Processes for producing carbon black using sustainable burner fuels and products manufactured from them

Abstract

The invention relates to methods for producing carbon black using a burner fuel comprising at least one sustainable burner fuel, such as, but not limited to, tire pyrolysis oil. The carbon blacks produced by these methods are described in more detail. The invention further relates to the advantages obtained through these methods.

Description

Title of Invention: Methods for producing carbon blacks using sustainable burner fuels and products made therefrom

[0001] The present invention relates to methods for producing carbon black produced from sustainable or alternative burner fuels. The present invention further relates to carbon blacks formed from the use of sustainable burner fuels in the process.

[0002] Carbon black has been used to modify mechanical, electrical, and optical properties in compositions. Carbon blacks and other fillers have been used as pigments, fillers, and / or reinforcing agents in the compounding and preparation of compositions used in rubber, plastic, paper, or textile applications. The properties of the carbon black or other fillers are important factors in determining various performance characteristics of these compositions. Important uses of elastomeric compositions are in the manufacture of tires, and additional components are often added to impart specific properties to the finished product or its components.Carbon blacks have been used to modify functional properties, electrical conductivity, rheology, surface properties, viscosity, appearance and other properties in elastomeric and other types of compositions.

[0003] The conventional and most common process for the industrial production of carbon blacks is the furnace process. In this process, a first carbon-containing liquid feedstock or primary carbon-containing liquid feedstock, such as decanter oil, is injected into a fuel-lean hot flue or combustion gas stream. The hot combustion stream is formed by oxidation of a burner fuel, typically natural gas or coal gas or a liquid fuel similar or identical to the primary feedstock, in air or oxygen-enriched air or oxygen. A portion of the feedstock pyrolyzes to produce carbon black and by-products (primarily hydrogen and carbon monoxide); the remainder oxidizes to produce CO2 and H2O.Conventional or traditional raw material is a settling oil, sludge oil, coker oil, coal tar derivative or heavy liquid residue from an ethylene cracking process. These carbon black raw materials are generally both heavy (specific gravity > 1.02), have an H:C atomic ratio less than 1.23, are rich in . aromatics (Bureau of Mines Correlation Index (BMCI) > 100) and are liquid at room temperature and pressure (e.g., 25°C at 1 atm). The amounts of hydrogen and carbon can be measured according to ASTM D5291 or equivalent methods. They are all generally derived from fossil fuels.

[0004] The furnace black manufacturing process differs from the tunnel black manufacturing process and the thermal black manufacturing process, both of which use natural gas as raw material.

[0005] It would be both economically useful and environmentally beneficial to use one or more sustainable burner fuels in an existing furnace carbon black manufacturing process. These burner fuels would not necessarily be based on fossil fuels. Examples of these include vegetable oils, oils derived from the pyrolysis of recycled tires (tire pyrolysis oil or TPO), plastics, municipal waste, biomass, or natural gas produced from landfills or agricultural waste.

[0006] Therefore, there is a need in the industry to provide a solution to be able to use (to enable the use of) large quantities of sustainable materials in an existing furnace carbon black manufacturing process, and still produce carbon blacks comparable to carbon blacks formed from traditional burner fuel and primary raw materials (e.g., produce carbon blacks with acceptable yields and / or with high specific surface areas and / or high structures). One way to achieve this is to use sustainable materials as the combustion fuel (where at least the majority of the total burner fuel is sustainable burner fuel).Using these sustainable burner fuels in an existing furnace process saves significant capital and development resources, instead of developing, designing and building a new process to use them.

[0007] All patents and publications mentioned herein are incorporated in their entirety by reference. SUMMARY OF THE PRESENT INVENTION

[0008] A feature of the present invention is to provide methods of preparing or producing carbon black using burner fuels that comprise at least one sustainable burner fuel.

[0009] An additional feature of the present invention is to provide carbon blacks made from processes that utilize burner fuels that include at least one sustainable burner fuel.

[0010] Another feature is to provide a method for producing carbon blacks using conventional carbon black-forming raw materials as well as burner fuels that include at least one sustainable burner fuel.

[0011] An additional feature is the provision of a method for producing carbon blacks using a burner fuel that comprises at least one sustainable burner fuel (e.g., where the majority by weight of the burner fuel is at least one sustainable burner fuel) and such that the resulting carbon black has an acceptable (e.g., good) yield, for a given acceptable (e.g., high) surface area and / or an acceptable structure (e.g., high structure).

[0012] To achieve these and other advantages, and in accordance with the objectives of the present invention, as embodied and broadly described herein, the present invention relates, in part, to a process for producing carbon black. The process comprises introducing into a carbon black reactor a burner fuel comprising at least one sustainable burner fuel, and then igniting and forming a hot gas stream from the burner fuel in the reactor. The process then comprises introducing into the carbon black reactor at least one carbon black-producing feedstock at one or more introduction points and combining the one or more carbon black-producing feedstocks with the hot gas stream to form carbon black in a reaction stream. The process further comprises quenching the reaction stream containing the carbon black and recovering the carbon black.

[0013] Further, the present invention relates, in part, to one or more carbon blacks wherein at least a portion or at least a majority of the burner fuel that is used is a sustainable burner fuel in the carbon black formation process.

[0014] The present invention further relates to products and / or articles, such as, but not limited to, elastomeric composites formed from one or more of the carbon blacks of the present invention.

[0015] It is to be understood that the above general description and the following detailed description are given by way of example only and are intended to provide further explanation of the present invention as claimed.

[0016] The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate various features of the present invention and, together with the description, serve to explain the principles of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] [Fig.1A] is a cross-sectional view of an example of a reactor suitable for preparing the carbon black of the present invention.

[0018] [Fig.lB] is a cross-sectional view of another example of a reactor suitable for preparing the carbon black of the present invention.

[0019] [Fig. 2] is a cross-sectional view of another example of a reactor suitable for preparing the carbon black of the present invention.

[0020] [Fig.3] is a graph showing OAC (%) and STSA (in m2 / g) for two examples of the present invention and a comparative example with different burner fuels used.

[0021] [Fig.4] is a graph showing the dimensionless efficiency and STSA (in m2 / g) for two examples of the present invention and a comparative example with different burner fuels used.

[0022] [Fig.5] is a graph showing COAN and STSA (in m2 / g) for two examples of the present invention and a comparative example with different burner fuels used.

[0023] [Fig.6] is a graph showing Tint and STSA (in m2 / g) for two examples of the present invention and a comparative example with different burner fuels used.

[0024] [Fig.7] is a graph showing the iodine index and STSA (in m2 / g) for two examples of the present invention and a comparative example with different burner fuels used. DETAILED DESCRIPTION OF THE PRESENT INVENTION

[0025] The present invention relates to methods for producing carbon blacks that utilize burner fuels that include one or more sustainable burner fuels, as defined and described herein. For purposes of the present invention, “sustainable” burner fuels, as that term is used herein, may be or include, for example, what are sometimes referred to as circular materials or recycled materials or may be referred to as “sustainable” materials and / or fuels derived from biological sources. Examples of burner fuels that may be used are described in detail below.

[0026] The present invention further relates to carbon blacks produced from one or more of these processes.

[0027] With the methods of the present invention, preferably, at least a majority of the total burner fuel used may be one or more sustainable burner fuels.

[0028] By the methods of the present invention, not only can large quantities of sustainable burner fuel be used as burner fuel, but this does not in any way compromise the quality of the carbon black produced. Thus, the methods of the present invention utilize sustainable burner fuels that are more desirable to use for environmental and / or other reasons, and yet produce carbon blacks that are at least comparable to, or even superior to, carbon blacks produced using 100% traditional burner fuels in furnace carbon black manufacturing processes.

[0029] A method for producing carbon black according to the present invention comprises or includes introducing, into a carbon black reactor, a burner fuel that comprises at least a portion of one or more sustainable burner fuels. The method further comprises igniting and forming a hot gas stream or a heated gas stream in the carbon black reactor (e.g., a furnace carbon black reactor). The method further comprises introducing, into the carbon black reactor, at least one carbon black-producing feedstock (or carbon black feedstock) by means of one or more introduction points. The method then comprises combining the carbon black-producing feedstock with the hot gas stream to form carbon black in a reaction stream.The process then comprises quenching the reaction stream containing the carbon black and recovering the carbon black. In the process, preferably, the sustainable burner fuel constitutes a majority of the total burner fuel and more preferably, constitutes at least 60% by weight of the total burner fuel.

[0030] The sustainable burner fuel may be a fuel derived from sources considered sustainable, biological and / or recycled. For example, the sustainable burner fuel may be or include ethylene, a gas at ambient temperature and pressure. The ethylene may be produced from biologically derived ethanol, for example from the fermentation of corn or other fermentations of plant materials. Alternatively or additionally, the sustainable burner fuel may be an oil derived from the hydrothermal liquefaction (HTL) of biomass or tires, plastics or other waste materials.

[0031] The sustainable burner fuel, for purposes of the present invention, may be a fuel that is not derived from fossil fuel-based gasoline production or coal cracking, or cracking to produce olefins. Thus, the sustainable burner fuel is a fuel other than coal tar liquid, petroleum refinery liquid, or ethylene cracking residue.

[0032] Other examples of sustainable burner fuel may include, but are not limited to, the following: tire pyrolysis oil, plastic pyrolysis oil, vegetable-derived oil, forest-derived oil, oil derived from the pyrolysis of municipal solid waste, an oil derived from the pyrolysis or decomposition of biomass (e.g., animal, plant, tree, or vegetable) or other agricultural waste, an oil derived from the processing of papermaking by-products, and / or another oil derived primarily from biomaterials or any combination thereof. These liquid feedstocks have an H:C atomic ratio greater than 1.23, or a specific gravity less than 1.02, or a BMCI value less than 100. Specific examples of sustainable liquid burner fuels are shown in [Table 1] below: Raw material example Tyre pyrolysis oil Bolder 350 Tyre pyrolysis oil Delta Energy DE-Solv Soybean oil Corn oil Peanut oil Atomic H:C 1.32 1.5 1.87 1.87 1.87 Specific gravity 1.00 0.94 0.93 0.92 0.91 BMCI 94 62.5 56 54 50 Sulphur content (% by weight) 1.08 1.03 0 0 0 Flash point (°C) 68 32 >110 321 315 Table 1.

[0033] Other examples of sustainable burner fuel may include, but are not limited to, the following: a sustainable feedstock, a bio-based or bio-derived feedstock, and / or another by-product of a refining process, or any combinations thereof.

[0034] Other examples of sustainable burner fuel may include, but are not limited to, the following: vegetable, fruit, nut, or other plant-derived oils (e.g., corn oil and / or distillers corn oil) or forest-derived oils.

[0035] Other examples of sustainable burner fuel may include, but are not limited to, the following: bio-based ethanol (from the fermentation of corn or other plant, vegetable, or fruit fermentation products).

[0036] Other examples of sustainable burner fuel may include, but are not limited to, the following: waxes and resins produced by plants or animals, such as lanolin or shellac.

[0037] Other examples of sustainable burner fuel may include, but are not limited to, the following: oils obtained from animal fats.

[0038] Other examples of sustainable burner fuel may include, but are not limited to, algae oils.

[0039] Other examples of sustainable burner fuel may include, but are not limited to, oils obtained from the pyrolysis of sewage sludge or agricultural waste.

[0040] Other examples of sustainable burner fuel may include, but are not limited to, the following: liquid by-products of processing biogenic materials.

[0041] Other examples of sustainable burner fuel may include, but are not limited to, the following: liquids produced by hydrothermal liquefaction of biomaterials, rubber, plastics, or other waste materials.

[0042] Other examples of sustainable burner fuel may include, but are not limited to, the following: crude tall oils, tall oil rosin, tall oil pitch, or tall oil fatty acids (e.g., from papermaking processes).

[0043] Other examples of sustainable burner fuel may include, but are not limited to, the following: sustainable raw materials such as oils produced from recycled materials.

[0044] Other examples of sustainable burner fuel may include, but are not limited to, the following: oils derived from the pyrolysis of poor quality, discarded, or end-of-life tires.

[0045] Other examples of sustainable burner fuel may include, but are not limited to, oils derived from the pyrolysis of discarded or recycled plastics.

[0046] Other examples of sustainable burner fuel may include, but are not limited to, the following: oils derived from the pyrolysis of municipal solid waste.

[0047] Other examples of sustainable burner fuel may include, but are not limited to, the following: oils derived from the pyrolysis of biomass (bio-oil), e.g., from animals or plants (e.g., vegetables) or trees, or crushed biochar.

[0048] Other examples of sustainable combustion fuels may include, but are not limited to, recovered or recycled or green or other sustainably produced hydrogen and / or ammonia.

[0049] In the present invention, the burner fuel may comprise, consist of, consist essentially of, or comprise at least one burner fuel. sustainable burner. The weight percentage of sustainable burner fuel relative to the total weight percentage of burner fuel may be any value from 5 wt% to 100 wt%, for example from 10 wt% to 100 wt%, or from 20 wt% to 100 wt%, or from 30 wt% to 100 wt%, or from 40 wt% to 100 wt%, or from 50 wt% to 100 wt%, or greater than 50 wt%. Preferably, but not necessarily, in the present invention, at least a majority (in wt%) of the total burner fuel used in certain methods of the present invention is one or more sustainable burner fuels. Preferably, this amount is at least 60 wt%, or at least 65 wt%, or at least 70 wt%, or at least 75 wt% weight, or at least 80% by weight, or at least 85% by weight, or at least 90% by weight, for example from 51% by weight to 95% by weight, or from 60% by weight to 95% by weight weight, or from 65% by weight to 95% by weight, or from 70% by weight to 95% by weight, or from 75% by weight to 95% by weight, or from 60% by weight to 95% by weight, or from 60% by weight to 90% by weight, or from 60% by weight to 85% by weight, or from 60% by weight to 80% by weight, or from 60% by weight to 75% by weight, based on the total weight percentage of all burner fuels used.

[0050] For any portion of the burner fuel that is not a sustainable burner fuel, the remaining portion may be any conventional burner fuel used in carbon black manufacturing processes utilizing a carbon black reactor. For example, the conventional burner fuel portion, if present, may be a readily combustible gas, vapor, or liquid stream, such as natural gas, hydrogen, carbon monoxide, methane, acetylene, alcohol, or kerosene.

[0051] A mixture of at least two sustainable burner fuels may be used.

[0052] When two different burner fuels are used (e.g., a) at least two durable burner fuels or b) at least one durable burner fuel and one non-durable burner fuel, such as a conventional burner fuel, the different burner fuels may be introduced into the carbon black reactor as a mixture, or introduced separately, or introduced sequentially through the same feed line or any combinations thereof, and may optionally be introduced at different locations.

[0053] With respect to the raw material producing carbon black, this raw material may be a carbon black raw material traditionally used in furnace carbon black manufacturing processes ("traditional" carbon black raw materials).

[0054] Carbon black feedstocks typically belong to the family of settling or sludge oils, coal tars or coal tar distillate fractions, or ethylene or phenol cracking residues. Their distinguishing characteristics, compared to carbon black production in a typical furnace process, are described in more detail below.

[0055] The carbon black raw material may have one or more or all of the following properties: 1. a BMCI greater than 100 (e.g., greater than 101, greater than 102, greater than 103, greater than 104, greater than 105, greater than 110, greater than 115, greater than 120, greater than 130, greater than 140, greater than 150, greater than 160, greater than 170, e.g., 100.1 to 180, 100.5 to 180, 101 to 180, 102 to 180, 103 to 180, 104 to 180, 105 to 180, 110 to 180, 115 to 180, 120 to 180, 130 to 180, 140 to 180, from 150 to 180, from 160 to 180, from 100.1 to 175, from 100.1 to 170, from 100.1 to 165, from 110 to 175, from 115 to 175, from 120 to 175, from 125 to 170, from 130 to 170), and / or 2. a specific gravity greater than 1.02 (e.g., greater than 1.025, greater than 1.03, greater than 1.035, greater than 1.04, greater than 1.05, such as 1.021 to 1.3, or 1.025 to 1.3, or 1.03 to 1.3, or 1.05 to 1.3, or 1.07 to 1.25), and / or 3. an H:C atomic ratio of less than 1.23 (e.g., less than 1.22, less than 1.21, less than 1.2, less than 1.15, less than 1.1, less than 1.05, less than 1, less than 0.9, less than 0.8, e.g., 1.225 to 0.7, 1.225 to 0.8, 1.225 to 0.9, 1.225 to 1, 1.225 to 1.1, 1.22 to 0.7, 1.21 to 0.7, 1.2 to 0.7), and / or 4. a liquid at room temperature and pressure (e.g., 25°C and 1 atm).

[0056] The carbon black raw material may have all four of these properties (BMCI, H:C atomic ratio, density and liquid property) or three of the four properties, or two of the four properties, optionally.

[0057] Examples of carbon black feedstocks are shown in Table 2 below and include coal tars, liquids distilled from coal tars, settling or sludge oils obtained from catalytic cracking, and residual oils from ethylene cracking. As described in Table 2, these feedstocks have an H:C of less than 1.23, a specific gravity of greater than 1.02, and a BMCI value of greater than 100.

[0058] [Table 2]: Example of raw material Ethylene steam cracking residue Ethylene steam cracking residue Settling oil A Settling oil B Coal tar distillate H:C atomic 0.94 0.91 0.94 1.01 0.85 Density 1.07 1.08 1.10 1.11 1.14 BMCI 127 146 132 134 161 Sulfur content (wt%) 0.2 0.17 2.1 0.95 0.6 Flash point (°C) 70 86 130 90 90 Example of raw material Crude coal tar Settling oil CH:C atomic 0.72 1.01 Density 1.22 1.10 BMCI 179 163 Sulphur content (% by weight) 0.38 1.36 Flash point (°C)

[0059] The carbon black feedstock may be a liquid or a tarry, sticky amorphous solid at room temperature. For purposes of the present invention, liquid is based on ambient conditions of temperature (e.g., 25 degrees F) and atmosphere (e.g., 1 atm). "Rich in aromatic species" means that the feedstock contains a high amount of aromatic compounds. For example, a high amount of aromatic compounds is one where the total weight percent of aromatics present is at least 20 wt.% or the BMCI is greater than 100 or both. The carbon black feedstock may be heated so that the feedstock is in vapor form or partially in vapor form and may thus become, or be practically used as, an aromatic species-rich vapor.

[0060] Optionally, the sustainable burner fuel is substantially or completely consumed and combusted as fuel and no portion of the sustainable burner fuel is used as a feedstock for pyrolysis to form carbon black.

[0061] Optionally, less than 5%, for example less than 1% by weight, of sustainable burner fuel, based on the total weight of the carbon black producing feedstock, is available to form carbon black. Alternatively or additionally, the sustainable burner fuel is almost completely consumed (burned) as fuel and less than 1% by weight of the total sustainable burner fuel used in the process is subjected to pyrolysis to form carbon black.

[0062] The amount of sustainable burner fuel used may be an amount sufficient to increase the yield of carbon black formed from 1% to 8% (e.g., from 2% to 8% or from 3% to 7%, or from 2% to 6%) relative to a burner fuel consisting of 100% natural gas.

[0063] The amount of sustainable burner fuel may be an amount sufficient to increase the CO AN of the formed carbon black from 1% to 8% (e.g., from 2% to 8% or from 3% to 7%, or from 2% to 6%) relative to a burner fuel consisting of 100% natural gas.

[0064] Optionally, a portion of the carbon black feedstock may be a low-yield carbon black feedstock as described in WO 2023 / 055931, herein incorporated by reference in its entirety. The low-yield carbon black feedstock may comprise at least 1 wt%, or at least 5 wt%, or at least 10 wt%, or at least 25 wt%, or at least 50 wt%, or at least 75 wt%, or from about 1 wt% to 90 wt%, based on the total amount of carbon black feedstock used.

[0065] With respect to the process steps of the present invention, the process comprises the step of introducing into a carbon black reactor a burner fuel which comprises at least one sustainable burner fuel as described in the present description. The burner fuel may be introduced into the reactor through one or more axial or radial or tangential pipes and / or lances and / or injectors and / or other feed lines.

[0066] The method comprises igniting and forming a hot gas stream from the burner fuel in the carbon black reactor (e.g., a furnace carbon black reactor).

[0067] The "hot gas stream" may be considered a heated gas stream or a hot combustion gas stream. The hot gas stream may be generated by contacting the burner fuel with a suitable oxidant stream such as, but not limited to, air, oxygen, air-oxygen mixtures, or the like. In order to facilitate the generation of hot combustion gases, the oxidant stream may be preheated. The heated gas stream is essentially created by ignition or combustion of the fuel and / or oxidant. Temperatures ranging from about 1000 °C to about 3500 °C for the heated gas stream can be achieved.

[0068] The carbon black reactor is preferably a furnace carbon black reactor. In some embodiments, the carbon black reactor is a version of the furnace reactor called a multi-stage carbon black reactor (e.g., multi-stage carbon black reactor or multi-stage reactor). “Multi-stage” means that the feedstock is introduced or injected at several axial locations along the long axis of the furnace.

[0069] For purposes of this and other processes described herein, a multi-stage carbon black reactor may be used, such as those described in U.S. Patent No. 4,383,973, U.S. Patent No. 7,829,057, U.S. Patent No. 5,190,739, U.S. Patent No. 5,877,251, U.S. Patent No. 6,153,684, or U.S. Patent No. 6,403,695, all of which are incorporated herein by reference in their entirety.

[0070] Alternatively or additionally, the sustainable burner fuel may be used to generate hot combustion gases for a process such as that described in US 10519298, the entire contents of which are incorporated herein by reference, in which core particles produced in situ or introduced into a reactor as preformed coated particles are coated with a layer of carbon.

[0071] The general process of forming carbon black using the carbon black reactor, such as a multi-stage reactor, and obtaining hot gases suitable for forming carbon black are described in more detail in the referenced patents identified above which are incorporated by reference in the present invention and may be applied in the present invention with the modifications described in this specification.

[0072] Figures Figures 1A and 1B show a cross-sectional view of a carbon black reactor (50 in [Fig.1A] and 80 in [Fig.1B]) that may be used. In [Fig.1A], a stream of hot gases or hot combustion gases is generated in a combustion zone or combustion chamber 1 by contacting burner fuel in the form of a liquid or gaseous fuel vapor 9 with an oxidant stream 5, for example air, oxygen, or mixtures of air and oxygen (also referred to in the art as "oxygen-enriched air"). The burner fuel may be in the form of readily combustible gas, vapor, or liquid streams.

[0073] In the present invention, the combustion step may completely or almost completely consume the burner fuel. In other words, the combustion or oxidation reaction of the burner fuel may closely approach chemical equilibrium. Oxygen, fuel selection, burner design, jet velocities, mixing conditions and / or profiles, ratios of the fuel with air, oxygen-enriched air or pure oxygen, temperatures and / or other factors can be adjusted or optimized.

[0074] The hot gas stream or hot combustion gas stream flows downstream from zones 1 and 2 to zones 3 and 4. The carbon black feedstock is introduced at one or more locations appropriate to the other reactor components and feedstocks. Zone 2 of the combustion chamber may be the location where one or more carbon black feedstocks are introduced. In [Fig.lA], an injector 10 and / or an injector 6 may be used to introduce a carbon black feedstock into the reactor. Injector 10, for example, may introduce or inject a carbon black feedstock into the reactor. Alternatively, the carbon black feedstock may also be introduced into the chamber using an axial pipe or axial lance (shown as pipe or lance 63 in [Fig.lB]).Alternatively, the carbon black feedstock may be injected or introduced by more than one process simultaneously. The lance or other injector exposed to the reactor or combustion chamber may need to be cooled or protected from excessive heat in the combustion chamber by methods known in the art.

[0075] Optionally, another carbon black raw material (which may for example be the same or different from the carbon black raw material) may be introduced into the reactor zone 3 at the injection point 7 by the injector 6. Zones 3 and 4 are reaction zones and zone 8 is the quenching zone. Q represents the length of zone 4 before the quenching zone 8.

[0076] The carbon black feedstock may be injected into the flue gas stream via one or more nozzles designed for optimal distribution of the feedstock into the flue gas stream. These nozzles may be single-fluid or dual-fluid. Dual-fluid nozzles may use, for example, steam, air, or nitrogen to atomize the feedstock. Single-fluid nozzles may be atomized under pressure, or the feedstock may be injected directly into the gas stream. In the latter case, atomization occurs by the force of the gas stream.

[0077] The carbon black raw material may be injected by an axial injection lance or a central pipe may be used and / or one or more radial lances arranged around the circumference of the reactor in a plane perpendicular to the flow direction. A reactor may contain several planes with radial lances along the flow direction. Spray or injection nozzles may be arranged on the head of the lances by means of which the raw material is mixed with the flow of the heated gas stream.

[0078] [Fig. 1B] illustrates a cross-section of another example of a carbon black reactor in the furnace process, which may be used in the present invention. In this example, as in [Fig. 1A], an oxidant stream 51 is combined in a combustion chamber 55 with a burner or combustion fuel 52.

[0079] The hot combusted or partially combusted gas stream prepared in chamber 55 flows in direction A toward a constriction or contraction 64. The carbon black feedstock is introduced into the furnace carbon black reactor 80. The carbon black feedstock may be introduced using an optional center pipe 63, or a lance or injector or lance assembly 56, or via lances or injectors placed at or near the constriction 64 as indicated by 57. The carbon black feedstock may be introduced at one of these locations, or simultaneously at two of these locations at the same time, or at all three locations simultaneously. The manner and distribution of the first feedstock injection, when more than one of these locations is used, may be varied to alter the product properties and process economics.The injectors as well as the combustion chamber itself (or parts thereof) can be cooled as required by methods known in the art.

[0080] In [Fig. 1B], the length between the optional center pipe injector 63 and the middle of the contraction 64 is referred to as length 60. If this center pipe is used, this length is preferably from IX (times) to 10X the narrowest diameter of the first contraction 64. If the center pipe is used simultaneously with a set of injectors or lances 57 for the introduction of the carbon black feedstock, then the length 60 may be as indicated above or may be as little as 0. Adjustment of this length may allow for structural balancing and process economy. Height or diameter 54 is indicated for the combustion chamber and this height is greater than height or diameter 64 and height or diameter 64 may be at least 20%, at least 30%, at least 40%, at least 50% smaller than height or diameter 54.

[0081] After the introduction of the carbon black feedstock, the hot gas stream mixed with the feedstock enters a first reaction chamber 58. The function of the chamber is to provide a residence time so that the pyrolysis reactions that produce carbon black can complete an induction time and begin, and eventually, produce a population of seed particles for subsequent structure growth, as taught in U.S. Patent No. 7,829,057. The length of this chamber 66 may typically be from IX to 20X the narrowest diameter of the first contraction 64.

[0082] At the end of the first reaction chamber 58, additional carbon black feedstock may optionally be introduced. It may be introduced using an injector or network of injectors 59 positioned within or near a second contraction 65. Alternatively, it may be introduced with a lance substantially upstream of the contraction 65, but within the chamber 58.

[0083] After the introduction of additional carbon black feedstock, the mixture flows into a second reaction chamber 61. Quenching is then performed using a liquid or vapor cooling spray 62, as is known in the art. The length from the injection point 59 of the additional carbon black feedstock to the quenching location 62 is indicated by 67 in [Fig.lB]. This length is defined to provide a residence time that controls certain product properties as is known in the furnace process art.

[0084] Another arrangement introduces the carbon black feedstock at locations 63 and / or 56, then introduces another optional carbon black feedstock at locations 57 and / or 59, which can be done simultaneously if both locations are used.

[0085] In general, any of the carbon black feedstocks that are used in any of the processes of the present invention may be injected into a reactor by a single stream or a plurality of streams using injectors, which penetrate the interior regions of the hot flue gas stream. An injector can better ensure a high rate of mixing and shearing of the hot flue gas and the one or more carbon black feedstocks. This ensures that the feedstock is pyrolyzed and preferably at a rapid rate and / or with a high yield to form the carbon black of the present invention.

[0086] [Fig. 2] illustrates a specific example of a reactor that can be used to practice the invention, and was used to produce the examples described below.

[0087] The carbon black feedstock may be introduced at a single location in the reactor or at multiple locations in the reactor. The introduction of this feedstock may be accomplished by one or more pipes or injectors 83 at the reactor throttle 76. The reactor 90 includes a combustion chamber 74 having a larger diameter Dchamber 75, in the reactor 90 as depicted, for example, in [Fig. 2]. The burner fuel may be introduced by means of one or more locations upstream of the location where the carbon black feedstock is initially introduced. One or more pipes or injectors 71 may be the location where the burner fuel, or at least a portion thereof, is introduced into the combustion chamber 74. One or more pipes or injectors 72 may be the location where an oxidant (e.g., air or oxygen) may be introduced into the combustion chamber 74.

[0088] In one embodiment of the present invention, the carbon black feedstock is introduced at one location (e.g., 83) in the reactor or at multiple locations in the reactor. The option of introducing additional carbon black feedstock may be accomplished with one or more injectors (e.g., one or more metal pipes located on the reactor wall) that introduce the feedstock into the combustion chamber of the reactor, as described, for example, in Figures 1A and 1B. The injector may include an injector head or a spray head on the tip. The injector on the tip may include, for example, one or more holes (2 or 3 or 4 or more) around the tip (typically multiple holes evenly spaced apart).

[0089] Optionally, the introduction of any carbon black feedstock into the reactor and into the reaction stream may be such that the feedstock is introduced perpendicular to the lateral flow of the reaction stream through the reactor, as depicted, for example, in Figures 1A and 1B. Perpendicular may be plus or minus 15 degrees from a true perpendicular injection of the feedstock into the reaction stream.

[0090] Optionally, the introduction of the carbon black feedstock into the reactor may be made at a location having a narrower diameter than the diameter of the reactor at the location where the initial carbon black was previously introduced. This location may be considered a "choke" in some carbon black reactors. Figures 1A and 1B provide an example of this choke or choke zone in a reactor. This narrower diameter may have a diameter that is at least 10% smaller, at least 20% smaller, or at least 30% smaller, or 10% to 40% smaller than the diameter of the reactor into which the initial carbon black was previously introduced. In [Fig. 2], this is Dchamber 75 vs. Dthroat 76.

[0091] Once the raw materials (the initial carbon black raw material and any other optional carbon black raw materials) are combined with the reaction stream, the methods of the present invention generally include the quenching step of the reaction. In [Fig. 2], this is the quench spray 81. The reaction zone after the choke 76 is represented by 80 having the largest diameter Dreactor. Lquench indicates the length from the location where the carbon black raw material is introduced to the location where quenching occurs. Lquench is the length from the last optional introduction of carbon black raw material into the reactor to the quench spray 81.

[0092] The reaction is stopped in the quench zone of the reactor (see zone 8 in [Fig.lA]). As described in [Fig.lA], quench 8 is located downstream of reaction zone 4 and sprays a quenching fluid, such as water, into the stream of newly formed carbon black particles. In general, quenching serves to cool the carbon black particles and reduce the temperature of the gas stream and decrease the reaction rate. Q is the distance from the start of zone 4 to the quench point 8, and will vary depending on the position of the quench. Optionally, quenching may be multi-stage or occur at multiple points in the reactor. Pressure spray, gas atomized spray, or other quenching techniques may be used.With respect to the complete quenching of the reactions to form carbon black, any conventional means for effecting the quenching of the reaction downstream of the introduction of the raw materials producing carbon black may be used and is known to those skilled in the art. For example, a quenching fluid may be injected, which may be water or other fluids suitable for stopping the chemical reaction.

[0093] After quenching, the cooled gases and carbon black pass downstream to any conventional cooling and separation means by which the product is recovered. Separation of the carbon black from the gas stream is readily accomplished by conventional means such as a precipitator, cyclone separator, bag filter, or other means known to those skilled in the art. Once the carbon black is separated from the gas stream, the carbon black may optionally be subjected to a granulation step.

[0094] Optionally, one or more of the burner fuels and / or carbon black feedstocks or other components used in the processes of the present invention may be preheated prior to their introduction into the reactor. Suitable preheating temperatures and / or preheating techniques may be used in the present invention as described in, for example, U.S. Pat. No. 3,095,273 issued June 25, 1963 to Austin; U.S. Pat. No. 3,288,696 issued November 29, 1966 to Orbach; U.S. Pat. No. 3,984,528 issued October 5, 1976 to Cheng et al.; U.S. Pat. No. 4,315,901 issued February 16, 1982 to Cheng et al.; U.S. Pat. No. 4,765,964 issued August 23, 1988 to Gravley et al.; U.S. Patent No. 5,997,837 issued December 7, 1999 to Lynum et al.; U.S. Patent No. 7,097,822 issued August 29, 2006 to Godai et al.; U.S. Patent No. 8,871,173B2 issued October 28, 2014 to Nester et al.or CA 682982, all documents being incorporated herein by reference in their entirety.

[0095] Optionally, the method is carried out in the absence of at least one substance which is or contains at least one element of group IA or group IIA (or an ion thereof) of the periodic table.

[0096] Optionally, in any of the methods of the present invention, the method may comprise the step of introducing at least one substance which is or contains at least one Group IA or Group IIA element (or an ion thereof) of the periodic table. Preferably, the substance contains at least one alkali metal or alkaline earth metal. Examples include lithium, sodium, potassium, rubidium, cesium, francium, calcium, barium, strontium or radium, or combinations thereof. Any mixtures of one or more of these components may be present in the substance. The substance may be a solid, a solution, a dispersion, a gas or any combination thereof. More than one substance having the same or a different Group IA or Group IIA metal may be used.If more than one substance is used, the substances may be added together, separately, sequentially, or at different reaction locations. In the context of the present invention, the substances may be the metal (or metal ion) itself, a compound containing one or more of these elements, including a salt containing one or more of these elements, and the like. Preferably, the substance allows a metal or metal ion to be introduced into the reaction that is taking place to form the carbon black product. For the purposes of the present invention, preferably, the substance is introduced before quenching is completed as described above.For example, the substance may be added at any point before quenching is complete, including before the introduction of one or both of the carbon black-producing raw materials; during the introduction of any of the carbon black-producing raw materials; after the introduction of one or all of the carbon black-producing raw materials; or after the introduction of all of the raw materials but before quenching is complete. More than one point of introduction of the substance may be used. The amount of substance containing a Group IA or Group IIA metal may be any amount as long as a carbon black product can be formed.For example, the amount of the substance may be added in an amount such that 10 ppm or more, or 30 ppm or more, or 50 ppm or more, or 100 ppm or more, or 200 ppm or more of the Group IA or Group IIA element is present in the carbon black product finally formed. Other amounts include from about 200 ppm to about 5,000 ppm or more and other ranges may be from about 300 ppm to about 1,000 ppm, or from about 500 ppm to about 1,000 ppm of the Group IA or Group IIA element present in the carbon black product that is formed. These levels may be relative to the metal ion concentration. As indicated, these amounts of the Group IA or Group IIA element present in the carbon black product formed may be relative to one or more Group IA or Group IIA elements. and would therefore be a combined amount of the Group IA or Group IIA elements present in the carbon black product formed. The substance may be added in any manner, including by any conventional means. In other words, the substance may be added in the same way that a carbon black-producing feedstock is introduced. The substance may be added as a gas, liquid, or solid, or any combination thereof. The substance may be added at one point or multiple points and may be added as a single stream or a plurality of streams. The substance may be mixed with the feedstock, fuel, and / or oxidant before or during their introduction.

[0097] With respect to the carbon black formed by any of the methods of the present invention, the carbon black formed or produced may be any reinforcing or non-reinforcing grade of carbon black. Examples of reinforcing grades are N10, N121, N220, N231, N234, N299, N326, N330, N339, N347, N351, N358 and N375. Examples of semi-reinforcing grades are N539, N550, N650, N660, N683, N762, N765, N774, N787 and / or N990.

[0098] The carbon black may be a furnace black.

[0099] In some embodiments, the formed carbon black may have a biogenic carbon content of less than or equal to 2%, or less than 2%, such as, but not limited to, less than 1.75%, less than 1.5%, less than 1.25%, less than 1%, less than 0.75%, or 0.5% to 2%, 0.6% to 2%, 0.7% to 2%, 0.8% to 2%, 0.9% to 2%, 1% to 2%, 1.1% to 2%, 1.2% to 2%, 1.3% to 2%, 1.4% to 2%, 1.5% to 2%, 1.6% to 2%, 0.5% to 1.9%, 0.5% to 1.8%, 0.5% to 1.7%, 0.5% to 1.6%, 0.5% to 1.5%, 0.5% to 1.4%, 0.5% to 1.3%, 0.5% to 1.2%, 0.5% to 1.1%, 0.5% to 1%, 0.5% to 0.9%, 0.5% to 0.8%, 0.5% to 0.7%, where % is % by weight and relative to the total weight of carbon black. Measurement of biogenic carbon content may be carried out according to ASTM D6866.The possible low biogenic content can be achieved when the carbon black-forming raw material contains little (e.g., less than 5% by weight) or no raw material of sustainable bio-based origin.

[0100] Carbon black may be characterized by specific surface area, structure, aggregate size, shape and distribution; and / or chemical and physical properties of the surface. Carbon black properties are determined analytically by tests known to those skilled in the art. For example, nitrogen adsorption surface area and statistical thickness surface area (STSA), another measure of surface area, are determined by nitrogen adsorption according to test procedure ASTM D6556-10. Iodine value may be measured using procedure ASTM D-1510-13. The “structure” of carbon black describes the size and complexity of carbon black aggregates formed by the fusion of primary carbon black particles to each other. As used herein, the structure of carbon black can be measured by the oil absorption number (OAN) for unground carbon black, expressed as milliliters of oil per 100 grams of carbon black, according to the procedure described in ASTM D-2414-13. The oil absorption number of compressed samples (COAN) measures the portion of the carbon black structure that is not readily altered by the application of mechanical stress. COAN is measured according to ATSM D3493-13. Aggregate size distribution (ASD) is measured according to ISO method 15825 using disk centrifuge photosedimentometry with a BLDCP model manufactured by Brookhaven Instruments.

[0101] Carbon black materials having properties suitable for a specific application may be selected and defined by ASTM standards (see, for example, ASTM D 1765-03 Standard Classification System for Carbon Blacks Used in Rubber Products), Cabot Corporation specifications (see website www.cabot-corp.com), or other commercial grade specifications.

[0102] The carbon black may have any STSA, for example in the range of 5 m2 / g to 250 m2 / g, 11 m2 / g to 250 m2 / g, 20 m2 / g to 250 m2 / g or higher, for example, at least 70 m2 / g, for example 70 m2 / g to 250 m2 / g, or 80 m2 / g to 200 m2 / g or 90 m2 / g to 200 m2 / g, or 100 m2 / g to 180 m2 / g, 110 m2 / g to 150 m2 / g, 120 m2 / g to 150 m2 / g and the like. Optionally, the carbon black may have an iodine value (12 No) of about 5 to about 35 mg I2 / g of carbon black (according to ASTM D1510).

[0103] The carbon black particles described herein may have a BET surface area, measured by the Brunauer / Emmett / Teller (BET) technique according to ASTM procedure D6556, of from 5 m2 / g to 300 m2 / g, for example, between 50 m2 / g and 300 m2 / g, for example, between 100 m2 / g and 300 m2 / g. The BET surface area may be from about 100 m2 / g to about 200 m2 / g or from about 200 m2 / g to about 300 m2 / g.

[0104] The oil adsorption index (OAN) may be 40 ml / 100 g and 200 ml / 100 g, for example between 60 ml / 100 g and 200 ml / 100 g, for example between 80 ml / 100 g and 200 ml / 100 g, for example between 100 ml / 100 g and 200 ml / 100 g or between 120 ml / 100 g and 200 ml / 100 g, 140 ml / 100 g and 200 ml / 100 g, 160 and 200 ml / 100 g or for example between 40 ml / 100 g and 150 ml / 100 g or 40 ml / 100 g and 150 ml / 100 g.

[0105] The CO AN may be in the range of about 40 ml / 100 g to about 150 ml / 100 g, for example between about 55 ml / 100 g and about 150 ml / 100 g, for example between about 80 ml / 100 g and about 150 ml / 100 g, or between about 80 ml / 100 g and about 120 ml / 100 g.

[0106] The carbon black may be a carbon product containing silicon-containing species and / or metal-containing species and the like, which may be obtained by including the additional step of introducing such species with or in addition of one or both raw materials producing carbon black. The carbon black may be, for the purposes of the present invention, a multi-phase aggregate comprising at least one carbon phase and at least one metal-containing species phase or one silicon-containing species phase (also referred to as silicon-treated carbon black, such as Cabot Corporation's ECOBLACK™ materials).

[0107] As indicated, the carbon black may be a rubber black, and in particular a reinforcing grade of carbon black or a semi-reinforcing grade of carbon black.

[0108] Optionally, the carbon black of the present invention may include functional groups or chemical groups (e.g., derived from small molecules or polymers, ionic or non-ionic) that are directly bonded to the carbon surface (e.g., covalently bonded). Examples of functional groups that may be directly bonded (e.g., covalently) to the surface of the carbon black particles and methods for effecting the surface modification are described, for example, in U.S. Patent No. 5,554,739 issued to Belmont on September 10, 1996 and U.S. Patent No. 5,922,118 issued to Johnson et al. on July 13, 1999, incorporated herein by reference in their entirety.For illustration, a surface-modified carbon black that can be used herein is obtained by treating carbon black with diazonium salts formed by the reaction of sulfanilic acid or para-aminobenzoic acid (PABA) with HCl and NaNO2. Surface modification by sulfanilic acid or para-aminobenzoic acid processes using diazonium salts, for example, results in carbon black containing effective amounts of hydrophilic moieties on the carbon coating.

[0109] Carbon black may be surface modified in accordance with U.S. Patent No. 8,975,316 to Belmont et al., the contents of which are incorporated herein by reference in their entirety.

[0110] Other techniques that may be used to provide functional groups bound to the surface of carbon black are described in U.S. Patent No. 7,300,964, issued to Niedermeier et al., on November 27, 2007.

[0111] Oxidized (modified) carbon black may be prepared in a manner similar to that used on carbon black, as described, for example, in U.S. Patent No. 7,922,805 issued to Kowalski et al. on April 12, 2011, and in U.S. Patent No. 6,471,763 issued to Karl on October 29, 2002, and incorporated herein by reference in their entirety. An oxidized carbon black is a carbon black that has been oxidized using an oxidizing agent to introduce ionic and / or ionizable groups onto the surface. These particles may have a higher degree of oxygen-containing groups on the surface. Oxidizing agents include, but are not limited to, oxygen gas, ozone, peroxides such as hydrogen peroxide, persulfates, including sodium and potassium persulfate, hypohalites such as sodium hypochlorite, oxidizing acids such as nitric acid, and oxidants containing transition metals, such as permanganate salts, osmium tetroxide, chromium oxides, or ceric ammonium nitrate. Mixtures of oxidants may also be used, including mixtures of gaseous oxidants such as oxygen and ozone. Other surface modification processes, such as chlorination and sulfonylation, may also be used to introduce ionic or ionizable groups.

[0112] The present innovation is based in part on a currently recognized need to develop a class of carbon blacks that can be manufactured using a lower overall burnup (OAC). Overall burnup is defined as the percentage of oxygen added to the entire reactor relative to the total amount of oxygen required to react stoichiometrically with all of the fuel streams added to the entire reactor. By reducing the OAC while producing the same or essentially the same carbon black (based on parameters such as nitrogen surface area and / or CO AN), a higher efficiency operation and improved economics for the carbon black manufacturing process can be achieved and / or a more environmentally friendly carbon black manufacturing operation can be achieved.

[0113] Carbon black can be used in various applications, such as, for example, as reinforcement in rubber products, for example tire components.

[0114] Carbon black may be incorporated into rubber articles, being used, for example, for a tire tread, particularly in a tread for passenger car, light vehicle, truck and bus tires, off-road ("OTR") tires, aircraft tires and the like; an undertread; a thin wire coating; sidewalls; a toe rubber for retreaded tires; and other uses in tires.

[0115] In other applications, the particles may be used in industrial rubber articles, such as engine mounts, hydraulic mounts, bearings, seismic isolators, tank tracks, tank tracks or treads, mining conveyors, hoses, gaskets, seals, blades, weather stripping, bumpers or anti-vibration parts and the like.

[0116] Carbon black may be added instead of or in addition to first reinforcing agents for tire components and / or other industrial end uses of rubber. Carbon black may be combined with rubber natural and / or synthetic in a suitable dry or wet mixing process based on an internal batch mixer, continuous mixer or roller mill.

[0117] Alternatively, the carbon black may be blended with the rubber via a liquid masterbatch process. For example, a slurry containing the particles described herein may also be combined with elastomeric latex in a tank and then coagulated by the addition of a coagulant, such as an acid, using the techniques described in U.S. Patent No. 6,841,606.

[0118] The carbon black may be introduced in accordance with U.S. Patent No. 6,048,923, issued to Mabry et al. on April 11, 2000, incorporated herein by reference in its entirety. For example, a method for preparing an elastomer masterbatch may involve simultaneously introducing a particulate filler fluid and an elastomer latex fluid into a mixing zone of a coagulum reactor. A coagulum zone extends from the mixing zone, the cross-sectional area preferably gradually increasing in the downstream direction from an inlet end to an outlet end. The elastomer latex may be natural or synthetic and the particulate filler comprises, consists essentially of, or consists of the material as described above.The particulate filler is introduced into the mixing zone, preferably as a continuous high-velocity jet of injected fluid, while the latex fluid is introduced at a low velocity. The velocity, flow rate, and particulate concentration of the particulate filler fluid are sufficient to cause mixing with high shear of the latex fluid and flow turbulence of the mixture in at least an upstream portion of the coagulum zone so as to substantially completely coagulate the elastomeric latex with the particulate filler prior to the discharge end. Substantially complete coagulation can occur without the need for an acidic or saline coagulating agent. As described in U.S. Patent No. 6,075,084, incorporated herein by reference in its entirety, additional elastomer can be added to the material exiting the discharge end of the coagulum reactor. As described in U.S. PatentNo. 6,929,783, incorporated herein by reference in its entirety, the coagulum may then be introduced into a dewatering extruder. Other examples of suitable masterbatch processes are described in U.S. Patent No. 6,929,783 to Chung et al.; US Application 2012 / 0264875A1 to Berriot et al.; US Application 2003 / 0088006Al to Yanagisawa et al.; and EP Patent 1,834,985 B1 issued to Yamada et al.

[0119] Carbon black may be evaluated in a suitable rubber formulation, using natural or synthetic rubber. Appropriate amounts of carbon black to be used may be determined by routine testing, calculations, taking into account factors such as typical loadings of ASTM furnace blacks in comparable manufacturing processes, parameters specific to the techniques and / or equipment used, the presence or absence of other additives, the desired properties of the final product, etc.

[0120] The performance of carbon black as a reinforcing agent for rubber compounds may be evaluated by determining, for example, the performance of a rubber composition using the particles relative to the performance of a comparative rubber composition that is similar in all respects except for the use of a grade of carbon black suitable for the application in question. In other approaches, the values ​​obtained for compositions prepared according to the invention may be compared to values ​​known in the art associated with the desired parameters in a given application.

[0121] Suitable tests include green rubber tests, cure tests, and hardened rubber tests. Among the suitable green rubber tests, ASTM D4483 describes a test method for the Mooney ML1+4 viscosity test at 100°C. The scorch time is measured according to ASTM D4818.

[0122] The curing curve is obtained by a Rubber Process Analyzer (RPA2000) at 0.5°, 100 cpm and 150 °C (NR) - 160 °C (SBR) according to ASTM D5289.

[0123] The performance characteristics of the cured samples can be determined by a series of appropriate tests. Tensile strength, elongation at break, and stress at different strains (e.g., 100% and 300%) are all obtained by Method A of ASTM D412. Dynamic mechanical properties, including storage modulus, loss modulus, and tan δ, are obtained by a strain sweep test at 10 Hz, 60°C, and different strain amplitudes from 0.1% to 63%. Shore A hardness is measured according to ASTM D2240. Tear resistance of die type B cured rubber samples is measured according to ASTM D624.

[0124] The undispersed area is calculated by analyzing images obtained by optical microscopy in reflection mode for cured rubber compounds of a cross-sectional area cut according to different methods described. The dispersion can also be represented by the Z value (measured, after crosslinking, according to the method described by S. Otto et al in Kautschuk Gummi Kunststoffe, 58 Jahrgang, NR 7-8 / 2005, article entitled New Reference value for the description of Filler Dispersion with the Dispergrader 1000NT). ISO 11345 describes visual methods for the rapid and comparative evaluation of the degree of macrodispersion of carbon black and carbon black / silica in rubber.

[0125] Abrasion resistance is quantified as an index based on the abrasion loss of the cured rubber by the Cabot abrasion machine (Lamboum type). Interesting abrasion resistance results may be indicative of advantageous wear properties. Good hysteresis results may be associated with low rolling resistance (and therefore higher fuel economy) for automotive tire applications, reduced heat buildup, tire durability, tread life and casing life, fuel economy characteristics for the automotive vehicle, etc.

[0126] Iodine value (12 No.) is determined according to ASTM test procedure D1510. STSA (statistical thickness area) is determined based on ASTM test procedure D-5816 (measured by nitrogen adsorption). OAN is determined based on ASTM D2414 or D1765 (e.g., D1765-20). CO AN is determined based on ASTM D3493 (e.g., D3493-20).

[0127] Unless otherwise indicated, all proportions of materials expressed herein as percentages are by weight.

[0128] The present invention will become more clearly apparent from the following examples which are given by way of example only.

[0129] Examples

[0130] For the purposes of the present invention and the examples presented herein, the following explanation of certain terms is provided.

[0131] Overall Burnup (OAC): Overall burnup is defined as the percentage of oxygen added to the entire reactor relative to the total amount of oxygen required to react stoichiometrically with all fuel streams (burner fuel and carbon black producing feedstock) added to the entire reactor. For stoichiometric conditions, the OAC is 100%. When the mixture is fuel rich, the OAC is less than 100% and when it is fuel lean, it is greater than 100%. Carbon black production preferably occurs when the OAC is substantially fuel rich, generally less than 60 and more often less than 40.

[0132] Primary combustion ratio (PC) (also called burner combustion ratio): This ratio is the same as the OAC, except that it only considers the fuel and oxygen streams introduced into the burner (74 in [Fig. 2]). It does not include fuel or oxygen streams (such as 84 in [Fig. 2]) introduced downstream of the burner. The primary combustion ratio (PC) is generally fuel-lean, with values ​​typically in the range of 110 to 600%

[0133] Yield: Yield is the mass of solid carbon obtained per total mass of feedstock injected into the carbon black reactor, excluding the burner fuel used for the combustion chamber in [Fig.2], and the units are [kg C / kg feedstock]. Yield is equal to the total mass rate of solid carbon produced in the reactor divided by the total mass rate of feedstock, and is calculated based on flow rate and composition measurements reactor inlet and tail gas composition. In some cases, the yield may include sulfur, ash, and other components of the carbon black in addition to carbon, but for these examples, the yield includes only the carbon content of the carbon black.

[0134] Extractable with toluene (SP20), I2, STSA, OAN and COAN.

[0135] OAN and CO AN are analyzed on dry granules and according to the ASTM standards identified above. I2 index and STSA are analyzed on dry granules according to the ASTM methods identified above.

[0136] Reactor configuration and operation

[0137] Example 1

[0138] In Example 1, decanting oil was used as the carbon black feedstock (Table 6), and heavy TPO (Table 4) alone (100 wt. % TPO) or about 50 wt. % heavy TPO with about 50 wt. % natural gas (Table 5) was used as the burner fuel. For comparison, 100 wt. % natural gas (Table 5) was used as the burner fuel.

[0139] Each of these three burner fuel combinations was tested over a range of overall combustion flow (OAC) conditions as described in Table 7. All conditions tested had a process air flow rate of 1600 Nm3 / h and a process air inlet temperature of 500 °C. The burner burnup was 150% for all cases. The inlet temperature of the carbon black feedstock, decanter oil, was 190 °C for all conditions. Table 7 shows the flow parameters that were varied for each condition, including natural gas flow rate, heavy TPO flow rate, OAC, carbon black feedstock flow rate, potassium additive flow rate, quench water flow rate, and Lquench length distance.

[0140] Using a furnace carbon black manufacturing process, burner fuel and hot process air are combined in a combustion chamber to provide a hot flue gas stream, as described in [Fig.2]. The combustion chamber was lined with refractory and its internal diameter is shown in Table 3.

[0141] Natural gas, TPO burner fuels and hot process air were introduced into the burner (71 and 72) with flow conditions according to Table 7. The liquid heavy TPO was atomized, and then the TPO and natural gas were mixed and combusted via typical state-of-the-art combustion devices.

[0142] Then the burnt gas from the chamber flowed in a contraction so that it entered a narrower constriction (76 in [Fig.2]). At the level of the throttle, for all cases in the example, the carbon black feedstock was injected radially, positioned perpendicular to the burnt gas flow direction, towards the center of the reactor through injector 83 as described in [Fig.2].

[0143] The throttle was attached to a refractory-lined reactor chamber. The reactor chamber provided a residence time for the feedstock to complete its pyrolysis into carbon black particles. At a distance Lquench 79 downstream of the injection plane shown in [Fig. 2], a water spray was used for quenching, as is typical for furnace carbon black manufacturing processes (see Table 7 for details). Downstream of the quench, a filter was used to separate the carbon black particles from the tail gas stream. The carbon black at the filter was sampled for I2 absorption and toluene extractables (SP20). The carbon black was then pelletized and dried for STSA, OAN, and COAN measurements.

[0144] The filtered waste gas was sampled, its composition was measured for each condition and the yields were determined. [Tables 3] Dimension Description Units Value Dchamber Combustion chamber diameter cm 20.3 Dthroat Throat diameter cm 10.7 Dreactor Reactor diameter cm 34.3 Table 3. Dimensions in the reactor shown in [Fig.2] for Example 1

[0145] The heavy TPO used as burner fuel has been distilled by the supplier to achieve a flash point at a higher temperature for easier storage. The TPO used (Polimix 330) has the following properties / characteristics: [Tables 4] Properties Test Method Value Density at 15.5°C ASTM D-4052 0.9246 Sulfur, wt. % IP-336 0.830 Ash, wt. % ASTM D-482 0.008 Asphaltenes, wt. % IP-143 0.30 Carbon, wt. % 88.28 Nitrogen, wt. % ASTM D-3228 0.46 Hydrogen, wt. % 10.37 Extracted sediment, wt. % ASTM D-473 0.01 MJ / kg, crude ASTM D-240 43.10

[0146] Natural gas, when introduced into the combustion chamber of [Fig. 2], has an average composition measured as described in [Table 5] for the examples. The components were measured by gas chromatography. Component % in mo Nitrogen % 2.97 Oxygen % 0.00 Carbon dioxide % 0.06 Methane % 92.2 Ethane % 4.40 Propane % 0.32 Isobutane % 0.01 n-Butane % 0.01 Isopentane % 0.00 n-Pentane % 0.00 Hexanes % 0.00 Hydrogen % 0.00 Ethylene % 0.00

[0147] Table 5. Average composition of natural gas for experimental data.

[0148] The liquid decanting oil in these examples was as described in [Table 6] below (methods D-xxxx are established by ASTM International). METHOD TEST RESULT D-4052 Density at 15.5°C 1.0628 IP-336 Sulfur, wt. % 2 D-5291-02 Elemental Analysis, wt. % Carbon 89.38 Hydrogen 8.09 D-3228 Nitrogen, wt. % 0.21 Table 6. Properties of decanting oil raw material. [Paintings?] Natural gas flow rate (N m3 / h) Heavy TPO flow rate (kg / h) OAC Carbon black raw material flow rate (kg / h) Potassium additive (ppm of eNC MP) Quench water flow rate (kg / h) Quench distance (L quench) (ft) 109.7 0.0 26.0 503 40 475 14 109.7 0.0 28.0 460 40 1745 14 109.7 0.0 30.0 422 40 1816 10 59.7 47.1 26.0 511 40 479 14 59.7 47.1 28.0 467 40 1760 14 59.7 47.1 30.0 428 40 1833 10 0.0 103.5 26.0 519 40 484 14 0.0 103.5 28.0 474 40 1790 14 0.0 103.5 30.0 435 40 1864 10 0.0 103.5 28.0 474 10 1790 19 0.0 103.5 28.5 464 5 1809 19 0.0 103.5 27.5 485 10 1769 19 0.0 103.5 27.8 480 8 1779 19 Table 7. Operating conditions of example 1.

[0149] Results.

[0150] The results are shown in Figures 3-7 (Figures 5-7 only show data for the addition of 40 ppm potassium). Carbon black formed from the tests in which the burner fuel was 100 wt% heavy TPO (HTPO, squares; dotted line), or about 50 wt% HTPO with about 50 wt% natural gas (NG, triangles, dotted line) or 100 wt% NG (diamonds; solid line) was obtained and analyzed. The primary combustion rate was in all cases 150%. [Fig. 3] shows that to achieve a certain surface area (STSA), a lower OAC is required when the burner fuel was 100% HTPO or HTPO / NG 50 / 50 compared to NG alone. In other words, the present invention provides a carbon black having a specific surface area particular but produced using a lower OAC. A lower OAC normally results in a higher yield.

[0151] [Fig.4] shows that the carbon black yield for a given STSA was actually higher, as expected based on the lower OAC, when the burner fuel was 100% HTPO or 50% / 50% HTPO / NG compared to NG alone.

[0152] [Fig.5] shows that the CO AN for a given STSA was higher when the burner fuel was 100% HTPO or 50% / 50% HTPO / NG compared to NG alone. A higher structure (OAN and / or CO AN) often has a higher value for carbon black.

[0153] [Fig.6] shows that the shade at a given STSA was essentially the same when the burner fuel was 100% HTPO or 50% / 50% HTPO / NG versus NG alone.

[0154] [Fig.7] shows that the iodine number at a given STSA was essentially the same when the burner fuel was 100% HTPO or 50% / 50% HTPO / NG versus NG alone.

[0155] Example 2

[0156] In Example 2, decanting oil is used as the carbon black feedstock (Table 6), and a liquid bio-oil (product of fast pyrolysis of biomass) is used at about 75 wt% with 25 wt% natural gas as the burner fuel. For comparison, 100 wt% natural gas (Table 5) was used as the burner fuel.

[0157] Each of these burner fuel combinations is tested under a range of overall combustion flow (OAC) conditions as described in Table 9 using a process air flow rate of 1800 Nm3 / h and a process air inlet temperature of 500°C. The decanter oil carbon black feedstock inlet temperature is maintained at 175°C for all conditions. Table 9 shows the flow parameters that are varied for each condition, including natural gas flow rate, bio-oil flow rate, OAC, carbon black feedstock flow rate, potassium additive flow rate, quench water flow rate, and Lquench length distance.

[0158] Using a furnace carbon black manufacturing process, burner fuel and hot process air are combined in a combustion chamber to provide a hot flue gas stream, as described in [Fig. 2]. The combustion chamber is refractory lined and its internal diameters are: Dchamber = 20.3 cm, Dthroat = 11.43 cm, Dreactor = 45.7 cm.

[0159] Natural gas and bio-oil burner fuels and hot process air are introduced into the burner (71 and 72) with flow conditions in accordance with Table 9. The bio-oil is atomized, and the bio-oil and natural gas are mixed and combusted via typical state-of-the-art combustion devices.

[0160] Then, the flue gas from the chamber flows in a contraction so that it enters a narrower constriction (76 in [Fig.2]). At the constriction, for all cases in the example, the carbon black feedstock is injected radially, positioned perpendicular to the flue gas flow direction, toward the center of the reactor via injector 83 as described in [Fig.2].

[0161] The throttle is attached to a refractory-lined reactor chamber. The reactor chamber provides a residence time for the feedstock to complete its pyrolysis into carbon black particles. At a distance Lquench 79 downstream of the injection plane shown in [Fig. 2], a water jet is used for quenching, as is typical for furnace carbon black manufacturing processes (see Table 8 for details). Downstream of quenching, a filter is used to separate the carbon black particles from the waste gas stream.

[0162] A typical bio-oil contains less sulfur, more ash, and more water than the TPO used in Example 1. However, it may contain fewer asphaltenes, or even no asphaltenes. It generally contains more water than the TPO used in Example 1 and may therefore be denser by mass but have a lower energy density. [Tables 8] Natural gas flow rate (Nm 3 / h) Bio-oil flow rate (kg / h) Burn urPC (%) Bio-oil / NG (mass) OAC (%) Carbon black raw material flow rate (kg / h) Potassium additive (ppm of NC raw material) Quench water flow rate (kg / h) Quench distance (Lquench) (ft) 105 0 180 0 / 100 31 494 10 640 40 106 0 180 0 / 100 27 583 10 550 40 106 0 170 0 / 100 31 583 10 660 16 106 0 170 0 / 100 27 583 10 526 40 49.5 111 171 75 / 25 31 501 0 673 16 49.5 110 171 75 / 25 27 592 0 522 40 57.3 128 148 75 / 25 27 570 0 554 40 60.1 129 148 75 / 25 31 480 0 670 16 54.5 117 161 75 / 25 29 533 0 600 25 30 167 156 85 / 15 29 533 0 616 25 95 40 162 30 / 70 29 527 0 552 25 72 177 117 75 / 25 27 538 0 590 40 72 177 117 75 / 25 31 449 0 760 16 49.5 110 171 75 / 25 31 501 0 721 16 Table 8. Operating conditions of example 2.

[0163] It is expected that any water in the bio-oil will result in slightly lower efficiency than the natural gas control, but that the use of bio-oil will provide similar surface area (STSA) development as a function of overall combustion (OAC) compared to 100% natural gas.

[0164] The present invention comprises the following aspects / embodiments / features in any order and / or in any combination: 1. The present invention relates to a method for producing carbon black comprising introducing into a carbon black reactor a burner fuel comprising at least one sustainable burner fuel; igniting and forming a hot gas stream from said burner fuel in said reactor; introducing into the carbon black reactor at least one carbon black-producing raw material at one or more introduction points; combining at least one carbon black-producing feedstock with the hot gas stream to form carbon black in a reaction stream, and reaction quenching the reaction stream containing the carbon black, and recovering said carbon black. 2. A method according to any of the preceding or following embodiments / features / aspects, wherein the sustainable burner fuel(s) is one or more of the following: tire pyrolysis oil, plastic pyrolysis oil, vegetable-derived oil, oil derived from the pyrolysis of municipal solid waste, oil derived from the pyrolysis or decomposition of biomass (e.g., animal, plant, tree, fruit, or vegetable) or other agricultural waste, oil derived from the processing of papermaking byproducts, and / or other oil derived primarily from biomaterials or any combinations thereof. 3. A method according to any one of the preceding or following embodiments / features / aspects, wherein the burner fuel comprises at least 50% by weight of said at least one sustainable burner fuel, relative to the total weight of the burner fuel. 4. A method according to any one of the preceding or following embodiments / features / aspects, wherein the sustainable burner fuel(s) is tire pyrolysis oil (TPO). 5. A method according to any one of the preceding or following embodiments / features / aspects, wherein the burner fuel comprises at least 50% by weight of said TPO, based on the total weight of the burner fuel. 6. A method according to any one of the preceding or following embodiments / features / aspects, wherein the burner fuel comprises at least 70% by weight of said at least one sustainable burner fuel, based on the total weight of the burner fuel. 7. A method according to any one of the preceding or following embodiments / features / aspects, wherein said carbon black has a biogenic carbon content of less than 2% by weight. 8. A method according to any one of the preceding or following embodiments / features / aspects, wherein the ignition and formation substantially or completely consume the sustainable burner fuel. 9. A method according to any one of the preceding or following embodiments / features / aspects, wherein less than 5% or less than 1% by weight of sustainable burner fuel, based on the total weight of the carbon black producing feedstock, is available to form carbon black. 10. A method according to any one of the preceding or following embodiments / features / aspects, wherein the sustainable burner fuel is present in an amount sufficient to increase the yield of carbon black formed from 1% to 8% relative to a burner fuel consisting of 100% natural gas. 11. A method according to any one of the preceding or following embodiments / features / aspects, wherein the sustainable burner fuel is present in an amount sufficient to increase the CO AN of the formed carbon black from 1% to 8% relative to a burner fuel consisting of 100% natural gas. 12. A method according to any one of the preceding or following embodiments / features / aspects, wherein the TPO comprises heavy TPO. 13. A method according to any one of the preceding or following embodiments / features / aspects, wherein the TPO comprises heavy TPO. 14. A method according to any one of the preceding or following embodiments / features / aspects, wherein said recovered carbon black is carbon black of grade NI 10, N121, N220, N231, N234, N299, N326, N330, N339, N347, N351, N358, N375, N539, N550, N650, N660, N683, N762, N765, N774, N787 or N990. 15. Carbon black formed or produced from the process according to any of the preceding or following embodiments / features / aspects.

[0165] The present invention may comprise any combination of these different features or different embodiments above and / or below, as described herein in sentences and / or paragraphs. Any combination of the features described herein is considered part of the present invention and no limitation is intended with respect to the combinable features.

[0166] Applicants specifically incorporate the entire contents of all cited references into this specification. Furthermore, where an amount, concentration, or other value or parameter is given as a range, preferred range, or list of preferred upper and preferred lower values, this is to be understood as specifically indicating all ranges formed from any pair of any upper preferred range limit or value and any lower preferred range limit or value, regardless of whether the ranges are separately described. Where a range of numerical values ​​is herein referred to, unless otherwise indicated, the range is intended to include its endpoints, as well as all integers and fractions within the range.It is not intended that the scope of the invention be limited to the specific values ​​set forth when defining a range.

[0167] Other embodiments of the present invention will become apparent to those skilled in the art from reading this specification and practicing the present invention described herein. It is to be understood that this specification and the examples are to be considered as exemplary only, with the true scope and spirit of the invention being indicated by the following claims and their equivalents.

Claims

Claims

1. A method of producing carbon black, said method comprising: introducing into a carbon black reactor a burner fuel comprising at least one sustainable burner fuel; igniting and forming a hot gas stream from said burner fuel in said reactor; introducing into the carbon black reactor at least one carbon black-producing feedstock at one or more introduction points; combining at least one carbon black-producing feedstock with the hot gas stream to form carbon black in a reaction stream, and quenching the reaction stream containing the carbon black, and recovering said carbon black.

2. The method of claim 1, wherein the sustainable burner fuel(s) is one or more of the following: tire pyrolysis oil, plastic pyrolysis oil, vegetable-derived oil, oil derived from the pyrolysis of municipal solid waste, oil derived from the pyrolysis or decomposition of biomass or other agricultural waste, oil derived from the processing of papermaking by-products, and / or other oil derived primarily from biomaterials or any combinations thereof.

3. A method according to any preceding claim, wherein the burner fuel comprises at least 50% by weight of said at least one sustainable burner fuel, based on the total weight of the burner fuel.

4. A method according to any preceding claim, wherein the sustainable burner fuel(s) is tire pyrolysis oil (TPO).

5. A method according to any preceding claim, wherein the burner fuel comprises at least 50% by weight of said TPO, based on the total weight of the burner fuel.

6. A method according to any preceding claim, wherein the burner fuel comprises at least 70% by weight of said at least one sustainable burner fuel, based on the total weight of the burner fuel.

7. A method according to any preceding claim, wherein said carbon black has a biogenic carbon content of less than or equal to 2% by weight.

8. A method according to any preceding claim, wherein the ignition and formation substantially or completely consume the sustainable burner fuel.

9. A method according to any preceding claim, wherein less than 5% or less than 1% by weight of sustainable burner fuel, based on the total weight of the carbon black producing feedstock, is available to form carbon black.

10. A method according to any preceding claim, wherein the sustainable burner fuel is present in an amount sufficient to increase the yield of carbon black formed from 1% to 8% relative to a burner fuel consisting of 100% natural gas.

11. A method according to any preceding claim, wherein the sustainable burner fuel is present in an amount sufficient to increase the CO AN of the formed carbon black from 1% to 8% relative to a burner fuel consisting of 100% natural gas.

12. A method according to any preceding claim, wherein the TPO comprises heavy TPO.

13. A method according to any preceding claim, wherein the TPO comprises heavy TPO.

14. A method according to any preceding claim, wherein said recovered carbon black is a carbon black of grade NI 10, N121, N220, N231, N234, N299, N326, N330, N339, N347, N351, N358, N375, N539, N550, N650, N660, N683, N762, N765, N774, N787 or N990.

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