NL2038981B1

NL2038981B1 - Methods of producing carbon blacks using sustainable burner fuel and products made from same

Info

Publication number: NL2038981B1
Application number: NL2038981A
Authority: NL
Inventors: S Crocker David
Original assignee: Cabot Corp
Priority date: 2023-11-03
Filing date: 2024-11-01
Publication date: 2025-09-22
Also published as: NL2038981A; FR3155004A1; WO2025096703A1

Abstract

Title: METHODS OF PRODUCING CARBON BLACKS USING SUSTAINABLE BURNER FUEL AND PRODUCTS MADE FROM SAME Abstract Methods to produce carbon black utilizing a burner fuel that includes at least one sustainable burner fuel, such as, but not limited to, tire pyrolysis oil is described. Carbon blacks produced from these methods are further described. The advantages achieved With the methods are further described.

Description

P138313NL00

Title: METHODS OF PRODUCING CARBON BLACKS USING

SUSTAINABLE BURNER FUEL AND PRODUCTS MADE

FROM SAME

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

[0002] Carbon black has been used to modify the mechanical, electrical, and optical properties in compositions. Carbon blacks and other fillers have been utilized 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 relate to the manufacture of tires and additional ingredients often are 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, appearances and other properties in elastomeric compositions and other types of compositions.

[0003] The conventional and most common process for industrial production of carbon blacks is the furnace process. In this process, a first or primary liquid carbon-bearing feedstock, such as decant oil, is injected into a fuel-lean hot combusted or combusting gas stream. The hot combusted stream is formed by oxidizing a burner fuel, typically natural gas or coal gas or a liquid fuel similar to or the same as the primary feedstock, in air or oxygen enriched air or oxygen. Some of the feedstock pyrolyzes to make carbon black and byproducts (mostly hydrogen and carbon monoxide); the rest oxidizes to make CO», and HO. The conventional or traditional feedstock is decant oil, slurry oil, coker oil, a coal tar derivative, or a heavy

Liquid residue from an ethylene cracker process. These carbon black feedstocks are typically simultaneously heavy (specific gravity > 1.02), have an atomic H:C ratio of less than 1.23, are rich in aromatics (Bureau of Mines

Correlation Index (BMCI) > 100), and are liquids at room temperature and pressure (e.g., 25 °C at 1 atm). Hydrogen and carbon amounts may be measured according to ASTM D5291 or equivalent methods. They are all generally derived from fossil fuels.

[0004] The furnace black process differs from the channel black process and thermal black process, both of which use natural gas as a feedstock.

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

[0006] Thus, there is a need in the industry to provide a solution to being able to use (to allow the use of) large amounts of sustainable material in an existing carbon black furnace process, and yet produce carbon blacks that are comparable to carbon blacks formed from traditional burner fuel and primary feedstock (e.g., produce carbon blacks with acceptable yields and/or with high surface areas, and/or high structures). One way to do this is to use sustainable materials as the burner fuel, (where at least a majority of the total burner fuel is a sustainable burner fuel). It saves large capital and development resources to use these sustainable burner fuels in an existing furnace process, instead of developing, designing, and building a new process to use them.

[0007] All of the patents and publications mentioned throughout are incorporated in their entirety by reference herein.

SUMMARY OF THE PRESENT INVENTION

[0008] A feature of the present invention is to provide methods to prepare or produce carbon black utilizing burner fuels that include 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] A further feature is to provide a method to produce carbon blacks utilizing conventional carbon black forming feedstocks along with burner fuels that include at least one sustainable burner fuel.

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

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

[0013] Further, the present invention, in part, relates to, carbon black(s) where at least a portion or at least a majority of the burner fuel that is utilized is sustainable burner fuel in the process to form the carbon black.

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

[0015] It 1s to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are intended to provide a 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 DRAWINGS

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

[0018] FIG. 1B 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 a further example of a reactor suitable for preparing the carbon black of the present invention.

[0020] FIG. 3 is a graph plotting OAC (%) and STSA (in m#/g) for two examples of the present invention and one comparative example with different burner fuels utilized.

[0021] FIG. 4 is a graph plotting dimensionless Yield and STSA (in m%/g) for two examples of the present invention and one comparative example with different burner fuels utilized.

[0022] FIG. 5 is a graph plotting COAN and STSA (in m?/g) for two examples of the present invention and one comparative example with different burner fuels utilized.

[0023] FIG. 6 is a graph plotting Tint and STSA (in m2/g) for two 5 examples of the present invention and one comparative example with different burner fuels utilized.

[0024] FIG. 7 is a graph plotting Iodine Number and STSA (in m?/g) for two examples of the present invention and one comparative example with different burner fuels utilized.

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, can be or include, for example, what are sometimes referred to as circular materials or recycled materials or can be referred to as ‘sustainable’ materials and/or fuels from biological sources. Examples of the burner fuels that can be used are described in detail below.

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

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

[0028] With the methods of the present invention, not only can large amounts of sustainable burner fuel be used as the burner fuel, there is no sacrifice with regard to the quality of carbon black produced. Thus, the methods of the present invention utilize sustainable burner fuels that are more desirable to use for environmental reasons and/or other reasons, and yet produce carbon blacks that are at least comparable to, if not better than,

carbon blacks produced using 100 % traditional burner fuels in furnace carbon black processes.

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

[0030] The sustainable burner fuel can be a fuel derived from what is considered to be sustainable, biological, and/or recycled sources. For example, the sustainable burner fuel can be or include ethylene, a gas at room temperature and pressure. The ethylene can be produced from bio-sourced ethanol, e.g., from corn fermentation or other plant material fermentations. Alternatively or in addition, the sustainable burner fuel can be an oil derived from hydrothermal liquefaction (HTL) of biomass or tire, plastics or other waste materials.

[0031] The sustainable burner fuel, for purposes of the present invention, can 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 that is other than coal tar liquid, an oil-refinery liquid, or an ethylene cracker residue.

[0032] Other examples of sustainable burner fuel can include, but are not limited to, the following: a tire pyrolysis oil, a plastic pyrolysis oil, a plant-derived oil, a tree-derived oil, an oil derived from pyrolysis municipal solid waste, an oil derived from the pyrolysis or decay of biomass (e.g., animal, plant, tree or vegetable), or other agricultural waste, an oil derived from the processing of paper production byproducts, and/or another oil sourced primarily from biomaterials or any combinations thereof. These

Liquid feedstocks have an atomic H:C ratio of greater than 1.23, or a specific gravity less than 1.02, or a BMCI value less than 100. Specific examples of liquid sustainable burner fuels are presented in Table 1 below:

Table 1:

Feedstock Bolder 350 Tire | Delta Energy DE-Solv | Soybean | Corn | Peanut

Specific 1.00 0.94 0.93 0.92 {091

Sulfur 1.08 1.03 0 0 0

Content = " [Il

Flash Point 32 >110 321 | 315 oon DOP

[0033] Other examples of sustainable burner fuel can include, but are not limited to, the following: a sustainable feedstock, a bio-sourced or bio-based feedstock, and/or other byproduct of a refining process, or any combinations thereof.

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

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

[0036] Other examples of sustainable burner fuel can include, but are not limited to, the following: plant- or animal-produced waxes and resins, such as lanolin or lac.

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

[0038] Other examples of sustainable burner fuel can include, but are not limited to, the following: algal oils.

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

[0040] Other examples of sustainable burner fuel can include, but are not limited to, the following: byproduct Liquids from processing of biogenic materials.

[0041] Other examples of sustainable burner fuel can include, but are not limited to, the following: liquids produced by hydrothermal liquefaction of biomaterial, rubber, plastics or other wastes

[0042] Other examples of sustainable burner fuel can 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 paper making processes).

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

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

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

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

[0047] Other examples of sustainable burner fuel can include, but are not limited to, the following: oils derived from the pyrolysis of biomass (bio-o1l), e.g., animals or plants (e.g., vegetable) or trees, or milled biochar.

[0048] Other examples of sustainable burner fuel can 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 can comprise, consists of, consists essentially of, or include at least one sustainable burner fuel. The wt.% of the sustainable burner fuel based on the total wt.% of burner fuel can be anywhere from 5 wt.% to 100 wt.%, such as 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 over 50 wt.%. Preferably, but not required, in the present invention, at least a majority (by wt.%) of the total burner fuel utilized in some 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.%, or at least 80 wt.%, or at least 85 wt.%, or at least 90 wt.%, such as from 51 wt.% to 95 wt.%, or from 60 wt.% to 95 wt.%, or from 65 wt.% to 95 wt.%, or from 70 wt.% to 95 wt.%, or from 75 wt.% to 95 wt.%, or from 60 wt.% to 95 wt.%, or from 60 wt.% to 90 wt.%, or from 60 wt.% to 85 wt.%, or from 60 wt.% to 80 wt.%, or from 60 wt.% to 75 wt.%, based on total weight percent of all burner fuels utilized.

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

[0051] A mixture of two or more sustainable burner fuels can be used.

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

[0053] With respect to the carbon black yielding feedstock, this feedstock can be a carbon black feedstock traditionally used in furnace carbon black processes (‘traditional’ carbon black feedstocks).

[0054] The carbon black feedstocks are typically from the family of decant or slurry oils, coal tars or coal tar distillate fractions, or ethylene or phenol cracker residues. Their defining characteristics, with respect to carbon black production in a typical furnace process are discussed further below.

[0055] The carbon black feedstock can have one or more or all of the following properties: 1) a BMCI of 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, such as from 100.1 to 180, from 100.5 to 180, from 101 to 180, from 102 to 180, from 103 to 180, from 104 to 180, from 105 to 180, from 110 to 180, from 115 to 180, from 120 to 180, from 130 to 180, from 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 of 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 from 1.021 to 1.3, or from 1.025 to 1.3, or from 1.03 to 1.3, or from 1.05 to 1.3, or from 1.07 to 1.25), and/or 3) an atomic H:C 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, such as from 1.225 to 0.7, from 1.225 to 0.8, from 1.225 to 0.9, from 1.225 to 1, from 1.225 to 1.1, from 1.22 to 0.7, from 1.21 to 0.7 from 1.2 to 0.7), and/or 4) aliquid at room temperature and pressure (e.g., 25 deg C and 1 atm).

[0056] The carbon black feedstock can have all of these four properties (BMCI, atomic H:C ratio, specific gravity and liquid property) or three of the four properties, or two of the four properties, as an option.

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

[0058] Table 2:

Ethylene Ethylene

Feedstock Decant | Decant | Coal Tar

Steam Cracker | Steam Cracker | _ oo

Example OlA | OilB | Distillate

Residue Residue

Atomic 0.94 0.91 0.94 1.01 0.85

H:C

Specific 1.07 1.08 1.10 1.11 1.14

Gravity

Sulfur

Content 0.2 0.17 2.1 0.95 (wt.%)

Flash 70 86 130 90

Point (°C)

Feedstock Crude Decant

Example Coal Tar | Oil C

Sulfur Content 0.38 1.36 (wt.%)

[0059] The carbon black feedstock can be a liquid or a tarry, pitch-like amorphous solid at room temperature. For purposes of the present invention, the liquid is based on room temperature (e.g., 25 deg F) and atmosphere (e.g., 1 atm) conditions. “Rich in aromatic species” means that the feedstock has a high amount of aromatic compounds present. For instance, a high amount of aromatic compounds is where the total weight percent of aromatics present is at least 20 wt.% or has a BMCI of greater than 100 or both. The carbon black feedstock can be heated so that the feedstock is in vapor form or partially vapor form and thus can become, or be used in practice as, a vapor rich In aromatic species.

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

[0061] As an option, less than 5 %, for example, less than 1 wt.%, sustainable burner fuel, based on total weight of the carbon black yielding feedstock, is available to form carbon black. Alternatively or in addition, the sustainable burner fuel is almost totally consumed (combusted) as a fuel and less than 1 wt.% of the total sustainable burner fuel utilized in the process is subjected to pyrolysis to form carbon black.

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

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

[0064] As an option, a portion of the carbon black feedstock can be a low-yielding carbon black feedstock as described in WO 2023/055931, incorporated in its entirety by reference herein. The low-yielding carbon black feedstock can 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 method steps of the present invention, the method includes the step of introducing into a carbon black reactor a burner fuel that includes at least one sustainable burner fuel as described herein.

The burner fuel can be introduced into the reactor by one or more axial or radial or tangential pipes and/or lances and/or injectors and/or other feed lines.

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

[0067] The ‘stream of hot gases’ can be considered a heated gas stream or a stream of hot combustion gases. The stream of hot gases can be generated by contacting the burner fuel with a suitable oxidant stream such as, but not limited to, air, oxygen, mixtures of air and oxygen, or the like. To facilitate the generation of hot gases, the oxidant stream may be preheated.

Essentially, the heated gas stream is created by igniting or combusting the fuel and/or oxidant. Temperatures such as from about 1000 deg C to about 3500 deg C for the heated gas stream can be obtained.

[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 staged carbon black reactor (e.g., multi-stage carbon black reactor or multi-stage reactor). “Staged” means that feedstock is introduced or injected at more than one axial location along the long axis of the furnace.

[0069] For purposes of this method as well as the other methods described herein, a multi-stage carbon black reactor can be used such as the ones 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 in their entirety by reference herein.

[0070] Alternatively or in addition, the sustainable burner fuel may be used to generate hot combustion gases for a process such as that disclosed in

US10519298, 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 through the carbon black reactor, such as a multi-stage reactor, and achieving appropriate hot gases to form carbon black are further described in the above-identified referenced patents which are incorporated by reference herein and can be applied in the present invention with the changes described herein.

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

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

[0074] The stream of hot gases or the hot combustion gas stream flows downstream from zones 1 and 2 into zones 3 and 4. The carbon black feedstock is introduced at one or more suitable locations relative to other reactor components and feeds. Zone 2 of the combustion chamber can be the location where one or more carbon black feedstocks are introduced. In FIG. 1A, an injector 10 and/or injector 6 can be used to introduce carbon black feedstock into the reactor. Injector 10, for instance, can introduce or inject a carbon black feedstock into the reactor. As an alternative, the carbon black feedstock may also be introduced into the chamber using an axial pipe or lance (shown as pipe or lance 63 in FIG. 1B). As a further alternative, the carbon black feedstock may be injected or introduced by multiple methods simultaneously. The lance or any 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] As an option, a further carbon black feedstock (e.g., that can be the same or different from the carbon black feedstock) can be introduced to reactor zone 3 at injection point 7 by injector 6. Zones 3 and 4 are reaction zones and zone 8 is the quench zone. Q represents the length of zone 4 prior to the quench zone 8.

[0076] The carbon black feedstock can be injected into the combustion gas stream through one or more nozzles designed for optimal distribution of the feedstock into the combustion gas stream. Such nozzles may be either single or bi-fluid. Bi-fluid nozzles may use, for example, steam, air, or nitrogen to atomize the feedstock. Single-fluid nozzles may be pressure atomized or the feedstock can be directly injected into the gas-stream. In the latter instance, atomization occurs by the force of the gas-stream.

[0077] The carbon black feedstock may be injected by an axial injection lance or a central pipe can be used and/or one or more radial lances arranged on 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 can be arranged on the head of the lances by means of which the feedstock is mixed into 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 can 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 the chamber 55 flows in direction A toward a throat or contraction 64. The carbon black feedstock is introduced to the furnace carbon black reactor 80.

The carbon black feedstock can be introduced using an optional central pipe 63, or a lance or injector or set of lances 56, or via lances or injectors placed at or near the throat 64 as indicated by 57. The carbon black feedstock can be introduced at one of these locations, or simultaneously in two of these locations at the same time, or in all three locations simultaneously. The manner and division of the first feedstock injection, when more than one location is used, among these locations can be varied to modify product properties and process economics. Injectors as well as the combustion chamber itself (or portions thereof), may be cooled as needed by methods known in the art.

[0080] In FIG. 1B, the length between the optional central pipe injector 63, and the middle of the contraction 64, is labeled as length 60. If this central pipe is used, this length is preferably from 1x (times) to 10x the narrowest diameter of the first contraction 64. If the central pipe is used simultaneously with an injector or lance array 57 for the introduction of the carbon black feedstock, then length 60 can be as stated above or may be as small as 0. Adjusting this length may allow balancing of structure and process economics. Height or diameter 54 is shown for the combustion chamber and this height is more than the height or diameter 64 and the height or diameter 64 can be at least 20 %, at least 30 %, at least 40 %, at least 50 % smaller than height or diameter 54.

[0081] Following the introduction of the carbon black feedstock, the hot gas stream mixed with the feedstock enters a first reaction chamber 58. The purpose of the chamber is to provide residence time so that pyrolysis reactions that produce carbon black may complete an induction time and begin, and optionally, to produce a seed particle population for later structure growth as taught in U.S. Patent No. 7,829,057. The length of this chamber 66 can be typically from 1x to 20x the narrowest diameter of the first contraction 64.

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

[0083] After introduction of any further carbon black feedstock, the mixture flows into a second reaction chamber 61. It is then quenched using a cooling spray of liquid or vapor 62, as is known in the art. The length from the further carbon black feedstock’s injection point 59 to quench location 62 is labeled as 67 in FIG. 1B. This length is set to provide a residence time that controls certain product properties as is known in the art of the furnace process.

[0084] An alternative arrangement introduces the carbon black feedstock at locations 63 and/or 56, and then introduces any further carbon black feedstock at locations 57 and/or 59, which can be simultaneously if both locations are used.

[0085] Generally, any of the carbon black feedstocks that are utilized in any of the methods of the present invention can be injected into a reactor by a single stream or a plurality of streams using injectors, which penetrate into the interior regions of the hot combustion gas stream. An injector can better ensure a high rate of mixing and shearing of the hot combustion gases and the carbon black feedstock(s). This ensures that the feedstock pyrolyzes and preferably at a rapid rate and/or high yield to form the carbon black of the present invention.

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

[0087] The carbon black feedstock can be introduced at one location in the reactor or at multiple locations in the reactor. The introducing of this feedstock can be done with one or more pipes or injectors 83 at the throat of the reactor 76. The reactor 90 has a combustion chamber 74 having a largest diameter Dehamber 75, In the reactor 90 as, for instance, shown in

FIG. 2. The burner fuel can be introduced by way of one or more locations upstream of where the carbon black feedstock is initially introduced. One or more pipes or injectors 71 can be where the burner fuel, or at least a portion thereof, is introduced into the combustion chamber 74. One or more pipes or injectors 72 can be where an oxidant (e.g., air or oxygen) can 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 of any further carbon black feedstock can be done with one or more injectors (e.g., a metal pipe(s) located on the wall of the reactor) which introduce the feedstock in the combustion chamber of the reactor, as for instance, shown in FIGS. 1A and 1B. The injector can have an injector head or spray head on the tip. The injector on the tip can have, for instance, one or multiple holes (2 or 3 or 4 or more) around the tip (generally evenly spaced multiple holes).

[0089] As an option, the introduction of the any carbon black feedstock into the reactor and into the reaction stream can be such that the feedstock is introduced perpendicular to the lateral flow of the reaction stream through the reactor, as for instance shown in FIGS. 1A and 1B.

Perpendicular can be plus or minus 15 degrees from a true perpendicular injection of the feedstock into the reaction stream.

[0090] As an option, the introduction of the any carbon black feedstock into the reactor can be at a location that has a narrower diameter than the diameter of the reactor where the initial carbon black was earlier introduced. This location can be considered a ‘throat’ in some carbon black reactors. FIGS. 1A and 1B provide an example of this throat or throat area in a reactor. This narrower diameter can have a diameter that is at least % smaller, at least 20 % smaller, or at least 30 % smaller, or from 10 % to 40 % smaller than the diameter of the reactor where the initial carbon black was earlier introduced. In FIG. 2, this is Daamber 75 vs. Dihroat 76. 10 [0091] After the feedstocks (the initial carbon black feedstock and any optional further carbon black feedstock) are combined with the reaction stream, the methods of the present invention generally include the step of quenching the reaction. In FIG. 2 this is Quench spray 81. The reaction zone, after throat 76 is shown as 80 have a largest diameter of Dreactor.

Lquench shows the length from where the carbon black feedstock 1s introduced to where quenching occurs. Lguench 18 the length from the last optional introduction of carbon black feedstock to the reactor until the quench spray 81.

[0092] The reaction is arrested in the quench zone of the reactor (see zone 8 of FIG 1A). As shown in FIG. 1A, quench 8 is located downstream of the reaction zone 4 and sprays a quenching fluid, such as water, into the stream of newly formed carbon black particles. In general, the quench serves to cool the carbon black particles and to reduce the temperature of the gaseous stream and decrease the reaction rate. Q is the distance from the beginning of reaction zone 4 to quench point 8, and will vary according to the position of the quench. Optionally, quenching may be staged, or take place at several points in the reactor. A pressure spray, a gas-atomized spray or other quenching techniques also can be utilized. With respect to completely quenching the reactions to form the carbon black, any conventional means to quench the reaction downstream of the introduction of the carbon black yielding feedstocks can be used and is known to those skilled in the art. For instance, a quenching fluid can be injected which may be water or other suitable fluids to stop the chemical reaction.

[0093] After quenching, the cooled gases and carbon black pass downstream into any conventional cooling and separating means whereby the product is recovered. The separation of the carbon black from the gas stream 1s readily accomplished by conventional means such as a precipitator, cyclone separator, bag filter or other means known to those skilled in the art. After the carbon black is separated from the gas stream, the carbon black can be optionally subjected to a pelletization step.

[0094] As an option, any one or more of the burner fuels and/or carbon black feedstocks or other components used in the methods of the present invention can be pre-heated prior to introduction into the reactor. Suitable pre-heating temperatures and/or pre-heating techniques can be used in the present invention as set forth in, for example, in U.S. Patent No. 3,095,273 1ssued on June 25, 1963 to Austin; U.S. Patent No. 3,288,696 issued on

November 29, 1966 to Orbach; U.S. Patent No. 3,984,528 issued on October 5, 1976 to Cheng et al.; U.S. Patent No. 4,315,901, issued on February 16, 1982 to Cheng ef al.; U.S. Patent No. 4,765,964 1ssued on August 23, 1988 to

Gravley et al.; U.S. Patent No. 5,997,837 issued on December 7, 1999 to

Lynum et al. U.S Patent No. 7,097,822 issued on August 29, 2006 to Godal et al.; U.S. patent No. 8,871,173B2, issued on October 28, 2014 to Nester et al. or CA 682982, all documents being incorporated herein by reference in their entirety.

[0095] As an option, the method is conducted in the absence of at least one substance that is or that contains at least one Group IA or Group ITA element (or ion thereof) of the Periodic Table.

[0096] As an option, in any of the methods of the present invention, the method can include the step of introducing at least one substance that is or that contains at least one Group IA or Group IIA element (or 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 can be present in the substance. The substance can be a solid, solution, dispersion, gas, or any combinations thereof. More than one substance having the same or different Group IA or Group IIA metal can be used. If multiple substances are used, the substances can be added together, separately, sequentially, or in different reaction locations. For purposes of the present invention, the substance can 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 is capable of introducing a metal or metal ion into the reaction that is ongoing to form the carbon black product. For purposes of the present invention, preferably, the substance is introduced prior to the complete quenching as described above. For instance, the substance can be added at any point prior to the complete quenching, including prior to the introduction of one or both of the carbon black yielding feedstocks; during the introduction of any of the carbon black yielding feedstocks; after the introduction of any or all of the carbon black yielding feedstocks; or after the introduction of the all of the feedstocks but prior to the complete quenching.

More than one point of introduction of the substance can be used. The amount of the Group IA or Group IIA metal containing substance can be any amount as long as a carbon black product can be formed. For instance, the amount of the substance can 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 ultimately formed. Other amounts include from about 200 ppm to about 5000 ppm or more and other ranges can be from about 300 ppm to about 1000 ppm, or from about 500 ppm to about 1000 ppm of the

Group IA or Group ITA element present in the carbon black product that is formed. These levels can be with respect to the metal ion concentration. As stated, these amounts of the Group IA or Group IIA element present in the carbon black product that is formed can be with respect to one element or more than one Group IA or Group IIA element and would be therefore a combined amount of the Group IA or Group IIA elements present in the carbon black product that is formed. The substance can be added in any fashion including any conventional means. In other words, the substance can be added in the same manner that a carbon black yielding feedstock 1s introduced. The substance can be added as a gas, liquid, or solid, or any combination thereof. The substance can be added at one point or several points and can be added as a single stream or a plurality of streams. The substance can be mixed in with the feedstock, fuel, and/or oxidant prior to 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 can be any reinforcing or non-reinforcing grade of carbon black. Examples of reinforcing grades are N110, N121, N220, N231, N234, N299, N326, N330, N339, N347,

N351, N358, and N375. Examples of semi-reinforcing grades are N539,

Nb550, N650, N660, N683, N762, N765, N774, N787, and/or N990.

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

[0099] In certain embodiments, the carbon black formed may have a biogenic carbon content of 2 % or less, 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 from 0.5 % to 2 %, from 0.6 % to 2 %, from 0.7 % to 2 %, from 0.8 % to 2 %, from 0.9 % to 2 %, from 1 % to 2 %, from 1.1 % to 2 %, from 1.2 % to 2 %, from 1.3 % to 2 %, from 1.4 % to 2 %, from 1.5 % to 2 %, from 1.6 % to 2 %, from 0.5 % to 1.9 %, from 0.5 % to 1.8 %, from 0.5 % to 1.7 %, from 0.5 % to 1.6 %, from 0.5 % to 1.5 %, from 0.5 % to 1.4 %, from 0.5% to 1.3%, from 0.5 % to 1.2 %, from 0.5 % to 1.1 %, from 0.5 % to 1 %,

from 0.5 % to 0.9 %, from 0.5 % to 0.8 %, from 0.5 % to 0.7 %, where % is % by weight and based on total weight of carbon black. The biogenic carbon content measurement can be made according to ASTM D6866. The optional low biogenic content is obtainable when the carbon black forming feedstock contains low (e.g., below 5 wt.%) or no sustainable biologically derived feedstock material.

[0100] The carbon black can be characterized by specific surface area, structure, aggregate size, shape, and distribution; and/or chemical and physical properties of the surface. The properties of carbon black are analytically determined by tests known to the art. For example, nitrogen adsorption surface area and Statistical Thickness Surface Area (STSA), another measure of surface area, are determined by nitrogen adsorption following ASTM test procedure D6556-10. The Iodine number can be measured using ASTM procedure D-1510-13. Carbon black “structure” describes the size and complexity of aggregates of carbon black formed by the fusion of primary carbon black particles to one another. As used here, the carbon black structure can be measured as the oil absorption number (OAN) for the uncrushed carbon black, expressed as milliliters of oil per 100 grams carbon black, according to the procedure set forth in ASTM

D-2414-13. The Compressed Sample Oil absorption number (COAN) measures that portion of the carbon black structure which is not easily altered by application of mechanical stress. COAN is measured according to

ATSM D3493-13. Aggregate size distribution (ASD) is measured according to ISO 15825 method using Disc Centrifuge Photosedimentometry with a model BI-DCP manufactured by Brookhaven Instruments.

[0101] Carbon black materials having suitable properties for a specific application may be selected and defined by the ASTM standards (see, e.g.,

ASTM D 1765-03 Standard Classification System for Carbon Blacks Used in

Rubber Products), by Cabot Corporation specifications (see, Web site www.cabot-corp.com), or other commercial grade specifications.

[0102] The carbon black can have any STSA such as ranging from 5 m?2/g to 250 m?/g, from 11 m2/g to 250 m?/g, from 20 m?/g to 250 m?/g or higher, for instance, at least 70 m2/g, such as from 70 m2/g to 250 m2/g, or from 80 m?/g to 200 m2/g, or from 90 m?/g to 200 m?/g, or from 100 m2/g to 180 m?/g, from 110 m2/g to 150 m?/g, from 120 m?/g to 150 m?/g and the like. As an option, the carbon black can have an Iodine Number (1: No) of from about 5 to about 35 mg I>/g carbon black (per ASTM D1510).

[0103] The carbon black particles disclosed herein can have a BET surface area, measured by Brunauer/Emmett/Teller (BET) technique according to the procedure of ASTM D6556, from 5 m?2/g to 300 m?/g, for instance between 50 m?/g and 300 m?/g, e.g., between 100 m2/g and 300 m2/g. The BET surface area can be from about 100 m?/g to about 200 m?/g or from about 200 m?/g to about 300 m?2/g.

[0104] The oil adsorption number (OAN) can be from 40 ml/100 g to 200 ml/100 g, for instance between 60 ml/100 g and 200 ml1/100 g, such as between 80 ml/100 g and 200 m1/100 g, e.g., between 100 ml/100 g and 200 ml/100 g or between 120 ml/100 g and 200 ml1/100 g, between 140 m1/100 g and 200 ml/100 g, or between 160 m1/100 g and 200 ml/100 g such as between 40 ml/100 g and 150 m1/100 g.

[0105] The COAN can be within the range of from about 40 ml/100 g to about 150 ml/100 g, e.g., between about 55 ml/100 g to about 150 ml/100 g, such as between about 80 ml/100 g to about 150 m1/100 g, or between about 80 ml/100 g to about 120 ml/100 g.

[0106] The carbon black can be a carbon product containing silicon-containing species and/or metal containing species and the like, which can be achieved by including the further step of introducing such a species with or in addition to either or both of the carbon black-yield feedstocks. The carbon black can be for purposes of the present invention, a multi-phase aggregate comprising at least one carbon phase and at least one metal-containing species phase or silicon-containing species phase (also known as silicon-treated carbon black, such as ECOBLACK™ materials from Cabot Corporation).

[0107] As stated, the carbon black can be a rubber black, and especially a reinforcing grade of carbon black or a semi-reinforcing grade of carbon black.

[0108] As an option, the carbon black of the present invention can have functional groups or chemical groups (e.g., derived from small molecules or polymers, either ionic or nonionic) that are directly attached to the carbon surface (e.g., covalently attached). Examples of functional groups that can be directly attached (e.g., covalently) to the surface of the carbon black particles and methods for carrying out 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 to Johnson ef al. on July 13, 1999, incorporated herein by reference in their entirety. As one illustration, a surface modified carbon black that can be employed here is obtained by treating carbon black with diazonium salts formed by the reaction of either sulfanilic acid or para-amino-benzoic acid (PABA) with HCI and NaNO:.

Surface modification by sulfanilic or para-amino-benzoic acid processes using diazonium salts, for example, results in carbon black having effective amounts of hydrophilic moieties on the carbon coating.

[0109] The carbon black can be surface modified according to 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 can be used to provide functional groups attached to the surface of the carbon black are described in U.S. Patent No. 7,300,964, issued to Niedermeier ef al., on November 27, 2007.

[0111] Oxidized (modified) carbon black can 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 one that that has been oxidized using an oxidizing agent in order to introduce ionic and/or ionizable groups onto the surface. Such 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 a sodium hypochlorite, oxidizing acids such a nitric acid, and transition metal containing oxidants, such as permanganate salts, osmium tetroxide, chromium oxides, or ceric ammonium nitrate. Mixtures of oxidants may also be used, particularly mixtures of gaseous oxidants such as oxygen and ozone. Other surface modification methods, such as chlorination and sulfonylation, may also be employed to introduce ionic or ionizable groups.

[0112] The present innovation is based in part on a presently recognized need to develop a class of carbon blacks that can be made utilizing a lower overall combustion (OAC). Overall combustion is defined as the percentage of oxygen added to the entire reactor compared to the total amount of oxygen required to stoichiometrically react with all the fuel streams added to the entire reactor. By reducing the OAC and yet producing the same or essentially the same carbon black (based on parameters such as nitrogen surface area and/or COAN), an operation of higher yield and improved economics for the process of making carbon black can be achieved and/or a more environmentally-friendly operation of making carbon black can be achieved.

[0113] The carbon black can be utilized in various applications, such as, for example, as reinforcement in rubber products, e.g., tire components.

[0114] The carbon black can be incorporated in rubber articles, being used, for instance, for tire tread, especially in tread for passenger car, light vehicle, truck and bus tires, off-the-road (“OTR”) tires, airplane tires and the like; sub-tread; wire skim; sidewalls; cushion gum for retread tires; and other tire uses.

[0115] In other applications, the particles can be used in industrial rubber articles, such as engine mounts, hydro-mounts, bridge bearings and seismic isolators, tank tracks or tread, mining belts, hoses, gaskets, seals, blades, weather stripping articles, bumpers, anti-vibration parts, and others.

[0116] The carbon black can be added as an alternative or in addition to first reinforcing agents for tire components and/or other industrial rubber end-uses. The carbon black can be combined with natural and/or synthetic rubber in a suitable dry or wet mixing process based on an internal batch mixer, continuous mixer or roll mill.

[0117] Alternatively, the carbon black may be mixed into rubber via a liquid masterbatch process. For instance, a slurry containing the particles described herein also can be combined with elastomer latex in a vat 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 can be introduced according to U.S. Patent No. 6,048,923, issued to Mabry ef al. on April 11, 2000, incorporated herein by reference in its entirety. For example, a method for preparing elastomer masterbatch can involve feeding simultaneously a particulate filler fluid and an elastomer latex fluid to a mixing zone of a coagulum reactor. A coagulum zone extends from the mixing zone, preferably progressively increasing in cross-sectional area in the downstream direction from an entry end to a discharge end. The elastomer latex may be either natural or synthetic and the particulate filler comprises, consists essentially of or consists of the material such as described above. The particulate filler is fed to the mixing zone preferably as a continuous, high velocity jet of injected fluid, while the latex fluid is fed at low velocity. The velocity, flow rate and particulate concentration of the particulate filler fluid are sufficient to cause mixture with high shear of the latex fluid and flow turbulence of the mixture within at least an upstream portion of the coagulum zone so as to substantially completely coagulate the elastomer latex with the particulate filler prior to the discharge end. Substantially complete coagulation can occur without the need of acid or salt coagulation agent. As disclosed in U.S. Patent No. 6,075,084, incorporated herein by reference in its entirety, additional elastomer may be added to the material that emerges from the discharge end of the coagulum reactor. As disclosed in U.S. Patent No. 6,929,783, incorporated herein by reference in its entirety, the coagulum may then be fed to a dewatering extruder. Other examples of suitable masterbatch processes are disclosed in U.S. Patent No. 6,929,783 to Chung et al;

US 2012/0264875A1 application of Berriot et al.; U.S. 2003/0088006A1 application of Yanagisawa et al.; and EP 1 834 985 B1 issued to Yamada et al.

[0119] Carbon black may be evaluated in a suitable rubber formulation, utilizing natural or synthetic rubber. Suitable amounts of carbon black to be used can be determined by routine experimentation, calculations, by taking into consideration factors such as typical loadings of standard ASTM furnace blacks in comparable manufacturing processes, parameters specific to the techniques and/or equipment employed, presence or absence of other additives, desired properties of the end product, and so forth.

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

[0121] Suitable tests include green rubber tests, cure tests, and cured rubber tests. Among appropriate green rubber tests, ASTM D4483 sets forth a test method for the ML1+4 Mooney Viscosity test at 100 °C. Scorch time is measured according to ASTM D4818.

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

ASTM D5289.

[0123] Performance characteristics of cured samples can be determined by a series of appropriate tests. Tensile strength, elongation at break, and stress at various strains (e.g. 100 % and 300 %) are all obtained via ASTM

D412 Method A. Dynamic mechanical properties including storage modulus, loss modulus, and tan ô are obtained by strain sweep test at 10 Hz, 60C and various strain amplitudes from 0.1 % to 63 %. Shore A hardness is measured according to ASTM D2240. Tear strength of die B type cured rubber samples are measured according to ATSM D624.

[0124] Undispersed area is calculated by analyzing images obtained by reflection mode optical microscopy for cured rubber compounds of a cut cross-sectional area according to various reported methods. Dispersion can also be represented by the Z value (measured, after reticulation, according to the method described by S. Otto and Al in Kautschuk Gummi

Kunststoffe, 58 Jahrgang, NR 7-8/2005, article titled New Reference value for the description of Filler Dispersion with the Dispergrader 1000NT.

Standard ISO 11345 sets forth visual methods for the rapid and comparative assessment of the degree of macrodispersion of carbon black and carbon black/silica in rubber.

[0125] Abrasion resistance is quantified as an index based on abrasion loss of cured rubber by the Cabot Abrader (Lambourn type). Attractive abrasion resistance results can be indicative of advantageous wear properties. Good hysteresis results can be associated with low rolling resistance (and correspondingly higher fuel economy) for motor vehicle tire applications, reduced heat build-up, tire durability, tread life and casing life, fuel economy features for the motor vehicle and so forth.

[0126] Iodine number (Iz No.) is determined according to ASTM Test

Procedure D1510. STSA (statistical thickness surface 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). COAN is determined based on ASTM D3493 (e.g., D3493-20).

[0127] Unless otherwise specified, all material proportions described as a percent herein are in weight percent.

[0128] The present invention will be further clarified by the following examples which are intended to be only exemplary in nature.

[0129] EXAMPLES

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

[0131] Overall Combustion (OAC) ratio: Overall combustion is defined as the percentage of oxygen added to the entire reactor compared to the total amount of oxygen required to stoichiometrically react with all the fuel streams (burner fuel and carbon black yielding feedstock) added to the entire reactor. For stoichiometric conditions the OAC is 100 %. When the mixture is fuel-rich the OAC 1s less than 100 % and when it is fuel-lean it is greater than 100 %. Carbon black production preferably occurs when OAC is substantially fuel rich, typically less than 60 and more often less than 40.

[0132] Primary Combustion ratio (PC) (also termed burner combustion ratio): This ratio is the same as the OAC except that it only considers the fuels and oxygen streams introduced into the burner (74 in FIG. 2). It does not include the fuels or oxygen streams (such as 84 in FIG. 2) introduced downstream of the burner. The primary combustion (PC) ratio is typically 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, not including any burner fuel used for the combustion chamber in FIG. 2, and 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 the feedstock, and is calculated based on measures of the reactor input rates and compositions and the composition of the tail gas. Sometimes yield may include sulfur, ash and other components of the carbon black besides carbon, but for these examples the yield only includes the carbon content of the carbon black.

[0134] Toluene Extractables (SP20), Iz, STSA, OAN, and COAN

[0135] The OAN and COAN are analyzed on dry pellets and follow the

ASTM standards identified above. I» number and STSA are analyzed on dry pellets by the ASTM methods identified above.

[0136] Reactor Configuration and Operation

[0137] Example 1

[0138] In Example 1, decant oil was used as the carbon black feedstock (Table 6), and a heavy TPO (Table 4) alone (100 wt.% TPO) or an approximately 50 wt.% heavy TPO with approximately 50 wt.% natural gas (Table 5) was used as the burner fuel. As a comparative, 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 (OAC) flow conditions as shown in Table 7. All the conditions tested had a process air rate of 1600 Nm?/h and a process air inlet temperature of 500 °C. The burner combustion ratio was 150 % for all the cases. The decant oil carbon black feedstock inlet temperature was 190 °C for all conditions. Table 7 shows the flow parameters that were varied for each condition including the natural gas flow rate, the heavy TPO flow rate, the OAC, the carbon black feedstock flow rate, the potassium additive rate, the quench water flow rate, and the quench length distance

Lguench.

[0140] Utilizing a carbon black furnace process, the burner fuel and hot process air are combined in a combustion chamber to provide a hot combusted gas stream, as shown in FIG. 2. The combustion chamber was refractory-lined and its inner diameter given in Table 3.

[0141] The natural gas and the TPO burner fuels and the hot process air were introduced to the burner (71 and 72) with flow conditions according to

Table 7. The liquid heavy TPO was atomized, and both TPO and natural gas were mixed and burned through combustion devices typical of the state-of the art.

[0142] Next, the combusted gas from the chamber flowed into a contraction so that it entered a narrower throat (76 in FIG. 2). At the throat, for all the cases in the example, the carbon black feedstock was injected radially, positioned perpendicular to the direction of the combusted gas flow, toward the center of the reactor through injector 83 as shown in FIG. 2.

[0143] The throat was attached to a refractory-lined reactor chamber.

The reactor chamber provided 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 to quench, as is typical for carbon black furnace processes (see Table 7 for the details).

Downstream of the quench, a filter was used to separate carbon black particles from the tail gas stream. The carbon black at the filter was sampled for Iz Absorption and Toluene Extractables (SP20). The carbon black was then pelletized and dried for measurements of STSA, OAN, and

COAN.

[0144] The filtered tail gas was sampled, and its composition was measured for each condition and yields determined.

Table 3: Dimensions in the reactor shown in FIG. 2 for Example 1

Throat Diameter

[0145] The heavy TPO used as the burner fuel was distilled by the supplier to obtain a higher temperature flash point for easier storage. The

TPO used (Polimix 330) has the following properties/characteristics:

Table 4:

Specific Gravity at 15.5 °C 0.9246

Carbon, wt.% Co] 88.28

Bass |e

[0146] The natural gas, when fed to the combustion chamber in FIG. 2 had a measured average composition as shown in Table 5 for the examples.

Components were measured by gas chromatography.

[0147]

Table 5. Natural gas average composition for the experimental data.

Comme | | ae en

Eene 00

Propane n-Butane % es

EL RL en ERLE ee ow

Ethylene % 000

[0148] The liquid decant oil in these examples was as shown in Table 6 below (D-xxxx methods are established by ASTM International).

Table 6: Decant oil feedstock properties

EE fee ew

Cen pw

D= = oo ~~

SE 2 § & 20 Jie |= iow 2 oir iv|lola lola o

DS SG I~ (= joo in tr 0 | in | In io [I= |t g - =

SD

2 vn 2 2 =

RE)

EBD

B

4 9 & = r= mS = x San s SCS &

S mm 2 2 TD 9

UO FH oa || = =f ho If | Fs (RF wn

S = an on gs 5 IA u

S IH 5 on» 8 a 5 np 0 0 ho |v hoe ho ho lo ee ng no no po no © SE Pl len fen on |e jes fed (es _ © jn IS S/S 8 SS sis v A A Hf tn pf SR a

S| a c c= rs og vo | H = —~ 12 B = |S

Se 5 5 Ellis mn jn

Ss ‚Ss Sz IS |S oo io ie <

HZ B&B 2 = |= 10 10 0 io IT” o

[0149] Results.

[0150] The results are set forth in FIGS. 3-7 (Figures 5-7 only show data for 40 ppm potassium addition). The carbon black formed from the experiments where the burner fuel was 100 wt.% heavy TPO (HTPO, squares; dotted link), or ~50 wt.% HTPO with ~50 wt.% natural gas (NG, triangles, dashed Line) or 100 wt.% NG (diamonds; solid line) was obtained and analyzed. The primary combustion ratio in all cases was 150 %. FIG. 3 shows that to achieve a certain surface area (STSA), a lower OAC is needed when the burner fuel was 100 % HTPO or 50/50 HTPO/NG compared to NG only. Put another way, the present invention provided carbon black having a particular surface area but produced utilizing a lower OAC. Lower OAC normally results in a higher yield.

[0151] FIG. 4 shows that the carbon black yield for a given STSA was in fact 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 COAN for a given STSA was higher when the burner fuel was 100 % HTPO or 50 % / 50 % HTPO/NG compared to NG alone. Higher structure (OAN and/or COAN) is often of higher value for carbon black.

[0153] FIG. 6 shows that the tint at a given STSA was essentially the same when the burner fuel was 100 % HTPO or 50 % / 50 % HTPO/NG compared to 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 compared to NG alone.

[0155] Example 2

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

As a comparative, 100 wt.% natural gas (Table 5) was used as the burner fuel.

[0157] Each of these burner fuel combinations is tested over a range of overall combustion (OAC) flow conditions as shown in Table 9 using a process air rate of 1800 Nm3/h and a process air inlet temperature of 500 °C.

The decant oil carbon black feedstock inlet temperature is held at 175 °C for all conditions. Table 9 shows the flow parameters that are varied for each condition including the natural gas flow rate, the bio-oil flow rate, the OAC, the carbon black feedstock flow rate, the potassium additive rate, the quench water flow rate, and the quench length distance Lyueneh.

[0158] Utilizing a carbon black furnace process, the burner fuel and hot process air are combined in a combustion chamber to provide a hot combusted gas stream, as shown in FIG. 2. The combustion chamber is refractory-lined and its inner diameters are as follows: Dehamber = 20.3 cm,

Dinhroat = 11.43 cm, Dreaetor = 45.7 cm.

[0159] The natural gas and the bio-oil burner fuels and the hot process air are introduced to the burner (71 and 72) with flow conditions according to Table 9. The bio-oil is atomized, and both bio-oil and natural gas are mixed and burned through combustion devices typical of the state-of the art.

[0160] Next, the combusted gas from the chamber flows into a contraction so that it enters a narrower throat (76 in FIG. 2). At the throat, for all the cases in the example, the carbon black feedstock is injected radially, positioned perpendicular to the direction of the combusted gas flow, toward the center of the reactor through injector 83 as shown in FIG. 2.

[0161] The throat is attached to a refractory-lined reactor chamber. The reactor chamber provides residence time for the feedstock to complete its pyrolysis into carbon black particles. At a distance Lquencn 79 downstream of the injection plane shown in FIG. 2, a water spray is used to quench, as is typical for carbon black furnace processes (see Table 8 for the details).

Downstream of the quench, a filter is used to separate carbon black particles from the tail gas stream.

[0162] A typical bio-oil has less sulfur, more ash, and more water than the TPO employed in Example 1. However, it may have less asphaltenes or even no asphaltenes. It typically has more water than the TPO employed in

Example 1 and consequently may be more dense from a mass standpoint but have less energy density.

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[0163] It 1s expected that any water in the bio-oil will result in a slightly lower yield than for the natural gas control but that the use of bio-oil permits similar development of surface area (STSA) as a function of overall combustion (OAC) in comparison to 100 % natural gas.

[0164] The present invention includes the following aspects/embodiments/features in any order and/or in any combination: 1. The present invention involves a method for producing a carbon black comprising introducing into a carbon black reactor a burner fuel comprising at least one sustainable burner fuel; igniting and forming a stream of hot gases from said burner fuel in said reactor; introducing into the carbon black reactor at least one carbon black yielding feedstock in one or more introduction points; combining the at least one carbon black yielding feedstock with the stream of hot gases to form carbon black in a reaction stream, and reaction quenching the reaction stream containing the carbon black, and recovering said carbon black. 2. The method of any preceding or following embodiment/feature/aspect, wherein the at least one sustainable burner fuel is one or more of the following: a tire pyrolysis oil, a plastic pyrolysis oil, a plant-derived oil, an oil derived from pyrolysis municipal solid waste, an oil derived from the pyrolysis or decay of biomass (e.g., animal, plant, tree, fruit, or vegetable), or other agricultural waste, an oil derived from the processing of paper production byproducts, and/or another oil sourced primarily from biomaterials or any combinations thereof. 3. The method of any preceding or following embodiment/feature/aspect, wherein the burner fuel comprises at least 50 % by weight of said at least one sustainable burner fuel, based on total weight of the burner fuel.

4. The method of any preceding or following embodiment/feature/aspect, wherein the at least one sustainable burner fuel is tire pyrolysis oil (TPO). 5. The method of any preceding or following embodiment/feature/aspect, wherein the burner fuel comprises at least 50 % by weight of said TPO, based on total weight of the burner fuel. 6. The method of any preceding or following embodiment/feature/aspect, wherein the burner fuel comprises at least 70 % by weight of said at least one sustainable burner fuel, based on total weight of the burner fuel. 7. The method of any preceding or following embodiment/feature/aspect, wherein said carbon black has a biogenic carbon content of less than 2 wt.%. 8. The method of any preceding or following embodiment/feature/aspect, wherein igniting and forming substantially or completely consumes the sustainable burner fuel. 9. The method of any preceding or following embodiment/feature/aspect, wherein less than 5 % or less than 1 wt.% sustainable burner fuel, based on total weight of the carbon black yielding feedstock, is available to form carbon black. 10. The method of any preceding or following embodiment/feature/aspect, wherein the sustainable burner fuel is present in an amount sufficient to increase the yield of the carbon black formed from 1 % to 8 % as compared to a burner fuel consisting of 100 % natural gas. 11. The method of any preceding or following embodiment/feature/aspect, wherein the sustainable burner fuel is present in an amount sufficient to increase the COAN of the carbon black formed from 1 % to 8 % as compared to a burner fuel consisting of 100 % natural gas. 12. The method of any preceding or following embodiment/feature/aspect, wherein the TPO comprises heavy TPO. 13. The method of any preceding or following embodiment/feature/aspect, wherein the TPO consists of heavy TPO.

14. The method of any preceding or following embodiment/feature/aspect, wherein said carbon black recovered is a N110, N121, N220, N231, N234,

N299, N326, N330, N339, N347, N351, N358, N375, N539, N550, N650,

N660, N683, N762, N765, N774, N787, or N990 grade carbon black. 15. Carbon black formed or produced from the method of any preceding or following embodiment/feature/aspect.

[0165] The present invention can include any combination of these various features or embodiments above and/or below as set forth in any sentences and/or paragraphs herein. Any combination of disclosed features herein is considered part of the present invention and no limitation is intended with respect to combinable features.

[0166] Applicants specifically incorporate the entire contents of all cited references in this disclosure. Further, when an amount, concentration, or other value or parameter is given as either a range, preferred range, or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range. It is not intended that the scope of the invention be limited to the specific values recited when defining a range.

[0167] Other embodiments of the present invention will be apparent to those skilled in the art from consideration of the present specification and practice of the present invention disclosed herein. It is intended that the present specification and examples be considered as exemplary only with a true scope and spirit of the invention being indicated by the following claims and equivalents thereof.

Claims

Conclusions

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

2. The method of claim 1, wherein the at least one more sustainable burner fuel is one or more of a tire pyrolysis oil, a plastics pyrolysis oil, a plant-derived oil, an oil derived from the pyrolysis of municipal solid waste, an oil derived from the pyrolysis or decay of biomass or other agricultural waste, an oil derived from the processing of papermaking by-products, and/or another oil having an origin primarily of biomaterials or any combinations thereof.

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

4. The method of any preceding claim, wherein the at least one sustainable burner fuel is tire pyrolysis oil (TPO).

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

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

7. The method of any preceding claim, wherein said carbon black has a biogenic carbon content of not more than 2 wt%.

8. The method of any preceding claim, wherein igniting and forming the sustainable burner fuel substantially or completely consumes it.

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

10. The method of 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% compared to a burner fuel consisting of 100% natural gas.

11. The method of any preceding claim, wherein the sustainable burner fuel is present in an amount sufficient to increase the COAN of the carbon black formed from 1% to 8% as compared to a burner fuel consisting of 100% natural gas.

12. The method of any preceding claim, wherein the TPA heavily comprises TPO.

13. The method of any preceding claim, wherein the TPO consists of heavy TPO.

14. The method of any preceding claim, wherein said recovered carbon black is an N110, N121, N220, N231, N234, N299, N326, N330, N339, N347, N351, N358, N375, N539, N550, N650, N660, N683, N762, N765, N774, N787 or N990 grade carbon black.