KR20190007453A - Internal Heat Generation Material Coupled Hydrocarbon Cracking - Google Patents

Abstract

Introducing and vaporizing a heat generating material (HGM) stream comprising a hydrocarbon feed and at least one aldehyde or ketone into a cracking reactor; and cracking the hydrocarbon feed. The hydrocarbon feed and the HGM stream may be vaporized and vaporized before or after introduction into the cracking reactor. The addition of HGM to the endothermic cracking process provides the heat required for cracking, and the entire process achieves thermal neutrality. The method comprises cracking the hydrocarbon feed to produce a cracking product, wherein the cracking product comprises C ₁ -C ₄ hydrocarbons and C ₅ + hydrocarbons.

Description

Internal Heat Generation Material Coupled Hydrocarbon Cracking

Cross-reference to related application

This application claims the benefit of U.S. Provisional Application No. 62 / 335,187, filed May 12, 2016, which is incorporated herein by reference.

Field

Embodiments of the present disclosure generally relate to the processing of hydrocarbons, and more particularly, to methods for cracking hydrocarbon feeds by a heat generating material coupled hydrocarbon cracking process.

Technical background

Energy consumption is a significant obstacle in the light olefin industry. Hydrocarbon cracking is a process that is very endothermic. During the hydrocarbon cracking process, the activation of the endothermic cracking process consumes heat faster than the reactor adds additional heat, so that the temperature of the reactor housing falls as the cracking reaction commences. The addition of additional heat to maintain the reactor temperature adds significant cost to the hydrocarbon cracking operation. For example, current steam-cracking processes operate at 800-1000 ° C., consuming as much as 40% of the energy used by the entire petrochemical sector. The specific energy consumption is about 4500 to 5000 kcal per kilogram of ethylene for the most recent steam-crackers. Overall, about 70% of the manufacturing cost in a typical ethane- or naphtha-based olefin plant is due to energy consumption.

Against this background, there is a continuing need for the development of efficient and economical routes for cracking hydrocarbon feedstocks to produce high demand petrochemical building blocks.

An embodiment of the present disclosure relates to a method of cracking a hydrocarbon feed using an exothermic heat generating material (HGM) to feed the energy requirements of an endothermic hydrocarbon cracking process. The methods and systems of this disclosure have industrial applicability in the oil and gas industry specifically because of the high energy costs traditionally required for hydrocarbon cracking. Without being bound by theory, the HGM of the present disclosure is added to help the hydrocarbon cracking process become energy neutral and approach energy neutrality, thereby reducing the overall energy cost associated with hydrocarbon cracking.

According to one embodiment, a method of cracking a hydrocarbon feed is provided. The method includes vaporizing a hydrocarbon feed and vaporizing a heat generating material (HGM) stream comprising at least one aldehyde or ketone. Additionally, the method includes introducing the vaporized hydrocarbon feed and the vaporized heat generating material stream into a cracking reactor. Finally, the method also includes cracking the hydrocarbon feed to produce a cracking product, wherein the cracking product comprises C ₁ -C ₄ hydrocarbons and C ₅ + hydrocarbons. The cracking product can include ethylene, propylene, butene, benzene, toluene, xylene, ethylbenzene, H _2, methane, ethane, LPG, naphtha, gasoline and gas oil.

According to yet another embodiment, a method of cracking a hydrocarbon feed is provided. The method includes vaporizing a hydrocarbon feed and vaporizing a heat generating material (HGM) stream comprising at least one aldehyde or ketone. Additionally, the method includes heating the vaporized hydrocarbon feed and the vaporized HGM stream to a pre-reaction temperature of at least 100 < 0 > C and introducing the vaporized hydrocarbon feed and the vaporized heat generating material stream into the cracking reactor do. Finally, the method also includes cracking the hydrocarbon feed to produce a cracking product, wherein the cracking product comprises C ₁ -C ₄ hydrocarbons and C ₅ + hydrocarbons. The cracking product can include ethylene, propylene, butene, benzene, toluene, xylene, ethylbenzene, H _2, methane, ethane, LPG, naphtha, gasoline and gas oil.

According to yet another embodiment, a method of cracking a hydrocarbon feed is provided. The method includes introducing into the cracking reactor a heat generating material (HGM) stream comprising a hydrocarbon feed and at least one aldehyde or ketone. The method further comprises vaporizing the hydrocarbon feed and the heat generating material stream in the cracking reactor. Finally, the method also includes cracking the hydrocarbon feed to produce a cracking product, wherein the cracking product comprises C ₁ -C ₄ hydrocarbons and C ₅ + hydrocarbons. The cracking product can include ethylene, propylene, butene, benzene, toluene, xylene, ethylbenzene, H _2, methane, ethane, LPG, naphtha, gasoline and gas oil.

Additional features and advantages of the described embodiments will be set forth in the description which follows, and in part will be readily apparent to those skilled in the art from the description, and may be learned by practice of the disclosed embodiments, including the detailed description, claims and accompanying drawings, Will be recognized.

It is to be understood that both the foregoing general description and the following detailed description are intended to describe various embodiments and provide an overview or framework for understanding the nature and character of the claimed subject matter. The accompanying drawings are included to provide a further understanding of the various embodiments, and are incorporated in and constitute a part of this specification. The drawings illustrate various embodiments described and serve to explain the principles and operation of the claimed subject matter with the description.

1 is a schematic illustration of an experimental scale reactor system for operation in accordance with one or more aspects of the present disclosure;
Figure 2 is a temperature profile of the catalyst bed temperature in the presence and absence of the heat producing material feed at a reaction temperature of 560 캜.
3 is a temperature profile of the catalyst bed temperature in the presence and absence of a heat producing material feed at a reaction temperature of 584 [deg.] C.

Reference will now be made in detail to embodiments of the improved cracking of hydrocarbon feeds using the HGM of the present disclosure. As previously described, hydrocarbon cracking is an endothermic process. By coupling the hydrocarbon cracking reaction with HGM, traditionally the endothermic cracking process can become thermally neutral or can reach thermal neutralization. Specifically, HGM generates pyrogenic heat when included in the hydrocarbon cracking process of the present disclosure. This exothermic heat can provide additional heat needed for the endothermic hydrocarbon cracking process. In addition, the HGM can also act as a diluent to prevent caulking, also acting as an oxidizing agent to promote hydrocarbon cracking. 1 The hydrocarbon cracking system is the laboratory setup provided for this discussion to follow; However, it should be understood that the present systems and methods include other configurations, including laboratory scale and industrial process planning.

Scale hydrocarbon cracking system 100 for cracking a hydrocarbon feed 4. Specifically, a hydrocarbon cracking system 100 includes a heat generating material (HGM) stream 2 To perform catalytic hydrocarbon cracking of the hydrocarbon feed ( 4 ).

The hydrocarbon feed 4 may refer to any hydrocarbon source derived from petroleum, coal liquids or biomaterials. Exemplary hydrocarbon sources include a full range of crude oil, distilled crude oil, residual oil, topped crude oil, liquefied petroleum gas (LPG), naphtha, gas oil, product stream from an oil refinery, product stream from a steam cracking process, , Liquid products recovered from oil or tar sand, bitumen, oil shale, biomass hydrocarbons, and the like. In the specific examples described in the following paragraphs, the hydrocarbon feed 4 may comprise n-hexane, naphtha, mixed butene, ethylene, and combinations thereof.

Mixed butenes are traditionally thought to be streams with lower values than propylene and ethylene. Pure butene-1 is worthy of polyethylene manufacture, but because of the technical difficulties of separating it from the mixed butene stream, butene-1 is usually prepared selectively from a direct process, such as ethylene dimerization to butene-1. The demand for propylene increased more than the demand for ethylene, as ethylene sales could be reduced and residual ethylene could be fed back into the cracking reactor to produce more propylene. The feed stream for the hydrocarbon cracking process can be adjusted based on the requirements for the product to produce the most preferred final product.

The HGM stream 2 may contain various components used to generate exothermic heat that can be used in the cracking process. In one or more embodiments, the HGM comprises at least one aldehyde or ketone. In one or more embodiments, the aldehyde is a formaldehyde. Since the formaldehyde is a gas at room temperature, it is usually distributed as 37% on a mass basis dissolved in water. This mixture is commonly known as 100% formalin. As a stabilizer, methanol may be added to the formalin to prevent oxidation and polymerization. Without being bound by theory, it has surprisingly been found that predictable side reactions, such as conversion of formaldehyde to CO and H ₂ , are inhibited by the simultaneous addition of hydrocarbons, so that methanol along with formaldehyde performs well with HGM.

In one or more embodiments, the ketone or aldehyde, for example an additional HGM stream ( 2 ) component other than formaldehyde, may comprise one or more additional aldehydes, additional ketones or alcohols. Mixing a plurality of aldehydes, ketones, alcohols, or combinations thereof, aids in promoting or hindering selectivity for a given reaction product. For example, the ratio of additional aldehyde, ketone or alcohol to formaldehyde or other aldehyde varies, so that the reaction product can migrate toward or away from light olefins.

Various concentrations of formaldehyde in the formalin and methanol mixtures are contemplated. For example, formalin (37 wt% formaldehyde in water) can be used in a non-dilute or dilute form to achieve the desired concentration needed for the spatial velocity of a particular cracking reaction. In one or more embodiments, the HGM 2 may comprise from 5 to 37% by weight of formaldehyde, or from 10 to 37% by weight of formaldehyde, or from 20 to 37% by weight of formaldehyde, or from 25 to 37% by weight of formaldehyde . The components of the HGM stream 2 may be obtained from a renewable source. In particular, the components such as aldehydes, ketones and alcohols can be obtained from the biomass fermentation process or syngas process.

Referring again to FIG. 1, the hydrocarbon cracking system 100 can include a reactor system having at least one catalyst bed reactor 10 , and optionally, additional reactors and units. For example, this additional optional unit may include a preheater reactor 12 connected to at least one catalyst bed reactor 10 and an additional heater or heat exchanger 18. [ On an industrial scale, the hydrocarbon cracking system 100 may also include a reactor system without a catalyst bed reactor. For example, a hydrocarbon cracking system 100 utilizing heat cracking without catalyst is contemplated.

As shown in the laboratory scale-scale reactor system of FIG. 1, the catalyst bed reactor 10 may comprise a solid acid catalyst bed 14 disposed in the catalyst bed reactor 10 . As previously been described, the operation of the catalytic reactor 10, the hydrocarbon feed is to generate the cracking of water (4) and create a cracking product 40, where the cracking product 40 is C ₁ -C ₄ light hydrocarbon, e.g. Ethylene and propylene, and heavy C ₅ + hydrocarbons. The cracking product 40 may comprise ethylene, propylene, butene, benzene, toluene, xylene, ethylbenzene, H2, methane, ethane, LPG, naphtha, gasoline and gas oil. The specific combination of products in the cracking product 40 depends on the constituents of the feed to the catalyst bed reactor 10 . The addition of HGM stream (2) of the reactor catalyst bed 10 reduces or eliminates an additional thermal energy input requirements in the catalytic reactor 10. Specifically, the HGM stream 2 undergoes an exothermic reaction in the catalyst bed reactor 10 , which offsets the endothermic cracking process, resulting in a thermally neutral total hydrocarbon cracking operation. Changes in both the makeup, flow rate, or makeup and flow rate of the HGM stream ( 2 ) can cause a total hydrocarbon cracking operation that is thermally negative or thermally neutral to thermally positive.

Various components are considered for the solid acid catalyst layer 14 of the catalyst bed reactor 10 . In one or more embodiments, the solid acid catalyst layer 14 may comprise an aluminosilicate zeolite, a silicate (e.g., silicalite), or a titanosilicate. In a further embodiment, the solid acid catalyst is an aluminosilicate zeolite having a Mordenite Framework Inverted (MFI) structure. For example, the aluminosilicate zeolite catalyst of the MFI structure may be a ZSM-5 catalyst, rather than a manner of limitation. In a further embodiment, the ZSM-5 catalyst can be an H-ZSM-5 catalyst, wherein at least some of the ZSM-5 catalyst ion exchange sites are occupied by H + ions. In addition, the aluminosilicate zeolite catalyst, such as the H-ZSM-5 catalyst, may have a Si / Al molar ratio of at least 10. In a further embodiment, the aluminosilicate zeolite catalyst may have a Si / Al molar ratio of at least 30, or at least 35, or at least 40. Additionally, the aluminosilicate zeolite catalyst may also comprise one or more additional components used to modify the structure and performance of the aluminosilicate zeolite catalyst. Specifically, the aluminosilicate zeolite catalyst may comprise phosphorous, boron, nickel, iron, tungsten, other metals, or combinations thereof. In various embodiments, the aluminosilicate zeolite catalyst may comprise from 0 to 10 weight percent of an additional component, from 1 to 8 weight percent of an additional component, or from 1 to 5 weight percent of an additional component. Rather than a mode of limitation, for example, this additional component can be wet impregnated in ZSM-5, followed by drying and calcination. The aluminosilicate zeolite catalyst may contain a mesoporous structure. The catalyst may be sized to have a diameter of 25 to 2500 micrometers (占 퐉). In a further embodiment, the catalyst may have a diameter of from 400 to 1200 μm, from 425 to 800 μm, from 800 to 1000 μm, or from 50 to 100 μm. The minimum size of the catalyst particles depends on the reactor design to prevent passage of the catalyst particles through the filter by the reaction product.

In one or more embodiments, the catalyst bed reactor 10 may be a fixed bed reactor, a fluidized bed reactor, a slurry reactor, or a mobile bed reactor. In a specific embodiment, the catalyst bed reactor 10 is a fixed bed reactor. In some embodiments with fixed bed reactors, the residence time of the combined hydrocarbon feed 4 and heat generating material stream 2 in the catalyst bed reactor 10 ranges from 0.05 second to hours. For example, the residence time is one hour to access the liquid feedstock for diesel hydrogen treatment and is typically in the range of 0.1 to 5 seconds in the FCC field. Therefore, in various embodiments, the residence time in the catalyst bed reactor 10 is 0.1 second to 5 seconds or 5 minutes to 1 hour. The desired residence times in the fixed bed reactors of the combined hydrocarbon feed 4 and the thermogenic material stream 2 for optimal hydrocarbon cracking are controlled by the solid acid catalyst layer 14 , the hydrocarbon feed 4 and the heat generating material stream 2 ) ≪ / RTI > operating temperature and composition. Additionally, in at least one embodiment, the void space exhibiting volume fraction occupied by voids is 0.2 to 1.0. In a further embodiment, the layer void ratio is 0.3 to 0.8.

The catalyst bed reactor 10 may have an operating temperature of 250 to 850 < 0 > C. In a further embodiment, the catalyst bed reactor 10 has an operating temperature of 450 to 650 占 폚, or 540 to 560 占 폚, or 575 to 595 占 폚. Without being bound by theory, it is believed that the addition of HGM ( 2 ) improves the catalyst lifetime of the solid acid catalyst layer 14. [ HGM ( 2 ) acts as a diluent and oxygenates the hydrocarbon feed to prevent caulking.

In addition, the solid acid catalyst layer 14 can be preheated in a gas stream containing the nitrogen (6) and heated in an oxygen flow rate sufficient to heat the solid acid catalyst layer (14). Oxygen may be provided as air. The preheated gas stream is heated from 250 캜 to 650 캜, or from 475 캜 to 525 캜, or from 490 캜 to 510 캜 in various embodiments.

Referring to Figure 1, in a laboratory scale reactor system, the method may further comprise preheating the hydrocarbon feed ( 4 ) upstream of the catalyst bed reactor ( 10 ). This preheating of the hydrocarbon feed ( 4 ) can be achieved in the preheater reactor ( 12 ). As shown, the fed hydrocarbon ( 4 ) can be heated in the presence of nitrogen ( 6 ). In one embodiment, the preheater reactor 12 can raise the temperature of the hydrocarbon feed 4 fed to the catalyst bed reactor 10 at a pre-reaction temperature of at least 100 ° C. The hydrocarbon feed 4 is typically heated to a pre-reaction temperature of 200 to 300 < 0 > C. The preliminary reaction temperature in this range is maintained low enough to prevent thermal cracking in the preheater reactor 12 prior to the catalyst bed reactor 10 . In contrast, pre-reaction temperature, cool hydrocarbon feed (4) adjacent to the catalyst layer 14 to the inlet to the catalyst bed reactor (10) so the cooling and so as not to affect the total conversion of the hydrocarbon feed (4), sufficiently elevated do. In one or more embodiments, the hydrocarbon cracking system 100 may also optionally include at least one hydrocarbon preheater 18 disposed upstream of the preheater reactor 12 . , The hydrocarbon pre-heater or pre-heater 18, as shown in Figure 1 is raised to at least one of the temperature of the hydrocarbon feed fed to the pre-heater reactor 12. The preheater 18 may include a heat exchanger or similar heater device familiar to those skilled in the art.

The hydrocarbon cracking system 100 may also include at least one heat generating material preheater 16 disposed upstream of the catalyst bed reactor 10 . The heat generating material preheater 16 raises the temperature of the heat generating material stream 2 supplied to the at least one catalyst bed reactor 10 . In an embodiment, the heat generating material preheater 16 raises the temperature of the heat producing material stream 2 to a pre-reaction temperature of at least 100 캜. The maximum reaction temperature of the preliminary heat generating material stream (2) to be limited by the cracking temperature of the heat generating material streams (2), the thermal cracking of the heat generating material streams (2) does not occur before the catalyst bed reactor (10). In a laboratory or pilot scale reactor, the hydrocarbon cracking system 100 may also include other heating components as shown. For example, the hydrocarbon cracking system 100 may comprise a hot box 22 surrounding the reactor oven 20 , or the catalyst bed reactor 10 , the preheater reactor 12 , the heat generating material preheater 16 and the hydrocarbon preheater 18 , . ≪ / RTI > The reactor oven 20 can help maintain the temperatures of the catalyst bed reactor 10 and the preheater reactor 12 . Similarly, hot box 22 acts to retain heat around catalyst bed reactor 10 , preheater reactor 12 , heat generating material preheater 16 and hydrocarbon preheater 18 to reduce heat loss.

The hydrocarbon preheater 19 , the preheater reactor 12 and the heat generating material preheater 16 also increase the temperature of both the hydrocarbon feed 4 and the heat generating material stream 2 before entering the catalyst bed reactor 10. [ To a single preheater.

In an industrial scale operation, the hydrocarbon feed 4 and the heat generating material stream 2 The hydrocarbon feed 4 and the heat generating material stream 2 are respectively vaporized. The hydrocarbon feed 4 and the heat generating material stream 2 may be mixed together and vaporized simultaneously in a single feed preheater. Alternatively, the hydrocarbon feed 4 and the heat generating material stream 2 can be independently combined, and vaporized by a separate feed preheater before being fed to the cracking reactor. Subsequently, the heated steam or other diluent may be fed to the vaporized hydrocarbon feed 4 , the vaporized heat generating material stream 2 , or the hydrocarbon feed 4 and the heat generating material stream 2 before being fed to the cracking reactor. Lt; RTI ID = 0.0 > vaporized < / RTI > Providing the diluent to the feed to the cracking reactor leaves the molecules of the hydrocarbon feed ( 4 ). Formaldehyde when used as a component of (formaldehyde 37 parts by weight of water%), the heat generating material streams (2), and formalin include water converted into steam for vaporization of the heat generating material stream (2) of the steam or other diluent It will be appreciated that addition may be unnecessary. It can also be appreciated that the vaporization of the hydrocarbon feed 4 and the thermogenic material stream 2 can be achieved in the cracking reactor rather than pre-pumped into the reactor.

In addition, balancing the amounts of heat generating material stream 2 and hydrocarbon feed 4 can facilitate a thermal neutralization cracking process. In a further embodiment, the HGM stream ( 2 ) and the hydrocarbon feed ( 4 ) are fed to the catalyst bed reactor ( 10 ) at a weight ratio of 1:10 to 10: 1. In a further embodiment, the heat generating material stream 2 and the hydrocarbon feed 4 may be supplied at a rate of 1: 6 to 6: 1, 1: 3, to 3: 1, or 1: 2 to 2: Is supplied to the reactor ( 10 ). In a still further embodiment, the heat generating material stream 2 and the hydrocarbon feed 4 are fed to the catalyst bed reactor 10 at a ratio of 2: 3 to 3: 2.

Referring again to FIG. 1, the cracking product 40 may comprise various hard C ₁ -C ₄ hydrocarbons and heavy C _{5 +} hydrocarbons. In one or more embodiments, the cracking product 40 is specifically selected from the group consisting of propylene, butenes such as 2-trans-butene, n-butene, iso-butene and 2-cis-butene, C ₅ olefins, aromatic, methane, ethane, Butane and pentane. The constituents of the cracking product 40 depend on the constituents of the hydrocarbon feed 4 and the heat generating material stream 2 . For example, formaldehyde is a reactive material effective to produce light olefins as well as to provide heat to offset the endothermic cracking process.

To separate the light hydrocarbons from the heavy hydrocarbons in the cracking product 40 , the hydrocarbon cracking system 100 may also include a condenser and at least one liquid / gas separator 24 . The liquid / gas separator 24 may include a flash drum or the like. The cracking product 40 is fed to the condenser as it exits the cracking reactor where the temperature of the gas cracking product 40 decreases and is partially condensed. The partially condensed feed is subsequently fed to the liquid / gas separator 24 where the liquid and vapor phases are separated. In particular, in the liquid / gas separator 24 , the light hydrocarbon stream 42 may be separated as gaseous light hydrocarbon, while the liquid heavy hydrocarbon stream 44 is discharged separately from the liquid / gas separator 24 . Additionally, on an industrial scale, to separate light hydrocarbons from heavy hydrocarbons in the cracking product 40 , the hydrocarbon cracking system 100 may comprise a multi-product distillation column. Industrial scale separation using distillation columns, stripping columns or extraction columns and other methods and processes for handling and separating the product stream are known to those skilled in the art and can be used equally.

Additional reactions for separating the desired propylene and ethylene from the light hydrocarbon stream 42 are contemplated. For example, the light hydrocarbon stream 42 may be cooled and collected as a liquid hydrocarbon product. At this time, propylene and ethylene can be separated through distillation, extractive distillation or membrane separation methodology.

In a further embodiment, the overall flow rate of steam or other diluent supplied to the HGM stream 2 , the hydrocarbon feed 4 , and the hydrocarbon cracking system 100 is adjusted to control the space velocity of the reaction. The weight hourly space velocity (WHSV) is defined as the flow of reactant, for example grams per hour (g / hr) divided by the weight of the catalyst in grams (g) divided by weight. The flow of reactant comprises an entire stream of HGM stream ( 2 ), hydrocarbon feed ( 4 ), and steam or other diluent. In at least one embodiment, the weight hourly space velocity of the reaction is from 0.01 to 100 h ^-1 (h ^-1 ). In a further embodiment, the weight hourly space velocity of the reaction is from 1 to 8 hr ^-1 , from 2 hr to 4 hr ^-1 , or from 2.8 hr to 3.4 hr ^-1 .

Ethylene and propylene are two of the major petrochemical building blocks used in various fields, such as the production of plastics and synthetic fibers. Specifically, ethylene is widely used to produce polyethylene, ethylene chloride and ethylene oxide, which are very useful in packaging, plastic processing, construction and textile industries. In addition, propylene is commonly used to make polypropylene, but it is also the basic product required to make propylene oxide, acrylic acid and many other chemical derivatives. The plastics processing, packaging, furniture industry and automotive industries are common users of propylene and its derivatives. Thus, increased yields of light olefins, such as ethylene and propylene, are desirable for supplying to a variety of industrial users.

Improved conversion of hydrocarbon feed 4 and light olefins (e.g., ethylene and propylene) is verified by experimental testing. Hexane Is provided to the experimental setup of the hydrocarbon cracking system 100 under conditions that vary with a varying ratio of heat generating material stream 2 .

Example

The following examples illustrate this embodiment and are not intended to limit the scope of the embodiments described in this disclosure.

Experimental data were obtained to demonstrate the effect of coupling the hydrocarbon cracking reaction with HGM. The catalytic reaction was carried out in a fixed bed flow reactor operated at atmospheric pressure. A catalyst having a mass of 9 to 12 grams palletized and sieved to a diameter of 425 to 800 micrometers (占 퐉) was loaded into the reactor. The catalyst was a microporous molecular sieve of ZSM-5 purchased from Nankai University Catalyst Co. Before the catalytic reaction, the catalyst was activated in a gas stream (120 cm < ³ > min ^-1 ) containing N ₂ at the desired reaction temperature and maintained overnight. The fixed bed flow reactor was heated to the desired reaction temperature using a three-zone electric heater. At the desired reaction temperature (typically 250 to 850 ° C), the reaction was initiated by introducing reactants selected from n-hexane, naphtha and formaldehyde (13.88% 37% solution stabilized in methanol) into the reactor.

The product from the catalytic reaction was analyzed by on-line gas chromatography equipped with an Agilent HP-Al / KCl (50 mx 0.53 mm ID, 15 m) column and measured by a Flame Ionization Detector (FID) detector. _{N 2, CH 4, C 2} H 6, C 2 H 4, C 3 H 8, C 3 H 6, nC 4 H 10, iC 4 H 10, 1-C 4 H 8, 2- cis -C ₄ H _8, 2- trans _{-C 4 H 8, iC 4 H} 8, nC 5 H 12, nC ₅ and H ₆ was used as the calibration standard. All lines and values between the fixed bed flow reactor and the outlet of gas chromatography are heated to 105 ° C to prevent condensation of heavier hydrocarbons.

Liquid products were collected separately using a low pressure liquid / gas separator. The organic part, if any, is separated from the water and its composition is analyzed by gas chromatography (GC) to determine the product, followed by gas chromatography (GC) to determine its concentration.

The conversion of hexane was determined as a weight percentage. The conversion rate is defined as the percentage of the weight of hexane converted to the final product. The equation for conversion of hexane is given as Equation (1) , where W _i is the weight of injected hexane and W _f is the weight of unreacted hexane detected by GC.

Conversion rate (%) = 100 x (W_i-W_f) / W_i (One)

In addition, as previously defined, the hourly space velocity (WHSV) was kept constant for the subgroup of trials to compare the HGM effect.

During the experiment, the typical reaction time was 35 minutes. After the reaction, the catalyst bed was purged with high purity nitrogen at a flow rate of 0.2 liter / min for 30 minutes to wash all reaction products and hydrocarbons before introducing air. The introduction of air is delayed because it may be a combustion hazard in the presence of hydrocarbons and reaction products. Following the flushing with nitrogen to remove the reaction products and hydrocarbons, the catalyst was regenerated using an air flow rate of 0.15 liters / min for 1 hour or until the temperature stabilized. Thereafter, the catalyst layer is again washed with nitrogen for 30 minutes to remove the combustion products.

The test is carried out with hexane as the hydrocarbon feed ( 4 ) in combination with the formaldehyde as the heat generating material stream ( 2 ) to demonstrate the effect of the heat generating material. Each test was run for 35 minutes. Table 1 lists the various cracking process parameters for the cracking product ( 40 ) when formaldehyde is present and when no formaldehyde is present. Coupling of hexane and formaldehyde gives rise to increased C ₆ conversion, ethylene yield and propylene yield.

Increased ethylene and propylene yields are desirable when the heat generating material stream 2 is provided with the hydrocarbon feed 4 . Additionally, Table 2, provided as follows, describes various cracking process parameters for the cracking product ( 40 ) when formaldehyde is present and the residence time varies. Each test was run for 35 minutes. The increased residence time results in increased C ₆ conversion.

The thermal neutrality of the hydrocarbon cracking process when the heat generating material stream 2 is added can be seen in Figures 2 and 3. Specifically, FIG. 2 demonstrates that the resulting temperature drop of the solid acid catalyst layer 14 decreases when hexane and heat generating material are provided in a 2: 1 ratio. The temperature layer of the solid acid catalyst layer 14 is greatly lowered when the hexane feed is fed, and the controller then reacts by increasing the wall temperature of the catalyst bed reactor 10 . By virtue of the hexane feed (hydrocarbon feed 4 ) and the heat generating material member, the wall temperature does not increase as rapidly as the temperature drop in the catalyst bed reactor 10 from the endothermic reaction. Conversely, by the simultaneous generation of heat generating material stream 2 introduced into the catalyst bed reactor 10 along with the hexane stream (hydrocarbon feed 4 ), the temperature of the solid acid catalyst layer 14 is controlled by the heat generating material and its exothermic Because of the reaction, the external heat from the controller that heats the walls of the catalyst bed reactor 10 is less destroyed as needed.

Similarly, referring to FIG. 3, the thermal neutrality of the hydrocarbon cracking process can be seen when the heat generating material stream 2 is added. Specifically, FIG. 3 demonstrates that the resulting temperature drop of solid acid catalyst layer 14 is eliminated when hexane and heat generating material are provided in a 1: 2 ratio. The higher percentage of heat generating material for hexane (hydrocarbons) causes the temperature of the solid acid catalyst layer 14 to rise. Conversely, without the heat generating material stream 2 , the temperature of the solid acid catalyst layer 14 drops immediately before starting to slowly increase after a period of time.

It is noted that the solid acid catalyst in the solid acid catalyst layer does not exhibit decay after 35 minutes of operation in the exemplary embodiment.

It should now be appreciated that various aspects of the method of cracking hydrocarbon feedstocks are described, and that such embodiments can be used with various other embodiments.

In a first aspect, the present disclosure provides a method of cracking a hydrocarbon feed. The method includes introducing a hydrocarbon feed into a cracking reactor, introducing a heat generating material (HGM) stream comprising at least one aldehyde or ketone into the cracking reactor, vaporizing the hydrocarbon feed and the HGM stream, and Cracking the hydrocarbon feed to produce a cracking product. The cracking products include C ₁ -C ₄ hydrocarbons and C ₅ + hydrocarbons.

In a second aspect, the present disclosure provides a method of the first aspect, wherein the hydrocarbon feed and the HGM stream are vaporized after introduction into the cracking reactor.

In a third aspect, the present disclosure provides a method of the first aspect wherein the hydrocarbon feed and the HGM stream are vaporized before introduction into the cracking reactor.

In a fourth aspect, the present disclosure provides a method of any of the first to third aspects, wherein the HGM stream comprises a ketone.

In a fifth aspect, the present disclosure provides a method of any one of the first to fourth aspects, wherein the HGM stream comprises an aldehyde.

In a sixth aspect, the disclosure provides a method of the fifth aspect, wherein the aldehyde is a formaldehyde dissolved in water.

In a seventh aspect, the present disclosure provides a method of the sixth aspect, wherein the formaldehyde dissolved in water is stabilized by an organic solvent.

In an eighth aspect, the present disclosure provides a method of the seventh aspect, wherein the organic solvent is methanol.

In a ninth aspect, the present disclosure provides a method of any one of the first to eighth aspects, wherein the HGM stream further comprises an alcohol, an additional ketone or an additional aldehyde.

In a tenth aspect, the present disclosure is, a first aspect to a cracking product containing ethylene, propylene, butene, benzene, toluene, xylene, ethylbenzene, H _2, methane, ethane, LPG, naphtha, gasoline and gas oil To < RTI ID = 0.0 > (9) < / RTI >

In an eleventh aspect, the present disclosure provides a method of any one of the first to tenth aspects, wherein the cracking reactor is at least one catalyst bed reactor.

In a twelfth aspect, the present disclosure provides a method of the eleventh aspect, wherein the catalyst bed reactor comprises a solid acid catalyst bed disposed in a catalyst bed reactor and the catalyst bed reactor is at a reaction temperature of from 250 to 850 캜.

In a thirteenth aspect, the present disclosure provides a method of the eleventh or twelfth aspect, wherein the catalyst bed reactor comprises a fluid bed reactor, a fixed bed reactor, a slurry reactor or a mobile bed reactor.

In a fourteenth aspect, the present disclosure provides a method of the eleventh or twelfth aspect, wherein the catalyst bed reactor is a fixed bed reactor.

In a fifteenth aspect, the present disclosure provides a method of any one of the twelfth to fourteenth aspects, wherein the solid acid catalyst is a ZSM-5 catalyst.

In a sixteenth aspect, the present disclosure provides a method of the fifteenth aspect, wherein the ZSM-5 catalyst has a Si / Al molar ratio of at least 10.

In a seventeenth aspect, the present disclosure provides a method of the fifteenth aspect, wherein the ZSM-5 catalyst has a Si / Al molar ratio of at least 30. [

In an eighteenth aspect, the present disclosure provides a method of the fifteenth aspect, wherein the ZSM-5 catalyst comprises phosphorus, boron, nickel, iron, tungsten, or a combination thereof.

In a nineteenth aspect, the present disclosure provides a process of any of the first to eighteenth aspects, wherein the HGM stream and the hydrocarbon feed stream are fed in a weight ratio of from 1:10 to 10: 1.

In a twentieth aspect, the present disclosure provides a process for producing a hydrocarbon feed stream, wherein the hydrocarbon feed stream comprises unfractionated or fractionated crude oil, hexane, naphtha, mixed butene, ethylene, and combinations thereof. One method is provided.

It should be apparent to those skilled in the art that various changes and modifications can be made to the embodiments described herein without departing from the spirit and scope of the claimed subject matter. It is therefore intended to cover modifications and variations of the various embodiments described herein, provided that such variations and modifications are within the scope of the appended claims and their equivalents.

A range is provided throughout this disclosure. It is contemplated that each distinct value included by the range is also included. Additionally, ranges that can be formed by each distinct value included by the explicitly disclosed ranges are equally contemplated.

Claims (20)

CLAIMS 1. A method for cracking a hydrocarbon feed,
Introducing the hydrocarbon feed into the cracking reactor;
Introducing into the cracking reactor a heat generating material (HGM) stream comprising at least one aldehyde or ketone;
Vaporizing the hydrocarbon feed and the HGM stream; And
Cracking the hydrocarbon feed to produce a cracking product comprising C ₁ -C ₄ hydrocarbons and C ₅ + hydrocarbons. The method of claim 1, wherein the hydrocarbon feed and the HGM stream are vaporized after introduction into the cracking reactor. The method of claim 1, wherein the hydrocarbon feed and the HGM stream are vaporized prior to introduction into the cracking reactor. 2. The method of claim 1, wherein the HGM stream comprises a ketone. 2. The method of claim 1, wherein the HGM stream comprises an aldehyde. 6. The method of claim 5, wherein the aldehyde is formaldehyde dissolved in water. 7. The method of claim 6, wherein the formaldehyde dissolved in the water is stabilized by an organic solvent. 8. The method of claim 7, wherein the organic solvent is methanol. 2. The method of claim 1, wherein the HGM stream further comprises an alcohol, an additional ketone or an additional aldehyde. The method of claim 1 wherein the cracking product cracking of ethylene, propylene, butene, benzene, toluene, xylene, ethylbenzene, H _2, methane, ethane, LPG, naphtha, gasoline, and the hydrocarbon feed comprises a gas oil Water How to. 2. The method of claim 1, wherein the cracking reactor is at least one catalyst bed reactor. 12. The method of claim 11, wherein the catalyst bed reactor comprises a solid acid catalyst bed disposed in the catalyst bed reactor, wherein the catalyst bed reactor is at a reaction temperature of 250 to 850 < 0 > C. 13. The method of claim 12, wherein the catalyst bed reactor comprises a fluid bed reactor, a fixed bed reactor, a slurry reactor or a mobile bed reactor. 14. The method of claim 13, wherein the catalyst bed reactor is a fixed bed reactor. 13. The method of claim 12, wherein the solid acid catalyst is a ZSM-5 catalyst. 16. The method of claim 15, wherein the ZSM-5 catalyst has a Si / Al molar ratio of at least 10. 16. The method of claim 15, wherein the ZSM-5 catalyst has a Si / Al molar ratio of at least 30. 16. The method of claim 15, wherein the ZSM-5 catalyst comprises phosphorous, boron, nickel, iron, tungsten, or a combination thereof. The method of claim 1, wherein the HGM stream and the hydrocarbon feed stream are fed in a weight ratio of from 1:10 to 10: 1. The method of claim 1, wherein the hydrocarbon feed stream comprises unfractionated or fractionated crude oil, hexane, naphtha, mixed butene, ethylene, and combinations thereof.

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