CN109536197A

CN109536197A - A kind of biomass liquefying process

Info

Publication number: CN109536197A
Application number: CN201811457583.5A
Authority: CN
Inventors: 林科; 郭立新
Original assignee: Beijing SJ Environmental Protection and New Material Co Ltd
Current assignee: Beijing Haixin Energy Technology Co ltd
Priority date: 2018-11-30
Filing date: 2018-11-30
Publication date: 2019-03-29
Anticipated expiration: 2038-11-30
Also published as: CN109536197B

Abstract

The invention belongs to biomass economy, the energy, chemical technology fields, and in particular to a kind of biomass liquefying process.The liquefaction process uses iron oxide, at least one of the regrowth of the useless agent of the desulfurization of iron oxide or the useless agent of the desulfurization of iron oxide is used as catalyst, and use aqueous slurry, the molar ratio of ferro element and element sulphur in reaction system is controlled simultaneously, it was found that can effectively utilize carbonylation in the presence of CO blocks free radical polycondensation of the biomass in cracking process, and realize that the shift activity hydrogen of CO and water adds hydrogen, in the liquefaction reaction, biomass is without dehydration, liquefaction reaction can directly be carried out, while improving liquefaction yield, the calorific value of obtained oil product can also be improved, after liquefaction reaction, a large amount of waste water will not be generated.

Description

A kind of biomass liquefying process

Technical field

The invention belongs to biomass economy, the energy, chemical technology fields, and in particular to a kind of biomass liquefying process.

Background technique

With the rapid development of social economy, the fossils class such as coal, crude oil, natural gas, oil shale non-renewable energy is increasingly Exhaustion, at the same time, generated CO after such fossil class non-renewable energy burning₂、SO₂、NO_xRing caused by equal pollutants Border pollution is also got worse, this forces the mankind to have to think deeply the approach for obtaining the energy and improve the method for environment.

Currently, biomass liquefying technology becomes a kind of new means for obtaining the energy, which is biomass resource utilization In important component, liquefaction mechanism is as follows: biomass is cracked into oligomer first, then again through dehydration, dehydroxylation, de- Hydrogen, deoxidation and decarboxylation and form small molecule compound, small molecule compound then pass through condensation, cyclisation, polymerization etc. react Generate new compound.The technology is broadly divided into indirect liquefaction and direct liquefaction two major classes at present, wherein biomass direct liquefaction Technology refers under the action of solvent or catalyst, using hydrolysis, supercritical liquefaction or hydrogen, inert gas is passed through, appropriate Temperature, biomass is directly liquefied as liquid from solid under pressure.In whole process, pyrolysis liquefaction, catalytic liquid are related generally to Change and pressurization hydrogenation liquefaction etc..

It in above-mentioned biomass liquefying process, before being liquefied, is required to be carried out dehydrating biomass material, increase Add drying cost, even if dry, after entire technique, can also generate a large amount of waste water.Furthermore above-mentioned liquefaction process is to anti- It answers atmosphere and catalyst requirement stringent, generally to use pure hydrogen atmosphere and noble metal catalyst, economy is poor.In addition, above-mentioned The calorific value for the oil product that liquefaction process obtains is relatively low.

Summary of the invention

Therefore, the technical problem to be solved in the present invention is that overcoming in existing biomass liquefying process, biomass material Need the defect that dehydration, reaction atmosphere and catalyst requirement are stringent, oil product calorific value is relatively low and waste water yield is big, Jin Erti For a kind of biomass material without dehydration, reaction atmosphere using atmosphere, oil product containing CO calorific value it is high, waste water yield is low, The biomass liquefying process even generated without waste water.

For this purpose, technical solution used by the present invention solves the above problems is as follows:

Biomass liquefying process provided by the present invention, includes the following steps:

Prepare the slurries containing catalyst and biomass, the catalyst be the VIIIth race transient metal sulfide and/or Oxide, the slurries are aqueous slurry；

Gasify to hydrocarbon, collects the gas containing CO；

The slurries and pure CO or the gas mixing containing CO are subjected to liquefaction reaction, ferro element and element sulphur in reaction system Molar ratio be 1:(0.5~5), be made oil product.

Further, the temperature of the gasification is 350-1600 DEG C, pressure 1MPa-20MPa；

The hydrocarbon is coal, mineral oil, coke, biomass, bio-regeneration oil, natural gas, methane, biogas, first At least one of alcohol, ethyl alcohol；

It is 1 that sulfur-containing compound molar ratio of ferro element and element sulphur into reaction system is added into the catalyst: (0.5~5), preferably 1:(0.5-2), more preferably 1:(1-2).

Further, the temperature of the gas containing CO is 250~600 DEG C.

Further, the sulfur-containing compound is at least one of sulphur, hydrogen sulfide, carbon disulfide.

Further, the water that the water in the aqueous slurry is carried from described biomass itself, with the biomass Total restatement, the moisture content of the biomass are 500ppm-20%, preferably 2%-10%；Or,

Water of the water from external world's addition in the aqueous slurry.

Further, the volume content of CO is optimal not less than 15%, preferably not less than 25% in the gas containing CO It is selected as not less than 50%.

Further, the gas containing CO is CO and H₂Gaseous mixture or gasification the product gas containing CO.

Further, the iron oxide desulfurization give up agent be using iron oxide as the useless agent of the desulfurizing agent of active component, With Fe_21.333O₃₂For the useless agent of the desulfurizing agent of active component, using FeOOH as at least one in the useless agent of the desulfurizing agent of active component Kind；Or,

The regrowth of the useless agent of the desulfurization of the iron oxide is using iron oxide as the useless agent of the desulfurizing agent of active component Regrowth, with Fe_21.333O₃₂For the regrowth of the useless agent of the desulfurizing agent of active component, using FeOOH as the desulfurizing agent of active component At least one of the regrowth of useless agent.

Further, the iron oxide is di-iron trioxide and/or ferroso-ferric oxide.

Further, the di-iron trioxide is α-Fe₂O₃、α-Fe₂O₃.H₂O、γ-Fe₂O₃、γ-Fe₂O₃.H₂O, without fixed Shape Fe₂O₃, amorphous Fe₂O₃.H₂At least one of O；

The ferroso-ferric oxide is the ferroso-ferric oxide of cubic system；

The FeOOH is in alpha-feooh, β-FeOOH, γ-FeOOH, δ-FeOOH, θ-FeOOH and amorphous FeOOH It is at least one.

Further, the regrowth of the useless agent of the desulfurization of the iron oxide is to be taken off by slurry method to iron oxide The regrowth that the useless agent of sulphur obtains after being aoxidized, vulcanized and being aoxidized.

Further, the regeneration method of the useless agent of the desulfurization of the iron oxide, includes the following steps:

The useless agent of the desulfurization of the iron oxide is mixed with water or aqueous slkali, is configured to slurries；

Oxidant is added into the slurries, and once oxidation reaction occurs；

Vulcanizing agent is added into the slurries after the oxidation reaction, and vulcanization reaction occurs；

Oxidant is added into the slurries after the vulcanization reaction, and secondary oxidation reaction occurs；

Circulation carries out the vulcanization reaction and secondary oxidation reaction；

Slurries after secondary oxidation reaction are separated by solid-liquid separation, the useless agent of desulfurization of the iron oxide is obtained Regrowth.

Further, the reaction pressure of the liquefaction reaction is 5-22MPa, and reaction temperature is 200-470 DEG C.

Further, the reaction time of the liquefaction reaction is not less than 15min, preferably 15-120min.

Further, in the slurries, the content of the catalyst is 0.1~10wt%；

The average grain diameter of the catalyst is 0.1 μm of -5mm, preferably 5 μm -1000 μm, most preferably 5-200 μm.

Further, the slurries and pure CO or gas mixing containing CO are subjected to liquefaction reaction, included the following steps:

Gas containing CO is passed through in reaction system, and liquefaction reaction occurs with the slurry entered in reaction system.

Further, the volume ratio of the gas containing CO and the slurries is (50-10000): 1, preferably (100- 5000): 1.

The pure CO or the gas containing CO are products after gasification, can be boosted after supercooling, purification, transformation into reaction System can also be directly entered reaction system.It is preferred that not boosting, liquefaction reaction system is directly entered without purifying, not converting.

Further, the reaction system is to carry out in the reactor, and the reactor is suspended-bed reactor, slurry bed system Any one of reactor, bubbling bed reactor, fluidized bed reactor, one-pot reaction device；Alternatively,

The reactor is suspended-bed reactor, paste state bed reactor, bubbling bed reactor, fluidized bed reactor, one-pot One or more progress serial or parallel connections during reactor is any one or more of.

Further, the biomass solid be agricultural crop straw, timber, kitchen garbage, excrement, in animal carcass extremely Few one kind.

Further, the biomass be biomass solid when, the preparation method of the slurries, include the following steps: by The biomass successively carries out just crushing, compression and separating twice, is then mixed to get mixture with the catalyst, will be described Slurrying is added into solvent in mixture, obtains the slurries that biomass content is 10~60wt%.

Further, it is not less than 0.4g/cm with the heap density of the compressed biomass by described just crush³, excellent It is selected as not less than 0.8g/cm³, more preferably in not less than 1g/cm³。

The average particle size of the biomass after the separating twice is not more than 5mm, preferably not greater than 1mm, more preferably Ground, average particle size are not more than 500 μm, are not more than 300 μm, are not more than 60 μm, are not more than 50 μm, are not more than 5 μm, no more than 1 μm.

Further, the pressure of the compression is 0.5~3MPa, temperature is 30-60 DEG C.

Further, the solvent is water and/or oil.

Further, oil content is not less than 20wt%, preferably not lower than 50wt% in the solvent, most preferably not low In 80wt%；

Further, the oil is one of animal and plant fat, mineral oil, distillate or described oil product or a variety of.

Above-mentioned technical proposal of the invention has the advantages that

1, biomass liquefying process provided by the present invention, using iron oxide, iron oxide desulfurization give up agent or At least one of the regrowth of the useless agent of the desulfurization of iron oxide is used as catalyst, and uses aqueous slurry, while controlling anti- The molar ratio of ferro element and element sulphur in system is answered, discovery can effectively utilize carbonylation in the presence of CO and biomass is blocked to split Free radical polycondensation in solution preocess, and realize that the shift activity hydrogen of CO and water adds hydrogen, in the liquefaction reaction, biomass is without de- Water can directly carry out liquefaction reaction, while improving liquefaction yield, moreover it is possible to improve the calorific value of obtained oil product, liquefaction is anti- After answering, a large amount of waste water will not be generated.Meanwhile the gas containing CO obtained after hydrocarbon gasification is directlyed adopt, it is rich Containing CO, H₂、H₂S、CO₂, methane etc., and temperature is up to 250~600 DEG C, without gas purification, takes full advantage of containing CO's The high moderate pressure of gas avoids the energy consumption that the gas containing CO is cooled to room temperature, reduces cooling system, cleaning equipment, gas The investment of body booster apparatus, gas heating equipment.

2, biomass liquefying process provided by the invention, further, the desulfurization of iron oxide give up agent as with iron oxide For the useless agent of the desulfurizing agent of active component, with Fe_21.333O₃₂For the useless agent of the desulfurizing agent of active component, using FeOOH as active component At least one of the useless agent of desulfurizing agent；The regrowth of the useless agent of the desulfurization of iron oxide is using iron oxide as active component The regrowth of the useless agent of desulfurizing agent, with Fe_21.333O₃₂It is activity for the regrowth of the useless agent of the desulfurizing agent of active component, with FeOOH At least one of the regrowth of the useless agent of the desulfurizing agent of ingredient, by being incorporated appropriate sulphur using above-mentioned catalyst, discovery exists Under CO atmosphere, these catalyst form carbonyls first in conjunction with CO, then are grafted carbon atom by the carbonyls It is formed by small molecule active position after biomass (such as biomass) thermal cracking, meanwhile, in the catalytic action of iron, element sulphur Under also realize the in situ effect for producing hydrogen and catalytic hydrodeoxygenation of CO transformation, reduce the oxygen content of oil product, substantially increase solid The liquefaction yield of body biomass and long chain are to the liquefied oil product yield of small molecule；

The give up regrowth of agent of the desulfurization of iron oxide is alternately to be vulcanized iron oxide by slurry method and oxygen Change the regrowth obtained after regeneration further to react by multiple vulcanization-oxidization, in this process iron oxide and iron Sulphur compound crystal phase experience reconstructs and liquefaction, in addition S^2-Ionic radius (0.18nm) is greater than O^2-Ionic radius (0.14nm), therefore with The liquefaction between Fe-O key and Fe-S key, the structure cell of iron oxide also undergo contraction and expansion, in turn result in script structure Stable iron oxide crystalline particle becomes loose and bursts apart, and generates a large amount of nanometer iron compounds, this nanometer of iron compound parent Sulphur is good, easily cures.Meanwhile the Nanoscale Iron compound surface covers one layer of nonpolar elemental sulfur layer, the elemental sulfur layer The reunion between nanometer iron compounds particle can not only be hindered to grow up, substantially increase its dispersibility, and can use between substance Existing similar compatibility characteristic, is highly dispersed at a nanometer iron compound in nonpolar oil product；Furthermore the Nanoscale Iron of sulphur covering Compound is because sulphur-iron is closely coupled and the lesser partial size of nanometer iron compound itself, so that sulphur and nanometer iron compound be made to exist Magnetic iron ore (the Fe for generating and there is inferior heavy oil hydrogenation activity can be reacted under low temperature_1-xS), finally obtain such method Regrowth partial size it is small, lipophilic good, structure slabbing nanostructure, the sulphur barrier being adsorbed between piece and piece avoids It is reunited, and the adsorption capacity of CO is substantially increased, and enhances carbonylation, transformation produces hydrogen and hydrogenation catalyst ability.

3, biomass liquefying process provided by the invention, by the way that biomass solid successively to be carried out to just crushing, compression and two Secondary crushing, is then mixed to get mixture with catalyst, feeds the mixture into and grinds slurrying into solvent, obtains biomass content For the slurries of 10~60wt%, the present invention is initiatively to biomass solid using the processing work of separating twice after first compressing Skill makes loose biomass solid that collapsing, closure etc. successively be undergone to arrange again by the way that biomass solid is carried out compression processing Position, mechanically deform stage thus can reduce the porosity of biomass so that the volume of biomass solid is greatly lowered, increase Its big density and specific gravity, are allowed to be conducive to be dispersed in oil product, and its content in oil product can be improved, increase reaction mass Concentration, the solid content in slurries may be up to 10~60wt%, simultaneously because the increase of biomass solid concentration also must in slurries Pump can so be improved within the unit time to the conveying capacity of biomass solid, to improve the efficiency of entire liquefaction process, reduce Industrial cost and energy consumption；In addition, the increase of biomass solid specific gravity also helps suspension of the biomass solid in slurries and divides It dissipates, thus can reduce the viscosity of slurries, realize the smooth flow of slurries in the duct, avoid blocking pipeline, realize the flat of pump Steady operating and conveying, while but also cannot function as the high viscosity waste oil of liquefaction solvent, such as used oil, trench in the prior art Oily, rancid oil etc., can also be utilized.

4, biomass liquefying process provided by the invention, by will just crush the heap density adjusting with compressed biomass To not less than 0.4g/cm³, by the regulation of the average particle size of the biomass after separating twice to less than 5mm, pass through above-mentioned regulation side Formula grinds slurrying convenient for being added into solvent, improves its solid content in slurries；

By controlling compression temperature at 30-60 DEG C, biology can be significantly increased at this temperature by compressing to biomass The rheological characteristic of matter solid reduces the viscosity of slurries, is achieved in the smooth flow of slurries in the duct, avoids the stifled of pipeline Plug realizes the steady operating and conveying of pump.

5, biomass liquefying process provided by the invention is delivered in reactor by reaction raw materials with containing the gas of CO, Under conditions of suitable temperature, pressure, gas liquid ratio and catalyst, cracking, carbonylation, transformation plus hydrogen etc. occur in reactor Reaction；Be further advanced by using paste state bed reactor, first by reaction raw materials by reactor bottom be sent into state bed reactor with It reacts, while injecting the gas containing CO into reactor again, gas, liquid, solid can be relied on so in reactor Difference in specific gravity variation caused by the yield of light-end products, realizes each phase flow velocity after the different specific weight and complex reaction of each material Otherness control, so that biomass solid raw material occurs cracking from the bottom to top in reactor, carbonylation, transformation, adds hydrogen, is anti- It answers, even if heavy biomass solid and catalyst solid particle are with gas and light-end products rising in the process, but Again return under the gas effect containing CO on top to participate in reacting again to bottom, the material according to reactor upper, middle and lower portion is close Degree appropriate adjustment enters the gas and its injection rate containing CO in the slurries of reactor, to realize not liquefied biomass anti- It answers the balance of the circulation and catalyst inside device to be discharged, thus can ensure that the abundant progress of various reactions, to be conducive to mention The liquefied fraction of high biomass and biological oil yield

6, biomass liquefying process provided by the invention, biomass do not need to be dehydrated, and reduce dry cost；It was reacting Cheng Zhongyong's is the gas containing CO, this contains the gas of CO either pure CO, can also be impure, such as in addition to containing CO, also It can also be the synthesis gas that coal, biomass, natural gas, mineral oil gasification produce containing hydrogen, hydrogen sulfide, methane etc., close At other than CO, remainder gas can be hydrogeneous, carbon dioxide or the mixture of methane, ethane, gas manufacturing cost in gas It substantially reduces；During being reacted, acted on the gas containing CO, and using cheap ferrum-based catalyst or useless agent Under, it realizes the process integrations such as cracking reaction, carbonylation, conversion reaction, hydrogenation reaction, is easy to provide sufficient free radical Group avoids the carbonization coking of biomass, and biomass conversion ratio and liquid yield are high, and reaction temperature and pressure are reduced；The liquid The oil product that chemical industry skill generates can be used for front and continued technique to prepare slurries.

Specific embodiment

Technical solution of the present invention will be clearly and completely described below, it is clear that described embodiment is this hair Bright a part of the embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not having Every other embodiment obtained under the premise of creative work is made, shall fall within the protection scope of the present invention.

Embodiment 1

A kind of biomass liquefying process is present embodiments provided, is included the following steps:

The pretreatment of biomass:

Rice straw and reed straw are as biomass solid, with total restatement of the biomass, the moisture content of the biomass It is 4%, the rice straw and reed straw is sent into micronizer and just crush, first smashed median is 100 μ First smashed rice straw and reed straw are then sent into cuber and are carried out under 30 DEG C of temperature, the pressure of 3MPa by m Compression, extrusion forming to its heap density are 0.8g/cm³, separating twice is carried out later, and the average particle size after separating twice is 3mm, it is spare；

Catalyst:

Catalyst is using FeOOH as the useless agent of the desulfurizing agent of active component, wherein described using FeOOH as active component In desulfurizing agent, soluble ferric iron salt Fe (NO₃)₃·9H₂O is 6g, molysite complexing agent triethanolamine 9g, amorphous FeOOH 15g；

Above-mentioned using FeOOH is the desulfurizing agent of active component for removing H in exhaust gas₂The process of S is as follows: by H₂S content is 5500mg/cm³Exhaust gas with 3000h^-1Air speed be passed through desulfurization section, desulphurization reaction is carried out at 30 DEG C, is gone out in the desulfurization section H in implication₂When content≤0.01ppm of S, the waste in the desulfurization section is collected, as in the present embodiment is with FeOOH The useless agent of the desulfurizing agent of active component；

Sulphur is added: using FeOOH as ferro element in the useless agent of the desulfurizing agent of active component and sulphur member in detection the present embodiment The molar ratio of element mixes solid sulfur powder into above-mentioned catalyst if the molar ratio of ferro element and element sulphur is not up to 1:5 It is 1:5 to the molar ratio of wherein ferro element and element sulphur, to guarantee that the molar ratio of ferro element and element sulphur is in reaction system 1:5；

If the molar ratio of ferro element and element sulphur is greater than 1:5, by solvent extraction or the modes such as molten sulphur can be heated, taken off Except extra sulphur；

The preparation of biomass slurry:

The biomass that pretreatment obtains is mixed to get mixture with above-mentioned catalyst, hogwash fat is added in said mixture Middle stirring simultaneously grinds slurrying, forms slurries, and through detecting, the total content of rice straw and reed straw is 60wt% in the slurries, The viscosity of the slurries is 500mPa ﹒ s (50 DEG C), and in above-mentioned slurries, the content of catalyst is 5wt%, the catalyst added Average grain diameter be 5 μm；

Gas containing CO:

Rice straw and reed straw are carried out to high temperature, high-pressure gasified under 800 DEG C, 15MPa pressure, collecting temperature is 250~600 DEG C of the gas containing CO；

Liquefaction reaction:

By gas (CO accounting 40% and H containing CO₂Accounting is 20%) directly to inject slurry by paste state bed reactor entrance In bed reactor, and cracking, carbonylation, transformation and hydrogenation reaction occurs with the slurries therein are entered, controls liquefaction reaction Reaction pressure be 20MPa, reaction temperature is 380 DEG C, reaction time 60min, the gas containing CO and the slurries Volume ratio is 3000:1, and oil product is made.

Embodiment 2

The pretreatment of biomass:

Wheat stalk and corn stover are as biomass solid, with total restatement of the biomass, the moisture content of the biomass It is 10%, the wheat stalk and corn stover is sent into micronizer and just crush, first smashed median is 300 μm, then first smashed wheat stalk and corn stover are sent into cuber under 60 DEG C of temperature, the pressure of 0.5MPa Carrying out compression extrusion forming to its heap density is 0.9g/cm³, separating twice, the average particle size after separating twice are carried out later It is spare for 5mm；

Catalyst:

Catalyst is using iron oxide as the useless agent of the desulfurizing agent of active component, wherein described using iron oxide as active component Desulfurizing agent in, calcium bicarbonate 10g, basic copper carbonate 12g, γ-Fe₂O₃18g, MnO₂For 8g, NiO 5g；

It is above-mentioned using iron oxide as the sweetening process of the desulfurizing agent of active component, be summarized as follows:

1) tail gas that coalite tar generates after fixed bed hydrogenation is catalyzed in collecting；

2) desulfurizing agent of the present embodiment is made to diameter is 1mm, length is 15mm cylindrical catalyst particle, and is filled in de- In sulphur tower, desulfurization layer is formed；

3) by above-mentioned tail gas with 2000h^-1Air speed by desulfurization layer, and occur at 50 DEG C with the desulfurizing agent in desulfurization layer Desulphurization reaction removes hydrogen sulfide in tail gas, and to the end of reacting, the useless agent of the desulfurizing agent after taking out reaction is cooled to room temperature, as In the application using iron oxide as the useless agent of the desulfurizing agent of active component；

Sulphur is added: using iron oxide as ferro element in the useless agent of the desulfurizing agent of active component and sulphur member in detection the present embodiment The molar ratio of element mixes solid sulfur powder into above-mentioned catalyst if the molar ratio of ferro element and element sulphur is not up to 1:1 It is 1:1 to the molar ratio of wherein ferro element and element sulphur, to guarantee that the molar ratio of ferro element and element sulphur is in reaction system 1:1；

If the molar ratio of ferro element and element sulphur is greater than 1:1, by solvent extraction or the usual manners such as molten sulphur can be heated, Remove extra sulphur；

The preparation of biomass slurry:

The biomass that pretreatment obtains is mixed to get mixture with above-mentioned catalyst, palm oil is added in said mixture In be dispersed with stirring slurrying, form slurries, through detecting, wheat stalk and the total content of corn stover are 50wt% in the slurries, should The viscosity of slurries is 1400mPa ﹒ s (50 DEG C), and in above-mentioned slurries, the content of catalyst is 1wt%, the catalyst added Average grain diameter is 10 μm；

Gas containing CO:

Residual oil in petroleum is gasified in 1200 DEG C, 8MPa, collects the gas containing CO that temperature is 250~600 DEG C；

Liquefaction reaction:

By gas (CO accounting 35% and H containing CO₂Accounting is 37%) by suspension bed reaction entrance injection suspension bed reaction In device, and cracking, carbonylation, transformation and hydrogenation reaction occurs with the slurries therein are entered, controls the reaction of liquefaction reaction Pressure is 15MPa, reaction temperature is 420 DEG C, reaction time 30min, the volume ratio of the gas containing CO and the slurries For 2000:1, oil product is made.

Embodiment 3

The pretreatment of biomass:

Cotton stalk is as biomass solid, and with total restatement of the biomass, the moisture content of the biomass is 1%, by this Cotton stalk is sent into micronizer and just crush, and first smashed median is 200 μm, then will first smashed cotton It is 0.9g/ that chopped straw stalk, which is sent into plodder and carries out compression extrusion forming to its heap density under 40 DEG C of temperature, the pressure of 2MPa, cm³, separating twice is carried out later, and the average particle size after separating twice is 1mm, spare；

Catalyst:

Catalyst is amorphous FeOOH；Sulphur is added: mixing solid sulfur powder in Xiang Shangshu catalyst to wherein iron member The molar ratio of element and element sulphur is 1:2, to guarantee that the molar ratio of ferro element and element sulphur is 1:2 in reaction system；

The preparation of biomass slurry:

The biomass that pretreatment obtains is mixed to get mixture with above-mentioned catalyst, said mixture is added to petroleum Disperse slurrying in base wax oil, form slurries, through detecting, the total content of cotton stalk is 50wt% in the slurries, which glues Degree is 400mPa ﹒ s (50 DEG C), and in above-mentioned slurries, the content of catalyst is 1wt%, the average grain diameter of the catalyst added It is 10 μm；

Gas containing CO:

By stalk particle under 900 DEG C, 5MPa high-temperature gasification, collecting temperature is 250~600 DEG C of the gas containing CO；

Liquefaction reaction:

By gas (CO accounting 50% and H containing CO₂Accounting is 20%) anti-by fluidized bed reactor entrance injection ebullated bed It answers in device, and cracking, carbonylation, transformation and hydrogenation reaction occurs with the slurries therein are entered, controls the anti-of liquefaction reaction Answering pressure is 16MPa, reaction temperature is 440 DEG C, reaction time 40min, the volume of the gas containing CO and the slurries Than oil product is made for 1000:1.

Embodiment 4

The pretreatment of biomass:

Sawdust and soybean stalk are as biomass solid, and with total restatement of the biomass, the moisture content of the biomass is 2%, the sawdust and soybean stalk are sent into micronizer and just crush, first smashed median is 150 μm, then First smashed sawdust and soybean stalk are sent into cuber to carry out compressing under 50 DEG C of temperature, the pressure of 1MPa and are squeezed into Type to its heap density is 1g/cm³, separating twice is carried out later, and the average particle size after separating twice is 4mm, spare；

Catalyst:

Catalyst is using iron oxide as the regrowth of the useless agent of the desulfurizing agent of active component, wherein described to be with iron oxide In the desulfurizing agent of active component, ferroso-ferric oxide 50g, calcium sulphate dihydrate 12g, basic zinc carbonate 20g and the carboxylic first of cubic system Base sodium cellulosate is 6g；

Above-mentioned catalyst carries out sweetening process to the petroleum containing hydrogen sulfide, and operating procedure is as follows:

(1) diameter is made in the desulfurizing agent of the present embodiment and is the catalyst granules of 1.5mm, and be filled in desulfurizing tower, shape At desulfurization layer；

(2) petroleum containing hydrogen sulfide is sprayed into desulfurization layer from the top of desulfurizing tower by nozzle, carry out elution desulfurization, The useless agent of desulfurizing agent after collecting desulfurization is the useless agent of the desulfurizing agent containing iron oxide in the application；

The regeneration method of the useless agent of the above-mentioned desulfurizing agent containing iron oxide, includes the following steps:

1) above-mentioned useless agent and water are stirred in slurry tank and is configured to slurries, the solid content of the slurries is 12wt%；

2) it is passed through sodium hypochlorite in Xiang Shangshu slurries, and carries out oxidation reaction under 60 DEG C, 1MPa, with oxidation regeneration；

3) Na is added into the slurries after oxidation again₂S, and vulcanization reaction is carried out under 10 DEG C, 5MPa；

4) it is passed through hydrogen peroxide into the slurries after vulcanization, and carries out oxidation reaction under 30 DEG C, 1.1MPa, with oxidation Regeneration；

5) step 3) and 4) once, the molar ratio of ferro element and element sulphur in the slurries after making the oxidation reaction are repeated 1:1.8；

6) slurries after the oxidation reaction are separated by solid-liquid separation, obtain the regrowth of above-mentioned useless agent；

Sulphur is added: the molar ratio that solid sulfur powder to wherein ferro element and element sulphur are mixed in Xiang Shangshu regrowth is 1:2, to guarantee that the molar ratio of ferro element and element sulphur is 1:2 in reaction system；

The preparation of biomass slurry:

The biomass that pretreatment obtains is mixed to get mixture with above-mentioned catalyst, rapeseed oil is added in said mixture Middle shearing slurrying forms slurries, and through detecting, the total content of sawdust and soybean stalk is 40wt%, the viscosity of the slurries in the slurries It by the regrowth content of the useless agent of the desulfurizing agent of active component of iron oxide is 2wt% in slurries for 1000mPa ﹒ s (50 DEG C), Being added is 400 μm by the average grain diameter of the regrowth of the useless agent of the desulfurizing agent of active component of iron oxide；

Gas containing CO:

By gutter oil, high temperature and pressure gasifies under 1100 DEG C, 19Mpa, collects the gas containing CO that temperature is 250~600 DEG C Body；

Liquefaction reaction:

By the gas (wherein the volume accounting of CO is 40%) containing CO by 4 notes on bubbling bed reactor side wall and bottom Entrance injects in bubbling bed reactor, and cracking, carbonylation, transformation and hydrogenation reaction occurs with the slurries therein are entered, The reaction pressure for controlling liquefaction reaction is 18MPa, reaction temperature is 380 DEG C, reaction time 100min, the gas containing CO Volume ratio with the slurries is 950:1, and oil product is made.

Embodiment 5

The pretreatment of biomass:

Pea stalk, broomcorn straw and rice straw are as biomass solid, with total restatement of the biomass, the biomass Moisture content be 15%, by the pea stalk, broomcorn straw and rice straw be sent into micronizer carry out just crush, just crush Median afterwards is 250 μm, and then first smashed pea stalk, broomcorn straw and rice straw are sent into plodder It is 0.9g/cm that compression extrusion forming to its heap density is carried out under 55 DEG C of temperature, the pressure of 1.5MPa³, two wheat-middlings are carried out later Broken, the average particle size after separating twice is 0.9mm, spare；

Catalyst:

Catalyst is with Fe_21.333O₃₂For the regrowth of the useless agent of the desulfurizing agent of active component, wherein it is described with Fe_21.333O₃₂For in the desulfurizing agent of active component, Fe_21.333O₃₂For 55g, Detitanium-ore-type Ti0₂22g, bentonite 15g；

It is above-mentioned with Fe_21.333O₃₂For the sweetening process of the desulfurizing agent of active component, operating procedure is as follows:

By above-mentioned Catalyst packing in fixed bed reactors, make containing H₂The gas water of S come into full contact with it anti- It answers, contact conditions are as follows: temperature is 35 DEG C, pressure 0.2MPa and volume space velocity 10000h^-1, catalyst after gas water desulfurization gives up agent As the application with Fe_21.333O₃₂For the useless agent of the desulfurizing agent of active component；

The regeneration method of above-mentioned useless agent, includes the following steps:

1) above-mentioned useless agent is dispersed in water, forms slurries；

2) above-mentioned slurries are heated to 45 DEG C under normal pressure, hydrogen peroxide are then added into slurries using peristaltic pump, and lead to Enter air, hydrogen peroxide flow control is 500mL/min, air flow control 100mL/min, magnetic agitation with promote to react into Row, reaction time 5min；

3) after the reaction was completed, filtering reacting liquid obtained precipitating is washed with water 3 times, natural airing, obtains above-mentioned useless agent Regrowth；

Sulphur is added: the molar ratio that solid sulfur powder to wherein ferro element and element sulphur are mixed in Xiang Shangshu regrowth is 1:4, to guarantee that the molar ratio of ferro element and element sulphur is 1:4 in reaction system；

The preparation of biomass slurry:

The biomass that pretreatment obtains is mixed to get mixture with above-mentioned catalyst, gutter oil is added in said mixture With homogeneous slurrying in the miscella of rapeseed oil, slurries are formed, the subsequent gutter oil and rapeseed oil with slurry used in the process is replaceable For oil product made from biomass liquefying process in the present embodiment, through detecting, pea stalk, broomcorn straw and rice straw in the slurries The total content of stalk is 40wt%, and the viscosity of the slurries is 820mPa ﹒ s (50 DEG C), with Fe in slurries_21.333O₃₂For active component The content of the regrowth of the useless agent of desulfurizing agent be 8wt%, added with Fe_21.333O₃₂For the useless agent of the desulfurizing agent of active component Regrowth average grain diameter be 300 μm；

Gas containing CO:

By fine coal under 1600 DEG C, 8MPa high-temperature gasification, collecting temperature is 250~600 DEG C of the gas containing CO；

Liquefaction reaction:

By the gas (wherein the volume accounting of CO is 47%) containing CO by 5 notes in paste state bed reactor bottom and side wall Entrance injects in paste state bed reactor, and cracking, carbonylation, transformation and hydrogenation reaction occurs with the slurries therein are entered, Control reaction pressure is 17MPa, reaction temperature is 400 DEG C, reaction time 50min, the gas containing CO and the slurries Volume ratio be 1500:1, be made oil product.

Embodiment 6

The pretreatment of biomass:

Wheat stalk and flax stalk are as biomass solid, with total restatement of the biomass, the moisture content of the biomass It is 9%, the wheat stalk and flax stalk is sent into micronizer and just crush, first smashed median is 300 μ First smashed wheat stalk and flax stalk are then sent into plodder and are carried out under 60 DEG C of temperature, the pressure of 3MPa by m Compression, extrusion forming to its heap density are 1.1g/cm³, separating twice is carried out later, and the average particle size after separating twice is 2mm, it is spare；

Catalyst:

Catalyst is using FeOOH as the regrowth of the useless agent of the desulfurizing agent of active component, wherein is aoxidized with hydroxyl Iron is the gross mass meter of the desulfurizing agent of active component, and alpha-feooh 30g, amorphous FeOOH is 20g, potassium oxide 8g, is glued Tie agent kaolin 10g；

It is above-mentioned to be used in industry produce after middle coalite tar adds hydrogen upgrading using FeOOH as the desulfurizing agent of active component The sweetening process of raw tail gas is as follows:

3) by above-mentioned tail gas with 2000h^-1Air speed by desulfurization layer, and occur at 50 DEG C with the desulfurizing agent in desulfurization layer Desulphurization reaction removes hydrogen sulfide in tail gas, and to the end of reacting, the useless agent of the desulfurizing agent after taking out reaction is cooled to room temperature, as The useless agent of the desulfurizing agent of active component in the application；

1) aqueous solution of above-mentioned useless agent and sodium hydroxide is stirred in slurry tank and is configured to slurries, maintain the pH value of slurries It is 8.0, the solid content of the slurries is 4wt%；

2) it is passed through air in Xiang Shangshu slurries, and carries out oxidation reaction under 90 DEG C, 0.1MPa, with oxidation regeneration；

3) hydrogen sulfide is passed through into the slurries after oxidation again, and carries out vulcanization reaction under 10 DEG C, 5MPa；

4) it is passed through air into the slurries after vulcanization, and carries out oxidation reaction under 90 DEG C, 0.1MPa, to aoxidize again It is raw；

5) step 3) and 4) once, the molar ratio of ferro element and element sulphur in the slurries after making the oxidation reaction are repeated 1:2；

The preparation of biomass slurry:

The biomass that pretreatment obtains is mixed to get mixture with above-mentioned catalyst, palm oil is added in said mixture With stirring pulping in the miscella of petroleum base wax oil, slurries are formed；Through detecting, wheat stalk and flax stalk is total in the slurries Content is 45wt%, and the viscosity of the slurries is 530mPa ﹒ s (50 DEG C), using FeOOH as the desulfurization of active component in slurries The content of the regrowth of the useless agent of agent be 0.3wt%, added using FeOOH as the useless agent of the desulfurizing agent of active component Regrowth average grain diameter be 20 μm；

Sulphur is added: the molar ratio that solid sulfur powder to wherein ferro element and element sulphur are mixed in Xiang Shangshu regrowth is 1:2.5, to guarantee that the molar ratio of ferro element and element sulphur is 1:2.5 in reaction system；

Gas containing CO:

By Sunflower Pole particle in 900 DEG C, high-temperature gasification under 3MPa collects the gas containing CO that temperature is 250~600 DEG C；

Liquefaction reaction:

By gas (CO accounting 60% and H containing CO₂Accounting is 10%) by 3 in paste state bed reactor bottom and side wall In inlet injection paste state bed reactor, and cracking, carbonylation occurs, convert and adds hydrogen anti-with the slurries therein are entered Answer, control reaction pressure be 19MPa, reaction temperature is 420 DEG C, reaction time 100min, the gas containing CO with it is described The volume ratio of slurries is 800:1, and oil product is made.

Embodiment 7

The pretreatment of biomass:

Rice straw and broad bean stalk are as biomass solid, with total restatement of the biomass, the moisture content of the biomass It is 10%, the rice straw and broad bean stalk is sent into micronizer and just crush, first smashed median particle size is 100 μm, then first smashed rice straw and broad bean stalk are sent into cuber under 30 DEG C of temperature, the pressure of 0.5MPa It is compressed, extrusion forming to its heap density is 1.0g/cm³, separating twice, the average particle size after separating twice are carried out later It is spare for 1mm；

Catalyst:

Catalyst is using iron oxide as the regrowth of the useless agent of the desulfurizing agent of active component, wherein described to be with iron oxide In the desulfurizing agent of active component, ferroso-ferric oxide 12g, the amorphous Fe of cubic system₂O₃24g, amorphous Fe₂O₃.H₂O 39g and NiO is 5g；

H in above-mentioned desulfurizing agent removing exhaust gas₂The matrix process of S, includes the following steps: H₂S content is 5500mg/cm³'s Exhaust gas is with 3000h^-1Air speed be passed through desulfurization section, desulphurization reaction is carried out at 30 DEG C, the H in the desulfurization section is worked off one's feeling vent one's spleen₂S's contains When amount≤0.01ppm, the waste in the desulfurization section is collected；

It is above-mentioned using iron oxide as the regeneration method of the useless agent of the desulfurizing agent of active component, include the following steps:

1) after above-mentioned useless agent being washed with water, the particle for being ground into 200 mesh with water in wet ball mill obtains useless agent powder；

2) the useless agent powder is made into the water slurry that solid masses percentage composition is 7%, is passed through compressed air, carried out anti- It answers；

3) water slurry after reaction is filtered, the solid material is placed in flotation cell, water is added, then leads to Enter air, is the regrowth of above-mentioned useless agent after the sediment drying of lower vessel portion；

Sulphur is added: the molar ratio that solid sulfur powder to wherein ferro element and element sulphur are mixed in Xiang Shangshu regrowth is 1:0.9, to guarantee that the molar ratio of ferro element and element sulphur is 1:0.9 in reaction system；

The preparation of biomass slurry:

The biomass that pretreatment obtains is mixed to get mixture with above-mentioned catalyst, is added the mixture in coal tar Disperse slurrying, form slurries, through detecting, rice straw and the total content of broad bean stalk are 55wt% in the slurries, the slurries Viscosity is 510mPa ﹒ s (50 DEG C), and the content of catalyst is 0.2wt% in the slurries, and the average grain diameter of the catalyst added is 2μm；

Gas containing CO:

By coal in 1400 DEG C, high-temperature gasification under 5MPa collects the gas containing CO that temperature is 250~600 DEG C；

Liquefaction reaction:

By gas (CO accounting 45% and H containing CO₂Accounting is 22%) by 3 inlets on paste state bed reactor side wall It injects in paste state bed reactor, and cracking, carbonylation, transformation and hydrogenation reaction, control occurs with the slurries therein are entered Reaction pressure is 20MPa, reaction temperature is 410 DEG C, reaction time 110min, the body of the gas containing CO and the slurries Oil product is made than being 650:1 in product.

Embodiment 8

The pretreatment of biomass:

Corn stover and ramie stalk stalk are as biomass solid, with total restatement of the biomass, the biomass it is aqueous Rate is 20%, and the corn stover and ramie stalk are sent into micronizer and just crush, first smashed median particle size is 300 μm, first smashed corn stover and ramie stalk are then sent into temperature, the pressure of 2.5MPa in cuber at 50 DEG C Under carry out compression extrusion forming to its heap density be 0.8g/cm³, separating twice is carried out later, the average grain after separating twice Degree is 3mm, spare；

Catalyst:

Catalyst is using FeOOH as the useless agent of the desulfurizing agent of active component, wherein described using FeOOH as active component In desulfurizing agent, amorphous FeOOH 70g, Co₂O₃It is 5g for 25g and NiO；

It is above-mentioned to remove H in exhaust gas by the desulfurizing agent of active component of FeOOH₂The basic process of S, include the following steps: by H₂S content is 5500mg/cm³Exhaust gas with 3000h^-1Air speed be passed through desulfurization section, desulphurization reaction is carried out at 30 DEG C, described Desulfurization section is worked off one's feeling vent one's spleen middle H₂When content≤0.01ppm of S, the waste in the desulfurization section is collected, as in the present embodiment Using FeOOH as the useless agent of the desulfurizing agent of active component；

Sulphur is added: it is 1 that solid sulfur powder to the molar ratio of wherein ferro element and element sulphur is mixed into above-mentioned useless agent: 3, to guarantee that the molar ratio of ferro element and element sulphur is 1:3 in reaction system；

The preparation of biomass slurry:

The biomass that pretreatment obtains is mixed to get mixture with above-mentioned catalyst, said mixture is added to trench Slurrying is emulsified in oil, forms slurries, and through detecting, the total content of corn stover and ramie stalk is 57wt%, the slurry in the slurries The viscosity of liquid is 1130mPa ﹒ s (50 DEG C), is by the content of the useless agent of the desulfurizing agent of active component of FeOOH in the slurries 4wt%, being added is 120 μm by the average grain diameter of the useless agent of the desulfurizing agent of active component of FeOOH；

Gas containing CO:

By petroleum wax oil in 1100 DEG C, high-temperature gasification under 16MPa collects the gas containing CO that temperature is 250~600 DEG C；

Liquefaction reaction:

Gas containing CO is injected in paste state bed reactor by 4 inlets in paste state bed reactor bottom and side wall, And with into the slurry cracking, carbonylation, transformation and hydrogenation reaction therein, control reaction pressure is 17MPa, reaction temperature It is 400 DEG C, reaction time 40min, the volume ratio of the gas containing CO and the slurries is 950:1, and oil product is made.

Embodiment 9

The pretreatment of biomass:

Catalyst:

Catalyst uses the useless agent using FeOOH as the desulfurizing agent of active component, wherein using FeOOH as the de- of active component The gross mass meter of sulphur agent, described by the content of amorphous FeOOH in the desulfurizing agent of active component of FeOOH is 60%, is carried The content of body diatomite is 30%, and the content of binder fiber element powder is 10%；

Sulphur is added: the molar ratio that solid sulfur powder to wherein ferro element and element sulphur are mixed in Xiang Shangshu catalyst is 1:4, to guarantee that the molar ratio of ferro element and element sulphur is 1:4 in reaction system；

The preparation of biomass slurry:

The biomass that pretreatment obtains is mixed to get mixture with above-mentioned catalyst, gutter oil is added in said mixture With homogeneous slurrying in the miscella of rapeseed oil, slurries are formed, the subsequent gutter oil and rapeseed oil with slurry used in the process is replaceable For oil product made from biomass liquefying process in the present embodiment, through detecting, pea stalk, broomcorn straw and rice straw in the slurries The total content of stalk is 40wt%, and the viscosity of the slurries is 820mPa ﹒ s (50 DEG C), using FeOOH as the desulfurization of active component in slurries The content of agent is 8wt%, and being added is 300 μm by the average grain diameter of the desulfurizing agent of active component of FeOOH；

Gas containing CO:

By broomcorn straw powder at 900 DEG C high-temperature gasification, collecting temperature is 250~600 DEG C of the gas containing CO；

Liquefaction reaction:

By the gas (wherein the volume accounting of CO is 40%) containing CO by 5 notes in paste state bed reactor bottom and side wall Entrance injects in paste state bed reactor, and cracking, carbonylation, transformation and hydrogenation reaction occurs with the slurries therein are entered, Control reaction pressure is 17MPa, reaction temperature is 380 DEG C, reaction time 50min, the gas containing CO and the slurries Volume ratio be 900:1, be made oil product.

Embodiment 10

The liquefaction process for present embodiments providing a kind of dregs of fat and excrement, includes the following steps:

The pretreatment of the dregs of fat and excrement:

The dregs of fat and excrement are as biomass solid, and with total restatement of the biomass, the moisture content of the biomass is 12%, will The dregs of fat and excrement are sent into micronizer and just crush, and first smashed median is 150 μm, after then just crushing The dregs of fat and excrement be sent into plodder in compressed under 55 DEG C of temperature, the pressure of 1.5MPa, extrusion forming is close to its heap Degree is 1.0g/cm³, separating twice is carried out later, and the average particle size after separating twice is 2mm, spare；

Catalyst:

Catalyst is amorphous FeOOH；

Sulphur is added: the molar ratio that solid sulfur powder to wherein ferro element and element sulphur are mixed in Xiang Shangshu catalyst is 1:1.5, to guarantee that the molar ratio of ferro element and element sulphur is 1:1.5 in reaction system；

The preparation of slurries:

The obtained dregs of fat of pretreatment and excrement and above-mentioned catalyst are mixed to get mixture, by said mixture be added to Disperse slurrying in petroleum base wax oil, form slurries, through detecting, the total content of the dregs of fat and excrement is 50wt%, the slurry in the slurries The viscosity of liquid is 400mPa ﹒ s (50 DEG C), and in above-mentioned slurries, the content of catalyst is 1wt%, and the catalyst added is put down Equal partial size is 10 μm；

Gas containing CO:

By coal in 1350 DEG C, high-temperature gasification under 6MPa collects the gas containing CO that temperature is 250~600 DEG C；

Liquefaction reaction:

By gas (CO accounting 45% and H containing CO₂Accounting is 25%) anti-by fluidized bed reactor entrance injection ebullated bed It answers in device, and cracking, carbonylation, transformation and hydrogenation reaction occurs with the slurries therein are entered, controls the anti-of liquefaction reaction Answering pressure is 16MPa, reaction temperature is 420 DEG C, reaction time 40min, the volume of the gas containing CO and the slurries Than oil product is made for 1000:1.

Embodiment 11

The co grinding method technique for present embodiments providing a kind of dregs of fat and wheat stalk, includes the following steps:

The pretreatment of the dregs of fat and wheat stalk:

The dregs of fat and wheat stalk are as biomass solid, and with total restatement of the biomass, the moisture content of the biomass is 5%, the dregs of fat and excrement are sent into micronizer and just crush, first smashed median is 200 μm, then will be first The smashed dregs of fat and excrement are sent into plodder to be compressed under 55 DEG C of temperature, the pressure of 1.5MPa, and extrusion forming is extremely Its heap density is 0.95g/cm³, separating twice is carried out later, and the average particle size after separating twice is 60 μm, spare；

Catalyst:

Catalyst is the regrowth of the useless agent of the desulfurizing agent containing FeOOH, wherein with total matter of the desulfurizing agent containing FeOOH Meter, the content of γ-FeOOH is 45% in the desulfurizing agent containing FeOOH, and the content of alpha-feooh is 35%, carrier molecule The content of sieve is 15%, and the content of binder sesbania powder is 5%；

H in above-mentioned catalyst removal exhaust gas₂The basic process of S includes the following steps: H₂S content is 5500mg/cm³'s Exhaust gas is with 3000h^-1Air speed be passed through desulfurization section, desulphurization reaction is carried out at 30 DEG C, the H in the desulfurization section is worked off one's feeling vent one's spleen₂S's contains When amount≤0.01ppm, collecting the waste in the desulfurization section is the useless agent of desulfurizing agent；

The regeneration method of the useless agent of above-mentioned desulfurizing agent are as follows: after the useless agent of the desulfurizing agent is washed with water, in wet ball mill Useless agent powder is obtained with the particle that water is ground into 80 mesh；The useless agent powder is made into the aqueous suspension that solid masses percentage composition is 8% Liquid is passed through compressed air, reacts inspection by sampling after a period of time, does not generate H when the sample of taking-up is reacted with hydrochloric acid₂When S, then give up Iron sulfide in agent is liquefied completely as FeOOH and elemental sulfur, slurry of the formation containing the FeOOH and elemental sulfur Liquid filters the slurries and obtains solid material, uses CC1₄The solid material obtained after extraction filtering, coextraction merge extraction three times Liquid, the elemental sulfur crystallized simultaneously with the method recycling design of distillation, and extract liquor separates rear remaining solid and binder The regrowth of the useless agent of above-mentioned desulfurizing agent is made in sesbania powder mixing, and wherein the dosage of binder sesbania powder is the solid masses 5%.

Carbon disulfide is added: the molar ratio that carbon disulfide to wherein ferro element and element sulphur are added in Xiang Shangshu catalyst is 1:2, to guarantee that the molar ratio of ferro element and element sulphur is 1:2 in reaction system；

The preparation of slurries:

The obtained dregs of fat of pretreatment and wheat stalk and above-mentioned catalyst are mixed to get mixture, by said mixture plus Enter and disperse slurrying into gutter oil, form slurries, through detecting, the total content of the dregs of fat and excrement is 55wt%, the slurry in the slurries The viscosity of liquid is 400mPa ﹒ s (50 DEG C), and in above-mentioned slurries, the content of catalyst is 10wt%, and the catalyst added is put down Equal partial size is 5mm；

Gas containing CO:

By hogwash fat under 1050 DEG C, 6MPa high-temperature gasification, collecting temperature is 250~600 DEG C of the gas containing CO；

Liquefaction reaction:

By gas (CO accounting 35% and H containing CO₂Accounting is 24%) anti-by fluidized bed reactor entrance injection ebullated bed It answers in device, and cracking, carbonylation, transformation and hydrogenation reaction occurs with the slurries therein are entered, controls the anti-of liquefaction reaction Answering pressure is 16MPa, reaction temperature is 360 DEG C, reaction time 60min, the volume of the gas containing CO and the slurries Than oil product is made for 5000:1.

Embodiment 12

A kind of biomass liquefying process is present embodiments provided, same as Example 4, unique difference, the present embodiment In the desulfurizing agent containing iron oxide useless agent regeneration method, include the following steps:

1) water vapour that pressure is 1.5MPa is passed through heating furnace, by steam heating to 450 DEG C；

2) water vapour after heating is passed into the desulfurizer for filling above-mentioned useless agent with the speed of 15m/s, is heated above-mentioned useless Agent；

3) guarantee the bed temperature of above-mentioned useless agent by steam heating to running 2h, steam use under conditions of 400 DEG C or more Amount is 6t/h；

4) analysis desulfurizer export pH, continuous 3 times be more than or equal to 7.5 when, a small amount of oven gas can be passed through into desulfurizer It is restored；

5) being passed through level-one in fine de-sulfur process adds the oven gas after hydrogen to go back with 800m3/h to ferric oxide desulfurizer agent of giving up It is former；

6) be passed through every primary inlet and outlet H2 concentration variation of 30min analysis after oven gas, when outlet H2 concentration stablize be greater than or Regrowth can be obtained equal to (3 analyses) after entrance H2 concentration.

Comparative example 1

This comparative example provides a kind of biomass liquefying process, and liquefaction process is same as Example 4, and difference exists In: sawdust and soybean stalk are as biomass solid in this comparative example, with total restatement of the biomass, the moisture content of the biomass For 80ppm；The molar ratio of ferro element and element sulphur is 1:0.1 in reaction system.

Test example 1

The distribution for the product that method using the embodiment of the present invention 1-12 is prepared with comparative example 1 is compared, product Test method it is as follows:

(solid remaining in gross mass-reaction product of solid biomass is raw in raw material by solid biomass liquefied fraction %= Material mass) gross mass of solid biomass in/raw material, " solid biomass " in the solid biomass liquefied fraction refers both to nothing Water, ash free basis (the same below)；

Solid biomass liquefaction oil yield %=solid biomass liquefies to be liquid phase oil product under normal temperature and pressure in product Solid biomass combined feed quality in quality/raw material；

Reaction generates water rate %=(total matter of the water quality of the reaction product-water that reaction starting is added or raw material is brought into Amount)/raw material combined feed quality.As this value < 0, it is denoted as "None"；

Corresponding test result is as shown in Table 1 and Table 2:

The comparison of 1 solid biomass liquefaction effect of table

The data from table 1 it is found that using gasification process the gas containing CO, under the conditions of high-temperature high-voltage reaction, catalyst The function of having played hydro-thermal transformation, deoxidation plus hydrogen, cracking, so that biomass solid is fully converted into biomass fuel, and does not have Extra water generates；In comparative example due in slurries water content it is less, and in catalyst sulphur with relatively low, cause biomass to turn Rate is low.

Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or It changes still within the protection scope of the invention.

Claims

1. a kind of biomass liquefying process, which comprises the steps of:

The slurries containing catalyst and biomass are prepared, the catalyst is transient metal sulfide and/or the oxidation of the VIIIth race Object, the slurries are aqueous slurry；

Gasify to hydrocarbon, collects the gas containing CO；

The slurries and the gas mixing containing CO are subjected to liquefaction reaction, the molar ratio of ferro element and element sulphur is in reaction system 1:(0.5~5), oil product is made.

2. biomass liquefying process according to claim 1, which is characterized in that the temperature of the gasification is 350-1600 DEG C, pressure 1MPa-20MPa；

The hydrocarbon is coal, mineral oil, coke, biomass, bio-regeneration oil, natural gas, methane, biogas, methanol, second At least one of alcohol；

Into the catalyst be added sulfur-containing compound into reaction system the molar ratio of ferro element and element sulphur be 1:(0.5~ 5), preferably 1:(0.5-2), more preferably 1:(1-2).

3. biomass liquefying process according to claim 2, which is characterized in that the sulfur-containing compound is sulphur, vulcanization At least one of hydrogen, carbon disulfide.

4. biomass liquefying process according to any one of claim 1-3, which is characterized in that in the aqueous slurry The water that water is carried from described biomass itself, with total restatement of the biomass, the moisture content of the biomass is 500ppm- 20%, preferably 2%-10%；Or,

Water of the water from external world's addition in the aqueous slurry.

5. biomass liquefying process described in any one of -4 according to claim 1, which is characterized in that in the gas containing CO The volume content of CO is not less than 15%, preferably not less than 25%, is most preferably not less than 50%.

6. biomass liquefying process according to claim 5, which is characterized in that the gas containing CO is CO and H₂It is mixed Close the product gas of gas or gasification containing CO.

7. biomass liquefying process according to claim 1 to 6, which is characterized in that the iron oxide The useless agent of desulfurization is using iron oxide as the useless agent of the desulfurizing agent of active component, with Fe_21.333O₃₂For active component desulfurizing agent it is useless Agent, using FeOOH as at least one of useless agent of the desulfurizing agent of active component；Or,

The regrowth of the useless agent of the desulfurization of the iron oxide is using iron oxide as the regeneration of the useless agent of the desulfurizing agent of active component Object, with Fe_21.333O₃₂For the regrowth of the useless agent of the desulfurizing agent of active component, using FeOOH as the useless agent of the desulfurizing agent of active component At least one of regrowth.

8. biomass liquefying process according to claim 7, which is characterized in that the iron oxide be di-iron trioxide and/ Or ferroso-ferric oxide.

9. biomass liquefying process according to claim 8, which is characterized in that the di-iron trioxide is α-Fe₂O₃、α- Fe₂O₃.H₂O、γ-Fe₂O₃、γ-Fe₂O₃.H₂O, amorphous Fe₂O₃, amorphous Fe₂O₃.H₂At least one of O；

The ferroso-ferric oxide is the ferroso-ferric oxide of cubic system；

The FeOOH be alpha-feooh, β-FeOOH, γ-FeOOH, δ-FeOOH, θ-FeOOH and amorphous FeOOH at least It is a kind of.

10. biomass liquefying process according to claim 1 to 9, which is characterized in that the iron oxide The give up regrowth of agent of desulfurization be to give up after agent is aoxidized, vulcanized and aoxidized to obtain to the desulfurization of iron oxide by slurry method Regrowth.

11. biomass liquefying process according to claim 10, which is characterized in that the useless agent of the desulfurization of the iron oxide Regeneration method, include the following steps:

Oxidant is added into the slurries, and once oxidation reaction occurs；

Slurries after secondary oxidation reaction are separated by solid-liquid separation, the regeneration of the useless agent of desulfurization of the iron oxide is obtained Object.

12. biomass liquefying process described in any one of -11 according to claim 1, which is characterized in that the liquefaction reaction Reaction pressure is 5-22MPa, and reaction temperature is 200-470 DEG C.

13. biomass liquefying process according to claim 12, which is characterized in that the reaction time of the liquefaction reaction is not Less than 15min, preferably 15-120min.

14. biomass liquefying process according to claim 1 to 13, which is characterized in that in the slurries, institute The content for stating catalyst is 0.1~10wt%；

15. biomass liquefying process described in any one of -14 according to claim 1, which is characterized in that by the slurries with contain The gas mixing of CO carries out liquefaction reaction, includes the following steps:

16. biomass liquefying process described in any one of -15 according to claim 1, which is characterized in that the pure CO contains CO Gas and the slurries volume ratio be (50-10000): 1, preferably (100-5000): 1.

17. biomass liquefying process described in any one of -16 according to claim 1, which is characterized in that the pure CO contains CO Gas be gasification after product, can boost after supercooling, purification, transformation enter reaction system, can also be directly entered instead Answer system.It is preferred that not boosting, liquefaction reaction system is directly entered without purifying, not converting.

18. biomass liquefying process described in any one of -17 according to claim 1, which is characterized in that the reaction system is It carries out in the reactor, the reactor is suspended-bed reactor, paste state bed reactor, bubbling bed reactor, ebullating bed reactor Any one of device, one-pot reaction device；Alternatively,

The reactor is suspended-bed reactor, paste state bed reactor, bubbling bed reactor, fluidized bed reactor, one-pot reaction One or more progress serial or parallel connections during device is any one or more of.