CN108219820A - A kind of technique for producing fuel oil and industrial chemicals using coal and biomass - Google Patents
A kind of technique for producing fuel oil and industrial chemicals using coal and biomass Download PDFInfo
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- CN108219820A CN108219820A CN201711431415.4A CN201711431415A CN108219820A CN 108219820 A CN108219820 A CN 108219820A CN 201711431415 A CN201711431415 A CN 201711431415A CN 108219820 A CN108219820 A CN 108219820A
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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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
- C10G1/08—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
-
- 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
-
- 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
-
- 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
Abstract
The present invention relates to clean energy technology fields, and in particular to a kind of coal and the common sweetening process of biomass.The present invention has successfully obtained the biomass coal-water slurry that solid content is high and can steadily be conveyed with pump by first carrying out " compression+crushing+crush again " processing to coal and biomass material, then prepare slurries.Present invention process causes coal first to be hydrolyzed with biomass, primary cracking, hydrogenation reaction and drastic cracking, hydrogenation reaction occur successively again for gained hydrolysate, so as to fulfill from coal and transformation of the biomass to fuel oil and industrial chemicals, coal is with biomass conversion ratio up to 95~99%, the yield of fuel oil is up to 65~85% or so, and green coke amount is less than 4%.
Description
Technical field
The present invention relates to clean energy technology fields, and in particular to a kind of coal and the common sweetening process of biomass.
Background technology
At present, using coal as main energy sources, traditional coal utilization mode is burning in China, but caused by coal burning
Atmosphere polluting problem getting worse；Also, the coal quality in China declines year by year so that raw coal cleaning percent carries year after year
Height, coal washing waste water bring serious water pollution.Severe environmental problem has made energy resource structure be adjusted to as China's energy development
One of vital task.However, the energy resources storage situation in China itself is oil-poor rich coal, need to rely on every year a large amount of
Petroleum import could meet production development demand, if by reducing to coal resources using adjusting the energy knot in China
Structure, the not only vacant energy resources of rich reserves, can also greatly increase the import volume of oil, this will seriously affect China
Energy security.
The Energy restructuring mode for being more suitable for China's national situation is to realize that the clean and effective of coal resources utilizes.Wherein,
Including lique faction of coal technology.The technology of refining is a kind of coal liquefaction technology to grow up in the recent period to kerosene altogether, has become coal cleaning
The research hotspot utilized.For example, Chinese patent literature CN102191072 discloses the coal liquefaction technology that a kind of kerosene refines altogether,
Coal particle and oil are configured to suspension by the technology first, make the suspension successively by two series connection added with catalyst and
The ebullated bed of hydrogen is further added so as to which liquefaction reaction occur, then by obtained lighter component feeding fixed bed reactors
Hydrogen reacts, and finally obtains naphtha, kerosene and/or diesel oil and heavy component.Reaction condition in described two ebullated beds according to
It is secondary be 325~420 DEG C, 16~20MPa and 350~450 DEG C, 16~20MPa, and the temperature of second ebullated bed is always
Higher than first 10 DEG C of ebullated bed or more；The reaction condition of the fixed bed reactors is 250~480 DEG C, 2~25MPa.
However, the technology has the following problems jointly with most kerosene calendering process in the prior art：
1. liquefaction efficiency is limited
The kerosene slurry obtained by coal dust and oil preparation needs to be conveyed into Hydrocracking device by pump, in order to ensure the steady of pump
Operating and conveying, the viscosity of kerosene slurry can not be too high, and as the heavy oil of dispersant, residual oil etc. is more sticky in coal
Liquid, this allow for kerosene altogether in refining technology in kerosene slurry coal dust can not excessively high it is limited so as to cause the concentration of reaction mass,
Cause liquefaction efficiency relatively low.
2. hydrogen-consuming volume is big
Coal to be hydrocracked mechanism as follows：
First stage, pyrolysis of coal generation preasphaltene, asphaltene, and adjoint some gases of generation, liquefaction oil and macromolecular
Condensation polymer.
Second stage, under rich hydrogen condition, a part of preasphaltene is hydrogenated to liquefaction oil, also there is part macromolecular polycondensation
Object again hydrocracking generation low molecule quality liquefaction oil.
When temperature is excessively high or hydrogen supply is insufficient, the insoluble organic matter in part in preasphaltene and asphaltene can generate charcoal or half
It is burnt.The hydrocracking reaction that the high concentration and high partial pressures of hydrogen are conducive to coal carries out, and reduce green coke to forward direction.So kerosene is total to
Often hydrogen-consuming volume is very high for refining technology.
In order to improve liquefaction efficiency, researcher is dedicated to improving the content of coal dust in kerosene slurry, such as attempts as far as possible
Reduction coal powder size, in the hope of improving the ratio of coal dust by increasing dispersibility of the coal dust in kerosene slurry.However, coal dust has
There is a large amount of pore structure, reduce the operation of coal powder size so that these micro-pores further expose, so as to adsorb largely
Water.As a result, being starched by the kerosene that the coal dust of smaller particle size is prepared, under identical coal dust weight proportion, viscosity is bigger instead
The kerosene slurry higher that the coal dust of particle is prepared can not realize the smooth transport of pump at all.
Researcher attempts have been made to oil be replaced to carry out lique faction of coal, technical paper as hydrogen supply dissolvent by the use of water《Water or
The Direct Hydrogenation liquefaction performance of Shengli Brown under naphthane medium》In disclose using water as medium carry out lignite hydrogenation liquefaction skill
Art scheme, the technology carry out the hydrogenation liquefaction reaction of lignite in autoclave at 380 DEG C, when making catalyst using FeS, hydrogen is made
During for atmosphere, the total conversion of lignite is only 40.6%, and hydrocarbon yield and asphalitine yield are respectively 39.2% and 1.4%.This
It is because of the hydrogen supply of water itself and dissolving H2Ability it is all weaker, can not fully meet the needs of pyrolysis of coal adds hydrogen, so causing
The conversion ratio of lignite is relatively low.
In order to reduce the consumption to hydrogen, researcher attempts to realize with the common hydrogenation of coal using biomass.Kerosene
The hydrogen source reacted in refining technology with the coal dust of cracking altogether mostlys come from：The hydrogen being dissolved in the water changes life under catalyst action
Into reactive hydrogen, water can be supplied to or transmission hydrogen, coal crack in itself caused by reactive hydrogen and reaction generation hydrogen.It is and biological
The H/C higher of matter, researcher wish just to reduce the hydrogen-consuming volume of coal liquefaction by using the hydrogen in biomass, slows down reaction
The severity of condition realizes the mild liquefaction of coal.
The liquefaction mechanism of biomass is as follows：Biomass is cracked into oligomer first, then again through dehydration, dehydroxylation, dehydrogenation,
Deoxidation and decarboxylation and form micromolecular compound, micromolecular compound is then by being condensed, being cyclized, the reaction such as polymerizeing and generate
New compound.Studies have reported that, wood powder, which is pyrolyzed the product to be formed, contributes to coal liquefaction intermediate product (preasphaltene and pitch
Alkene) hydrogenation reaction, and then formed liquid oil；The addition of biomass also helps the pyrolysis removing of sulphur and nitrogen in coal, and prevents
Cohering between particle during pyrolysis of coal.
But since kerosene slurry has had very high viscosity in itself, the addition of biological particles can cause viscosity further
It increases and can not be conveyed with pump, so being limited only to utilize in the lab for the common liquefaction of coal and biomass at present
The relatively low naphthane of viscosity carries out the dispersion of coal dust and biological particles as solvent.We once attempt molten as hydrogen supply using water
Agent carries out the co grinding method technique of coal and biomass, but due to the characteristic of biomass, it is obtained only under extremely low concentration
Slurries just have mobility, that is to say the biomass coal-water slurry that the higher concentration with preferable mobility can not be made at all,
Lead to it because can not can not industrially realize that hydrogenation liquefaction reacts with when pumping conveying and be unfavorable for the dispersion of catalyst.
In conclusion how to improve the liquefaction efficiency of coal liquefaction, and further reduce the glutinous of biomass and the common slurrying of coal
Degree so as to fulfill the mixing of coal and biomass, reduces hydrogen consumption, is the still unsolved technical barrier of current those skilled in the art.
Invention content
Technical problems to be solved first of the invention are to overcome the coal dust content of coal slurry in the prior art limited and cause
The problem of liquefaction efficiency is relatively low, and further overcome be not carried out coal in the prior art on this basis, the slurrying of biomass mixes
The defects of refining production technology, and then provide a kind of hydrogen consumption less, the high coal of liquefaction oil yield and biomass production fuel oil and chemical industry
The technique of raw material.
For this purpose, technical solution is as follows used by the present invention solves the above problems：
A kind of technique that fuel oil and industrial chemicals are produced using coal and biomass, is included the following steps：
The preparation of biomass coal-water slurry：
Biomass collection simultaneously controls moisture content to be less than 2wt%, and it is 100~300 μm to be then crushed to median；
Biomass after crushing is subjected to compression forming, compression pressure is 2~5MPa, and compression temperature is 30~60 DEG C；
By the pulverization process again of the biomass after compression forming, it is 30~50 μm to be crushed to median, obtains biomass powder
End；
It collects coal and moisture content is controlled to be less than 2wt%, it is 50~100 μm to be then crushed to median, and compression temperature is
30~60 DEG C；
Compression forming is carried out to the coal after crushing, compression pressure is 5~15MPa；
To the pulverization process again of the coal after compression forming, it is 30~100 μm to be crushed to median, obtains coal dust；
By the powdered biomass, the coal dust, the first catalyst, vulcanizing agent mix with solvent naphtha, grind slurrying and obtain
Biomass coal-water slurry, the powdered biomass and the coal dust account for 55~65wt% of the biomass coal-water slurry altogether；
The preparation of catalyst slurry：Second catalyst, vulcanizing agent and water are mixed to prepare catalyst slurry, for use；
Level-one hydrogenation reaction：Hydrogen is passed through into the biomass coal-water slurry so that level-one hydrogenation reaction occurs, and is controlled anti-
It is 15~20MPa to answer pressure, reaction temperature is 200~300 DEG C, obtains level-one hydrogenation products；
Secondary hydrogenation reacts：The catalyst slurry is added in into the level-one hydrogenation products and is passed through hydrogen to occur two
Grade hydrogenation reaction, control reaction pressure is 15~20MPa, reaction temperature is 380~420 DEG C, obtains secondary hydrogenation product；
The separation of product：By the secondary hydrogenation product carry out gas, liquid, solid three phase separation, then the bio oil to obtaining into
Row distillation, the distillate that 200 DEG C of ＜ are used to prepare industrial chemicals, remaining is used as fuel oil；
In the preparation steps of biomass coal-water slurry, when carrying out the mixing, for first by the powdered biomass and described
Coal dust carries out ash disposal and after being pre-mixed with first catalyst and the vulcanizing agent, then by gained premix with it is described
Water mixes, alternatively, directly to mix the powdered biomass, the coal dust, the catalyst, the vulcanizing agent and the water
It closes.
In the biomass coal-water slurry, a concentration of 15~30wt% of biomass, a concentration of 35~50wt% of coal dust.
Moisture content is controlled using drying and dewatering, the drying and dewatering temperature is 50~70 DEG C, the drying and dewatering time for 3~
5h。
The heap density that the powdered biomass is controlled in the preparation steps of biomass coal-water slurry is 300~500kg/m3, control
The heap density for making the coal dust is 1200~1300kg/m3。
The time of the grinding slurrying is 2~8min.
In the step of biomass coal-water slurry is prepared：
The granularity of first catalyst is 5~500 μm.
The mass ratio of the vulcanizing agent and first catalyst is (0.4~1)：1；
The additive amount of first catalyst is 0.1~10wt% of the biomass coal-water slurry quality, preferably
2wt%.
The specific method that hydrogen is passed through in the level-one hydrogenation reaction step is：
High pressure hydrogen is injected into the biomass coal-water slurry, and controls the high pressure hydrogen and the biomass coal-water slurry
Volume ratio be (600~1000)：1, so as to form first order reaction raw material；The first order reaction raw material is sent into the first slurry bed system
Level-one hydrogenation reaction occurs in reactor, while the cold hydrogen of high pressure is injected into first paste state bed reactor, described in control
Total gas velocity in first paste state bed reactor is 0.02~0.2m/s, preferably 0.05~0.08m/s；
The pressure of the high pressure hydrogen and the cold hydrogen of high pressure is 15~25MPa, and the temperature of the cold hydrogen of the high pressure is 50~135
℃。
The high pressure hydrogen is injected into two times in the biomass coal-water slurry, specially：
Biomass coal-water slurry heat exchange is risen after injecting high pressure medium temperature hydrogen for the first time into the biomass coal-water slurry
Temperature then injects high pressure-temperature hydrogen for the second time into the biomass coal-water slurry again to 200~350 DEG C；
The temperature of the high pressure medium temperature hydrogen is 180~350 DEG C, and the temperature of the high pressure-temperature hydrogen is 360~510
℃。
In the secondary hydrogenation reaction step：
The mass ratio of the second catalyst described in the catalyst slurry and the solvent naphtha is (1~2)：10；
The additive amount of second catalyst is 0.5~2wt% of the level-one hydrogenation products quality；
The mass ratio of the vulcanizing agent and second catalyst is (0.01~1)：1；
The granularity of second catalyst is 5~500 μm..
The method that hydrogen is passed through in the secondary hydrogenation reaction step is：
The mixture of the level-one hydrogenation products and the catalyst slurry is warming up to 380~480 DEG C, preferably 430
DEG C, then the mixture is fed through in the second paste state bed reactor and to be passed through high pressure-temperature hydrogen anti-secondary hydrogenation occurs
Should, while the cold hydrogen of high pressure is injected into second paste state bed reactor, and control total in second paste state bed reactor
Gas velocity is 0.06~0.1m/s, and the volume ratio of hydrogen and the level-one hydrogenation products is (1000~1500)：1；
The pressure of the high pressure-temperature hydrogen and the cold hydrogen of high pressure is 13~27MPa, the temperature of the high pressure-temperature hydrogen
It it is 430~480 DEG C, the temperature of the cold hydrogen of high pressure is 50~135 DEG C.
Storage of first catalyst in first paste state bed reactor is controlled in first slurry reactor
5~30wt% of liquid phase quality in device, storage of second catalyst in second paste state bed reactor are controlled in institute
State 5~30wt% of liquid phase quality in the second paste state bed reactor.
The time of the level-one hydrogenation reaction is 30~60min, and the time of the secondary hydrogenation reaction is 30~60min.
Pressure is additionally included in be 7~23MPa, carry out the secondary hydrogenation product under conditions of temperature is 250~460 DEG C
The step of hydroforming.
First catalyst is the biomass carbon that load has the first active component, and first active component is oxidation
It is one or more in iron, FeOOH or iron hydroxide；Second catalyst is the life that load has the second active component
Substance charcoal, second active component are one or more in the oxide of Mo, W, Fe, Co, Ni or Pd；
Or first catalyst be amorphous Fe oxides, second catalyst be load have the unformed of third active component
Aluminium oxide, one kind in the oxide of the third active component selected from periodic table of elements Section VI B, VIIB or group VIII metal or
It is a variety of.
The coal is low-order coal.
(load has for the first catalyst (load has the biomass carbon of the first active component) and the second catalyst in the present invention
The biomass carbon of two active components) preparation method it is as follows：
The preparation of first catalyst：
(1) it is the first biomass carbon carrier to choose biomass carbon；
(2) the first active component is carried on the first biomass carbon carrier, the first catalyst is made.
In terms of metallic element quality, first active component account for the first biomass carbon carrier quality 10%~
50%.
The detailed process that first active component is carried on to the first biomass carbon carrier is：By described
The aqueous solution of one active component and the first biomass carbon carrier are hybridly prepared into suspension, add in precipitating reagent by the first active component
It is deposited on the first biomass carbon carrier, it is washed, dry that first catalyst is made；Wherein, the precipitating reagent is ammonium hydroxide
Or the aqueous solution of at least one of the carbonate of alkali metal, bicarbonate, hydroxide, the control of precipitation process temperature for 30 DEG C~
90 DEG C, pH value is 7~9.
The preparation of second catalyst：
(1) biomass carbon is acidified or basification after, the second biomass carbon carrier is made；
(2) by the second active component and the second biomass carbon carrier mixed grinding, the second catalyst is made.
In terms of metallic element quality, second active component account for the second biomass carbon carrier quality 1%~
5%.
The mixed grinding step by the second active component and the second biomass carbon carrier is：Described second is lived
Property component and the second biomass carbon carrier through vibro-grinding and/or plane lapping and/or ball milling obtain grain size for 5 μm~
500 μm of the second catalyst.
H in the acid medium of the acidification+Substance withdrawl syndrome be 0.5mol/L~5mol/L；The biomass
Charcoal is 1 with the acid medium volume ratio:5~1:15, souring temperature is 30~80 DEG C, and acidificatoin time is 1h~10h；The alkali
Change OH in the alkaline medium of processing-Substance withdrawl syndrome be 0.5mol/L~5mol/L；The biomass carbon and the alkalinity
Medium volume ratio is 1:5~1:15, alkalization temperature is 30 DEG C~80 DEG C, and alkalization time is 1h~10h.
The above-mentioned technical proposal of the present invention has the following advantages that：
1st, the coal that realizes for the first time of the invention liquefies with mixing of the biomass using water as hydrogen supply dissolvent.By to life
Substance, coal be dehydrated, crushed, being compressed, being crushed again, first this technological process of slurry, grinding slurrying, and is passed through to crushing
Grain size and contractive condition it is preferred, be successfully made biomass and coal content reach 55~65wt%, and viscosity be only 450~
The biomass coal-water slurry of 1100mPas (50 DEG C).
Compression processing coal is enabled to cave in, be closed with the pore structure inside biological material, occur plastic flow with
Plastic deformation, so as to substantially increase the density of coal and biomass material, good can be dispersed in water；Meanwhile hole
Caving in and being closed for gap structure avoids coal and absorption of the biomass to water so that water can give full play to it as dispersant
Effect；It was found that compression temperature has a significant impact for the degree of plastic flow and plastic deformation, temperature is higher obtain it is close
Degree is bigger, however temperature is excessively high, and material can be caused to decompose or bring other problems, so using 30~60 DEG C as pressure
Temperature during contracting.Compressed crushing operation again increases the accessible area of raw material so that raw material and catalyst and water
It can preferably contact, the transmission of hydrogen can be strengthened, greatly reducing raw material can not be with hydrogen and catalysis when being in hole shape structure
Agent contact is so as to the situation of reaction.
" crushing+compression+crush again " provided by the invention, which can be suitable for all inside, has the coal material of pore structure
Material and biological material, the especially biomass material to the porosity and looseness such as the low-order coals such as lignite raw material and stalk, rice husk；
The paste-forming properties of high-concentration raw substance water-coal-slurry obtained are good, and mobility is high, can not only can effectively be carried directly with the steady conveying of pump
High transport system running stability, liquefying plant utilization ratio and liquefaction efficiency meet the feed needs of subsequent treatment process, also
The clean and effective for realizing colm and biomass utilizes；Coal and biomass it is close adjacent so that caused by biomass pyrolytic
Hydrogen can add the part hydrogen source of hydrogen as pyrolysis of coal, reduce the consumption to hydrogen.
Present invention process causes coal and the hydrolysate of biomass that primary cracking, hydrogenation reaction and depth occur successively and splits
Change, hydrogenation reaction, so as to fulfill from coal and transformation of the biomass to fuel oil and industrial chemicals, coal and biomass conversion ratio are reachable
95~99%, the yield of fuel oil is up to 65~85% or so, and green coke amount is less than 4%.
2nd, the present invention further coordinates the process screened to solid material, can ensure to prepare bio-oil coal slurry
Solid grain size is uniform, makes gained biomass coal-water slurry stability more preferable, is not easy to settle in transportational process, avoid
Blocking to transport pipeline and the damage to liquefaction device.
By will first expect to mix with the first catalyst and vulcanizing agent admittedly, the surface energy of biomass powder can be preferably utilized
The first catalyst is made to be attached to the surface of solid biomass powder, such first catalyst can be coal and biomass water in time
It solves product and hydrogen migration is provided, so that it is guaranteed that coke polycondensation will not be generated in entire technical process, achieve the purpose that reduce green coke amount.
The present invention by face hydrogen and using the amorphous Fe oxides after vulcanizing treatment as the first catalyst, through vulcanizing treatment
Load regulation VIB, VIIB afterwards or the unformed aluminium oxide of group VIII metal oxide under conditions of the second catalyst or with
It is the first catalyst that load, which has one or more biomass carbons in iron oxide, FeOOH or iron hydroxide, with load
There are one or more biomass carbons in the oxide of Mo, W, Fe, Co, Ni or Pd under conditions of the second catalyst so that
Primary cracking, hydrogenation reaction and drastic cracking, hydrogenation reaction occur successively for coal and the hydrolysate of biomass, improve fuel oil receipts
Rate, and reduce green coke amount.There is preferable Hydrogenation after noble metal vulcanization, can further avoid green coke；Unformed aluminium oxide
With acidity, enable to cracking more abundant.
3rd, reaction raw materials are first sequentially sent in above-mentioned reactor by the present invention by using at least two paste state bed reactors
Hydrogenation reaction occurs, while cold hydrogen is injected into these reactors again, gas, liquid can be relied on so in two reactors
Difference in specific gravity variation after the different specific weight and complex reaction of each material of body, solid caused by the yield of light-end products, realizes each phase
The otherness control of state flow velocity so that coal occurs hydrolysis, cracking in reactor with biomass material, adds hydrogen anti-from the bottom to top
Should, even if the larger coal of proportion, biomass and catalyst solid particle are with gas and light-end products rising in the process, but
It is again return under the cold hydrogen effect on top to participate in reacting again to bottom, it is appropriate according to the material density in reactor upper, middle and lower portion
The hydrogen content being adjusted into the biomass coal-water slurry of reactor and cold hydrogen injection rate, so as to fulfill unconverted coal and biology
Matter is discharged in the cycle of inside reactor and the balance of catalyst, thus can ensure that the abundant of the reactions such as hydrolysis, cracking plus hydrogen
It carries out, so as to be conducive to improve coal and biomass conversion ratio and fuel oil yield.
4th, it is provided by the invention a kind of using coal and the technique of biomass production fuel oil and industrial chemicals, by by high pressure
Hydrogen is injected into biomass coal-water slurry in three times, i.e., a high pressure hydrogen is respectively injected before and after heating up to biomass coal-water slurry,
Then one is reinjected before the mixture of the level-one hydrogenation products and second catalyst enters the second paste state bed reactor
Sub-high pressure hydrogen, the injection of first time high pressure hydrogen can increase the disturbance of heat exchanger endogenous substance water-coal-slurry, so as to avoid coal, life
The deposition of substance and catalyst.High pressure hydrogen is injected in three times, and gas velocity can be realized to various liquid, solid, catalyst
Speed supply, and the difference for rising, stopping is realized in reactor by the phase of mixture, density variation, while can root
According to the density contrast of interlayer each in reactor, by the hydrogen injection mouth supplement adjustment tolerance of reactor outer wall, ensure hydrolysis, split
Change, the abundant progress of hydrogenation reaction.
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.
Coal described in following each embodiment and comparative examples and the conversion ratio of biomass, biological oil yield and residue content
Calculation formula is as follows：
Coal and the conversion ratio of biomass=(quality of quality-water of secondary hydrogenation product quality-hydrogenation catalyst)/(coal
With the quality of biomass and)
The quality of biological oil yield=bio oil/(quality of coal and biomass and)
Residue content=mass of residue/(quality of coal and biomass and).
Embodiment 1
The preparation of first catalyst：
(1) it is the first biomass carbon carrier to choose biomass carbon；
(2) the first active component is carried on the first biomass carbon carrier, the first catalyst is made.
Wherein, first active component is iron oxide, and in terms of metallic element quality, first active component accounts for described
The 50% of first biomass carbon carrier quality；
Load in step (2) the specific steps are：By the aqueous solution of first active component and first biomass
High-area carbon is hybridly prepared into suspension, and adding in precipitating reagent makes the first active ingredient precipitation on the first biomass carbon carrier, then into
Row washing, drying are to get first catalyst；Wherein, the precipitating reagent is ammonium hydroxide or carbonate, the bicarbonate of alkali metal
The aqueous solution of at least one of salt, hydroxide, the control of precipitation process temperature are 90 DEG C, pH value 9.
The preparation of second catalyst：
(1) using H+The acid medium of a concentration of 5mol/L, with 15 at 80 DEG C:1 volume ratio carries out biomass carbon
Acidification 10h is to get to biomass carbon carrier；As a kind of alternative of the present embodiment, OH can also be used-It is a concentration of
The alkaline medium of 0.5mol/L, with 5 at 30 DEG C:1 volume ratio carries out acidification 10h to biomass carbon.
(2) oxide of Mo and W and the biomass carbon carrier are subjected to vibro-grinding jointly, that is, realize that active component exists
Load on biomass carbon carrier obtains the second catalyst that grain size is 200 μm~300 μm.It is described in terms of metallic element quality
Second active component accounts for the 5% of the biomass carbon carrier quality.
Embodiment 2
A kind of technique that fuel oil and industrial chemicals are produced using coal and biomass, is included the following steps：
The pretreatment of coal raw material：
(1) lignite is taken, is baked to be dehydrated, it is 50 μm to be crushed to median, is then fed into cuber and is squeezed into
Type, briquetting pressure 5MPa obtain lignite compression material.
(2) lignite is compressed into material and is sent into ball mill, crushed, obtained the lignite crushed material that median is 30 μm, treat
With.
The preparation of biomass coal-water slurry and liquefaction reaction：
To there are the biomass carbon of FeOOH and vulcanizing agent to mix with load after the progress ash disposal of above-mentioned lignite crushed material
Mixture is obtained, the mixture is added in into the mixture of animal oil and water, so as to form the biomass coal-water slurry, to
Hydrogen is passed through in the biomass coal-water slurry to react, and to control reaction pressure be 15MPa, reaction temperature is 200 DEG C, is obtained
To level-one hydrogenation products.
There are biomass carbon, vulcanizing agent and the animal oil of molybdenum oxide and water to be mixed to prepare catalyst slurry load, then
It adds in into above-mentioned level-one hydrogenation products, and is passed through hydrogen so that secondary hydrogenation reaction occurs, control reaction pressure is 20MPa, instead
It is 380 DEG C to answer temperature, obtains secondary hydrogenation product.
The secondary hydrogenation product is detached again, you can respectively obtain fuel oil and industrial chemicals.
Embodiment 3
A kind of technique that fuel oil and industrial chemicals are produced using coal and biomass, is included the following steps：
The pretreatment of biomass material：
(1) reed is taken, it is 1wt% to be baked to dehydration to water content, is then fed into airslide disintegrating mill and crushes processing,
Obtain crushed material of reed, grain size D50It is 200 μm.
(2) crushed material of reed is sent into cuber or plodder carries out extrusion forming, briquetting pressure 3MPa is obtained
Reed compression material.
(3) reed is compressed into material and is sent into airslide disintegrating mill, carried out separating twice, obtain reed separating twice material, grain size D50
It it is 40 μm, for use.
The pretreatment of coal raw material：
(1) refreshing eastern jet coal is taken, is baked to be dehydrated, is then fed into ball mill and crushes processing, obtains refreshing eastern long flame
Crushed material of coal, grain size D50It is 100 μm.
(2) refreshing eastern crushed material of jet coal is sent into cuber or plodder carries out extrusion forming, briquetting pressure is
12MPa obtains refreshing eastern jet coal compression material.
(3) refreshing eastern jet coal compression material is sent into ball mill, carries out separating twice, obtain refreshing eastern jet coal separating twice
Material, grain size D50It it is 100 μm, for use.
The preparation of biomass coal-water slurry and liquefaction reaction：
The separating twice material of reed and coal is mixed to get mixture after ash disposal with amorphous Fe oxides and vulcanizing agent, will
The mixture is added in into water, forms biomass coal-water slurry.13MPa, 180 DEG C of height are injected into above-mentioned biomass coal-water slurry
Medium temperature hydrogen is pressed, then biomass coal-water slurry heat exchange is warming up to 200 DEG C, then injects 13MPa, 510 DEG C of high pressure thereto again
High-temperature hydrogen, and the mass ratio of the hydrogen injected twice and biomass coal-water slurry is controlled to reach 600:1 is former to form first order reaction
Material.
First order reaction raw materials are sent into the first paste state bed reactor, and injects and is passed through into the first paste state bed reactor
27MPa, the cold hydrogen of 50 DEG C of high pressure, control reactor in total gas velocity be 0.05m/s, reaction pressure 15MPa, reaction temperature are
300 DEG C, level-one hydrogenation reaction is carried out, obtains level-one hydrogenation products.
Unformed aluminium oxide, vulcanizing agent and animal oil and water that load has W oxides and Ni oxides are mixed to prepare
Catalyst slurry is then added into above-mentioned level-one hydrogenation products and is passed through hydrogen so that secondary hydrogenation reaction occurs, and control is anti-
It is 15MPa to answer pressure, reaction temperature is 420 DEG C, obtains secondary hydrogenation product.
Secondary hydrogenation product is carried out separation can respectively obtain fuel oil and industrial chemicals.
Embodiment 4
A kind of technique that fuel oil and industrial chemicals are produced using coal and biomass, is included the following steps：
The pretreatment of biomass material：
(1) it is 0.5wt% by sea grass drying and dewatering to water content, is then fed into airslide disintegrating mill and crushes processing, obtain
To crushed material of sea grass, grain size D50It is 300 μm.
(2) crushed material of sea grass is sent into cuber or plodder carries out extrusion forming, briquetting pressure 3MPa is obtained
Sea grass compression material.
(3) sea grass is compressed into material and is sent into airslide disintegrating mill, carried out separating twice, obtain sea grass separating twice material, grain size D50
It is 40 μm.
The pretreatment of coal raw material：
(1) refreshing eastern jet coal is taken, is baked to be dehydrated, is then fed into ball mill and crushes processing, obtains refreshing eastern long flame
Crushed material of coal, grain size D50It is 90 μm.
(2) refreshing eastern crushed material of jet coal is sent into cuber or plodder carries out extrusion forming, briquetting pressure is
15MPa obtains refreshing eastern jet coal compression material.
(3) refreshing eastern jet coal compression material is sent into ball mill, carries out separating twice, obtain refreshing eastern jet coal separating twice
Material, grain size D50It it is 60 μm, for use.
The preparation of biomass coal-water slurry and liquefaction reaction：
The separating twice material of sea grass and coal and load there are into the biomass carbon of FeOOH (the first catalyst), vulcanizing agent
And water is mixed to form biomass coal-water slurry jointly.Wherein, the mass ratio of vulcanizing agent and the first catalyst is 0.4:1；First urges
The granularity of agent is 5~100 μm, and additive amount is the 10% of biomass coal-water slurry quality；It is described in the biomass coal-water slurry
The content of sea grass is 30wt%, and the content of the coal is 35wt%.
27MPa, 350 DEG C of high pressure medium temperature hydrogen are injected into above-mentioned biomass coal-water slurry, then by biomass coal-water slurry
Heat exchange is warming up to 350 DEG C, then 27MPa, 360 DEG C of high pressure-temperature hydrogen are injected into biomass coal-water slurry, and controls and note twice
The hydrogen and the volume ratio of biomass coal-water slurry entered reaches 1000:1 to form first order reaction raw material.
First order reaction raw material is sent into the first paste state bed reactor, and is passed through 13MPa, the cold hydrogen of 135 DEG C of high pressure, is controlled
Total gas velocity in reactor is 0.08m/s, and reaction pressure 20MPa, reaction temperature are 300 DEG C of progress level-one hydrogenation reactions, are obtained
To level-one hydrogenation products.
Biomass carbon (the second catalyst), vulcanizing agent and water that load has nickel oxide are mixed to prepare catalyst slurry, to
In level-one hydrogenation products add in catalyst slurry and be passed through hydrogen with occur secondary hydrogenation reaction, control reaction pressure be 25MPa,
Reaction temperature is 430 DEG C, obtains secondary hydrogenation product, and the mass ratio of the second catalyst and water is 1 in the catalyst slurry：
10, the granularity of the second catalyst is 400~500 μm, and additive amount is the 0.5wt% of level-one hydrogenation products quality, vulcanizing agent and the
The mass ratio of two catalyst is 0.4：1.
Secondary hydrogenation product is detached, respectively obtains fuel oil and industrial chemicals.
Embodiment 5
A kind of technique that fuel oil and industrial chemicals are produced using coal and biomass, is included the following steps：
The pretreatment of biomass material：
(1) straw is taken, it is 10wt% to be baked to dehydration to water content, it is then fed into airslide disintegrating mill and crushes place
Reason, obtains crushed material of straw, grain size D50It is 150 μm.
(2) crushed material of straw is sent into cuber or plodder carries out extrusion forming, briquetting pressure 2MPa is obtained
Straw compression material.
(3) straw is compressed into material and is sent into airslide disintegrating mill, carried out separating twice, obtain straw separating twice material, grain size D50
It is 45 μm.
The pretreatment of coal raw material：
(1) lignite is taken, is baked to be dehydrated, ball mill is then fed into and crushes processing, obtains crushed material of lignite,
Grain size D50It is 50 μm.
(2) crushed material of lignite is sent into cuber and carries out extrusion forming, briquetting pressure 5MPa obtains lignite compression
Material.
(3) lignite is compressed into material and is sent into ball mill, carried out separating twice, obtain lignite separating twice material, grain size D50For 45 μ
M, for use.
The separating twice material of above-mentioned straw and lignite is screened, 90 μm of straw of grain size ＞ are isolated with lignite
Come, then handled again with follow-up charging in input compression link or second of crushing link, it is more uniform to obtain
Grain size, so as to obtain more stable biomass coal-water slurry.
The preparation of biomass coal-water slurry and liquefaction reaction：
Straw and separating twice material of the lignite by screening have the biomass carbon of iron oxide after ash disposal with load, and (first urges
Agent) and vulcanizing agent be mixed to get mixture, the mixture is added to the water to obtain biomass coal-water slurry.In the life
In substance coal slurry, the mass ratio of vulcanizing agent and the first catalyst is 1:1, the granularity of the first catalyst is 400~500 μm, is added
Dosage is the 2% of biomass coal-water slurry quality, and the content of straw is 20wt%, and the content of coal is 40wt%.
Biomass coal-water slurry is exchanged heat after injecting 20MPa, 250 DEG C of high pressure medium temperature hydrogen into above-mentioned biomass coal-water slurry
300 DEG C are warming up to, then injects 20MPa, 450 DEG C of high pressure-temperature hydrogen into biomass coal-water slurry again, and control and note twice
The hydrogen and the volume ratio of biomass coal-water slurry entered reaches 800:1 to form first order reaction raw material.
First order reaction raw materials are sent into the first paste state bed reactor, and 17MPa, 100 DEG C of height are injected into reactor
Press cold hydrogen, it is 0.02m/s to control total gas velocity in the first paste state bed reactor, reaction pressure 18MPa, reaction temperature 270
DEG C, level-one hydrogenation reaction 30min is carried out, obtains level-one hydrogenation products.
There are the biomass carbon of nickel oxide and iron oxide (the second catalyst), vulcanizing agent and water to be mixed to prepare catalyst load
Gained catalyst slurry is added in into above-mentioned level-one hydrogenation products, then heats to 430 DEG C, is re-fed into the second slurry by slurries
In bed reactor, 13MPa, 480 DEG C of high pressure-temperature hydrogen are passed through so that secondary hydrogenation reaction occurs, while anti-to the second slurry bed system
Injection 13MPa, 135 DEG C of cold hydrogen of high pressure in device are answered, it is 0.1m/s to control total gas velocity in the second paste state bed reactor, and is controlled anti-
Answering pressure, reaction temperature is 400 DEG C, and reaction time 40min obtains secondary hydrogenation product for 17MPa.Hydrogen and one is injected twice
The volume ratio of grade hydrogenation products is 1000：1；It is the second slurry to control storage of second catalyst in the second paste state bed reactor
5~20wt% of liquid phase quality in bed reactor.
The mass ratio of the second catalyst and water is 2 in the catalyst slurry：10, the granularity of the second catalyst for 100~
200 μm, additive amount is the 1wt% of level-one hydrogenation products quality, and the mass ratio of vulcanizing agent and the second catalyst is 1：1.
Hydroforming is carried out to secondary hydrogenation product under conditions of pressure is 7MPa, temperature is 460 DEG C, is then divided
Fuel oil and industrial chemicals are respectively obtained from rear.
Embodiment 6
A kind of technique that fuel oil and industrial chemicals are produced using coal and biomass, is included the following steps：
The pretreatment of biomass material：
(1) the soybean oil dregs of fat are taken, micronizer is then fed into and crushes processing, the soybean oil dregs of fat is obtained and once crushes
Material, grain size D50It is 300 μm.
(2) crushed material of the soybean oil dregs of fat is sent into cuber or plodder carries out extrusion forming, briquetting pressure is
4MPa obtains soybean oil dregs of fat compression material.
(3) the soybean oil dregs of fat are compressed into material and is sent into micronizer, carried out separating twice, obtain two wheat-middlings of the soybean oil dregs of fat
Particle, grain size D50It it is 40 μm, for use.
The pretreatment of coal raw material：
(1) refreshing eastern jet coal is taken, is baked to be dehydrated, is then fed into ball mill and crushes processing, obtains refreshing eastern long flame
Crushed material of coal, grain size D50It is 100 μm.
(2) refreshing eastern crushed material of jet coal is sent into cuber or plodder carries out extrusion forming, briquetting pressure is
10MPa obtains refreshing eastern jet coal compression material.
(3) refreshing eastern jet coal compression material is sent into ball mill, carries out separating twice, obtain refreshing eastern jet coal separating twice
Material, grain size D50It it is 60 μm, for use.
The preparation of biomass coal-water slurry and hydrolysis hydrogenation reaction：
First catalyst used in the present embodiment and the second catalyst are prepared according to the method that embodiment 1 provides
's.
The separating twice material and the first catalyst of refreshing eastern jet coal and the soybean oil dregs of fat and vulcanizing agent are added in into water jointly
In, wherein, the mass ratio of vulcanizing agent and the first catalyst is 0.7:1, the granularity of the first catalyst is 5~200 μm, and additive amount is
The 10% of biomass coal-water slurry quality, in the biomass coal-water slurry, the content of the soybean oil dregs of fat is 20wt%, and the content of coal is
45wt%.
18MPa, 300 DEG C of high pressure medium temperature hydrogen are injected into above-mentioned biomass coal-water slurry, then by biomass coal-water slurry
Heat exchange is warming up to 250 DEG C, then 18MPa, 400 DEG C of high pressure-temperature hydrogen are injected into biomass coal-water slurry, and controls and note twice
The hydrogen and the volume ratio of biomass coal-water slurry entered reaches 900:1 to form first order reaction raw material.
First order reaction raw material is sent into the first paste state bed reactor, and be passed through 17MPa, the cold hydrogen of 100 DEG C of high pressure to occur
Level-one hydrogenation reaction controls total gas velocity in the first paste state bed reactor as 0.02m/s, the storage of the first catalyst in reactor
20~30wt% for liquid phase quality；Reaction pressure is 20MPa, reaction temperature is 300 DEG C, reacts 60min, obtains level-one and add hydrogen
Product.
Second catalyst, vulcanizing agent and water are mixed to prepare catalyst slurry, wherein, the matter of vulcanizing agent and the second catalyst
Amount is than being 0.01：1, the mass ratio of the second catalyst and water is 2：10, the granularity of the second catalyst is 100~200 μm.It will be above-mentioned
Catalyst slurry is added in into level-one hydrogenation products so that the additive amount of the second catalyst is the 1% of hydrogenation products quality, is obtained
The second order reaction raw material is warming up to after 430 DEG C and is sent into the second paste state bed reactor by second order reaction raw material, and be passed through 13MPa,
480 DEG C of high pressure-temperature hydrogen is injected so that secondary hydrogenation reaction occurs from sidewall of reactor by 3~5 inlets
13MPa, the cold hydrogen of 135 DEG C of high pressure, it is 0.1m/s to control total gas velocity in the second paste state bed reactor, and hydrogen adds hydrogen to produce with level-one
The volume ratio of object is 1000：1；Reaction pressure is 17MPa, reaction temperature is 390 DEG C, reacts 50min, obtains secondary hydrogenation production
Object, the storage for controlling the second catalyst in the second paste state bed reactor are 20~30wt% of liquid phase quality.
By the hydroforming under conditions of pressure is 23MPa, temperature is 250 DEG C of above-mentioned secondary hydrogenation product, then carry out
Separation respectively obtains fuel oil and industrial chemicals.
Comparative example 1
The technique that fuel oil and industrial chemicals are produced using coal and biomass that this comparative example provides, it is basic with embodiment 4
Unanimously, differ only in control the first paste state bed reactor in reaction pressure be 10MPa, reaction temperature is 400 DEG C.
Comparative example 2
The technique that fuel oil and industrial chemicals are produced using coal and biomass that this comparative example provides, it is basic with embodiment 4
Unanimously, differ only in control the second paste state bed reactor in reaction pressure be 30MPa, reaction temperature is 200 DEG C.
Experimental example
Technological effect using the embodiment of the present invention and comparative example is compared, it is as shown in table 1 below.
The technological effect comparison of 1 embodiment and comparative example of table
As it can be seen from table 1 relative to comparative example 1-2, coal and biomass that embodiment technique using the present invention obtains
Conversion ratio and the yield of bio oil are higher, and green coke amount then significantly reduces, and are generated almost without green coke, so as to learn the present invention
Method can significantly improve the yield of coal and biomass conversion ratio and light oil, reduce green coke amount.In addition, multistage liquefaction causes
Hydrogenation reaction is more abundant, the quality higher of light oil.
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 (15)
1. a kind of technique for producing fuel oil and industrial chemicals using coal and biomass, which is characterized in that include the following steps：
The preparation of biomass coal-water slurry：
Biomass collection simultaneously controls moisture content to be less than 2wt%, and it is 100~300 μm to be then crushed to median；
Biomass after crushing is subjected to compression forming, compression pressure is 2~5MPa, and compression temperature is 30~60 DEG C；
By the pulverization process again of the biomass after compression forming, it is 30~50 μm to be crushed to median, obtains powdered biomass；
Collect coal and simultaneously control moisture content less than 2wt%, it is 50~100 μm to be then crushed to median, compression temperature for 30~
60℃；
Compression forming is carried out to the coal after crushing, compression pressure is 5~15MPa；
To the pulverization process again of the coal after compression forming, it is 30~100 μm to be crushed to median, obtains coal dust；
By the powdered biomass, the coal dust, the first catalyst, vulcanizing agent mix with solvent naphtha, grind slurrying and obtain biology
Matter water-coal-slurry, the powdered biomass and the coal dust account for 55~65wt% of the biomass coal-water slurry altogether；
The preparation of catalyst slurry：Second catalyst, vulcanizing agent and water are mixed to prepare catalyst slurry, for use；
Level-one hydrogenation reaction：Hydrogen is passed through into the biomass coal-water slurry so that level-one hydrogenation reaction occurs, and controls reaction pressure
Power is 15~20MPa, reaction temperature is 200~300 DEG C, obtains level-one hydrogenation products；
Secondary hydrogenation reacts：The catalyst slurry, which is added in, into the level-one hydrogenation products and is passed through hydrogen is added so that two level occurs
Hydrogen reacts, and control reaction pressure is 15~20MPa, reaction temperature is 380~420 DEG C, obtains secondary hydrogenation product；
The separation of product：The secondary hydrogenation product is subjected to gas, liquid, solid three phase separation, then obtained bio oil is steamed
It evaporates, the distillate that 200 DEG C of ＜ is used to prepare industrial chemicals, remaining is used as fuel oil；
It is first by the powdered biomass and the coal dust when carrying out the mixing in the preparation steps of biomass coal-water slurry
Carry out ash disposal and after being pre-mixed with first catalyst and the vulcanizing agent, then gained premix and the water are mixed
It closes, alternatively, directly to mix the powdered biomass, the coal dust, the catalyst, the vulcanizing agent with the water.
2. the technique of coal according to claim 1 and biomass production fuel oil and industrial chemicals, which is characterized in that described
In biomass coal-water slurry, a concentration of 15~30wt% of biomass, a concentration of 35~50wt% of coal dust.
3. the technique of coal according to claim 1 or 2 and biomass production fuel oil and industrial chemicals, which is characterized in that
Moisture content is controlled using drying and dewatering, the drying and dewatering temperature is 50~70 DEG C, and the drying and dewatering time is 3~5h.
4. according to claim 1-3 any one of them coal and the technique of biomass production fuel oil and industrial chemicals, feature
It is, the heap density that the powdered biomass is controlled in the preparation steps of biomass coal-water slurry is 300~500kg/m3, control institute
The heap density for stating coal dust is 1200~1300kg/m3。
5. according to claim 1-4 any one of them coal and the technique of biomass production fuel oil and industrial chemicals, feature
It is, the time of the grinding slurrying is 2~8min.
6. according to claim 1-5 any one of them coal and the technique of biomass production fuel oil and industrial chemicals, feature
It is, in the step of biomass coal-water slurry is prepared：
The granularity of first catalyst is 5~500 μm.
The mass ratio of the vulcanizing agent and first catalyst is (0.4~1)：1；
The additive amount of first catalyst is the 0.1~10wt%, preferably 2wt% of the biomass coal-water slurry quality.
7. according to claim 1-6 any one of them coal and the technique of biomass production fuel oil and industrial chemicals, feature
It is, the specific method that hydrogen is passed through in the level-one hydrogenation reaction step is：
High pressure hydrogen is injected into the biomass coal-water slurry, and controls the body of the high pressure hydrogen and the biomass coal-water slurry
Product is than being (600~1000)：1, so as to form first order reaction raw material；The first order reaction raw material is sent into the first slurry reactor
Level-one hydrogenation reaction occurs in device, while the cold hydrogen of high pressure is injected into first paste state bed reactor, control described first
Total gas velocity in paste state bed reactor is 0.02~0.2m/s, preferably 0.05~0.08m/s；
The pressure of the high pressure hydrogen and the cold hydrogen of high pressure is 15~25MPa, and the temperature of the cold hydrogen of the high pressure is 50~135 DEG C.
8. the technique of coal according to claim 7 and biomass production fuel oil and industrial chemicals, which is characterized in that by institute
It states high pressure hydrogen to be injected into two times in the biomass coal-water slurry, specially：
Biomass coal-water slurry heat exchange is warming up to after injecting high pressure medium temperature hydrogen for the first time into the biomass coal-water slurry
200~350 DEG C, then inject high pressure-temperature hydrogen for the second time into the biomass coal-water slurry again；
The temperature of the high pressure medium temperature hydrogen is 180~350 DEG C, and the temperature of the high pressure-temperature hydrogen is 360~510 DEG C.
9. according to claim 1-8 any one of them coal and the technique of biomass production fuel oil and industrial chemicals, feature
It is, in the secondary hydrogenation reaction step：
The mass ratio of the second catalyst described in the catalyst slurry and the solvent naphtha is (1~2)：10；
The additive amount of second catalyst is 0.5~2wt% of the level-one hydrogenation products quality；
The mass ratio of the vulcanizing agent and second catalyst is (0.01~1)：1；
The granularity of second catalyst is 5~500 μm..
10. according to claim 1-9 any one of them coal and the technique of biomass production fuel oil and industrial chemicals, feature
It is, the method that hydrogen is passed through in the secondary hydrogenation reaction step is：
The mixture of the level-one hydrogenation products and the catalyst slurry is warming up to 380~480 DEG C, preferably 430 DEG C, and
The mixture is fed through in the second paste state bed reactor afterwards and is passed through high pressure-temperature hydrogen so that secondary hydrogenation reaction occurs, together
When the cold hydrogen of high pressure is injected into second paste state bed reactor, and control total gas velocity in second paste state bed reactor to be
0.06~0.1m/s, and the volume ratio of hydrogen and the level-one hydrogenation products is (1000~1500)：1；
The pressure of the high pressure-temperature hydrogen and the cold hydrogen of high pressure is 13~27MPa, and the temperature of the high pressure-temperature hydrogen is 430
~480 DEG C, the temperature of the cold hydrogen of high pressure is 50~135 DEG C.
It is 11. special according to claim 7-10 any one of them coal and the technique of biomass production fuel oil and industrial chemicals
Sign is that storage of first catalyst in first paste state bed reactor is controlled in first paste state bed reactor
5~30wt% of interior liquid phase quality, storage of second catalyst in second paste state bed reactor are controlled described
5~30wt% of liquid phase quality in second paste state bed reactor.
It is 12. special according to claim 1-11 any one of them coal and the technique of biomass production fuel oil and industrial chemicals
Sign is that the time of the level-one hydrogenation reaction is 30~60min, and the time of the secondary hydrogenation reaction is 30~60min.
It is 13. special according to claim 1-12 any one of them coal and the technique of biomass production fuel oil and industrial chemicals
Sign is, is additionally included in pressure and is 7~23MPa, the secondary hydrogenation product is carried out under conditions of temperature is 250~460 DEG C
The step of hydroforming.
It is 14. special according to claim 1-13 any one of them coal and the technique of biomass production fuel oil and industrial chemicals
Sign is, first catalyst is the biomass carbon that load has the first active component, first active component is iron oxide,
It is one or more in FeOOH or iron hydroxide；Second catalyst is the biomass that load has the second active component
Charcoal, second active component are one or more in the oxide of Mo, W, Fe, Co, Ni or Pd；
Or first catalyst be amorphous Fe oxides, second catalyst be to load to have the unformed oxidation of third active component
Aluminium, one kind or more in the oxide of the third active component selected from periodic table of elements Section VI B, VIIB or group VIII metal
Kind.
It is 15. special according to claim 1-14 any one of them coal and the technique of biomass production fuel oil and industrial chemicals
Sign is that the coal is low-order coal.
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