CN108264918A - A kind of hydrolysis hydrogenation technique of biomass - Google Patents

A kind of hydrolysis hydrogenation technique of biomass Download PDF

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Publication number
CN108264918A
CN108264918A CN201711420301.XA CN201711420301A CN108264918A CN 108264918 A CN108264918 A CN 108264918A CN 201711420301 A CN201711420301 A CN 201711420301A CN 108264918 A CN108264918 A CN 108264918A
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biomass
slurries
hydrogen
high pressure
stalk
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CN108264918B (en
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林科
李林
郭立新
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Beijing Haixin Energy Technology Co ltd
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Beijing SJ Environmental Protection and New Material Co Ltd
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Priority to PCT/CN2018/122667 priority patent/WO2019128867A1/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
    • C10G1/065—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation in the presence of a solvent
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/008—Controlling or regulating of liquefaction processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
    • C10G1/083—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts in the presence of a solvent
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
    • C10G1/086—Characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1003—Waste materials
    • C10G2300/1007—Used oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C10G2300/1014—Biomass of vegetal origin
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects
    • C10G2300/703—Activation

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

Abstract

The present invention relates to field of biological energy source, more particularly to a kind of hydrolysis hydrogenation technique of biomass, the preparation steps of its slurries are, stalk is dried successively, just crush, compress and separating twice, mixture then is mixed to get with catalyst, feeds the mixture into oil product slurries of the grinding slurrying up to a concentration of 30~60wt% of stalk.The present invention it is initiative stalk is first compressed after separating twice treatment process, by the way that biomass is carried out compression processing, making loose stalk, successively experience ranks again, the stages such as machinery denaturation and moulding rheology, so that the volume of stalk is greatly lowered, thus the porosity of stalk can be reduced, increase its density and proportion, it is allowed to be conducive to be dispersed in oil product, and its content in oil product can be improved, increase the concentration of reaction mass, pump is improved within the unit interval to the conveying capacity of biomass, it ensure that the steady operating and conveying of pump, the conversion ratio of biomass is improved simultaneously.

Description

A kind of hydrolysis hydrogenation technique of biomass
Technical field
The present invention relates to field of biological energy source, and in particular to a kind of hydrolysis hydrogenation technique of biomass.
Background technology
The fossils non-renewable energy such as coal, crude oil, natural gas, oil shale is increasingly withered with the fast development of social economy Exhaust and they burn after the CO that generates2、SO2、NOxThe environmental pollution of getting worse caused by grade pollutants, this causes people Class has to think better of the approach for obtaining the energy and the method for improving environment.Biomass refers to all directly or indirectly using green The organic substance that color photosynthesis of plant is formed, including plant, animal, microorganism and its excretion and metabolin, it has can be again Natural disposition, low stain and widely distributed property, therefore, from energy security and environmental protection, the utilization of biomass have become Strategic emphasis for current development regenerative resource.
Biomass liquefying technology is the important component in biomass resource utilization, and the liquefaction mechanism of biomass is as follows： Biomass is cracked into oligomer first, then forms small molecule chemical combination through dehydration, dehydroxylation, dehydrogenation, deoxidation and decarboxylation again Object, micromolecular compound is then by being condensed, being cyclized, the reaction such as polymerizeing and generate new compound.Between can be divided mainly at present Two major class of liquefaction and direct liquefaction is connect, wherein, biomass Direct liquefaction technology refers under the action of solvent or catalyst, uses Hydrolysis, supercritical liquefaction are passed through hydrogen, inert gas etc., by biomass directly from solid liquid under appropriate temperature, pressure It is melted into liquid.Biomass Direct liquefaction technology mainly has pyrolysis liquefaction, catalytic liquefaction and pressurization hydrogenation liquefaction etc., especially with pressurization Hydrogenation liquefaction product yield is high, quality is good, generally comprises solid material drying, crushing, slurrying, heating, pressurization, reaction, divides From etc. complicated procedures of forming.For example, Chinese patent literature CN103242871A, which discloses a kind of heavy oil-biomass, adds hydrogen co grinding method work Skill, the technique by will be mixed to form slurry with heavy oil again after dry biomass precomminution to 40~100 mesh, and to this Catalyst and vulcanizing agent are added in slurry, and is placed in slurry bed system hydrogenation reactor, controlling reaction temperature is 370 DEG C -430 DEG C, hydrogen partial pressure 4-8MPa carries out heat from hydrogenation cracking reaction, and reaction product obtains bio oil and coke after being fractionated into.
Above-mentioned technique realizes the conversion from biomass to bio oil, but in above-mentioned technology, on the one hand, by biomass and again The slurry needs that oil is formed are delivered to by pump in slurry bed system hydrogenation reactor, and most biomass (such as stalk) are because with abundant Porosity cause its proportion relatively low, be allowed to relatively be insoluble in biomass liquefying solvent, cause the concentration of biomass in slurries compared with Low (biomass only accounts for 5~20wt% of heavy oil quality in above-mentioned technology), so as to cause pump within the unit interval to biomass Conveying capacity is limited, causes that the production efficiency of above-mentioned plus hydrogen co grinding method technique is relatively low, industrial cost is higher, energy consumption is larger；The opposing party Face, the biomass with porosity easily floats on liquefaction solvent surface, in addition larger as the furol viscosity of slurry solvent so that Above-mentioned slurry is not easy to flow, and easily causes the blocking of conveyance conduit so as to be difficult to realize the smooth transport of pump.Although the prior art is tasted Examination adds in dispersant to improve concentration and dispersibility of the biomass in slurries in slurries, but the addition of dispersant often shadow The quality of bio oil made from sound.In addition, biomass conversion ratio is relatively low (its conversion ratio is only 90% or so) in above-mentioned technology.
For this purpose, how existing biomass liquefying process is improved to increase the concentration of biomass in slurries, improve In unit interval pump to the conveying capacity of biomass, the smooth transport for realizing pump, reduce energy consumption, improve biomass conversion ratio this for A technical barrier urgently to be resolved hurrily is remained for those skilled in the art.
Invention content
Therefore, the technical problem to be solved in the present invention is to overcome in existing biomass liquefying process, pumps to biomass Conveying capacity it is few and the defects of transport is unstable, biomass conversion ratio is low, high energy consumption, and then a kind of hydrolysis of biomass is provided and is added Hydrogen technique.
For this purpose, technical solution is as follows used by the present invention solves the above problems：
A kind of hydrolysis hydrogenation technique of biomass, includes the following steps：
The slurries containing catalyst and biomass are prepared, hydrogen is passed through into the slurries to react, and are controlled anti- It is 15-20MPa to answer pressure, reaction temperature is 380-420 DEG C, and bio oil is finally made；
The biomass is stalk, and the preparation steps of the slurries are that stalk is dried successively, just crushes, compresses And separating twice, mixture then is mixed to get with the catalyst, the mixture is added in, slurrying is ground into oil product, obtained To the slurries of a concentration of 30~60wt% of stalk.
Stalk in the present invention can be wheat, rice, corn, reed, sorghum, the cereal crops stalk such as millet, It can also be the legumes stalk such as soybean, red bean, mung bean, broad bean, pea, can also be cotton, flax, ramie, hemp etc. It can also be the biomass material that a variety of stalks collectively constitute that fibre crops stalk, which can be a kind of stalk,.
By the pressure that the stalk compresses it is 0.5~3MPa, temperature 30-60 in the preparation steps of the slurries ℃。
In the preparation steps of the slurries, the drying temperature of the stalk is 50-70 DEG C, time 3-5h, the stalk Dried moisture content is less than 2wt%；Median particle size after just crushing is 100-300 μm；Median particle size is after separating twice 30-50 μm, heap density is 400-500kg/m after separating twice3。
In the slurries, the viscosity of the slurries is 500-1400mPa ﹒ s (50 DEG C).
In the slurries, the content of the biomass is 55~60wt%.
In the preparation steps of the slurries, the oil product is waste animal and vegetable oil, waste mineral oil, mineral oil or distillate In it is one or more.
Further, the waste animal and vegetable oil is one or more in gutter oil, hogwash fat or rancid oil；
The waste mineral oil is one or both of waste lubricating oil or used oil；
The mineral oil is one or more in heavy oil, residual oil, carbolineum or washing oil.
The grinding slurrying is stirring pulping, dispersion slurrying, emulsification slurrying, shears slurrying or homogeneous slurrying.
In the slurries, the content of the catalyst is 0.1~10wt%, preferably 2wt%；The grain of the catalyst Diameter is 5 μm -500 μm；
The specific method that hydrogen is passed through into the slurries is：
High pressure hydrogen is injected into the slurries, and control the volume ratios of the high pressure hydrogen and the slurries for (600~ 1000)：1, so as to form reaction raw materials；
The reaction raw materials are sent into paste state bed reactor to occur hydrolysis, cracking and hydrogenation reaction, while to described The injection cold hydrogen of high pressure in paste state bed reactor, it is 0.02~0.2m/s to control total gas velocity in the paste state bed reactor, preferably For 0.05~0.08m/s；
Wherein, the pressure of the high pressure hydrogen and the cold hydrogen of high pressure is 15-22MPa, and the temperature of the cold hydrogen of the high pressure is 50 ~135 DEG C.
The high pressure hydrogen is injected into two times in the slurries, specially：
380-420 is warming up to after high pressure medium temperature hydrogen is injected for the first time into the slurries, and by slurries heat exchange DEG C, then inject high pressure-temperature hydrogen for the second time into the slurries again；
Wherein, the temperature of the high pressure medium temperature hydrogen is 360-420 DEG C, the temperature of the high pressure-temperature hydrogen for 430~ 510℃。
The cold hydrogen is injected via 3~5 inlets on the paste state bed reactor side wall.
Storage of the catalyst in the paste state bed reactor controls the liquid phase quality in the paste state bed reactor 5~30wt%.
The time of the reaction is 30-120min.
Biomass carbon of the catalyst for the active component of load through vulcanizing treatment, the active component is oxidation It is one or more in iron, FeOOH or iron hydroxide, in terms of active component and the gross mass of biomass carbon, active component Content be 10~50wt%；
The preparation method of the biomass carbon of the active component of load includes：
(1) it is biomass high-area carbon to take biomass carbon；
(2) active component is carried on the biomass carbon carrier, the catalyst is made.
It is by the specific method that active component is carried on the biomass carbon carrier：
The biomass carbon carrier, the active component aqueous solution are hybridly prepared into suspension, adding in precipitating reagent will be living Property components precipitate on biomass carbon carrier, it is washed, dry that the catalyst is made；Wherein, the precipitating reagent for ammonium hydroxide or The aqueous solution of at least one of the carbonate of alkali metal, bicarbonate, hydroxide, the control of precipitation process temperature are 30 DEG C~90 DEG C, pH value is 7~9.
Or the catalyst is the unformed FeOOH through vulcanizing treatment.
The above-mentioned technical proposal of the present invention has the following advantages that：
1st, the hydrolysis hydrogenation technique of biomass provided by the invention, the preparation steps of slurries are to do stalk successively Dry, first crushing, compression and separating twice, are then mixed to get mixture with catalyst, feed the mixture into and ground into oil product Slurrying up to a concentration of 30~60wt% of stalk slurries, the present invention it is initiative stalk is first compressed after separating twice Treatment process, by the way that biomass is carried out compression processing, make loose stalk successively experience cave in, be closed etc. rank again, The stage of mechanically deform so that the volume of stalk is greatly lowered, and thus can reduce the porosity of stalk, increases its density and ratio Weight, is allowed to be conducive to be dispersed in oil product, and can improve its content in oil product, increases the concentration of reaction mass, this hair Content of the bright stalk in slurries may be up to 30~60wt%, 5~16wt% significantly larger than of the prior art, simultaneously because slurry The increase of biomass concentration will necessarily also improve pump within the unit interval to the conveying capacity of biomass in liquid, so as to improve entire life The efficiency of substance liquefaction process reduces industrial cost and energy consumption；It is being starched in addition, the increase of stalk proportion also helps biomass Thus suspension and dispersion in liquid can reduce the viscosity of biomass slurry, realize biomass it is slurry after slurries in the duct Smooth flow, avoid the blocking of pipeline, realize the steady operating and conveying of pump, while but also in the prior art cannot As the high viscosity waste oil of biomass liquefying solvent, such as used oil, gutter oil, rancid oil etc., can also be utilized.
The present invention is by preparing the slurries containing catalyst and biomass, then be passed through hydrogen into above-mentioned slurries to occur instead Should, and to control reaction pressure be 15-20MPa, reaction temperature is 380-420 DEG C, and bio oil is finally made, present invention process is facing Under the action of hydrogen and catalyst so that cracking, hydrogenation reaction occur for biomass, so as to fulfill turning from biomass to bio oil Change, and improve the conversion ratio of biomass, in present invention process, biomass conversion ratio may be up to 95-99%.
2nd, the hydrolysis hydrogenation technique of substance provided by the invention, by controlling compression temperature at 30-60 DEG C, then this temperature Under the rheological characteristic that can significantly increase stalk is compressed to stalk, reduce the viscosity of biomass slurry, after tested, present invention process In the viscosity of slurries that is formed by stalk and oil product be 500-1400mPa ﹒ s (50 DEG C), it is thus achieved that after biomass is slurry The smooth flow of slurries in the duct, avoids the blocking of pipeline, realizes the steady operating and conveying of pump.
3rd, the hydrolysis hydrogenation technique of biomass provided by the invention, by using paste state bed reactor, first by reaction raw materials It is sent into paste state bed reactor by reactor bottom to react, while injects cold hydrogen into reactor again, so reacted It can be by caused by the yield of light-end products after gas, liquid, the different specific weight of each material of solid and complex reaction in device Difference in specific gravity changes, and realizes the otherness control of each phase flow velocity so that water occurs from the bottom to top in reactor for biomass material Solution, cracking, hydrogenation reaction, even if heavy biomass and catalyst solid particle are with gas and light oil in the process Product rise, but top cold hydrogen effect under again it is return participate in reacting again to bottom, according to the object in reactor upper, middle and lower portion Material density is suitably adjusted into hydrogen content and cold hydrogen injection rate in the slurries of reactor, so as to fulfill unconverted biomass In the cycle of inside reactor and the balance discharge of catalyst, the abundant progress of the reactions such as hydrolysis plus hydrogen thus can ensure that, from And be conducive to improve biomass conversion ratio and biological oil yield.
4th, the hydrolysis hydrogenation technique of biomass provided by the invention, by the way that high pressure hydrogen is injected into slurries in two times, A high pressure hydrogen is respectively injected i.e. before and after heating up to slurries, the injection of previous sub-high pressure hydrogen can increase slurries in heat exchanger Disturbance, so as to avoid the deposition of solid biomass and catalyst.
5th, the hydrolysis hydrogenation technique of biomass provided by the invention, the catalyst added in slurries have passed through at vulcanization It manages, the catalyst after vulcanizing treatment has preferable Hydrogenation, can further avoid green coke so that hydrolysis hydrogenation reaction is more filled Point.
Specific embodiment
Technical scheme of the present invention will be clearly and completely described below, it is clear that described embodiment is this hair Bright 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 All other embodiments obtained under the premise of creative work are made, shall fall within the protection scope of the present invention.In addition, below Involved technical characteristic as long as they do not conflict with each other can be mutual in described different embodiments of the present invention With reference to.
Embodiment 1
A kind of hydrolysis hydrogenation technique of biomass, includes the following steps：
The pretreatment of biomass
Rice straw and reed straw are sent into drying machine at 50 DEG C dry 5h to water content less than 2wt%, then Micronizer is sent into just crush, the median after just crushing for 100 μm, then by the rice straw after first crush and Reed straw is sent into cuber and carries out compression extrusion forming under 30 DEG C of temperature, the pressure of 3MPa, carries out two wheat-middlings later Broken, the median particle size after separating twice is 30 μm, and the heap density after separating twice is 500kg/m3, it is spare.
The preparation of catalyst
(1) it is biomass high-area carbon to take biomass carbon；
(2) iron oxide is carried on above-mentioned biomass carbon carrier, vulcanizing treatment, catalyst is made.
It is by the specific method that iron oxide is carried on above-mentioned biomass carbon carrier：
The aqueous solution of above-mentioned biomass carbon carrier, iron oxide is hybridly prepared into suspension, adds in the carbon as precipitating reagent Iron oxide is deposited on biomass carbon carrier by the aqueous solution of sour sodium and ammonium hydroxide, and catalysis is made in washed, dry, vulcanizing treatment Agent, the temperature of precipitation process is 90 DEG C, pH value 7, in terms of the gross mass of iron oxide and biomass carbon carrier, the content of iron oxide For 50wt%.
The preparation of biomass slurry
Obtained biomass will be pre-processed and catalyst is mixed to get mixture, said mixture is added in hogwash fat and Stirring pulping in the miscella of residual oil forms slurries, and after testing, the total content of rice straw and reed straw is in the slurries 60wt%, the viscosity of the slurries is 500mPa ﹒ s (50 DEG C), and in above-mentioned slurries, the content of catalyst is 10wt%, is added Catalyst grain size be 5 μm.
Hydrolyze hydrogenation reaction：
Hydrogen is passed through into biomass slurry to react, control reaction pressure is 20MPa, reaction temperature is 380 DEG C, Bio oil is made；
The specific method for being passed through hydrogen is：High pressure hydrogen is injected into slurries, and controls the volume of high pressure hydrogen and slurries Than being 600：1, so as to form reaction raw materials；Will above-mentioned reaction raw materials be sent into paste state bed reactor in occur hydrolysis, cracking and Hydrogenation reaction, while the cold hydrogen of high pressure is injected into above-mentioned paste state bed reactor, total gas velocity in control paste state bed reactor is 0.2m/s；Wherein, the pressure of high pressure hydrogen and the cold hydrogen of high pressure is 22MPa, and the temperature of the cold hydrogen of high pressure is 135 DEG C；
The cold hydrogen of high pressure is injected via 3 inlets on paste state bed reactor side wall.Catalyst is in slurry reactor Storage in device accounts for the 30wt% of liquid phase quality in paste state bed reactor, reaction time 30min.
Embodiment 2
A kind of hydrolysis hydrogenation technique of biomass, includes the following steps：
The pretreatment of biomass
Wheat stalk and maize straw are sent into drying machine at 70 DEG C and do 3h to water content less than 2wt%, is then sent Enter micronizer just crush, the median after just crushing is 300 μm, then by the wheat stalk and jade after first crush Rice stalk is sent into cuber carries out compression extrusion forming under 60 DEG C of temperature, the pressure of 0.5MPa, carries out two wheat-middlings later Broken, the median particle size after separating twice is 50 μm, and the heap density after separating twice is 400kg/m3, it is spare.
The preparation of catalyst
(1) it is biomass high-area carbon to take biomass carbon；
(2) FeOOH is carried on above-mentioned biomass carbon carrier, vulcanizing treatment, catalyst is made.
It is by the specific method that FeOOH is carried on above-mentioned biomass carbon carrier：
The aqueous solution of above-mentioned biomass carbon carrier, FeOOH is hybridly prepared into suspension, is added in as precipitating reagent Sodium bicarbonate and potassium hydroxide aqueous solution, FeOOH is deposited on biomass carbon carrier, washed, dry, sulphur Change processing and catalyst is made, the temperature of precipitation process is 30 DEG C, pH value 9, with the total of FeOOH and biomass carbon carrier Quality meter, the content of FeOOH is 10wt%.
The preparation of biomass slurry
Obtained biomass will be pre-processed and catalyst is mixed to get mixture, said mixture is added in waste lubricating oil With disperse slurrying in the miscella of used oil, form slurries, after testing, the total content of wheat stalk and maize straw in the slurries For 50wt%, the viscosity of the slurries is 1400mPa ﹒ s (50 DEG C), and in above-mentioned slurries, the content of catalyst is 0.1wt%, institute The grain size of the catalyst added is 500 μm.
Hydrolyze hydrogenation reaction：
Hydrogen is passed through into biomass slurry to react, control reaction pressure is 15MPa, reaction temperature is 420 DEG C, Bio oil is made；
The specific method for being passed through hydrogen is：High pressure hydrogen is injected into slurries, and controls the volume of high pressure hydrogen and slurries Than being 1000：1, so as to form reaction raw materials；Will above-mentioned reaction raw materials be sent into paste state bed reactor in occur hydrolysis, cracking and Hydrogenation reaction, while the cold hydrogen of high pressure is injected into above-mentioned paste state bed reactor, total gas velocity in control paste state bed reactor is 0.02m/s；Wherein, the pressure of high pressure hydrogen and the cold hydrogen of high pressure is 15MPa, and the temperature of the cold hydrogen of high pressure is 50 DEG C；
The cold hydrogen of high pressure is injected via 5 inlets on paste state bed reactor side wall.Catalyst is in slurry reactor Storage in device accounts for the 5wt% of liquid phase quality in paste state bed reactor, reaction time 120min.
Embodiment 3
A kind of hydrolysis hydrogenation technique of biomass, includes the following steps：
The pretreatment of biomass
Cotton stalk is dried, cotton stalk is sent into drying machine at 60 DEG C dry 4h and is less than to water content 2wt% is then fed into micronizer and just crush, and the median after just crushing is 200 μm, then will be after first crush Cotton stalk is sent into plodder and carries out compression extrusion forming under 40 DEG C of temperature, the pressure of 2MPa, carries out two wheat-middlings later Broken, the median particle size after separating twice is 40 μm, and the heap density after separating twice is 450kg/m3, it is spare.
The preparation of catalyst
(1) it is biomass high-area carbon to take biomass carbon；
(2) iron hydroxide and FeOOH are carried on above-mentioned biomass carbon carrier, vulcanizing treatment, catalysis is made Agent.
It is by the specific method that iron hydroxide and FeOOH are carried on above-mentioned biomass carbon carrier：
By above-mentioned biomass carbon carrier, the aqueous solution of iron hydroxide and FeOOH is hybridly prepared into suspension, adds in As the ammonium hydroxide of precipitating reagent and the aqueous solution of sodium hydroxide, iron hydroxide and FeOOH are deposited in biomass carbon carrier On, washed, dry, vulcanizing treatment is made catalyst, and the temperature of precipitation process is 40 DEG C, pH value 7.5, with iron hydroxide, The total content of the gross mass meter of FeOOH and biomass carbon carrier, iron hydroxide and FeOOH is 40wt%.
The preparation of biomass slurry
Obtained biomass will be pre-processed and catalyst is mixed to get mixture, said mixture is added in heavy oil and washed Slurrying is emulsified in the miscella of oil, forms slurries, after testing, the content of cotton stalk is 55wt% in the slurries, the slurries Viscosity is 650mPa ﹒ s (50 DEG C), and in above-mentioned slurries, the content of catalyst is 2wt%, and the grain size of the catalyst added is 300μm。
Hydrolyze hydrogenation reaction：
Hydrogen is passed through into biomass slurry to react, control reaction pressure is 16MPa, reaction temperature is 400 DEG C, Bio oil is made；
The specific method for being passed through hydrogen is：High pressure hydrogen is injected into slurries, and controls the volume of high pressure hydrogen and slurries Than being 900：1, so as to form reaction raw materials；Will above-mentioned reaction raw materials be sent into paste state bed reactor in occur hydrolysis, cracking and Hydrogenation reaction, while the cold hydrogen of high pressure is injected into above-mentioned paste state bed reactor, total gas velocity in control paste state bed reactor is 0.1m/s；Wherein, the pressure of high pressure hydrogen and the cold hydrogen of high pressure is 19MPa, and the temperature of the cold hydrogen of high pressure is 105 DEG C；
The cold hydrogen of high pressure is injected via 4 inlets on paste state bed reactor side wall.Catalyst is in slurry reactor Storage in device accounts for the 15wt% of liquid phase quality in paste state bed reactor, reaction time 40min.
Embodiment 4
A kind of hydrolysis hydrogenation technique of biomass, includes the following steps：
The pretreatment of biomass
Cotton stalk and soybean stalk are sent into drying machine at 65 DEG C dry 3h to water content less than 2wt%, then Micronizer is sent into just crush, the median after just crushing for 150 μm, then by the cotton stalk after first crush and Soybean stalk is sent into cuber and carries out compression extrusion forming under 50 DEG C of temperature, the pressure of 1MPa, carries out two wheat-middlings later Broken, the median particle size after separating twice is 40 μm, and the heap density after separating twice is 420kg/m3, it is spare.
The preparation of biomass slurry
Obtained biomass will be pre-processed and mixed as the unformed FeOOH through vulcanizing treatment of catalyst To mixture, said mixture is added in into rancid oil shearing slurrying and forms slurries, after testing, in the slurries cotton stalk and The total content of soybean stalk is 30wt%, and the viscosity of the slurries is 1000mPa ﹒ s (50 DEG C), the content of unformed FeOOH For 2wt%, the grain size of unformed FeOOH added is 400 μm.
Hydrolyze hydrogenation reaction：
Hydrogen is passed through into biomass slurry to react, control reaction pressure is 18MPa, reaction temperature is 380 DEG C, Bio oil is made；
The specific method for being passed through hydrogen is：Inject high pressure hydrogen in two times into biomass slurry, specially：To slurries After middle first time injection high pressure medium temperature hydrogen, and slurries heat exchange is warming up to 380 DEG C, then second of injection is high into slurries again Super pressure-high temperature hydrogen；Wherein, the temperature of high pressure medium temperature hydrogen is 360 DEG C, and the temperature of high pressure-temperature hydrogen is 510 DEG C；The height being passed through It is 950 to press the total volume of medium temperature hydrogen and high pressure-temperature hydrogen and the volume ratio of slurries：1, so as to form reaction raw materials；It will be above-mentioned Reaction raw materials are sent into paste state bed reactor to occur to hydrolyze hydrogenation reaction, while inject high pressure into above-mentioned paste state bed reactor Cold hydrogen, it is 0.05m/s to control total gas velocity in paste state bed reactor；Wherein, the pressure of high pressure hydrogen and the cold hydrogen of high pressure is 21MPa, the temperature of the cold hydrogen of high pressure is 75 DEG C；
The cold hydrogen of high pressure is injected via 4 inlets on paste state bed reactor side wall.Catalyst is in slurry reactor Storage in device accounts for the 15wt% of liquid phase quality in paste state bed reactor, reaction time 40min.
Embodiment 5
A kind of hydrolysis hydrogenation technique of biomass, includes the following steps：
The pretreatment of biomass
Pea stalk, broomcorn straw and rice straw are sent into drying machine at 50 DEG C dry 3h to be less than to water content 2wt% is then fed into micronizer and just crush, and the median after just crushing is 250 μm, then will be after first crush Pea stalk, broomcorn straw and rice straw are sent into plodder to carry out compressing under 55 DEG C of temperature, the pressure of 1.5MPa and be squeezed It is molded, separating twice is carried out later, and the median particle size after separating twice is 45 μm, and the heap density after separating twice is 440kg/m3, it is spare.
The preparation of biomass slurry
Obtained biomass will be pre-processed to mix with the unformed FeOOH through vulcanizing treatment as catalyst To mixture, said mixture is added in homogeneous slurrying in the miscella of hogwash fat and residual oil, forms slurries, it after testing, should The total content of pea stalk, broomcorn straw and rice straw is 40wt% in slurries, and the viscosity of the slurries is 820mPa ﹒ s (50 DEG C), the content of unformed FeOOH is 8wt%, and the grain size of unformed FeOOH added is 300 μm.
Hydrolyze hydrogenation reaction：
Hydrogen is passed through into biomass slurry to react, control reaction pressure is 17MPa, reaction temperature is 420 DEG C, Bio oil is made；
The specific method for being passed through hydrogen is：Inject high pressure hydrogen in two times into the slurries, specially：Into slurries For the first time after injection high pressure medium temperature hydrogen, and slurries heat exchange is warming up to 420 DEG C, then injects high pressure for the second time into slurries again High-temperature hydrogen；Wherein, the temperature of high pressure medium temperature hydrogen is 420 DEG C, and the temperature of high pressure-temperature hydrogen is 430 DEG C；The high pressure being passed through The volume ratio of the total volume and slurries of medium temperature hydrogen and high pressure-temperature hydrogen is 900：1, so as to form reaction raw materials；It will be above-mentioned anti- Raw material is answered to be sent into paste state bed reactor that hydrolysis plus hydrogen occursReaction, while injection high pressure is cold into above-mentioned paste state bed reactor Hydrogen, it is 0.08m/s to control total gas velocity in paste state bed reactor；Wherein, the pressure of high pressure hydrogen and the cold hydrogen of high pressure is 20MPa, the temperature of the cold hydrogen of high pressure is 95 DEG C；
The cold hydrogen of high pressure is injected via 5 inlets on paste state bed reactor side wall.Catalyst is in slurry reactor Storage in device accounts for the 25wt% of liquid phase quality in paste state bed reactor, reaction time 50min.
Embodiment 6
A kind of hydrolysis hydrogenation technique of biomass, includes the following steps：
The pretreatment of biomass
Wheat stalk and flax stalk are sent into drying machine at 70 DEG C dry 5h to water content less than 2wt%, then Micronizer is sent into just crush, the median after just crushing for 300 μm, then by the wheat stalk after first crush and Flax stalk is sent into plodder and carries out compression extrusion forming under 60 DEG C of temperature, the pressure of 3MPa, carries out two wheat-middlings later Broken, the median particle size after separating twice is 48 μm, and the heap density after separating twice is 490kg/m3, it is spare.
The preparation of biomass slurry
Obtained biomass will be pre-processed to mix with the unformed FeOOH through vulcanizing treatment as catalyst To mixture, said mixture is added in stirring pulping in the miscella of carbolineum and recycle fraction oil, forms slurries；Through inspection It surveys, the total content of wheat stalk and flax stalk is 45wt% in the slurries, and the viscosity of the slurries is 530mPa ﹒ s (50 DEG C), nothing The content of sizing FeOOH is 0.3wt%, and the grain size of unformed FeOOH added is 20 μm.
Hydrolyze hydrogenation reaction：
Hydrogen is passed through into biomass slurry to react, control reaction pressure is 19MPa, reaction temperature is 390 DEG C, Bio oil is made；
The specific method for being passed through hydrogen is：Inject high pressure hydrogen in two times into the slurries, specially：Into slurries For the first time after injection high pressure medium temperature hydrogen, and slurries heat exchange is warming up to 390 DEG C, then injects high pressure for the second time into slurries again High-temperature hydrogen；Wherein, the temperature of high pressure medium temperature hydrogen is 400 DEG C, and the temperature of high pressure-temperature hydrogen is 490 DEG C；The high pressure being passed through The volume ratio of the total volume and slurries of medium temperature hydrogen and high pressure-temperature hydrogen is 800：1, so as to form reaction raw materials；It will be above-mentioned anti- Raw material is answered to be sent into paste state bed reactor that hydrolysis plus hydrogen occursReaction, while injection high pressure is cold into above-mentioned paste state bed reactor Hydrogen, it is 0.07m/s to control total gas velocity in paste state bed reactor；Wherein, the pressure of high pressure hydrogen and the cold hydrogen of high pressure is 22MPa, the temperature of the cold hydrogen of high pressure is 105 DEG C；
The cold hydrogen of high pressure is injected via 5 inlets on paste state bed reactor side wall.Catalyst is in slurry reactor Storage in device accounts for the 23wt% of liquid phase quality in paste state bed reactor, reaction time 100min.
Embodiment 7
A kind of hydrolysis hydrogenation technique of biomass, includes the following steps：
The pretreatment of biomass
Hemp stalk and broad bean stalk are sent into drying machine at 55 DEG C dry 3.5h to water content less than 2wt%, so It is sent into micronizer afterwards just crush, the median particle size after just crushing is 100 μm, then by the hemp stalk after first crush It is sent into cuber with broad bean stalk and carries out compression extrusion forming under 30 DEG C of temperature, the pressure of 0.5MPa, carry out two later Secondary crushing, the median particle size after separating twice are 33 μm, and the heap density after separating twice is 500kg/m3, it is spare.
The preparation of catalyst
(1) it is biomass high-area carbon to take biomass carbon；
(2) iron oxide is carried on above-mentioned biomass carbon carrier, vulcanizing treatment, catalyst is made.
It is by the specific method that iron oxide is carried on above-mentioned biomass carbon carrier：
The aqueous solution of above-mentioned biomass carbon carrier, iron oxide is hybridly prepared into suspension, adds in the hydrogen as precipitating reagent Iron oxide is deposited on biomass carbon carrier by the aqueous solution of sodium oxide molybdena and ammonium hydroxide, and washed, dry, vulcanizing treatment, which is made, urges Agent, the temperature of precipitation process is 80 DEG C, pH value 7.5, in terms of the gross mass of iron oxide and biomass carbon carrier, iron oxide Content is 50wt%.
The preparation of biomass slurry
Obtained biomass will be pre-processed and above-mentioned catalyst is mixed to get mixture, added the mixture to gutter oil Middle dispersion slurrying forms slurries, and after testing, hemp stalk and the total content of broad bean stalk are 55wt% in the slurries, the slurries Viscosity for 510mPa ﹒ s (50 DEG C), the content of catalyst is 0.2wt%, and the grain size of the catalyst added is 12 μm.
Hydrolyze hydrogenation reaction：
Hydrogen is passed through into biomass slurry to react, control reaction pressure is 20MPa, reaction temperature is 410 DEG C, Bio oil is made；
The specific method for being passed through hydrogen is：Inject high pressure hydrogen in two times into the slurries, specially：Into slurries For the first time after injection high pressure medium temperature hydrogen, and slurries heat exchange is warming up to 410 DEG C, then injects high pressure for the second time into slurries again High-temperature hydrogen；Wherein, the temperature of high pressure medium temperature hydrogen is 410 DEG C, and the temperature of high pressure-temperature hydrogen is 480 DEG C；The high pressure being passed through The volume ratio of the total volume and slurries of medium temperature hydrogen and high pressure-temperature hydrogen is 650：1, so as to form reaction raw materials；It will be above-mentioned anti- Raw material is answered to be sent into paste state bed reactor so that hydrolysis, cracking occurs and adds hydrogenReaction, while noted into above-mentioned paste state bed reactor Enter the cold hydrogen of high pressure, it is 0.07m/s to control total gas velocity in paste state bed reactor；Wherein, the pressure of high pressure hydrogen and the cold hydrogen of high pressure It is 22MPa, the temperature of the cold hydrogen of high pressure is 130 DEG C；
The cold hydrogen of high pressure is injected via 3 inlets on paste state bed reactor side wall.Catalyst is in slurry reactor Storage in device accounts for the 7wt% of liquid phase quality in paste state bed reactor；The time of reaction is 110min.
Embodiment 8
A kind of hydrolysis hydrogenation technique of biomass, includes the following steps：
The pretreatment of biomass
Maize straw and ramie stalk are sent into drying machine at 65 DEG C dry 4.5h to water content less than 2wt%, so It is sent into micronizer afterwards just crush, the median particle size after just crushing is 300 μm, then by the maize straw after first crush It is sent into cuber with ramie stalk and carries out compression extrusion forming under 50 DEG C of temperature, the pressure of 2.5MPa, carry out two later Secondary crushing, the median particle size after separating twice are 44 μm, and the heap density after separating twice is 410kg/m3, it is spare.
The preparation of biomass slurry
Obtained biomass will be pre-processed and mixed as the unformed FeOOH through vulcanizing treatment of catalyst To mixture, said mixture is added in, slurrying is emulsified into gutter oil, form slurries, after testing, maize straw in the slurries It is 57wt% with the total content of ramie stalk, the viscosity of the slurries is 1130mPa ﹒ s (50 DEG C), the unformed hydroxyl through vulcanizing treatment The content of base iron oxide is 4wt%, and the grain size of the unformed FeOOH through vulcanizing treatment added is 120 μm.
Hydrolyze hydrogenation reaction：
Hydrogen is passed through into biomass slurry to react, control reaction pressure is 17MPa, reaction temperature is 400 DEG C, Bio oil is made；
The specific method for being passed through hydrogen is：Inject high pressure hydrogen in two times into the slurries, specially：Into slurries For the first time after injection high pressure medium temperature hydrogen, and slurries heat exchange is warming up to 400 DEG C, then injects high pressure for the second time into slurries again High-temperature hydrogen；Wherein, the temperature of high pressure medium temperature hydrogen is 410 DEG C, and the temperature of high pressure-temperature hydrogen is 500 DEG C；The high pressure being passed through The volume ratio of the total volume and slurries of medium temperature hydrogen and high pressure-temperature hydrogen is 950：1, so as to form reaction raw materials；It will be above-mentioned anti- Raw material is answered to be sent into paste state bed reactor that hydrolysis plus hydrogen occursReaction, while injection high pressure is cold into above-mentioned paste state bed reactor Hydrogen, it is 0.05m/s to control total gas velocity in paste state bed reactor；Wherein, the pressure of high pressure hydrogen and the cold hydrogen of high pressure is 21MPa, the temperature of the cold hydrogen of high pressure is 75 DEG C；
The cold hydrogen of high pressure is injected via 4 inlets on paste state bed reactor side wall.Catalyst is in slurry reactor Storage in device accounts for the 15wt% of liquid phase quality in paste state bed reactor, reaction time 40min.
Test example 1
The distribution of product prepared by embodiment 1-8 methods using the present invention is compared, it is as shown in table 1 below.
1 embodiment 1-8 product profiles versus of table
As it can be seen from table 1 the biomass conversion ratio that method using the present invention obtains is 95-99%, oil phase yield is 70-80%, level of residue be less than 0.1wt%, and in obtained oil phase carbon content be 73-90wt%, hydrogen content 5-17wt%, oxygen Content is 5-10wt%.
Obviously, the above embodiments are merely examples for clarifying the description, and is not intended to 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 the obvious variation thus extended out or Among changing still in the protection domain of the invention.

Claims (11)

1. the hydrolysis hydrogenation technique of a kind of biomass, which is characterized in that include the following steps：
The slurries containing catalyst and biomass are prepared, hydrogen are passed through into the slurries to react, and control reaction pressure Power is 15-20MPa, reaction temperature is 380-420 DEG C, and bio oil is finally made；
The biomass be stalk, the preparation steps of the slurries be stalk is dried successively, just crush, compress and two Secondary crushing is then mixed to get mixture with the catalyst, the mixture is added in, slurrying is ground into oil product, obtain straw The slurries of a concentration of 30~60wt% of stalk.
2. the hydrolysis hydrogenation technique of biomass according to claim 1, which is characterized in that the preparation steps of the slurries In, by the pressure that the stalk compresses be 0.5~3MPa, temperature is 30-60 DEG C.
3. the hydrolysis hydrogenation technique of biomass according to claim 1 or 2, which is characterized in that the preparation step of the slurries In rapid,
The drying temperature of the stalk is 50-70 DEG C, time 3-5h, and the dried moisture content of stalk is less than 2wt%；Just Median particle size after crushing is 100-300 μm；Median particle size is 30-50 μm after separating twice, heap density is after separating twice 400-500kg/m3。
4. according to the hydrolysis hydrogenation technique of claim 1-3 any one of them biomass, which is characterized in that in the slurries In, the content of the biomass is 55~60wt%.
5. according to the hydrolysis hydrogenation technique of claim 1-4 any one of them biomass, which is characterized in that the slurries are matched In step processed, the oil product is one or more in waste animal and vegetable oil, waste mineral oil, mineral oil or distillate.
6. according to the hydrolysis hydrogenation technique of claim 1-5 any one of them biomass, which is characterized in that in the slurries In, the content of the catalyst is 0.1~10wt%；The grain size of the catalyst is 5 μm -500 μm.
7. according to the hydrolysis hydrogenation technique of claim 1-6 any one of them biomass, which is characterized in that
The specific method that hydrogen is passed through into the slurries is：
High pressure hydrogen is injected into the slurries, and control the volume ratios of the high pressure hydrogen and the slurries for (600~ 1000)：1, so as to form reaction raw materials；
The reaction raw materials are sent into paste state bed reactor to occur hydrolysis, cracking and hydrogenation reaction, while to the slurry The injection cold hydrogen of high pressure in bed reactor, it is 0.02~0.2m/s to control total gas velocity in the paste state bed reactor, preferably 0.05~0.08m/s；
Wherein, the pressure of the high pressure hydrogen and the cold hydrogen of high pressure is 15~22MPa, the temperature of the cold hydrogen of the high pressure for 50~ 135℃。
8. the hydrolysis hydrogenation technique of biomass according to claim 7, which is characterized in that by the high pressure hydrogen in two times It is injected into the slurries, specially：
380-420 DEG C is warming up to after high pressure medium temperature hydrogen is injected for the first time into the slurries, and by slurries heat exchange, and Inject high pressure-temperature hydrogen for the second time into the slurries again afterwards；
Wherein, the temperature of the high pressure medium temperature hydrogen is 360-420 DEG C, and the temperature of the high pressure-temperature hydrogen is 430~510 ℃。
9. the hydrolysis hydrogenation technique of biomass according to claim 7 or 8, which is characterized in that the catalyst is described Storage in paste state bed reactor controls 5~30wt% of the liquid phase quality in the paste state bed reactor.
10. according to the hydrolysis hydrogenation technique of claim 1-9 any one of them biomass, which is characterized in that the reaction Time is 30-120min.
11. according to the hydrolysis hydrogenation technique of claim 1-10 any one of them biomass, which is characterized in that the catalyst For the biomass carbon of the active component of load through vulcanizing treatment, the active component is iron oxide, FeOOH or hydrogen-oxygen Change one or more in iron；
Or the catalyst is the unformed FeOOH through vulcanizing treatment.
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