CN109355098A - A kind of low grade oils multi-stage conversion process - Google Patents

A kind of low grade oils multi-stage conversion process Download PDF

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Publication number
CN109355098A
CN109355098A CN201811092023.4A CN201811092023A CN109355098A CN 109355098 A CN109355098 A CN 109355098A CN 201811092023 A CN201811092023 A CN 201811092023A CN 109355098 A CN109355098 A CN 109355098A
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reaction
low grade
grade oils
agent
conversion process
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CN109355098B (en
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林科
郭立新
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Beijing Haixin Energy Technology Co ltd
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Beijing SJ Environmental Protection and New Material Co Ltd
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Priority to CN201811092023.4A priority Critical patent/CN109355098B/en
Priority to PCT/CN2018/122668 priority patent/WO2019205681A1/en
Priority to SG11201912750PA priority patent/SG11201912750PA/en
Priority to MYPI2019007207A priority patent/MY192483A/en
Priority to EP18916095.5A priority patent/EP3608388B1/en
Publication of CN109355098A publication Critical patent/CN109355098A/en
Priority to US16/426,886 priority patent/US11492563B2/en
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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
    • C10G65/00Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/12Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps

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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)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention belongs to biomass economy, the energy, chemical technology fields, and in particular to a kind of low grade oils multi-stage conversion process.The conversion process uses iron oxide, at least one of the regrowth of the useless agent of the desulfurization of iron oxide or the useless agent of the desulfurization of iron oxide is used as catalyst, and use aqueous slurry, the molar ratio of ferro element and element sulphur in reaction system is controlled simultaneously, it was found that can effectively utilize carbonylation in the presence of CO blocks free radical polycondensation of the low grade oils in cracking process, and realize that the shift activity hydrogen of CO and water adds hydrogen, in the conversion reaction, low grade oils can directly carry out conversion reaction, while improving liquefaction yield, after conversion reaction, a large amount of waste water will not be generated.

Description

A kind of low grade oils multi-stage conversion process
Technical field
The invention belongs to biomass economy, the energy, chemical technology fields, and in particular to a kind of low grade oils multi-stage conversion work Skill.
Background technique
With the rapid development of social economy, the fossils class such as coal, crude oil, natural gas, oil shale non-renewable energy is increasingly Exhaustion, at the same time, generated CO after such fossil class non-renewable energy burning2、SO2、NOxRing caused by equal pollutants Border pollution is also got worse, this forces the mankind to have to think deeply the approach for obtaining the energy and improve the method for environment.
Currently, low grade oils transformation technology becomes a kind of new means for obtaining the energy, poor oil refers to prior art hardly possible With the oil product of processing, such as: tar sand oil, viscous crude, waste mineral oil, used oil, hogwash fat, gutter oil, wood tar, coal tar, acid The one such or mixtures such as oil, mineral heavy oil, oxygen-containing vegetable and animals oils, the hydrocarbon miscella of organic matter are lost, they have weight The features such as aromatic hydrocarbons, metal, organic acid, oxygen, sulphur, nitrogen, chlorine, alkene, residual carbon content height are usually by low grade oils in the prior art In the presence of a catalyst, under certain temperature and pressure, hydrogenation reaction is directly carried out with pure hydrogen, is translated into light oil Product, or carry out generating coke and low-grade oil product using coking process.
In above-mentioned low grade oils transformation technology, using the method for direct hydrogenation, it can bring and be not easy to react, thermal discharge is big, urges Agent be easy poisoning and deactivation, can not the unfavorable factors such as long-cycle production, using coking process, and oil product can be brought to waste, generated Solid coke, the low defect of oil product yield.In addition, above-mentioned low grade oils transformation technology can generate a large amount of waste water, product quality and Economy is also poor.
Summary of the invention
Therefore, the technical problem to be solved in the present invention is that overcome in existing low grade oils conversion process reaction atmosphere and The defect that catalyst requirement is stringent, waste water yield is big, and then a kind of reaction of high order is provided, in the different stages of reaction, use Different reaction atmosphere, catalyst or process operation parameters realizes efficient low grade oils multi-stage conversion process.
For this purpose, technical solution used by the present invention solves the above problems is as follows:
Low grade oils multi-stage conversion process provided by the present invention, includes the following steps:
The aqueous slurry containing catalyst and low grade oils is prepared, the catalyst is iron oxide, iron oxide Give up agent or the desulfurization of iron oxide of desulfurization give up at least one of the regrowth of agent;
Aqueous slurry and pure CO or the gas mixing containing CO are subjected to level-one conversion reaction, collect converted product, described one The molar ratio of ferro element and element sulphur is 1 in grade conversion reaction control reaction system: it is carried out under conditions of (0.5~5), it is described The reaction pressure of level-one conversion reaction is 5-22MPa, and reaction temperature is 200-480 DEG C;
Converted product and the gas rich in hydrogen are subjected to second level conversion reaction, the reaction pressure of the second level conversion reaction For 5-22MPa, reaction temperature is 250-450 DEG C, and oil product is made.
Further, the molar ratio of sulphur-containing substance ferro element and element sulphur into reaction system is added into the catalyst It is 1: (0.5~5), preferably 1: (0.5-2), more preferably 1: (1-2).
Further, the sulphur-containing substance is at least one of sulphur, hydrogen sulfide, carbon disulfide.
Further, the volume content of CO is optimal not less than 15%, preferably not less than 25% in the gas containing CO It is selected as not less than 50%;
The volume content of hydrogen is optimal to be not less than 80%, preferably not less than 90% in the gas rich in hydrogen Pure hydrogen.
Further, the gas containing CO is CO and H2Gaseous mixture or synthesis gas.
Further, the iron oxide desulfurization give up agent be using iron oxide as the useless agent of the desulfurizing agent of active component, With Fe21.333O32For the useless agent of the desulfurizing agent of active component, using FeOOH as at least one in the useless agent of the desulfurizing agent of active component Kind;Or,
The regrowth of the useless agent of the desulfurization of the iron oxide is using iron oxide as the useless agent of the desulfurizing agent of active component Regrowth, with Fe21.333O32For the regrowth of the useless agent of the desulfurizing agent of active component, using FeOOH as the desulfurizing agent of active component At least one of the regrowth of useless agent.
Preferably, the iron oxide is di-iron trioxide and/or ferroso-ferric oxide.
Further, the di-iron trioxide is α-Fe2O3、α-Fe2O3.H2O、γ-Fe2O3、γ-Fe2O3.H2O, without fixed Shape Fe2O3, amorphous Fe2O3.H2At least one of O;
The ferroso-ferric oxide is the ferroso-ferric oxide of cubic system;
The FeOOH is in alpha-feooh, β-FeOOH, γ-FeOOH, δ-FeOOH, θ-FeOOH and amorphous FeOOH It is at least one.
Further, the regrowth of the useless agent of the desulfurization of the iron oxide is to be taken off by slurry method to iron oxide The regrowth that the useless agent of sulphur obtains after being aoxidized, vulcanized and being aoxidized.
Further, the regeneration method of the useless agent of the desulfurization of the iron oxide, includes the following steps:
The useless agent of the desulfurization of the iron oxide is mixed with water or aqueous slkali, is configured to slurries;
Oxidant is added into the slurries, and once oxidation reaction occurs;
Vulcanizing agent is added into the slurries after the oxidation reaction, and vulcanization reaction occurs;
Oxidant is added into the slurries after the vulcanization reaction, and secondary oxidation reaction occurs;
Circulation carries out the vulcanization reaction and secondary oxidation reaction;
Slurries after secondary oxidation reaction are separated by solid-liquid separation, the useless agent of desulfurization of the iron oxide is obtained Regrowth.
Further, the level-one conversion reaction is in paste state bed reactor, bubbling bed reactor or suspended-bed reactor Middle progress;
The second level conversion reaction is anti-in paste state bed reactor, bubbling bed reactor, suspended-bed reactor or fixed bed It answers in device and carries out, under the atmosphere rich in hydrogen, be hydrocracked and refining reaction;Preferably fixed bed reactors.
Further, the reaction time of the level-one conversion reaction is not less than 15min, preferably 15-120min, more excellent It is selected as 30~90min;
The reaction time of secondary conversion reaction not less than 15min, preferably 15-180min, more preferably 15~ 90min。
Further, in the slurries, the content of the catalyst is 0.1~10wt%;
The average grain diameter of the catalyst is 0.1 μm of -5mm, preferably 5 μm -100 μm, most preferably 5-50 μm.
Further, the aqueous slurry and pure CO or gas mixing containing CO are subjected to level-one conversion reaction, including such as Lower step: by pure CO or gas pressurized containing CO to 5-22MPa, be heated up to 150-600 DEG C after, be passed through in reaction system, and with Conversion reaction occurs into the aqueous slurry in reaction system.
Further, the aqueous slurry and pure CO or gas mixing containing CO are subjected to level-one conversion reaction, including such as Lower step: by the pure CO in part or gas pressurized containing CO to 5-22MPa, be heated up to 150-600 DEG C after, be passed through the aqueous slurry In, and enter with the aqueous slurry and conversion reaction occurs in reaction system;
It after rest part is forced into 5-22MPa, is heated up to 300-600 DEG C, is passed through in reaction system, and therein with entering Conversion reaction occurs for the aqueous slurry.
Further, the volume ratio of the pure CO or gas and the aqueous slurry containing CO is (200-10000): 1, it is excellent It is selected as (1000-5000): 1;
The volume ratio of the gas and converted product rich in hydrogen is 200~5000: 1, preferably 300~3000: 1.
It further, further include adding that hydrogen is added to urge into the converted product before carrying out the second level conversion reaction The step of agent and/or the catalyst.
Further, the hydrogenation catalyst is made of the active constituent of carrier and load thereon, with the hydrogenation catalyst Total restatement of agent, the load capacity of the active constituent are 0.5-15%.
The active constituent is one of oxide of Mo, Mn, W, Fe, Co, Ni or Pd or a variety of;
The carrier is at least one of silica, aluminum oxide, zeolite, molecular sieve.
In addition, the low grade oils refer to the unmanageable oil product of the prior art, and such as: tar sand oil, viscous crude, mineral waste Oil, used oil, hogwash fat, gutter oil, wood tar, coal tar, rancid oil, mineral heavy oil, oxygen-containing vegetable and animals oils, organic matter are hydrocarbon One such or a variety of mixture such as miscella, they have heavy aromatics, metal, organic acid, oxygen, sulphur, nitrogen, chlorine, alkene The features such as hydrocarbon, residual carbon content height are at least one of palm oil, tar sand oil, gutter oil, petroleum base wax oil, rapeseed oil.
Above-mentioned technical proposal of the invention has the advantages that
1, low grade oils multi-stage conversion process provided by the present invention, using the desulfurization of iron oxide, iron oxide At least one of the regrowth of useless agent or the useless agent of the desulfurization of iron oxide is used as catalyst, and uses aqueous slurry, simultaneously The molar ratio of ferro element and element sulphur in reaction system is controlled, discovery can effectively utilize carbonylation in the presence of CO and block poor quality Free radical polycondensation of the oil product in cracking process, and realize that the transformation of CO and water (water generated in low grade oils conversion process) is living Property hydrogen add hydrogen, in the conversion reaction, low grade oils can directly carry out conversion reaction, improve liquefy yield while, conversion A large amount of waste water will not be generated after reaction.Meanwhile by carrying out secondary conversion reaction to low grade oils, poor quality can be effectively improved The conversion ratio etc. of oil product.
2, low grade oils multi-stage conversion process provided by the invention, further, the desulfurization of iron oxide give up agent be with Iron oxide is the useless agent of the desulfurizing agent of active component, with Fe21.333O32It is living for the useless agent of the desulfurizing agent of active component, with FeOOH At least one of the useless agent of desulfurizing agent of property component;It is active that the regrowth of the useless agent of the desulfurization of iron oxide, which is with iron oxide, The regrowth of the useless agent of the desulfurizing agent of component, with Fe21.333O32For the regrowth of the useless agent of the desulfurizing agent of active component, with FeOOH For at least one of the regrowth of the useless agent of the desulfurizing agent of active constituent, appropriate sulphur is incorporated by the above-mentioned catalyst of utilization, It was found that these catalyst form carbonyls first in conjunction with CO, then by the carbonyls that carbon is former under CO atmosphere Son is formed by small molecule active position after being grafted on low grade oils thermal cracking, meanwhile, iron, element sulphur catalytic action under also It realizes the CO transformation effect in situ for producing hydrogen and catalytic hydrodeoxygenation, reduces the oxygen content of oil product, substantially increase poor oil The oil product yield that the conversion yields and long chain of product are converted to small molecule;
The give up regrowth of agent of the desulfurization of iron oxide is alternately to be vulcanized iron oxide by slurry method and oxygen Change the regrowth obtained after regeneration further to react by multiple vulcanization-oxidization, in this process iron oxide and iron Sulphur compound crystal phase experience reconstructs and conversion, in addition S2-Ionic radius (0.18nm) is greater than O2-Ionic radius (0.14nm), therefore with The conversion between Fe-O key and Fe-S key, the structure cell of iron oxide also undergo contraction and expansion, in turn result in script structure Stable iron oxide crystalline particle becomes loose and bursts apart, and generates a large amount of nanometer iron compounds, this nanometer of iron compound parent Sulphur is good, easily cures.Meanwhile the Nanoscale Iron compound surface covers one layer of nonpolar elemental sulfur layer, the elemental sulfur layer The reunion between nanometer iron compounds particle can not only be hindered to grow up, substantially increase its dispersibility, and can use between substance Existing similar compatibility characteristic, is highly dispersed at a nanometer iron compound in nonpolar oil product;Furthermore the Nanoscale Iron of sulphur covering Compound is because sulphur-iron is closely coupled and the lesser partial size of nanometer iron compound itself, so that sulphur and nanometer iron compound be made to exist Magnetic iron ore (the Fe for generating and there is inferior heavy oil hydrogenation activity can be reacted under low temperature1-xS), finally obtain such method Regrowth partial size it is small, lipophilic good, structure slabbing nanostructure, the sulphur barrier being adsorbed between piece and piece avoids It is reunited, and the adsorption capacity of CO is substantially increased, and enhances carbonylation, transformation produces hydrogen and hydrogenation catalyst ability.
3, low grade oils multi-stage conversion process provided by the invention is delivered to reaction by reaction raw materials with containing the gas of CO In device, under conditions of suitable temperature, pressure, gas liquid ratio and catalyst, in reactor occur cracking, carbonylation, transformation, Hydrogen etc. is added to react;It is further advanced by using paste state bed reactor, reaction raw materials is first sent into the reaction of state bed by reactor bottom To react in device, while the gas containing CO is injected into reactor again, gas, liquid can be relied on so in reactor Difference in specific gravity variation caused by the yield of light-end products, realizes each phase flow velocity after the different specific weight and complex reaction of each material Otherness control, so that cracking, carbonylation, transformation plus hydrogen, reaction occur from the bottom to top in reactor for raw material, in this process Even if heavy catalyst solid particle rises with gas and light-end products in, but under the gas effect containing CO on top It is again return to participate in reacting again to bottom, the slurry of reactor is entered according to the material density appropriate adjustment in reactor upper, middle and lower portion The gas and its injection rate containing CO in liquid, to realize unconverted low grade oils in the circulation and catalysis of inside reactor The balance of agent is discharged, and thus can ensure that the abundant progress of various reactions, to be conducive to improve conversion ratio and the life of low grade oils Object oil yield
4, low grade oils multi-stage conversion process provided by the invention, during the reaction be the gas containing CO, this contains The gas of CO, can also be impure either pure CO, for example in addition to containing CO, can also contain hydrogen, hydrogen sulfide, methane Deng, it can also be the synthesis gas that coal, biomass, natural gas, low grade oils gasification produce, in synthesis gas other than CO, remainder Divide gas that can substantially reduce for hydrogeneous, carbon dioxide or the mixture of methane, ethane, gas manufacturing cost;What is reacted In the process, with the gas containing CO, and using under cheap ferrum-based catalyst or useless agent effect, cracking reaction, carbonyl are realized Change the process integrations such as reaction, conversion reaction, hydrogenation reaction, is easy to provide sufficient free group, avoids the carbonization of low grade oils Coking, low grade oils conversion ratio and liquid yield are high, and reaction temperature and pressure are reduced;The oil product that the liquefaction process generates It can be used for front and continued technique to prepare slurries.
Specific embodiment
Technical solution of the present invention will be clearly and completely described below, it is clear that described embodiment is this hair Bright a part of the embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not having Every other embodiment obtained under the premise of creative work is made, shall fall within the protection scope of the present invention.
Embodiment 1
A kind of hogwash fat conversion process is present embodiments provided, is included the following steps:
Catalyst:
Catalyst is using FeOOH as the useless agent of the desulfurizing agent of active component, wherein described using FeOOH as active component In desulfurizing agent, soluble ferric iron salt Fe (NO3)3·9H2O is 6g, molysite complexing agent triethanolamine 9g, amorphous FeOOH 15g;
Above-mentioned using FeOOH is the desulfurizing agent of active component for removing H in exhaust gas2The process of S is as follows: by H2S content is 5500mg/cm3Exhaust gas with 3000h-1Air speed be passed through desulfurization section, desulphurization reaction is carried out at 30 DEG C, is gone out in the desulfurization section H in implication2When content≤0.01ppm of S, the waste in the desulfurization section is collected, as in the present embodiment is with FeOOH The useless agent of the desulfurizing agent of active component;
Sulphur is added: using FeOOH as ferro element in the useless agent of the desulfurizing agent of active component and sulphur member in detection the present embodiment The molar ratio of element mixes solid sulfur powder into above-mentioned catalyst if the molar ratio of ferro element and element sulphur is not up to 1: 2 It is 1: 2 to the molar ratio of wherein ferro element and element sulphur, to guarantee that the molar ratio of ferro element and element sulphur is 1 in reaction system :2;
If the molar ratio of ferro element and element sulphur is greater than 1: 2, by solvent extraction or the usual manners such as molten sulphur can be heated, Remove extra sulphur;
The preparation of slurries:
Hogwash fat and above-mentioned catalyst are mixed to get mixture, and is added into mixture and accounts for mixture quality 5% Water, stirring pulping form slurries, and the average grain diameter of the catalyst added is that 5 μm of low grade oils multistages provided by the invention turn Chemical industry skill, catalyst account for the 3% of slurry weight;
Conversion reaction:
By CO and H2Gaseous mixture (CO accounting 60% and H2Accounting is after 40%) being forced into 17MPa, being heated up to 400 DEG C, with It is pressurized to 17MPa, is heated up to 320 DEG C of slurries together out of reactor bottom injection suspended-bed reactor, generation cracking, carbonyl Change, transformation and hydrogenation reaction, the reaction pressure for controlling conversion reaction is 16.5MPa, reaction temperature is 350 DEG C, and the reaction time is The gaseous mixture of 60min, the CO and H2 and the volume ratio of the slurries are 2000: 1, collect converted product;
Secondary conversion reaction:
Pure hydrogen is mixed with converted product, enters after being forced into 16MPa, being heated up to 300 DEG C and adds hydrogen agent equipped with nickel molybdenum In fixed bed reactors, the nickel molybdenum adds hydrogen agent to be made of molecular sieve and the MoO and NiO that load thereon, with the hydrogenation catalyst Total restatement of agent, the load capacity that the load capacity of MoO is 2%, NiO are 6%, and the dosage of the hydrogenation catalyst is converted product The 3wt% of quality;In reactor occur cracking and hydrogenation reaction, control secondary conversion reaction reaction pressure be 15.5MPa, Reaction temperature is 350 DEG C, the volume ratio of reaction time 45min, hydrogen and converted product is 2000: 1, and clear gusoline is made.
Embodiment 2
A kind of wood tar and rancid oily cotransformation technique are present embodiments provided, is included the following steps:
Catalyst:
Catalyst is to contain Fe21.333O32Desulfurizing agent useless agent regrowth, wherein it is described to contain Fe21.333O32It is de- In sulphur agent, magnetic iron oxide red Fe21.333O32For 55g, copper oxide 12g, carrier di-iron trioxide 21g;
Above-mentioned catalyst is as follows to the sweetening process of hydrogen sulfide containing coal pyrolysis gas:
(1) compressed coal pyrolysis gas is cooled to 30~35 DEG C, and it is above-mentioned to be mixed into filling for next air with air pump Mainly using iron oxide as in the desulfurizing tower of the desulfurizing agent of active constituent, using the process of bottom in and top out, to avoid have liquid water into Enter desulfurizing agent bed removing hydrogen sulfide;
(2) above-mentioned desulfurizing agent becomes useless agent after being used for multiple times, and takes out from desulfurizing agent bed, as containing in the application Fe21.333O32Desulfurizing agent useless agent;
It is above-mentioned to contain Fe21.333O32Desulfurizing agent useless agent regeneration method, include the following steps:
1) above-mentioned useless agent is dispersed in water, forms slurries;
2) above-mentioned slurries are heated to 60 DEG C under normal pressure, hydrogen peroxide, flow are then added into slurries using peristaltic pump Control is 500mL/min, and magnetic agitation is to promote reaction to carry out, reaction time 10min;
3) after the reaction was completed, filtering reacting liquid obtained precipitating is washed with water 2 times, natural airing, obtains above-mentioned useless agent Regrowth;
The preparation of slurries:
Wood tar, rancid oil and above-mentioned catalyst are mixed to get mixture, and is added into mixture and accounts for compounding substances The water of amount 0.5%, stirring pulping form slurries, and the average grain diameter of the catalyst added is 300 μm;The concentration of catalyst is 5wt%.
Conversion reaction:
By CO and H2Gaseous mixture (CO accounting 40% and H2Accounting is after 60%) being forced into 12MPa, being heated up to 370 DEG C, with It is pressurized to 12MPa, is heated up to 300 DEG C of slurries together out of reactor bottom injection bubbling bed reactor, generation cracking, carbonyl Change, transformation and hydrogenation reaction, the reaction pressure for controlling conversion reaction is 11.5MPa, reaction temperature is 340 DEG C, and the reaction time is The gaseous mixture of 90min, the CO and H2 and the volume ratio of the slurries are 1000: 1, collect converted product;
Secondary conversion reaction:
Fe-series catalyst is first added into converted product, Fe-series catalyst is amorphous FeOOH, amorphous hydroxyl The dosage of iron oxide is the 0.5wt% of converted product quality;
It will be enriched in the gas (H of hydrogen2Volume accounting is 90%) to mix with level-one conversion reaction product, and pressurize 8.8MPa, Enter after being heated up to 320 DEG C, paste state bed reactor entrance injects in paste state bed reactor, and Hydrocracking reaction, control two occurs The reaction pressure of grade conversion reaction is 8MPa, reaction temperature is 380 DEG C, reaction time 60min, hydrogen rich gas and converted product Volume ratio is 1500: 1, and clear gusoline is made.
Embodiment 3
A kind of tar sand oil conversion process is present embodiments provided, is included the following steps:
Catalyst:
Catalyst is using iron oxide as the useless agent of the desulfurizing agent of active component, wherein described using iron oxide as active component Desulfurizing agent in, calcium bicarbonate 10g, basic copper carbonate 12g, γ-Fe2O318g, MnO2For 8g, NiO 5g;
It is above-mentioned using iron oxide as the sweetening process of the desulfurizing agent of active component, be summarized as follows:
1) tail gas that coalite tar generates after fixed bed hydrogenation is catalyzed in collecting;
2) desulfurizing agent of the present embodiment is made to diameter is 1mm, length is 15mm cylindrical catalyst particle, and is filled in de- In sulphur tower, desulfurization layer is formed;
3) by above-mentioned tail gas with 2000h-1Air speed by desulfurization layer, and occur at 50 DEG C with the desulfurizing agent in desulfurization layer Desulphurization reaction removes hydrogen sulfide in tail gas, and to the end of reacting, the useless agent of the desulfurizing agent after taking out reaction is cooled to room temperature, as In the application using iron oxide as the useless agent of the desulfurizing agent of active component;
Sulphur is added: using iron oxide as ferro element in the useless agent of the desulfurizing agent of active component and sulphur member in detection the present embodiment The molar ratio of element mixes solid sulfur powder into above-mentioned catalyst if the molar ratio of ferro element and element sulphur is not up to 1: 1 It is 1: 1 to the molar ratio of wherein ferro element and element sulphur, to guarantee that the molar ratio of ferro element and element sulphur is 1 in reaction system :1;
If the molar ratio of ferro element and element sulphur is greater than 1: 1, by solvent extraction or the usual manners such as molten sulphur can be heated, Remove extra sulphur;
The preparation of slurries:
Tar sand oil and above-mentioned catalyst are mixed to get mixture, and is added into mixture and accounts for mixture quality 5%d's Water, stirring pulping form slurries, and the average grain diameter of the catalyst added is 10 μm, catalyst concn 2wt%;
Conversion reaction:
By CO and H2Gaseous mixture (CO accounting 30% and H2Accounting is 70%) by paste state bed reactor bottom and side wall In 3 inlet injection paste state bed reactors, and cracking, carbonylation, transformation and plus hydrogen occurs with into the slurries therein Reaction, control reaction pressure is 19MPa, reaction temperature is 460 DEG C, reaction time 90min, the CO and H2Gaseous mixture with The volume ratio of the slurries is 800: 1, collects converted product;
Secondary conversion reaction:
It will be enriched in the gas (H of hydrogen2Accounting is 92%) to mix with conversion reaction product, is forced into 18MPa, is heated up to Enter in fixed bed reactors after 330 DEG C, reactor is provided with hydrogenation catalyst, and the hydrogenation catalyst is by zeolite and loads it On MoO, NiO and CoO composition, with total restatement of the hydrogenation catalyst, the load capacity of MoO is that the load capacity of 2%, NiO is The load capacity of 6%, MoO are 3%, and the dosage of the hydrogenation catalyst is the 2wt% of converted product quality;It is sent out in reactor Raw cracking and hydrogenation reaction, the reaction pressure of control secondary conversion reaction is 18MPa, reaction temperature is 390 DEG C, the reaction time is The volume ratio of 40min, hydrogen and a converted product are 1000: 1, and clear gusoline is made.
Embodiment 4
A kind of coal tar and palm oil conversion process are present embodiments provided, is included the following steps:
Catalyst:
Catalyst is using iron oxide as the regrowth of the useless agent of the desulfurizing agent of active component, wherein described to be with iron oxide In the desulfurizing agent of active component, ferroso-ferric oxide 50g, calcium sulphate dihydrate 12g, basic zinc carbonate 20g and the carboxylic first of cubic system Base sodium cellulosate is 6g;
Above-mentioned catalyst carries out sweetening process to the petroleum containing hydrogen sulfide, and operating procedure is as follows:
(1) diameter is made in the desulfurizing agent of the present embodiment and is the catalyst granules of 1.5mm, and be filled in desulfurizing tower, shape At desulfurization layer;
(2) petroleum containing hydrogen sulfide is sprayed into desulfurization layer from the top of desulfurizing tower by nozzle, carry out elution desulfurization, The useless agent of desulfurizing agent after collecting desulfurization is the useless agent of the desulfurizing agent containing iron oxide in the application;
The regeneration method of the useless agent of the above-mentioned desulfurizing agent containing iron oxide, includes the following steps:
1) above-mentioned useless agent and water are stirred in slurry tank and is configured to slurries, the solid content of the slurries is 12wt%;
2) it is passed through sodium hypochlorite into above-mentioned slurries, and carries out oxidation reaction under 60 DEG C, 1MPa, with oxidation regeneration;
3) Na is added into the slurries after oxidation again2S, and vulcanization reaction is carried out under 10 DEG C, 5MPa;
4) it is passed through hydrogen peroxide into the slurries after vulcanization, and carries out oxidation reaction under 30 DEG C, 1.1MPa, with oxidation Regeneration;
5) step 3) and 4) once, the molar ratio of ferro element and element sulphur in the slurries after making the oxidation reaction are repeated 1:1.8;
6) slurries after the oxidation reaction are separated by solid-liquid separation, obtain the regrowth of above-mentioned useless agent;
Sulphur is added: the molar ratio that solid sulfur powder to wherein ferro element and element sulphur are mixed into above-mentioned regrowth is 1: 2, to guarantee that the molar ratio of ferro element and element sulphur is 1: 2 in reaction system;
The preparation of slurries:
Coal tar, palm oil and above-mentioned catalyst are mixed to get mixture, and is added into mixture and accounts for compounding substances The water of amount 2%, stirring pulping form slurries, and the average grain diameter of the catalyst added is 400 μm, and catalyst concn is 4wt%;
Conversion reaction:
By CO and H2Gaseous mixture (CO accounting 50% and H2Accounting is 50%) and slurries are together by paste state bed reactor side wall On 3 inlets injection paste state bed reactor in, and cracking, carbonylation, transformation and hydrogenation reaction occur wherein, control is anti- Answering pressure is 20MPa, reaction temperature is 430 DEG C, reaction time 30min, the CO and H2Gaseous mixture and the slurries Volume ratio is 650: 1, collects converted product;
Secondary conversion reaction:
The Fe-series catalyst in the present embodiment is first added into converted product, the dosage of Fe-series catalyst is converted product The 1.9wt% of quality;
Again by pure hydrogen pressurize 15.6MPa, be heated up to 320 DEG C after, into fixed bed reactors, and with slurries therein Raw cracking and hydrogenation reaction occurs, the reaction pressure of control secondary conversion reaction is 15MPa, 350 DEG C of reaction temperature, reaction time Volume ratio for 90min, pure hydrogen and converted product is 800: 1, and clear gusoline is made.
Embodiment 5
A kind of viscous crude and used oil conversion process are present embodiments provided, is included the following steps:
Catalyst:
Catalyst is the regrowth of the useless agent of the desulfurizing agent containing FeOOH, wherein with total matter of the desulfurizing agent containing FeOOH Meter, the content of γ-FeOOH is 45% in the desulfurizing agent containing FeOOH, and the content of alpha-feooh is 35%, carrier molecule The content of sieve is 15%, and the content of binder sesbania powder is 5%;
H in above-mentioned catalyst removal exhaust gas2The basic process of S includes the following steps: H2S content is 5500mg/cm3's Exhaust gas is with 3000h-1Air speed be passed through desulfurization section, desulphurization reaction is carried out at 30 DEG C, the H in the desulfurization section is worked off one's feeling vent one's spleen2S's contains When amount≤0.01ppm, collecting the waste in the desulfurization section is the useless agent of desulfurizing agent;
The regeneration method of the useless agent of above-mentioned desulfurizing agent are as follows: after the useless agent of the desulfurizing agent is washed with water, in wet ball mill Useless agent powder is obtained with the particle that water is ground into 80 mesh;The useless agent powder is made into the aqueous suspension that solid masses percentage composition is 8% Liquid is passed through compressed air, reacts inspection by sampling after a period of time, does not generate H when the sample of taking-up is reacted with hydrochloric acid2When S, then give up Iron sulfide in agent is fully converted to FeOOH and elemental sulfur, forms the slurry containing the FeOOH and elemental sulfur Liquid filters the slurries and obtains solid material, uses CC14The solid material obtained after extraction filtering, coextraction merge extraction three times Liquid, the elemental sulfur crystallized simultaneously with the method recycling design of distillation, and extract liquor separates rear remaining solid and binder The regrowth of the useless agent of above-mentioned desulfurizing agent is made in sesbania powder mixing, and wherein the dosage of binder sesbania powder is the solid masses 5%.
Carbon disulfide is added: the molar ratio that carbon disulfide to wherein ferro element and element sulphur are added into above-mentioned catalyst is 1: 2, to guarantee that the molar ratio of ferro element and element sulphur is 1: 2 in reaction system;
The preparation of slurries:
Viscous crude, used oil and above-mentioned catalyst are mixed to get mixture, and is added into mixture and accounts for mixture quality 5% water, stirring pulping form slurries, and the average grain diameter of the catalyst added is 5mm, catalyst concn 2wt%;
Conversion reaction:
By CO and H2Gaseous mixture (CO accounting 20% and H2Accounting be 80%) pressurize 18.4MPa, be heated up to 400 DEG C after, by In 3 inlets injection paste state bed reactor on paste state bed reactor side wall, and split with into the slurries therein Solution, carbonylation, transformation and hydrogenation reaction, control reaction pressure is 18MPa, reaction temperature is 440 DEG C, reaction time 30min, The CO and H2Gaseous mixture and the slurries volume ratio be 800: 1, collect converted product;
Secondary conversion reaction:
The Fe-series catalyst in the present embodiment is first added into converted product, the dosage of Fe-series catalyst is converted product The 1.9wt% of quality;
It will be enriched in the gas (H of hydrogen again2Volume accounting be 92%) pressurize 17MPa, be heated up to 390 DEG C after, be sent into solid In fixed bed reactor, and cracking and hydrogenation reaction, the reaction of control secondary conversion reaction occurs with converted product therein is entered The volume ratio that pressure is 16MPa, reaction temperature is 400 DEG C, reaction time 120min, the gas rich in hydrogen and converted product It is 600: 1, clear gusoline is made.
Test example 1
Distribution to product prepared by the method using the embodiment of the present invention 1-5, the test method of corresponding product are as follows:
(low grade oils combined feed mid-boiling point is greater than oil product in quality-product of 360 DEG C of materials to low grade oils conversion ratio %= Liquid oil gross mass greater than 360 DEG C)/low grade oils combined feed mid-boiling point be greater than 360 DEG C of materials quality;
Low grade oils convert quality/raw material low grade oils of liquid phase oil product under normal temperature and pressure in oil yield %=converted product Combined feed quality;
Reaction generates water rate %=(total matter of the water quality of the reaction product-water that reaction starting is added or raw material is brought into Amount)/raw material combined feed quality.As this value < 0, it is denoted as "None";
Corresponding test result is as shown in table 1:
Product profiles versus after the conversion of 1 low grade oils raw material of table
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or It changes still within the protection scope of the invention.

Claims (17)

1. a kind of low grade oils multi-stage conversion process, which comprises the steps of:
Prepare the aqueous slurry containing catalyst and low grade oils, the catalyst be iron oxide, iron oxide it is de- At least one of the regrowth of the useless agent of sulphur or the useless agent of the desulfurization of iron oxide;
Aqueous slurry and pure CO or the gas mixing containing CO are subjected to level-one conversion reaction, collect converted product, the level-one turns Changing the molar ratio of ferro element and element sulphur in reaction controlling reaction system is 1: being carried out under conditions of (0.5~5), the level-one The reaction pressure of conversion reaction is 5-22MPa, and reaction temperature is 200-480 DEG C;
Converted product and the gas rich in hydrogen are subjected to second level conversion reaction, the reaction pressure of the second level conversion reaction is 5- 22MPa, reaction temperature are 250-450 DEG C, and oil product is made.
2. low grade oils multi-stage conversion process according to claim 1, which is characterized in that be added and contain into the catalyst Sulfur material molar ratio of ferro element and element sulphur into reaction system is 1: (0.5~5), preferably 1: (0.5-2), more preferably 1∶(1-2)。
3. low grade oils multi-stage conversion process according to claim 2, which is characterized in that the sulphur-containing substance be sulphur, At least one of hydrogen sulfide, carbon disulfide.
4. low grade oils multi-stage conversion process according to any one of claim 1-3, which is characterized in that described containing CO's The volume content of CO is not less than 15%, preferably not less than 25% in gas, is most preferably not less than 50%;
The volume content of hydrogen is not less than 80%, preferably not less than 90% in the gas rich in hydrogen, and optimal is pure hydrogen Gas.
5. low grade oils multi-stage conversion process according to claim 4, which is characterized in that the gas containing CO be CO with H2Gaseous mixture or synthesis gas.
6. low grade oils multi-stage conversion process according to any one of claims 1-5, which is characterized in that the iron oxidation The useless agent of desulfurization for closing object is using iron oxide as the useless agent of the desulfurizing agent of active component, with Fe21.333O32For the desulfurizing agent of active component Useless agent, using FeOOH as at least one of useless agent of the desulfurizing agent of active component;Or,
The regrowth of the useless agent of the desulfurization of the iron oxide is using iron oxide as the regeneration of the useless agent of the desulfurizing agent of active component Object, with Fe21.333O32For the regrowth of the useless agent of the desulfurizing agent of active component, using FeOOH as the useless agent of the desulfurizing agent of active component At least one of regrowth.
7. low grade oils multi-stage conversion process according to claim 6, which is characterized in that the iron oxide is three oxidations two Iron and/or ferroso-ferric oxide.
8. low grade oils multi-stage conversion process according to claim 7, which is characterized in that the di-iron trioxide is α- Fe2O3、α-Fe2O3.H2O、γ-Fe2O3、γ-Fe2O3.H2O, amorphous Fe2O3, amorphous Fe2O3.H2At least one of O;
The ferroso-ferric oxide is the ferroso-ferric oxide of cubic system;
The FeOOH be alpha-feooh, β-FeOOH, γ-FeOOH, δ-FeOOH, θ-FeOOH and amorphous FeOOH at least It is a kind of.
9. low grade oils multi-stage conversion process according to claim 1 to 8, which is characterized in that the iron oxidation The regrowth for closing the useless agent of desulfurization of object is after being aoxidized, vulcanized and aoxidized by the useless agent of desulfurization of the slurry method to iron oxide Obtained regrowth.
10. low grade oils multi-stage conversion process according to claim 9, which is characterized in that the iron oxide takes off The regeneration method of the useless agent of sulphur, includes the following steps:
The useless agent of the desulfurization of the iron oxide is mixed with water or aqueous slkali, is configured to slurries;
Oxidant is added into the slurries, and once oxidation reaction occurs;
Vulcanizing agent is added into the slurries after the oxidation reaction, and vulcanization reaction occurs;
Oxidant is added into the slurries after the vulcanization reaction, and secondary oxidation reaction occurs;
Circulation carries out the vulcanization reaction and secondary oxidation reaction;
Slurries after secondary oxidation reaction are separated by solid-liquid separation, the regeneration of the useless agent of desulfurization of the iron oxide is obtained Object.
11. low grade oils multi-stage conversion process according to claim 1 to 10, the level-one conversion reaction are It is carried out in paste state bed reactor, bubbling bed reactor or suspended-bed reactor;
The second level conversion reaction is in paste state bed reactor, bubbling bed reactor, suspended-bed reactor or fixed bed reactors Middle progress is hydrocracked and refining reaction under the atmosphere rich in hydrogen.
12. low grade oils multi-stage conversion process described in any one of -11 according to claim 1, which is characterized in that the level-one The reaction time of conversion reaction is not less than 15min, preferably 15-120min, more preferably 30~90min;
The reaction time of the secondary conversion reaction is not less than 15min, preferably 15-180min, more preferably 15~90min.
13. low grade oils multi-stage conversion process described in any one of -12 according to claim 1, which is characterized in that the slurries In, the content of the catalyst is 0.1~10wt%;
The average grain diameter of the catalyst is 0.1 μm of -5mm, preferably 5 μm -100 μm, most preferably 5-50 μm.
14. low grade oils multi-stage conversion process according to claim 1 to 13, which is characterized in that contain by described in Gas mixing of the aqueous slurry with pure CO or containing CO carries out level-one conversion reaction, includes the following steps: by pure CO or containing the gas of CO After being forced into 5-22MPa, being heated up to 150-600 DEG C, be passed through in reaction system, and with enter reaction system in the aqueous slurry Conversion reaction occurs for material.
15. low grade oils multi-stage conversion process described in any one of -14 according to claim 1, which is characterized in that contain by described in Gas mixing of the aqueous slurry with pure CO or containing CO carries out level-one conversion reaction, includes the following steps: by the pure CO in part or containing CO's Gas pressurized to 5-22MPa, be heated up to 150-600 DEG C after, be passed through in the aqueous slurry, and enter with the aqueous slurry anti- It answers and conversion reaction occurs in system;
It after rest part is forced into 5-22MPa, is heated up to 300-600 DEG C, is passed through in reaction system, and therein described with entering Conversion reaction occurs for aqueous slurry.
16. low grade oils multi-stage conversion process described in any one of -15 according to claim 1, which is characterized in that the pure CO Or the volume ratio of the gas containing CO and the aqueous slurry is (200-10000): 1, preferably (1000-5000): 1;
The volume ratio of the gas and converted product rich in hydrogen is 200~5000: 1, preferably 300~3000: 1.
17. low grade oils multi-stage conversion process described in any one of -16 according to claim 1, which is characterized in that carrying out institute Before stating second level conversion reaction, further include the steps that adding hydrogenation catalyst and/or the catalyst into the converted product.
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MYPI2019007207A MY192483A (en) 2018-04-28 2018-12-21 Conversion process for an inferior oil
EP18916095.5A EP3608388B1 (en) 2018-04-28 2018-12-21 Substandard oil product conversion process
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