WO2023236390A1 - Procédé et système de production de combustible d'aviation de biomasse alkylée à partir d'huiles et de graisses usées - Google Patents

Procédé et système de production de combustible d'aviation de biomasse alkylée à partir d'huiles et de graisses usées Download PDF

Info

Publication number
WO2023236390A1
WO2023236390A1 PCT/CN2022/121404 CN2022121404W WO2023236390A1 WO 2023236390 A1 WO2023236390 A1 WO 2023236390A1 CN 2022121404 W CN2022121404 W CN 2022121404W WO 2023236390 A1 WO2023236390 A1 WO 2023236390A1
Authority
WO
WIPO (PCT)
Prior art keywords
hydrogen
reaction
stripping
isomerization
oil
Prior art date
Application number
PCT/CN2022/121404
Other languages
English (en)
Chinese (zh)
Inventor
沈健
李元博
王艳涛
章金富
傅俊红
Original Assignee
浙江嘉澳环保科技股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 浙江嘉澳环保科技股份有限公司 filed Critical 浙江嘉澳环保科技股份有限公司
Publication of WO2023236390A1 publication Critical patent/WO2023236390A1/fr

Links

Images

Classifications

    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/34—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances
    • B01D3/38—Steam distillation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/60—Controlling or regulating the processes
    • 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
    • C10G7/00—Distillation of hydrocarbon oils
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1003—Waste materials
    • C10G2300/1007—Used oils

Definitions

  • the invention relates to the field of biomass energy, and specifically relates to a method and system for producing alkylated biomass aviation fuel from waste oil.
  • the patent document with document number CN 111909720 A discloses a method for hydrogenating waste animal and vegetable oils.
  • the steps include: a) mixing the waste animal and vegetable oils with the product oil obtained in step c) to obtain a mixture; b) the mixture and hydrogen Mix and carry out hydrogenation reaction; c) separate the gas and product oil through hot and high-pressure separation; d) part of the product oil obtained in step c) is returned to step a) and mixed with waste animal and vegetable oil raw materials, and the remaining product oil and gas are separated by cold and high pressure.
  • the conventional technical route for using oils and fats to prepare aviation dyes is: "waste animal and vegetable oils ⁇ hydrorefining ⁇ high and low pressure separation ⁇ stripping ⁇ isomerization ⁇ high and low pressure separation ⁇ fractionation”.
  • the existing waste grease hydrogenation device produces biomass aviation fuel.
  • the hydrorefining catalyst is an acidic active catalyst, and the refining reaction system must add 300-700ppm dimethyl disulfide (C 2 H 6 S 2 ), this substance produces H 2 when it encounters hydrogen. S circulates with the circulating hydrogen in the entire reaction system, and part of it is reacted to generate oil first to reach a high temperature.
  • the high temperature operating conditions are 40 to 50°C, 4.0 to 5.5 MPa, and then Reduce the pressure to cold low fraction to remove excess light hydrocarbons and a small amount of hydrogen sulfide.
  • the low fraction operating conditions are 40-50°C, 1.0-1.8MPa.
  • the operating conditions are 180 ⁇ 200°C, 0.5 ⁇ 1.5MPa, to reach the second stage hydroisomerization device. During this period, the temperature changes a lot, and the materials undergo a lot of phase changes. It requires moving equipment to boost the pressure to the isomerization reaction pressure before entering the isomerization device.
  • the operating conditions are 280 ⁇ 360°C, the pressure is 2.5 ⁇ 3.5MPa, and it consumes a lot of electricity.
  • Oil containing hydrogen sulfide will corrode equipment and pipelines to a certain extent. In order to reduce the risk of corrosion, the investment cost of equipment and pipes needs to be increased.
  • the present invention provides a method for producing alkylated biomass aviation fuel from waste grease.
  • a high-efficiency stripping separator to directly strip the products generated by the refining reaction and separate the gas and liquid phases, hydrogen sulfide and water vapor are completely removed.
  • the generated oil at the bottom of the high-efficiency separator enters the isomerization reaction system under pressure, effectively effectively Reduce process energy consumption and production processes.
  • a method for producing alkylated biomass aviation fuel from waste oil, using feed oil and mixed hydrogen as the main raw materials including sequential and continuous hydrofining reactions, stripping separation and isomerization reactions.
  • the isomerization reaction yields The product is cooled, gas-liquid separated and fractionated to obtain the aviation fuel;
  • the oil phase material obtained by the hydrorefining reaction is directly subjected to the stripping separation after heat exchange with the raw material of the hydrorefining reaction;
  • the stripping and separation operation uses high-pressure hydrogen as the stripping working fluid, and the hydrogen containing hydrogen sulfide recovered by stripping and separating is used as circulating hydrogen and is combined with supplementary hydrogenation to be used as the mixed hydrogen; the oil phase material obtained by stripping and separated is mixed with the foreign matter.
  • the product materials of the isomerization reaction are directly subjected to the isomerization reaction after heat exchange.
  • metals and/or O and/or S and/or N, etc. in the raw oil can be removed; through the stripping separation operation, the metal-containing and/or O and/or N in the oil phase can be removed.
  • /or S and/or N products and short-chain hydrocarbons with low boiling points, etc. The hydrofinishing reaction and the isomerization reaction are both carried out in the presence of a catalyst, and at the same time, the consumed hydrogen is added in the hydrofining reaction and the isomerization reaction.
  • a method for producing alkylated biomass aviation fuel from waste grease includes:
  • the cooled circulating hydrogen (40 ⁇ 45°C, 5.0MPa) removes the sulfur-containing sewage in the cold high-pressure separator, and the remaining small amount of circulating hydrogen containing hydrogen sulfide continues to be recycled to reduce dimethyl disulfide amount of injection.
  • the hydrorefining reaction conditions are: pressure is 3.5-6MPa, temperature is 240-360°C, space velocity is 0.4-2.0h -1 , and hydrogen-oil ratio is 1000-1400:1 (V/V).
  • the operating conditions of stripping separation are: stripping temperature is 200-280°C, and pressure is 4-5.5MPa.
  • the gas operation directly uses high-pressure hydrogen. On the one hand, it can achieve high-temperature stripping, which can more thoroughly remove impurities in the product oil; it also facilitates the recycling of hydrogen.
  • the reaction conditions of the isomerization reaction are: pressure is 1.5-3.5MPa, temperature is 240-370°C, space velocity is 0.2-0.8h -1 , and hydrogen-oil ratio is 500-700:1 (V/V) .
  • the operating conditions are: temperature 260-360°C, pressure 2.5-3.5MPa.
  • the dimethyl disulfide, feed oil and mixed hydrogen are mixed first, and then the hydrorefining reaction is performed.
  • the present invention uses low-pressure sulfur injection to maintain high activity of the hydrorefining catalyst during the deoxygenation reaction.
  • the hydrorefining reaction includes one or more of deoxygenation reaction, desulfurization reaction, denitrification reaction and demetallization reaction using hydrogen.
  • the temperature of the raw material for the hydrorefining reaction and the oil phase material obtained by the hydrorefining reaction is increased to 190-210°C after heat exchange, and then heated to 280-340°C.
  • the temperature drops to 240-280°C and the pressure is 4.5-5.5MPa.
  • the amount of hydrogen used in stripping separation is 5.5 to 6.5 MPa; the added amount is 3 to 10% of the feed amount.
  • the gas phase separated by stripping is cooled to 40-50°C by a high-pressure air cooler, and then enters a cold high-pressure separator.
  • a part of the hydrogen-containing hydrogen separated by the cold high-pressure separator is pressurized and used as the circulating hydrogen.
  • the short-chain hydrocarbons separated by the cold high-pressure separator and the cooling material obtained by the isomerization reaction are combined into the gas-liquid separation.
  • a part of the water phase obtained by the cold high-pressure separator is combined with newly injected water and returned to the high-pressure air cooler for desalination. .
  • the content of hydrogen sulfide in the circulating hydrogen is 200 to 700 ppm.
  • the amount of dimethyl disulfide added can be controlled according to the hydrogen sulfide content in the system.
  • the oil phase obtained by stripping and separation is mixed with isomeric circulating hydrogen and supplementary hydrogenation, and then reacts with isomerization to form biological heat exchange to 260-350°C; and then heats it to 300-360°C through heating equipment; isomerization
  • the product obtained by the reaction is first exchanged with the oil phase separated by stripping, and then cooled to 40-45°C by high-pressure air cooling, and then gas-liquid separation is performed, and part of the obtained hydrogen is reused as isomerized circulating hydrogen.
  • a three-layer supported catalyst is used in order from the raw material inlet, which is a low-activity demetallization catalyst with simultaneous desulfurization and deoxygenation functions, an active demetallization catalyst, and a high-activity demetallization catalyst.
  • the main agent of each catalyst is Co-Mo-Ni;
  • two layers of supported catalysts are used in sequence from the raw material inlet, which are active oxidation state metal desulfurization catalysts and high activity condensation reducing isomerization catalysts.
  • the main agent of the active oxidation state metal desulfurization catalyst is CaO ⁇ ZnO.
  • the main agent of the high activity pour point isomerization catalyst is Pt/Pd.
  • the catalyst compositions are as follows:
  • Low activity demetallization catalyst carrier: Y-Al 2 O 3 , 3 to 5%; auxiliary: supported molecular sieve 75 to 85%; main agent: Co-Mo-Ni metal component, 10 to 20%;
  • Highly active demetallization catalyst carrier: Y-Al 2 O 3 , 5 to 8%; additive: supported molecular sieve 60 to 70%; main agent: Co-Mo-Ni metal component, 25 to 35%;
  • Highly active demetallization catalyst carrier: mixture of alkaline metal oxide and Y-Al 2 O 3 , 10 to 20%; auxiliary: active molecular sieve 45 to 55%; main agent: Co-Mo metal component, 35 to 45 %;
  • Active oxidation state metal desulfurization catalyst carrier: Y-Al 2 O 3 , 15-25%; auxiliary agent: active molecular sieve 25-35%; main agent: CaO ⁇ ZnO, 45-55%;
  • Highly active pour point isomerization catalyst carrier: Y-Al 2 O 3 , 40 to 45.5%; auxiliary agent: molecular sieve 45 to 55%; main agent: Pt/Pd, 0.5 to 5%.
  • a method for producing alkylated biomass aviation fuel from waste grease includes:
  • a large amount of oxygen and a small amount of sulfur and nitrogen in the oil react to produce alkylated hydrocarbons, hydrogen sulfide, water, a small amount of ammonia and other reaction products.
  • the temperature is 240 ⁇ 280°C ( For example, 260°C)
  • the pressure is about 4.5 ⁇ 5.5MPa (for example, the pressure is 5.2MPa).
  • high-pressure hydrogen of 5.5-6.5MPa (6.0MPa) greater than 3% of the feed amount is passed through the bottom of the high-efficiency stripping separator to strip the oil produced by the reaction at high pressure to remove short-term components.
  • Part of the sulfur-containing sewage produced by the cold high-pressure separator is reused to the water injection point, and part of it is discharged to the sewage treatment device when the ammonium salt concentration is high.
  • a small amount of hydrocarbons are sent to the cold low-pressure separator.
  • the circulating hydrogen is pressurized by the circulating hydrogen compressor and mixed with the raw oil again and enters the reaction system for recycling.
  • the hydrogen lost in the reaction system is replenished by a new hydrogen compressor.
  • the reaction of removing water vapor and hydrogen sulfide in the high-efficiency stripping separator produces oil (240-280°C, preferably 260°C). Under the action of its own pressure, it is mixed with the isomeric circulating hydrogen from the bottom outlet pipeline of the high-efficiency stripping separator. , reacts with isomerization to form biological heat exchange, and then is heated to about 300-360°C by the isomerization feed heating furnace, and then enters the isomerization reactor to selectively crack the molecules of long-chain hydrocarbons, from the original C18 , C16 is cracked into biomass aviation fuel components such as C9 ⁇ C14. Isomerizes most normal paraffins into isoparaffins, thereby lowering the cold plugging point of the isomerized oil.
  • the oil produced by the isomerization reaction is cooled by heat exchange in the isomerization feed heat exchanger, and then cooled to 40-45°C by high-pressure air cooling. After air cooling, the isomeric products enter the isomeric cold low fraction liquid, and the liquid phase directly enters the subsequent process for fractionation.
  • the jet fuel component at 160-270°C and the biodiesel component at 270-320°C were extracted respectively.
  • the naphtha part goes directly to the hydrogen production or fuel gas system with the dry gas.
  • the gas phase system is compressed by the heterogeneous cycle hydrogen compressor and the cycle continues.
  • the consumed hydrogen is replenished in time by the new hydrogen compressor. Isomerization consumes a small amount of hydrogen, and a new hydrogen compressor is shared with hydrorefining.
  • a device for producing alkylated biomass aviation fuel from waste grease including:
  • a hydrofinishing reactor for carrying out the hydrofinishing reaction
  • a stripping separator for performing the stripping and separation operation the material inlet of the stripping separator is connected to the product outlet of the hydrorefining reactor through a pipeline, and the gas inlet is connected to a high-pressure hydrogen pipeline;
  • the gas phase post-processing unit cools the gas phase obtained by stripping and separation, and performs gas-liquid separation
  • the circulating hydrogen compressor has an inlet connected to the gas phase outlet of the gas phase post-processing unit, and the recovered hydrogen containing hydrogen sulfide is used as circulating hydrogen and supplementary hydrogenation to be used as the mixed hydrogen;
  • An isomerization reactor for carrying out the isomerization reaction, the raw material inlet and the liquid outlet of the stripping separator are connected through a pipeline;
  • the isomerization product post-processing unit is connected to the product outlet of the isomerization reactor to finally obtain the alkylated biomass aviation fuel;
  • Heat exchanger I is thermally connected between the product pipeline of the hydrorefining reactor and the raw material pipeline of the hydrorefining reactor to realize heat exchange;
  • Heat exchanger II is thermally connected between the product pipeline of the isomerization reactor and the feed pipeline of the hydrotreating reactor to achieve heat exchange.
  • the gas phase post-processing unit includes: a high-pressure air cooler for air-cooling the gas phase obtained by stripping and separation, a cold high-pressure separator for gas-liquid separation of the air-cooled materials of the high-pressure air cooler; the cold high-pressure separator
  • the separated water phase is partially returned to the high-pressure air cooler and partially output to the generated water pump of the water treatment unit.
  • the hydrogen containing hydrogen sulfide separated by the cold high-pressure separator is pressurized by a circulating hydrogen compressor and recycled.
  • the short-chain alkanes separated by the cold high-pressure separator are combined with the isomerization products and recovered.
  • the isomerized product post-processing unit includes: a heterogeneous high-pressure air cooler for air-cooling the isomerized materials, and a cold low-pressure separator for gas-liquid separation of the air-cooled materials.
  • the cold low-pressure separator also receives the short-chain alkanes obtained from the cold high-pressure separator; part of the hydrogen obtained from the cold low-pressure separator is recycled and used, and part of the hydrogen is discharged to the fuel system; the liquid material obtained from the cold low-pressure separator is fractionated to obtain respectively Jet fuel components, biodiesel components and naphtha components.
  • the waste oils and fats of the present invention may be one or more of waste catering oil, gutter oil, swill oil, palmitated oil, coconut oil, palm oil, etc.
  • the raw material oil is waste grease mainly containing C16-C18, the acid value in the raw material oil is 15-25 mg/g; the iodine value is 80-120g/100g.
  • the process of hydrorefining and isomerizing high-oxygen waste grease to produce biomass aviation fuel that we independently developed does not require multiple cooling, depressurizing, and then heating and pressurizing processes, which reduces the number of phase changes. Improved energy utilization and reduced energy consumption.
  • the products generated by the refining reaction are directly fed into the high-efficiency stripping separator for stripping and gas-liquid two-phase separation. It makes full use of the heat generated by the hydrorefining itself and the high pressure of high-pressure hydrogen to completely remove hydrogen sulfide, water vapor, Ammonia etc.
  • the generated oil at the bottom of the high-efficiency stripping separator enters the isomerization reaction system under self-pressure.
  • the generated oil after the reaction directly enters fractionation for rectification. There is no H 2 S and no additional power equipment is required, which accordingly reduces the cost of some equipment pipes. Invest.
  • the gas phase at the top is cooled by high-pressure air cooling to about 40-45°C and enters the cold high temperature zone to remove acidic water, circulate hydrogen and then return to the compressor inlet for pressurized circulation.
  • the products are alkylated biomass aviation fuel, biodiesel and biomass naphtha, and the raw materials are waste animal and vegetable oils and fats.
  • Such products have positive significance for reducing carbon emissions, and some European Union
  • the national mandatory policy has increased the proportion of biomass aviation fuel in aviation fuel, which has good policy incentives and broad market prospects.
  • the hydrorefining catalyst maintains high activity during the deoxygenation reaction.
  • the oil generated from the reaction at the bottom of the high-pressure gas separator has a relatively high temperature and does not require excessive heat exchange or a high-pressure feed pump. It is pressed to the isomerization system by its own pressure. The investment cost of moving equipment is reduced and the power loss is reduced.
  • the water separated by cold high fractionation can be effectively reused, which can reduce safety problems caused by ammonium salt crystallization and corrosion, and can also reduce sewage treatment costs.
  • Figure 1 is a system diagram for producing alkylated biomass aviation fuel from waste grease used in some embodiments of the present invention.
  • Figure 1 is a system diagram for producing alkylated biomass aviation fuel from waste grease in this embodiment, including a new hydrogen compressor 101, a feed oil feed pump 102, a hydrorefining reactor 103, a heat exchanger 104, Hydrogen heating furnace 105, stripping separator 106, high-pressure air cooler 107, cold high-pressure separator 108, generated water pump 109, circulating hydrogen compressor 110, heat exchanger II 111, isomerization heating furnace 112, isomerization reactor 113 , heterogeneous high-pressure air cooler 114, cold low-pressure separator 115, heterogeneous cycle hydrogen compressor 116.
  • the hydrotreating reactor 103, the stripping separation operation 106, and the isomerization reactor 113 are connected in sequence.
  • the outlet of the raw oil feed pump 102 is connected to the low-temperature pipeline inlet of the heat exchanger I 104 through a pipeline, and the low-temperature pipeline outlet of the heat exchanger I 104 is connected to the feed port of the hydrogenation heating furnace 105 through a pipeline, and the hydrogenation heating
  • the discharge port of the furnace 105 is connected to the feed port of the hydrotreating reactor 103 through a pipeline.
  • the outlet of the hydrorefining reactor 103 is connected to the high-temperature pipeline inlet of the heat exchanger 1104 through a pipeline, and the high-temperature pipeline outlet of the heat exchanger 1104 is connected to the material inlet of the stripping separation operation 106 through a pipeline.
  • the stripping separation operation 106 is also provided with a new hydrogen feeding port.
  • the bottom of the stripping separation operation 106 is the reaction generated oil outlet, which is connected to the low-temperature pipeline inlet of the heat exchanger II 111 through a pipeline, and the low-temperature pipeline outlet of the heat exchanger II 111 is connected to the inlet of the heterogeneous heating furnace 112 through a pipeline.
  • the outlet of the isomerization heating furnace 112 is connected to the feed port of the isomerization reactor 113 through a pipeline.
  • the top of the stripping and separation operation 106 is a gas phase outlet, which is connected to the high-pressure air cooler 107 and the cold high-pressure separator 108 in sequence through pipelines.
  • a part of the wastewater separated by the cold high-pressure separator 108 is circulated to the inlet of the high-pressure air cooler 107 using the generated water pump 109
  • the other part of the pipeline is sent directly to the water treatment unit.
  • the hydrogen containing hydrogen sulfide recovered by the cold high-pressure separator 108 is output through its hydrogen outlet, connected to the circulating hydrogen compressor 110 through a pipeline, and then returned to the outlet of the raw oil feed pump 102 to be mixed with raw oil, new hydrogen, etc. Return to hydrotreater.
  • the outlet of the isomerization reactor 113 is located at the bottom and is connected to the high-temperature pipeline inlet of the heat exchanger II 111 through a pipeline.
  • the high-temperature pipeline outlet of the heat exchanger II 111 is connected to the inlet of the heterogeneous high-pressure air cooler 114 through a pipeline.
  • the outlet of the structural air cooler 114 is connected to the cold low-pressure separator 115 through a pipeline.
  • dimethyl disulfide (generally 0.005% of the feed oil) is added to the inlet of the feed oil feed pump. After the feed oil is pressurized to 6.0MPa by the hydrogenation feed pump, it is mixed with mixed hydrogen as a reaction. Feed.
  • the mixed reaction feed is heated to about 190-210°C through a heat exchanger (reaction effluent/reactor feed heat exchanger), and then heated to about 280-340°C by the start-up heating furnace before entering hydrofining.
  • the reactor reacts with the demetallization catalyst in the first bed of the reactor to remove a small amount of metal elements and phospholipids in the raw material.
  • Hydrofining reactions are carried out in the lower two beds to remove a large amount of oxygen and a small amount of oxygen in the raw oil.
  • Elements such as sulfur and nitrogen react to produce alkylated hydrocarbons, hydrogen sulfide, water, a small amount of ammonia and other reaction products.
  • the temperature is 260°C and the pressure is about 5.2MPa.
  • the bottom of the high-efficiency stripping separator passes 6.0MPa high-pressure hydrogen of more than 3% of the feed amount, and performs high-pressure stripping on the reaction oil to remove short-chain hydrocarbons, hydrogen, Dry gas, liquefied gas, water vapor, hydrogen sulfide, ammonia and other substances.
  • the gas phase material at the top of the high-efficiency stripping separator enters air cooling (high-pressure air cooler 107), desalted water is injected to wash away the ammonium salt generated during the air cooling stage to prevent ammonium salt from scaling and blocking the air cooling tube bundle.
  • the cooled circulating hydrogen (40-45°C, 5.0MPa) removes the sulfur-containing sewage in the cold high-pressure separator 108, and the remaining small amount of circulating hydrogen containing hydrogen sulfide continues to be recycled to reduce the concentration of dimethyl disulfide. Injection volume. Part of the sulfur-containing sewage produced by the cold high-pressure separator is reused to the water injection point, and part of it is discharged to the sewage treatment device when the ammonium salt concentration is high.
  • a small amount of hydrocarbons is sent to the cold low-pressure separator 115.
  • the circulating hydrogen is pressurized by the circulating hydrogen compressor 110 (the pressure is 6.0 MPa) and mixed with the raw oil again and enters the reaction system for recycling.
  • the hydrogen lost in the reaction system is replenished by a new hydrogen compressor (controlled by the pressure of the hydrofining reactor 103).
  • the reaction of removing water vapor and hydrogen sulfide generates oil (260°C).
  • the bottom outlet pipeline of the high-efficiency stripping separator and the isomeric circulating hydrogen Mix exchange heat with the isomerization reaction product, and then pass through the isomerization feed heating furnace (isomerization heating furnace 112) to heat to about 300-360°C, and then enter the isomerization reactor 113 to convert the molecules of long-chain hydrocarbons into Selective cracking is carried out to crack the original C18 and C16 into biomass aviation fuel components such as C9 ⁇ C14.
  • the oil produced by the isomerization reaction is cooled by heat exchange in the isomerization feed heat exchanger, and then cooled to 40-45°C in the isomerization high-pressure air cooler 114. After air cooling, the isomeric products enter the isomeric cold low-pressure separator 115 for liquid separation, and the liquid phase directly enters the subsequent process for fractionation.
  • the jet fuel component at 160-270°C and the biodiesel component at 270-320°C were extracted respectively.
  • the naphtha part goes directly to the hydrogen production or fuel gas system with the dry gas.
  • the gas phase separated by the cold low-pressure separator 115 is compressed by the isomerization cycle hydrogen compressor 116 (pressure is 3.5MPa), continues to circulate, and is mixed with new hydrogen and then mixed with the oil phase at the bottom of the stripping separation operation 106 and enters the heat exchanger II 111 .
  • the consumed hydrogen is replenished in time by the new hydrogen compressor. Isomerization consumes a small amount of hydrogen, and a new hydrogen compressor is shared with hydrorefining.
  • the reaction stage is mainly realized by the catalyst in the hydrofining reactor and the hydroisomerization reactor (isomerization reactor 113).
  • HDO hydrodeoxygenation
  • HDCO hydrodecarbonylation
  • HDCO2 decarboxylation
  • alkanes, water, carbon monoxide and carbon dioxide are produced.
  • the raw material contains a small amount of sulfur and nitrogen, which are removed during the hydrorefining process to generate hydrogen sulfide and ammonia.
  • Normal alkanes generate branched isoparaffins under the combined action of molecular sieves and active metal Pt/Pd catalysts.
  • the high-efficiency gas separator separates hydrogen sulfide and water vapor in the purified reaction product to the greatest extent, ensuring that the heteronoble metal catalyst is free from any pollution and operates efficiently.
  • Temperature raising and cooling are mainly achieved by heat exchangers and air cooling.
  • the key point is the high-efficiency stripping separator.
  • This equipment is the bridge and hub between two reaction systems with completely different conditions: hydrorefining and isomerization. While protecting isomeric precious metals from being polluted and poisoned by hydrogen sulfide, the greater significance of this equipment is to further strip the hydrogen sulfide and water vapor in the oil produced by the reaction to the circulating cold high-pressure separator for separation of sulfur-containing sewage. It reduces the amount of dimethyl disulfide added in the refining system and effectively reduces the risk of corrosion of the generated oil in subsequent pipelines. The energy-saving effect is more prominent in terms of power loss.
  • the following table shows the analysis data of the hydrogen gas sample from the top circulation of the high-efficiency gas separator in this example:
  • the following table shows the yield of each embodiment: (The pressure of the isomerization reactor is constant at 3.5MPa, the temperature is constant based on the reactor inlet temperature of 345°C, the hydrogen-to-oil ratio is constant at 600:1, and the three space velocities with different reactions are changed by 0.6h. -1 ; the hydrotreating reactor parameters remain unchanged: pressure (5.4MPa); temperature (350°C); space velocity (1.0h - 1).
  • Example 1 Example 2 Example three airspeed 1.8h -1 1.2h -1 0.6h -1 CO+CO2 0.23 0.37 0.49 Dry air 0.15 0.98 1.39 Liquefied gas 0.42 1.83 2.51 Naphtha 0.98 3.88 3.99 biojet fuel 40.6 50.8 67.1 biodiesel 44.8 27.8 10.6
  • the present invention uses a high-efficiency stripping separator to directly strip the products generated by the refining reaction and separate the gas-liquid phases, completely removing hydrogen sulfide and water vapor, and the generated oil at the bottom of the high-efficiency separator enters under pressure.
  • Heterogeneous reaction system effectively reduces process energy consumption and production procedures.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

La présente invention divulgue un procédé et un système de production d'un combustible d'aviation de biomasse alkylée à partir d'huiles et de graisses usées. Le procédé comprend : la prise d'huile brute et d'hydrogène mélangé en tant que matières premières principales, la soumission successive de ceux-ci à une réaction d'hydroaffinage, à la séparation par décapage et à une réaction d'isomérisation, qui sont effectuées en continu, et la soumission du produit obtenu par la réaction d'isomérisation à un refroidissement, à une séparation gaz-liquide et à un fractionnement pour obtenir un combustible d'aviation, le matériau de phase huileuse obtenu à partir de la réaction d'hydroraffinage et des matières premières pour la réaction d'hydroaffinage étant soumis à un échange de chaleur puis directement à la séparation de décapage; pendant l'opération de la séparation de décapage, un hydrogène gazeux à haute pression est utilisé en tant que milieu de travail de décapage, et l'hydrogène gazeux contenant du sulfure d'hydrogène récupéré par la séparation de décapage est utilisé en tant qu'hydrogène de recyclage et est combiné à de l'hydrogène supplémentaire pour servir d'hydrogène mélangé pour une utilisation; et le matériau de phase huileuse obtenu à partir de la séparation de décapage et un matériau de produit pour la réaction d'isomérisation sont soumis à un échange de chaleur puis directement à la réaction d'isomérisation. Dans la présente invention, au moyen d'un séparateur de décapage efficace, du sulfure d'hydrogène et de la vapeur d'eau sont complètement éliminés; et de l'huile générée au fond du séparateur efficace entre dans un système de réaction d'isomérisation au moyen d'une autopression, de sorte que la consommation d'énergie dans le processus et les procédures de production sont efficacement réduites.
PCT/CN2022/121404 2022-06-06 2022-09-26 Procédé et système de production de combustible d'aviation de biomasse alkylée à partir d'huiles et de graisses usées WO2023236390A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202210652417.0A CN115044388A (zh) 2022-06-06 2022-06-06 一种废弃油脂生产烷基化生物质航空燃料的方法及系统
CN202210652417.0 2022-06-06

Publications (1)

Publication Number Publication Date
WO2023236390A1 true WO2023236390A1 (fr) 2023-12-14

Family

ID=83162242

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/121404 WO2023236390A1 (fr) 2022-06-06 2022-09-26 Procédé et système de production de combustible d'aviation de biomasse alkylée à partir d'huiles et de graisses usées

Country Status (2)

Country Link
CN (1) CN115044388A (fr)
WO (1) WO2023236390A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118048173A (zh) * 2024-04-16 2024-05-17 东营联合石化有限责任公司 一种尾油加氢裂化节能装置

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115044388A (zh) * 2022-06-06 2022-09-13 浙江嘉澳环保科技股份有限公司 一种废弃油脂生产烷基化生物质航空燃料的方法及系统

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090321311A1 (en) * 2008-06-27 2009-12-31 Uop Llc Production of diesel fuel from renewable feedstocks containing phosphorus
CN102027098A (zh) * 2008-03-17 2011-04-20 环球油品公司 从可再生原料中生产运输燃料
CN103059902A (zh) * 2011-10-24 2013-04-24 中国石油化工股份有限公司 一种以动植物油为原料制备喷气燃料调合组分的方法
CN103937527A (zh) * 2014-05-05 2014-07-23 抚顺新瑞催化剂有限公司 生物质油加氢精制-异构降凝制备低凝点柴油组分的方法
CN109666509A (zh) * 2017-10-17 2019-04-23 中国石化工程建设有限公司 一种生产航空生物燃料的加氢方法
CN115044388A (zh) * 2022-06-06 2022-09-13 浙江嘉澳环保科技股份有限公司 一种废弃油脂生产烷基化生物质航空燃料的方法及系统

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102027098A (zh) * 2008-03-17 2011-04-20 环球油品公司 从可再生原料中生产运输燃料
US20090321311A1 (en) * 2008-06-27 2009-12-31 Uop Llc Production of diesel fuel from renewable feedstocks containing phosphorus
CN103059902A (zh) * 2011-10-24 2013-04-24 中国石油化工股份有限公司 一种以动植物油为原料制备喷气燃料调合组分的方法
CN103937527A (zh) * 2014-05-05 2014-07-23 抚顺新瑞催化剂有限公司 生物质油加氢精制-异构降凝制备低凝点柴油组分的方法
CN109666509A (zh) * 2017-10-17 2019-04-23 中国石化工程建设有限公司 一种生产航空生物燃料的加氢方法
CN115044388A (zh) * 2022-06-06 2022-09-13 浙江嘉澳环保科技股份有限公司 一种废弃油脂生产烷基化生物质航空燃料的方法及系统

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118048173A (zh) * 2024-04-16 2024-05-17 东营联合石化有限责任公司 一种尾油加氢裂化节能装置

Also Published As

Publication number Publication date
CN115044388A (zh) 2022-09-13

Similar Documents

Publication Publication Date Title
RU2607771C2 (ru) Способ переоборудования обычного нефтеперерабатывающего предприятия в предприятие по получению топлива из биологического сырья
US9024095B2 (en) Method and apparatus for preparing fuel components from crude tall oil
CN102504866B (zh) 餐厨废油和矿物柴油混合加氢制备生物柴油的方法
CN104946306B (zh) 一种煤焦油全馏分悬浮床加氢裂化和固定床加氢改质组合方法
JP6501898B2 (ja) フィッシャー・トロプシュ合成油を使用するディーゼル燃料およびジェット燃料製造システムおよび方法
US8318996B2 (en) Systems and methods for treating hydrogen recycle gas in a process for converting biorenewable feedstock into renewable fuels and chemicals
CN103897718A (zh) 一种由动植物油脂生产柴油馏分和航空燃料馏分的方法
CN105419867A (zh) 一种利用生物质油生产绿色环保运输燃料的组合加氢方法及装置
CN102041023A (zh) 一种掺炼生物油脂改进渣油加氢的方法
US10683459B2 (en) Liquid-phase hydroisomerization system and process therefor and use thereof
US20150057477A1 (en) Systems and methods for producing fuel from a renewable feedstock
CN107974266A (zh) 一种由废弃油脂生产航空燃料组分的方法及系统
CN109666509A (zh) 一种生产航空生物燃料的加氢方法
WO2023236390A1 (fr) Procédé et système de production de combustible d'aviation de biomasse alkylée à partir d'huiles et de graisses usées
CN107974265A (zh) 一种由废弃油脂生产航空燃料组分的方法
CN102585899B (zh) 一种煤焦油的全液相加氢方法
CN103571533A (zh) 一种煤焦油加氢系统及方法
CN102260527B (zh) 高硫、高酸劣质重油临氢催化热裂解-加氢处理新工艺
CN104004541B (zh) 一种煤基高芳烃潜含量原料油的制备方法
CN103937527B (zh) 生物质油加氢精制-异构降凝制备低凝点柴油组分的方法
CN204874343U (zh) 一种沼气与焦炉煤气联合生产甲醇装置
CN210560278U (zh) 一种加氢裂化和加氢脱硫联合装置
CN102807900B (zh) 一种富氧煤焦油高值化利用方法
CN115537231B (zh) 一种改变物料流向而实现减油增化的方法
CN100489064C (zh) 一种在加氢裂化工艺中提浓循环氢的方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22945522

Country of ref document: EP

Kind code of ref document: A1