0167] The samples were clear solutions with a slight oily layer on the sides of the plastic container. These were further diluted 100-fold to ensure compatibility and concentration levels suitable for LC-MS conditions. The diluted samples were analyzed using LC-UV-MS in both positive and negative modes, using a 15-minute chromatographic run time (see gradient conditions for details) with an additional organic solvent wash to limit carryover between samples.

[0168] result Most of the peaks eluted within the first 15 min of the chromatogram, indicating that the sample was primarily composed of polar and semi-non-polar compounds. UV correlated well with nBPC, suggesting that color-forming anions, likely phenolic and aromatic acids, were more prevalent in the sample.

[0169] The top 10 compounds (based on LC-MS peak area) in the sample are shown in Table B.

[0170] [Table B]

[0171] Other compounds of particular interest derived from polyethylene are: - 18-hydroxypregna-1,4,20-trien-3-one - Propafenone - 2-phenyl-1,3-propanediyl monocarbamate It was.

[0172] Example 2 - LCMS analysis of tire rubber 100 g of tire rubber (purchased from the open waste market, e.g., a 1 tonne dump bag from Waste Tyre Specialists UK) was subjected to the hydrolysis process described above. The aqueous fraction was concentrated and then prepared for analysis using the following procedure.

[0173] Sample preparation Sample preparation was carried out as described above in Example 1.

[0174] result Most of the peaks eluted within the first 15 min of the chromatogram, indicating that the sample was primarily composed of polar and semi-non-polar compounds. UV correlated well with nBPC, suggesting that color-forming anions, likely phenolic and aromatic acids, were more prevalent in the sample. The top 10 compounds (based on peak area) in the sample are shown in Table C.

[0175] [Table C]

[0176] Other compounds of particular interest generated from tire rubber (using negative mode detection) are: - 18-hydroxypregna-1,4,20-trien-3-one (CHEBI:186912); - Vanillylpyruvic acid; - Piperic acid; - 4,5-hydroxypropafenone; - 5,3-(2-furyl)acrolein It was.

[0177] Other compounds of particular interest generated from tire rubber (using positive mode detection) are: - Triethyl citrate; - 8-Isoquinoline Methanamine It was.

[0178] Example 3 - LCMS analysis of PVC 100 g of PVC (e.g. waste PVC cable covering from Doncaster Cables UK) was treated with the hydrolysis process described above for polyethylene. The aqueous fraction was concentrated and then prepared for analysis in a manner similar to that described for Example 1 above.

[0179] Sample preparation Sample preparation was carried out as described for Example 1 above.

[0180] result Most of the peaks eluted within the first 15 min of the chromatogram, indicating that the sample was primarily composed of polar and semi-non-polar compounds. UV correlated well with nBPC, suggesting that color-forming anions, likely phenolic and aromatic acids, were more prevalent in the sample.

[0181] The top 10 compounds (based on peak area) in the sample are shown in Table D.

[0182] [Table D]

[0183] Other compounds of particular interest derived from PVC are: - 4,4,methylenedioxybenzoic acid (piperonyl acid); - 18-hydroxypregna-1,4,20-trien-3-one (CHEBI:186912); - Hydroxypropafenone; - Mono-2-ethylhexyl phthalate (MEHP) It was.

[0184] Overall conclusions of Examples 1-3 Overall, mainly small organic acids and phenolic acids were detected in the hydrolyzed samples, with the majority present in the tire rubber sample (Example 2).

[0185] Example 4 - GC-MS analysis of tire rubber GC-MS analysis was used to identify the presence of non-polar compounds in the oil fraction of the sample.

[0186] 100 g of tire rubber (purchased from the open waste market, e.g., a 1 tonne dump bag from Waste Tyre Specialists UK) was subjected to the hydrolysis process described above. The aqueous fraction was concentrated and then prepared for analysis using the following procedure.

[0187] Sample preparation Samples were prepared for analysis by performing a liquid-liquid extraction: approximately 2 mL of sample was mixed with 2 mL of n-hexane (GC grade), the sample was vortexed, and the top n-hexane layer was collected for analysis.

[0188] Chromatographic Separation and Detection An Agilent 8890 gas chromatography (GC) system coupled with an Agilent 5977B MSD (MS) was used for the analysis. A single-taper, Ultra Inert wool inlet liner (Agilent 5190-2293) was used, with a 1 μL split injection at a split ratio of 50:1 (20 mL / min split flow rate). The inlet was heated to 250 °C with a 3 mL / min septum purge flow. An Agilent HP-5MS (30 m, 0.25 mm, 0.25 μm) column was used with a constant flow rate of 1.0 mL / min and He (BOC, N5.5) as the carrier gas. The column oven gradient started at 70 °C, held for 4 min, then increased to 200 °C at 10 °C / min and held for 3 min, for a total analysis time of 20 min. The MSD transfer line was set to 250°C, the MSD source to 230°C, and the MSD quad temperature to 150°C. After an initial solvent delay of 6.5 min, MSD detection was performed using full scan mode in the range of 30–300 m / z, with a scan speed of 1562 μs and a gain factor of 15. Data analysis was performed with Agilent Qualitative Analysis v.10.0 using the NIST 17 library to identify and confirm compounds by spectral matching.

[0189] The sample was a clear solution with a slight oily layer on the sides of the plastic container. Liquid-liquid extraction was performed to extract non-polar compounds to ensure compatibility with GC-MS analysis.

[0190] The MS / MS data were extracted from the peaks and searched against the NIST 17 library to identify putative compounds. The compound hit score represents the confidence of the prediction, with the most confident predictions approaching 100.

[0191] result Numerous organic sulfur compounds and heterocyclic aromatic compounds were detected in the tire rubber sample. Based on the peak area, the main component was the peak at 12.5 minutes, which represented 1,2-benzisothiazole. This compound is commonly used as a vulcanization accelerator in rubber production.

[0192] The top 10 compounds produced are shown in Table E below.

[0193] [Table E]

[0194] Example 5 - GC-MS analysis of PVC 100 g of PVC (e.g., waste PVC cable covers from Doncaster Cables UK) was treated with the hydrolysis process described above. The aqueous fraction was concentrated and then prepared for analysis using the following procedure.

[0195] Sample preparation Sample preparation was performed as described in Example 4 above.

[0196] result The PVC sample contained putative short-chain alcohols such as 2-ethyl-1-hexanol and 3-methyl-3-heptanol. Based on peak volume, the peak at 8.8 min, which represents 2-ethyl-2-hexanol, was the most prominent compound.

[0197] The top 10 compounds produced are shown in Table F below.

[0198] [Table F]

[0199] Example 6 - Wood Hydrolysis 100 g of wood (chainsaw chips obtained from the felling of mature ash and pine trees, containing a mixture of ash and pine with a moisture content of 20%) was treated with the hydrolysis process described above. The sample was treated for approximately 40 minutes, and 40 grams of carbon (charcoal) residue was obtained from the reaction chamber. The aqueous fraction was concentrated and then prepared for analysis using the following procedure.

[0200] Sample preparation The sample was diluted 100-fold by adding 10 μL of the yellow liquid to 990 μL of 10% MeOH (MeOH, VWR, LC-MS grade).

[0201] Chromatographic separation and detection LC-MS analysis was performed using an Agilent QTOF 6545 equipped with a Jetstream ESI spray source connected to an Agilent 1260 Infinity II quaternary pump HPLC equipped with a 1260 autosampler, column oven compartment, and variable wavelength detector (VWD). The MS was performed with separate sample injections in positive or negative ionization mode at a gas temperature of 250 °C, 12 L / min drying gas, and 45 psi (3.10 bar) nebulizer gas. The sheath gas temperature and flow rate were set to 350 °C and 12 L / min, respectively. The MS was calibrated using a reference calibrant introduced from a separate ESI reference sprayer. The VCap, fragmentor, and skimmer were set to 3500, 125, and 45 V, respectively. The MS was operated in all-ion mode with three collision energy scan segments at 0, 20, and 40 eV. Chromatographic separation of 5 μL sample injections was performed on an InfinityLab Poroshell 120 EC-C18 (3.0 × 50 mm, 2.7 μm) column using 0.1% by volume formic acid (FA, Fluka) in HO (Merck, LC-MS grade) and 0.1% by volume FA in methanol (MeOH, VWR, HiPerSolv) as mobile phases A and B, respectively. The column was operated at a flow rate of 0.4 mL / min at 50°C, starting with 5% mobile phase B, as shown in Table G.

[0202] [Table G]

[0203] The VWD was set to detect at wavelengths of 254 and 320 nm and a frequency of 2.5 Hz. Data processing was automated using the Qual 10 software package, and molecular feature extraction was set to the 20 most intense compounds for [M+H]+, [MH]-, and [M-EFICOO]- ions. Results were searched against the Metlin database (containing 80,058 compound entries) with a forward score of 25 and a reverse score of 70, and a mass tolerance within 5 ppm of the reference library match.

[0204] result The sample was a clear yellow solution that was diluted 100-fold for analysis to ensure suitability and concentration levels compatible with LC-MS conditions. The solution was analyzed using LC-UV-MS in both positive and negative modes using a chromatographic run time of 18.5 minutes with an additional organic wash to limit carryover between samples (see gradient conditions for details).

[0205] The chromatographic separation was performed on a reversed-phase (C18 end-capped) column, and the initial elution profile suggested a large proportion of polar molecules that did not undergo extensive interactions with the stationary phase, resulting in early elution. Comparing the MS data between the two ionization modes revealed a high correlation between the peaks detected by UV and those ionized in negative mode. This suggested a greater abundance of acidic molecules than basic molecules, which are typically preferentially ionized in positive mode.

[0206] The molecular feature extraction (MFE) workflow was used for an untargeted screening approach, where precursor masses were confirmed for charge carrier type (i.e., [M-H]- and [M-EFICOO]-, etc.) and checked for isotopic distribution (e.g., C abundance and spacing) before being matched against a curated database with over 80K entries. If no match was found in the database, predictive equations were calculated for the mass properties.

[0207] The top 10 compounds (based on peak area) in the sample are shown in Table H.

[0208] [Table H]

[0209] Other compounds of particular interest derived from wood chips are: - methoxycinnamic acid; - dimethyl maleate; - dimethyl succinate; - Piperic acid; - Karpathin; - Diethyl L-tartrate; - methyl acrylate; - 2-Methoxy-1,4-hydroquinone (MHQ); - Dehydronuciferine; - (S)-(-)-5-hydroxymethyl-2(5H) It was.

[0210] conclusion Hundreds of predicted molecules, ranging from phenolic acids and furyl / furanone compounds to sugars, were detected in the hydrolyzed wood samples.

[0211] Without being bound by any theory, it is believed that the results for wood chips are representative of other agricultural and forestry waste products.

Claims

1. 1. A method for treating waste using superheated steam in an apparatus, comprising: The device includes: a treatment vessel containing a treatment zone, with at least one steam inlet located at one end of the treatment zone and at least one steam outlet located at an opposite end of the treatment zone; The method includes: a. an input step comprising inputting the waste material into the treatment zone at a temperature less than 50°C; b. Processing steps including: i. supplying superheated steam at a temperature of from 300°C to 800°C to said treatment zone through at least one said steam inlet; and ii. removing steam and any gaseous reaction products through at least one said steam outlet; and c. A removing step comprising removing any remaining solid product from the processing vessel after the processing step. wherein any additional heat added to the treatment zone during the treatment step, apart from the superheated steam, increases the temperature of the treatment zone by 100°C or less.

2. 2. The method according to claim 1, wherein the temperature of the superheated steam at at least one of the inlets is between 400 and 600°C, preferably between 400 and 550°C.

3. 3. The method of claim 1 or 2, wherein the method is a continuous process.

4. 4. The method of claim 3, wherein during the treatment step, the waste is caused to flow in one direction through the treatment zone and the steam is caused to flow in an opposite direction through the treatment zone.

5. 5. The method of claim 4, wherein the processing vessel is a tubular processing vessel, and the apparatus comprises: an auger feed configured to deliver the waste to the treatment zone; and a paddle agitator configured to move the waste material through the treatment zone and to agitate the waste material during the treatment step; Further comprising: where: - the step of introducing includes introducing the waste into the tubular treatment vessel and moving the waste to the treatment zone using an auger feed; and The method wherein said treating step further comprises using said paddle agitator to move said waste through said treatment zone.

6. 3. The method of claim 1 or 2, which is a batch process, and optionally the process vessel has a volume of about 0.001 to 0.75 m ３ , preferably about 0.01 to 0.5 m ３ A method having a volume of.

7. 10. A method according to any one of the preceding claims, wherein apart from the superheated steam, no additional heat is applied to the treatment zone during the treatment step.

8. A method according to any one of the preceding claims, wherein the pressure in the treatment zone is between 50 and 200 kPa, preferably between 50 and 100 kPa.

9. 10. The method of any one of the preceding claims, wherein the solid product has a carbon content of at least 40%.

10. 10. The method according to any one of the preceding claims, wherein the duration of the treatment step is from 1 to 20 minutes, preferably from 1 to 10 minutes, more preferably from 1 to 5 minutes.

11. 10. A method according to any one of the preceding claims, wherein at least 80% v / v of the waste material in step (a) has a particle size of less than 37.5 mm as determined by sieve analysis using a British Standard test sieve shaker.

12. 10. A method according to any one of the preceding claims, wherein the waste is mixed waste.

13. 10. The method according to any one of the preceding claims, wherein the waste is selected from the group consisting of municipal solid waste, agricultural waste, forestry waste, (post-consumer) electronic waste, plastic waste, scrap tires and tire-related waste, or combinations thereof.

14. 10. The method of any one of the preceding claims, further comprising the step of condensing said vapor from at least one said vapor outlet to obtain a liquid reaction product.

15. 15. The method according to claim 13 or 14, wherein the waste material is scrap tires and / or tire-related waste material.

16. 16. The method of claim 15, wherein: - condensing said vapor from at least one said vapor outlet to obtain a liquid reaction product; - separating oily products from said liquid reaction products; - optionally purifying said oily product to obtain a product containing at least 80% triethyl citrate. The method further comprises:

17. The method according to any one of claims 1 to 14 and 16, the waste is electronic waste, and the method optionally further comprising treating the solid product from step (c) in a cyclone or with a jet of gas to remove any carbonaceous material and glass fibres and obtain a concentrate of metals, ceramics and / or semiconductors; method.

18. 10. The method of any one of the preceding claims, wherein the method comprises the input step, the treatment step, and the removal step, and wherein the temperature of the steam at the steam inlet is constant throughout the treatment steps.

19. 10. The method of any one of the preceding claims, wherein the temperature difference between the superheated steam at the inlet and the steam at the steam outlet is at least 10°C, preferably at least 50°C, more preferably at least 100°C.

20. 10. A method according to any one of the preceding claims, wherein the waste is substantially lime-free and no lime is added to the treatment vessel during the treatment step.

21. 10. The method of any one of the preceding claims, wherein the apparatus further comprises a heat exchanger, and the method comprises the step of feeding the steam from at least one of the steam outlets through the heat exchanger to recover residual heat from the steam.

22. 22. A solid product obtainable by the method of any one of claims 1 to 21.

23. 22. A product which is a mixture of steam and gaseous reaction products obtainable by the method of any one of claims 1 to 21.

24. 22. A gaseous reaction product obtainable by the method of any one of claims 1 to 21.

25. 22. A liquid reaction product obtainable by the process according to any one of claims 14 to 21.

26. 22. An apparatus for carrying out the method according to any one of claims 1 to 21, comprising: a treatment vessel having a treatment zone, - Boilers for generating steam; a superheater, including a heat exchanger, a conduction heater, or a radiant heater, for superheating the steam from the boiler; - a line connecting the superheater with the steam inlet; Including, wherein at least one steam inlet and at least one steam outlet are located at opposite ends of said treatment zone.

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