JP6895993B2 - Hydrocarbon decomposition combined with internal heat generating material - Google Patents

Description

Cross-reference with related application

This application claims the priority benefit of US Provisional Application No. 62 / 335,187 filed May 12, 2016, which is incorporated herein by reference in its entirety.

Embodiments of the present disclosure generally relate to the treatment of hydrocarbons, specifically to methods of decomposing hydrocarbon raw materials using a hydrocarbon decomposition process combined with a heating material.

Energy consumption is a major obstacle in the light olefin industry. Hydrocarbon decomposition is a highly endothermic process. During the hydrocarbon decomposition process, activation of the endothermic decomposition process consumes heat faster than the reactor applies additional heat, so that the temperature of the reactor housing drops as the decomposition reaction begins. Adding additional heat to maintain the reactor temperature adds significant cost to the hydrocarbon decomposition operation. For example, current steam decomposition processes operate at 800-1000 ° C and consume 40% of the energy used throughout the petrochemical industry. With the latest steam crackers, the specific energy consumption is about 4000-5000 kcal / kg ethylene. Overall, about 70% of the manufacturing cost in a typical ethane or naphtha olefin plant is due to energy consumption.

Against the above background, there is a continuing need for the development of efficient and economical pathways for decomposing hydrocarbon raw materials in order to obtain high demand petrochemical components.

Embodiments of the present disclosure relate to a method of decomposing a hydrocarbon feedstock using a heat-generating material (HGM) to meet the energy requirements of an endothermic hydrocarbon decomposition process. The methods and systems of the present disclosure have industrial applicability in the petroleum and gas industry, specifically due to the high energy costs conventionally required for hydrocarbon decomposition. Without limitation of theory, the HGMs of the present disclosure are added to help the hydrocarbon decomposition process become or approach energy neutrality, and thereby the whole associated with hydrocarbon decomposition. Reduce energy costs.

According to one embodiment, a method for decomposing a hydrocarbon raw material is provided. The method comprises vaporizing the hydrocarbon feedstock and vaporizing a flow of exothermic material (HGM) containing at least one aldehyde or ketone. In addition, the method involves introducing a vaporized hydrocarbon feedstock and a vaporized exothermic material stream into the decomposition reactor. Finally, the method also includes generating a decomposition product to decompose the hydrocarbon feed, degradation products, including C ₁ -C ₄ hydrocarbons and C _{5 +} hydrocarbons. Degradation products can include ethylene, propylene, butenes, benzene, toluene, xylenes, ethylbenzene, H2, methane, ethane, LPG, naphtha, gasoline, and gas oils.

According to another embodiment, a method for decomposing a hydrocarbon raw material is provided. The method comprises vaporizing the hydrocarbon feedstock and vaporizing a flow of exothermic material (HGM) containing at least one aldehyde or ketone. Further, the method comprises heating the vaporized hydrocarbon raw material and the vaporized HGM stream to a pre-reaction temperature of at least 100 ° C. and introducing the vaporized hydrocarbon raw material and the vaporized exothermic material stream into the decomposition reactor. Finally, the method also includes generating a decomposition product to decompose the hydrocarbon feed, degradation products, including C ₁ -C ₄ hydrocarbons and C _{5 +} hydrocarbons. Degradation products are benzene, toluene, xylenes, ethylbenzene, _{H 2,} may include methane, ethane, LPG, naphtha, gasoline, and gas oils.

Yet another embodiment provides a method of decomposing a hydrocarbon raw material. The method comprises introducing a hydrocarbon feedstock and exothermic material (HGM) stream containing at least one aldehyde or ketone into the decomposition reactor. The method further comprises vaporizing the hydrocarbon raw material and the exothermic material stream in the decomposition reactor. Finally, the method also includes generating a decomposition product to decompose the hydrocarbon feed, degradation products, including C ₁ -C ₄ hydrocarbons and C _{5 +} hydrocarbons. Decomposition products, ethylene, propylene, butenes, benzene, toluene, xylenes, ethylbenzene, _{H 2,} may include methane, ethane, LPG, naphtha, gasoline, and gas oils.

Further features and advantages of the described embodiments are described in the detailed description below and are readily apparent to those skilled in the art from the description, or the detailed description below, claims, and attachments. Will be recognized by implementing the described embodiments, including the drawings of.

Both the general description above and the detailed description below are intended to illustrate the various embodiments and provide an overview or framework for understanding the nature and characteristics of the claimed subject matter. Please understand that. The accompanying drawings are included to provide a better understanding of the various embodiments and are incorporated herein by them. The drawings exemplify the various embodiments described and, along with the description, serve to explain the principles and operations of the claimed subject matter.

FIG. 3 is a schematic of a laboratory scale reactor system for operation according to one or more embodiments of the present disclosure. A temperature profile of catalyst bed temperature with and without exothermic material material at a reaction temperature of 560 ° C. A temperature profile of catalyst bed temperature with and without exothermic material material at a reaction temperature of 584 ° C.

The embodiments for improved degradation of hydrocarbon raw materials using HGM of the present disclosure are referred to in detail. As mentioned above, hydrocarbon decomposition is an endothermic process. By combining the hydrocarbon decomposition reaction with HGM, the conventional endothermic decomposition process may become or approach thermal neutrality. Specifically, HGM produces exothermic heat when included in the hydrocarbon decomposition processes of the present disclosure. This exothermic heat may provide the additional heat required for the endothermic hydrocarbon decomposition process. In addition, HGM can act as a diluent to prevent caulking, while also acting as an oxidant to accelerate the decomposition of hydrocarbons. The hydrocarbon decomposition system of FIG. 1 is a laboratory configuration provided for this discussion below, however, the system and method may include other configurations, including large scale and industrial process planning. Should be understood.

Referring to the embodiment of FIG. 1, a laboratory-scale hydrocarbon decomposition system 100 for decomposing a hydrocarbon raw material 4 is shown. Specifically, the hydrocarbon decomposition system 100 executes catalytic hydrocarbon decomposition of the hydrocarbon raw material 4 in the presence of the heat generating material (HGM) stream 2.

The hydrocarbon raw material 4 can refer to any hydrocarbon source derived from petroleum, coal liquor, or biomaterials. Examples of hydrocarbon sources include a full range of crude oil, distilled crude oil, residual oil, top crude oil, liquefied petroleum gas (LPG), naphtha, gas oil, product streams from refineries, product streams from vapor cracking processes, liquefaction. Includes liquid products recovered from coal, oil or tar sand, bitumen, oil shale, biomass hydrocarbons and the like. In certain embodiments described in the following paragraphs, the hydrocarbon feedstock 4 may include n-hexane, naphtha, mixed butenes, ethylene, and combinations thereof.

Mixed butenes are traditionally considered to be of lower value than propylene and ethylene. Pure butene-1 is valuable for polyethylene production, but because it is technically difficult to separate from the mixed butene stream, butene-1 is usually a direct method such as ethylene dimerization to butene-1. Manufactured selectively from. As the demand for propylene increased beyond the demand for ethylene, ethylene sales could be reduced and excess ethylene could be resupplied to the decomposition reactor to produce more propylene. The raw material flow to the hydrocarbon decomposition process can be adjusted based on the demand for the product to produce the most desirable final product.

The HGM stream 2 may contain various components utilized to generate exothermic heat that can be used in the decomposition process. In one or more embodiments, the HGM comprises at least one aldehyde or ketone. In one or more embodiments, the aldehyde is formaldehyde. Since formaldehyde is gaseous at room temperature, it is typically distributed as 37% by weight dissolved in water. This mixture is commonly known as 100% formalin. As a stabilizer, methanol can be added to formalin to prevent oxidation and polymerization. Since it was surprisingly found that co-addition of hydrocarbons inhibits predictable side reactions such as the conversion of formaldehyde to CO and H _{2, formaldehyde, including methanol, is not limited to theory.} Works well as an HGM.

In one or more embodiments, the additional HGM stream 2 components beyond the ketone or aldehyde, eg formaldehyde, may comprise one or more additional aldehydes, additional ketones or alcohols. Mixing multiple aldehydes, ketones, alcohols, or combinations thereof helps to promote or prevent selectivity for a particular reaction product. For example, changes in the ratio of additional aldehydes, ketones or alcohols to formaldehyde or other aldehydes can cause the reaction product to approach or depart from the light olefin.

Various concentrations of formaldehyde in the mixture of formalin and methanol are possible. For example, formalin (37 wt% formaldehyde in water) can be used in undiluted or diluted form to achieve the desired concentration required for the spatial rate of a particular degradation reaction. In one or more embodiments, HGM2 may contain 5 to 37% by weight formaldehyde, or 10 to 37% by weight formaldehyde, or 20 to 37% by weight formaldehyde, or 25 to 37% by weight formaldehyde. The components of HGM stream 2 can be obtained from renewable sources. Specifically, components such as aldehydes, ketones, and alcohols can be obtained from fermentation processes of biomass or syngas processes.

With reference to FIG. 1 again, the hydrocarbon decomposition system 100 can include at least one catalytic bed reactor 10, and optionally a reactor system with additional reactors and units. For example, any of these additional units can include at least one catalytic bed reactor 10 and a preheater reactor 12 connected to an additional heater or heat exchanger 18. On an industrial scale, the hydrocarbon decomposition system 100 can also include a reactor system without a catalytic bed reactor. For example, a hydrocarbon decomposition system 100 that utilizes thermal decomposition without a catalyst is envisioned.

As shown in the laboratory scale reactor system of FIG. 1, the catalyst bed reactor 10 can include a solid acid catalyst bed 14 disposed within the catalyst bed reactor 10. As described above, the operation of the catalytic bed reactor 10 decomposes the hydrocarbon feed 4, resulted in the production of degradation products 40, the degradation product 40, light C ₁ -C _4, such as ethylene and propylene hydrocarbons, as well as heavy C _{5 +} hydrocarbons. The decomposition product 40 may include ethylene, propylene, butenes, benzene, toluene, xylenes, ethylbenzene, H2, methane, ethane, LPG, naphtha, gasoline, and gas oils. The particular combination of products in the decomposition product 40 depends on the composition of the raw material to the catalyst bed reactor 10. The addition of HGM stream 2 to the catalyst bed reactor 10 reduces or eliminates the additional thermal energy input requirement in the catalyst bed reactor 10. Specifically, the HGM stream 2 causes an exothermic reaction in the catalyst bed reactor 10 to offset the endothermic decomposition process, resulting in a thermally neutral overall hydrocarbon decomposition operation. By changing both the composition, the flow rate, or the composition and the flow rate of the HGM stream 2, an overall hydrocarbon decomposition operation from thermally negative to thermally neutral and thermally positive can occur.

Various components are considered for the solid acid catalyst bed 14 of the catalyst bed reactor 10. In one or more embodiments, the solid acid catalyst bed 14 may comprise aluminosilicate zeolite, silicate (eg, silicalite), or titanosilicate. In a further embodiment, the solid acid catalyst is an aluminosilicate zeolite with a Mordenite Framework Inverted (MFI) structure. By way of example, but not limited to, the MFI structured aluminosilicate zeolite catalyst can be a ZSM-5 catalyst. In a further embodiment, the ZSM-5 catalyst can be an H-ZSM-5 catalyst in which at least a portion of the ZSM-5 catalyst ion exchange site is occupied by H + ions. In addition, aluminosilicate zeolite catalysts, such as H-ZSM-5 catalysts, can have a Si / Al molar ratio of at least 10. In a further embodiment, the aluminosilicate zeolite catalyst can have a Si / Al molar ratio of at least 30, or at least 35, or at least 40. Additionally, the aluminosilicate zeolite catalyst can also contain one or more additional components used to modify the structure and performance of the aluminosilicate zeolite catalyst. Specifically, the aluminosilicate zeolite catalyst may include phosphorus, boron, nickel, iron, tungsten, other metals, or combinations thereof. In various embodiments, the aluminosilicate zeolite catalyst can contain 0-10% by weight of additional component, 1-8% by weight of additional component, or 1-5% by weight of additional component. For example, but not limited to, these additional ingredients can be wet impregnated with ZSM-5, followed by drying and calcination. The aluminosilicate zeolite catalyst can include mesoporous structures. The catalyst can be sized to have a diameter of 25 to 2,500 micrometers (μ). In a further embodiment, the catalyst can have a diameter of 400-1200 μm, 425-800 μm, 800-1000 μm, or 50-100 μm. The minimum size of the catalyst particles depends on the reactor design to prevent the catalyst particles from passing through the filter with the reaction product.

In one or more embodiments, the catalytic bed reactor 10 can be a fixed bed reactor, a fluidized bed reactor, a slurry reactor, or a moving bed reactor. In certain embodiments, the catalytic bed reactor 10 is a fixed bed reactor. In some embodiments using a fixed bed reactor, the residence time of the combined hydrocarbon raw material 4 and the exothermic material stream 2 in the catalytic bed reactor 10 is in the range of 0.05 seconds to 1 hour. For example, the residence time can approach one hour in the case of diesel, which hydrogenates a liquid raw material, and is generally in the range of 0.1 to 5 seconds for FCC applications. Thus, in various embodiments, the residence time in the catalyst bed reactor 10 is 0.1 seconds to 5 seconds or 5 minutes to 1 hour. The desired residence time of the combined hydrocarbon feedstock 4 and exothermic material stream 2 in the fixed bed reactor for optimal hydrocarbon degradation is the operating temperature and the composition of both the solid acid catalyst bed 14, the hydrocarbon feedstock 4, and the hydrocarbon feedstock 4. It depends on the heat generating material flow 2. Additionally, in one or more embodiments, the floor porosity, which represents the volume fraction occupied by the voids, is 0.2-1.0. In a further embodiment, the floor porosity is 0.3-0.8.

The catalyst bed reactor 10 can have an operating temperature of 250-850 ° C. In a further embodiment, the catalytic bed reactor 10 has an operating temperature of 450-650 ° C, or 540-560 ° C, or 575-595 ° C. Without limitation of theory, the addition of HGM2 is believed to improve the catalyst life of the solid acid catalyst bed 14. HGM2 acts as a diluent and oxidizes the hydrocarbon raw material to prevent caulking.

Further, the solid acid catalyst bed 14 can be preheated in a gas stream containing heated nitrogen 6 and oxygen at a flow rate sufficient to heat the solid acid catalyst bed 14. Oxygen can be provided as air. The preheated gas stream is heated at 250-650 ° C., or 475-525 ° C., or 490-510 ° C. in various embodiments.

With reference to the laboratory-scale reactor system of FIG. 1, preheating the hydrocarbon raw material 4 can be further included upstream of the catalyst bed reactor 10. This preheating of the hydrocarbon raw material 4 can be achieved in the preheater reactor 12. As shown, the supplied 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 raw material 4 supplied to the catalyst bed reactor 10 to a pre-reaction temperature of at least 100 ° C. The hydrocarbon raw material 4 is typically heated to a pre-reaction temperature of 200-300 ° C. This range of pre-reaction temperatures is maintained low enough to prevent thermal decomposition in the preheater reactor 12 in front of the catalyst bed reactor 10. On the contrary, the preliminary reaction temperature rises sufficiently so that the low-temperature hydrocarbon raw material 4 does not cool the catalyst bed 14 near the inlet of the catalyst bed reactor 10 and does not affect the total conversion rate of the hydrocarbon raw material 4. .. In one or more embodiments, the hydrocarbon decomposition system 100 can also optionally include at least one hydrocarbon preheater 18 located upstream of the preheater reactor 12. As shown in FIG. 1, the hydrocarbon preheater or the plurality of preheaters 18 raises the temperature of the hydrocarbon raw material supplied to at least one preheater reactor 12. The preheater 18 can include a heat exchanger or similar heating device well known to those skilled in the art.

The hydrocarbon decomposition system 100 can also include at least one exothermic material preheater 16 located upstream of the catalyst bed reactor 10. The exothermic material preheater 16 raises the temperature of the exothermic material stream 2 supplied to at least one catalyst bed reactor 10. In the embodiment, the heating material preheater 16 raises the temperature of the heating material flow 2 to a pre-reaction temperature of at least 100 ° C. The maximum pre-reaction temperature of the exothermic material stream 2 is limited by the decomposition temperature of the exothermic material stream 2 so that the thermal decomposition of the exothermic material stream 2 does not occur in front of the catalyst bed reactor 10. In a laboratory or pilot scale reactor, the hydrocarbon decomposition system 100 can also include other heating components as shown. For example, the hydrocarbon decomposition system 100 can include a catalyst bed reactor 10, a preheater reactor 12, a heating material preheater 16, and a reactor reactor 20 or a hot box 22 surrounding the hydrocarbon preheater 18. The reactor reactor 20 can help maintain the temperatures of the catalyst bed reactor 10 and the preheater reactor 12. Similarly, the hot box 22 serves to retain heat around the catalyst bed reactor 10, the preheater reactor 12, the heating material preheater 16, and the hydrocarbon preheater 18 so as to reduce heat loss.

The hydrocarbon preheater 19, the preheater reactor 12, and the heating material preheater 16 are single to raise the temperature of both the hydrocarbon raw material 4 and the heating material flow 2 before entering the catalyst bed reactor 10. Can be combined with a preheater.

In an industrial scale operation, the hydrocarbon raw material 4 and the heating material flow 2 are heated until the hydrocarbon raw material 4 and the heating material flow 2 are vaporized, respectively. The hydrocarbon raw material 4 and the heating material stream 2 can be mixed together and vaporized simultaneously in a single raw material preheater. Alternatively, the hydrocarbon raw material 4 and the exothermic material stream 2 can be independently evaporated in separate raw material preheaters before being combined and supplied to the decomposition reactor. Subsequently, the vaporized hydrocarbon raw material 4, the vaporized heating material stream 2, or the hydrocarbon raw material 4 and the heating material flow 2 are combined before the heating stream or other diluent is supplied to the decomposition reactor. Can be injected into the vaporized stream. By providing a diluent as a feedstock to the decomposition reactor, the molecules of the hydrocarbon raw material 4 are separated. When formalin (37% by weight formaldehyde in water) is used as a component of the exothermic material stream 2, formalin contains water that is converted during the exothermic material stream 2 vaporization, so no addition of steam or other diluent is required. It will be understood that. It can also be understood that the vaporization of the hydrocarbon raw material 4 and the exothermic material stream 2 can be achieved inside the decomposition reactor and not before injection into the reactor.

Further, by balancing the amounts of the heat generating material flow 2 and the hydrocarbon raw material 4, the thermally neutral decomposition process can be facilitated. In a further embodiment, the HGM stream 2 and the hydrocarbon raw material 4 are supplied to the catalyst bed reactor 10 in a weight ratio of 1:10 to 10: 1. Further, in a further embodiment, the heating material stream 2 and the hydrocarbon raw material 4 are in a ratio of 1: 6 to 6: 1, 1: 3 to 3: 1, or 1: 2 to 2: 1 for the catalyst bed reactor 10. Is supplied to. In a further embodiment, the heating material stream 2 and the hydrocarbon raw material 4 are supplied to the catalyst bed reactor 10 in a ratio of 2: 3 to 3: 2.

Referring again to FIG. 1, the decomposition products 40 can include a variety of light _C 1 _C ₄ hydrocarbons and heavy _{C 5+} hydrocarbons. In one or more embodiments, the degradation product 40 is specifically a butene such as propylene, 2-trans-butene, n-butene, iso-butene and 2-cis-butene, C ₅ olefins. Includes aromatic compounds, methane, ethane, propane, butene, and pentane. The composition of the decomposition product 40 depends on the components of the hydrocarbon raw material 4 and the heat generating material flow 2. For example, formaldehyde not only provides heat to offset the endothermic decomposition process, but is also an effective reactant for the production of light olefins.

To separate the light hydrocarbons in the decomposition product 40 from the heavy hydrocarbons, the hydrocarbon decomposition system 100 can 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 decomposition product 40 is supplied to the condenser as the temperature of the gaseous decomposition product 40 decreases and leaves the partially condensed decomposition reactor. The partially condensed raw material is subsequently fed to the liquid / gas separator 24, where the liquid and gas phases are separated. Specifically, in the liquid / gas separator 24, the light hydrocarbon stream 42 can be separated as a gas phase light hydrocarbon, and the liquid phase heavy hydrocarbon stream 44 can be discharged separately from the liquid / gas separator 24. .. In addition, on an industrial scale, the hydrocarbon decomposition system 100 may include a multi-product distillation column to separate light hydrocarbons from the heavy hydrocarbons in the decomposition product 40. Industrial scale separations utilizing distillation columns, stripping columns, or extraction columns, as well as other methods and processes for handling and separating product streams are known to those of skill in the art and can be utilized equally.

Further reactions are conceivable to separate the desired propylene and ethylene from the light hydrocarbon stream 42. For example, the light hydrocarbon stream 42 can be cooled and recovered as a liquid hydrocarbon product. At this point, propylene and ethylene can be separated by distillation, extraction distillation, or membrane separation methods.

In a further embodiment, the total flow rate of the HGM stream 2, the hydrocarbon feedstock 4, and the steam or other diluent supplied to the hydrocarbon decomposition system 100 is adjusted to control the space velocity of the reaction. The weight-time-space velocity (WHSV) is defined as, for example, the flow of the reactant at gram / hour (g / hr) divided by the weight of the catalyst weight, for example gram (g). The reaction stream includes the total flow rate of the HGM stream 2, the hydrocarbon feedstock 4, and the vapor or other diluent. In one or more embodiments, the weight-time-space velocity of the reaction is 0.01-100 hours- ¹ (h- ¹ ). In a further embodiment, the weight hourly space velocity of the reaction, 1 to 8 hours ^-1, 2 to 4 hr ^-1 or 2.8～3.4H ^-1.

Ethylene and propylene are two of the major petrochemical components used in a variety of applications, including 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 the packaging, plastic processing, construction and textile industries. In addition, although propylene is commonly used to make polypropylene, it is also a basic product required to make propylene oxide, acrylic acid and many other chemical derivatives. The plastics processing, packaging industry, furniture sector, and automobile industry are frequent users of propylene and its derivatives. Therefore, it is desirable to increase the yield of light olefins such as ethylene and propylene in order to supply to a large number of industrial users.

Improved conversion of hydrocarbon raw material 4 and light olefin (eg ethylene and propylene) yields is confirmed by experimental testing. Hexanes have been provided for experimental configurations of hydrocarbon decomposition systems 100 under different conditions and with different exothermic material flow 2 ratios.

The following examples illustrate this embodiment and do not limit the scope of the described embodiments of the present disclosure.

Experimental data were obtained to demonstrate the effect of binding the hydrocarbon decomposition reaction with HGM. The catalytic reaction was carried out in a fixed bed flow reactor operating at atmospheric pressure. The reactor was filled with a catalyst having a mass of 9-12 g, which was palletized and sieved to a diameter of 425 to 800 micrometers (μm). The catalyst is Nankai University Catalyst Co., Ltd. It was a ZSM-5 microporous molecular sieve purchased from. Prior to the catalytic reaction, the catalyst was activated to the desired reaction temperature in a gas stream containing _{N 2} (120 cm ³ min ^{-1) and held overnight.} The fixed bed flow reactor was heated to the desired reaction temperature using a 3-zone electric heater. At the desired reaction temperature (typically 250-850 ° C.), a reactant selected from n-hexane, naphtha, and formaldehyde (37% solution stabilized in 13.88% methanol) is introduced into the reactor. And started the reaction.

The products from the catalytic reaction were analyzed on an online gas chromatograph equipped with an Agilent HP-Al / KCl (50 m × 0.53 mm ID, 15 μm) column and detected by a frame ionization detector (FID) detector. N ₂ , CH ₄ , C ₂ H ₆ , C ₂ H ₄ , C ₃ H ₈ , C ₃ H ₆ , n-C ₄ H ₁₀ , i-C ₄ H ₁₀ , 1-C ₄ H ₈ , 2-cis -C ₄ H ₈ , 2-trans-C ₄ H ₈ , i-C ₄ H ₈ , n-C ₅ H ₁₂ , and n-C ₅ H ₆ were used as calibration standards. All lines and valves between the outlet of the fixed bed flow reactor and the outlet of the gas chromatograph were heated to 105 ° C. to prevent condensation of heavy hydrocarbons.

Liquid products were collected separately using a low pressure liquid / gas separator. If present, the organic moiety was separated from water and its composition was analyzed by gas chromatography-mass spectrometry (GCMS) to identify the product, followed by gas chromatography (GC) to measure its concentration.

The conversion of hexane was measured as a weight percent. Conversion is defined as a percentage of the weight of hexane converted to the final product. Wherein the hexane conversion is, the weight of the injected hexane and W _i, when the weight of unreacted hexane detected by GC and W _f, is given as an expression (1).
_{Conversion% = 100x (W i -W f} ) / W i (1)

In addition, the previously defined weight-time-spatial velocity (WHSV) was maintained in a constant test to compare HGM effects.

During the experiment, the normal reaction time was 35 minutes. After the reaction, the catalyst bed was purged with high purity nitrogen for 30 minutes at a flow rate of 0.2 liters / min to flush all reaction products and hydrocarbons before introducing air. The introduction of air is delayed due to the potential for combustion hazards in the presence of hydrocarbons and reaction products. After flushing with nitrogen to remove reaction products and hydrocarbons, the catalyst was regenerated at an air flow rate of 0.154 liters / min for 1 hour or until the temperature stabilized. The catalyst bed was then flushed again with nitrogen for 30 minutes to remove combustion products.

In order to demonstrate the effect of the heat generating material, a test was conducted using hexane as the hydrocarbon raw material 4 in combination with formaldehyde as the heat generating material flow 2. Each test was performed for 35 minutes. Table 1 details the various decomposition process parameters of the decomposition product 40 in the presence of formaldehyde and in the absence of formaldehyde. The binding of hexane to formaldehyde results in increased C6 conversion, ethylene yield, and propylene yield.

It is desirable to increase the yields of ethylene and propylene when the exothermic material stream 2 is provided with the hydrocarbon raw material 4. In addition, Table 2, provided below details the various decomposition process parameters of the decomposition product 40 in the presence of formaldehyde and varying residence times. Each test was performed for 35 minutes. The residence time is prolonged, C ₆ conversion rate increases.

The thermal neutrality of the hydrocarbon decomposition process when the exothermic material stream 2 is added can be seen in FIGS. 2 and 3. Specifically, FIG. 2 shows that the temperature drop of the solid acid catalyst bed 14 is reduced when hexane and the heating material are provided in a 2: 1 ratio. The temperature bed of the solid acid catalyst bed 14 drops very extensively when the hexane feedstock is introduced, and the controller then reacts by raising the wall temperature of the catalyst bed reactor 10. When only the hexane raw material (hydrocarbon raw material 4) is used and no heat generating material is used, the wall temperature does not rise as fast as the temperature drop from the endothermic reaction of the catalyst bed reactor 10. Conversely, when the simultaneous exothermic material stream 2 is introduced into the catalyst bed reactor 10 together with the hexane stream (hydrocarbon raw material 4), the wall of the catalyst bed reactor 10 is heated due to the exothermic material and its exothermic reaction. The temperature of the solid acid catalyst bed 14 does not decrease because less external input is required from the control device.

Similarly, referring to FIG. 3, the thermal neutrality of the hydrocarbon decomposition process when the exothermic material stream 2 is added can be seen. Specifically, FIG. 3 shows that the 1: 2 ratio of hexane and exothermic material eliminates the drop resulting from the temperature of the solid acid catalyst bed 14. When the ratio of the heat generating material to hexane (hydrocarbon) is high, the temperature of the solid acid catalyst bed 14 immediately rises. On the contrary, in the absence of the heat generating material flow 2, the temperature of the solid acid catalyst bed 14 drops immediately before it starts to rise slowly after a certain period of time.

Solid Acid Catalyst It should be noted that the solid acid catalyst in the bed did not show disintegration after 35 minutes of operation in the examples.

It should be understood that various aspects of methods for decomposing hydrocarbon raw materials have been described and that such aspects can be utilized in connection with various other aspects.

In a first aspect, the present disclosure provides a method of decomposing a hydrocarbon raw material. This method introduces the hydrocarbon raw material into the decomposition reactor, introduces a heating material (HGM) stream containing at least one aldehyde or ketone into the decomposition reactor, and vaporizes the hydrocarbon raw material and the HGM stream. This includes decomposing the hydrocarbon raw material to produce a decomposition product. Decomposition _products, including C 1 -C ₄ hydrocarbons and _{C 5} + hydrocarbons.

In a second aspect, the disclosure provides the method according to the first aspect, which vaporizes the hydrocarbon feedstock and the HGM stream after introduction into a decomposition reactor.

In a third aspect, the disclosure provides the method according to the first aspect, which vaporizes the hydrocarbon feedstock and the HGM stream prior to introduction into the decomposition reactor.

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

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

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

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

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

In a ninth aspect, the present disclosure provides the method according to 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 includes degradation products, ethylene, propylene, butenes, benzene, toluene, xylenes, ethylbenzene, H _2, methane, ethane, LPG, naphtha, gasoline, and gas oils , The method according to any one of the first to ninth aspects.

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

In a twelfth aspect, the present disclosure relates to an eleventh aspect in which the catalyst bed reactor comprises a solid acid catalyst bed arranged in the catalyst bed reactor and the catalyst bed reactor is at a reaction temperature of 250-850 ° C. Provides a method of.

In a thirteenth aspect, the present disclosure provides the method according to eleventh or twelfth aspect, wherein the catalytic bed reactor comprises a fluidized bed reactor, a fixed bed reactor, a slurry reactor or a moving bed reactor. To do.

In a fourteenth aspect, the present disclosure provides the method according to eleventh or twelfth aspect, wherein the catalytic bed reactor is a fixed bed reactor.

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

In a nineteenth aspect, the present disclosure relates to any one of the first to eighteenth aspects, wherein the HGM stream and the hydrocarbon feedstock stream are supplied in a weight ratio of 1:10 to 10: 1. Provide a method.

In a twentieth aspect, the present disclosure comprises one of the first to nineteenth aspects, wherein the hydrocarbon feedstock stream comprises unfractional or fractionated oils, hexane, naphtha, mixed butenes, ethylene, and combinations thereof. The method according to any one is provided.

It will be apparent to those skilled in the art that various modifications and variations can be made to the embodiments described herein without departing from the spirit and scope of the subject matter described in the claims. Accordingly, the present specification includes modifications and variations of the various embodiments described herein, such modifications and modifications are within the scope of the appended claims and their equivalents. Is intended to be.

Scope is provided through this disclosure. It is expected that each separate value included in the range will also be included. In addition, the range that can be formed by each separate value contained within the explicitly disclosed range is equally assumed.
Hereinafter, preferred embodiments of the present invention will be described in terms of terms.
Embodiment 1
It is a method of decomposing hydrocarbon raw materials.
Introducing hydrocarbon raw materials into the decomposition reactor and
Introducing an exothermic material (HGM) stream containing at least one aldehyde or ketone into the decomposition reactor.
To vaporize the hydrocarbon raw material and the HGM flow,
Decomposing the hydrocarbon raw material to produce a decomposition product,
Wherein the said decomposition _products, including C 1 -C ₄ hydrocarbons and _{C 5} + hydrocarbons, method.
Embodiment 2
The method according to embodiment 1, wherein the hydrocarbon raw material and the HGM stream are vaporized after being introduced into the decomposition reactor.
Embodiment 3
The method according to embodiment 1, wherein the hydrocarbon raw material and the HGM stream are vaporized before being introduced into the decomposition reactor.
Embodiment 4
The method of embodiment 1, wherein the HGM stream comprises a ketone.
Embodiment 5
The method of embodiment 1, wherein the HGM stream comprises an aldehyde.
Embodiment 6
The method according to embodiment 5, wherein the aldehyde is formaldehyde dissolved in water.
Embodiment 7
The method according to embodiment 6, wherein the formaldehyde dissolved in water is stabilized by an organic solvent.
8th Embodiment
The method according to embodiment 7, wherein the organic solvent is methanol.
Embodiment 9
The method of embodiment 1, wherein the HGM stream further comprises an alcohol, an additional ketone, or an additional aldehyde.
Embodiment 10
The degradation products, ethylene, propylene, butenes, benzene, toluene, xylenes, ethylbenzene, H _2, methane, ethane, LPG, naphtha, gasoline, and gas oils, method of embodiment 1.
Embodiment 11
The method according to embodiment 1, wherein the decomposition reactor is at least one catalyst bed reactor.
Embodiment 12
11. The method of embodiment 11, wherein the catalyst bed reactor comprises a solid acid catalyst bed disposed in the catalyst bed reactor, and the catalyst bed reactor is at a reaction temperature of 250-850 ° C.
Embodiment 13
12. The method of embodiment 12, wherein the catalytic bed reactor comprises a fluidized bed reactor, a fixed bed reactor, a slurry reactor, or a moving bed reactor.
Embodiment 14
13. The method of embodiment 13, wherein the catalytic bed reactor is a fixed bed reactor.
Embodiment 15
12. The method of embodiment 12, wherein the solid acid catalyst is a ZSM-5 catalyst.
Embodiment 16
15. The method of embodiment 15, wherein the ZSM-5 catalyst has a Si / Al molar ratio of at least 10.
Embodiment 17
The method of embodiment 15, wherein the ZSM-5 catalyst has a Si / Al molar ratio of at least 30.
Embodiment 18
15. The method of embodiment 15, wherein the ZSM-5 catalyst comprises phosphorus, boron, nickel, iron, tungsten, or a combination thereof.
Embodiment 19
The method according to the first embodiment, wherein the HGM stream and the hydrocarbon raw material stream are supplied in a weight ratio of 1:10 to 10: 1.
20th embodiment
The method according to embodiment 1, wherein the hydrocarbon raw material stream comprises unfractional or fractionated crude oil, hexane, naphtha, mixed butenes, ethylene, and combinations thereof.

Claims (9)

It is a method of decomposing hydrocarbon raw materials.
Heating the hydrocarbon raw material to a pre-reaction temperature of 200-300 ° C.
Introducing a hydrocarbon raw material that is a liquid at the preliminary reaction temperature into the decomposition reactor, wherein the decomposition reactor is at least one catalyst bed reactor, and the catalyst bed reactor is a catalyst bed reactor. Containing a solid acid catalyst bed containing a solid acid catalyst having a size of 25 to 2,500 μm arranged within.
Wherein introducing a heat generating material consisting of formaldehyde (HGM) flow in the decomposition reactor, wherein said as formaldehyde and water is supplied to the cleavage reactor as formalin, and also to flow of water in the decomposition reactor Supply,
The hydrocarbon feedstock and vaporizing the HGM flow, and the hydrocarbon feedstock is decomposed without the application of heat energy added by the catalyst bed reactor, C ₁ -C ₄ hydrocarbons and C _{5 +} hydrocarbons To produce decomposition products containing ,
Only including,
The weight-time-spatial rate of supply of the HGM and the reactants containing the hydrocarbon raw material to which the HGM flow and the hydrocarbon raw material flow are supplied in a weight ratio of 2: 1 to 10: 1 and which are supplied to the decomposition reactor 0.01-100 hours ^-1 (h ^-1 ) , method. The degradation products, ethylene, propylene, butenes, including benzene, toluene, xylenes, ethylbenzene, H _2, methane, ethane, LPG, naphtha, gasoline, and gas oils, The method of claim 1. Before SL said catalytic bed reactor containing a solid body acid catalyst bed is at a reaction temperature of 250-850 ° C., The method according to claim 1 or 2. The method according to any one of claims 1 to 3, wherein the catalytic bed reactor includes a fluidized bed reactor, a fixed bed reactor, a slurry reactor, or a moving bed reactor. The method according to claim 4 , wherein the catalytic bed reactor is a fixed bed reactor. The method according to any one of claims 1 to 5, wherein the solid acid catalyst is a ZSM-5 catalyst having a Si / Al molar ratio of at least 10. The method of claim 6 , wherein the ZSM-5 catalyst comprises phosphorus, boron, nickel, iron, tungsten, or a combination thereof. The method according to any one of claims 1 to 7 , wherein the HGM flow and the hydrocarbon raw material flow are supplied in a weight ratio of 2: 1 to 6: 1. The method according to any one of claims 1 to 8 , wherein the hydrocarbon raw material stream contains unfractional or fractionated crude oil, hexane, naphtha, mixed butenes, ethylene, and a combination thereof.

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