CN107557075B - Biomass indirect liquefaction synthetic oil technique and its system - Google Patents
Biomass indirect liquefaction synthetic oil technique and its system Download PDFInfo
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- CN107557075B CN107557075B CN201710995689.XA CN201710995689A CN107557075B CN 107557075 B CN107557075 B CN 107557075B CN 201710995689 A CN201710995689 A CN 201710995689A CN 107557075 B CN107557075 B CN 107557075B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
Abstract
The invention discloses a kind of biomass indirect liquefaction synthetic oil technique and its system, technique includes biomass pressurized gasification, purified synthesis gas, oil product synthesis, tail gas decarburization, tail gas oil wash, tail gas reformation, tail gas hydrogen manufacturing, oil product processing and tail gas desulfurization step；In biomass pressurized gasification step, gasification furnace pressure is 3~5MPa (G), 500 DEG C of drying section temperature < in gasification furnace, distilling period temperature is 500~1000 DEG C, gasification section temperature is 1000~1100 DEG C, burning zone temperature is 1100~2000 DEG C, and slag section temperature is 1700~2000 DEG C；The tar that biomass pressurized gasification step and purified synthesis gas step generate carries out mixing refining as the intermediate synthetic oil that the raw material and oil product synthesis step of oil product procedure of processing obtain takes synthesis oil product.The technique and its system carry out whole consideration to each technique unit and related process matched therewith, carry out process optimization from whole angle, reasonable disposition realizes the efficient utilization of biomass new energy.
Description
Technical field
The present invention relates to the development and utilization technologies of new energy, in particular to a kind of biomass indirect liquefaction synthetic oil work
Skill and its system.
Background technique
With the increasingly reduction of traditional fossil energy (coal, petroleum, natural gas) reserves, fossil energy uses bring environment
The even more serious problem such as destruction catastrophic to the earth, directly threatens the survival and development of the mankind when pollution and exploitation, must
The common recognition that palpus is paid attention to and fast development is renewable, the environmentally friendly friendly energy has become the mankind.
Biomass indirect liquefaction synthetic oil is consistent in principle with ICL for Indirect Coal Liquefaction oil and gas liquefaction, all
It is to convert hydrocarbon material to hydrogen and carbon monoxide, then converts oil product for hydrogen and carbon monoxide synthesis.From
Conceptually, biomass indirect liquefaction synthetic oil and ICL for Indirect Coal Liquefaction liquefaction are increasingly similar, because coal is originally from number
Biomass before 1000000 years, it is therefore contemplated that the difference of biomass indirect liquefaction synthetic oil and ICL for Indirect Coal Liquefaction liquefaction exists
The process that biomass is converted into coal is shortened by chemical method in the former, makes to replace non-renewable energy using renewable energy
Source becomes a reality.Biomass is the organic substance that plant is generated by photosynthesis, and biomass energy is because having widely distributed, reserves
Infinitely, renewable, CO2The features such as zero-emission and the extensive concern for causing people, pass through the methods of heat chemistry, biochemistry, energy
It is enough clean gas or liquid fuel by Biomass, to generate electricity, produce the raw material of industry, chemical products etc., with complete
Face substitutes the potentiality of fossil energy, becomes the new energy that countries in the world are first developed.But for a long time, biomass energy is extensive
Development and utilization are affected because of its distribution dispersion by traffic condition, collect the reasons such as difficulty is larger and there are variety of problems.Therefore
The manufacturing technique method and system for finding a kind of suitable biomass synthetic oil become the vital issue faced at present.
Currently, both at home and abroad in research achievement all only with regard to biomass be converted to synthetic oil some unit or several units into
Row research, the systematization and rationalization of non-overall thinking biomass economy, or prepare the raw material of synthetic oil and belong to fossil
How the energy, rather than biomass energy optimize configuration to all technique units and the related process matched therewith of production on the whole,
The utilization efficiency for improving biomass to the maximum extent, becomes as technical problem urgently to be resolved.Such as: a kind of prepared by biomass is given birth to
The method of substance oil and synthesis gas, this method comprises: biomass is carried out cracking reaction, is obtained under the conditions of biomass through pyrolysis
To oil gas and coke；The oil gas is subjected to Oil-gas Separation, isolates cracking gas and bio-oil；Under gasification condition, by institute
It states coke and gasifying medium carries out gasification reaction, isolate synthesis gas from gasification reaction product.Preceding method can use life
Substance prepares bio-oil and synthesis gas simultaneously, and substantially free of tar in the synthesis gas prepared；This method just for
The biomass pyrolytic and gasification process of biomass liquefaction are studied, a whole set of production technology not from the point of view of the overall situation,
And the bio-oil of this method production application field under conditions of no downstream processing is handled is limited；This method requires former
The pretreatment partial size of material is raw having a size of 0.05~5mm, and for biomass material larger for size, pretreatment cost is relatively
It is high.The method of another coal base synthetic oil coproduction LNG, step, which includes: feed coal, obtains raw gas through gasification；Raw gas is through low
Warm methanol master washes section removing sour gas, obtains synthesis gas；Synthesis gas through F-T synthetic reaction, is obtained in oil product synthesis unit
Between product, the intermediate products be heavy distillate, light fraction oil, heavy wax, F-T synthetic water and F-T synthesis tail gas；It is intermediate
In product, the heavy distillate, light fraction oil and heavy wax process unit hydrofinishing and hydrocracked, treated through oil product,
Obtain gasoline and diesel oil；For the F-T synthesis tail gas through membrane separation, obtained impermeable gas arrives LNG through cryogenic separation
Product.Preceding method coproduction LNG while coal oil, and the sour gas generated and F-T synthetic water and tail can be recycled
Gas；This method produces synthetic oil as raw material using coal, finally obtains gasoline and diesel oil through processing, and co-production LNG is produced
Product, but the feed coal that the technique uses still falls within fossil energy.In addition, a kind of carbonaceous material gasification is at producing liquid after synthesis gas
The method of fuel, electric energy, hydrogen, the technique include stock, gasification, purified synthesis gas transformation, hydrogen retrieval, F- T synthesis, oil product
Seven upgrading, fuel gas generation processes are divided into three strands after gasification institute's production of synthetic gas purification transformation, one synthesis gas is used to convert system
Hydrogen, one synthesis gas are used to F- T synthesis preparing liquid fuel, one synthesis gas is used to combustion power generation, and Fischer-Tropsch process exhaust is also used
Carry out combustion power generation.Previous process realizes oily Electricity Federation and produces, synthesis needed for can leading to adjusting biomass material inlet amount, a F- T synthesis
The parameters such as synthesis throughput needed for throughput, combustion power generation realize fecund oil or fecund electricity, and specific embodiment can be according to raw material
Supply and the market demand are regulated and controled, but the technique Fischer-Tropsch process exhaust, without circulation, Fischer-Tropsch synthesis conversion ratio is not high, takes
Hold in the palm most of unreacted synthesis gas (H in tail gas2+ CO) it is used to combustion power generation, purpose is not single production synthetic oil.
Summary of the invention
Present invention aim to provide a kind of biomass indirect liquefaction synthetic oil technique and its system, the technique and
Its system realizes the efficient utilization of biomass new energy.
To achieve the above object, the technical solution adopted by the present invention is that: a kind of biomass indirect liquefaction synthetic oil technique,
It is reformed including biomass pressurized gasification, purified synthesis gas, oil product synthesis, tail gas decarburization, tail gas oil wash, tail gas, tail gas hydrogen manufacturing, oil
Product processing and tail gas desulfurization step；In the biomass pressurized gasification step, gasification furnace pressure is 3~5MPa, is dried in gasification furnace
Dry 500 DEG C of section temperature <, distilling period temperature are 500~1000 DEG C, and gasification section temperature is 1000~1100 DEG C, and burning zone temperature is
1100~2000 DEG C, slag section temperature is 1700~2000 DEG C；The biomass pressurized gasification step and the purified synthesis gas
The intermediate synthetic oil that the tar that step generates is obtained as the raw material of the oil product procedure of processing and the oil product synthesis step into
Row mixes refining and takes synthesis oil product.
Further, the tail gas decarbonation process uses hot potash decarbonization technique.
Further, the tail gas oil wash step uses low temperature oil wash technique or cryogenic condensation technique, the processing of tail gas oil wash
Afterwards, what the purified gas and the tail gas hydrogen production step that a part is obtained as circulating air with the purified synthesis gas step obtained
Hydrogen mixes the raw material as the oil product synthesis step；Raw material of the another part as the tail gas reforming step.
Further, the tail gas reforming step uses self-heating recapitalization technique, partial oxidation technology, steam reforming technique
Or carbon dioxide and steam reforming technique or MDEA decarbonization process.
Further, the tail gas hydrogen production step uses PSA separating technology, and hydrogen a part obtained is as the oil product
The raw material of synthesis step, to adjust hydrogen-carbon ratio in synthesis gas, raw material of the another part as the oil product procedure of processing, to divide
Solve the Long carbon chain organic matter in synthetic oil.
Further, the tail gas desulfurization step uses alkali absorption method, direct oxidation method or CTS Complexing Iron sulfur recovery work
Skill.
Further, the intermediate synthetic oil that is obtained using the oil product synthesis step, described in the oil product procedure of processing
Tar that tar that biomass pressurized gasification step obtains, the purified synthesis gas step obtain, the tail gas oil wash step obtain
To the obtained hydrogen of oil wash naphtha and the tail gas hydrogen production step carry out oil product working process as raw material, obtain synthetic oil
Product.
Further, in the oil product synthesis step, the decontaminating syngas that the purified synthesis gas step is obtained and institute
It states after the hydrogen that tail gas hydrogen production step obtains and the part oil wash tail gas that the tail gas oil wash step obtains mixing in F- T synthesis
Between synthetic oil.
Further, it is additionally provided with biomass pre-treatment step before the biomass pressurized gasification step, the biomass is pre-
In processing step, biomass is crushed to a length of 20~60mm, width is 20~60mm, dry to aqueous with a thickness of 10~20mm
Amount is 10~35wt%.
It further, further include biomass power generation step, in the biomass power generation step, using biomass boiler conduct
The solar power system of auxiliary thermal source provides electric energy and thermal energy for the biomass indirect liquefaction synthetic oil technique.
It further, further include space division, water process, exhaust-gas treatment, fixed-end forces, oil product storage, oil loading step；
The water treatment steps include raw water water intaking, purificating raw water, reuse water process, fire water water supply, sewage treatment；At the exhaust gas
Step is managed, using RTO heat accumulating type organic exhaust gas burning process.
A kind of biomass indirect liquefaction system synthesis oil system, including gasification furnace, the crude synthesis gas of the gasification furnace export
It is connected with gas cleaning plant, the decontaminating syngas outlet of the gas cleaning plant is connect with oil product synthesizer；The oil product
The synthesis tail gas outlet of synthesizer is connect with tail gas decarbonization device, the decarburization outlet and tail gas of the tail gas decarbonization device
Oil-washing apparatus connection, the first oil wash offgas outlet of the tail gas oil-washing apparatus are connect with tail gas reformer, the tail gas weight
The reformation gas outlet of engagement positions is connect with tail gas device for producing hydrogen, the hydrogen outlet and oil product processing unit (plant) of the tail gas device for producing hydrogen
Connection；The intermediate synthesis oil export of the oil product synthesizer is connect with the oil product processing unit (plant), the oil product processing unit (plant)
Acid tail gas outlet connect with tail gas desulfurization device；The tar of the tar outlet of the gasification furnace and the gas cleaning plant
Outlet is connect with the oil product processing unit (plant) respectively.
The tar outlet of mouth and the gas cleaning plant is connect with the oil product processing unit (plant) respectively.
Further, the second oil wash offgas outlet of the tail gas oil-washing apparatus is connect with the oil product synthesizer.
Further, the hydrogen outlet of tail gas device for producing hydrogen is also connect with oil product synthesizer.
Further, the acid tail gas outlet of the gas cleaning plant is connect with the tail gas desulfurization device；The tail
The fuel gas outlet of desulfurization device is connect with oil product processing unit (plant).
Further, the oil wash naphtha outlet of the tail gas oil-washing apparatus is connect with the oil product processing unit (plant).
Compared with prior art, the invention has the following advantages that
First, the crude synthesis gas after gasifying in the present invention does not need to convert, after gas purification units desulfurization and decarburization
The raw material production synthetic oil that can be used as oil product synthesis unit F- T synthesis shortens in this way, save Water gas shift/WGS process
Process flow, reduces purification device load, reduces energy consumption, reduces investment, make to operate simpler, flexible.
Second, the present invention uses raw material of the full biomass as gasification of biomass unit, what gasification of biomass unit generated
The tar that tar and gas purification units generate can be used as the raw material of oil product processing unit and intermediate synthetic oil carries out mixing refining, without
It needs to be equipped with additional tar processing technique, simplifies process flow, save the cost.
Third, a variety of biomass materials that the present invention because gasification of biomass cell pressure is higher, is suitable for, size 20~
Agriculture and forestry organic waste material within the scope of 60mm can be utilized directly, after the pelletized forming of 20mm biomass below be used as raw material, 60mm with
On biomass can be sliced or is broken after as raw material, for the biomass normal pressure that compares gasification, feed stock chip break process at
Originally it substantially reduces.Biomass material lesser for partial size can be supplied to biomass fermentation boiler as raw material and generate electricity, and not need
Carry out molding granulation processing, save the cost.
Fourth, the present invention, because gasification of biomass cell pressure is higher, the crude synthesis gas that gasification of biomass unit generates is not required to
Downstream gas cleaning unit can be directly fed through overcompression, pressure drop is about 0.5MPa after gas purification units are handled, thick to close
The oil product synthesis unit in downstream can be directly entered after gas purification units purify at gas, the pressure for meeting oil product synthesis unit is wanted
It asks, saves compression energy consumption, meanwhile, at elevated pressures, gasification of biomass unit and subsequent handling unit and line size
It is relatively small, construction cost is saved, is conducive to improve plant capacity.
Fifth, present system is reformed using F- T synthesis, tail gas decarburization, tail gas oil wash, tail gas, tail gas hydrogen manufacturing forms
Gas body-internal-circulation and outer circulation sufficiently remove CO useless in tail gas2, the H in reaction end gas is recycled to greatest extent2, CO and light
Hydrocarbon increases Fischer-Tropsch synthesis device entrance synthesis gas effective component concentration, improves the total conversion of Fischer-Tropsch synthesis, thus
Realize that the green high-efficient of biomass renewable energy utilizes.
Sixth, present system is using tail gas Hydrogen Unit production hydrogen to the hydrogen carbon of oil product synthesis unit feed synthesis gas
Ratio carries out flexible modulation, keeps oil product synthesis unit entrance synthesis gas hydrogen-carbon ratio adjustable range more wide in range, is conducive to oil product conjunction
Flexible choice is carried out to catalyst at unit, correspond to different hydrogen-carbon ratios and requires selection differences to urge the different of Fischer-Tropsch synthetic
The fischer-tropsch synthesis process of agent, or the more set fischer-tropsch synthesis process combined using multiple catalysts, make to produce more flexible.No
Other techniques are same as, this system recycles synthetic reaction tail gas in system inside enclosed by tail gas reforming hydrogen manufacturing unit, maximum
The useful component of limit recycled in tail gas, saves biomass material consumption, reduces CO2Discharge, meets " eating dry bleed "
And the environmentally friendly new concept of " zero-emission ".Oil product processing unit of the present invention passes through the optimum organization of hydrofinishing and hydrocracking process
Come handle gasification of biomass produce tar and F- T synthesis produce it is light, again, wax oil, to produce naphtha, diesel oil；Gasification of biomass
Tar is one of the innovative point of this unit by hydrotreating, and same device has no configured in this way.
Seventh, biomass gasifying furnace is suitable for the biomass that water capacity is 10~35wt% in the present invention, in many areas
Humidity when raw material is collected can reach requirement, substantially can to meet gasification furnace wet to biomass without being dried
The requirement of content, to save the dry high energy consumption cost of biomass.In addition, preventing from may cause because of reasons such as weather
Biomass moisture content can not be up to standard, and biomass pretreatment unit is equipped with technique low temperature exhaust heat and preheats biomass, adoptable technique
Low temperature exhaust heat have recirculated water and process-stream heat exchange take out low-grade remaining heat, can also be used fume waste heat come heating biological matter into
Material.
Eighth, the present invention uses heat accumulation type off-gas incineration technology (RTO technology), be conducive to environmental protection.It is estimated that if
National whole organic exhaust gas is handled using heat accumulation type off-gas incineration technology, and the discharge amount of volatile organic compounds can be reduced
90% or more, it will significantly improve air quality.When heat accumulating type organic waste gas furnace stable operation, the destruction of VOC is removed
97.5% or more rate；For organic exhaust gas concentration in 2000PPM or more, RTO device is not required to addition auxiliary fuel substantially, and mutually exists together
The heating power incinerator of reason ability is compared, and is realized and is saved 87.7% or more fuel.Destruction of the heat accumulating type organic waste gas furnace to VOC
Removal rate integrally improves 10~15 percentage points or more than existing incinerator, and unburned hydrocarbons content is far below state in flue gas
Numerical value as defined in family's standard；In addition significantly energy saving compared with heating power incinerator.
Ninth, cogeneration system of the system using matched biomass and solar energy complemental power-generation, entire to be
Uniting, it is outer for thermoelectricity to be not necessarily to, and realizes the industrial energy product for being converted into the form of ownership such as heat, electricity, oil, gas by biomass completely, thorough
Bottom gets rid of dependence of the traditional energy industry to fossil energy, and making biomass energy really becomes renewable, can plant, and alternative
The green energy resource of fossil energy.
Tenth, the characteristics such as low-sulfur, low nitrogen, low ash point that bio-oil has will using efficient biomass switch technology
Discarded biomass resource is converted to high-grade bio-oil fuel, Agricultural Output not only can be improved, but also can reduce dirt
Dye promotes the benign cycle of ecology, makes up the dependence to fossil energy.Present invention process is particularly suitable for 100 kilometers of models of radius
The interior region that can supply enough biomass materials is enclosed, can effectively solve the problem that biomass economy rationalizes, Systematization.
Detailed description of the invention
Fig. 1 is a kind of biomass indirect liquefaction synthetic oil system structure diagram.
Fig. 2 is a kind of biomass indirect liquefaction synthetic oil process flow chart.
Specific embodiment
The following further describes the present invention in detail with reference to the accompanying drawings and specific embodiments, convenient for more clearly understanding this
Invention, but they limiting the invention.
A kind of biomass indirect liquefaction system as shown in Figure 1 synthesizes oil system, including gasification furnace, the thick synthesis of gasification furnace 1
Gas cleaning plant 2 is connected in gas outlet, the decontaminating syngas outlet of gas cleaning plant 2 is connect with oil product synthesizer 3；Oil
The synthesis tail gas outlet of product synthesizer 3 is connect with tail gas decarbonization device 4, the decarburization outlet and tail of tail gas decarbonization device 4
Gas and oil cleaning device 5 connects, and the first oil wash offgas outlet of tail gas oil-washing apparatus 5 is connect with tail gas reformer 6, and tail gas reforms dress
It sets 6 reformation gas outlet connect with tail gas device for producing hydrogen 7, the hydrogen outlet of tail gas device for producing hydrogen 7 and the company of oil product processing unit (plant) 8
It connects；The intermediate synthesis oil export of oil product synthesizer 3 is connect with oil product processing unit (plant) 8, and the acid tail gas of oil product processing unit (plant) 8 goes out
Mouth is connect with tail gas desulfurization device 9；The tar outlet of gasification furnace 1 and the tar outlet of gas cleaning plant 2 add with oil product respectively
Tooling sets 8 connections.Second oil wash offgas outlet of tail gas oil-washing apparatus 5 is connect with oil product synthesizer 3.Tail gas device for producing hydrogen 7
Hydrogen outlet also connect with oil product synthesizer 3.Acid tail gas outlet and the tail gas desulfurization device 9 of gas cleaning plant 2 connect
It connects；The fuel gas outlet of tail gas desulfurization device 9 is connect with oil product processing unit (plant) 8.The oil wash naphtha of tail gas oil-washing apparatus 5 exports
It is connect with oil product processing unit (plant) 8.
The present invention is that synthesis gas is manufactured by gasified bio-matter, and the process of the inverted production synthetic oil of synthesis gas is main
To add including gasification of biomass, gas purification, oil product synthesis, tail gas decarburization, tail gas oil wash, tail gas reformation, tail gas hydrogen manufacturing, oil product
Nine processing steps of work and tail gas desulfurization and matched pretreatment of raw material, biomass power generation, space division, water process, exhaust gas
Processing, fixed-end forces, oil product storage, oil loading.Each step is specific as follows:
1) biomass material pre-processes: biomass material grows into 20~60mm, width 20 through biomass pretreatment processing
~60mm, if raw material particle size is too small, needs it to be formed processing with a thickness of 10~20mm, is in rodlike, diameter 10 after forming
~18mm, 20~50mm of length, the material quantity of the partial size that meets the requirements should be not less than 70%, for a length of 5~20mm, width is 5~
20mm, thickness are the raw material of 5~20mm, and content should be not more than 25%.It is less than the sawdust of 5mm for partial size, content should be not more than
5%.Biomass material is dry to 10~35wt% of water content.
2) gasification of biomass: in gasification furnace 1 using in air oxygen or oxygen carrier make gasifying agent, will be in biomass
Oxidation of coal generate fuel gas process.Using biomass gasification technology, to treated, biomass material gasifies, gas
The product for changing furnace 1 is synthesis gas (H2+ CO) and tar；The purified dedusting of the synthesis gas of gasification furnace 1 out obtains crude synthesis gas, thick to close
Purified treatment is carried out at the gas cleaning plant 2 that gas enters downstream, tar then enters oil product processing unit (plant) 8 and is processed.
Gasification of biomass is used as raw material using 100% biomass, and pressure is 4MPa (G) in gasification furnace 1；Drying section temperature in gasification furnace 1
Lower than 500 DEG C, distilling period temperature be 500~1000 DEG C, gasification section temperature be 1000~1100 DEG C, burning zone temperature be 1100~
2000 DEG C, slag section temperature is 1700~2000 DEG C；Gasification furnace 1 is slag tap.The tar that gasification of biomass generates can be direct
The intermediate synthetic oil generated into oil product processing unit (plant) 8 and oil product synthesizer 3 carries out mixing refining, obtains qualified synthetic oil and produces
Product.
3) gas purification: in gas cleaning plant 2 using gas purification technique gasification of biomass unit is generated it is thick
Synthesis gas carries out purified treatment, synthesis gas is purified, to meet the feed needs of oil product synthesis unit；Gas purification units produce
Raw tar can be directly entered the intermediate synthetic oil that oil product processing unit (plant) 8 and oil product synthesizer 3 generate and carry out mixing refining, be closed
The synthesis oil product of lattice.
4) oil product synthesizes: oil product synthesizer 3 is by the decontaminating syngas from gas cleaning plant 2 and comes from tail gas hydrogen manufacturing
It is converted into intermediate synthetic oil after the hydrogen mixing of device 7, as the raw material of downstream oil product processing unit (plant) 8, oil product synthesizer 3
Synthesis tail gas successively passes through tail gas decarbonization device 4, tail gas oil-washing apparatus 5, tail gas reformer 6 and tail gas device for producing hydrogen 7 and obtains
Hydrogen.Oil product synthesizer 3 carries out liquid conversion, synthesis reactor feed hydrogen carbon to decontaminating syngas using F- T synthesis technology
Than requiring the catalyst difference control used according to F- T synthesis in different range, it is catalyzed at present using more mature indirect liquefaction
Agent mainly has iron series and cobalt system two major classes, and oil product synthesis unit can be used ferrum-based catalyst fischer-tropsch synthesis process, cobalt can also be used
Base catalyst fischer-tropsch synthesis process, when using different catalysts and different type reactor, the temperature of reactor, pressure with
And the hydrogen-carbon ratio range of synthesis gas is all different, and all adjustable in a certain range, precipitated iron catalyst preference temperature is
220~250 DEG C, 2.5~3.3MPa of pressure (a) hydrogen-carbon ratio range 1.6~2.5；Fused iron catalysts preference temperature be 280~
340 DEG C, 2.3~2.4MPa of pressure (a) hydrogen-carbon ratio range 2.4~2.8, Co catalysts preference temperature is 170~220 DEG C.
5) it tail gas decarburization: after carrying out carbonization treatment from the synthesis tail gas of oil product synthesizer 3, takes off in synthesis tail gas
CO2, the tail gas oil-washing apparatus 5 in downstream is entered after synthesis tail gas decarburization, removes C2 or more the heavier component in tail gas, tail gas
Oil wash rear portion returns to the entrance of oil product synthesizer 3, raw material of the another part as tail gas reformer unit as circulating air
Into tail gas reformer 6, the CO of removing2Gas is directly vented.Hot potash decarbonization technology can be used in tail gas decarburization unit, this is de-
Carbon technique can accomplish no hydrocarbon loss substantially, and process flow is simple, technology maturation is reliable.It should be noted that tail gas decarburization list
Member includes hot potash decarbonization but not limited to this, the MDEA decarbonization process of current industrial application can also be used for this process system.
6) tail gas oil wash: by the synthesis tail gas from tail gas decarbonization device 4 after oil wash is handled, a part is used as circulating air
Return to the entrance and the purified gas from gas cleaning plant 2 and the hydrogen from tail gas device for producing hydrogen 7 of oil product synthesizer 3
Mix the raw material as oil product synthesizer 8；A part enters tail gas reformer 6 as the raw material of tail gas reformer unit, passes through
Oil wash naphtha after oil wash enters oil product processing unit (plant) 8 and is processed.Low temperature oil wash, low can be used in tail gas oil wash unit
The techniques such as temperature condensation.
7) tail gas is reformed: the oil wash tail gas from tail gas oil-washing apparatus 5 obtains reforming gas after tail gas is reformed, and it is rich to reform gas
Hydrogen produces hydrogen into tail gas Hydrogen Unit.Tail gas reformer unit uses ATR self-heating recapitalization technique, uses non-catalytic portion
The reaction heat of point oxidation process release is not needed as steam reformation come amount of heat needed for providing highly endothermic reforming reaction
External heating is needed, it can be achieved that adiabatic reaction generation CO and H occurs in ATR reburner for hydro carbons in decarbonated exhaust gas2, then pass through
CO is converted H by total transform2, raw material as PSA tail gas Hydrogen Unit.It should be noted that this system process is illustrated
Tail gas reforming process include ATR (self-heating recapitalization) technique but not limited to this, such as POX (partial oxidation), SMR (vapor
Reform) and the technologies such as carbon dioxide, steam reforming be also used equally for this process system.
8) tail gas hydrogen manufacturing: reformation gas is carried out isolated purity using PSA technology and is greater than 99% by tail gas Hydrogen Unit
Hydrogen, a part of hydrogen are organic as the Long carbon chain that the raw material of oil product processing unit is sent in oil product processing unit decomposition oil product
Object, another part are used to adjust the hydrogen-carbon ratio in the charging of oil product synthesis unit as oil product synthesis unit raw material.
9) tail gas desulfurization: the acid tail gas from gas cleaning plant 2 and oil product processing unit (plant) 8 is mixed into tail gas desulfurization
Device 9, the sulfur-containing impurities in acid tail gas are fallen in removing after lye absorbs, and the tail gas after desulfurization adds as oil product processing unit
The fuel of hot stove is sent to oil product processing unit (plant) 8.Alkali absorption method, direct oxidation method, CTS Complexing Iron can be used in tail gas desulfurization unit
Sulfur recovery technology etc..
10) oil product is processed: the intermediate synthetic oil from oil product synthesizer 3, comes from gas at the tar from gasification furnace 1
The tar of purification device 2, the oil wash naphtha from tail gas oil-washing apparatus 5 and the hydrogen conduct from tail gas device for producing hydrogen 7
Raw material enters oil product processing unit (plant) 8 and carries out hydrocracking and hydrofinishing working process, obtains synthesis oil product.
11) biomass power generation: biomass fermentation electric unit uses solar power generation system of the biomass boiler as auxiliary thermal source
System for whole set process system provides electric energy and thermal energy, and the unit is by solar concentrating heat collector, biomass boiler device, steamer
Electricity generation system combines, and solar concentrating heat collector may be provided in the stock ground warehouse roof of biomass pretreatment unit, does not have to another
Outer occupancy construction area.Biomass fermentation electric unit is equipped with small-sized online power station, can be by extra electricity simultaneously in the case that power supply is sufficient
Enter power grid, meets the needs of not enough power supply using external power supply in the case where electricity shortage.Biology needed for biomass boiler
Matter raw material can be lesser agriculture and forestry organic waste material of the partial sizes such as rice husk, straw dust etc., can be used in biomass pretreatment unit and obtains
The lesser biomass material of the partial size arrived, without carrying out granulating and forming working process, save the cost.
12) oxygen, nitrogen, instrument air etc. space division: are provided for a whole set of biomass synthetic oil process system.Air separation unit
The electric energy and thermal energy provided using biomass fermentation electric unit, when whole system technique production scale is little, air separation unit compressor
It can be used and be driven by electricity, when whole system technique production scale is larger, steam drive, biomass is can be used in air separation unit compressor
Generator unit can do appropriate distribution to electric energy and heat yields according to the needs of production technology.
13) water process: water process includes raw water water intaking unit, clean water treatment unit, reuse water treatment unit, fire water list
Member, sewage treatment unit and sewage treatment unit.Raw water water intaking unit is fetched water to needed for whole set process system with water；Water purification
Processing unit carries out purification working process to water intaking, meets process requirements；Reuse water treatment unit adds technique recycle-water
Work processing, meets technique quality of reused water requirement；Fire-fighting water unit provides fire demand water for whole set process system, it is ensured that safety is raw
It produces；Sewage treatment unit carries out purified treatment, the sewage discharge mark of meet the requirement of environmental protection to the production waste of whole set process system
It is quasi-.
14) exhaust-gas treatment: exhaust gas treatment unit carries out purified treatment to the production exhaust gas of whole set process system, reaches environmental protection
It is required that waste gas emission standard.Exhaust gas treatment unit uses RTO heat accumulating type organic exhaust gas incineration technology, and heat accumulating type organic exhaust gas is burnt
Burning furnace is that most energy saving, the most effective method for reducing volatile organic compounds discharge, this method use heat accumulating type in the world at present
Heat recovery mode, can in high-temperature flue gas 90% or more thermal energy recycle, flue gas discharge temperature can be down to 180 DEG C of left sides
It is right.When organic matter reaches a certain concentration or more in exhaust gas to be processed, additional heat can not be needed in operation, therefore transport
Row cost is extremely low.
15) fixed-end forces: fixed-end forces unit carries out purified treatment to the solid waste that whole set process system generates, and reaches
The solid waste discharge standard of environmental requirement.Fixed-end forces unit carries out classification processing to the solid waste that different process unit generates,
The solid slag that gasification of biomass unit generates can be used as agricultural organic fertilizer or construction material, the useless catalysis of solid after processing
Agent material properly manages, and is recycled company by special catalyst and carries out relevant treatment.
16) oil product storage: oil product storage unit stores the product oil of whole set process system production；Oil product storage list
All oil product storage tanks of member are all made of nitrogen envelope design, it is ensured that production safety.
17) oil loading: oil loading unit carries out entrucking etc. to the oil product for needing to send outside in oil product storage unit.Oil product
Synthesis unit and oil product processing unit and oil product storage and all oil pipelines of oil loading system and equipment all use acid-proof
Corrosion treatment material.
Present invention process can convert biomass efficient to naphtha and diesel product, and full factory's complex energy transformation efficiency is
35%~42%.Because biomass material type is different, the processes specific choice such as gasification of biomass, oil product synthesis, oil product processing
The difference of technology, end product quality and ratio are slightly different, and generally produce the equivalent consumption biomass 5 of product oil per ton
~9 tons.Consumption of raw materials and product yield are specifically shown in Table 1.
Table 1
Present invention process is integrally considered by the overall process of biomass to product oil (BTL), is closed to whole system
Distributing rationally for reason, fully considers the advance and operability of technology, at the same to the logistics of whole system key node at
Divide and requires to be shown in Table 2.
Table 2
Embodiment 1
As shown in Fig. 2, for producing 200000 tons of synthetic oil product process flow per year, the technique mistake of the specific method
Journey be follow these steps (1.~) carry out:
For the present embodiment using biomass as raw material, biomass material property data see the table below 3.
Table 3
| Unit | Numerical value | |
| Net heating value | MJ/kg | 18.5-20(dry) |
| Moisture content | % | 10-35 |
| Bulk density | Kg/loose m3 | 250-300 |
| Dust burdening | % | 0.4-1.2 |
| Grey deformation temperature (DT) | ℃ | 935-1020 |
| Solid carbon | % | NA |
| Volatile matter | % | 80-90 |
| At being grouped as (dry weight) | ||
| Carbon | % | 48-52 |
| Hydrogen | % | 6-6.5 |
| Oxygen | % | 38-42 |
| Sulphur | % | < 0.05 |
| Nitrogen | % | < 0.2 |
| Chlorine | % | < 0.01 |
| Sodium | mg/kg | 1000-65000 |
| Potassium | mg/kg | < 3000 |
Raw material processing is grown into 20~60mm through biomass pretreatment unit, width is 20~60mm, with a thickness of 10~
The blocky size of 20mm, it is dry to 15%~35wt%, pressurized gasification unit is sent into 167t/h amount and carries out gasification of biomass, is obtained
To the tar of 175.67t/h crude synthesis gas and 3.04t/h, crude synthesis gas ingredient is shown in Table 4.
Table 4
| Composition | H2 | CO | CO2 | CH4 | N2 | H2S | C2H4 | C2H6 | C3H8 | H2O |
| Molar fraction, % | 25.75 | 36.23 | 27.32 | 8.4 | 1.5 | 0.1 | 0.1 | 0.1 | 0.3 | 0.2 |
The crude synthesis gas that pressurized gasification generates enters low-temp methanol and washes unit progress gas purification, removes in crude synthesis gas
CO2With sulfur-containing impurities etc., to meet the feed needs of downstream F- T synthesis unit.89.95t/h is obtained after low-temp methanol is washed
(5178.73kmol/h) decontaminating syngas, composition see the table below 5, meanwhile, obtain the acid tail of 0.0068t/h (6.75kmol/h)
Gas, composition are shown in Table 6.
Table 5
| Composition | H2 | CO | CO2 | CH4 | N2 | H2S | C2H4 | C2H6 | C3H8 |
| Molar fraction % | 35.55 | 49.71 | 0.82 | 11.30 | 2.04 | < 0.1ppm | 0.14 | 0.022 | 0.003 |
Table 6
| Composition | CO | CO2 | CH4 | N2 | H2S | C2H4 | C2H6 | C3H8 |
| Molar fraction % | 0.01 | 78.93 | 0.01 | 13.52 | 7.03 | 0.1 | 0.2 | 0.2 |
Purified gas goes out low-temp methanol and washes the hydrogen come after unit with tail gas Hydrogen Unit to carry out Mixed adjustment hydrogen-carbon ratio laggard
Enter F- T synthesis unit, is 3.75t/h (1874.27kmol/h) for adjusting the amounts of hydrogen of hydrogen-carbon ratio, wherein hydrogen content is big
In 99.9%.Purified gas, that is, F- T synthesis fresh feed throughput after adjusted hydrogen-carbon ratio is 94.50t/h (7053kmol/
H), composition is shown in Table 7.
Table 7
| Composition | H2 | CO | CO2 | CH4 | N2 | H2S | C2H4 | C2H6 | C3H8 |
| Molar fraction % | 52.8 | 36.5 | 0.6 | 8.3 | 1.5 | < 0.1ppm | 0.1 | 0.016 | 0.002 |
F- T synthesis fresh feed gas converts after mixing with the circulating air from tail gas oil wash unit through F- T synthesis liquid
Obtain intermediate synthetic oil and 172.52t/h (11227.3kmol/h) synthesis tail gas, the intermediate synthetic oil product composition of F- T synthesis
8 are shown in Table, the synthesis tail gas composition of F- T synthesis is shown in Table 9.
Table 8
| Name of material | Quantity | Unit |
| Light oil | 3.84 | t/h |
| Mink cell focus | 4.16 | t/h |
| Heavy wax | 9.80 | t/h |
Table 9
Fischer-Tropsch process exhaust enters hot potash decarbonization unit removing CO2, it is de- to obtain 144.56t/h (10578.4kmol/h)
Carbon tail gas, composition are shown in Table 10.
Table 10
| Composition | H2 | CO | CO2 | CH4 | N2 | C2H4 | C2H6 | C3H8 | C3H6 | C4H8 |
| Molar fraction % | 41.4 | 17.1 | 0.1 | 33.1 | 5.4 | 0.5 | 1.1 | 0.2 | 0.6 | 0.1 |
Decarbonated exhaust gas enters tail gas oil wash unit and carries out low temperature oil wash, and 140.80t/h is obtained after oil wash
(10523.8kmol/h) oil wash tail gas and 3.64t/h oil wash naphtha, oil wash tail gas composition are shown in Table 11.
Table 11
| Composition | H2 | CO | CO2 | CH4 | N2 | C2H4 | C2H6 | C3H8 | C3H6 |
| Molar fraction, % | 41.6 | 17.2 | 0.1 | 33.2 | 5.4 | 0.5 | 1.1 | 0.2 | 0.6 |
Oil wash tail gas enters ATR unit progress tail gas and reforms to obtain 56.62t/h (4090.41kmol/h) reformation gas, group
At being shown in Table 12.
Table 12
| Composition | H2 | CO | CO2 | CH4 | N2 | H2O |
| Molar fraction, % | 70.3 | 0.5 | 26 | 0.2 | 2.6 | 0.4 |
The PSA Hydrogen Unit that gas enters downstream is reformed, obtains product hydrogen 4.93t/h (2445.24kmol/h), wherein hydrogen
Gas content is greater than 99.9%.Product hydrogen a part is sent to F- T synthesis unit as raw material, and a part is sent to hydrocracking and adds
Hydrogen refined unit is as raw material.
Tar, the low-temp methanol that intermediate synthetic oil that F- T synthesis unit obtains, pressurized gasification unit obtain are washed unit and are obtained
To tar, the obtained oil wash naphtha of tail gas oil wash unit enter as the product hydrogen of raw material and PSA Hydrogen Unit plus
Hydrogen Hydrocracking refined unit is processed, and obtains synthesis oil product and 1.51t/h (53.20kmol/h) acid tail gas,
Synthetic oil product composition is shown in Table 13, and synthetic oil product property is shown in Table 14, and acid tail gas composition is shown in Table 15.
Table 13
| Name of material | Quantity | Unit |
| Naphtha | 8.25 | t/h |
| Diesel oil | 17.63 | t/h |
Table 14
Table 15
| Composition | H2 | CO2 | CH4 | C2H6 | C3H8 | C4H10 | C5H12 |
| Molar fraction, % | 39 | 5.2 | 0.7 | 21.3 | 28.1 | 38.7 | 6.8 |
From low-temp methanol wash the acid tail gas of unit and from hydrocracking hydrofinishing unit acid tail gas mixing
It is handled into caustic wash desulfuration unit, the purified gas 1.44t/h (52.06kmol/h) obtained after processing is used as hydrocracking
The fuel gas of hydrofinishing unit heating furnace, composition are shown in Table 16.
Table 16
| Composition | H2 | CO | CH4 | N2 | H2O | C2H4 | C2H6 | C3H8 | C3H6 | C4H8 | C4H10 | C5H12 |
| Molar fraction, % | 36.62 | 0.31 | 3.48 | 3.05 | 1.22 | 0.54 | 19.58 | 14.08 | 0.35 | 0.16 | 15.55 | 3.99 |
Biomass solar power generation unit provides electric energy and thermal energy for whole set process system.Air separation unit is whole set process system
Public work gas and technique, instrument gas demand needed for system provides production.Water treatment unit is to needed for whole set process system
Water intaking processing is carried out with water, meets process water requirement；And purified treatment is carried out to the production waste of whole set process system, reach
The sewage drainage standard of environmental requirement；Security against fire guarantee is provided for plant area.Exhaust gas treatment unit purifies production exhaust gas
Processing, the waste gas emission standard of meet the requirement of environmental protection.Fixed-end forces unit carries out the solid waste that whole set process system generates
Purified treatment, the solid waste discharge standard of meet the requirement of environmental protection.Oil product storage unit to the product oil of whole set process system production into
Row storage.Oil loading unit carries out entrucking etc. to the oil product for needing to send outside in oil product storage unit.
Claims (14)
1. a kind of biomass indirect liquefaction synthetic oil technique, it is characterised in that: net including biomass pressurized gasification, synthesis gas
Change, oil product synthesis, tail gas decarburization, tail gas oil wash, tail gas reformation, tail gas hydrogen manufacturing, oil product processing and tail gas desulfurization step；The life
In substance pressurized gasification step, gasification furnace pressure is 3~5MPa, 500 DEG C of drying section temperature < in gasification furnace, and distilling period temperature is
500~1000 DEG C, gasification section temperature is 1000~1100 DEG C, and burning zone temperature is 1100~2000 DEG C, and slag section temperature is
1700~2000 DEG C；The tar that the biomass pressurized gasification step and the purified synthesis gas step generate is as the oil product
The intermediate synthetic oil that the raw material of procedure of processing and the oil product synthesis step obtain, which carries out mixing refining, takes synthesis oil product；
In the oil product synthesis step, decontaminating syngas and the tail gas hydrogen production step that the purified synthesis gas step is obtained
Synthetic oil among F- T synthesis after the part oil wash tail gas mixing that obtained hydrogen and the tail gas oil wash step obtains；
Further include biomass power generation step, in the biomass power generation step, using biomass boiler as auxiliary thermal source too
Positive energy electricity generation system provides electric energy and thermal energy for the biomass indirect liquefaction synthetic oil technique.
2. biomass indirect liquefaction synthetic oil technique according to claim 1, it is characterised in that: the tail gas decarbonation process
Using hot potash decarbonization technique or MDEA decarbonization process.
3. biomass indirect liquefaction synthetic oil technique according to claim 1, it is characterised in that: the tail gas oil wash step
Using low temperature oil wash technique or cryogenic condensation technique, after the processing of tail gas oil wash, a part is net as circulating air and the synthesis gas
Change the original of the purified gas that step obtains and the hydrogen mixing that the tail gas hydrogen production step obtains as the oil product synthesis step
Material；Raw material of the another part as the tail gas reforming step.
4. the according to claim 1 or 2 or 3 biomass indirect liquefaction synthetic oil techniques, it is characterised in that: the tail gas weight
Synchronizing uses self-heating recapitalization technique, partial oxidation technology, steam reforming technique or carbon dioxide and steam reforming technique suddenly.
5. the according to claim 1 or 2 or 3 biomass indirect liquefaction synthetic oil techniques, it is characterised in that: the tail gas system
Hydrogen step uses PSA separating technology, raw material of the hydrogen a part obtained as the oil product synthesis step, to adjust synthesis gas
Middle hydrogen-carbon ratio, raw material of the another part as the oil product procedure of processing, with the Long carbon chain organic matter in local behavior oil.
6. the according to claim 1 or 2 or 3 biomass indirect liquefaction synthetic oil techniques, it is characterised in that: the tail gas is de-
Sulphur step uses alkali absorption method, direct oxidation method or CTS Complexing Iron sulfur recovery technology.
7. the according to claim 1 or 2 or 3 biomass indirect liquefaction synthetic oil techniques, it is characterised in that: the oil product adds
During work step is rapid, coke that the intermediate synthetic oil that is obtained using the oil product synthesis step, the biomass pressurized gasification step are obtained
The oil wash naphtha and the tail gas system that tar that oily, the described purified synthesis gas step obtains, the tail gas oil wash step obtain
The hydrogen that hydrogen step obtains carries out oil product working process as raw material, obtains synthesis oil product.
8. the according to claim 1 or 2 or 3 biomass indirect liquefaction synthetic oil techniques, it is characterised in that: the biomass
It is additionally provided with biomass pre-treatment step before pressurized gasification step, in the biomass pre-treatment step, biomass is crushed to length
For 20~60mm, width is 20~60mm, and with a thickness of 10~20mm, drying to water content is 10~35wt%.
9. the according to claim 1 or 2 or 3 biomass indirect liquefaction synthetic oil techniques, it is characterised in that: further include sky
Divide, water process, exhaust-gas treatment, fixed-end forces, oil product storage, oil loading step；The water treatment steps include raw water water intaking,
Purificating raw water, reuse water process, fire water water supply, sewage treatment；The exhaust gas polishing steps, using RTO heat accumulating type organic waste
Gas burning process.
10. a kind of biomass indirect liquefaction system synthesizes oil system, including gasification furnace (1), which is characterized in that the gasification furnace (1)
Crude synthesis gas outlet on be connected with gas cleaning plant (2), the outlet of the decontaminating syngas of the gas cleaning plant (2) and oil product
Synthesizer (3) connection；The synthesis tail gas outlet of the oil product synthesizer (3) is connect with tail gas decarbonization device (4), the tail
The decarburization outlet of gas decarbonization device (4) is connect with tail gas oil-washing apparatus (5), the first oil of the tail gas oil-washing apparatus (5)
Washing tail-gas outlet is connect with tail gas reformer (6), the outlet of reformation gas and the tail gas device for producing hydrogen of the tail gas reformer (6)
(7) it connects, the hydrogen outlet of the tail gas device for producing hydrogen (7) is connect with oil product processing unit (plant) (8)；The oil product synthesizer
(3) intermediate synthesis oil export is connect with the oil product processing unit (plant) (8), and the acid tail gas of the oil product processing unit (plant) (8) goes out
Mouth is connect with tail gas desulfurization device (9)；The tar outlet of the gasification furnace (1) and the tar of the gas cleaning plant (2) go out
Mouth is connect with the oil product processing unit (plant) (8) respectively.
11. biomass indirect liquefaction system synthesizes oil system according to claim 10, it is characterised in that: the tail gas oil wash dress
The the second oil wash offgas outlet for setting (5) is connect with the oil product synthesizer (3).
12. biomass indirect liquefaction system synthesizes oil system according to claim 10, it is characterised in that: tail gas device for producing hydrogen
(7) hydrogen outlet is also connect with oil product synthesizer (3).
13. biomass indirect liquefaction system synthesizes oil system according to claim 10, it is characterised in that: the gas purification dress
The acid tail gas outlet for setting (2) is connect with the tail gas desulfurization device (9)；The fuel gas of the tail gas desulfurization device (9) exports
It is connect with oil product processing unit (plant) (8).
14. biomass indirect liquefaction system synthesizes oil system according to claim 10, it is characterised in that: the tail gas oil wash dress
The oil wash naphtha outlet for setting (5) is connect with the oil product processing unit (plant) (8).
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