WO2012034295A1 - 一种裂解反应制备低碳烯烃的设备及方法 - Google Patents

一种裂解反应制备低碳烯烃的设备及方法 Download PDF

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WO2012034295A1
WO2012034295A1 PCT/CN2010/077759 CN2010077759W WO2012034295A1 WO 2012034295 A1 WO2012034295 A1 WO 2012034295A1 CN 2010077759 W CN2010077759 W CN 2010077759W WO 2012034295 A1 WO2012034295 A1 WO 2012034295A1
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reactor
reaction
fuel
cracking
raw material
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French (fr)
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王仲华
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林月蓉
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G9/00Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J12/00Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor
    • B01J12/005Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor carried out at high temperatures, e.g. by pyrolysis
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0006Controlling or regulating processes
    • B01J19/0013Controlling the temperature of the process
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053Details of the reactor
    • B01J19/006Baffles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24Stationary reactors without moving elements inside
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/26Nozzle-type reactors, i.e. the distribution of the initial reactants within the reactor is effected by their introduction or injection through nozzles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J4/00Feed or outlet devices; Feed or outlet control devices
    • B01J4/001Feed or outlet devices as such, e.g. feeding tubes
    • B01J4/002Nozzle-type elements
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049Controlling or regulating processes
    • B01J2219/00051Controlling the temperature
    • B01J2219/00074Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00076Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements inside the reactor
    • B01J2219/00083Coils
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049Controlling or regulating processes
    • B01J2219/00051Controlling the temperature
    • B01J2219/00074Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00076Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements inside the reactor
    • B01J2219/00085Plates; Jackets; Cylinders
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049Controlling or regulating processes
    • B01J2219/00051Controlling the temperature
    • B01J2219/00157Controlling the temperature by means of a burner
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049Controlling or regulating processes
    • B01J2219/00164Controlling or regulating processes controlling the flow
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2400/00Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20C2-C4 olefins

Definitions

  • the present invention relates to a petrochemical process, and further to an apparatus and method for preparing a light olefin by a cracking reaction.
  • the production technology of ethylene and propylene at home and abroad adopts the tubular steam cracking technology, that is, the pyrolysis raw material is subjected to thermal cracking reaction under high temperature, short residence time and low hydrocarbon partial pressure with steam as a diluent in the tubular furnace tube.
  • Tubular steam cracking technology that is, the pyrolysis raw material is subjected to thermal cracking reaction under high temperature, short residence time and low hydrocarbon partial pressure with steam as a diluent in the tubular furnace tube.
  • the production process of the tubular steam cracking technology is as follows: The pre-heated cracking feedstock is heated and heated in the convection section of the tubular cracking furnace, and the dilution steam is also injected into the crack at a certain ratio (usually 0.5-0.8) at a certain position of the convection section.
  • the raw materials are heated and vaporized together, so that the temperature reaches the thermal decomposition temperature of the raw material when the convection section enters the radiant section; in the radiant section, the raw material is rapidly heated to undergo thermal cracking reaction in a very short period of 0.1-0.5 seconds to produce ethylene propylene and Other products, at the exit of the radiant section, the quenching boiler is rapidly quenched to a temperature below 500 ° C to terminate the reaction and recover its high temperature heat; the quenched gas after quenching enters the next quench oil, quench water unit and compression separation unit, further separation and Recovery of ethylene, propylene, C4 hydrocarbons and other products.
  • the core of the tube furnace steam cracking technology is the process and equipment of the cracking furnace.
  • the technology has been continuously improved and improved in terms of furnace type, furnace tube size and arrangement, as well as furnace tube materials and burners. It is still the main technology of olefin production at home and abroad, and has an important position in the petrochemical industry. And role.
  • tubular steam cracking technology still has certain deficiencies and difficulties, which are mainly solved in the following aspects:
  • the flow rate drops, and as the flow rate decreases so that the tube wall temperature rises above the allowable value, the feed must be stopped and charred or the machine shut down.
  • the cracking cycle of the cracking furnace is 40-60 days, and it takes 2-3 days to complete the scorching operation.
  • Such a periodic defocusing operation not only reduces the operating rate of the cracking furnace, but also increases the number of furnaces accordingly.
  • frequent furnace switching operations can affect the safety and stability of production.
  • Tube furnace thermal cracking to olefins requires a large amount of fuel.
  • the thermal efficiency of the tube furnace is generally 92-94%, and 6-8% of the heat is lost to the atmosphere.
  • the present invention proposes a novel method and apparatus for producing low-carbon olefins which overcomes the deficiencies of the prior art and which can improve the production level of the olefin industry. Summary of the invention
  • An object of the present invention is to provide a reactor for a cracking reaction for producing a low-carbon olefin, and a process for producing a low-carbon olefin by using the reactor.
  • a reactor for cracking a reaction to produce a low carbon olefin having an inlet end 1 and an outlet end 2, the ends being in opposite positions on the reactor; a 1/4 space from the inlet end of the reactor is a combustion zone 3, the remaining space being a reaction zone 4; the inlet end 1 is provided with a fuel and oxygen nozzle 5 leading to the combustion zone 3, the ports other than the nozzle being closed; in the combustion zone 3 and the reaction zone 4 A raw material nozzle 6 is disposed on the side wall of the reactor, and the outlet end 2 is provided with a product outlet 7; the fuel and oxygen nozzle 5 and the raw material nozzle 6 are one or more nozzle structures.
  • the inner diameter of the inlet end 1 and the outlet end 2 of the reactor is preferably smaller than the inner diameter of the reaction zone 4.
  • the inside of the inlet end 1 preferably has a reduced diameter structure, and more preferably has a venturi structure.
  • a flow restricting structure 8 is disposed inside the reaction zone 4 to minimize the occurrence of backmixing of the internal airflow; the current limiting structure is further preferably a plurality of axially distributed flow restricting plates.
  • the middle portion of the combustion zone 3 is provided with a temperature-regulating steam inlet 9.
  • the combustion zone 3 can also be provided with a cooling device 10 on the outer wall, preferably a cooling jacket, interlayer or coil.
  • the reactor of the present invention may also be provided with various control devices, for example: a raw material distributor is arranged at the raw material nozzle; a probe type flame combustion detecting system is provided in the combustion zone; and a low point is provided in the reaction zone. Dust collector and dust outlet; a flow distributor or the like is arranged in the middle of the combustion zone.
  • the reactor lining material can use various conventional refractory insulating materials.
  • the inlet end of the reactor may be connected to an existing fuel and oxygen supply system according to a conventional method; the raw material nozzle may be connected to an existing cracking raw material preheating system according to a conventional method; the outlet end may be conventional The method is connected to an existing quenching device.
  • the reactor of the present invention can be prepared into a reactor shape acceptable to any petrochemical industry; it can also be applied in a form acceptable to any petrochemical industry such as vertical, horizontal, etc.; and does not limit the inlet and outlet ends. Up, down or left and right positions.
  • the present invention also provides a process for producing a low-carbon olefin by a cleavage reaction using the above reactor, comprising the steps of:
  • Step 1) The obtained raw material gas stream enters the reactor through the raw material nozzle 6 of the reactor, and is rapidly contacted with the high temperature gas generated by the combustion in the step 2), and the raw material is rapidly heated to 800 to 1000 ° C.
  • the cleavage reaction, the cleavage reaction time (residence time) is 0.1-0.3 seconds, the reaction pressure is 0.1-0.5 MPa, and the cracking gas formed by the reaction contains low-carbon olefins, formamidine, hydrogen and other by-products;
  • the cracking temperature of naphtha is 820-900 °C
  • the light diesel oil is 800-860 °C
  • the light hydrocarbon is 850-900 °C.
  • the heavy oil is 750 ⁇ 850.
  • the temperature of the cracking reaction of the present technology is 5-50 ° C higher than the existing tubular furnace method ;
  • the residence time is determined at the time of reactor design, since the raw material of the present invention is directly heated by fuel combustion, heat conduction Very rapid, so the residence time can be reduced to 0.1-0.3 seconds, 0.2 seconds lower than the tube furnace cracking method;
  • the reaction pressure is also significantly reduced, the pressure drop of the reaction system is greatly reduced due to the different reactor structure, and the invention
  • the carbon dioxide and water vapor generated by the combustion in the method are used as a diluent to reduce the partial pressure of hydrocarbons of the feedstock hydrocarbons, so the pressure of the cracking reaction is lower than the existing tubular method, between 0.1 and 0.5 MPa, the actual operation Description
  • the pressure is regulated by a subsequent quench system.
  • the amount of the raw material which enters the reactor per unit time can be determined based on the annual output of the reactor and the annual start-up time.
  • step 3 The product cracking gas generated by the reaction of step 3) is directly passed into the cooling device through the product outlet 7 of the reactor to be cooled to below 500 ° C to terminate the secondary reaction and recover high temperature heat, and then subjected to quenching, compression, and deep cooling and separation steps to obtain a final quality-polymerized olefins; the compression process also must be decontaminated, i.e. off C0 2, water and acid gases.
  • the subsequent process can be seen in Figure 3.
  • the cracking feedstock is preferably light hydrocarbons (eg, liquefied petroleum gas (LPG), liquefied natural gas (LNG), acetamidine, propylene carbonate, butyl hydrazine, etc.), naphtha, light diesel oil fraction, heavy diesel oil fraction, Hydrogenated tail oil or heavy oil.
  • LPG liquefied petroleum gas
  • LNG liquefied natural gas
  • acetamidine propylene carbonate
  • butyl hydrazine etc.
  • naphtha e.g, light diesel oil fraction, heavy diesel oil fraction, Hydrogenated tail oil or heavy oil.
  • Step 1) The preheating can be performed by a heat exchanger or a heating furnace.
  • Step 1) In addition to preheating, it is also possible to carry out an appropriate gasification treatment according to the nature of the raw material by using an existing method, for example, introducing steam into the raw material.
  • the fuel is preferably a gaseous fuel or a liquid fuel.
  • the gaseous fuel is preferably a mixture of acetamethylene, acetamidine, acetamethylene and acetonide or natural gas; the liquid fuel is preferably gasoline, diesel or ethanol.
  • Step 2 The flow rate of the fuel and oxygen entering the reactor is determined according to the design capacity of the reactor, and is related to the type of the cracking raw material. Usually, the heat required for the cracking reaction of the cracked raw material per ton is about 2.5-4.0 GL. Based on this, the amount of fuel required for different raw materials is converted, and the flow rate of fuel and oxygen entering the reactor is finally determined in combination with the design capability of the reactor.
  • Step 2 The high temperature flue gas temperature generated by the combustion of the fuel and oxygen can be adjusted by controlling the fuel flow rate, and the fuel flow rate is preferably controlled in combination with the method of introducing the temperature-regulating steam.
  • Step 3) The control of the cracking reaction temperature can be achieved by various existing methods, or by adjusting the fuel feed amount and/or the temperature control steam flow, and the specific method can be: in the combustion zone and the reactor
  • the upper, middle, lower and cracked gas are connected to the cooling equipment.
  • the fuel flow and oxygen flow measurement and proportional adjustment equipment are provided.
  • the operator can reach the properties of the cracking raw materials and the needs.
  • the cracking depth sets the reaction temperature, and the temperature control system automatically adjusts the fuel flow, the corresponding oxygen flow rate and/or the tempering steam flow rate.
  • the above-mentioned temperature-regulating steam can enter the reactor through the temperature-regulating steam inlet 9 of the reactor, or can enter the reactor through the raw material nozzle 6 together with the raw material.
  • the invention Compared with the existing tubular steam cracking technology, the invention has a great change in the conditions for cracking and olefin production by changing the reactor and the process flow and the process parameters, and the technically beneficial effects are mainly reflected in :
  • the thermal cracking of hydrocarbons to produce low-carbon olefins is not carried out in tube furnace tubes, but in reactors where the feedstock hydrocarbons are in direct contact with the fuel, which can overcome or significantly improve tube furnace steam cracking.
  • the shortcomings of the method enable the combustion gas stream to provide heat to the cracking raw material continuously, directly and rapidly, and the conditions of high temperature short reaction time can be easily realized.
  • the reactor of the tube furnace cracking technology needs hundreds of sets of furnace tubes.
  • One cracking furnace has dozens of furnace tubes with a diameter of 50-80 ⁇ m.
  • the pressure drop of the furnace tubes is large, 0.2-0.3 MPa.
  • the reactor of the present invention has a simple structure and a large volume, and the pressure drop of the raw materials and the reaction product is expected to be reduced by 0.1 to 0.15 MPa.
  • the combustion generated 0 2 and 3 ⁇ 40 are used as the partial pressure reduction of hydrocarbons.
  • the dilution gas is used, and the dilution ratio can reach 30-50% without adding steam. Combining the above two factors, the hydrocarbon partial pressure of the raw material of the cracking reaction of the present technology is 30-40% lower than that of the tubular method when the dilution steam is not used or used less.
  • This technology can be applied to heavier cracking feedstocks, broadening the composition and range of low-carbon olefin feedstocks, and reducing the increase in ethylene propylene in petrochemical development compared to existing tubular steam cracking technologies. , especially the dependence on the demand for chemical light oil.
  • Figure 1 is a cross-sectional view showing the structure of a reactor of Example 1.
  • Figure 2 is a cross-sectional view showing the structure of the reactor of Example 2.
  • FIG. 3 is a general flow diagram of a process for the preparation of lower olefins of the present invention. detailed description
  • a reactor for the preparation of light olefins by a thermal cracking reaction which is in a vertical state, and whose structure is shown in Fig. 1, comprising an inlet end 1 at the upper portion and an outlet end 2 at the lower portion.
  • the space inside the inlet end 1 and 1/4 of the length of the entire reactor is the combustion zone 3, and the remaining space is the reaction zone 4, and the inner wall of the entire combustion zone 3 has a venturi-type variable diameter structure.
  • a fuel and oxygen nozzle 5 is disposed in the center of the inlet end, a temperature regulating steam nozzle 9 is arranged in the middle of the combustion zone 3, and three raw material nozzles 6 are arranged in the expanded section of the combustion zone 3 into the reaction zone 4;
  • the end 2 is provided with a product outlet 7.
  • a flow control system and a raw material distributor are provided at the raw material nozzle 6, a flow control system is further provided at the fuel and oxygen nozzle 5, and a probe type flame combustion detecting system is provided inside the combustion zone 3.
  • a reactor for the preparation of light olefins by a thermal cracking reaction in a horizontal state, the structure of which is shown in Fig. 2, comprising an inlet end 1 on the left side and an outlet end 2 on the right side.
  • the combustion zone 3 inside the inlet end 1, the space occupying 1/4 of the length of the entire reactor is the combustion zone 3, and the remaining space is the reaction zone 4, and the inner wall of the entire combustion zone 3 is a venturi-reducing structure, and the outer wall of the combustion zone is provided with cooling.
  • Jacket 10 10
  • the space inside the inlet end 1 and occupying 1/4 of the entire reactor length is the combustion zone 3, and the remaining space is the reaction zone 4, the inner diameter of the combustion zone 3 is smaller than the inner diameter of the reaction zone 4, and is disposed inward at the center of the inlet end 1
  • a flow control system and a raw material distributor are provided at the raw material nozzle 6, a flow control system is further provided at the fuel and oxygen nozzle 5, and a probe type flame combustion detecting system is provided inside the combustion zone 3.
  • a method for preparing a low-carbon olefin by a cracking reaction using naphtha as a raw material, and selecting the reactor of the second embodiment comprises the following steps:
  • the naphtha gas stream obtained by the step 1) is sprayed into the reaction zone 4 of the reactor through the raw material nozzle 6 of the reactor, and is rapidly contacted with the high temperature gas generated by the combustion in the combustion zone 3 in the step 2), and the stone brain
  • the oil gas flow rapidly rises, adjusts the flow rate of fuel and raw materials, and controls the reaction temperature in the range of 820-900 °C to carry out the cracking reaction.
  • the time of the cracking reaction is about 0.2 seconds, and the reaction pressure is controlled at 0.1-0.3 MPa.
  • the cracking gas produced by the reaction contains about 32.5% (w/w) of ethylene, 16.8% (w/w) of propylene, and also contains hydrogen, formamidine, butadiene, gasoline aromatics, fuel oil and other by-products;
  • step 4) The cracking gas generated by the reaction of step 3) is directly passed into the quenching boiler through the product outlet 7 of the reactor to be cooled to below 500 ° C to terminate the secondary reaction and recover high temperature heat, and then pass through the quenching unit and the compression unit ( At the same time, water, C0 2 and acid gas are removed, the cryogenic unit and the separation unit are processed to finally obtain the polymerization grade quality of low-carbon olefin ethylene and propylene; the heat recovered by the quenching boiler is used for generating high-pressure steam for use throughout the plant.
  • a method for preparing a low-carbon olefin by a cracking reaction using a hydrogenated tail oil as a raw material, and selecting the reactor of Example 3 comprises the following steps:
  • the hydrogenated tail gas stream obtained by the step 1) is injected into the reaction zone 4 of the reactor through the raw material nozzle 6 of the reactor, and is rapidly contacted with the high temperature gas generated by the combustion in the combustion zone 3 in the step 2),
  • the hydrogen tail gas stream is rapidly heated to 830-850 ° C for cracking reaction, the time of the cracking reaction is 0.2 seconds, and the reaction pressure is 0.2-0.4 MPa.
  • the gas flow is controlled by the current limiting plate 8 disposed inside the reactor.
  • the cracking gas produced by the reaction contains about 31.5% (w/w) of ethylene, 16.2% (w/w) of propylene, and further contains hydrogen, formamidine, butadiene, gasoline aromatics, fuel oil and other by-products;
  • step 4) The cracking gas generated by the reaction of step 3) is directly passed into the quenching boiler through the product outlet 7 of the reactor to be cooled to below 500 ° C to terminate the secondary reaction and recover high temperature heat, and then pass through the quenching unit and the compression unit ( At the same time, water, C0 2 and acid gas), cryogenic unit and separation unit are processed to finally obtain low-carbon olefins, formamidine, hydrogen and other by-products of polymerization grade quality;
  • step 5 returning the hydrogen and formazan separated in step 4) to the step 2) through the pipeline, entering the reactor as fuel through the fuel and oxygen nozzle 5, gradually replacing the natural gas used initially; returning other by-products as raw materials to step 1);
  • the heat recovered from the quenching boiler is used to generate high pressure steam for use throughout the plant.
  • a method for preparing a low-carbon olefin by a cracking reaction using liquefied petroleum gas as a raw material, and selecting the reactor of Example 2 comprises the following steps:
  • the liquefied petroleum gas stream obtained by the step 1) is injected into the reaction zone 4 of the reactor through the raw material nozzle 6 of the reactor, and is rapidly contacted with the high-temperature gas generated by the combustion in the combustion zone 3 in the step 2), and the liquefied petroleum gas is liquefied.
  • the gas stream is rapidly heated to 860-920 ° C for the cleavage reaction, the cleavage reaction time is 0.1-0.2 sec, the reaction pressure is controlled at 0.2-0.5 MPa, and the cracking gas produced by the reaction contains about 30.8% (w/w) of ethylene.
  • Propylene 15.7% (w/w) also contains hydrogen, formamidine, butadiene, gasoline aromatics, fuel oil and other by-products
  • step 4) The cracking gas generated by the reaction of step 3) is directly passed into the quenching boiler through the product outlet 7 of the reactor to be cooled to below 500 ° C to terminate the secondary reaction and recover high temperature heat, and then pass through the quenching unit and the compression unit ( At the same time, water, C0 2 and acid gas), cryogenic unit and separation unit are processed to finally obtain low-carbon olefins, formamidine, hydrogen and other by-products of polymerization grade quality;
  • step 5 Return the hydrogen and formazan separated in step 4) to the step 2) through the pipeline, and enter the reactor as fuel through the fuel and oxygen nozzle 5, gradually replacing the initially used mixture of formazan and acetonitrile;
  • the by-product is returned as raw material to step 1); the heat recovered by the quenching boiler is used to generate high-pressure steam for use in the whole plant.
  • a method for preparing a low-carbon olefin by a cracking reaction using a residue as a raw material, and selecting the reactor of the second embodiment comprises the following steps:
  • step 1) The residue obtained by the step 1) is sprayed into the reaction zone 4 of the reactor through the raw material nozzle 6 of the reactor, and is rapidly contacted with the high temperature gas generated by the combustion in the combustion zone 3 in the step 2), and the residual oil is rapidly heated.
  • the cleavage reaction is carried out at 760-820 ° C, the cleavage reaction time is 0.1-0.2 seconds, and the reaction pressure is controlled at
  • the cracking gas produced by the reaction contains about 27.2% (w/w) of ethylene, 13.5% (w/w) of propylene, and also contains hydrogen, formamidine, butadiene, gasoline aromatics, fuel oil and others. by-product;
  • step 3 The cracking gas generated by the reaction of step 3) directly enters the chiller through the product outlet 7 of the reactor, and the temperature of the quenched oil injected is cooled to below 450 ° C to terminate the secondary reaction and recover the high temperature heat.
  • step 5 Return the hydrogen and formazan separated in step 4) to the step 2) through the pipeline, and enter the reactor as fuel through the fuel and oxygen nozzle 5, gradually replacing the initially used mixture of formazan and acetonitrile;
  • the by-product is returned as raw material to step 1); the heat recovered by the quenching boiler is used to generate high-pressure steam for use in the whole plant.
  • the cracking feedstock is naphtha.
  • the product is 300,000 tons of ethylene with 99.9% purity per year, 150,000 tons of 99.5% propylene, and butadiene and C5. Pyrolysis of gasoline, tar, etc.; operating rate is 8,000 hours / year;
  • the flow rate of naphtha feedstock is 124 ton / hr. After the heat exchange, the temperature reaches 150 ° C and enters the preheating furnace. 12 tons / hr of gasification steam is added in the middle of the preheating furnace. The outlet temperature is 550-600 °C. ;
  • the preheated gasified naphtha feedstock is injected into the reactor through the raw material nozzle 6 of the reactor at a flow rate of 124 ton / hr, and is rapidly contacted with the high temperature flue gas generated in the combustion zone to a suitable cracking temperature of 860.
  • the cracking temperature control is adjusted by the fuel flow rate, the temperature regulating steam and the cracking feedstock flow rate, the reaction pressure is 0.2-0.3MPa, the residence time is 0.1-0.2 seconds, and the composition of the reaction product can be referred to Table 1;
  • step 5) Return the hydrogen and formazan separated in step 4) to the step 2) through the pipeline, and enter the reactor as fuel through the fuel and oxygen nozzle 5, gradually replacing the natural gas used initially; the heat recovered by the quenching boiler is used for high pressure steam supply. Used throughout the plant.

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Description

说 明 书 一种裂解反应制备低碳烯烃的设备及方法 技术领域
本发明涉及一种石油化工工艺, 进一步涉及一种裂解反应制备低碳烯烃的 设备和方法。
背景技术
目前国内外乙烯和丙烯的生产技术都采用管式法蒸汽裂解技术, 即裂解原 料在管式炉管里用蒸汽作为稀释剂在高温、 短停留时间和低烃分压的条件下进 行热裂解反应, 生产乙烯、 丙烯, 并副产碳四烯烃、 碳五、 裂解汽油等产品。 此技术已有几十年的历史, 代表性的专利技术有美国的鲁姆斯 (LUMMUS)、 斯 韦 (S.W)、 凯洛格 (KBR)以及德国的林德 (LIND)等。 典型的烯烃生产工艺加工流 程主要有裂解、 急冷、 压缩、 分离几大工序, 具有专利技术代表性的是裂解单 元, 裂解技术是烯烃生产工艺的关键, 它直接影响各项技术经济指标及安全稳 定的生产。
管式法蒸汽裂解技术的生产流程是: 预热后的裂解原料进入管式裂解炉的 对流段加热升温, 稀释蒸汽也在对流段一定的位置按一定的比例 (一般是 0.5-0.8) 注入裂解原料中一齐加热气化, 使温度在出对流段进入辐射段时达到原料的热 分解温度; 在辐射段, 原料在 0.1-0.5秒极短的时间里快速升温进行热裂解反应, 生成乙烯丙烯及其它产物, 在辐射段出口由急冷锅炉快速将裂解物流急冷到 500°C以下终止反应并回收其高温热量; 急冷后的裂解气进入下一个急冷油、 急 冷水单元以及压缩分离单元, 进一步分离和回收乙烯、 丙烯、 C4烃及其它产物。
管式炉蒸汽裂解技术的核心是裂解炉的工艺和设备。 几十年来该技术在炉 型、 炉管尺寸和排列方式以及炉管的材质、 燃烧器等方面有不断改进和提高, 仍然是当前国内外烯烃生产的主要技术, 在石油化工领域具有重要的地位和作 用。 尽管如此, 管式蒸汽裂解技术还存在一定的不足和困难不好解决, 主要有 以下方面:
(1)烃类裂解要求高温、 短停留时间的反应条件, 要求炉管要具有很高的热 通量和良好的高温机械性能。 但目前即便用最好的材料, 炉管管壁温度上限也 只能允许达到 1150°C, 这个壁温的限制使再进一步提高裂解深度难度很大。
(2)裂解原料如石脑油、 尾油等烃类在裂解反应中, 除生成乙烯丙烯外还会 生成焦油和焦炭, 它们沉积在炉管内壁生焦并堵塞炉管, 会造成某一路炉管的 说 明 书
流量下降, 并且由于流量减少使管壁温度升高超过允许值, 必须停止进料并进 行烧焦或停炉机械清焦。 一般裂解炉的清焦周期为 40-60天, 每次完成烧焦操作 要用 2-3天。 这样周期性的清焦操作不仅降低了裂解炉的开工率, 而且由此使炉 子的数量也要相应的增加。 另外经常性的炉子切换操作会影响生产的安全稳定 性。
(3)目前大型裂解炉单台的能力为 10-15万吨乙烯 /年.台, 一个规模为 100万吨 /年的乙烯装置要配置 7-10台裂解炉, 由于炉管的材料费贵造价高, 炉区的投资 要占全装置的大约 1/3, 这对烯烃生产的投资和成本会有显着的影响。
(4)目前乙烯工厂用的裂解原料 60%以上是石脑油, 还有乙垸、 丙垸、 碳四 等轻烃组分, 较重些的如轻柴油、 加氢尾油只占 10-30%。 这些用做裂解原料的 化工轻油和轻烃都来自炼油厂, 随着烯烃需求的不断增加使化工轻油供应日趋 紧张, 资源配置的矛盾会越发突出。 因此扩大原料来源、 提高裂解装置对原料 范围的适应性成为了当务之急。
(5)管式炉热裂解制烯烃需要消耗大量的燃料, 管式加热炉的热效率一般为 92-94%, 会有 6-8%的热量损失到大气中, 同时有大量的 C02、 CO、 NO、 N02 排向大气, 对环境污染较大。
鉴于上述现有技术的缺陷, 本发明提出一种新的低碳烯烃制备方法和设备, 克服了现有技术的不足, 可以提高烯烃产业的生产水平。 发明内容
本发明的目的在于: 提供一种用于裂解反应制备低碳烯烃的反应器, 以及 利用该反应器制备低碳烯烃的工艺方法。
本发明的上述目的是通过以下技术方案实现的:
提供一种用于裂解反应制备低碳烯烃的反应器, 具有入口端 1和出口端 2, 且该两端在反应器上处于相对的位置; 反应器内部自入口端起的 1/4空间为燃烧 区 3, 其余空间为反应区 4; 所述入口端 1设有通向燃烧区 3的燃料和氧气喷嘴 5, 该喷嘴以外的端口是封闭的; 在所述燃烧区 3和反应区 4之间的反应器侧壁上设 有原料喷嘴 6, 所述出口端 2设有产物出口 7; 所述的燃料和氧气喷嘴 5和原料喷 嘴 6是一个或两个以上的喷嘴结构。
所述反应器的入口端 1和出口端 2的内径优选小于反应区 4的内径。
所述入口端 1内部优选呈变径结构, 进一步优选呈文丘里结构。 说 明 书
所述反应区 4内部设有限流结构 8, 以尽量减少内部气流的返混现象发生; 所述限流结构进一步优选若干轴向分布的限流板。
所述的燃烧区 3中部优选设有调温蒸汽入口 9。
所述的燃烧区 3还可以在外壁设有冷却设备 10,优选冷却夹套、夹层或盘管。 另外, 本发明所述的反应器还可以设置多种控制设备, 例如: 所述原料喷 嘴处设有原料分配器; 在燃烧区设有探头式火焰燃烧检测系统; 在反应区的低 点设有排尘器和排尘出口; 所述的燃烧区中部设有流量分配器等。
所述反应器内衬材料可以使用各种常规的耐火隔热材料。
所述的反应器入口端可以按照常规方法与现有的燃料、 氧气供应系统相连 接; 所述原料喷嘴可以按照常规方法与现有的裂解原料预热系统相连接; 所述 出口端可以按照常规方法与现有的急冷设备相连接。
本发明所述的反应器可以制备成任意石油化工工业可接受的反应器形状; 也可以以立式、 卧式等任意石油化工工业可接受的形式应用; 并且不限制所述 入口端和出口端的上、 下或左、 右位置。
本发明还提供一种利用上述反应器通过裂解反应制备低碳烯烃的工艺方 法, 包括以下步骤:
1) 预热裂解原料至 150~700°C ;
2 ) 让燃料和氧气按照完全燃烧的比例经所述反应器的燃料和氧气喷嘴 5进 入反应器的燃烧区进行燃烧, 生成的 C02、 H20和烟气温度保持在 1000~1500°C ;
3 ) 步骤 1 ) 处理得到的原料气流经所述反应器的原料喷嘴 6进入所述的反应 器, 与步骤 2)燃烧产生的高温气体快速接触换热, 原料迅速升温至 800~1000°C 进行裂解反应, 裂解反应时间(停留时间)为 0.1-0.3秒, 反应压力在 0.1-0.5MPa, 反应生成的裂解气中含有低碳烯烃、 甲垸、 氢气以及其他副产品;
上述裂解反应中, 反应的温度和停留时间由原料的不同而有所区别, 石脑 油的裂解温度为 820-900 °C, 轻柴油为 800-860 °C, 轻烃为 850-900°C, 重油为 750~850。 总的来看, 本技术的裂解反应的温度要比现有的管式炉法高 5-50°C ; 停留时间在反应器设计时确定, 由于本发明的原料是通过燃料燃烧直接加热, 导热十分迅速, 因此可以将停留时间降为 0.1-0.3秒, 比管式炉裂解法降低 0.2秒; 反应压力也有显着的降低, 由于反应器结构不同使反应系统压降大幅减少, 另 本发明的方法中燃烧生成的二氧化碳和水汽是作为稀释剂又用于降低原料烃的 烃分压, 因此裂解反应的压力低于现有的管式法, 在 0.1-0.5MPa之间, 实际操作 说 明 书
压力由后续的急冷系统进行调控。
另外, 上述反应中, 单位时间内进入反应器的原料量可以根据反应器的年 产量和年开工时间进行计算后加以确定。
4) 步骤 3 ) 的反应生成的产物裂解气经所述反应器的产物出口 7直接进入冷 却设备冷却至 500°C以下, 以终止二次反应并回收高温热量, 然后再经过急冷、 压缩、 深冷和分离步骤最终获得聚合级品质的低碳烯烃; 所述的压缩过程中还 需要进行净化处理, 即脱 C02、 酸性气体和水。 后续流程可见附图 3所示。
步骤 1 ) 所述的裂解原料优选轻烃 (如, 液化石油气 (LPG) 、 液化天然气 (LNG) 、 乙垸、 丙垸、 丁垸等) 、 石脑油、 轻柴油馏分、 重柴油馏分、 加氢 尾油或重油等。
步骤 1 ) 所述的预热可以通过换热器或加热炉加热。
步骤 1 ) 除了预热以外, 还可以根据原料的性质采用现有的方法进行适当地 气化处理, 例如向原料中通入水蒸汽。
步骤 2) 所述的燃料优选气体燃料或液体燃料。
所述的气体燃料优选乙垸、 丙垸、 乙垸和丙垸的混合物或天然气; 所述的 液体燃料优选汽油、 柴油或乙醇。
步骤 2) 所述的燃料和氧气进入反应器的流量根据反应器的设计能力来确 定, 并与裂解原料的品种有关, 通常每吨裂解原料裂解反应需要燃料提供的热 量约为 2.5-4.0GL 可以据此换算出不同原料所需要的燃料用量, 并结合反应器 的设计能力最终确定燃料和氧气进入反应器的流量。
步骤 2)所述燃料和氧气燃烧生成的高温烟气温度可以通过控制燃料流量来 调节, 优选控制燃料流量结合通入调温蒸汽的方式进行双重调节。
步骤 3 ) 所述的裂解反应温度的控制可以通过多种现有方法实现, 也可以通 过调节燃料的通入量和 /或调温蒸汽流量来实现, 具体方法可以是: 在燃烧区和 反应器的上、 中、 下和裂解气体通往冷却设备的管道内设多个温度测量点, 同 时设有燃料流量和氧气流量的测量和比例调节设备, 操作员可以根据裂解原料 的性质和需要达到的裂解深度设定反应温度, 温度控制系统会自动调节燃料流 量, 相应的氧气流量和 /或调温蒸汽流量。
还可以将步骤 4)所述的分离步骤分离出的甲垸和氢气作为燃料再次回到步 骤 2) 的反应器循环使用; 将步骤 4) 所述的分离步骤分离出的其他副产品作为 原料再次回到步骤 1 ) 进行预热。 说 明 书
上述调温蒸汽既可以通过反应器的调温蒸汽入口 9进入反应器, 也可以同原 料一起通过原料喷嘴 6进入反应器。
与现有的管式法蒸汽裂解技术相比, 本发明通过对反应器和工艺流程及工 艺参数的改变, 使裂解制烯烃的条件有较大的改变, 在技术方面产生的有益效 果主要体现在:
1.使烃类的热裂解制取低碳烯烃的反应不在管式炉炉管中进行,而是在原料 烃和燃料直接接触的反应器中进行, 可以克服或显着改善管式炉蒸汽裂解法的 不足之处, 使燃烧的气流不断、 直接、 快速地向裂解原料提供热量, 可以容易 的实现高温短反应时间的条件。
2.管式炉裂解技术的反应器需要上百组的炉管,一台裂解炉有几十组直径为 50-80亳米的炉管组成, 炉管的压降较大, 有 0.2-0.3MPa。 而本发明的反应器结 构简捷, 容积大, 原料和反应产物的压降预计可以减少 0.1-0.15MPa, 另一方面, 在本发明中, 将燃烧生成的 02和¾0作为降低烃分压的稀释气体使用, 不加入 蒸汽的情况下稀释比已可达到 30-50%。 以上两个因素综合起来, 本技术裂解反 应原料的烃分压在稀释蒸汽不用或少用的情况下, 要比管式法技术低 30-40%。
3.由于本发明反应器结构特点, 不易结焦, 操作简便, 可以加工较重质馏 分的原料, 如加氢尾油、 重柴油、 重油等。
在经济效益和环境保护方面的得益阐述如下:
1 )对同一裂解原料而言, 由于裂解反应条件的进一步改善使乙烯和丙烯的 约可以增加 1-5% , 见下表 1所示:
Figure imgf000007_0001
说 明 书
2) 使得裂解单元及配套部分的投资可以减少 20-30%, 施工工期缩短, 高温 合金钢用量大大减少。
3) 本技术可适用于较重质的裂解原料, 拓宽了低碳烯烃原料的组分和范围, 较现有的管式炉蒸汽裂解技术减少了石油化工发展中乙烯丙烯的增量对油品, 尤其是化工轻油需求的依赖程度。
4) 乙烯丙烯的能耗和生产成本降低 5-10% , 运行更加安全稳定。
5 ) 由于燃料用量减少和裂解反应气中的 ( 02可以回收利用, 使乙烯工厂的烟 气排放大户——裂解单元的烟气排放量减少 30-40%。 对改善环境条件会有较大 的贡献。
附图说明
附图 1为实施例 1所述的反应器的结构剖视图。
附图 2为实施例 2所述的反应器的结构剖视图。
附图 3为本发明制备低碳烯烃方法的总流程图。 具体实施方式
实施例 1.
一种用于热裂解反应制备低碳烯烃的反应器, 工作状态为立式, 其结构见 附图 1, 包括处于上部的入口端 1和处于下部的出口端 2。 其中, 在入口端 1内部、 占整个反应器长度 1/4的空间是燃烧区 3, 其余空间为反应区 4, 整个燃烧区 3空间 内壁呈文丘里式变径结构。 入口端中心位置向内设有 1个燃料和氧气喷嘴 5, 在 燃烧区 3中部设有调温蒸汽喷头 9, 在燃烧区 3进入反应区 4的扩径处设有 3个原料 喷嘴 6; 出口端 2设有产物出口 7。 另外, 在原料喷嘴 6处还设有流量控制系统和 原料分配器, 在燃料和氧气喷嘴 5处还设有流量控制系统, 在燃烧区 3内部设有 探头式火焰燃烧检测系统。
实施例 2.
一种用于热裂解反应制备低碳烯烃的反应器, 工作状态为卧式, 其结构见 附图 2, 包括处于左侧的入口端 1和处于右侧的出口端 2。 其中, 在入口端 1内部、 占整个反应器长度 1/4的空间是燃烧区 3, 其余空间为反应区 4, 整个燃烧区 3空间 内壁成文丘里式变径结构, 燃烧区外壁设有冷却夹套 10。 入口端中心位置向内 设有 3个燃料和氧气喷嘴 5, 在燃烧区 3中部设有调温蒸汽喷头 9, 在燃烧区 3进入 反应区 4的扩径处设有 3个原料喷嘴 6; 出口端 2设有产物出口 7。 另外, 在原料喷 说 明 书
嘴 6处还设有流量控制系统和原料分配器, 在燃料和氧气喷嘴 5处还设有流量控 制系统, 在燃烧区 3内部设有探头式火焰燃烧检测系统。
实施例 3.
一种用于裂解反应制备低碳烯烃的反应器, 工作状态为立式, 其结构见附 图 1, 包括处于下部的入口端 1和处于上部的出口端 2。 其中在入口端 1内部、 占 整个反应器长度 1/4的空间是燃烧区 3, 其余空间为反应区 4, 燃烧区 3的内径小于 反应区 4的内径, 在入口端 1中心位置向内设有 2个燃料和氧气喷嘴 5 ; 燃烧区 3进 入反应区 4的扩径处设有 1个向内的原料喷嘴 6; 出口端 2设有产物出口 7; 在反应 区 4的内部空间还设有 5块轴向平行分布的限流板 8。 另外, 在原料喷嘴 6处还设 有流量控制系统和原料分配器, 在燃料和氧气喷嘴 5处还设有流量控制系统, 在 燃烧区 3内部设有探头式火焰燃烧检测系统。
实施例 4.
一种以石脑油为原料通过裂解反应制备低碳烯烃的方法, 选择实施例 2的反 应器进行, 包括以下步骤:
1) 通过换热器预热石脑油至 580-650°C, 以接近其裂解温度, 同时在预热过 程中注入少量水蒸汽, 使其气化率达到 100%;
2) 以天然气或甲垸为燃料, 与氧气按照完全燃烧的比例经反应器的燃料和 氧气喷嘴 5喷入反应器中进行燃烧, 生成 ( 02和¾0, 通过调温蒸汽喷头 9向反应 器内喷入调温蒸汽, 使燃烧区 3温度保持在 1100~1300°C区间;
3 ) 经步骤 1 ) 处理得到的石脑油气流经反应器的原料喷嘴 6喷入反应器的反 应区 4, 与步骤 2) 中在燃烧区 3燃烧产生的高温气体快速接触换热, 石脑油气流 迅速升温, 调节燃料和原料流量使反应温度控制在 820-900 °C区间, 进行裂解反 应, 裂解反应的时间约 0.2秒, 反应压力控制在 0.1-0.3MPa。 反应生成的裂解气 含有约乙烯 32.5%(w/w), 丙烯 16.8%(w/w), 另外还含有氢气、 甲垸、 丁二烯、 汽油芳烃、 燃料油及其它副产品;
4) 步骤 3 ) 的反应生成的裂解气经所述反应器的产物出口 7直接进入急冷锅 炉冷却至 500°C以下, 以终止二次反应并回收高温热量, 然后再经过急冷单元、 压缩单元(同时脱去水、 C02和酸性气体) 、 深冷单元和分离单元处理最终获得 聚合级品质的低碳烯烃乙烯和丙烯; 急冷锅炉回收的热量用于发生高压蒸汽供 全厂使用。 说 明 书
实施例 5.
一种以加氢尾油为原料通过裂解反应制备低碳烯烃的方法, 选择实施例 3的 反应器进行, 包括以下步骤:
1) 通过加热炉预热加氢尾油至 500-580°C, 以接近其裂解温度, 同时在加热 过程中注入水蒸汽, 使其气化率达到 90%;
2 ) 以天然气为燃料, 与氧气按照完全燃烧的比例经反应器的燃料和氧气喷 嘴 5喷入反应器的燃烧区 3中进行燃烧, 生成 ( 02和¾0, 使燃烧区 3的温度保持 在 1200~1300°C ;
3 ) 经步骤 1 ) 处理得到的加氢尾油气流经反应器的原料喷嘴 6喷入反应器的 反应区 4, 与步骤 2 ) 中在燃烧区 3燃烧产生的高温气体快速接触换热, 加氢尾油 气流迅速升温至 830-850°C进行裂解反应, 裂解反应的时间为 0.2秒, 反应压力为 0.2-0.4MPa, 整个反应过程中, 通过反应器内部设置的限流板 8控制气流的返混, 反应生成的裂解气约含有乙烯 31.5%(w/w), 丙烯 16.2%(w/w), 另外还含有氢气、 甲垸、 丁二烯、 汽油芳烃、 燃料油及其它副产物;
4) 步骤 3 ) 的反应生成的裂解气经所述反应器的产物出口 7直接进入急冷锅 炉冷却至 500°C以下, 以终止二次反应并回收高温热量, 然后再经过急冷单元、 压缩单元(同时脱去水、 C02和酸性气体) 、 深冷单元和分离单元处理后最终获 得聚合级品质的低碳烯烃、 甲垸、 氢气及其他副产物;
5 ) 将步骤 4) 分离出的氢气和甲垸通过管道返回步骤 2) , 作为燃料经燃料 和氧气喷嘴 5进入反应器, 逐渐替代初始使用的天然气; 将其他副产物作为原料 返回步骤 1 ) ; 急冷锅炉回收的热量用于发生高压蒸汽供全厂使用。
实施例 6.
一种以液化石油气为原料通过裂解反应制备低碳烯烃的方法, 选择实施例 2 的反应器进行, 包括以下步骤:
1) 通过加热炉预热液化石油气至 550-650°C, 以接近其裂解温度, 并使其气 化比例达到 100%;
2) 以甲垸和乙垸的混合气体为燃料, 与氧气按照完全燃烧的比例经反应器 的燃料和氧气喷嘴 5喷入反应器的燃烧区 3中进行燃烧, 生成 ( 02和1120, 通过调 温蒸汽喷头 9向反应器内喷入调温蒸汽, 使燃烧区 3温度保持在 1300~1500°C ; 同 时通过燃烧区 3外壁的冷却夹套 10来回收热量; 说 明 书
3 ) 经步骤 1 ) 处理得到的液化石油气气流经反应器的原料喷嘴 6喷入反应器 的反应区 4, 与步骤 2) 中在燃烧区 3燃烧产生的高温气体快速接触换热, 液化石 油气气流迅速升温至 860-920°C进行裂解反应, 裂解反应的时间为 0.1-0.2秒, 反 应压力控制在 0.2-0.5MPa, 反应生成的裂解气含约有乙烯 30.8%(w/w), 丙烯 15.7%(w/w), 另外还含有氢气、 甲垸、 丁二烯、 汽油芳烃、 燃料油及其它副产
4) 步骤 3 ) 的反应生成的裂解气经所述反应器的产物出口 7直接进入急冷锅 炉冷却至 500°C以下, 以终止二次反应并回收高温热量, 然后再经过急冷单元、 压缩单元(同时脱去水、 C02和酸性气体) 、 深冷单元和分离单元处理后最终获 得聚合级品质的低碳烯烃、 甲垸、 氢气及其他副产物;
5 ) 将步骤 4) 分离出的氢气和甲垸通过管道返回步骤 2) , 作为燃料经燃料 和氧气喷嘴 5进入反应器, 逐渐替代初始使用的甲垸、 乙垸混合气; 将分离出的 其他副产物作为原料返回步骤 1 ) ; 急冷锅炉回收的热量用于发生高压蒸汽供全 厂使用。
实施例 7.
一种以渣油为原料通过裂解反应制备低碳烯烃的方法, 选择实施例 2的反应 器进行, 包括以下步骤:
1) 通过加热炉预热渣油至 250-350°C, 以接近其裂解温度并调节其粘度符合 雾化喷嘴的要求;
2) 以柴油为燃料, 与氧气按照完全燃烧的比例经反应器的燃料和氧气喷嘴 5喷入反应器的燃烧区 3中进行燃烧, 生成 ( 02和¾0, 通过调温蒸汽喷头 9向反 应器内喷入调温蒸汽, 使燃烧区 3温度保持在 1000~1200°C ; 同时通过燃烧区 3外 壁的冷却夹套 10来回收热量;
3 ) 经步骤 1 ) 处理得到的渣油经反应器的原料喷嘴 6喷入反应器的反应区 4, 与步骤 2 ) 中在燃烧区 3燃烧产生的高温气体快速接触换热, 渣油迅速升温至 760-820°C进行裂解反应, 裂解反应的时间为 0.1-0.2秒, 反应压力控制在
0.2-0.5MPa, 反应生成的裂解气含约有乙烯 27.2%(w/w), 丙烯 13.5%(w/w), 另外 还含有氢气、 甲垸、 丁二烯、 汽油芳烃、 燃料油及其它副产物;
4)步骤 3 )的反应生成的裂解气经所述反应器的产物出口 7直接进入急冷器, 由喷入的急冷油将其温度冷却至 450°C以下, 以终止二次反应并回收高温热量, 说 明 书
然后再经过急冷单元、 压缩单元(同时脱去水、 co2和酸性气体) 、 深冷单元和 分离单元处理后最终获得聚合级品质的低碳烯烃、 甲垸、 氢气及其他副产物;
5 ) 将步骤 4) 分离出的氢气和甲垸通过管道返回步骤 2) , 作为燃料经燃料 和氧气喷嘴 5进入反应器, 逐渐替代初始使用的甲垸、 乙垸混合气; 将分离出的 其他副产物作为原料返回步骤 1 ) ; 急冷锅炉回收的热量用于发生高压蒸汽供全 厂使用。
实施例 8.
一个乙烯生产能力为 30万吨 /年的乙烯装置, 裂解原料为石脑油, 产品是每 年 30万吨纯度为 99.9%的乙烯、 15万吨 99.5%的丙烯、 还有丁二烯、 C5、 裂解汽 油、 焦油等; 开工率是 8000小时 /年;
1 )石脑油原料流量为 124吨 /时, 经换热后温度达到 150°C进入预热炉, 在预 热炉中部加入 12吨 /时的气化蒸汽, 出口温度为 550-600 °C ;
2 ) 燃料天然气和氧气由反应器入口端 1的燃料和氧气喷嘴 5进入燃烧区 3, 将反应器升温并用调温蒸汽把反应器的燃烧区 3的温度保持在 1200-1500°C,天然 气流量约 6-9吨 /时, 氧气约 20000-25000NM3/时, 反应器釆用实施例 3的结构, 反 应区 4内径 1.2-1.5米, 反应区长 5-6米;
3 )预热气化后的石脑油原料以喷射方式经反应器的原料喷嘴 6以 124吨 /时的 流量进入反应器, 与燃烧区产生的高温烟气快速接触升温至适宜的裂解温度 860-900 °C, 裂解温度的控制由燃料流量、 调温蒸汽及裂解原料流量串级调整, 反应压力在 0.2-0.3MPa, 停留时间在 0.1-0.2秒, 反应产物的组成可参考表 1 ;
4) 反应生成的裂解气经所述反应器的产物出口 7直接进入急冷锅炉冷却至 500°C以下, 以终止二次反应并回收高温热量, 然后再经过急冷单元、 压缩单元
(同时脱去水、 C02和酸性气体) 、 深冷单元和分离单元处理后最终获得聚合级 品质的低碳烯烃;
5 ) 将步骤 4) 分离出的氢气和甲垸通过管道返回步骤 2) , 作为燃料经燃料 和氧气喷嘴 5进入反应器, 逐渐替代初始使用的天然气; 急冷锅炉回收的热量用 于发生高压蒸汽供全厂使用。

Claims

权 利 要 求 书
1.一种用于裂解反应制备低碳烯烃的反应器, 其特征在于: 具有入口端 (1) 和出口端 (2), 且该两端在反应器上处于相对的位置; 反应器内部自入口端起的 1/4空间为燃烧区 (3), 其余空间为反应区 (4); 所述入口端 (1)设有通向燃烧区 (3) 的燃料和氧气喷嘴 (5), 该喷嘴以外的端口是封闭的; 在所述燃烧区 (3)和反应区 (4)之间的反应器侧壁上设有原料喷嘴 (6), 所述出口端 (2)设有产物出口 (7); 所述 的燃料和氧气喷嘴 (5)和原料喷嘴 (6)是一个或两个以上的喷嘴结构。
2.权利要求 1所述的反应器, 其特征在于: 所述反应器的入口端 (1)和出口端 (2)的内径小于反应区 (4)的内径; 优选入口端 (1)内部呈变径结构; 进一步优选呈 文丘里式变径结构。
3.权利要求 1所述的反应器, 其特征在于: 所述反应区 (4)内部设有限流结构 (8); 优选若干轴向分布的限流板。
4.权利要求 1所述的反应器, 其特征在于: 所述的燃烧区 (3)中部设有调温蒸 汽入口 (9) ; 所述的燃烧区 (3)外壁设有冷却设备 (10), 优选冷却夹套、 夹层或盘
5.一种利用权利要求 1所述的反应器通过裂解反应制备低碳烯烃的方法, 包 括以下步骤:
1) 预热裂解原料至 150~700°C ;
2) 让燃料和氧气按照完全燃烧的比例经所述反应器的燃料和氧气喷嘴 (5) 进入反应器的燃烧区进行燃烧, 生成的 C02、 H20和烟气温度保持在
1000-1500 °C ;
3 ) 步骤 1 ) 处理得到的原料气流经所述反应器的原料喷嘴 (6)进入所述的反 应器,与步骤 2 )燃烧产生的高温气体快速接触换热,原料迅速升温至 800~1000°C 进行裂解反应, 裂解反应时间为 0.1-0.3秒, 反应压力在 0.1-0.5MPa, 反应生成的 裂解气中含有低碳烯烃、 甲垸、 氢气以及其他副产品;
4) 步骤 3 ) 的反应生成的产物裂解气经所述反应器的产物出口 (7)直接进入 冷却设备冷却至 500°C以下, 以终止二次反应并回收高温热量,然后再经过急冷、 压缩、 深冷和分离步骤最终获得聚合级品质的低碳烯烃; 所述的压缩过程中还 需要进行净化处理, 即脱 C02、 酸性气体和水。
6.权利要求 5所述的制备低碳烯烃的方法, 其特征在于: 步骤 1 ) 所述的裂 解原料包括轻烃、 石脑油、 轻柴油馏分、 重柴油馏分、 加氢尾油或重油。 权 禾 U 要 求 书
7.权利要求 5所述的制备低碳烯烃的方法, 其特征在于: 步骤 2) 所述的燃 料为气体燃料或液体燃料。
8.权利要求 7所述的制备低碳烯烃的方法, 其特征在于: 所述的气体燃料选 自乙垸、 丙垸、 乙垸和丙垸混合物或天然气; 所述的液体燃料选自乙醇、 柴油 或汽油。
9.权利要求 5所述的制备低碳烯烃的方法, 其特征在于: 步骤 1 ) 所述的预 热是通过换热器或加热炉加热; 步骤 2)所述燃料和氧气燃烧生成的高温烟气温 度通过控制燃料流量结合通入调温蒸汽的方式进行双重调节。
10. 权利要求 5所述的制备低碳烯烃的方法, 其特征在于: 将步骤 4)所述 的分离步骤分离出的甲垸和氢气作为燃料再次回到步骤 2) 的反应器循环使用; 将步骤 4) 所述的分离步骤分离出的其他副产品作为原料再次回到步骤 1 ) 进行 预热。
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