CN110437873B - Utilization method of hydrocarbon oil rich in carbon four-carbon pentaalkane - Google Patents
Utilization method of hydrocarbon oil rich in carbon four-carbon pentaalkane Download PDFInfo
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- CN110437873B CN110437873B CN201810416050.6A CN201810416050A CN110437873B CN 110437873 B CN110437873 B CN 110437873B CN 201810416050 A CN201810416050 A CN 201810416050A CN 110437873 B CN110437873 B CN 110437873B
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- 238000000034 method Methods 0.000 title claims abstract description 80
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- 239000003502 gasoline Substances 0.000 claims abstract description 49
- 239000002994 raw material Substances 0.000 claims abstract description 27
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a method for utilizing hydrocarbon oil rich in carbon four-carbon pentaalkane, which mainly takes reformed topped oil as a raw material, fully utilizes the characteristic of the hydrocarbon oil rich in carbon four-carbon pentaalkane, adopts the process combination of catalytic dehydrogenation technology, etherification technology and aromatization technology to produce etherified gasoline, aromatization oil and propylene, and simultaneously produces hydrogen as a byproduct. Both etherified gasoline and aromatized oil can be used as high octane number gasoline additive components to improve gasoline pool composition, the generated propylene can be used as raw material of polypropylene device, and hydrogen can be used by other hydrogen consuming devices in the plant. Provides an effective way for utilizing hydrocarbon oil such as reforming topping oil, and improves the utilization rate and the added value of the hydrocarbon oil such as reforming topping oil.
Description
Technical Field
The invention provides a method for producing high-octane gasoline components and propylene and simultaneously producing hydrogen as a byproduct by using hydrocarbon oil rich in carbon four-carbon pentaalkane such as reformed topped oil as a raw material and adopting a combined process of a catalytic dehydrogenation technology, an etherification technology and an aromatization technology.
Background
With the increasingly stringent environmental protection requirements and the need for technological development, the global clean fuel standards are continuously increasing and being put into practice. The Catalytic Cracking (FCC) gasoline in the finished gasoline in China accounts for about 80%, and the gasoline has high olefin content, high sulfur content and poor gasoline stability, and becomes a major problem in upgrading gasoline quality. In 2014, China will execute the national IV automobile gasoline quality standard in all aspects and has executed the national V automobile gasoline quality standard in part of regions. The refining enterprises face the serious challenge of upgrading the quality of the gasoline, and the development of the gasoline additive component with low sulfur, low olefin content and high octane number becomes a practical problem which is urgently needed to be solved by each refining enterprise. According to the specific conditions of China, the addition of the reformed gasoline is properly increased, the problem of high olefin content of the gasoline can be basically solved, and the octane number can be met.
After the raw material of the reforming device passes through the prefractionator, the fraction with the temperature lower than 80 ℃ can be separated from the top of the tower, and the fraction is called as reforming topped oil. The reformed topped oil is a very precious petroleum resource, has light components and stable properties, is basically saturated alkane after passing through a pre-hydrogenation reaction system of a reforming device, mainly comprises saturated carbon five components, and accounts for more than 70 percent of the total amount, wherein n-pentane and isopentane are more, the main treatment method of the reformed topped oil is to mix the reformed topped oil into gasoline, and the octane number of the reformed topped oil is not high, so that the octane number of the gasoline mixed with the reformed topped oil is reduced, and the reformed topped oil is an undesirable gasoline additive component. If the reformed topped oil is sold, the loss of benefit is serious because of the influence of the tax collection on the light carbon five. Therefore, the reformed will head oil is fully utilized, the added value of the product is improved, and the method is an effective way for resource utilization.
Cn201210097626.x discloses a method for producing high-octane gasoline from a C4, C5, C6 alkane-rich feedstock. The method utilizes olefins generated after dehydrogenation of C4, C5 and C6 to carry out aromatization reaction to obtain C three-C four-C five-C hexaalkane, a gasoline component and a diesel component. Although a certain amount of gasoline and diesel oil are obtained by the method, the content of liquefied gas in the product is still higher, and the utilization rate of raw materials has a further potential digging space.
CN201210097758.2 discloses a process for producing high-octane gasoline by using a raw material rich in four-carbon five-carbon sulfur alkane. The method comprises the steps of mixing raw materials with hydrogen, carrying out dehydrogenation reaction, sending a dehydrogenation product to an aromatization unit, and finally circulating carbon four carbon five carbon six separated from the aromatization product to a catalytic dehydrogenation unit. The hydrogenation reaction of fischer tropsch requires the mixing of the feedstock with hydrogen, which increases the production cost.
CN201210097629.3 discloses a process for producing high octane gasoline from a carbon-four carbon-five carbon-six alkane-rich raw material. The method carries out aromatization reaction after the raw materials are dehydrogenated to obtain the high-octane gasoline component. However, the method can obtain a certain amount of hydrocarbons besides the gasoline component, and the method does not describe the utilization of the hydrocarbons, so that the resource utilization rate is slightly insufficient.
CN201210097890.3 discloses a method for producing high octane gasoline from a carbon-four carbon-five carbon-six alkane-rich raw material. The method mixes the raw material with hydrogen to carry out catalytic dehydrogenation reaction, and the dehydrogenated product is sent to an aromatization unit to carry out aromatization. The obtained products are dry gas, liquefied gas, gasoline and diesel oil. Although the method provides a utilization way for the application of the C-V-hexaalkane, the method also has the problem that the liquefied gas resource in the obtained product is still not fully utilized.
CN201510435659.4 discloses a method for producing high-octane gasoline components from low-carbon hydrocarbons, which mainly utilizes a stream rich in carbon four-carbon five-carbon hexaalkane and a stream rich in olefin to produce hydrocarbon streams of butadiene and pentadiene through catalytic dehydrogenation and oxidative dehydrogenation, and the hydrocarbon streams enter a low-temperature aromatization reactor to produce gasoline components. The invention mainly provides a combined process combining catalytic dehydrogenation technology, oxidative dehydrogenation technology and low-temperature aromatization technology, and a method for producing high-octane gasoline components and diolefins by mixing low-carbon hydrocarbons such as refinery topping oil, pentane oil, catalytic cracking carbon four, cracking carbon four and the like.
CN201610415085.9 discloses a process method for producing high-octane gasoline from naphtha, which is mainly characterized in that naphtha is heated and then sent into an atmospheric fractionation device, components below 90 ℃ are separated out from the top of the tower through atmospheric fractionation, and components above 90 ℃ are separated out from the bottom of the tower. The tower top product is sent to an isomerization device, the components with the temperature of more than 90 ℃ are sent to a light hydrocarbon aromatization device, and the mixture of the isomerization product and the aromatization product is sent to a gas-liquid separation device, so that dry gas rich in hydrogen, liquefied petroleum gas and high-octane gasoline are obtained.
CN201510435396.7 discloses a conversion process of low-carbon hydrocarbons, which is a method for producing butadiene, pentadiene and gasoline components rich in high-octane ether compounds by utilizing the mixture of topped oil, coked light naphtha, oil field light hydrocarbon and catalytic cracking C4 and cracking C4 rich in olefin of a pentane lamp, which take C4/C5/C6 alkane as main components.
CN201510435112.4 discloses a process for improving the added value of light hydrocarbons of topped oils by conversion, which comprises subjecting a material flow rich in four-carbon five-carbon hexaalkane to catalytic dehydrogenation and oxidative dehydrogenation to produce butadiene, pentadiene and high-octane gasoline additive components. An oxidative dehydrogenation diene production unit and a diene separation unit are added between the catalytic dehydrogenation reaction unit and the low-temperature aromatization reaction unit, so that a certain amount of diene is produced as a byproduct while high-octane gasoline components are produced.
CN201510435111.X discloses a method for converting light hydrocarbons of topped oil, which uses topped oil with C4/C5/C6 alkane as main component, coked light naphtha, light hydrocarbons in oil field and pentane lamp to produce butadiene, pentadiene and high octane gasoline additive component. The method for producing the diene and gasoline additive components is realized by combining a catalytic dehydrogenation technology, an oxidative dehydrogenation technology and an etherification technology.
CN201510379026.6 discloses a method for optimizing and utilizing light naphtha, which separates light naphtha to obtain a product rich in isoparaffin and a product rich in normal paraffin. The product rich in normal alkane and the product rich in isoparaffin which directly act on the ethylene cracking raw material are obtained by adopting an adsorption separation-rectification separation coupling process, and the product rich in isoparaffin is rectified to obtain high-purity isopentane and a gasoline blending product rich in isomeric carbon six.
CN201510384425.1 discloses a method for producing isopentane products, which adopts a rectification-adsorption coupling process to produce the isopentane products by utilizing a hydrocarbon mixture rich in isopentane. The hydrocarbon mixture rich in isopentane is sent into an adsorption separation unit for adsorption separation, the adsorption separation unit at least comprises four adsorption towers which are connected in parallel and work in an alternating and cyclic mode, the adsorption towers alternately operate in a period, and each period comprises the processes of adsorption, pressure reduction, reverse release, resolution, pressure increase and stamping.
The analysis of the patent documents disclosed above shows that the utilization of light hydrocarbons containing C4 and C5 is basically involved, and the analysis of the utilization approaches of the above patent documents to raw materials shows that resources rich in C4 and C5 alkanes, such as reformed topped oil, can be further developed and utilized to generate more high value-added products and improve the utilization rate of the resources.
Disclosure of Invention
The invention aims to provide a method for utilizing hydrocarbon oil such as reformed topping oil, which fully utilizes the carbon four-carbon pentaalkane rich in the hydrocarbon oil such as reformed topping oil, adopts the process combination of catalytic dehydrogenation technology, etherification technology and aromatization technology to produce etherified gasoline, aromatization oil and propylene, and produces hydrogen as a byproduct, wherein the etherified gasoline and aromatization oil can be used as high-octane gasoline additive components, the propylene can provide raw materials for polypropylene devices, and the hydrogen can be used by other hydrogen consuming devices in a factory. The invention provides an effective way for utilizing hydrocarbon oil such as reforming topping oil, and improves the utilization rate and the added value of the hydrocarbon oil such as reforming topping oil.
The utilization method of the hydrocarbon oil rich in the carbon four-carbon pentaalkane mainly comprises a depropanization unit, a catalytic dehydrogenation unit 1#, an etherification unit, an aromatization unit and a catalytic dehydrogenation unit 2#, and mainly comprises the following steps:
(1) sending the hydrocarbon raw material (stream a) rich in the C-pentaalkane to a depropanization unit, and removing propane (stream b) in the hydrocarbon raw material to obtain mixed C-pentaalkane.
(2) And (3) sending the mixed C-V (material flow c) into a catalytic dehydrogenation unit No. 1, wherein the mixed C-V (material flow c) mainly comprises C-V and C-V alkanes, and isobutane and isopentane are dehydrogenated to generate isobutene and isopentene under the action of a dehydrogenation catalyst to obtain a dehydrogenation product (material flow d).
(3) The dehydrogenation product (stream d) is mixed with methanol (stream e), preheated and fed into the etherification unit. And (3) carrying out etherification reaction on the dehydrogenation product (material flow d) and methanol (material flow e) in an etherification reactor to obtain an etherification product, sending the etherification product (material flow f) to an etherification product separation tower, obtaining unreacted carbon four-carbon five (material flow g) at the tower top, and obtaining the etherification gasoline (material flow h) at the tower bottom. Sending the unreacted carbon four-carbon five (material flow g) to a methanol extraction tower, and performing methanol extraction by using water (material flow i) as an extracting agent to obtain a mixture (material flow k) of the carbon four-carbon five (material flow j) after the ether and water and methanol.
(4) The etherified carbon four carbon five (stream j) is sent to an aromatization unit. Under the action of an aromatization catalyst, carrying out aromatization reaction on butane in the etherified carbon four-carbon five (material flow j) in an aromatization reactor to obtain an aromatization product (material flow l), and separating the aromatization product by an aromatization product separation tower to obtain aromatization tail gas (material flow m) and aromatization oil (material flow n).
(5) Sending the aromatization tail gas (material flow m) and the propane (material flow b) obtained in the step (1) to a catalytic dehydrogenation unit 2 #. The main component of the aromatization tail gas (stream m) is propane, and propylene (stream o) is obtained by dehydrogenation of propane in the unit, and hydrogen is produced as a byproduct.
In the invention, the hydrocarbon raw material rich in the carbon four-carbon pentaalkane is preferably reformed topped oil, and other oil field light hydrocarbons rich in the carbon four-carbon pentaalkane can be selected and can be one or a mixture of more of the hydrocarbon raw material rich in the carbon four-carbon pentaalkane. For hydrocarbon feedstocks rich in C, and C, pentaalkanes in the present invention preferably have a C, and C, alkane content of not less than 27%, more preferably not less than 32%. The content of penta-carbon paraffins is not less than 43%, preferably not less than 45%.
The method can be realized by the following steps:
fig. 1 is a flow chart of a process applying the present invention.
The depropanization unit in the step (1) is a depropanization process and comprises a depropanization tower. Because hydrocarbon oil such as the reforming topping oil contains a certain amount of propane, the propane is removed in a depropanizer, the propane is obtained at the tower top, the purity of the propane is not lower than 99 percent, and the mixed carbon of four carbon and five carbon is obtained at the tower bottom.
The catalytic dehydrogenation unit 1# in the step (2) is a technological process of dehydrogenation reaction and comprises a dehydrogenation reactor. And (3) sending the mixed C, C and V to a dehydrogenation reactor of the unit, wherein the main components of the mixed C, C and V are C, C and V alkanes, and isobutane and isopentane undergo dehydrogenation reaction to generate isobutene and isopentene. The dehydrogenation catalyst is filled in the dehydrogenation reactor.
The catalyst used in the dehydrogenation reactor in catalytic dehydrogenation unit # 1 is a art dehydrogenation catalyst such as a platinum or chromium based catalyst.
Dehydrogenation catalyst with Al2O3The carrier is loaded with one of Pt, Cr, Mo and V as active component and one or more of Ni, Cu, K, La, Ca and Mg as assistant. The catalyst is preferably prepared by a coprecipitation method or an impregnation method. When the catalyst is prepared by adopting a coprecipitation method, nitrate with a proper ratio is dissolved in deionized water, ammonia water/ammonium carbonate is dropwise added under vigorous stirring, and aging is carried out for 3-48 h. Then filtering, washing, drying and roasting to form the catalyst. When the catalyst is prepared by adopting an impregnation method, aluminum and nitrate of an active component in a proper proportion are dissolved in a certain amount of deionized water, a carrier is added, the mixture is slowly dried at the temperature of 40-150 ℃, and then the catalyst is obtained through drying, pre-decomposition and roasting. The dehydrogenation catalyst comprises 50-90% of a carrier, 1-40% of active component elements and 0.1-30% of auxiliary agent elements.
The catalytic dehydrogenation reaction conditions recommended by the invention are as follows: the reaction temperature is 450-800 ℃, the preferable temperature is 500-700 ℃, the reaction pressure is 0.01-2 MPa, the preferable pressure is 0.1-0.5 MPa, and the feeding airspeed is 1.0-10.0 h-1Preferably 2.0 to 6.0 hours-1. In catalytic dehydrogenation unit # 1, the dehydrogenation product (stream d) is obtained, which is sent to the etherification unit.
The dehydrogenation reactor in the catalytic dehydrogenation unit 1# is not limited to the type of dehydrogenation reactor, and may be one of a fixed bed reactor or a fluidized bed reactor.
The dehydrogenation catalyst used in the dehydrogenation reactor in catalytic dehydrogenation unit # 1 can be an extruded catalyst suitable for a fixed bed or a microspherical catalyst suitable for a fluidized bed. The dehydrogenation reactor can be a fixed bed reactor or a fluidized bed reactor according to different catalyst forms.
The etherification unit in the step (3) comprises three processes of etherification reaction, product separation and methanol extraction, and comprises an etherification reactor, an etherification product separation tower and a methanol extraction tower. The etherification reactor and the etherification product separation tower can be selected from a combination form of a fixed bed reactor and a plate separation tower or a combination form of a fixed bed reactor and a catalytic distillation tower, and the invention recommends the use of the combination form of the fixed bed reactor and the catalytic distillation tower. Wherein the number of the fixed bed reactors is one or two. When two fixed bed reactors are used, the distribution mode is series connection or parallel connection, and the distribution mode is realized by the following connection mode: the upper parts and the upper parts, the lower parts and the lower parts, and the upper parts and the lower parts of the two fixed bed reactors are sequentially connected by valves and pipelines, and the two fixed bed reactors are connected in series or in parallel by switching the valves, as shown in figure 2. When the two fixed bed reactors are operated in series, the depth of the etherification reaction can be increased, and when the two fixed bed reactors are operated in parallel, the feeding can be switched on line to complete the on-line replacement of the catalyst.
An etherification catalyst is filled in the fixed bed reactor and the catalytic distillation tower, the catalyst is a macroporous cation exchange resin catalyst, the mass total exchange capacity is 2-10 mmol/g, the water content is 1-9%, and the wet apparent density is 0.6-1.5 g/ml. And (3) mixing the dehydrogenation product with methanol, and then feeding the mixture into a fixed bed reactor, wherein the reaction temperature is 20-90 ℃, preferably 30-70 ℃, and the etherification reaction temperature is not the inlet temperature of the reactor, but the reaction temperature of a catalyst bed layer in the etherification reactor. At the same time, it is generally required that the maximum temperature of the catalyst bed (hot spot) not exceed the maximum temperature that the catalyst can withstand. The reaction pressure is 0.01-3.0 MPa, preferably 0.3-1.5 MPa, and the reaction pressure is controlled by a pressure control valve. The alcohol-to-olefin ratio is 0.5 to 3.0, preferably 0.8 to 2.0. The alcohol-to-olefin ratio refers to the molar ratio of methanol to the sum of isobutylene and isoamylene. Under the action of an etherification catalyst, isobutene, isoamylene and methanol are subjected to etherification reaction to generate an etherification product with methyl tert-butyl ether (MTBE) and methyl tert-amyl ether (TAME) as main components. Sending the etherified product to a catalytic distillation tower, wherein the catalytic distillation tower is filled with a filler besides a macroporous cation exchange resin catalyst. Therefore, the etherification reaction and the separation of the etherification product can be simultaneously carried out in the catalytic distillation column. Unreacted carbon four-carbon five is obtained at the top of the catalytic distillation tower, etherified gasoline is obtained at the bottom of the catalytic distillation tower, the best yield of MTBE in the etherified gasoline is not lower than 98%, the yield of TAME is not lower than 98%, and the generated etherified gasoline can be used as a high-octane gasoline additive component. Because the unreacted carbon four-carbon five contains a certain amount of methanol, the unreacted carbon four-carbon five is introduced into a methanol extraction tower for methanol extraction, the methanol extraction tower adopts a plate tower, water is used as an extracting agent, the feeding temperature of the extraction tower is 20-70 ℃, preferably 30-60 ℃, and the pressure is 0.1-1.0 MPa, preferably 0.4-0.8 MPa. And (3) obtaining the four-carbon five after ether from the top of the methanol extraction tower, wherein the content of methanol in the four-carbon five after ether is less than 1%, and obtaining a mixture of water and methanol from the bottom of the tower.
The aromatization unit in the step (4) comprises two processes of aromatization reaction and aromatization product separation, and comprises an aromatization reactor and an aromatization product separation tower. Feeding the ether carbon four-carbon five obtained in the step three into an aromatization reactor, wherein the reaction temperature is 300-600 ℃, the reaction temperature is 350-550 ℃ preferably, the reaction pressure is 0.05-4.0 MPa preferably 0.08-4.0 MPa, and the liquid hourly space velocity is 0.01-10 h under the action of a catalyst-1Preferably 0.05 to 5 hours-1Under the condition, butane is subjected to aromatization reaction to obtain an aromatization product, and the aromatization product is separated by an aromatization product separation tower to obtain aromatization tail gas and aromatization oil. Wherein the yield of the aromatized oil is not less than 20 percent, and the Research Octane Number (RON) is not less than 90. The main component of the aromatization tail gas is propane, and generally, the content of propane is not less than 85%.
The catalyst in the aromatization reactor is an aromatization catalyst used in the art, preferably a molecular sieve catalyst such as ZSM-5 or a metal modified HZSM-5 molecular sieve catalyst.
In the present invention, the aromatization product separation column is not limited to the type of column and may be one of a plate column or a packed column, and the use of a plate column is recommended in the present invention.
The catalytic dehydrogenation unit 2# in the step (5) is a dehydrogenation reaction process and comprises a dehydrogenation reactor. And (4) sending the aromatization tail gas obtained in the step (5) and the propane obtained in the step (to a catalytic dehydrogenation unit 2 #. Under the action of the catalyst, propane is dehydrogenated in the dehydrogenation reactor to produce propylene and hydrogen as by-product.
The catalyst used in the dehydrogenation reactor in catalytic dehydrogenation unit # 2 is a dehydrogenation catalyst of the art, such as a platinum-based or chromium-based catalyst.
The dehydrogenation catalyst may be Al2O3The supported active component is one of Pt, Cr, Mo and V elements, and the supported auxiliary agent is one or more of Ni, Cu, K, La, Ca and Mg elements. The catalyst is preferably prepared by a coprecipitation method or an impregnation method. When the catalyst is prepared by adopting a coprecipitation method, nitrate with a proper ratio is dissolved in deionized water, ammonia water/ammonium carbonate is dropwise added under vigorous stirring, and aging is carried out for 3-48 h. Then filtering, washing, drying and roasting to form the catalyst. When the catalyst is prepared by adopting an impregnation method, aluminum and nitrate of an active component in a proper proportion are dissolved in a certain amount of deionized water, a carrier is added, the mixture is slowly dried at the temperature of 40-150 ℃, and then the catalyst is obtained through drying, pre-decomposition and roasting. The dehydrogenation catalyst comprises 50-90% of a carrier, 1-40% of active component elements and 0.1-30% of auxiliary agent elements.
The catalytic dehydrogenation reaction conditions recommended by the invention are as follows: the reaction temperature is 450-800 ℃, the preferable temperature is 500-700 ℃, the reaction pressure is 0.01-2 MPa, the preferable pressure is 0.1-0.5 MPa, and the feeding airspeed is 1.0-10.0 h-1Preferably 2.0 to 6.0 hours-1。
The dehydrogenation reactor in the catalytic dehydrogenation unit 2# is not limited to the type of dehydrogenation reactor, and may be one of a fixed bed reactor or a fluidized bed reactor.
The catalyst used in the dehydrogenation reactor in catalytic dehydrogenation unit # 2 can be an extruded catalyst suitable for a fixed bed or a microspherical catalyst suitable for a fluidized bed. The dehydrogenation reactor can be a fixed bed reactor or a fluidized bed reactor according to different catalyst forms.
In the present invention, the pressure refers to gauge pressure unless otherwise specified.
In the invention, the percentage is mass percentage content if no special designation is provided.
The airspeed referred to in the present invention is the mass airspeed.
The raw material of the invention is reforming topped oil, and can also be hydrocarbons rich in carbon four-carbon pentaalkane such as light hydrocarbon of oil field, and can be one or more of them.
The methanol used in the invention preferably meets the national first-class quality standard, wherein the density is 0.791-0.793 g.cm-3。
The invention has the advantages that: hydrocarbon oil such as reformed topped oil is used as a raw material, the characteristic of the hydrocarbon oil rich in four-carbon pentaalkane is fully utilized, the combination of the catalytic dehydrogenation technology, the etherification technology and the aromatization technology is adopted to produce etherified gasoline, aromatized oil and propylene, and hydrogen is produced as a byproduct. Wherein, etherified gasoline and aromatized oil can be used as high octane number gasoline additive components to improve the gasoline pool composition, the generated propylene can be used as the raw material of a polypropylene device, and hydrogen can be used by other hydrogen consumption devices in a factory. The invention provides an effective way for utilizing hydrocarbon oil such as reforming topping oil, and improves the utilization rate and the added value of the hydrocarbon oil such as reforming topping oil.
Drawings
FIG. 1 is a process flow diagram of the application of the present invention.
In fig. 1: i-depropanization unit, II-catalytic dehydrogenation unit 1#, III-etherification unit, IV-aromatization unit and V-catalytic dehydrogenation unit 2 #.
In fig. 1: 1-depropanizer; 2-a first dehydrogenation reactor; 3-etherification reactor; 4-etherified product separation tower, 5-methanol extraction tower; 6-aromatization reactor, 7-aromatization product separation tower and 8-second dehydrogenation reactor.
In fig. 1: stream a-hydrocarbon raw material, stream b-propane, stream c-mixed C-V, stream d-dehydrogenation product, stream e-methanol, stream f-etherification product, stream g-unreacted C-V, stream h-etherified gasoline, stream i-water, stream j-etherified C-V, stream k-water and methanol mixture, stream l-aromatization product, stream m-aromatization tail gas, stream n-aromatization oil and stream o-propylene.
FIG. 2 is a schematic diagram of the connection of an etherification unit according to the present invention using two fixed bed reactors.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Example 1
The reformed topped oil is used as the raw material in the method of the invention, and the composition of the raw material is shown in table 1.
TABLE 1 reformate detailed family compositions
The reformed topped oil, the hydrocarbon feedstock (stream a), is sent to depropanizer 1 in depropanizer unit i. The content of the carbon four and carbon five alkane in the mixed carbon four carbon five (material flow c) after propane removal is not less than 70 percent. Sending the mixed C, C and V (material flow c) to a first dehydrogenation reactor 2 in a catalytic dehydrogenation unit 1# II, wherein the first dehydrogenation reactor 2 is a fluidized bed reactor, the dehydrogenation catalyst is prepared by adopting an immersion method and is made of Al2O3The carrier is simultaneously loaded with Cr, Ni, Cu and K elements. The dehydrogenation reaction temperature in the catalytic dehydrogenation unit 1# II is 610 ℃, the reaction pressure is 0.2MPa, and the space velocity is 2.5h-1. The main components of the dehydrogenation product (stream d) are isobutene and isoamylene, the content of the isobutene and the isoamylene is not less than 10%, and the dehydrogenation product (stream d) and methanol (stream e) are mixed and then sent to an etherification unit III. The methanol (stream e) properties are shown in Table 2.
In the etherification unit III, the etherification reactor 3 adopts a fixed bed reactor, and the etherification product separation tower 4 adopts a catalytic distillation tower. Macroporous cation resin catalysts are respectively filled in the etherification reactor 3 and the catalytic distillation tower 4. The catalyst has a mass total exchange capacity of 2-10 mmol/g, a water content of 1-9%, and a wet apparent density of 0.6-1.5 g/ml. The catalyst is filled in the etherification reactor 3 in sections, so that an expansion space of the catalyst in a reaction state is reserved, and the formation of hot spots is well avoided. Under the conditions of reaction temperature of 40 ℃, reaction pressure of 0.8MPa and alcohol-olefin ratio of 0.9, the dehydrogenation product (material flow d) and methanol (material flow e) are subjected to etherification reaction, the etherification product (material flow f) enters a catalytic distillation tower 4, an etherification catalyst and a filler are filled in the catalytic distillation tower 4, and the catalyst in the catalytic distillation tower 4 is filled in a filling member in ZL201520508723.2 in example 1. The catalytic distillation tower 4 can simultaneously carry out etherification reaction and separation of etherification products, unreacted carbon four-carbon five (material flow g) is obtained at the tower top, and etherified gasoline (material flow h) is obtained at the tower bottom. Sending unreacted C-V (stream g) to a methanol extraction tower 5 for methanol extraction, wherein the feeding temperature is 45 ℃, the pressure is 0.6Mpa, and obtaining the C-V (stream j) after extraction, wherein the content of methanol is 0.02 percent, and a mixture of water and methanol (stream k).
TABLE 2 methanol compliance with GB 338-
The etherified four-carbon five (stream j) is sent to an aromatization reactor 6 in an aromatization unit IV, the aromatization catalyst in the aromatization reactor 6 adopts an aromatization catalyst, adopts a catalyst in a patent CN1586721A to prepare the aromatization catalyst SIHZSM-5(A) -01 prepared in example 7, the reaction temperature is 440 ℃, the reaction pressure is 1.5MPa, and the space velocity is 1.5h-1Under the conditions of (1), carrying out aromatization reaction. The aromatization product (stream l) is separated by an aromatization product separation tower 7 to obtain aromatization oil (stream n) and aromatization tail gas (stream m). The aromatization tail gas (stream m) and propane (stream b) from the depropanization unit I in the step are sent to a second dehydrogenation reactor 8 in a catalytic dehydrogenation unit 2# V together, the second dehydrogenation reactor 8 is a fixed bed reactor, and a dehydrogenation catalyst adopts a coprecipitation method to prepare a dehydrogenation catalystPrepared with Al2O3The carrier is simultaneously loaded with Cr, Ni, Cu, K and La elements. The dehydrogenation reaction temperature in the dehydrogenation unit 2# V is 600 ℃, the reaction pressure is 0.2MPa, and the space velocity is 2.5h-1。
The mass yield of each component of the system in the process is as follows: 4.15% of dry gas, 15.8% of etherified gasoline, 17.93% of aromatized oil, 26% of propylene and 36.12% of propane, wherein the hydrogen in the dry gas accounts for 94.95 vol%.
Example 2
A different reformate, i.e., a hydrocarbon feed (stream a), was used than in example 1, with feed properties shown in table 3. The process conditions, procedure and aromatization catalyst used in example 2 were the same as in example 1. Wherein, the content of methanol in C, C and C (material flow j) after the top ether of the methanol extraction tower 5 is 0.023 percent.
The mass yield of each component of the system in the process is as follows: 3.86% of dry gas, 12.41% of etherified gasoline, 20.81% of aromatized oil, 26.34% of propylene and 36.58% of propane, wherein the hydrogen in the dry gas accounts for 96.50 vol%.
TABLE 3 reformate detailed family compositions
Example 3
The same raw materials as in example 1, the same methanol as in example 1 and the same process flow as in example 1 were used. The difference lies in that:
the dehydrogenation catalyst used in the catalytic dehydrogenation unit 1# II is prepared by an immersion method and is made of Al2O3Is a carrier and simultaneously loads Cr, Ni, Cu, K and Mg elements. The dehydrogenation reaction temperature is 590 ℃, the reaction pressure is 0.15MPa, and the space velocity is 2.0h-1。
In an etherification reactor 3 in the etherification unit III, etherification reaction is carried out at the temperature of 48 ℃, the reaction pressure of 0.9MPa and the alcohol-hydrocarbon ratio of 1.1, an etherification product (material flow f) enters a catalytic distillation tower 4, an etherification catalyst and a filler are filled in the catalytic distillation tower 4, and a catalyst direct filling component adopts the filling component in the embodiment 1 in ZL 201520508723.2. In the methanol extraction column 5, the unreacted carbon four carbon five (stream g) was fed at a temperature of 48 ℃ and a pressure of 0.7 MPa. The methanol content in the C-V (material flow j) after the top ether of the methanol extraction tower 5 is 0.021%.
③ aromatization catalyst the aromatization catalyst SIHZSM-5(A) -02 prepared in example 7 was prepared using the catalyst of patent CN1586721A, the reaction temperature was 430 deg.C, the reaction pressure was 2.5MPa, and the space velocity was 2.0h-1Under the conditions of (1), carrying out aromatization reaction.
Fourthly, the dehydrogenation catalyst used in the catalytic dehydrogenation unit 2# V is prepared by a coprecipitation method and is made of Al2O3Is a carrier and simultaneously loads Cr, Ni, Cu, K, Mg and Ca elements. The dehydrogenation reaction temperature is 590 ℃, the reaction pressure is 0.15MPa, and the space velocity is 2.0h-1。
The mass yield of each component of the system in the process is as follows: 4.12% of dry gas, 15.75% of etherified gasoline, 17.71% of aromatized oil, 24.74% of propylene and 37.68% of propane, wherein hydrogen in the dry gas accounts for 94.84 vol%.
Example 4
The same raw materials as in example 1, the same methanol as in example 1 and the same process flow as in example 1 were used. The difference lies in that
The dehydrogenation catalyst used in the catalytic dehydrogenation unit 1# II is prepared by an immersion method and is made of Al2O3The carrier is used for simultaneously loading Cr, Ni, Cu, K, La, Mg and Ca elements. The dehydrogenation reaction temperature is 595 ℃, the reaction pressure is 0.15MPa, and the space velocity is 2.5h-1。
In an etherification reactor 3 in the etherification unit III, etherification reaction is carried out at the temperature of 43 ℃, the reaction pressure of 0.8MPa and the alcohol-hydrocarbon ratio of 1.2, an etherification product (material flow f) enters a catalytic distillation tower 4, an etherification catalyst and a filler are filled in the catalytic distillation tower 4, and a catalyst direct filling component adopts the filling component in the embodiment 1 in ZL 201520508723.2. In the methanol extraction column 5, the unreacted carbon four carbon five (stream g) was fed at 42 ℃ and a pressure of 0.6 MPa. The content of methanol in the carbon four-carbon five (material flow j) after the top of the methanol extraction tower 5 is 0.026 percent.
③ aromatization catalyst the aromatization catalyst SIHZSM-5(A) -03 prepared in example 7 was prepared using the catalyst of patent CN1586721A, the reaction temperature was 440 ℃, the reaction pressure was 3.0MPa, and the space velocity was 2.5h-1Under the conditions of (1), carrying out aromatization reaction.
Fourthly, the dehydrogenation catalyst used in the catalytic dehydrogenation unit 2# V is prepared by a coprecipitation method and is made of Al2O3The carrier is used for simultaneously loading Cr, Ni, Cu, K, La and Mg elements. The dehydrogenation reaction temperature is 605 ℃, the reaction pressure is 0.15MPa, and the space velocity is 2.5h-1。
The mass yield of each component of the system in the process is as follows: 4.09% of dry gas, 15.77% of etherified gasoline, 17.78% of aromatized oil, 24.10% of propylene and 38.26% of propane, wherein the hydrogen in the dry gas accounts for 94.77 vol%.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that all such changes and modifications as fall within the true spirit and scope of the invention be considered as within the following claims.
Claims (19)
1. A utilization method of hydrocarbon oil rich in carbon, four carbon and five alkane is characterized in that the method comprises a depropanization unit, a catalytic dehydrogenation unit 1#, an etherification unit, an aromatization unit and a catalytic dehydrogenation unit 2#, and comprises the following steps:
(1) sending the hydrocarbon raw material rich in the C-pentaalkane to a depropanization unit, and removing propane in the depropanization unit to obtain mixed C-pentaalkane;
(2) sending the mixed C, C and V into a catalytic dehydrogenation unit No. 1, and dehydrogenating isobutane and isopentane in the catalytic dehydrogenation unit under the action of a dehydrogenation catalyst to generate isobutene and isopentene to obtain a dehydrogenation product;
(3) mixing the dehydrogenation product with methanol, preheating, feeding the mixture into an etherification unit for etherification reaction to obtain an etherification product, feeding the etherification product into an etherification product separation tower, obtaining unreacted carbon four-carbon five at the tower top, and obtaining etherified gasoline at the tower bottom; sending unreacted C, C and V to a methanol extraction tower, and performing methanol extraction by using water as an extractant to obtain a mixture of water and methanol and C, C and V after etherification;
(4) sending the etherified carbon four-carbon five to an aromatization unit, carrying out aromatization reaction on butane in the etherified carbon four-carbon five in an aromatization reactor under the action of an aromatization catalyst to obtain an aromatization product, and separating the aromatization product by an aromatization product separation tower to obtain aromatization tail gas and aromatization oil;
(5) sending the aromatization tail gas and the propane obtained in the step (1) to a catalytic dehydrogenation unit 2#, wherein the aromatization tail gas also contains propane, and the propane is dehydrogenated in the unit to obtain propylene and simultaneously produce hydrogen as a byproduct.
2. The method of utilizing a hydrocarbon oil rich in carbon four-carbon five-alkanes according to claim 1, wherein the hydrocarbon feedstock rich in carbon four-carbon five-alkanes has a carbon four-alkanes content of not less than 27 wt% and a carbon five-alkanes content of not less than 43 wt%.
3. The method of utilizing a hydrocarbon oil rich in carbon four-carbon five-alkanes according to claim 2, wherein the hydrocarbon feedstock rich in carbon four-carbon five-alkanes has a carbon four-alkanes content of not less than 32 wt% and a carbon five-alkanes content of not less than 45 wt%.
4. The method of utilizing hydrocarbon oil rich in carbon four-carbon five-alkane according to claim 1, wherein the hydrocarbon feedstock rich in carbon four-carbon five-alkane is reformed topping oil.
5. The method according to claim 1, wherein the dehydrogenation catalyst is a platinum-based or chromium-based catalyst, and the reactor filled with the dehydrogenation catalyst is a fixed bed reactor or a fluidized bed reactor.
6. Method for utilizing hydrocarbon oils rich in carbon four-carbon five-alkanes according to claim 1, characterized in that the dehydrogenation catalyst is Al2O3The carrier is used, the loaded active component is selected from one of Pt, Cr, Mo and V elements, and the loaded auxiliary agent is selected from one or more of Ni, Cu, K, La, Ca and Mg elements; based on the catalyst, the content of the carrier is 50-90 wt%, the content of active component elements is 1-40 wt%, and the content of auxiliary agent elements is 0.1-30 wt%.
7. The method for utilizing hydrocarbon oil rich in carbon four-carbon five-alkane according to claim 1, wherein the catalytic dehydrogenation reaction conditions of the catalytic dehydrogenation unit 1# are as follows: the reaction temperature is 450-800 ℃, the reaction pressure is 0.01-2 MPa, and the mass space velocity of the feeding is 1.0-10.0 h-1。
8. The method for utilizing hydrocarbon oil rich in carbon, four-carbon, five-alkane according to claim 7, wherein the catalytic dehydrogenation reaction conditions of the catalytic dehydrogenation unit No. 1 are as follows: the reaction temperature is 500-700 ℃, the reaction pressure is 0.1-0.5 MPa, and the feeding mass space velocity is 2.0-6.0 h-1。
9. The method for utilizing hydrocarbon oil rich in carbon four-carbon five-alkane according to claim 1, characterized in that the etherification unit comprises one or two fixed bed reactors.
10. The method for utilizing hydrocarbon oil rich in carbon, four-carbon, five-alkane according to claim 9, characterized in that the etherification unit uses two fixed bed reactors, and is realized by the following connection mode: the upper parts and the upper parts, the lower parts and the lower parts, and the upper parts and the lower parts of the two fixed bed reactors are sequentially connected by valves and pipelines, and the two fixed bed reactors are connected in series or in parallel by switching the valves.
11. The method for utilizing hydrocarbon oil rich in carbon four-carbon five-alkane according to claim 1, characterized in that the methanol content in the etherified carbon four-carbon five is less than 1 wt%.
12. The method for utilizing hydrocarbon oil rich in carbon, four-carbon and five-alkane according to claim 1, wherein the reaction temperature of the etherification reaction is 20 to 90 ℃, the reaction pressure is 0.01 to 3.0MPa, and the molar ratio of the methanol to the sum of isobutene and isoamylene in the dehydrogenation product is 0.5 to 3.0.
13. The method for utilizing hydrocarbon oil rich in carbon, four-carbon and five-alkane according to claim 12, wherein the reaction temperature of the etherification reaction is 30 to 70 ℃, the reaction pressure is 0.3 to 1.5MPa, and the molar ratio of the methanol to the sum of isobutylene and isoamylene in the dehydrogenation product is 0.8 to 2.0.
14. The method for utilizing hydrocarbon oil rich in carbon, four-carbon, five-alkane according to claim 1, wherein the feed temperature of the methanol extraction tower is 20 to 70 ℃, and the pressure is 0.1 to 1.0 MPa.
15. The method for utilizing hydrocarbon oil rich in carbon, four-carbon, five-alkane according to claim 14, wherein the feed temperature of the methanol extraction tower is 30 to 60 ℃, and the pressure is 0.4 to 0.8 MPa.
16. The method of utilizing hydrocarbon oil rich in carbon four-carbon five-alkanes according to claim 1, characterized in that the aromatization catalyst is a molecular sieve catalyst.
17. The method for utilizing hydrocarbon oil rich in carbon four-carbon five-alkane according to claim 16, wherein the molecular sieve catalyst is ZSM-5 or a metal-modified HZSM-5 molecular sieve catalyst.
18. The method of claim 1, wherein the aromatization unit has a reaction temperature of 300-600 ℃, a reaction pressure of 0.05-4.0 MPa, and a mass space velocityIs 0.01 to 10 hours-1。
19. The method for utilizing hydrocarbon oil rich in carbon-tetracarbon pentaalkane according to claim 18, wherein the reaction temperature of the aromatization unit is 350-550 ℃, the reaction pressure is 0.08-4.0 MPa, and the mass space velocity is 0.05-5 h-1。
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| US4252541A (en) * | 1975-11-28 | 1981-02-24 | Texaco Inc. | Method for preparation of ethers |
| CN103361113A (en) * | 2012-04-05 | 2013-10-23 | 中国石油天然气股份有限公司 | Process for producing high-octane gasoline by using raw material rich in carbon, four carbon, five carbon and six alkane |
| CN103361114A (en) * | 2012-04-05 | 2013-10-23 | 中国石油天然气股份有限公司 | Process for producing high-octane gasoline from carbon-rich four-carbon five-carbon hexaalkane raw material |
| CN103361115A (en) * | 2012-04-05 | 2013-10-23 | 中国石油天然气股份有限公司 | Method for producing high-octane gasoline by using raw material rich in C4, C5 and C6 alkanes |
| CN102701918A (en) * | 2012-06-11 | 2012-10-03 | 凯瑞化工股份有限公司 | Method for producing MTBE (Methyl Tert Butyl Ether) by taking gas phase isobutene as raw material |
| CN103509601A (en) * | 2012-06-21 | 2014-01-15 | 中国石油天然气股份有限公司 | Technological process for co-production of propane by aromatization of carbon tetrad-hydrocarbon |
| CN103739423A (en) * | 2013-12-24 | 2014-04-23 | 山东滨州裕华化工厂有限公司 | Process for recovering C5 from etherified liquefied gas |
| CN104945228A (en) * | 2014-03-28 | 2015-09-30 | 中国石油化工股份有限公司 | Method for preparing MTBE or isobutylene by adopting mixed butane |
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