CN109321269B - Method for preparing bio-oil and monoterpene alkane by simultaneously cracking and hydrogenating pine tree effluent - Google Patents

Method for preparing bio-oil and monoterpene alkane by simultaneously cracking and hydrogenating pine tree effluent Download PDF

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CN109321269B
CN109321269B CN201811059786.9A CN201811059786A CN109321269B CN 109321269 B CN109321269 B CN 109321269B CN 201811059786 A CN201811059786 A CN 201811059786A CN 109321269 B CN109321269 B CN 109321269B
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pine tree
effluent
oil
monoterpene
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CN109321269A (en
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王琳琳
陈小鹏
梁杰珍
韦小杰
周丹
范孝雄
殷理江
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Guangxi University
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C10G2300/1014—Biomass of vegetal origin
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects
    • 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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  • Oil, Petroleum & Natural Gas (AREA)
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  • General Chemical & Material Sciences (AREA)
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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 method for preparing bio-oil and monoterpene alkane by simultaneously cracking and hydrogenating pine tree effluent, which comprises the following operation steps: (1) putting the purified pine tree effluent and a catalyst into a reaction kettle for reaction; (2) cooling and discharging after the reaction is finished, and removing the catalyst by suction filtration to obtain a pine tree effluent cracking-hydrogenation product; (3) and (3) carrying out reduced pressure distillation on the pine tree effluent cracking-hydrogenation product obtained in the step (2), collecting fractions at 100-102 ℃ to obtain the monoterpene alkane of the pinane and the p-menthane, and obtaining the rest part of the bio-oil. The method can obtain high-quality bio-oil with low acid value, low viscosity, high saturation, low bromine value, light color and good stability, and can also prepare fine chemicals of pinane and p-menthane monoterpene alkane.

Description

Method for preparing bio-oil and monoterpene alkane by simultaneously cracking and hydrogenating pine tree effluent
Technical Field
The invention relates to a method for preparing bio-oil and monoterpene alkane, in particular to a method for preparing bio-oil and monoterpene alkane by simultaneously cracking and hydrogenating pine tree effluent.
Background
Pine tree effluent, namely pine tree natural resin secreted by secretory cells in a resin channel of living pine trees or pine trunk resin channels, is a renewable non-grain natural product and is known as 'petroleum grown on trees'. Distilling the pine tree effluent to obtain primary rosin and turpentine oil, wherein the main chemical component of the rosin is rosin resin acid which is monocarboxylic acid containing 2 unsaturated double bonds and having tricyclic phenanthrene skeleton; the main chemical components of turpentine are monoterpene components, wherein most of the components are pinene of bicyclic monoterpene and monocyclic monoterpene of p-menthene structure, and can provide C containing circular ring or bridged ring and double bond10The molecular skeleton, rosin and turpentine are important chemical raw materials. China has rich pine forest resources, the pine forest area is 2246 hectares, the pine forest resources capable of collecting resin are large, and the storage amount of pine tree effluent is 162.5 million/year, provinces and autonomous regions such as Guangxi, Guangdong, Yunnan, Fujian, Jiangxi and Hunan are main producing regions of pine natural resin, and pine species for collecting resin mainly comprise Pinus massoniana (P.massoniana), Pinus yunnanensis (P.yunnanensis), Pinus kesiyaar (P.langbianensis), Pinus elliotii (P.elliotiii) and Pinus nanensis (P.latiteri), wherein the resin storage capacity of Pinus massoniana is the largest and accounts for about 56.3%, and the Pinus yunnanensis and the Pinus kesiya are the second and the Pinus kesiya also have certain resin collection capacity. The pine natural resin processing series products relate to the output value of related industries which accounts for 1/10 of the total economic value of China, but most of the pine natural resins in China are supplied to the market by primary products of rosin and turpentine oil obtained by distillation, the deep processing utilization rate is only 40 percent, and developed countries such as Europe and America are close to 100 percent.
At present, the main energy resources in the world are non-renewable fossil fuels such as petroleum, coal and natural gas, and most of the bulk chemical raw materials also mainly depend on non-renewable resources of fossil-based hydrocarbons. With the continuous depletion of fossil resources and the serious environmental pollution caused by fossil fuels, energy shortage and environmental problems have become one of the most serious problems facing the world today. Renewable biomass resources are receiving increasing attention to be converted into liquid biofuel and fine chemical raw materials, thermal cracking/cracking and catalytic cracking/cracking technologies of biomass are one of the main methods for producing bio-oil at present, and the following invention patents have been applied to the related invention technologies.
CN201711118926.0 discloses a CO2A method for preparing bio-oil by two-step grading hydrothermal liquefaction of lignocellulose under atmosphere; CN201711282928.3 discloses a method for preparing environment-friendly bio-oil by taking wheat straw, corn straw, soybean straw, rice straw, various wood chips, bagasse and the like as raw materials; CN200910086766.5 discloses a method for producing microbial oil by solid fermentation of lignocellulose raw material, which obtains unsaturated fatty acid or biodiesel oil source; CN200510039170.1 and CN200910155887.0 disclose methods for preparing biodiesel and biofuel from rosin after cracking and compounding. The monoterpene alkane as the product of turpentine hydrogenation reaction mainly includes pinane and p-menthane, and pinane is important in the synthesis of perfumeIntermediate, can be used as raw material for synthesizing high-grade perfume and vitamin A, E, K; the p-menthane can be used for synthesizing rubber initiator and is also an important intermediate for synthesizing various fine chemical products. Rosin-based bio-oils and pinanes and p-menthanes are typically prepared in a two-step process: firstly, carrying out steam distillation on the purified pine tree effluent to respectively obtain rosin and turpentine; secondly, rosin is used as a raw material, active clay or molecular sieve and other cracking catalysts are used for preparing rosin-based bio-oil, turpentine is used as a raw material, and a Pd/C hydrogenation catalyst is used for preparing monoterpene, wherein dicyclic monoterpene in the turpentine is hydrogenated to obtain pinane, and monocyclic monoterpene in the turpentine is hydrogenated to obtain p-menthane, so that the preparation process is long in flow and high in energy consumption, and 1t of rosin is produced by distillation of pine effluent, and 1.667-2.038 GJ is consumed more; and the obtained rosin-based bio-oil has the defects of high oxygen content, high viscosity, strong acidity, unstable and easy deterioration of double-bond-containing components and the like.
In summary, the conventional method for preparing the bio-oil only adopts a single cracking method, and has the problems of high oxygen content, high viscosity, strong acidity of the product, instability and easy deterioration of double-bond-containing components and the like. How to change the double bond unsaturated products contained in the cracked bio-oil into saturated compounds is the key point for preparing the bio-oil. Meanwhile, the preparation of the rosin-based bio-oil and the monoterpene alkane has the defects of long process flow and high energy consumption.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Disclosure of Invention
The invention aims to provide a method for simultaneously preparing bio-oil and monoterpene alkane chemicals, which has a simple production process and aims to obtain a method capable of simultaneously preparing pinane and p-menthane monoterpene alkane fine chemicals, and the high-quality bio-oil which has low acid value, low viscosity, high saturation, low bromine value, light color and good stability can be obtained.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
a process for the simultaneous pyrolysis-hydrogenation of pine tree effluent to produce bio-oil and monoterpene alkanes comprising the following operative steps:
(1) putting the purified pine tree effluent and a catalyst into a high-pressure stirring reaction kettle, sealing an upper cover, sequentially vacuumizing the high-pressure stirring reaction kettle, and introducing H2Pressure maintaining leak detection, H2Replacing and starting the high-pressure kettle stirrer and the heating system to heat for reaction, wherein the reaction temperature is 190-370 ℃, the reaction pressure is 1.0-10.0 MPa, the stirring speed is 200-600 r/min, and the reaction time is 1.5-4.5 h; wherein the amount of the catalyst is 2-15% of the mass of the pine tree effluent;
(2) after the reaction is finished, cooling to normal temperature, emptying to normal pressure, discharging, and removing the catalyst by suction filtration to obtain pine tree effluent cracking-hydrogenation products;
(3) and (3) carrying out reduced pressure distillation on the pine tree effluent cracking-hydrogenation product obtained in the step (2) for 1.5-3 h under 550-650 mmHg, collecting fractions at 100-102 ℃ to obtain the monoterpene alkane of the pinane and the p-menthane, wherein the rest light yellow transparent low-viscosity liquid is the biological oil.
Preferably, the purification in step (1) is a liquid substance obtained by heating pine tree effluent to 90-105 ℃ for dissolution and filtering off residues while the solution is hot.
Preferably, the pine effluent is one of masson pine effluent, Yunnan pine effluent, pinus khasys pine effluent or slash pine effluent.
Preferably, the catalyst in the step (1) is a cracking-hydrogenation bifunctional double non-noble metal catalyst obtained by loading one of Co-Mo, Ni-W, Ni-Mo or Cu-Co with an FCC catalyst.
Preferably, the total loading amount of the catalyst is 15-35% (wt%), and the mass ratio of the double non-noble metals Co to Mo, Ni to W or Cu to Co is 1: 1-1: 20, i.e. Co to Mo is 1: 1-1: 20, Ni to W is 1: 1-1: 20, and Cu to Co is 1: 1-1: 20.
Preferably, the FCC catalyst is a fresh FCC catalyst or a spent FCC catalyst.
Preferably, the preparation method of the catalyst in the step (1) comprises the following operation steps:
(a) pretreatment of a carrier FCC catalyst: putting a fresh FCC catalyst into a drying oven, and drying at 105-120 ℃ for 2-5 h to remove the moisture in the carrier; or the waste FCC catalyst is roasted for 1.5 to 4.5 hours for activation, and the roasting temperature is 450 to 700 ℃;
(b) dipping by a solution dipping method: preparing precursor solution of Co, Mo, Ni, W or Cu, Co at normal temperature according to the required metal loading capacity by taking an FCC catalyst carrier as a reference, then slowly dropwise adding the precursor solution into the FCC catalyst carrier under continuous stirring, continuously stirring for 5 minutes after the dropwise adding is finished, and standing for 2-6 hours at normal temperature after the dropwise adding is finished;
(c) and (3) drying: putting the soaked sample into a drying oven to be dried for 8-10 h at the temperature of 110-130 ℃;
(d) roasting: calcining the dried sample in a box-type muffle furnace at 500 ℃ for 3h to obtain a catalyst precursor;
(e) reduction: catalyst precursor was placed in a tube furnace in H2Reducing for 2.5 to 6 hours under the atmosphere at the temperature of 450 to 560 ℃, and H2The flow rate is 40 mL/min-1And naturally cooling to obtain the FCC catalyst supported bimetallic catalyst.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method directly takes the pine tree effluent as the raw material to prepare the biological oil and the monoterpene hydrocarbon chemical products by catalytic cracking-hydrogenation at the same time, and overcomes the defects of complex process, long flow, high pollution, high energy consumption and the like in the traditional production process; fully utilizes the excellent cracking performance and H of FCC catalyst2The acid generated by hydrogen overflow in the atmosphere is used for promoting the cracking of rosin resin acid by concerted catalysis, and the C-C, C-O bond breaking, decarboxylation and hydrogenation effects of the double non-noble metal catalyst are realized, so that the tricyclic and multi-carbon rosin resin acid is cracked, the double bond component in the cracked product is also saturated, and the purpose of synchronously carrying out hydrogenation and quality improvement on the cracked and synthesized bio-oil and the unsaturated bio-oil is achieved;
(2) the invention not only obtains high-quality biological oil with low acid value, low viscosity, high saturation, low bromine value, light color and good stability, but also synthesizes the biological oilPinane and p-menthane; the carbon number between C can be obtained by reduced pressure distillation12～C20The acid value of the saturated naphthenic hydrocarbon and aliphatic hydrocarbon bio-oil is less than 1.50mgKOH g-1Bromine number is less than 1.62Br/100g, cetane number is 30-45, and coproduce pinane and p-menthane, and the yield of monoterpene alkane is 35-50%.
Drawings
FIG. 1 is a biological oil prepared from rosin by a prior art pyrolysis method, wherein a is the biological oil on the day of preparation, and b is the biological oil after being left for 5 days.
Fig. 2 is a bio-oil prepared according to the present invention, wherein a is the bio-oil on the day of preparation, and b is the bio-oil after being left for 1 month.
Detailed Description
The following detailed description is to be read in connection with the accompanying drawings, but it is to be understood that the scope of the invention is not limited to the specific embodiments. The raw material sources in the following examples: pine tree effluents are provided by rosin manufacturers or purchased on the market; FCC catalyst (FCC) is purchased from petrochemical catalyst manufacturers, and spent FCC catalyst (SFCC) is provided by petrochemical enterprises.
In the following examples, the operation of pine tree effluent cracking-hydrogenation reaction in the high-pressure stirred tank reactor was vacuum pumped, pressure-maintained, leak-tested, and replaced with the operation of a conventional high-pressure reactor; the high-pressure stirring reaction kettle is commercially available and has the capacity of 2L.
Example 1
The preparation method of the catalyst comprises the following operation steps:
(a) pretreatment of a carrier FCC catalyst: drying fresh FCC catalyst in an oven at 105 deg.C for 2h to remove water in the carrier;
(b) dipping by a solution dipping method: preparing a precursor solution of Co to Mo by using cobalt nitrate, ammonium molybdate and deionized water at normal temperature according to the required total metal loading capacity of 15 percent (wt%) by taking an FCC catalyst carrier as a reference, wherein the mass ratio of the double non-noble metal Co to Mo is 1:1, then slowly dropwise adding the precursor solution into the FCC catalyst carrier under continuous stirring, continuously stirring for 5 minutes after dropwise adding is finished, and standing for 2 hours at normal temperature after finishing dropwise adding;
(c) and (3) drying: putting the soaked sample into an oven to be dried for 8 hours at the temperature of 110 ℃;
(d) roasting: calcining the dried sample in a box-type muffle furnace at 500 ℃ for 3h to obtain a catalyst precursor;
(e) reduction: catalyst precursor was placed in a tube furnace in H2Reducing for 2.5H, H at 450 ℃ under atmosphere2The flow rate is 40 mL/min-1Naturally cooling to obtain the FCC catalyst supported bimetallic catalyst; and (5) standby.
A method for preparing bio-oil and monoterpene alkane by cracking-hydrogenating pine tree effluent simultaneously comprises the following steps:
(1) heating the masson pine effluent to 90-105 ℃ for dissolution, filtering the solution while the solution is hot to remove residues to obtain a liquid substance, namely the purified pine effluent containing 35% of turpentine for later use; putting 700g of the cleaned masson pine effluent for standby and the catalyst for standby into a high-pressure stirring reaction kettle, sealing the high-pressure stirring reaction kettle by an upper cover, vacuumizing the high-pressure stirring reaction kettle in sequence, and introducing H2Pressure maintaining leak detection, H2Replacing and starting the high-pressure kettle stirrer and the heating system to heat for reaction, wherein the reaction temperature is 190 ℃, the reaction pressure is 1.0MPa, the stirring speed is 200 r/min-600 r/min, and the reaction time is 1.5 h; wherein the amount of the catalyst is 2 percent of the mass of the pine tree effluent;
(2) after the reaction is finished, cooling to normal temperature, emptying to normal pressure, discharging, and removing the catalyst by suction filtration to obtain pine tree effluent cracking-hydrogenation products;
(3) distilling the cracking-hydrogenation product of pine tree effluent obtained in step (2) under 550mmHg for 2.0h, collecting 100 deg.C fraction to obtain monoterpene alkane of pinane and p-menthane, and collecting the rest light yellow transparent low viscosity transparent liquid as biological oil with carbon number between C12～C20. Wherein the content of pinane and p-menthane is 75%, the yield of monoterpene alkane is 36%, and the density of the biological oil is 960.1 kg.m-3(20 ℃ C.), a cetane index of 32 and an acid value of 1.46 mgKOH. g-1Kinematic viscosity (40 ℃)18.26mm2·s-1The bromine number was 1.56Br/100 g.
Example 2
The preparation method of the catalyst comprises the following operation steps:
(a) the waste FCC catalyst is roasted for 1.5h and activated under the condition that the temperature is kept at 450 ℃;
(b) dipping by a solution dipping method: preparing a precursor solution of Co to Mo by using cobalt nitrate, ammonium molybdate and deionized water at normal temperature according to the required total metal loading capacity of 20 percent (wt%) by taking an activated FCC catalyst carrier as a reference, wherein the mass ratio of the double non-noble metal Co to Mo is 1:10, then slowly dropwise adding the precursor solution into the FCC catalyst carrier under continuous stirring, continuously stirring for 5 minutes after dropwise adding is finished, and standing for 6 hours at normal temperature after finishing adding;
(c) and (3) drying: drying the impregnated sample in an oven at 130 ℃ for 10 h;
(d) roasting: calcining the dried sample in a box-type muffle furnace at 500 ℃ for 3h to obtain a catalyst precursor;
(e) reduction: catalyst precursor was placed in a tube furnace in H2Reducing for 3H at 500 ℃ under the atmosphere2The flow rate is 40 mL/min-1Naturally cooling to obtain the FCC catalyst supported bimetallic catalyst; and (5) standby.
A method for preparing bio-oil and monoterpene alkane by cracking-hydrogenating pine tree effluent simultaneously comprises the following steps:
(1) heating the effluent of Yunnan pine tree to 90-105 deg.C for dissolving, filtering to remove residue while it is hot to obtain liquid substance, which is purified pine tree effluent containing turpentine 35% for use; putting 720g of the purified Yunnan pine tree effluent and the catalyst into a high-pressure stirring reaction kettle, sealing the high-pressure stirring reaction kettle by an upper cover, vacuumizing the high-pressure stirring reaction kettle in sequence, and introducing H2Pressure maintaining leak detection, H2Replacing and starting the high-pressure kettle stirrer and the heating system to heat for reaction, wherein the reaction temperature is 250 ℃, the reaction pressure is 3.0MPa, the stirring speed is 200-600 r/min, and the reaction time is 2 hours; wherein the using amount of the catalyst is 6 percent of the mass of the pine tree effluent;
(2) after the reaction is finished, cooling to normal temperature, emptying to normal pressure, discharging, and removing the catalyst by suction filtration to obtain pine tree effluent cracking-hydrogenation products;
(3) distilling the cracking-hydrogenation product of pine tree effluent obtained in step (2) under reduced pressure of 600mmHg for 1.5h, collecting 101 deg.C fraction to obtain monoterpene alkane of pinane and p-menthane, and collecting the rest light yellow transparent low viscosity transparent liquid as biological oil with carbon number between C12～C20. Wherein the content of pinane and p-menthane is 72 percent, the yield of monoterpene alkane is 40 percent, and the detection shows that the density of the biological oil is 946.1 kg.m-3(20 ℃ C.), a cetane index of 36 and an acid value of 1.37 mgKOH. g-1Kinematic viscosity (40 ℃)12.85mm2·s-1The bromine number was 1.62Br/100 g.
Example 3
The preparation method of the catalyst comprises the following operation steps:
(a) pretreatment of a carrier FCC catalyst: putting fresh FCC catalyst into an oven, and drying at 120 ℃ for 5h to remove moisture in the carrier;
(b) dipping by a solution dipping method: preparing a precursor solution of Co to Mo by using cobalt nitrate, ammonium molybdate and deionized water at normal temperature according to the required metal total loading amount of 30 percent (wt%) by taking an FCC catalyst carrier as a reference, wherein the mass ratio of the double non-noble metal Co to Mo is 1:20, then slowly dropwise adding the precursor solution into the FCC catalyst carrier under continuous stirring, continuously stirring for 5 minutes after dropwise adding is finished, and standing for 3 hours at normal temperature after finishing dropwise adding;
(c) and (3) drying: drying the impregnated sample in an oven at 120 ℃ for 9 hours;
(d) roasting: calcining the dried sample in a box-type muffle furnace at 500 ℃ for 3h to obtain a catalyst precursor;
(e) reduction: catalyst precursor was placed in a tube furnace in H2Reducing for 4H, H under the atmosphere at 560 DEG C2The flow rate is 40 mL/min-1Naturally cooling to obtain the FCC catalyst supported bimetallic catalyst; and (5) standby.
A method for preparing bio-oil and monoterpene alkane by cracking-hydrogenating pine tree effluent simultaneously comprises the following steps:
(1) heating the effluent of pinus khasys pine to 90-105 deg.C for dissolving, filtering to remove residue to obtain liquid substanceThe pine tree effluent after being purified contains 40 percent of turpentine for later use; putting 770g of the purified pinus khasys pine effluent and the catalyst into a high-pressure stirring reaction kettle, sealing the high-pressure stirring reaction kettle by an upper cover, vacuumizing the high-pressure stirring reaction kettle in sequence, and introducing H2Pressure maintaining leak detection, H2Replacing and starting the high-pressure kettle stirrer and the heating system to heat for reaction, wherein the reaction temperature is 370 ℃, the reaction pressure is 10.0MPa, the stirring speed is 200-600 r/min, and the reaction time is 4 hours; wherein the amount of the catalyst is 15 percent of the mass of the pine tree effluent;
(2) after the reaction is finished, cooling to normal temperature, emptying to normal pressure, discharging, and removing the catalyst by suction filtration to obtain pine tree effluent cracking-hydrogenation products;
(3) distilling the cracking-hydrogenation product of pine tree effluent obtained in step (2) under reduced pressure of 600mmHg for 2h, collecting 100 deg.C fraction to obtain monoterpene alkane of pinane and p-menthane, and collecting the rest light yellow transparent low viscosity transparent liquid as biological oil with carbon number between C12～C20. Wherein the content of pinane and p-menthane is 80%, the yield of monoterpene alkane is 40%, and the density of the biological oil is 932.1 kg.m-3(20 ℃ C.), a cetane index of 45 and an acid value of 1.03 mgKOH. g-1Kinematic viscosity (40 ℃)9.01mm2·s-1The bromine number was 0.95Br/100 g.
Example 4
The preparation method of the catalyst comprises the following operation steps:
(a) pretreatment of a carrier FCC catalyst: roasting the waste FCC catalyst at 700 ℃ for 4.5h for activation;
(b) dipping by a solution dipping method: preparing a Ni: W precursor solution by using nickel nitrate, ammonium metatungstate and deionized water at normal temperature according to the required metal total loading amount of 30 percent (wt percent) by taking an FCC catalyst carrier as a reference, wherein the mass ratio of the double non-noble metal Ni to W is 1:20, then slowly dropwise adding the precursor solution into the FCC catalyst carrier under continuous stirring, continuously stirring for 5 minutes after dropwise adding is finished, and standing for 3.5 hours at normal temperature after finishing dropwise adding;
(c) and (3) drying: drying the impregnated sample in an oven at 115 ℃ for 8.5 h;
(d) roasting: calcining the dried sample in a box-type muffle furnace at 500 ℃ for 3h to obtain a catalyst precursor;
(e) reduction: catalyst precursor was placed in a tube furnace in H2Reducing for 6H at 500 ℃ under the atmosphere2The flow rate is 40 mL/min-1Naturally cooling to obtain the FCC catalyst supported bimetallic catalyst; and (5) standby.
A method for preparing bio-oil and monoterpene alkane by cracking-hydrogenating pine tree effluent simultaneously comprises the following steps:
(1) heating the effluent of the slash pine to 90-105 ℃ for dissolution, filtering the effluent while the effluent is hot to remove residues to obtain a liquid substance, namely the purified effluent of the pine, which contains 37 percent of turpentine for later use; putting 760g of cleaned slash pine tree effluent and the catalyst into a high-pressure stirring reaction kettle, sealing the high-pressure stirring reaction kettle by an upper cover, vacuumizing the high-pressure stirring reaction kettle in sequence, and introducing H2Pressure maintaining leak detection, H2Replacing and starting the high-pressure kettle stirrer and the heating system to heat for reaction, wherein the reaction temperature is 300 ℃, the reaction pressure is 10.0MPa, the stirring speed is 200-600 r/min, and the reaction time is 4 hours; wherein the using amount of the catalyst is 5 percent of the mass of the pine tree effluent;
(2) after the reaction is finished, cooling to normal temperature, emptying to normal pressure, discharging, and removing the catalyst by suction filtration to obtain pine tree effluent cracking-hydrogenation products;
(3) distilling the cracking-hydrogenation product of pine tree effluent obtained in step (2) under 650mmHg for 3h, collecting 102 deg.C fraction to obtain monoterpene alkane of pinane and p-menthane, and collecting the rest light yellow transparent low viscosity transparent liquid as biological oil with carbon number between C12～C20. Wherein the content of pinane and p-menthane is 80%, the yield of monoterpene alkane is 50%, and the detection shows that the density of the biological oil is 912.1 kg.m-3(20 ℃ C.), a cetane index of 45 and an acid value of 0.97 mgKOH. g-1Kinematic viscosity (40 ℃)10.21mm2·s-1The bromine number was 1.07Br/100 g.
Example 5
The preparation method of the catalyst comprises the following operation steps:
(a) pretreatment of a carrier FCC catalyst: putting fresh FCC catalyst into an oven, and drying at 110 ℃ for 4h to remove moisture in the carrier;
(b) dipping by a solution dipping method: preparing a precursor solution of Ni: W by using nickel nitrate, ammonium metatungstate and deionized water at normal temperature according to the required metal total load of 27 percent (wt percent) by taking an FCC catalyst carrier as a reference, wherein the mass ratio of the double non-noble metal Ni: W is 1:15, then slowly dropwise adding the precursor solution into the FCC catalyst carrier under continuous stirring, continuously stirring for 5 minutes after dropwise adding is finished, and standing for 4 hours at normal temperature after finishing adding;
(c) and (3) drying: drying the soaked sample in an oven at 125 ℃ for 8.5 h;
(d) roasting: calcining the dried sample in a box-type muffle furnace at 500 ℃ for 3h to obtain a catalyst precursor;
(e) reduction: catalyst precursor was placed in a tube furnace in H2Reducing for 5H under atmosphere at 470 DEG C2The flow rate is 40 mL/min-1Naturally cooling to obtain the FCC catalyst supported bimetallic catalyst; and (5) standby.
A method for preparing bio-oil and monoterpene alkane by cracking-hydrogenating pine tree effluent simultaneously comprises the following steps:
(1) heating the masson pine effluent to 90-105 ℃ for dissolution, filtering the solution while the solution is hot to remove residues to obtain a liquid substance, namely the purified pine effluent containing 37 percent of turpentine for later use; putting 760g of the purified masson pine effluent for standby and the catalyst for standby into a high-pressure stirring reaction kettle, sealing the high-pressure stirring reaction kettle by an upper cover, vacuumizing the high-pressure stirring reaction kettle in sequence, and introducing H2Pressure maintaining leak detection, H2Replacing and starting the high-pressure kettle stirrer and the heating system to heat for reaction, wherein the reaction temperature is 320 ℃, the reaction pressure is 6MPa, the stirring speed is 200-600 r/min, and the reaction time is 3.5 h; wherein the using amount of the catalyst is 8 percent of the mass of the pine tree effluent;
(2) after the reaction is finished, cooling to normal temperature, emptying to normal pressure, discharging, and removing the catalyst by suction filtration to obtain pine tree effluent cracking-hydrogenation products;
(3) cracking-hydrogenating pine tree effluent obtained in the step (2)Distilling the product under 580mmHg for 3 hr, collecting 100 deg.C fraction to obtain monoterpene alkane of pinane and p-menthane, and collecting the rest light yellow transparent low viscosity transparent liquid as biological oil with carbon number between C12～C20. Wherein the content of pinane and p-menthane is 85%, the yield of monoterpene alkane is 47%, and the density of the bio-oil is 960.2 kg.m-3(20 ℃ C.), a cetane index of 37 and an acid value of 1.2 mgKOH. g-1Kinematic viscosity (40 ℃)9.87mm2·s-1The bromine number was 1.19Br/100 g.
Example 6
The preparation method of the catalyst comprises the following operation steps:
(a) pretreatment of a carrier FCC catalyst: roasting the waste FCC catalyst at 600 ℃ for 3h for activation;
(b) dipping by a solution dipping method: preparing a precursor solution of Ni: W by using nickel nitrate, ammonium metatungstate and deionized water at normal temperature according to the required metal total loading amount of 16 percent (wt percent) by taking an FCC catalyst carrier as a reference, wherein the mass ratio of the double non-noble metal Ni: W is 1:9, then slowly dropwise adding the precursor solution into the FCC catalyst carrier under continuous stirring, continuously stirring for 5 minutes after dropwise adding is finished, and standing for 5.5 hours at normal temperature after finishing dropwise adding;
(c) and (3) drying: drying the soaked sample in an oven at 125 ℃ for 9.0 h;
(d) roasting: calcining the dried sample in a box-type muffle furnace at 500 ℃ for 3h to obtain a catalyst precursor;
(e) reduction: catalyst precursor was placed in a tube furnace in H2Reducing for 5H at 500 ℃ under the atmosphere2The flow rate is 40 mL/min-1Naturally cooling to obtain the FCC catalyst supported bimetallic catalyst; and (5) standby.
A method for preparing bio-oil and monoterpene alkane by cracking-hydrogenating pine tree effluent simultaneously comprises the following steps:
(1) heating the masson pine effluent to 90-105 ℃ for dissolution, filtering the solution while the solution is hot to remove residues to obtain a liquid substance, namely the purified pine effluent containing 40% of turpentine for later use; mixing 800g of cleaned masson pine effluent for later use with the mixture for later usePutting the catalyst into a high-pressure stirring reaction kettle, sealing an upper cover, vacuumizing the high-pressure stirring reaction kettle in sequence, and introducing H2Pressure maintaining leak detection, H2Replacing and starting the high-pressure kettle stirrer and the heating system to heat for reaction, wherein the reaction temperature is 290 ℃, the reaction pressure is 7.0MPa, the stirring speed is 200 r/min-600 r/min, and the reaction time is 2 hours; wherein the amount of the catalyst is 12 percent of the mass of the pine tree effluent;
(2) after the reaction is finished, cooling to normal temperature, emptying to normal pressure, discharging, and removing the catalyst by suction filtration to obtain pine tree effluent cracking-hydrogenation products;
(3) distilling the cracking-hydrogenation product of pine tree effluent obtained in step (2) under 650mmHg for 2.5h, collecting 102 deg.C fraction to obtain monoterpene alkane of pinane and p-menthane, and collecting the rest light yellow transparent low viscosity transparent liquid as biological oil with carbon number between C12～C20. Wherein the content of pinane and p-menthane is 78%, the yield of monoterpene alkane is 48%, and the detection shows that the density of the biological oil is 937.5 kg.m-3(20 ℃ C.), a cetane index of 40, and an acid value of 1.2 mgKOH. g-1Kinematic viscosity (40 ℃)11.27mm2·s-1The bromine number was 0.93Br/100 g.
Example 7
The preparation method of the catalyst comprises the following operation steps:
(a) pretreatment of a carrier FCC catalyst: putting fresh FCC catalyst into an oven, and drying at 107 ℃ for 4.5h to remove moisture in the carrier;
(b) dipping by a solution dipping method: preparing a precursor solution of Ni and Mo by using nickel nitrate, ammonium molybdate and deionized water at normal temperature according to the required metal total load of 17 percent (wt%) by taking an FCC catalyst carrier as a reference, wherein the mass ratio of the double non-noble metal Ni to the Mo is 1:9, then slowly dropwise adding the precursor solution into the FCC catalyst carrier under continuous stirring, continuously stirring for 5 minutes after dropwise adding is finished, and standing for 3 hours at normal temperature after finishing dropwise adding;
(c) and (3) drying: drying the soaked sample in an oven at 117 ℃ for 9.5 h;
(d) roasting: calcining the dried sample in a box-type muffle furnace at 500 ℃ for 3h to obtain a catalyst precursor;
(e) reduction: catalyst precursor was placed in a tube furnace in H2Reducing for 5.5H at 490 ℃ under the atmosphere2The flow rate is 40 mL/min-1Naturally cooling to obtain the FCC catalyst supported bimetallic catalyst; and (5) standby.
A method for preparing bio-oil and monoterpene alkane by cracking-hydrogenating pine tree effluent simultaneously comprises the following steps:
(1) heating the effluent of Yunnan pine tree to 90-105 deg.C for dissolving, filtering to remove residue while it is hot to obtain liquid substance, which is purified pine tree effluent containing turpentine 35% for use; putting 750g of the clean Yunnan pine tree effluent for standby and the catalyst for standby into a high-pressure stirring reaction kettle, sealing an upper cover, sequentially vacuumizing the high-pressure stirring reaction kettle, and introducing H2Pressure maintaining leak detection, H2Replacing and starting the high-pressure kettle stirrer and the heating system to heat for reaction, wherein the reaction temperature is 210 ℃, the reaction pressure is 8.0MPa, the stirring speed is 200-600 r/min, and the reaction time is 4 hours; wherein the using amount of the catalyst is 10 percent of the mass of the pine tree effluent;
(2) after the reaction is finished, cooling to normal temperature, emptying to normal pressure, discharging, and removing the catalyst by suction filtration to obtain pine tree effluent cracking-hydrogenation products;
(3) distilling the cracking-hydrogenation product of pine tree effluent obtained in step (2) under 590mmHg for 3h, collecting 101 deg.C fraction to obtain monoterpene alkane of pinane and p-menthane, and collecting the rest light yellow transparent low viscosity transparent liquid as biological oil with carbon number between C12～C20. Wherein the content of pinane and p-menthane is 75%, the yield of monoterpene alkane is 42%, and the detection shows that the density of the biological oil is 951.7 kg.m-3(20 ℃ C.), a cetane index of 35, and an acid value of 1.3 mgKOH. g-1Kinematic viscosity (40 ℃)16.92mm2·s-1The bromine number was 1.60Br/100 g.
Example 8
The preparation method of the catalyst comprises the following operation steps:
(a) pretreatment of a carrier FCC catalyst: roasting the waste FCC catalyst at 700 ℃ for 1.5h for activation;
(b) dipping by a solution dipping method: preparing a precursor solution of Ni and Mo by using nickel nitrate, ammonium molybdate and deionized water at normal temperature according to the required metal total load of 25 percent (wt%), wherein the mass ratio of the double non-noble metal Ni to the Mo is 1:15, then slowly dropwise adding the precursor solution into the FCC catalyst carrier under continuous stirring, continuously stirring for 5 minutes after dropwise adding is finished, and standing for 2 hours at normal temperature after finishing dropwise adding;
(c) and (3) drying: putting the impregnated sample into an oven to be dried for 10 hours under 110 ℃;
(d) roasting: calcining the dried sample in a box-type muffle furnace at 500 ℃ for 3h to obtain a catalyst precursor;
(e) reduction: catalyst precursor was placed in a tube furnace in H2Reducing for 2.5H under the atmosphere at 560 DEG C2The flow rate is 40 mL/min-1Naturally cooling to obtain the FCC catalyst supported bimetallic catalyst; and (5) standby.
A method for preparing bio-oil and monoterpene alkane by cracking-hydrogenating pine tree effluent simultaneously comprises the following steps:
(1) heating the effluent of pinus khasys to 90-105 deg.C for dissolving, filtering to remove residue while it is hot to obtain liquid substance, i.e. purified pine effluent containing 40% turpentine; putting 780g of the purified pinus khasys pine effluent for standby and the catalyst for standby into a high-pressure stirring reaction kettle, sealing the high-pressure stirring reaction kettle by an upper cover, vacuumizing the high-pressure stirring reaction kettle in sequence, and introducing H2Pressure maintaining leak detection, H2Replacing and starting the high-pressure kettle stirrer and the heating system to heat for reaction, wherein the reaction temperature is 280 ℃, the reaction pressure is 9.0MPa, the stirring speed is 200 r/min-600 r/min, and the reaction time is 4.5 h; wherein the using amount of the catalyst is 7 percent of the mass of the pine tree effluent;
(2) after the reaction is finished, cooling to normal temperature, emptying to normal pressure, discharging, and removing the catalyst by suction filtration to obtain pine tree effluent cracking-hydrogenation products;
(3) distilling the cracking-hydrogenation product of pine tree effluent obtained in step (2) under reduced pressure of 620mmHg for 2.5h, collecting 100 deg.C fraction to obtain monoterpene alkane of pinane and p-menthane, and collecting the rest light yellow transparent low viscosityThe clear liquid is biological oil with carbon number between C12～C20. Wherein the content of pinane and p-menthane is 72 percent, the yield of monoterpene alkane is 46 percent, and the detection shows that the density of the biological oil is 915.6 kg.m-3(20 ℃ C.), a cetane index of 37 and an acid value of 0.82 mgKOH. g-1Kinematic viscosity (40 ℃)10.87mm2·s-1The bromine number was 1.21Br/100 g.
Example 9
The preparation method of the catalyst comprises the following operation steps:
(a) pretreatment of a carrier FCC catalyst: putting fresh FCC catalyst into an oven, and drying at 120 ℃ for 5h to remove moisture in the carrier;
(b) dipping by a solution dipping method: preparing a precursor solution of Ni and Mo by using nickel nitrate, ammonium molybdate and deionized water at normal temperature according to the required metal total load of 32 percent (wt%) by taking an FCC catalyst carrier as a reference, wherein the mass ratio of the double non-noble metal Ni to the Mo is 1:8, then slowly dropwise adding the precursor solution into the FCC catalyst carrier under continuous stirring, continuously stirring for 5 minutes after dropwise adding is finished, and standing for 3 hours at normal temperature after finishing dropwise adding;
(c) and (3) drying: putting the soaked sample into an oven to be dried for 8hh at the temperature of 130 ℃;
(d) roasting: calcining the dried sample in a box-type muffle furnace at 500 ℃ for 3h to obtain a catalyst precursor;
(e) reduction: catalyst precursor was placed in a tube furnace in H2Reducing for 4H, H at 500 ℃ under atmosphere2The flow rate is 40 mL/min-1Naturally cooling to obtain the FCC catalyst supported bimetallic catalyst; and (5) standby.
A method for preparing bio-oil and monoterpene alkane by cracking-hydrogenating pine tree effluent simultaneously comprises the following steps:
(1) heating the effluent of the slash pine to 90-105 ℃ for dissolution, filtering the effluent while the effluent is hot to remove residues to obtain a liquid substance, namely the purified effluent of the pine, which contains 35 percent of turpentine for later use; putting 700g of the cleaned slash pine effluent and the catalyst into a high-pressure stirring reaction kettle, sealing the high-pressure stirring reaction kettle by an upper cover, and sequentially pumping out the high-pressure stirring reaction kettleVacuum, introducing H2Pressure maintaining leak detection, H2Replacing and starting the high-pressure kettle stirrer and the heating system to heat for reaction, wherein the reaction temperature is 360 ℃, the reaction pressure is 10.0MPa, the stirring speed is 200-600 r/min, and the reaction time is 2 hours; wherein the using amount of the catalyst is 3 percent of the mass of the pine tree effluent;
(2) after the reaction is finished, cooling to normal temperature, emptying to normal pressure, discharging, and removing the catalyst by suction filtration to obtain pine tree effluent cracking-hydrogenation products;
(3) distilling the cracking-hydrogenation product of pine tree effluent obtained in step (2) under 610mmHg for 3h, collecting 101 deg.C fraction to obtain monoterpene alkane of pinane and p-menthane, and collecting the rest light yellow transparent low viscosity transparent liquid as biological oil with carbon number between C12～C20. Wherein the content of pinane and p-menthane is 78%, the yield of monoterpene alkane is 37%, and the detection shows that the density of the biological oil is 937.3 kg.m-3(20 ℃ C.), a cetane index of 39, and an acid value of 0.96 mgKOH. g-1Kinematic viscosity (40 ℃)9.25mm2·s-1The bromine number was 0.76Br/100 g.
Example 10
The preparation method of the catalyst comprises the following operation steps:
(a) pretreatment of a carrier FCC catalyst: roasting the waste FCC catalyst for 3.5h for activation, wherein the roasting temperature is 600 ℃;
(b) dipping by a solution dipping method: preparing a precursor solution of Cu and Co by using copper nitrate, cobalt nitrate and deionized water at normal temperature according to the required total metal loading of 15-35% (wt%) by taking an FCC catalyst carrier as a reference, wherein the mass ratio of the double non-noble metal Cu to Co is 1:20, slowly dropwise adding the precursor solution into the FCC catalyst carrier under continuous stirring, continuously stirring for 5 minutes after dropwise adding is finished, and standing for 5.5 hours at normal temperature after finishing dropwise adding;
(c) and (3) drying: drying the impregnated sample in an oven at 120 ℃ for 9 hours;
(d) roasting: calcining the dried sample in a box-type muffle furnace at 500 ℃ for 3h to obtain a catalyst precursor;
(e) reduction: catalyst precursor was placed in a tube furnace in H2Under an atmosphere of 530 deg.CReduction at the temperature of 4.5H, H2The flow rate is 40 mL/min-1Naturally cooling to obtain the FCC catalyst supported bimetallic catalyst; and (5) standby.
A method for preparing bio-oil and monoterpene alkane by cracking-hydrogenating pine tree effluent simultaneously comprises the following steps:
(1) heating the masson pine effluent to 90-105 ℃ for dissolution, filtering the solution while the solution is hot to remove residues to obtain a liquid substance, namely the purified pine effluent containing 38 percent of turpentine for later use; putting 720g of the cleaned masson pine effluent and the catalyst into a high-pressure stirring reaction kettle, sealing the high-pressure stirring reaction kettle by an upper cover, vacuumizing the high-pressure stirring reaction kettle in sequence, and introducing H2Pressure maintaining leak detection, H2Replacing and starting the high-pressure kettle stirrer and the heating system to heat for reaction, wherein the reaction temperature is 350 ℃, the reaction pressure is 1.0MPa, the stirring speed is 200-600 r/min, and the reaction time is 4.5 h; wherein the amount of the catalyst is 15 percent of the mass of the pine tree effluent;
(2) after the reaction is finished, cooling to normal temperature, emptying to normal pressure, discharging, and removing the catalyst by suction filtration to obtain pine tree effluent cracking-hydrogenation products;
(3) distilling the cracking-hydrogenation product of pine tree effluent obtained in step (2) under 550mmHg for 1.5h, collecting 100 deg.C fraction to obtain monoterpene alkane of pinane and p-menthane, and collecting the rest light yellow transparent low viscosity transparent liquid as biological oil with carbon number between C12～C20. Wherein the content of pinane and p-menthane is 80%, the yield of monoterpene alkane is 50%, and the detection shows that the density of the biological oil is 952.7 kg.m-3(20 ℃ C.), a cetane index of 40, and an acid value of 1.49 mgKOH. g-1Kinematic viscosity (40 ℃)9.32mm2·s-1The bromine number was 0.85Br/100 g.
Example 11
The preparation method of the catalyst comprises the following operation steps:
(a) pretreatment of a carrier FCC catalyst: putting fresh FCC catalyst into an oven, and drying at 110 ℃ for 4.5h to remove moisture in the carrier;
(b) dipping by a solution dipping method: preparing a precursor solution of Cu and Co by using copper nitrate, cobalt nitrate and deionized water at normal temperature according to the required metal total loading capacity of 11 percent (wt%) by taking an FCC catalyst carrier as a reference, wherein the mass ratio of the double non-noble metal Cu to Co is 1:3, then slowly dropwise adding the precursor solution into the FCC catalyst carrier under continuous stirring, continuously stirring for 5 minutes after dropwise adding is finished, and standing for 5.5 hours at normal temperature after finishing dropwise adding;
(c) and (3) drying: drying the impregnated sample in an oven at 115 ℃ for 8.5 h;
(d) roasting: calcining the dried sample in a box-type muffle furnace at 500 ℃ for 3h to obtain a catalyst precursor;
(e) reduction: catalyst precursor was placed in a tube furnace in H2Reducing for 3H at 500 ℃ under the atmosphere2The flow rate is 40 mL/min-1Naturally cooling to obtain the FCC catalyst supported bimetallic catalyst; and (5) standby.
A method for preparing bio-oil and monoterpene alkane by cracking-hydrogenating pine tree effluent simultaneously comprises the following steps:
(1) heating the effluent of Yunnan pine tree to 90-105 deg.C for dissolving, filtering to remove residue while it is hot to obtain liquid substance, which is purified pine tree effluent containing turpentine 35% for use; putting 760g of purified Yunnan pine tree effluent and the catalyst into a high-pressure stirring reaction kettle, sealing the high-pressure stirring reaction kettle by an upper cover, vacuumizing the high-pressure stirring reaction kettle in sequence, and introducing H2Pressure maintaining leak detection, H2Replacing and starting the high-pressure kettle stirrer and the heating system to heat for reaction, wherein the reaction temperature is 230 ℃, the reaction pressure is 5.0MPa, the stirring speed is 200 r/min-600 r/min, and the reaction time is 1.5 h; wherein the amount of the catalyst is 15 percent of the mass of the pine tree effluent;
(2) after the reaction is finished, cooling to normal temperature, emptying to normal pressure, discharging, and removing the catalyst by suction filtration to obtain pine tree effluent cracking-hydrogenation products;
(3) distilling the cracking-hydrogenation product of pine tree effluent obtained in step (2) under 550mmHg for 3h, collecting 102 deg.C fraction to obtain monoterpene alkane of pinane and p-menthane, and collecting the rest light yellow transparent low viscosity transparent liquid as biological oil with carbon number between C12～C20. Wherein the content of pinane and p-menthane is 80%, the yield of monoterpene alkane is 45%, and the detection shows that the density of the biological oil is 939.5 kg.m-3(20 ℃ C.), a cetane index of 37 and an acid value of 1.27 mgKOH. g-1Kinematic viscosity (40 ℃)13.74mm2·s-1The bromine number was 1.59Br/100 g.
Example 12
The preparation method of the catalyst comprises the following operation steps:
(a) pretreatment of a carrier FCC catalyst: roasting the waste FCC catalyst at 660 ℃ for 3h for activation;
(b) dipping by a solution dipping method: preparing a precursor solution of Cu and Co by using copper nitrate, cobalt nitrate and deionized water at normal temperature according to the required metal total loading capacity of 11 percent (wt%) by taking an FCC catalyst carrier as a reference, wherein the mass ratio of the double non-noble metal Cu to Co is 1:10, then slowly dropwise adding the precursor solution into the FCC catalyst carrier under continuous stirring, continuously stirring for 5 minutes after dropwise adding is finished, and standing for 6 hours at normal temperature after finishing dropwise adding;
(c) and (3) drying: putting the soaked sample into an oven to be dried for 8 hours at 125 ℃;
(d) roasting: calcining the dried sample in a box-type muffle furnace at 500 ℃ for 3h to obtain a catalyst precursor;
(e) reduction: catalyst precursor was placed in a tube furnace in H2Reducing for 5.5H at 530 ℃ under the atmosphere2The flow rate is 40 mL/min-1Naturally cooling to obtain the FCC catalyst supported bimetallic catalyst; and (5) standby.
A method for preparing bio-oil and monoterpene alkane by cracking-hydrogenating pine tree effluent simultaneously comprises the following steps:
(1) heating the masson pine effluent to 90-105 ℃ for dissolution, filtering the solution while the solution is hot to remove residues to obtain a liquid substance, namely the purified pine effluent containing 35% of turpentine for later use; putting 700g of the cleaned masson pine effluent for standby and the catalyst for standby into a high-pressure stirring reaction kettle, sealing the high-pressure stirring reaction kettle by an upper cover, vacuumizing the high-pressure stirring reaction kettle in sequence, and introducing H2Pressure maintaining leak detection, H2Replacement, starting of autoclave stirrer and heatingThe system is heated for reaction, the reaction temperature is 260 ℃, the reaction pressure is 6.0MPa, the stirring speed is 200 r/min-600 r/min, and the reaction time is 4 hours; wherein the using amount of the catalyst is 10 percent of the mass of the pine tree effluent;
(2) after the reaction is finished, cooling to normal temperature, emptying to normal pressure, discharging, and removing the catalyst by suction filtration to obtain pine tree effluent cracking-hydrogenation products;
(3) distilling the cracking-hydrogenation product of pine tree effluent obtained in step (2) under reduced pressure of 600mmHg for 3h, collecting 101 deg.C fraction to obtain monoterpene alkane of pinane and p-menthane, and collecting the rest light yellow transparent low viscosity transparent liquid as biological oil with carbon number between C12～C20. Wherein the content of pinane and p-menthane is 76%, the yield of monoterpene alkane is 42%, and the detection shows that the density of the biological oil is 950.2 kg.m-3(20 ℃ C.), a cetane index of 36 and an acid value of 1.15 mgKOH. g-1Kinematic viscosity (40 ℃)12.16mm2·s-1The bromine number was 1.47Br/100 g.
Fig. 1 shows a bio-oil prepared by a rosin cracking method in documents of "nieuxian, jiang spring, davidia, and so on" preliminary study on synthesis and performance of rosin-based biodiesel [ J ]. forest chemical and industry, 2007,27(04):79-81 ", wherein a is the bio-oil on the day of preparation, and the bio-oil is light brown and transparent; b is biological oil which is placed for 5 days and is orange red and transparent. The rosin-based bio-oil prepared by the cracking method still has unsaturated double bond components, the active double bond structure is unstable, and the rosin-based bio-oil is easy to oxidize and deteriorate along with the increase of storage time to deepen the color.
FIG. 2 is a bio-oil prepared according to the present invention, wherein a is the bio-oil on the day of preparation, and is light yellow transparent; b is biological oil after being placed for 1 month, and is light yellow and transparent. The bio-oil is prepared by adopting a cracking-hydrogenation coupling technology, and double non-noble metals with the hydrogenation and decarboxylation capabilities and functions are used as catalysts, so that the tricyclic multi-carbon resin acid in the pine tree effluent is cracked, the double-bond component in the cracked product is saturated, the aim of synchronously performing hydrogenation and quality improvement on the cracked synthetic bio-oil and the unsaturated bio-oil is fulfilled, and the obtained bio-oil is high in saturation and good in stability.
The foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.

Claims (6)

1. A process for the simultaneous pyrolysis-hydrogenation of pine tree effluents to produce bio-oil and monoterpene alkanes, characterized in that it comprises the following operative steps:
(1) putting the purified pine tree effluent and a catalyst into a reaction kettle, wherein the reaction temperature is 190-370 ℃, the reaction pressure is 1.0-10.0 MPa, and the reaction time is 1.5-4.5 h; wherein the amount of the catalyst is 2-15% of the mass of the pine tree effluent;
(2) cooling and discharging after the reaction is finished, and removing the catalyst by suction filtration to obtain a pine tree effluent cracking-hydrogenation product;
(3) carrying out reduced pressure distillation on the pine tree effluent cracking-hydrogenation product obtained in the step (2) for 1.5-3 h under 550-650 mmHg, collecting fractions at 100-102 ℃ to obtain monoterpene alkane of pinane and p-menthane, and obtaining the rest of bio-oil;
wherein, the catalyst in the step (1) is a double non-noble metal catalyst obtained by loading one of Co-Mo, Ni-W, Ni-Mo or Cu-Co with an FCC catalyst.
2. The method of claim 1, wherein: the purification in the step (1) is a liquid substance obtained by heating pine tree effluent to 90-105 ℃ for dissolution and filtering the solution to remove residues while the solution is hot.
3. The method of claim 1, wherein: the pine tree effluent in the step (1) is one of masson pine tree effluent, Yunnan pine tree effluent, pinus khasys pine tree effluent or slash pine tree effluent.
4. The method of claim 1, wherein: the total metal loading mass of the catalyst is 15-35%, and the mass ratio of the double non-noble metal Co to Mo, the non-noble metal Ni to W or the non-noble metal Cu to Co is 1: 1-1: 20.
5. The method of claim 1, wherein: the FCC catalyst is either fresh FCC catalyst or spent FCC catalyst.
6. The method of claim 5, wherein: the preparation method of the catalyst in the step (1) comprises the following operation steps:
(a) pretreatment of a carrier FCC catalyst: putting a fresh FCC catalyst into an oven, and drying at 105-120 ℃ for 2-5 h to remove water in the carrier; or roasting the waste FCC catalyst for 1.5 to 4.5 hours for activation, wherein the roasting temperature is 450 to 700 ℃;
(b) dipping by a solution dipping method: preparing precursor solution of Co, Mo, Ni, W or Cu, Co by taking an FCC catalyst carrier as a reference, then dropwise adding the precursor solution into the FCC catalyst carrier under continuous stirring, continuously stirring after the dropwise adding is finished, and standing for 2-6 h after the dropwise adding is finished;
(c) and (3) drying: drying the dipped sample at 110-130 ℃ for 8-10 h;
(d) roasting: calcining the dried sample at 500 ℃ for 3h to obtain a catalyst precursor;
(e) reduction: the catalyst precursor is added in H2Reducing for 2.5-6H at 450-560 ℃ in atmosphere, H2The flow rate is 40mL ∙ min-1And cooling to obtain the FCC catalyst supported bimetallic catalyst.
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