CN109321269A - The method that pine tree effluent cracked-hydrogenate simultaneously preparation bio oil and monoterpene alkane - Google Patents
The method that pine tree effluent cracked-hydrogenate simultaneously preparation bio oil and monoterpene alkane Download PDFInfo
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- CN109321269A CN109321269A CN201811059786.9A CN201811059786A CN109321269A CN 109321269 A CN109321269 A CN 109321269A CN 201811059786 A CN201811059786 A CN 201811059786A CN 109321269 A CN109321269 A CN 109321269A
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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
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
- C10G3/46—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof in combination with chromium, molybdenum, tungsten metals or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
- C11C1/002—Sources of fatty acids, e.g. natural glycerides, characterised by the nature, the quantities or the distribution of said acids
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
- C10G2300/1014—Biomass of vegetal origin
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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- Life Sciences & Earth Sciences (AREA)
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of methods that pine tree effluent cracked-hydrogenate simultaneously preparation bio oil and monoterpene alkane, include following operating procedure: (1) will react in the pine tree effluent and catalyst investment reaction kettle after net system；(2) cooling discharging, suction filtration remove catalyst, obtain pine tree effluent cracking-hydrogenated products after reaction；(3) pine tree effluent cracking-hydrogenated products obtained by step (2) are evaporated under reduced pressure, collect 100 DEG C~102 DEG C of fraction up to pinane with to the monoterpene alkane of Meng's alkane, remainder is bio oil.The method of the present invention not only can get acid value is low, viscosity is low, the high bromine number of saturation degree is low, of light color and stability is good high-quality biological oil, but also can prepare pinane simultaneously and to Meng's alkane monoterpene alkane fine chemicals.
Description
Technical field
The present invention relates to a kind of method for preparing bio oil and monoterpene alkane, in particular to a kind of pine tree effluent is split simultaneously
Solution-hydrogenation preparation bio oil and monoterpene alkane method.
Background technique
The pine natural resin that resinosis cell is secreted in pine tree effluent, that is, living body pine tree or conifer trunk resin canal, is one
The reproducible non-grain natural products of kind, is known as " lignicolous petroleum ".Pine tree effluent can obtain primary product pine through distillation
Fragrant and turpentine oil, the main chemical compositions of rosin are rosin acid, it is that one kind contains 2 unsaturated double-bonds, has tricyclic
The monocarboxylic acid of luxuriant and rich with fragrance skeleton；Terebinthine main chemical compositions are monoterpene olefinic constituent, and wherein most is the firpene of bicyclic diterpene
With the monocyclic monoterpene alkene of Foxlene structure, it is possible to provide the C containing annulus or bridged ring and double bond10Molecular skeleton, therefore rosin and turpentine
Oil is important industrial chemicals.Pine forest is resourceful in China, and pine forest area has 22,460,000 hectares, can resin tapping pine forest resource compared with
Greatly, the reserves of pine tree effluent are 162.5 ten thousand t/, and Guangxi, Guangdong, Yunnan, Fujian, Jiangxi and Hunan etc., which are saved with autonomous region, is
Mainly there are masson pine (P.massoniana), pinus yunnanensis in the major production areas of pine natural resin for the pine tree tree species of resin tapping
(P.yunnanensis), pinus khasys (P.kesiyaar.langbianensis), wet-land pine tree (P.elliottii) and pinus finlaysoniana
(P.latteri), wherein the rouge reserves of masson pine are maximum, account for about 56.3%, followed by pinus yunnanensis and pinus khasys, wet-land pine tree also has
Certain Oleoresin output.The output value that pine natural resin processing series of products are related to relevant industries accounts for the Chinese national economy gross output value
1/10, but the most pine natural resin in China supplies to be put on sale at present to distill obtained rosin and turpentine oil primary product
, deep processing and utilization rate is only 40%, and the developed countries such as America and Europe are then close to 100%.
Currently, main energy resources are the non-renewable fossil fuel such as petroleum, coal and natural gas, Duo Shuo great in the world
Ancestor's industrial chemicals also depends on the fossil base hydrocarbon of non-renewable resources.With the continuous exhaustion of fossil resource,
And fossil fuel bring Heavy environmental pollution, energy shortage and environmental problem have become the world today faced it is most severe
One of the problem of.Reproducible biomass resource is converted into liquid bio fuel oil and fine chemicals raw material just increasingly by pass
Note, thermal cracking/cracking of biomass and catalytic pyrolysis/cracking technology are one of the main methods of current bio oil preparation, related
Inventive technique applied for following patent of invention.
CN201711118926.0 discloses a kind of CO2Two step of lignocellulosic classification hydrothermal liquefaction preparation biology under atmosphere
The method of oil；CN201711282928.3 disclose it is a kind of with wheat stalk, it is corn stover, soybean stalk, rice straw, various
Sawdust and bagasse etc. are the method that raw material prepares environment protection biological oil；CN200910086766.5 discloses a kind of solid fermentation
The method of lignocellulosic material producing microbial grease obtains unsaturated fatty acid or biodiesel oil sources；
CN200510039170.1 and CN200910155887.0, which is disclosed, to be cracked by rosin and prepares biodiesel and life after compounding
The method of object fuel oil.Turpentine oil hydrogenation reaction product monoterpene alkane mainly includes pinane and to Meng's alkane, and pinane is important fragrance
Synthetic intermediate can be used as the raw material for synthesizing fine perfumery and vitamin A, E, K；To Meng's alkane can synthetic rubber initiator, and
Synthesize the important intermediate of a variety of fine chemical products.Abietyl bio oil and pinane and two step method system is generallyd use to Meng's alkane
Standby: the pine tree effluent after net system is carried out steam distillation and obtains rosin and turpentine oil respectively by the first step；Second step is distinguished again
Abietyl bio oil is prepared by catalyst for cracking such as raw material, atlapulgite or molecular sieves of rosin, is used by raw material of turpentine oil
Monoterpene alkane is made in Pd/C hydrogenation catalyst, and wherein the bicyclic monoterpene in turpentine oil adds hydrogen to obtain pinane, the monocycle in turpentine oil
Monoterpene adds hydrogen to obtain to Meng's alkane, it is seen that its preparation process flow is long and energy consumption is high, only pine tree effluent distillation production 1t rosin
With regard to needing the 1.667~2.038GJ that consume energy more；And gained abietyl bio oil is there are oxygen-containing height, large viscosity, acidity is strong and contains double
The defects of key component is unstable perishable.
In conclusion traditional prepare bio oil only with single cleavage method, there are the oxygen-containing height of product, large viscosity,
The problems such as acidity is strong and component containing double bond is unstable perishable.The double bond unsaturation product that bio oil contains how will be cracked to become
It is the key point for preparing bio oil for saturated compounds.The preparation of abietyl bio oil and monoterpene alkane simultaneously there is also
The defect that process flow is long and energy consumption is high.
The information disclosed in the background technology section is intended only to increase the understanding to general background of the invention, without answering
When being considered as recognizing or imply that the information constitutes the prior art already known to those of ordinary skill in the art in any form.
Summary of the invention
The purpose of the present invention is being directed to the deficiency of the above method, the bio oil and monoterpene alkane of a kind of simple production process are provided
Hydrocarbon chemicals simultaneously prepare method, it is intended to obtain it is a kind of both can get acid value is low, viscosity is low, the high bromine number of saturation degree is low, color
Shallow and good stability high-quality biological oil, and pinane and the method to Meng's alkane monoterpene alkane fine chemicals can be prepared simultaneously.
To achieve the above object, technical solution provided by the invention is as follows:
A kind of method that pine tree effluent cracked-hydrogenate simultaneously preparation bio oil and monoterpene alkane, walks comprising following operation
It is rapid:
(1) by the pine tree effluent and catalyst investment high-pressure stirring reaction kettle after net system, upper cover is sealed, then successively
High-pressure stirring reaction kettle is vacuumized, is passed through H2Pressure maintaining leak detection, H2Displacement, starting autoclave stirrer and heating system heats into
Row reaction, 190 DEG C~370 DEG C of reaction temperature, reaction pressure 1.0MPa~10.0MPa, speed of agitator 200r/min~600r/
Min, reaction time 1.5h~4.5h；Wherein, catalyst amount is that pine tree flows out the 2%~15% of amount of substance；
(2) it is cooled to room temperature and is vented to normal pressure after reaction and discharged, filter and remove catalyst, obtain pine tree effluent
Cracking-hydrogenated products；
(3) pine tree effluent cracking-hydrogenated products obtained by step (2) are evaporated under reduced pressure at 550mmHg~650mmHg
1.5h~3h collects 100 DEG C~102 DEG C of fraction up to pinane with to the monoterpene alkane of Meng's alkane, and remaining light yellow clear is low
Viscosity liquid is bio oil.
Preferably, net system described in step (1) is that pine tree effluent is heated to 90 DEG C~105 DEG C dissolutions, while hot mistake
Filter out the liquid that residue obtains.
Preferably, the pine tree effluent be masson pine pine tree effluent, pinus yunnanensis pine tree effluent, Simao loosely
Set one of effluent or wet-land pine tree pine tree effluent.
Preferably, catalyst described in step (1) is using FCC catalyst load C o-Mo, Ni-W, Ni-Mo or Cu-
The difunctional double non-noble metal catalyst of cracking-hydrogenation that one of Co is obtained.
Preferably, the total load amount of the catalyst is 15%~35% (wt%), double non-noble metal Co:Mo, Ni:
The mass ratio of Mo, Ni:W or Cu:Co are all 1:1~1:20, i.e. Co:Mo=1:1~1:20, Ni:Mo=1:1~1:20, Ni:W
=1:1~1:20, Cu:Co=1:1~1:20.
Preferably, the FCC catalyst is fresh FCC catalyst or useless FCC catalyst.
Preferably, the preparation method of catalyst described in step (1) includes following operating procedure:
(a) carrier FCC catalyst pre-processes: fresh FCC catalyst is put into baking oven at 105 DEG C~120 DEG C dry 2h
~5h removes the moisture in carrier；Or useless FCC catalyst is subjected to roasting 1.5h~4.5h activation, maturing temperature is 450 DEG C~700
℃；
(b) solution dipping method impregnates: on the basis of FCC catalyst carrier, matching at normal temperature according to required content of metal
Precursor solution is slowly added dropwise to by the precursor solution of Co:Mo, Ni:Mo, Ni:W or Cu:Co processed under constant stirring later
Continue in FCC catalyst carrier, after completion of dropwise addition stirring 5 minutes, after under room temperature stand 2h~6h；
(c) dry: the sample after dipping is put into baking oven at 110 DEG C~130 DEG C dry 8h~10h；
(d) it roasts: the sample after drying is obtained into catalyst precursor in 500 DEG C of calcining 3h of box Muffle furnace；
(e) it restores: catalyst precursor is placed in tube furnace in H2Under atmosphere at 450 DEG C~560 DEG C reductase 12 .5h
~6h, H2Flow is 40mLmin-1, FCC catalyst supported bimetal catalyst is obtained after natural cooling.
Compared with prior art, the invention has the following beneficial effects:
(1) directly using pine tree effluent as raw material, catalytic pyrolysis-hydrogenation prepares bio oil and monoterpene hydrocarbonylation to the present invention simultaneously
Product overcome Conventional process complex process, long flow path, pollute the defects of big, energy consumption is high；Make full use of FCC catalyst excellent
Cracking performance and H more2The acid concerted catalysis that Hydrogen spillover generates under atmosphere promotes the cracking of rosin acid, double non-noble metal
Disconnected C-C, C-O key and decarboxylation ability of catalyst and hydrogenation had not only cracked the rosin acid of the more carbon of tricyclic but also be saturated cracking
Double bond component in product achievees the purpose that crack synthesising biological oil adds hydrogen upgrading is synchronous to carry out with unsaturated bio oil；
(2) present invention not only obtains the height that acid value is low, viscosity is low, the high bromine number of saturation degree is low, of light color and stability is good
Quality bio oil, also simultaneously synthesizing pinane and to Meng's alkane；Carbon number can be obtained between C through vacuum distillation in the present invention12~C20It is full
It is less than 1.50mgKOHg with the acid value of cycloalkane and aliphatic hydrocarbon bio oil, bio oil-1, bromine number be less than 1.62Br/100g, 16
Alkane value is 30~45, and coproduction pinane and to Meng's alkane simultaneously, and the yield of monoterpene alkane is 35%~50%.
Detailed description of the invention
Fig. 1 is to prepare gained bio oil using rosin using prior art cracking process, and wherein a is the biology on the preparation same day
Oil, b are the bio oil after placing 5 days.
Fig. 2 is obtained bio oil produced according to the present invention, and wherein a is the bio oil on the preparation same day, and b is to place 1 month
Bio oil afterwards.
Specific embodiment
Specific embodiment is described in detail with reference to the accompanying drawing, it is to be understood that protection scope of the present invention not by
The limitation of specific embodiment.Raw material sources in the following example: pine tree effluent provides or is purchased from city by rosin production producer
?；FCC catalyst (FCC) is purchased from Effect of Catalysis In Petrochemistry agent manufacturer, and useless FCC catalyst (SFCC) is provided by petroleum chemical enterprise.
The pine tree effluent cracking-hydrogenation operation carried out in the following example mesohigh stirred autoclave vacuumizes
Pressure maintaining leak detection, the operation for being replaced into conventional high pressure reaction assembly；High-pressure stirring reaction kettle is commercially available, capacity 2L.
Embodiment 1
The preparation method of catalyst, operating procedure are as follows:
(a) carrier FCC catalyst pre-processes: fresh FCC catalyst being put into baking oven at 105 DEG C dry 2h and removes carrier
In moisture；
(b) solution dipping method impregnates: on the basis of FCC catalyst carrier, according to required metal total load amount 15%
(wt%) precursor solution of Co:Mo is prepared using cobalt nitrate and ammonium molybdate and deionized water at normal temperature, double non-noble metal Co:
The mass ratio of Mo is 1:1, is later slowly added dropwise to precursor solution in FCC catalyst carrier under constant stirring, completion of dropwise addition
After continue stirring 5 minutes, after stand 2h under room temperature；
(c) dry: the sample after dipping is put into baking oven at 110 DEG C dry 8h；
(d) it roasts: the sample after drying is obtained into catalyst precursor in 500 DEG C of calcining 3h of box Muffle furnace；
(e) it restores: catalyst precursor is placed in tube furnace in H2Under atmosphere at 450 DEG C reductase 12 .5h, H2Flow is
40mL·min-1, FCC catalyst supported bimetal catalyst is obtained after natural cooling；It is spare.
A kind of method that pine tree effluent cracked-hydrogenate simultaneously preparation bio oil and monoterpene alkane, operating procedure are as follows:
(1) masson pine pine tree effluent is heated to 90 DEG C~105 DEG C dissolutions, is filtered to remove the liquid that residue obtains while hot
Substance is the pine tree effluent after net system, contains turpentine oil 35%, spare；By the masson pine pine tree stream after above-mentioned spare net system
Out in object 700g and above-mentioned spare catalyst investment high-pressure stirring reaction kettle, upper cover sealing is then successively anti-to high-pressure stirring
It answers kettle to vacuumize, be passed through H2Pressure maintaining leak detection, H2Displacement, starting autoclave stirrer and heating system heats are reacted, reaction temperature
190 DEG C, reaction pressure 1.0MPa, speed of agitator 200r/min~600r/min of degree, reaction time 1.5h；Wherein, catalyst is used
Amount is that pine tree flows out the 2% of amount of substance；
(2) it is cooled to room temperature and is vented to normal pressure after reaction and discharged, filter and remove catalyst, obtain pine tree effluent
Cracking-hydrogenated products；
(3) pine tree effluent cracking-hydrogenated products obtained by step (2) are evaporated under reduced pressure 2.0h at 550mmHg, collected
100 DEG C of fraction up to pinane with to the monoterpene alkane of Meng's alkane, make a living by the transparent liquid of remaining light yellow clear low-viscosity
Object oil, carbon number is between C12~C20.Wherein pinane and be 75% to Meng's alkane content, the yield of monoterpene alkane is 36%, through detecting,
The density 960.1kgm of bio oil-3(20 DEG C), cetane index 32, acid value 1.46mgKOHg-1, dynamic viscosity
(40℃)18.26mm2·s-1, bromine number 1.56Br/100g.
Embodiment 2
The preparation method of catalyst, operating procedure are as follows:
(a) useless FCC catalyst is kept temperature is 450 DEG C of roasting 1.5h activation；
(b) solution dipping method impregnates: on the basis of the FCC catalyst carrier after activating, according to required metal total load amount
20% (wt%) prepares the precursor solution of Co:Mo, your double non-gold using cobalt nitrate and ammonium molybdate and deionized water at normal temperature
The mass ratio for belonging to Co:Mo is 1:10, is later slowly added dropwise to precursor solution in FCC catalyst carrier under constant stirring, is dripped
Continue after adding stirring 5 minutes, after stand 6h under room temperature；
(c) dry: the sample after dipping is put into baking oven at 130 DEG C dry 10h；
(d) it roasts: the sample after drying is obtained into catalyst precursor in 500 DEG C of calcining 3h of box Muffle furnace；
(e) it restores: catalyst precursor is placed in tube furnace in H23h, H are restored under atmosphere at 500 DEG C2Flow is
40mL·min-1, FCC catalyst supported bimetal catalyst is obtained after natural cooling；It is spare.
A kind of method that pine tree effluent cracked-hydrogenate simultaneously preparation bio oil and monoterpene alkane, operating procedure are as follows:
(1) pinus yunnanensis pine tree effluent is heated to 90 DEG C~105 DEG C dissolutions, is filtered to remove the liquid that residue obtains while hot
Substance is the pine tree effluent after net system, contains turpentine oil 35%, spare；By the pinus yunnanensis pine tree stream after above-mentioned spare net system
Out in object 720g and above-mentioned spare catalyst investment high-pressure stirring reaction kettle, upper cover sealing is then successively anti-to high-pressure stirring
It answers kettle to vacuumize, be passed through H2Pressure maintaining leak detection, H2Displacement, starting autoclave stirrer and heating system heats are reacted, reaction temperature
250 DEG C, reaction pressure 3.0MPa, speed of agitator 200r/min~600r/min of degree, reaction time 2h；Wherein, catalyst amount
Flow out amount of substance for pine tree 6%；
(2) it is cooled to room temperature and is vented to normal pressure after reaction and discharged, filter and remove catalyst, obtain pine tree effluent
Cracking-hydrogenated products；
(3) pine tree effluent cracking-hydrogenated products obtained by step (2) are evaporated under reduced pressure 1.5h at 600mmHg, collected
101 DEG C of fraction up to pinane with to the monoterpene alkane of Meng's alkane, make a living by the transparent liquid of remaining light yellow clear low-viscosity
Object oil, carbon number is between C12~C20.Wherein pinane and be 72% to Meng's alkane content, the yield of monoterpene alkane is 40%, through detecting,
The density 946.1kgm of bio oil-3(20 DEG C), cetane index 36, acid value 1.37mgKOHg-1, dynamic viscosity
(40℃)12.85mm2·s-1, bromine number 1.62Br/100g.
Embodiment 3
The preparation method of catalyst, operating procedure are as follows:
(a) carrier FCC catalyst pre-processes: fresh FCC catalyst being put into baking oven at 120 DEG C dry 5h and removes carrier
In moisture；
(b) solution dipping method impregnates: on the basis of FCC catalyst carrier, according to required metal total load amount 30%
(wt%) precursor solution of Co:Mo is prepared using cobalt nitrate and ammonium molybdate and deionized water at normal temperature, double non-noble metal Co:
The mass ratio of Mo is 1:20, is later slowly added dropwise to precursor solution in FCC catalyst carrier under constant stirring, completion of dropwise addition
After continue stirring 5 minutes, after stand 3h under room temperature；
(c) dry: the sample after dipping is put into baking oven at 120 DEG C dry 9h；
(d) it roasts: the sample after drying is obtained into catalyst precursor in 500 DEG C of calcining 3h of box Muffle furnace；
(e) it restores: catalyst precursor is placed in tube furnace in H24h, H are restored under atmosphere at 560 DEG C2Flow is
40mL·min-1, FCC catalyst supported bimetal catalyst is obtained after natural cooling；It is spare.
A kind of method that pine tree effluent cracked-hydrogenate simultaneously preparation bio oil and monoterpene alkane, operating procedure are as follows:
(1) pinus khasys pine tree effluent is heated to 90 DEG C~105 DEG C dissolutions, is filtered to remove the liquid that residue obtains while hot
Substance is the pine tree effluent after net system, contains turpentine oil 40%, spare；By the pinus khasys pine tree stream after above-mentioned spare net system
Out in object 770g and above-mentioned spare catalyst investment high-pressure stirring reaction kettle, upper cover sealing is then successively anti-to high-pressure stirring
It answers kettle to vacuumize, be passed through H2Pressure maintaining leak detection, H2Displacement, starting autoclave stirrer and heating system heats are reacted, reaction temperature
370 DEG C, reaction pressure 10.0MPa, speed of agitator 200r/min~600r/min of degree, reaction time 4h；Wherein, catalyst amount
Flow out amount of substance for pine tree 15%；
(2) it is cooled to room temperature and is vented to normal pressure after reaction and discharged, filter and remove catalyst, obtain pine tree effluent
Cracking-hydrogenated products；
(3) pine tree effluent cracking-hydrogenated products obtained by step (2) are evaporated under reduced pressure at 600mmHg 2h, collect 100
DEG C fraction up to pinane with to the monoterpene alkane of Meng's alkane, the transparent liquid of remaining light yellow clear low-viscosity is biology
Oil, carbon number is between C12~C20.Wherein pinane and be 80% to Meng's alkane content, the yield of monoterpene alkane is 40%, is detected, raw
The density 932.1kgm of object oil-3(20 DEG C), cetane index 45, acid value 1.03mgKOHg-1, dynamic viscosity (40
℃)9.01mm2·s-1, bromine number 0.95Br/100g.
Embodiment 4
The preparation method of catalyst, operating procedure are as follows:
(a) carrier FCC catalyst pre-processes: useless FCC catalyst is carried out 700 DEG C of roasting 4.5h activation；
(b) solution dipping method impregnates: on the basis of FCC catalyst carrier, according to required metal total load amount 30%
(wt%) Ni:W precursor solution, double non-noble metal Ni:W are prepared using nickel nitrate and ammonium metatungstate and deionized water at normal temperature
Mass ratio be 1:20, precursor solution is slowly added dropwise in FCC catalyst carrier under constant stirring later, after completion of dropwise addition
Continue stirring 5 minutes, after stand 3.5h under room temperature；
(c) dry: the sample after dipping is put into baking oven at 115 DEG C dry 8.5h；
(d) it roasts: the sample after drying is obtained into catalyst precursor in 500 DEG C of calcining 3h of box Muffle furnace；
(e) it restores: catalyst precursor is placed in tube furnace in H26h, H are restored under atmosphere at 500 DEG C2Flow is
40mL·min-1, FCC catalyst supported bimetal catalyst is obtained after natural cooling；It is spare.
A kind of method that pine tree effluent cracked-hydrogenate simultaneously preparation bio oil and monoterpene alkane, operating procedure are as follows:
(1) wet-land pine tree pine tree effluent is heated to 90 DEG C~105 DEG C dissolutions, is filtered to remove the liquid that residue obtains while hot
Substance is the pine tree effluent after net system, contains turpentine oil 37%, spare；By the wet-land pine tree pine tree stream after above-mentioned spare net system
Out in object 760g and above-mentioned spare catalyst investment high-pressure stirring reaction kettle, upper cover sealing is then successively anti-to high-pressure stirring
It answers kettle to vacuumize, be passed through H2Pressure maintaining leak detection, H2Displacement, starting autoclave stirrer and heating system heats are reacted, reaction temperature
300 DEG C, reaction pressure 10.0MPa, speed of agitator 200r/min~600r/min of degree, reaction time 4h；Wherein, catalyst amount
Flow out amount of substance for pine tree 5%；
(2) it is cooled to room temperature and is vented to normal pressure after reaction and discharged, filter and remove catalyst, obtain pine tree effluent
Cracking-hydrogenated products；
(3) pine tree effluent cracking-hydrogenated products obtained by step (2) are evaporated under reduced pressure at 650mmHg 3h, collect 102
DEG C fraction up to pinane with to the monoterpene alkane of Meng's alkane, the transparent liquid of remaining light yellow clear low-viscosity is biology
Oil, carbon number is between C12~C20.Wherein pinane and be 80% to Meng's alkane content, the yield of monoterpene alkane is 50%, is detected, raw
The density 912.1kgm of object oil-3(20 DEG C), cetane index 45, acid value 0.97mgKOHg-1, dynamic viscosity (40
℃)10.21mm2·s-1, bromine number 1.07Br/100g.
Embodiment 5
The preparation method of catalyst, operating procedure are as follows:
(a) carrier FCC catalyst pre-processes: fresh FCC catalyst being put into baking oven at 110 DEG C dry 4h and removes carrier
In moisture；
(b) solution dipping method impregnates: on the basis of FCC catalyst carrier, according to required metal total load amount 27%
(wt%) precursor solution of Ni:W, double non-noble metal are prepared using nickel nitrate and ammonium metatungstate and deionized water at normal temperature
The mass ratio of Ni:W is 1:15, is later slowly added dropwise to precursor solution in FCC catalyst carrier under constant stirring, and knot is added dropwise
Continue after beam stirring 5 minutes, after stand 4h under room temperature；
(c) dry: the sample after dipping is put into baking oven at 125 DEG C dry 8.5h；
(d) it roasts: the sample after drying is obtained into catalyst precursor in 500 DEG C of calcining 3h of box Muffle furnace；
(e) it restores: catalyst precursor is placed in tube furnace in H25h, H are restored under atmosphere at 470 DEG C2Flow is
40mL·min-1, FCC catalyst supported bimetal catalyst is obtained after natural cooling；It is spare.
A kind of method that pine tree effluent cracked-hydrogenate simultaneously preparation bio oil and monoterpene alkane, operating procedure are as follows:
(1) masson pine pine tree effluent is heated to 90 DEG C~105 DEG C dissolutions, is filtered to remove the liquid that residue obtains while hot
Substance is the pine tree effluent after net system, contains turpentine oil 37%, spare；By the masson pine pine tree stream after above-mentioned spare net system
Out in object 760g and above-mentioned spare catalyst investment high-pressure stirring reaction kettle, upper cover sealing is then successively anti-to high-pressure stirring
It answers kettle to vacuumize, be passed through H2Pressure maintaining leak detection, H2Displacement, starting autoclave stirrer and heating system heats are reacted, reaction temperature
320 DEG C, reaction pressure 6MPa, speed of agitator 200r/min~600r/min of degree, reaction time 3.5h；Wherein, catalyst amount
Flow out amount of substance for pine tree 8%；
(2) it is cooled to room temperature and is vented to normal pressure after reaction and discharged, filter and remove catalyst, obtain pine tree effluent
Cracking-hydrogenated products；
(3) pine tree effluent cracking-hydrogenated products obtained by step (2) are evaporated under reduced pressure at 580mmHg 3h, collect 100
DEG C fraction up to pinane with to the monoterpene alkane of Meng's alkane, the transparent liquid of remaining light yellow clear low-viscosity is biology
Oil, carbon number is between C12~C20.Wherein pinane and be 85% to Meng's alkane content, the yield of monoterpene alkane is 47%, is detected, raw
The density 960.2kgm of object oil-3(20 DEG C), cetane index 37, acid value 1.2mgKOHg-1, dynamic viscosity (40
℃)9.87mm2·s-1, bromine number 1.19Br/100g.
Embodiment 6
The preparation method of catalyst, operating procedure are as follows:
(a) carrier FCC catalyst pre-processes: useless FCC catalyst is carried out 600 DEG C of roasting 3h activation；
(b) solution dipping method impregnates: on the basis of FCC catalyst carrier, according to required metal total load amount 16%
(wt%) precursor solution of Ni:W, double non-noble metal are prepared using nickel nitrate and ammonium metatungstate and deionized water at normal temperature
The mass ratio of Ni:W is 1:9, is later slowly added dropwise to precursor solution in FCC catalyst carrier under constant stirring, and knot is added dropwise
Continue after beam stirring 5 minutes, after stand 5.5h under room temperature；
(c) dry: the sample after dipping is put into baking oven at 125 DEG C dry 9.0h；
(d) it roasts: the sample after drying is obtained into catalyst precursor in 500 DEG C of calcining 3h of box Muffle furnace；
(e) it restores: catalyst precursor is placed in tube furnace in H25h, H are restored under atmosphere at 500 DEG C2Flow is
40mL·min-1, FCC catalyst supported bimetal catalyst is obtained after natural cooling；It is spare.
A kind of method that pine tree effluent cracked-hydrogenate simultaneously preparation bio oil and monoterpene alkane, operating procedure are as follows:
(1) masson pine pine tree effluent is heated to 90 DEG C~105 DEG C dissolutions, is filtered to remove the liquid that residue obtains while hot
Substance is the pine tree effluent after net system, contains turpentine oil 40%, spare；By the masson pine pine tree stream after above-mentioned spare net system
Out in object 800g and above-mentioned spare catalyst investment high-pressure stirring reaction kettle, upper cover sealing is then successively anti-to high-pressure stirring
It answers kettle to vacuumize, be passed through H2Pressure maintaining leak detection, H2Displacement, starting autoclave stirrer and heating system heats are reacted, reaction temperature
290 DEG C, reaction pressure 7.0MPa, speed of agitator 200r/min~600r/min of degree, reaction time 2h；Wherein, catalyst amount
Flow out amount of substance for pine tree 12%；
(2) it is cooled to room temperature and is vented to normal pressure after reaction and discharged, filter and remove catalyst, obtain pine tree effluent
Cracking-hydrogenated products；
(3) pine tree effluent cracking-hydrogenated products obtained by step (2) are evaporated under reduced pressure 2.5h at 650mmHg, collected
102 DEG C of fraction up to pinane with to the monoterpene alkane of Meng's alkane, make a living by the transparent liquid of remaining light yellow clear low-viscosity
Object oil, carbon number is between C12~C20.Wherein pinane and be 78% to Meng's alkane content, the yield of monoterpene alkane is 48%, through detecting,
The density 937.5kgm of bio oil-3(20 DEG C), cetane index 40, acid value 1.2mgKOHg-1, dynamic viscosity
(40℃)11.27mm2·s-1, bromine number 0.93Br/100g.
Embodiment 7
The preparation method of catalyst, operating procedure are as follows:
(a) carrier FCC catalyst pre-processes: fresh FCC catalyst is put into baking oven at 107 DEG C dry 4.5h except unloading
Moisture in body；
(b) solution dipping method impregnates: on the basis of FCC catalyst carrier, according to required metal total load amount 17%
(wt%) precursor solution of Ni:Mo is prepared using nickel nitrate and ammonium molybdate and deionized water at normal temperature, double non-noble metal Ni:
The mass ratio of Mo is 1:9, is later slowly added dropwise to precursor solution in FCC catalyst carrier under constant stirring, completion of dropwise addition
After continue stirring 5 minutes, after stand 3h under room temperature；
(c) dry: the sample after dipping is put into baking oven at 117 DEG C dry 9.5h；
(d) it roasts: the sample after drying is obtained into catalyst precursor in 500 DEG C of calcining 3h of box Muffle furnace；
(e) it restores: catalyst precursor is placed in tube furnace in H25.5h, H are restored under atmosphere at 490 DEG C2Flow is
40mL·min-1, FCC catalyst supported bimetal catalyst is obtained after natural cooling；It is spare.
A kind of method that pine tree effluent cracked-hydrogenate simultaneously preparation bio oil and monoterpene alkane, operating procedure are as follows:
(1) pinus yunnanensis pine tree effluent is heated to 90 DEG C~105 DEG C dissolutions, is filtered to remove the liquid that residue obtains while hot
Substance is the pine tree effluent after net system, contains turpentine oil 35%, spare；By the pinus yunnanensis pine tree stream after above-mentioned spare net system
Out in object 750g and above-mentioned spare catalyst investment high-pressure stirring reaction kettle, upper cover sealing is then successively anti-to high-pressure stirring
It answers kettle to vacuumize, be passed through H2Pressure maintaining leak detection, H2Displacement, starting autoclave stirrer and heating system heats are reacted, reaction temperature
210 DEG C, reaction pressure 8.0MPa, speed of agitator 200r/min~600r/min of degree, reaction time 4h；Wherein, catalyst amount
Flow out amount of substance for pine tree 10%；
(2) it is cooled to room temperature and is vented to normal pressure after reaction and discharged, filter and remove catalyst, obtain pine tree effluent
Cracking-hydrogenated products；
(3) pine tree effluent cracking-hydrogenated products obtained by step (2) are evaporated under reduced pressure at 590mmHg 3h, collect 101
DEG C fraction up to pinane with to the monoterpene alkane of Meng's alkane, the transparent liquid of remaining light yellow clear low-viscosity is biology
Oil, carbon number is between C12~C20.Wherein pinane and be 75% to Meng's alkane content, the yield of monoterpene alkane is 42%, is detected, raw
The density 951.7kgm of object oil-3(20 DEG C), cetane index 35, acid value 1.3mgKOHg-1, dynamic viscosity (40
℃)16.92mm2·s-1, bromine number 1.60Br/100g.
Embodiment 8
The preparation method of catalyst, operating procedure are as follows:
(a) carrier FCC catalyst pre-processes: useless FCC catalyst is carried out 700 DEG C of roasting 1.5h activation；
(b) solution dipping method impregnates: on the basis of FCC catalyst carrier, according to required metal total load amount 25%
(wt%) precursor solution of Ni:Mo is prepared using nickel nitrate and ammonium molybdate and deionized water at normal temperature, double non-noble metal Ni:
The mass ratio of Mo is 1:15, is later slowly added dropwise to precursor solution in FCC catalyst carrier under constant stirring, completion of dropwise addition
After continue stirring 5 minutes, after stand 2h under room temperature；
(c) dry: the sample after dipping being put into baking oven and dries 10h under 110；
(d) it roasts: the sample after drying is obtained into catalyst precursor in 500 DEG C of calcining 3h of box Muffle furnace；
(e) it restores: catalyst precursor is placed in tube furnace in H2Under atmosphere at 560 DEG C reductase 12 .5h, H2Flow is
40mL·min-1, FCC catalyst supported bimetal catalyst is obtained after natural cooling；It is spare.
A kind of method that pine tree effluent cracked-hydrogenate simultaneously preparation bio oil and monoterpene alkane, operating procedure are as follows:
(1) Simao pine tree effluent is heated to 90 DEG C~105 DEG C dissolutions, is filtered to remove the liquid object that residue obtains while hot
Matter is the pine tree effluent after net system, contains turpentine oil 40%, spare；By the pinus khasys pine tree outflow after above-mentioned spare net system
In object 780g and above-mentioned spare catalyst investment high-pressure stirring reaction kettle, then upper cover sealing successively reacts high-pressure stirring
Kettle vacuumizes, is passed through H2Pressure maintaining leak detection, H2Displacement, starting autoclave stirrer and heating system heats are reacted, reaction temperature
280 DEG C, reaction pressure 9.0MPa, speed of agitator 200r/min~600r/min, reaction time 4.5h；Wherein, catalyst amount
Flow out amount of substance for pine tree 7%；
(2) it is cooled to room temperature and is vented to normal pressure after reaction and discharged, filter and remove catalyst, obtain pine tree effluent
Cracking-hydrogenated products；
(3) pine tree effluent cracking-hydrogenated products obtained by step (2) are evaporated under reduced pressure 2.5h at 620mmHg, collected
100 DEG C of fraction up to pinane with to the monoterpene alkane of Meng's alkane, make a living by the transparent liquid of remaining light yellow clear low-viscosity
Object oil, carbon number is between C12~C20.Wherein pinane and be 72% to Meng's alkane content, the yield of monoterpene alkane is 46%, through detecting,
The density 915.6kgm of bio oil-3(20 DEG C), cetane index 37, acid value 0.82mgKOHg-1, dynamic viscosity
(40℃)10.87mm2·s-1, bromine number 1.21Br/100g.
Embodiment 9
The preparation method of catalyst, operating procedure are as follows:
(a) carrier FCC catalyst pre-processes: fresh FCC catalyst being put into baking oven at 120 DEG C dry 5h and removes carrier
In moisture；
(b) solution dipping method impregnates: on the basis of FCC catalyst carrier, according to required metal total load amount 32%
(wt%) precursor solution of Ni:Mo is prepared using nickel nitrate and ammonium molybdate and deionized water at normal temperature, double non-noble metal Ni:
The mass ratio of Mo is 1:8, is later slowly added dropwise to precursor solution in FCC catalyst carrier under constant stirring, completion of dropwise addition
After continue stirring 5 minutes, after stand 3h under room temperature；
(c) dry: the sample after dipping is put into baking oven at 130 DEG C dry 8hh；
(d) it roasts: the sample after drying is obtained into catalyst precursor in 500 DEG C of calcining 3h of box Muffle furnace；
(e) it restores: catalyst precursor is placed in tube furnace in H24h, H are restored under atmosphere at 500 DEG C2Flow is
40mL·min-1, FCC catalyst supported bimetal catalyst is obtained after natural cooling；It is spare.
A kind of method that pine tree effluent cracked-hydrogenate simultaneously preparation bio oil and monoterpene alkane, operating procedure are as follows:
(1) wet-land pine tree pine tree effluent is heated to 90 DEG C~105 DEG C dissolutions, is filtered to remove the liquid that residue obtains while hot
Substance is the pine tree effluent after net system, contains turpentine oil 35%, spare；By the wet-land pine tree pine tree stream after above-mentioned spare net system
Out in object 700g and above-mentioned spare catalyst investment high-pressure stirring reaction kettle, upper cover sealing is then successively anti-to high-pressure stirring
It answers kettle to vacuumize, be passed through H2Pressure maintaining leak detection, H2Displacement, starting autoclave stirrer and heating system heats are reacted, reaction temperature
360 DEG C, reaction pressure 10.0MPa, speed of agitator 200r/min~600r/min of degree, reaction time 2h；Wherein, catalyst amount
Flow out amount of substance for pine tree 3%；
(2) it is cooled to room temperature and is vented to normal pressure after reaction and discharged, filter and remove catalyst, obtain pine tree effluent
Cracking-hydrogenated products；
(3) pine tree effluent cracking-hydrogenated products obtained by step (2) are evaporated under reduced pressure at 610mmHg 3h, collect 101
DEG C fraction up to pinane with to the monoterpene alkane of Meng's alkane, the transparent liquid of remaining light yellow clear low-viscosity is biology
Oil, carbon number is between C12~C20.Wherein pinane and be 78% to Meng's alkane content, the yield of monoterpene alkane is 37%, is detected, raw
The density 937.3kgm of object oil-3(20 DEG C), cetane index 39, acid value 0.96mgKOHg-1, dynamic viscosity (40
℃)9.25mm2·s-1, bromine number 0.76Br/100g.
Embodiment 10
The preparation method of catalyst, operating procedure are as follows:
(a) carrier FCC catalyst pre-processes: useless FCC catalyst being carried out roasting 3.5h activation, maturing temperature is 600 DEG C；
(b) solution dipping method impregnate: on the basis of FCC catalyst carrier, according to required metal total load amount 15%~
35% (wt%) prepares the precursor solution of Cu:Co, your double non-gold using copper nitrate and cobalt nitrate and deionized water at normal temperature
The mass ratio for belonging to Cu:Co is 1:20, is later slowly added dropwise to precursor solution in FCC catalyst carrier under constant stirring, is dripped
Continue after adding stirring 5 minutes, after stand 5.5h under room temperature；
(c) dry: the sample after dipping is put into baking oven at 120 DEG C dry 9h；
(d) it roasts: the sample after drying is obtained into catalyst precursor in 500 DEG C of calcining 3h of box Muffle furnace；
(e) it restores: catalyst precursor is placed in tube furnace in H24.5h, H are restored under atmosphere at 530 DEG C2Flow is
40mL·min-1, FCC catalyst supported bimetal catalyst is obtained after natural cooling；It is spare.
A kind of method that pine tree effluent cracked-hydrogenate simultaneously preparation bio oil and monoterpene alkane, operating procedure are as follows:
(1) masson pine pine tree effluent is heated to 90 DEG C~105 DEG C dissolutions, is filtered to remove the liquid that residue obtains while hot
Substance is the pine tree effluent after net system, contains turpentine oil 38%, spare；By the masson pine pine tree stream after above-mentioned spare net system
Out in object 720g and above-mentioned spare catalyst investment high-pressure stirring reaction kettle, upper cover sealing is then successively anti-to high-pressure stirring
It answers kettle to vacuumize, be passed through H2Pressure maintaining leak detection, H2Displacement, starting autoclave stirrer and heating system heats are reacted, reaction temperature
350 DEG C, reaction pressure 1.0MPa, speed of agitator 200r/min~600r/min of degree, reaction time 4.5h；Wherein, catalyst is used
Amount is that pine tree flows out the 15% of amount of substance；
(2) it is cooled to room temperature and is vented to normal pressure after reaction and discharged, filter and remove catalyst, obtain pine tree effluent
Cracking-hydrogenated products；
(3) pine tree effluent cracking-hydrogenated products obtained by step (2) are evaporated under reduced pressure 1.5h at 550mmHg, collected
100 DEG C of fraction up to pinane with to the monoterpene alkane of Meng's alkane, make a living by the transparent liquid of remaining light yellow clear low-viscosity
Object oil, carbon number is between C12~C20.Wherein pinane and be 80% to Meng's alkane content, the yield of monoterpene alkane is 50%, through detecting,
The density 952.7kgm of bio oil-3(20 DEG C), cetane index 40, acid value 1.49mgKOHg-1, dynamic viscosity
(40℃)9.32mm2·s-1, bromine number 0.85Br/100g.
Embodiment 11
The preparation method of catalyst, operating procedure are as follows:
(a) carrier FCC catalyst pre-processes: fresh FCC catalyst is put into baking oven at 110 DEG C dry 4.5h except unloading
Moisture in body；
(b) solution dipping method impregnates: on the basis of FCC catalyst carrier, according to required metal total load amount 11%
(wt%) precursor solution of Cu:Co is prepared using copper nitrate and cobalt nitrate and deionized water at normal temperature, double non-noble metal Cu:
The mass ratio of Co is 1:3, is later slowly added dropwise to precursor solution in FCC catalyst carrier under constant stirring, completion of dropwise addition
After continue stirring 5 minutes, after stand 5.5h under room temperature；
(c) dry: the sample after dipping is put into baking oven at 115 DEG C dry 8.5h；
(d) it roasts: the sample after drying is obtained into catalyst precursor in 500 DEG C of calcining 3h of box Muffle furnace；
(e) it restores: catalyst precursor is placed in tube furnace in H23h, H are restored under atmosphere at 500 DEG C2Flow is
40mL·min-1, FCC catalyst supported bimetal catalyst is obtained after natural cooling；It is spare.
A kind of method that pine tree effluent cracked-hydrogenate simultaneously preparation bio oil and monoterpene alkane, operating procedure are as follows:
(1) pinus yunnanensis pine tree effluent is heated to 90 DEG C~105 DEG C dissolutions, is filtered to remove the liquid that residue obtains while hot
Substance is the pine tree effluent after net system, contains turpentine oil 35%, spare；By the pinus yunnanensis pine tree stream after above-mentioned spare net system
Out in object 760g and above-mentioned spare catalyst investment high-pressure stirring reaction kettle, upper cover sealing is then successively anti-to high-pressure stirring
It answers kettle to vacuumize, be passed through H2Pressure maintaining leak detection, H2Displacement, starting autoclave stirrer and heating system heats are reacted, reaction temperature
230 DEG C, reaction pressure 5.0MPa, speed of agitator 200r/min~600r/min of degree, reaction time 1.5h；Wherein, catalyst is used
Amount is that pine tree flows out the 15% of amount of substance；
(2) it is cooled to room temperature and is vented to normal pressure after reaction and discharged, filter and remove catalyst, obtain pine tree effluent
Cracking-hydrogenated products；
(3) pine tree effluent cracking-hydrogenated products obtained by step (2) are evaporated under reduced pressure at 550mmHg 3h, collect 102
DEG C fraction up to pinane with to the monoterpene alkane of Meng's alkane, the transparent liquid of remaining light yellow clear low-viscosity is biology
Oil, carbon number is between C12~C20.Wherein pinane and be 80% to Meng's alkane content, the yield of monoterpene alkane is 45%, is detected, raw
The density 939.5kgm of object oil-3(20 DEG C), cetane index 37, acid value 1.27mgKOHg-1, dynamic viscosity (40
℃)13.74mm2·s-1, bromine number 1.59Br/100g.
Embodiment 12
The preparation method of catalyst, operating procedure are as follows:
(a) carrier FCC catalyst pre-processes: useless FCC catalyst is carried out 660 DEG C of roasting 3h activation；
(b) solution dipping method impregnates: on the basis of FCC catalyst carrier, according to required metal total load amount 11%
(wt%) precursor solution of Cu:Co is prepared using copper nitrate and cobalt nitrate and deionized water at normal temperature, double non-noble metal Cu:
The mass ratio of Co is 1:10, is later slowly added dropwise to precursor solution in FCC catalyst carrier under constant stirring, completion of dropwise addition
After continue stirring 5 minutes, after stand 6h under room temperature；
(c) dry: the sample after dipping is put into baking oven at 125 DEG C dry 8h；
(d) it roasts: the sample after drying is obtained into catalyst precursor in 500 DEG C of calcining 3h of box Muffle furnace；
(e) it restores: catalyst precursor is placed in tube furnace in H25.5h, H are restored under atmosphere at 530 DEG C2Flow is
40mL·min-1, FCC catalyst supported bimetal catalyst is obtained after natural cooling；It is spare.
A kind of method that pine tree effluent cracked-hydrogenate simultaneously preparation bio oil and monoterpene alkane, operating procedure are as follows:
(1) masson pine pine tree effluent is heated to 90 DEG C~105 DEG C dissolutions, is filtered to remove the liquid that residue obtains while hot
Substance is the pine tree effluent after net system, contains turpentine oil 35%, spare；By the masson pine pine tree stream after above-mentioned spare net system
Out in object 700g and above-mentioned spare catalyst investment high-pressure stirring reaction kettle, upper cover sealing is then successively anti-to high-pressure stirring
It answers kettle to vacuumize, be passed through H2Pressure maintaining leak detection, H2Displacement, starting autoclave stirrer and heating system heats are reacted, reaction temperature
260 DEG C, reaction pressure 6.0MPa, speed of agitator 200r/min~600r/min of degree, reaction time 4h；Wherein, catalyst amount
Flow out amount of substance for pine tree 10%；
(2) it is cooled to room temperature and is vented to normal pressure after reaction and discharged, filter and remove catalyst, obtain pine tree effluent
Cracking-hydrogenated products；
(3) pine tree effluent cracking-hydrogenated products obtained by step (2) are evaporated under reduced pressure at 600mmHg 3h, collect 101
DEG C fraction up to pinane with to the monoterpene alkane of Meng's alkane, the transparent liquid of remaining light yellow clear low-viscosity is biology
Oil, carbon number is between C12~C20.Wherein pinane and be 76% to Meng's alkane content, the yield of monoterpene alkane is 42%, is detected, raw
The density 950.2kgm of object oil-3(20 DEG C), cetane index 36, acid value 1.15mgKOHg-1, dynamic viscosity (40
℃)12.16mm2·s-1, bromine number 1.47Br/100g.
Fig. 1 is that " Nie little An, Jiang Jianchun, Dai Weidi wait the synthesis of Biodiesel Oil from Rosin and performance preliminary using document
[J] chemistry of forest product and industrial, 2007,27 (04): the bio oil that the rosin cracking process of 79-81 " is prepared are studied, wherein a is
The bio oil on the same day is prepared, which is in light brown transparence；B is the bio oil after placing 5 days, is in transparent salmon shape.
This is because the abietyl bio oil of cracking process preparation still has unsaturated double bond component, active double bond structure is unstable
It is fixed, oxidation easily occurs with the increase of resting period and going bad leads to color burn.
Fig. 2 is obtained bio oil produced according to the present invention, and wherein a is the bio oil on the preparation same day, is in light yellow clear
Shape；B is the bio oil after placing 1 month, is in light yellow clear shape.This is because the present invention is using cracking-hydrogenation coupled technology
Bio oil is prepared, adds hydrogen and the ability of decarboxylation and the double non-noble metal of effect as catalyst to be provided simultaneously with, both cracks pine tree stream
The resin acid of the more carbon of tricyclic out in object, and the double bond component being saturated in pyrolysis product reach cracking synthesising biological oil and insatiable hunger
The purpose of progress synchronous with bio oil plus hydrogen upgrading, resulting bio oil saturation degree is high, and stability is good.
The aforementioned description to specific exemplary embodiment of the invention is in order to illustrate and illustration purpose.These descriptions
It is not wishing to limit the invention to disclosed precise forms, and it will be apparent that according to the above instruction, can much be changed
And variation.The purpose of selecting and describing the exemplary embodiment is that explaining specific principle of the invention and its actually answering
With so that those skilled in the art can be realized and utilize a variety of different exemplary implementation schemes of the invention and
Various chooses and changes.The scope of the present invention is intended to be limited by claims and its equivalents.
Claims (7)
1. a kind of pine tree effluent simultaneously crack-hydrogenate preparation bio oil and monoterpene alkane method, which is characterized in that comprising with
Lower operating procedure:
(1) the pine tree effluent after net system is put into reaction kettle with catalyst, 190 DEG C~370 DEG C of reaction temperature, reaction pressure
1.0MPa~10.0MPa, reaction time 1.5h~4.5h；Wherein, catalyst amount be pine tree flow out amount of substance 2%~
15%；
(2) cooling discharging, suction filtration remove catalyst, obtain pine tree effluent cracking-hydrogenated products after reaction；
(3) by pine tree effluent cracking-hydrogenated products obtained by step (2) be evaporated under reduced pressure at 550mmHg~650mmHg 1.5h~
3h collects 100 DEG C~102 DEG C of fraction up to pinane with to the monoterpene alkane of Meng's alkane, and remainder is bio oil.
2. according to the method described in claim 1, it is characterized by: net system described in step (1) is that pine tree effluent is heated
To 90 DEG C~105 DEG C dissolutions, it is filtered to remove the liquid that residue obtains while hot.
3. according to the method described in claim 1, it is characterized by: pine tree effluent described in step (1) be horse hair loosely
Set one of effluent, pinus yunnanensis pine tree effluent, pinus khasys pine tree effluent or wet-land pine tree pine tree effluent.
4. according to the method described in claim 1, it is characterized by: catalyst described in step (1) is negative using FCC catalyst
Carry the double non-noble metal catalyst that one of Co-Mo, Ni-W, Ni-Mo or Cu-Co are obtained.
5. according to the method described in claim 4, it is characterized by: the total load amount of the catalyst is 15%~35%
(wt%), the mass ratio of double non-noble metal Co:Mo, Ni:Mo, Ni:W or Cu:Co is all 1:1~1:20.
6. according to the method described in claim 4, it is characterized by: the FCC catalyst is that fresh FCC catalyst or useless FCC are touched
Matchmaker.
7. according to the method described in claim 1, it is characterized by: the preparation method of catalyst described in step (1), comprising with
Lower operating procedure:
(a) carrier FCC catalyst pre-processes: fresh FCC catalyst is put into baking oven at 105 DEG C~120 DEG C dry 2h~5h
Remove the moisture in carrier；Or useless FCC catalyst is subjected to roasting 1.5h~4.5h activation, maturing temperature is 450 DEG C~700 DEG C；
(b) solution dipping method impregnates: on the basis of FCC catalyst carrier, preparing the presoma of Co:Mo, Ni:Mo, Ni:W or Cu:Co
Precursor solution is added dropwise in FCC catalyst carrier by solution under constant stirring later, continues to stir after completion of dropwise addition, is terminated
Afterwards in standing 2h~6h；
(c) it dries: the sample after dipping is dried into 8h~10h at 110 DEG C~130 DEG C；
(d) it roasts: the sample after drying is obtained into catalyst precursor in 500 DEG C of calcining 3h；
(e) it restores: by catalyst precursor in H2Under atmosphere at 450 DEG C~560 DEG C reductase 12 .5h~6h, H2Flow is
40mL·min-1, FCC catalyst supported bimetal catalyst is obtained after cooling.
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| CN113150845A (en) * | 2020-01-22 | 2021-07-23 | 北京化工大学 | Liquid fuel additive, liquid fuel and preparation method and application thereof |
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