CN105602612B - Method for hydrofinishing biological crude oil by using high temperature gas cooled reactor - Google Patents
Method for hydrofinishing biological crude oil by using high temperature gas cooled reactor Download PDFInfo
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Abstract
The invention discloses a waterproof and heatproof hydrogenation catalyst. The catalyst is a meso-porous molecular sieve SBA-15 doped with active metal and grafted with an organic functional group, wherein the doped active metal is one or more of Pt, Pd, Zr, Ru, Ni, Co and Mo, and the grafted organic functional group is one or more of an amino group, a carboxyl group and a sulfonyl group. The invention also discloses a method for hydrofinishing biological crude oil by using a high temperature gas cooled reactor. The method comprises the following steps: heating second helium flow with high temperature helium from the core of the high temperature gas cooled reactor, driving a thermochemical circulating hydrogen production process by the second helium flow, preheating and gasifying total components of the oil phase and the water phase of biological crude oil by the second helium flow to form biological crude oil steam, and hydrofinishing the biological crude oil steam and prepared hydrogen under the action of the catalyst to obtain biofuel oil and a non-condensable fuel gas.
Description
Technical field
The present invention relates to the use of high temperature gas-cooled nuclear reactor (organic in including oil phase and water phase to bio-crude oil full constituent
Component) hydrorefined method is carried out, belong to using nuclear energy field and recyclable organism mass-energy field.
Background technology
The energy and environment are the two principal themes of human development, and current fossil energy reserves are limited, peter out, fossil energy
Using bringing serious environmental pollution, therefore Renewable Energy Development to contribute to reducing the dependence to fossil resource again, with weight
Want meaning.China Transportation Industry energy consumption is huge, and rises year by year, more than the 20% of social whole total energy consumption is accounted at present, in recent years
It is expected to same developed country and equally reaches 1/3.Because compared with fuel engines, electric automobile can not provide various road conditions and exercise institute
The very strong driving force for needing, therefore the traffic energy consumption overwhelming majority (more than 95%) relies on liquid fuel so that the demand of liquid fuel
Very huge, it is contemplated that to the year two thousand fifty, the demand of China's liquid fuel is about 4～500,000,000 tons.Domestic petroleum yield is difficult to meet and wants
Ask, breach more than half needs from other approach to supplement, therefore it is very urgent to develop reproducible liquid fuel.Biomass are
The regenerative resource of liquid fuel can be uniquely produced, therefore the technology that exploitation prepares liquid fuel by biomass energy very must
Will.
It is that biomass are most important, maximally effective utilization that biomass are converted into bio-crude oil by thermochemical methods such as thermal crackings
One of mode, bio-crude oil also needs to further hydrofinishing and can just be converted into the transportation power fuel of high-quality.Subtractive process
A large amount of heat energy and hydrogen are consumed, this is one of Main Bottleneck of restriction bio-crude oil utilization and extention.
Nuclear energy is the primary energy of cleaning, and current nuclear energy uses form is mainly based on generating, it is impossible to directly obtain liquid
Fuel, it is difficult to into traffic energy consumption field.
The heat produced using high-temperature gas-cooled reactor, can be made on a large scale by the thermochemical cycles such as iodine-sulfur process process
Cheap hydrogen is obtained, the process heat of high temperature nuclear reactor and obtained hydrogen is used for into the hydrofinishing of bio-crude oil, from energy reformulationses
From the perspective of, nuclear energy is injected into the production process of liquid fuel in the way of core hydrogen and nuclear heat, and nuclear energy is realized in an indirect way
Utilization in traffic and transport field.
Compared with other prior arts, Estimation of Nuclear Hydrogen Production is with the beneficial effect of bio-crude oil integrated technique：
(1) gasification hydrofinishing is carried out to bio-crude oil using the nuclear heat and obtained core hydrogen of HTGR, in biology
While fuel economy cost is significantly reduced, the CO2 emissions in bio-crude oil subtractive process are also significantly reduced.
(2) hot, electric, the hydrogen alliance of high temperature nuclear reactor, improves the utilization ratio of high temperature nuclear reactor, extends the than an electrical utility neck of nuclear energy
Domain.Additionally, nuclear energy is injected into into the production process of liquid fuel in the form of nuclear heat and core hydrogen so that nuclear energy enters into friendship indirectly
The big market of logical transport field.
Simple computation related data is as follows：The annual available different kind organism matter raw material total amount of China is about 1,000,000,000 tons, profit
20% is pressed with rate, it is contemplated that substitute therein 1/4 with the new method of the present invention, then it is 25,000,000 tons that bio-crude oil is obtained, when refining
Hydrogen-consuming volume is calculated by 8%, then total hydrogen-consuming volume is 2,000,000 tons；High temperature nuclear reactor module is calculated by 250MWt, and the heating demand factor takes 85%,
Calorific value needed for 25000000 tons of bio oil hydrofinishings is 144.18 ten thousand tons of standard coals, needs 6.3 high temperature nuclear reactor modules, carbon dioxide
Reduce discharging 3,840,000 tons；Nuclear energy accounts for 26% in the bio oil being refining to obtain.
Now simply Estimation of Nuclear Hydrogen Production is described below with bio-crude oil Hydrofining Technology：
1. it is biological to crack hydrogenation crude purification techniques
Biomass are the regenerative resources that can be uniquely converted into liquid fuel, its with yield it is huge, renewable and
The advantages of neutral carbon, has caused the extensive concern in the whole world.
It is that biomass economy is most heavy that low-density solid biomass raw material is converted into into the higher liquid fuel of energy density
One of content wanted, biomass thermal chemical transformation is one of main method by biomass material production liquid fuel, is had
Good economy, it is not necessary to which government subsidy achieves that profit, and suitable for large-scale production.In optimum reaction condition
Under, typically in 50-70%, the calorific value of bio oil is 16-20MJ/kg, about diesel oil calorific value to the yield of biomass pyrolytic bio oil
2/5.
The annual available different kind organism matter raw material total amount of China is not less than 1,000,000,000 tons, if wherein 20% is used to pyrolysis
Preparing bio-oil, then can obtain more than 100,000,000 tons of bio oil for 1 year, can be thus every year the original that country reduces 40,000,000 tons by equivalent
Oil inlet.In addition compared with using fossil fuel, often CO can be reduced using 1 ton of bio oil2Discharge 800kg, environmental benefit also ten
Divide notable.
Biomass thermal chemical conversion gained product liquid is referred to as bio oil or bio-crude oil (bio-oil or bio-crude)
Or biomass cracking crude oil, with oxygen content it is high, calorific value is low, stability is poor and with deficiencies such as corrosivity, it is necessary to it is carried out
Refinement treatment, reduces oxygen content and adjusts the ratio of C, H, so as to improve combustion heat value, obtains the fuel used to generate power of fine quality
Oil.
The refined of biomass cracking crude oil is current international research and development focus, and the catalysis of wherein biomass cracking crude oil adds
The refined corresponding technique and technology that can use for reference petrochemical field of hydrogen, is also capable of achieving bio-crude oil and mixes refining altogether with petrochemical industry crude oil,
Therefore there is good industrial prospect.The catalytic hydrogenation of biomass cracking crude oil is in pressure 7-20MPa, temperature 250-400
At DEG C, under conditions of hydrogen or hydrogen supply dissolvent, hydrotreating is carried out to biomass cracking crude oil, the oxygen element in biomass with
The form removing of water.
Bio oil Hydrobon there is also obvious deficiency, and main is that hydrogenation process can consume substantial amounts of hydrogen, into
This is higher.The complete deoxidation of per kilogram bio oil need to consume 600-1000L hydrogen (equivalent to the 6-9% of biological oil quality, with
Coal liquefaction is similar), wherein in consumed hydrogen about 50% be for deoxygenation, other hydrogen play a part of in oil improve H/C.But
Due to H2Itself it is the higher fuel containing energy of price, the catalytic hydrogenation process of biomass cracking crude oil is difficult to extensively development.
2. Estimation of Nuclear Hydrogen Production technology
From from the perspective of nuclear energy uses efficiency, current nuclear energy uses form mainly based on generating, and in world's terminal
In energy consumption structure, electric power proportion is not high, and the proportion shared by China in 2009 is 18.5%, and mass energy is with non-electrical
Form is consumed.Have that temperature is high, security is good due to high temperature nuclear reactor, can modularization the features such as flexibly arrange, thus become optimum
One of heap-type in the non-electrical domain application such as process heat, wherein generating electricity, process heat application and hydrogen manufacturing will be that HTGR is most heavy
The three big applications wanted.
Although the hydrofinishing of the thermochemical study of biomass and subsequent bio matter cracking crude oil has obviously excellent
Gesture, product yield high, gained fuel oil quality better, but weak point are to need to consume substantial amounts of energy and hydrogen, high cost.Hydrogen
Chemical property it is active, exist without pure hydrogen in nature, need to be obtained by other primary energy productions.Nuclear energy is cleaning
Primary energy, Estimation of Nuclear Hydrogen Production is exactly the energy of the heat that produced by the use of nuclear reactor as hydrogen manufacturing, by selecting suitable technique, energy
Enough realize efficient, the extensive preparation of hydrogen；The discharge of greenhouse gases is decreased or even eliminated simultaneously.
Thermochemical water decomposition cyle for hydrogen production is one of most promising method, compared with Direct Resolution water hydrogen manufacturing, heat chemistry
Circulation hydrogen manufacturing can both reduce reaction temperature, and hydrogen-oxygen separation problem can be avoided again.Thermochemical cycle for hydrogen production has various ways, its
In iodo- sulphur thermochemical cycles be considered as one of most promising flow process.The step of flow process the 1st be high temperature (800～950 DEG C),
By H under low pressure2SO4It is decomposed into H2O、SO2And O2, and by O2Separate；2nd step is iodo- sulphur process, i.e. I at a lower temperature2
With SO2And H2O (steam) reacts, and generates HI and H2SO4(exothermic reaction), under moderate temperature (200～500 DEG C), HI is decomposed into
H2And I2。
In the various reactor heap-type of current research, the HTGR with helium as cooling agent, its highest outlet temperature
Degree can reach 950-1000 DEG C, the maximum temperature needed for iodo- sulphur thermochemical cycles process can well be met, so as to drive
Hydrogen manufacturing system, overall hydrogen production efficiency is up to more than 50%.Therefore, HTGR is considered as always the heap for being best suitable for hydrogen manufacturing
Type.
3. core-hydrogen-biomass
Biomass material has dispersiveness, and nuclear reactor has high concentration, and both Regional Distribution height are not
Match somebody with somebody, the core hydrogen that in addition nuclear reactor is produced there is also storage and the difficult and inconvenience transported.In order to adapt to such case, biomass
Thermochemical study method can adopt dispersion liquefaction, concentrate the refined mode of production, according to the characteristics of biomass material high degree of dispersion,
Thermochemical study point is set up nearby, and sets up refinery on high temperature nuclear reactor side, in scattered liquefaction plant by biomass material nearby
Highdensity liquid biological crude oil is converted into, then these bio-crude oils are transported the refinery concentrated to reactor side and be hydrogenated with
It is refined.
The refined of bio-crude oil is a process for consuming hydrogen and heat dissipation, and HTGR can just provide energy and system
Energy needed for hydrogen, by high temperature nuclear reactor the unifining process of bio-crude oil is used for, and can well realize its hydrogen manufacturing and process heat
The advantage for utilizing, which forms the concept of " core-hydrogen-biomass ".
Compared with nuclear reactor is had at present, high temperature nuclear reactor has more preferable inherent safety, is to set up biological in its vicinity
Crude oil refinery provides strong guarantee.This addresses the problem biomass material high degree of dispersion and nuclear reactor high concentration
Regional Distribution contradiction.In addition to biomass thermal chemical conversion, other biological matter Land use systems are difficult to solve this Regional Distribution not
Matching, therefore biomass thermal chemical conversion and HTGR are the excellent combinations of " core-hydrogen-biomass " concept.
" core-hydrogen-biomass process " has very big facilitation to nuclear energy and biomass energy：(1) to the promotion of nuclear energy：
Hydrogen, heat, CCHP, nuclear reactor totality utilization ratio increases, and greatly expands application of the high temperature nuclear reactor in non-electrical domain；Make nuclear energy
Communications and transportation energy resource system is injected in the form of nuclear heat and core hydrogen；(2) to the promotion of biomass energy：Significantly improve biomass
Energy transformation efficiency, the economy market competitiveness of liquid biofuel is significantly increased.
4. bio-crude oil oil phase and water phase hydrogen addition technology
The biomass cracking crude oil obtained after biomass cracking is mainly by oil phase and the phase composition of water phase two, wherein water phase volume
10-30% is accounted for, other are oil phase, water-oil phase Jing is often coexisted with emulsion mixed form, could be caused by extra addition water
Water-oil phase split-phase.
Contained about 10～20% organic carbon and hydrogen (equivalent 15～25% initial feed energy) is all in biomass material
In being transformed into water phase, therefore the high-efficiency resource recycling of water phase is non-negligible.Water phase organic component is mainly acetic acid and propionic acid etc.
Small carboxylic acid molecules' (including with levulic acid etc., wherein based on acetic acid), these carboxylic acids account for the 50% of water phase organic matters total amount with
On；Additionally, the also chaff aldehyde material such as furfural, 5 hydroxymethyl furfural.
These water phase small molecules can be converted into corresponding small molecule hydro carbons after hydrogenation reaction, finally exist in gaseous form.
It can also happen that ketonization reaction generates ketone, these ketones are further under the catalysis of basic group for these small carboxylic acid molecules
There is aldol reaction with chaff aldehyde material and obtain macromolecular hydrophobic organic compound, can further be hydrogenated with water natural separation
After become liquid fuel.In a word, fuel gas can have both been become after bio-oil phase small molecule hydrogenation, also can further be condensed into
Oil phase macromolecular, improves the yield of liquid fuel.
If jointly vaporization is hydrogenated with for oil phase and water phase full constituent after biomass cracking, just the hydrothermal stability of catalyst is carried
Very high requirement is gone out.Molecular sieve is the conventional catalyst of hydrogenation or catalyst carrier, it is contemplated that had in bio oil many long
Chain macromolecular, the microporous molecular mesh size commonly used in petrochemical processing is too little, it is difficult to utilize, and the mesopore molecular sieve such as SBA-15 can be with
Hydrogenation reaction for macromolecular provides suitable reaction compartment.But these mesopore molecular sieve heat endurances are very poor, usually not more than
200 DEG C are crossed, has stability in the presence of moisture worse, and the common temperature of biomass cracking crude oil Hydrobon is in 300-
400 DEG C, therefore, preparation can simultaneously tolerate high temperature and the meso-porous molecular sieve material of tolerance high moisture content is particularly significant.
The content of the invention
It is an object of the invention to provide a kind of profit two-phase of utilization high temperature gas-cooled nuclear reactor to biomass cracking crude oil
Full component carries out hydrorefined method simultaneously, and the method provides hydrofinishing with high temperature gas-cooled nuclear reactor and its hydrogen generating system
Required hydrogen and heat, hydrofinishing is carried out to biological crude water phase and oil phase full constituent simultaneously.
One aspect of the present invention provides one kind and has a water resisting property and resistant to elevated temperatures hydrogenation catalyst, and catalyst is doping activity gold
The mesoporous molecular sieve SBA-15 of category and grafting organo-functional group (can be represented, wherein M represents active metal, X with M-SBA-15-X
Represent organo-functional group)；The active metal that wherein adulterates is one or more in Pt, Pd, Zr, Ru, Ni, Co, Mo, and grafting has
Machine functional group is one or more in amino, carboxyl and sulfonic group.
The method of catalyst doping active metal is comprised the following steps：A certain amount of slaine ultrasonic vibration dissolving is weighed respectively
In absolute ethyl alcohol：Acetic anhydride：The volume ratio of concentrated hydrochloric acid is 60:5:In 2 mixed solutions prepared, a certain amount of preparing is added
SBA-15, alternately after 0.5h, mixture is uniformly transferred to surface plate, in 30 DEG C of evaporation solvents to glue for ultrasonic vibration and stirring
Shape, the aging 24h at 65 DEG C, the product for obtaining is warming up to 550 DEG C in Muffle furnace with 2 DEG C/min, after calcining 5h at 550 DEG C
Gained pressed powder is the mesoporous molecular sieve SBA-15 of doping active metal.
Slaine is the one kind in platinum nitrate, palladium nitrate, zirconium nitrate, ruthenium trichloride, nickel nitrate, cobalt nitrate and nitric acid molybdenum
Or several mixtures, the amount of slaine is ethanol：Mol ratio=1600 of metal：1～320:1；The SBA-15 amounts are second
Alcohol：Mol ratio=32 of the Si in SBA-15:1～320:1.
The method of grafting organo-functional group is comprised the following steps：The SBA-15 of a certain amount of doping active metal is taken, is added
To in absolute ethyl alcohol or hydrochloric acid solution, ultrasonic disperse is subsequently adding a certain amount of modifying agent to suspending completely, at 120 DEG C next time
Stream 24h, cooled and filtered, and with absolute ethanol washing 3～5 times, after oxidized or acidifying, it is filtrated to get white solid, room temperature
The mesoporous molecular sieve SBA-15 of as doping active metal and grafting organo-functional group (can use M-SBA-15-X tables after drying
Show).
The modifying agent of addition is aminopropyl trimethoxysilane, mercapto phenylpropyl trimethoxy silane, nitrile propyl group trimethoxy
One or more of base silane, the amount that modifying agent is added is in hetero atom N or S and mesoporous molecular sieve SBA-15 in modifying agent
The mol ratio of Si is 0.02～0.10.
Present invention design is prepared for the Multifunctional nursing pore zeolite catalyst of novel fire resistant hydro-thermal, improves the catalyst
Resistance to water and heat resistance so as to suitable for being hydrogenated with to oil phase after biomass cracking and water phase full constituent.Wherein introducing has
On the one hand machine functional group is closed the hydroxyl on mesopore molecular sieve surface by silanization method, so as to further improve gained molecular sieve
Hydrothermal stability, the harsh conditions needed for adapt to catalytic reforming bio oil, on the other hand introducing organo-functional group can be
Acid or basic functionality is introduced on catalyst, and gives other catalysis activities, for example：Acidic functionality is for dehydration and decarboxylation
There is higher catalysis activity Deng reaction, and basic functionality has higher catalysis activity for the reaction such as condensation.
Another aspect of the present invention provides a kind of profit two-phase of utilization high temperature gas-cooled nuclear reactor to biomass cracking crude oil
Full component carries out hydrorefined method simultaneously, and the method includes three relatively independent flow processs：
(1) high-temperature heat supply flow process：First strand of helium Jing high temperature gas-cooled nuclear reactor reactor core is set to be heated to 800-1000 DEG C, Jing
First heat exchanger is crossed, is exchanged heat with second strand of helium, be recycled back into high temperature gas-cooled core after first burst of helium cooling anti-
Heap reactor core is answered to heat；
(2) Hydrogen making technological process, from second strand of helium of 800-950 DEG C out of the hot device of the first heat exchange, through hydrogen production reaction
Device, drives thermochemical cycle for hydrogen production process, decomposition water to obtain hydrogen and oxygen, and second strand of helium is reduced to 400-500 DEG C
Middle temperature, referred to as middle temperature helium；The thermochemical cycle for hydrogen production process in Hydrogen making technological process is iodo- sulfur cycle process.
(3) biomass cracking hydrogenation crude rectification flow, the full component of biomass cracking crude oil profit two-phase initially enters
Two heat exchangers, with middle temperature helium heat exchange is carried out, and is converted into 300-400 DEG C of biomass cracking crude oil steam, then with hydrogen manufacturing
Hydrogenation fixed bed reactors are entered after flow process gained hydrogen mixing, at mesoporous point of adulterate active metal and grafting organo-functional group
The refined biological oil vapour being converted in the presence of son sieve SBA-15 catalyst based on hydrocarbon component, through condensation and gas-liquid point
Liquid fuel and flammable fixed gas are obtained after.
It is the height that temperature is 800-950 DEG C from first heat exchanger second strand of helium out in high-temperature heat supply flow process
Warm helium, the high temperature helium initially enters Hydrogen making technological process, becomes middle temperature helium after being cooled to 400-500 DEG C, middle temperature helium Jing again
After the second heat exchanger heat exchange, being cooled to 200-300 DEG C becomes low-temperature helium, and the low-temperature helium enters first heat exchanger
Carry out heat exchange with first strand of helium of 800-1000 DEG C from high temperature gas-cooled nuclear reactor reactor core out again；In whole flow process
In, the heat of second strand of helium is utilized in cascading fashion.
The oil phase included in the profit two-phase of biomass cracking crude oil and water are not mutually separated, directly to profit two-phase full constituent
It is hydrogenated with after vaporization.
Hydrogenation temperature scope is 200～400 DEG C, preferably 250～350 DEG C；Pressure be 2～20Mpa, preferably 5～
15MPa；Bio-crude oil full constituent:Hydrogen (mass ratio) is 100:5～100:10, preferably 100:7～100:9.
Advantages of the present invention is as follows：
1) catalyst of the invention was not only water-fast but also heat-resisting, was suitable for the full component of profit two-phase to biomass cracking crude oil same
Shi Jinhang hydrofinishings, and first biomass cracking crude oil need not be carried out into water-oil separating.This is equivalent in whole hydrogenation technique mistake
Water-oil separating step at least one times is saved in journey.According to the biomass cracking hydrogenation crude technique before the present invention, because catalysis
Agent is neither water-fast also non-refractory, therefore need first to carry out water-oil separating to biomass cracking crude oil, then only oil phase is carried out plus
Hydrogen, and because also wanting deoxidation to produce substantial amounts of water in hydrogenation process, therefore second oil water separation process is needed after hydrogenation, could obtain
To biomass fuel.And the present invention then without the need for hydrogenation before water-oil separating step, can directly to biomass cracking crude oil
The full component of profit two-phase carries out hydrofinishing simultaneously, simplifies technological process, has saved equipment investment.
2) because simultaneously hydrofinishing can be carried out to the full component of profit two-phase of biomass cracking crude oil, therefore can be to water
Organic matter in phase is hydrogenated with, and improves the utilization rate of organic matter, increased the yield of biomass fuel, decreases water phase
Subsequent treatment expense.
3) the unique utilization high temperature gas-cooled nuclear reactor of the present invention is same to the full component of profit two-phase of biomass cracking crude oil
The hydrorefined methods of Shi Jinhang, to the heat from high temperature gas-cooled nuclear reactor cascade utilization is carried out, and improves overall energy
Source utilization ratio.
Description of the drawings
Fig. 1 is the catalyst composition and structural representation of the present invention.
Fig. 2 carries out bio-crude oil profit two-phase full constituent hydrofinishing side simultaneously for the present invention using high-temperature gas-cooled reactor
The process flow diagram of method.
Reference implication is as follows：
1st, high temperature gas-cooled nuclear reactor reactor core；2nd, hot gas mixing chamber；3rd, helium circulator；4th, first heat exchanger；5th, I-S circulations
Hydrogen-manufacturing reactor；6th, gas mixer；7th, second heat exchanger；8th, catalytic hydrogenation reaction device；9th, beds；10th, gas-liquid
Separator；
Specific embodiment
A kind of utilization high temperature gas-cooled nuclear reactor proposed by the present invention enters simultaneously to the profit two-phase full constituent of bio-crude oil
The hydrorefined method of row, describes in detail in conjunction with the accompanying drawings and embodiments as follows.
Technical process is summarized as follows：
First strand of helium is high into HTGR reactor core 1, and Jing after the heating of high temperature nuclear reactor reactor core after the pressurization of helium circulator 3
After warm helium is well mixed in hot gas mixing chamber 2, temperature is 800-1000 DEG C, and through high temperature helium-helium heat exchanger, (the first heat is handed over
Parallel operation) 4, after cooling again helium circulator 3 pressurization after use into HTGR reactor core heat cycles；
From the hot device 4 of heat exchange, out rear temperature is 800-950 DEG C of high temperature helium to another strand of helium, through hydrogen-manufacturing reactor 5,
Thermochemical cycles reaction, decomposition water is driven to obtain hydrogen and oxygen, helium is reduced to 400-500 DEG C of middle temperature；Middle temperature helium enters
Enter heat exchanger (second heat exchanger) 7, carry out after heat exchange, being changed into the low of temperature 200-300 DEG C with the bio-crude oil for entering
Warm helium.Bio-crude oil steam is sufficiently mixed with the hydrogen obtained by Hydrogen making technological process in gas mixer 6, because gas is mixed
The insulation of clutch and catalytic hydrogenation fixed bed reactors, so bio-crude oil steam and hydrogen can keep higher temperature to guarantee
Hydrogenation reaction can occur.In catalytic bed 9 of the mixed gas including the organic component in oil phase and gas phase in hydrogenation reactor 8
Doping active metal and the mesoporous molecular sieve SBA-15 catalyst action of grafting organo-functional group under there is hydrogenation reaction, convert
It is the refined biological oil vapour based on hydrocarbon component, liquid fuel is obtained after condensation and gas-liquid separation and flammable is not coagulated
Gas.The complete hydrogen of reacted biological oil vapour and unreacted enters gas-liquid separator 10.In gas-liquid separator 10, gaseous mixture
It is divided into several phases after body condensation：Gas is mainly the complete hydrogen of small molecule hydro carbons and unreacted, can use as gaseous fuel, oil phase
It is the key targets of the present invention, also water phase for liquid hydrocarbon fuel.Water phase in Relative biological crude oil, it is condensed
Content of organics in water phase is considerably less.
In mass ratio oil phase is 75% in embodiment 1, biomass cracking crude oil, and water is mutually 25%, and oil phase oxygen content is
30%, calorific value is 22MJ/kg.(both mass ratioes are 100 to biological oil vapour with hydrogen:7) fix into catalytic hydrogenation after mixing
In bed reactor 8, hydrogenation reaction temperature is 350 DEG C, and Hydrogen Vapor Pressure is 15MPa.Catalyst is that Pt adulterates and addition amino is organic
The mesoporous molecular sieve SBA-15 of functional group.Hydrogenation reaction terminates and gained oil phase accounts for 80% after condensation separation, and oil phase oxygen content is
2.5%, calorific value is 39MJ/kg, and gas phase accounts for 3%, and other are water phase.
In mass ratio oil phase is 75% in embodiment 2, bio-crude oil, and water is mutually 25%, and oil phase oxygen content is 30%, calorific value
For 22MJ/kg.(both mass ratioes are 100 to biological oil vapour with hydrogen:6) catalytic hydrogenation fixed bed reactors 8 are entered after mixing
In, hydrogenation reaction temperature is 280 DEG C, and Hydrogen Vapor Pressure is 4MPa.Catalyst is that Pd-Co adulterates and while grafting amino, carboxyl have
The mesoporous molecular sieve SBA-15 of machine functional group.Hydrogenation reaction terminates and gained oil phase accounts for 80% after condensation separation, oil phase oxygen content
For 0.5%, calorific value is 41.2MJ/kg, and gas phase accounts for 4%, and other are water phase.
In mass ratio oil phase is 75% in embodiment 3, bio-crude oil, and water is mutually 25%, and oil phase oxygen content is 30%, calorific value
For 22MJ/kg.(both mass ratioes are 100 to biological oil vapour with hydrogen:9) catalytic hydrogenation fixed bed reactors 8 are entered after mixing
In, hydrogenation reaction temperature is 320 DEG C, and Hydrogen Vapor Pressure is 10MPa.Catalyst is Pt-Ni doping and while grafting amino, sulfonic acid
The mesoporous molecular sieve SBA-15 of base organo-functional group.Hydrogenation reaction terminates and gained oil phase accounts for 80% after condensation separation, oil phase oxygen
Content is 1.5%, and calorific value is 40MJ/kg, and gas phase accounts for 5%, and other are water phase.
In mass ratio oil phase is 75% in embodiment 4, bio-crude oil, and water is mutually 25%, and oil phase oxygen content is 30%, calorific value
For 22MJ/kg.(both mass ratioes are 100 to biological oil vapour with hydrogen:6) catalytic hydrogenation fixed bed reactors 8 are entered after mixing
In, hydrogenation reaction temperature is 300 DEG C, and Hydrogen Vapor Pressure is 12MPa.Catalyst is Mo doping and grafting sulfonic group organo-functional group
Mesoporous molecular sieve SBA-15.Hydrogenation reaction terminates and gained oil phase accounts for 79% after condensation separation, and oil phase oxygen content is 3.5%,
Calorific value is 37.5MJ/kg, and gas phase accounts for 2%, and other are water phase.
Claims (9)
1. a kind of to have a water resisting property and heat-resisting hydrogenation catalyst, the catalyst is doping active metal and grafting organic functional
The mesoporous molecular sieve SBA-15 of group；The active metal that wherein adulterates is one or more in Pt, Pd, Zr, Ru, Ni, Co, Mo, is transferred
The organo-functional group for connecing is one or more in amino, carboxyl and sulfonic group；It is characterized in that the catalyst doping activity
The method of metal is comprised the following steps：Weigh slaine ultrasonic vibration and be dissolved in absolute ethyl alcohol:Acetic anhydride:The volume of concentrated hydrochloric acid
Than for 60:5:In 2 mixed solution, SBA-15 is subsequently adding, ultrasonic vibration and stirring replace after 0.5h, and mixture is uniformly shifted
To surface plate, in 30 DEG C of evaporation solvents to glue, the then aging 24h at 65 DEG C, the product for obtaining in Muffle furnace with 2 DEG C/
Min is warming up to 550 DEG C, and gained pressed powder is the SBA-15 of doping active metal after calcining 5h at 550 DEG C.
2. catalyst according to claim 1, it is characterised in that described slaine be platinum nitrate, palladium nitrate, zirconium nitrate,
The mixture of one or more in ruthenium trichloride, nickel nitrate, cobalt nitrate and nitric acid molybdenum, the amount of described slaine is ethanol:
Mol ratio=1600 of metal:1～320:1；The SBA-15 amounts are mol ratio=32 of ethanol and the Si in SBA-15:1～
320:1。
3. catalyst according to claim 1, it is characterised in that the method for grafting organo-functional group is comprised the following steps：Take
The SBA-15 of doping active metal, in being added to absolute ethyl alcohol or hydrochloric acid solution, ultrasonic disperse is subsequently adding and changes to suspending completely
Property reagent, flow back 24h at 120 DEG C, cooled and filtered, and with absolute ethanol washing 3-5 time, after oxidized or acidifying, filters
White solid is obtained, the mesoporous molecular sieve SBA-15 of as adulterate after drying at room temperature active metal and grafting organo-functional group.
4. catalyst according to claim 3, it is characterised in that described modifying agent be aminopropyl trimethoxysilane,
One or more in mercapto phenylpropyl trimethoxy silane, nitrile propyl trimethoxy silicane, the amount that modifying agent is added is modified
The mol ratio of the Si in hetero atom N or S and mesoporous molecular sieve SBA-15 in reagent is 0.02～0.10.
5. one kind carries out hydrorefined method using HTGR to bio-crude oil, it is characterised in that the method includes three
Relatively independent flow process：
(1) high-temperature heat supply flow process：First strand of helium Jing high temperature gas-cooled nuclear reactor reactor core is set to be heated to 800-1000 DEG C, Jing Guo
One heat exchanger, is exchanged heat with second strand of helium, and after first burst of helium cooling high temperature gas-cooled nuclear reactor is recycled back into
Reactor core is heated；
(2) Hydrogen making technological process, from second strand of helium of 800-950 DEG C out of the hot device of the first heat exchange, through hydrogen-manufacturing reactor, drives
Dynamic thermochemical cycle for hydrogen production process, decomposition water obtains hydrogen and oxygen, and second strand of helium is reduced to 400-500 DEG C of middle temperature,
Referred to as middle temperature helium；
(3) bio-crude oil hydrofinishing flow process, bio-crude oil profit two-phase full constituent initially enters second heat exchanger, and described
Middle temperature helium carries out heat exchange, is converted into 300-400 DEG C of bio-crude oil steam, then mixes laggard with Hydrogen making technological process gained hydrogen
Enter to be hydrogenated with fixed bed reactors, be converted in the presence of catalyst according to claim 1 refined based on hydrocarbon component
Biological oil vapour, after condensation and gas-liquid separation liquid fuel and flammable fixed gas are obtained.
6. utilization HTGR according to claim 5 carries out hydrorefined method to bio-crude oil, and its feature exists
In the thermochemical cycle for hydrogen production process in the Hydrogen making technological process is iodo- sulfur cycle process.
7. utilization HTGR according to claim 5 carries out hydrorefined method to bio-crude oil, and its feature exists
The oil phase included in bio-crude oil and water are not mutually separated, directly to carrying out adding after the vaporization of bio-crude oil profit two-phase full constituent
Hydrogen.
8. utilization HTGR according to claim 7 carries out hydrorefined method to bio-crude oil, and its feature exists
It it is 200～400 DEG C in hydrogenation temperature scope, pressure is the quality of 2～20Mpa, bio-crude oil profit two-phase full constituent and hydrogen
Than for 100:5～100:10.
9. utilization HTGR according to claim 7 carries out hydrorefined method to bio-crude oil, and its feature exists
It it is 250～350 DEG C in hydrogenation temperature scope, pressure is the quality of 5～15MPa, bio-crude oil profit two-phase full constituent and hydrogen
Than for 100:7～100:9.
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