CN109294612A - A method of add hydrogen to prepare fuel oil altogether using sawdust and mink cell focus - Google Patents
A method of add hydrogen to prepare fuel oil altogether using sawdust and mink cell focus Download PDFInfo
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- CN109294612A CN109294612A CN201811187460.4A CN201811187460A CN109294612A CN 109294612 A CN109294612 A CN 109294612A CN 201811187460 A CN201811187460 A CN 201811187460A CN 109294612 A CN109294612 A CN 109294612A
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- Prior art keywords
- sawdust
- catalyst
- fuel oil
- cell focus
- mink cell
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- 239000000295 fuel oil Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 52
- 241000772415 Neovison vison Species 0.000 title claims abstract description 44
- 239000001257 hydrogen Substances 0.000 title claims abstract description 43
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 43
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 75
- 239000003921 oil Substances 0.000 claims abstract description 29
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 17
- 239000003426 co-catalyst Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000000284 extract Substances 0.000 claims abstract description 11
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 10
- 238000004821 distillation Methods 0.000 claims abstract description 7
- 230000000694 effects Effects 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 34
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 20
- 229910052723 transition metal Inorganic materials 0.000 claims description 18
- 229910052742 iron Inorganic materials 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 150000003624 transition metals Chemical class 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 9
- 239000005864 Sulphur Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 150000002898 organic sulfur compounds Chemical class 0.000 claims description 5
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims description 5
- 229910052683 pyrite Inorganic materials 0.000 claims description 5
- 239000011028 pyrite Substances 0.000 claims description 5
- 239000002699 waste material Substances 0.000 claims description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 4
- 239000003245 coal Substances 0.000 claims description 4
- 239000011280 coal tar Substances 0.000 claims description 4
- 229910001507 metal halide Inorganic materials 0.000 claims description 4
- 150000005309 metal halides Chemical class 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- 230000005587 bubbling Effects 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 238000005485 electric heating Methods 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 3
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 claims description 3
- 239000002905 metal composite material Substances 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 239000003209 petroleum derivative Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 3
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 238000002485 combustion reaction Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 239000012299 nitrogen atmosphere Substances 0.000 abstract description 2
- 239000002028 Biomass Substances 0.000 description 9
- 238000000605 extraction Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000000446 fuel Substances 0.000 description 5
- 239000003610 charcoal Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000010025 steaming Methods 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910002588 FeOOH Inorganic materials 0.000 description 2
- 238000000944 Soxhlet extraction Methods 0.000 description 2
- 239000003225 biodiesel Substances 0.000 description 2
- 238000007233 catalytic pyrolysis Methods 0.000 description 2
- 150000001924 cycloalkanes Chemical class 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000011276 wood tar Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- -1 Sulphur compound Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 238000000508 aqueous-phase reforming Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
Landscapes
- 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)
Abstract
The present invention relates to a kind of methods for adding hydrogen to prepare fuel oil altogether using sawdust and mink cell focus, comprising the following steps: 1) sawdust is crushed, it is dry；2) the sawdust powder that step 1) obtains is reacted under conditions of heating up and pressurizeing with hydrocracking catalyst, co-catalyst, mink cell focus, is cooled to room temperature, extracts later, distillation.In method provided by the present invention, using the hydrocracking catalyst of high activity, sawdust is carried out to face being hydrocracked under nitrogen atmosphere, the high conversion rate of sawdust, oil yield is high, and obtained fuel oil oxygen content is low, and quality is good.
Description
Technical field
The invention belongs to bioenergy chemical fields, and in particular to a kind of to add hydrogen to prepare fuel altogether using sawdust and mink cell focus
The method of oil.
Background technique
Sawdust refer to when carrying out timber processing because cutting and from trees the fragment of fallen timber itself or
Foam shape object.Sawdust is the tailing or waste material after timber processing, makes sawdust-board or charcoal, remaining big portion in previous part of it
Divide and fuel is made by peasant household, not only added value is low for both Land use systems, and pollutes environment.
With the development of industrial society, the mankind are higher and higher to the degree of dependence of the energy, and the demand to clean fuel oil is got over
Come more vigorous.Sawdust sulphur, nitrogen content are low, therefore produce fuel oil and chemicals to protecting ecology by raw material of reproducible sawdust
Environment, Development of Social Economy, implementing energy sustainable development strategy has major and immediate significance.
Currently, mainly have in such a way that the biomass such as sawdust produce fuel or chemicals thermal cracking, gasification, solvent extraction,
Hydrolysed ferment, catalytic pyrolysis etc..
The Chinese invention patent application of Publication No. CN105622315A, which discloses, a kind of prepares low-carbon alkene by sawdust
Method, this method obtain mixing six-carbon monosaccharide first with solvent and catalyst from sawdust, and six-carbon monosaccharide is by being condensed, adding
Hydrogen, cracking, can be obtained low-carbon alkene.
The Chinese invention patent application of Publication No. CN105623702A discloses a kind of utilization sawdust synthesis aviation kerosine
Sawdust catalytic pyrolysis is first low-carbon aromatic hydrocarbons by the method for cycloalkane and aromatised fraction, this method, its orientation is then made to be converted into virtue
Hydrocarbon finally converts cycloalkane for aromatic hydrogenation again, can be used as aromatic hydrocarbons and naphthenic components in biological aviation kerosine.
The Chinese invention patent application of Publication No. CN106349740A, which discloses, a kind of extracts fuel with residual branch sawdust
Sawdust, is first broken into powdered by method, and cleans filtering, is then extracted with alcohol, by after extraction dye liquor concentration, drying just
Available fuel product.
Notification number is that the Chinese utility model patent of CN201785354U discloses a kind of high-efficiency sawdust oil steaming device, its energy
The high-temperature flue gas enough generated using flame, steams the sawdust oil of high added value from sawdust, and does not influence sawdust exercise use.
But the device for obtaining oil by steaming saw dusts energy consumption is high, and sawdust oil yield is very low.
The Chinese invention patent application of Publication No. CN101407727A discloses one kind and is prepared by biomass catalyzing and liquefying
The method of biomass liquefied oil, this method, using unitary alcohol solution as extractant, pass through catalytic extraction using solid acid as catalyst
Mode liquefaction oil has been obtained from biomass.
The Chinese invention patent application of Publication No. CN103328618A discloses a kind of from biomass production bio-fuel
Method, this method first with aqueous medium extraction biomass obtain extraction mixture, extraction mixture connect by purification matrix
Sulphur compound and nitrogen compound are removed in touching, the intermediate that the substance after purification process is largely aoxidized by aqueous phase reforming, and one
Moiety intermediate finally obtains the feedstock oil that can be used to prepare fuel oil after alkylated reaction.
The Chinese invention patent application of Publication No. CN106367096A disclose it is a kind of using agricultural, forestry waste system
The process for taking biodiesel mixes drying, smashed biomass castoff and solvent, auxiliary agent, catalyst, additive
It closes, obtains biodiesel oil product after heating reaction, distillation.
The Chinese invention patent application of Publication No. CN101353583A discloses a kind of biomass processing method, method
It is that will enter pyrolysis reactor after biomass drying and crushing, obtains oil gas product and charcoal, charcoal goes life after gasifier gasification
At carbon monoxide, oil gas product obtains wood tar after sedimentation, separation, filtering, cooling, and wood tar obtains vapour after adding hydrogen
Diesel fuel mixtures.
It can thus be seen that the above-mentioned prior art extracts chemicals or production fuel oil from sawdust, there are following
Problem: first is that product yield is low, and second is complex process, and complex steps, third is to add hydrogen and hydrogen supply dissolvent due to lacking, system
Standby obtained oil product is with acid brownish black liquid organic mixture, and chemical composition is relative complex, and it is strong to generate oily corrosivity；
And the oily oxygen content of generation is high (40-50%), thereby results in the problems such as thermal stability is poor, calorific value is low, low volatility, and it is subsequent
Hydrofinishing needs exacting terms that can just obtain clean fuel oil products.
Summary of the invention
In view of the deficiencies of the prior art, hydrogen is added to prepare fuel oil altogether using sawdust and mink cell focus the present invention provides a kind of
Method, the process characteristic of this method are by way of catalytic hydrogenation, are fuel oil, obtained combustion by sawdust and heavy oil conversion
Expect that oil yield is high, oxygen content is low, can obtain clean petrol and diesel oil or chemicals by conventional mild upgrading processing.
In order to reach above-mentioned purpose, present invention employs following technical solutions:
A method of add hydrogen to prepare fuel oil altogether using sawdust and mink cell focus, comprising the following steps:
1) sawdust is crushed, it is dry；
2) the sawdust powder for obtaining step 1) and hydrocracking catalyst, co-catalyst, mink cell focus are in heating pressurization
Under the conditions of react, be cooled to room temperature later, extract, distillation.
Further, crushing device used is wherein crushed described in step 1) to be high shear crusher, ball mill or grind
Grinding machine, granularity is 300 μm or less after being crushed.
Further, wherein dry drying device used described in step 1) is baking oven or Muffle furnace, and drying temperature is
120-250 DEG C, preferably 150-200 DEG C, drying time 0.5-3.0h, preferably 1-2.0h.
Further, wherein step 2) specifically: by step 1) it is broken it is dry after sawdust powder and hydrocracking catalyst
Agent, co-catalyst, mink cell focus are added in reactor by a certain percentage, and reactor is filled with hydrogen, are warming up to 350-500 DEG C, pressurization
To 1-30MPa, after constant temperature keeps 0.5-4.0h, after being cooled to room temperature, the liquid after reaction is consolidated product and is extracted with n-hexane, just
After hexane solubles remove extractant, the fuel oil as obtained, n-hexane insoluble matter is unconverted sawdust；Or after reaction
Liquid is consolidated product and is distilled in distilling apparatus, and the product liquid distilled is fuel oil, and solid is unconverted sawdust.
Further, wherein the sawdust includes the leftover bits and pieces, sawdust or forestry waste of wood-working factory；The sawdust
The additional amount that reactor is added after broken drying is 20~95%, preferably the 40~90% of mink cell focus weight.
Further, wherein the catalyst is hydrocracking catalyst, the hydrocracking catalyst is selected from by transition
In metallic catalyst, metal halide catalyst, Fe-series catalyst and iron series-transition metal composite catalyst composition group
It is a kind of.
Further, wherein the transition-metal catalyst be in the group being made of platinum, rhenium, cobalt, molybdenum and nickel extremely
Few a kind of oxide or sulfide powder.
Further, wherein the transition-metal catalyst is powder carrier catalyst.
Further, wherein the active metal in the transition-metal catalyst is selected from and is made of molybdenum, iron, tungsten, nickel and cobalt
At least one of group.
Further, wherein the catalyst carrier in the transition-metal catalyst is selected from by inorganic oxide, carbon nanometer
At least one of the group of pipe and molecular sieve composition.
Further, wherein the metal halide catalyst is selected from ZnCl2Or SnCl2。
Further, wherein the Fe-series catalyst is selected from by iron-containing natural crystal, iron-containing industrial residue and pure state
One of the group of the compound composition of iron.
Further, wherein the Fe-series catalyst is ultra-fine dispersed catalysts.
Further, wherein the Fe-series catalyst is ultra-fine pyrite or nanoscale hydrated ferric oxide (FeOOH).
Further, wherein the powdered granule that the catalyst is 1-200 μm of partial size, additive amount are the 0.5- of sawdust weight
6.0%, preferably 1.0-3.0%.
Further, wherein the co-catalyst is sulphur or organic sulfur compound.
Further, wherein the organic sulfur compound is carbon disulfide or dimethyl disulfide.
Further, wherein the additive amount of the co-catalyst is S/ catalyst activity component=0.5-3.0 (molar ratio)；
Wherein, S is the element sulphur in co-catalyst, and catalyst active component is active metal.
Further, wherein the mink cell focus is selected from by coal tar, black petroleum products, liquefied coal coil, clarified oil, Atmospheric vacuum slag
At least one of group of oil and catalytic cracked oil pulp composition or their certain section of distillate.
Further, wherein the reactor is the autoclave with stirring and external heating system of intermittent operation,
Either continuous forced circulation suspension bed, bubbling bed, slurry bed system or circulation flow reactor.
Further, wherein when using batch autoclave, speed of agitator 20-1500r/min, preferably 300-
1000r/min；The heating method of the batch autoclave is electric heating or oil bath or salt bath, heating rate is 2-50 DEG C/
min。
By above-mentioned technical proposal, the present invention is at least had the advantage that
1. method provided by the present invention prepares fuel oil using reproducible sawdust as raw material, it is raw to open fuel oil
Produce diversification of feedstock road, to solve China's oil shortage, guarantee the energy it is safe and stable supply have Great significance and
Strategic importance；
It mainly include the broken drying of raw material, mixed hydrogenation, that liquid consolidates product separation is several 2. method provided by the present invention
A step, process flow is simple, and operating cost is low, is easy to industrialization promotion；
3. method provided by the present invention uses the hydrocracking catalyst of high activity, sawdust is carried out to face nitrogen atmosphere
Under be hydrocracked, the high conversion rate of sawdust, oil yield is high, and obtained fuel oil oxygen content is low, and quality is good.
Specific embodiment
It is of the invention to reach the technical means and efficacy that predetermined goal of the invention is taken further to illustrate, below in conjunction with
Preferred embodiment, to its specific implementation of the method proposed according to the present invention for adding hydrogen to prepare fuel oil altogether using sawdust and mink cell focus
Mode, feature and its effect, detailed description is as follows.
Following material or reagent are unless stated otherwise commercially available.
The present invention provides a kind of methods for adding hydrogen to prepare fuel oil altogether using sawdust and mink cell focus, comprising the following steps:
1) sawdust is crushed, it is dry；
The broken crushing device used can be high shear crusher, can also be with ball mill or grinder, after being crushed
Granularity requirements are 300 μm or less；Drying device used in the drying can be baking oven or Muffle furnace, and drying temperature is generally
120-250 DEG C, preferably 150-200 DEG C, drying time 0.5-3.0h, preferably 1-2.0h, preferably rear sawdust moisture content
It is low.
2) the sawdust powder for obtaining step 1) and catalyst, co-catalyst, mink cell focus are anti-under conditions of heating pressurization
It answers, is cooled to room temperature later, extract, distillation.
Above-mentioned steps 2) specifically: by the sawdust powder and catalyst, co-catalyst, mink cell focus after the broken drying of step 1)
It is added in reactor by a certain percentage, reactor is filled with hydrogen, is warming up to 350-500 DEG C, is forced into 1-30MPa, and constant temperature is kept
After 0.5-4.0h, after being cooled to room temperature, the liquid after reaction is consolidated product and is extracted with n-hexane, and n-hexane soluble matter removes extraction
After agent, the fuel oil as obtained, n-hexane insoluble matter is unconverted sawdust；Or the product liquid after reaction can distill
Device is distilled, and the product liquid distilled is fuel oil, and solid is unconverted sawdust.
The sawdust includes the leftover bits and pieces of wood-working factory, sawdust, forestry waste such as trunk, branch etc., and sawdust is through broken
The additional amount that reactor is added after broken drying is 20~95%, preferably the 40~90% of mink cell focus weight.
The catalyst is hydrocracking catalyst, can be transition-metal catalyst, metal halide catalyst, iron
Series catalysts or iron series-transition metal composite catalyst.Transition-metal catalyst is at least the one of platinum, rhenium, cobalt, molybdenum, nickel etc.
The oxide or sulfide powder of kind；The active metal of transition-metal catalyst is at least one of molybdenum, iron, tungsten, nickel and cobalt；Institute
Stating the catalyst carrier in transition-metal catalyst is at least one of inorganic oxide, carbon nanotube or molecular sieve.Metal
Halide catalyst such as ZnCl2、SnCl2；Fe-series catalyst is iron-containing natural crystal (such as pyrite), iron-containing industrial residue
The compound (oxide, hydroxide and the sulfide of such as iron) of (such as red mud) or pure state iron.The catalyst is preferably ultra-fine
Dispersed catalysts, such as ultra-fine pyrite, nanoscale hydrated ferric oxide (FeOOH).
The powdered granule that the catalyst is 1-200 μm of partial size, additional amount are the 0.5-6.0% of sawdust weight, preferably
For 1.0-3.0%.
The co-catalyst can be sulphur or organic sulfur compound such as carbon disulfide, dimethyl disulfide etc., co-catalyst
Additive amount is usually S/ catalyst activity component=0.5-3.0 (molar ratio) (catalyst loading is determined by the amount of S)；Wherein, S
For the element sulphur in co-catalyst, catalyst active component is active metal；In addition, different catalyst, active component are different
Sample, if transition-metal catalyst active component is transition metal, Fe-series catalyst active component is iron.
The mink cell focus can be coal tar, black petroleum products, liquefied coal coil, clarified oil, Atmospheric vacuum residual oil, cycle oil
At least one or their certain section of distillate of slurry etc..
The reactor can be the autoclave with stirring and external heating system of intermittent operation, be also possible to connect
Forced circulation suspension bed, bubbling bed, slurry bed system or the circulation flow reactor of continuous formula.When using batch autoclave, speed of agitator
For 20-1500r/min, preferably 300-1000r/min, the preferably rear above method adds hydrogen effect good, and fuel oil quality is good；Add
Hot mode is electric heating or oil bath or salt bath, and heating rate is 2-50 DEG C/min.
Below in conjunction with specific embodiment, invention is further explained.
Embodiment 1
Using the sawdust for being derived from certain wood-working factory as raw material, partial size is obtained in 300 μm of sawdust powder after broken drying.It will
15g wood dust, 25g high temperature coal-tar (its property is shown in Table 1), (granularity is uneven, and partial size is in 1- for 0.2g pyrite catalyst powder
Between 100 microns), 0.1g sulphur be separately added into 500ml autoclave, with air 3 times in hydrogen displacement kettle after sealing, use hydrogen
Being charged to pressure is 10MPa, is then turned on stirring, speed of agitator 800r/min.420 are warming up to the heating rate of 5 DEG C/min
DEG C, after keeping 1h in this state, heating mantle is removed, room temperature is naturally cooling under conditions of being kept stirring.Take out high pressure
Liquid in kettle consolidates product, using n-hexane as extractant, consolidates product to liquid using soxhlet extraction instrument and extracts, and extract is to contain
There is the fuel oil of extractant, extract remainder is unconverted sawdust.The result shows that sawdust conversion ratio is 77.30%, fuel oil yield is
56.71%.
Embodiment 2
Using the sawdust powder of embodiment 1 as raw material.By coalite tar in 10g wood dust, 25g (its property is shown in Table 1),
0.1g nanoscale aqua oxidation iron powder, 0.2g dimethyl disulfide are added in 500ml autoclave, with hydrogen displacement kettle after sealing
Interior air 3 times, being charged to pressure with hydrogen is 12MPa, is then turned on stirring, speed of agitator 800r/min.With the liter of 5 DEG C/min
Warm rate is warming up to 440 DEG C, after keeping 1.5h in this state, heating mantle is removed, is dropped naturally under conditions of being kept stirring
It warms to room temperature.The liquid taken out in autoclave consolidates product, using n-hexane as extractant, consolidates product to liquid using soxhlet extraction instrument and carries out
Extraction, extract are the fuel oil containing extractant, and extract remainder is unconverted sawdust.The result shows that sawdust conversion ratio is
82.43%, fuel oil yield is 60.18%.
Embodiment 3
Using the sawdust powder of embodiment 1 as raw material, mink cell focus is the distillate of 200-400 DEG C of coal liquefaction crude oil.By 120g
Wood dust, 200g mink cell focus (its property is shown in Table 1), 2.2g molybdenum oxide powder (granularity is 5-60 microns), 1.5g carbon disulfide add
Entering in the autoclave of 2L, with air 3 times in hydrogen displacement kettle after sealing, being charged to pressure with hydrogen is 8MPa, it is then turned on stirring,
Speed of agitator is 1000r/min.430 DEG C are warming up to the heating rate of 10 DEG C/min, after keeping 2h in this state, will be heated
Set is removed, and room temperature is naturally cooling under conditions of being kept stirring.The liquid taken out in autoclave consolidates product, utilizes simple distillation dress
It sets and is distilled, obtain the liquid fuel oil product that the end point of distillation is 450 DEG C, remaining non-steaming thing is unconverted sawdust.As a result table
Bright sawdust conversion ratio is 84.64%, and fuel oil yield is 61.12%.
Heavy oil nature in 1 embodiment 1-3 of table
The above described is only a preferred embodiment of the present invention, being not intended to limit the present invention in any form.Base
It is obtained by those of ordinary skill in the art without making creative efforts every other in the embodiment of the present invention
Embodiment shall fall within the protection scope of the present invention.
Claims (21)
1. a kind of method for adding hydrogen to prepare fuel oil altogether using sawdust and mink cell focus, which comprises the following steps:
1) sawdust is crushed, it is dry；
2) the sawdust powder that step 1) obtains is reacted under conditions of heating up and pressurizeing with catalyst, co-catalyst, mink cell focus, it
After be cooled to room temperature, extract, distillation.
2. the method for adding hydrogen to prepare fuel oil altogether using sawdust and mink cell focus as described in claim 1, which is characterized in that step
1) it is high shear crusher, ball mill or grinder that crushing device used is crushed described in, after being crushed granularity be 300 μm with
Under.
3. the method for adding hydrogen to prepare fuel oil altogether using sawdust and mink cell focus as described in claim 1, which is characterized in that step
1) dry drying device used described in is baking oven or Muffle furnace, and drying temperature is 120-250 DEG C, drying time 0.5-
3.0h。
4. the method for adding hydrogen to prepare fuel oil altogether using sawdust and mink cell focus as described in claim 1, which is characterized in that step
2) specifically: the sawdust powder after the broken drying of step 1) is added instead by a certain percentage with catalyst, co-catalyst, mink cell focus
It answers in device, reactor is filled with hydrogen, is warming up to 350-500 DEG C, is forced into 1-30MPa and is cooled to after constant temperature keeps 0.5-4.0h
After room temperature, the liquid after reaction is consolidated product and is extracted with n-hexane, after n-hexane soluble matter removes extractant, the combustion that as obtains
Material oil, n-hexane insoluble matter are unconverted sawdust；Or the liquid after reaction is consolidated product and is distilled in distilling apparatus, distillation obtains
Product liquid be fuel oil, solid is unconverted sawdust.
5. the method for adding hydrogen to prepare fuel oil altogether using sawdust and mink cell focus as claimed in claim 4, which is characterized in that described
Sawdust includes the leftover bits and pieces, sawdust or forestry waste of wood-working factory；Reactor is added after broken drying in the sawdust
Additional amount is the 20~95% of mink cell focus weight.
6. the method for adding hydrogen to prepare fuel oil altogether using sawdust and mink cell focus as claimed in claim 4, which is characterized in that described
Catalyst is hydrocracking catalyst, and the hydrocracking catalyst is selected from by transition-metal catalyst, metallic halid catalyst
Agent, Fe-series catalyst and iron series-transition metal composite catalyst composition one of group.
7. the method for adding hydrogen to prepare fuel oil altogether using sawdust and mink cell focus as claimed in claim 6, which is characterized in that described
Transition-metal catalyst is oxide or sulfide powder selected from least one of the group being made of platinum, rhenium, cobalt, molybdenum and nickel
End.
8. the method for adding hydrogen to prepare fuel oil altogether using sawdust and mink cell focus as claimed in claim 7, which is characterized in that described
Transition-metal catalyst is powder carrier catalyst.
9. the method for adding hydrogen to prepare fuel oil altogether using sawdust and mink cell focus as claimed in claim 8, which is characterized in that described
Active metal in transition-metal catalyst is selected from least one of the group being made of molybdenum, iron, tungsten, nickel and cobalt.
10. the method for adding hydrogen to prepare fuel oil altogether using sawdust and mink cell focus as claimed in claim 9, which is characterized in that institute
The catalyst carrier in transition-metal catalyst is stated in the group being made of inorganic oxide, carbon nanotube and molecular sieve extremely
Few one kind.
11. the method for adding hydrogen to prepare fuel oil altogether using sawdust and mink cell focus as claimed in claim 6, which is characterized in that institute
It states metal halide catalyst and is selected from ZnCl2Or SnCl2。
12. the method for adding hydrogen to prepare fuel oil altogether using sawdust and mink cell focus as claimed in claim 6, which is characterized in that institute
State one of Fe-series catalyst in the group that the compound by iron-containing natural crystal, iron-containing industrial residue and pure state iron forms
Kind.
13. the method for adding hydrogen to prepare fuel oil altogether using sawdust and mink cell focus as claimed in claim 12, which is characterized in that institute
Stating Fe-series catalyst is ultra-fine dispersed catalysts.
14. the method for adding hydrogen to prepare fuel oil altogether using sawdust and mink cell focus as claimed in claim 13, which is characterized in that institute
Stating Fe-series catalyst is ultra-fine pyrite or nanoscale hydrated ferric oxide.
15. the method for adding hydrogen to prepare fuel oil altogether using sawdust and mink cell focus as claimed in claim 4, which is characterized in that institute
The powdered granule that catalyst is 1-200 μm of partial size is stated, additive amount is the 0.5-6.0% of sawdust weight.
16. the method for adding hydrogen to prepare fuel oil altogether using sawdust and mink cell focus as claimed in claim 4, which is characterized in that institute
Stating co-catalyst is sulphur or organic sulfur compound.
17. the method for adding hydrogen to prepare fuel oil altogether using sawdust and mink cell focus as claimed in claim 16, which is characterized in that institute
Stating organic sulfur compound is carbon disulfide or dimethyl disulfide.
18. the method for adding hydrogen to prepare fuel oil altogether using sawdust and mink cell focus as claimed in claim 17, which is characterized in that institute
The additive amount for stating co-catalyst is S/ catalyst activity component=0.5-3.0 (molar ratio)；Wherein, S is the sulphur in co-catalyst
Element, catalyst active component are active metal.
19. the method for adding hydrogen to prepare fuel oil altogether using sawdust and mink cell focus as claimed in claim 4, which is characterized in that institute
It states mink cell focus and is selected from and be made of coal tar, black petroleum products, liquefied coal coil, clarified oil, Atmospheric vacuum residual oil and catalytic cracked oil pulp
At least one of group or their certain section of distillate.
20. the method for adding hydrogen to prepare fuel oil altogether using sawdust and mink cell focus as claimed in claim 4, which is characterized in that institute
Stating reactor is the outstanding with stirring and the autoclave of external heating system or continuous forced circulation of intermittent operation
Floating bed, bubbling bed, slurry bed system or circulation flow reactor.
21. the method for adding hydrogen to prepare fuel oil altogether using sawdust and mink cell focus as claimed in claim 20, which is characterized in that when
When using batch autoclave, speed of agitator 20-1500r/min, preferably 300-1000r/min；The intermittent high-pressure
The heating method of kettle is electric heating or oil bath or salt bath, and heating rate is 2-50 DEG C/min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110218573A (en) * | 2019-06-18 | 2019-09-10 | 太原理工大学 | A kind of no catalyst coal base heavy component method for upgrading |
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