CN102433148A - Method for preparing bio-fuel by unsulfurized catalyst - Google Patents

Method for preparing bio-fuel by unsulfurized catalyst Download PDF

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CN102433148A
CN102433148A CN2011103211123A CN201110321112A CN102433148A CN 102433148 A CN102433148 A CN 102433148A CN 2011103211123 A CN2011103211123 A CN 2011103211123A CN 201110321112 A CN201110321112 A CN 201110321112A CN 102433148 A CN102433148 A CN 102433148A
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catalyst
oil
adopts
preparation
biofuel
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荣龙
刘静
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Beihang University
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Beihang University
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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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • 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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Abstract

A method for preparing a bio-fuel by an unsulfurized catalyst is disclosed, which comprises the following steps of: (1) dissolving transition metal salts, then soaking the transition metal salts on a carrier, drying, and then roasting in a muffle furnace to obtain a bimetallic catalyst containing MoO3 or WO3 in a mass fraction of 5-25% and NiO in a mass fraction of 1-10%; (2) soaking the catalyst obtained in the step 1 in solution containing diammonium hydrogen phosphate or rare-earth metal salts, drying, and then roasting in the muffle furnace to obtain a polymetallic catalyst containing P2O5 in a mass fraction of 1-10% or La2O3 and CeO2 in a mass fraction of 0.5-5%; and (3) placing the catalyst obtained in the step 2 in a reactor to reduce, then adding plant oil in the reactor, and reacting under the conditions that a hydrogen partial pressure is 1-7 MPa, a hydrogen-oil ratio is 500-1500, an airspeed is 0.5-5 h<-1>, and a temperature is 200-400 DEG C, so as to obtain a bio-fuel. A sulfuration is not needed during the preparation process of the method, so that the corrosion on equipment by hydrogen sulphide, the pollution on environment and the harm on human body are avoided; and the preparation technique using a catalyst is simple, cheap, high in raw material conversion rate, high in product yield, and good in stability.

Description

A kind of method that adopts unvulcanised Preparation of Catalyst biofuel
(1) technical field
The present invention provides a kind of method that adopts unvulcanised Preparation of Catalyst biofuel, belongs to the derived energy chemical technical field.
(2) background technology
The world today is faced with the two big crises that go from bad to worse of fossil fuel worsening shortages and environment, and for the Sustainable development utilization of the energy, the preparation method of biofuel is by broad research.Biofuel is meant that with oil crops or engineering microalgae etc. be raw oil, the recyclable fuel of the alternative petrifaction diesel of processing through ester exchange process.The ester exchange process working method is to react under catalyst action through vegetables oil or animal tallow and methyl alcohol or ethanol to generate fatty acid methyl ester or ethyl ester and glycerine.Be raw material with the ears of an ox or cow maple oil among the patent CN1789377A for example, add methyl alcohol or ethanol, transesterify production biofuel under alkalescence or an acidic catalyst effect; Be raw material with the sewer oil among the patent CN1888019A, sulfuric acid is made catalyzer, adds methanol esterification and decolours and obtain biofuel etc.The advantage of the biofuel that ester exchange process obtains is high cetane value, good combustionproperty; Sulphur content is low, pollutes little; Flash-point is high, and is safe in utilization; Use renewable raw materials etc.But, because biofuel is the mixture of the high complicated organic composition of oxygen level, comprise ether, ester, aldehyde, ketone, phenol, organic acid, alcohol etc., make its oxidative stability poor, zero pour height then low-temperature fluidity is poor, and mover is had corrodibility.
In order to overcome the drawback of this type of biofuel; In recent years, another kind of preparation method of bio-diesel oil is emerged in large numbers gradually, promptly adopts existing hydrogenation unit technical process of petrochemical refining and equipment; Adopt suitable catalyzer and process conditions; Vegetables oil or vegetables oil mixed being converted into fat hydrocarbon with petroleum base diesel oil, such hydrocarbon polymer and petroleum base diesel oil molecules structure are more approaching, so this oxygen-free biofuel is also referred to as green diesel.For example among the patent CN101029245A petroleum base diesel oil such as raw material straight-run diesel oil are mixed with soybean wet goods vegetables oil; At 250～400 ℃ of temperature, hydrogen partial pressure is to carry out hydrofining reaction under the condition that exists of 3.0～8.0MPa and catalyzer; Or be to carry out hydrocracking reaction under the condition that exists of 4.5～20.0MPa and catalyzer at 300～450 ℃ of temperature, hydrogen partial pressure; Vegetables oil is converted into biofuel, and the catalyzer that the contriver adopts is the metallic sulfide of group vib and VIIIB family; Mixture with vegetable and animals oils or vegetable and animals oils and fossil oil oil among the patent CN101270300A transforms the generation biofuel through hydrogenation deoxidation; Can make hydrogenation catalyst keep advantages of higher stability through in reaction raw materials, adding appropriate supplement sulphur reagent, the catalyzer that the contriver adopts is the sulphided state of base metal nickel, molybdenum, cobalt, tungsten.
Though the adding of sulphur can improve activity of such catalysts and stability; But the hydrogen sulfide that produces in the sulfidation has corrodibility and toxicity; Oozing out of element sulphur can influence oil quality in the sulphurized catalyst, so we have invented a kind of method of unvulcanised Preparation of Catalyst biofuel, when avoiding sulphur pollution; The biofuel of better quality be can access, biogasoline, biological kerosene and green diesel comprised.
(3) summary of the invention
The object of the invention is exactly a weak point of avoiding above-mentioned prior art, proposes a kind of method that adopts unvulcanised Preparation of Catalyst biofuel.This method adds the rare earth metal auxiliary agent on present custom catalysts group vib and VIIIB group 4 transition metal basis, adopt the immersion process for preparing catalyzer; With many metal loads on carrier, vegetables oil under certain condition, through this catalyzer; Be converted into biofuel; According to the actual requirements, the product oil of different catalysts preparation is in harmonious proportion proportioning, obtains required biogasoline, biological kerosene and green diesel.This method prepares and need not sulfuration in the process, has avoided hydrogen sulfide to corrosion on Equipment, to the pollution of environment and to the harm of human body, and catalyst preparation process is simple, cheapness, and feed stock conversion is high, and product yield is high, good stability.
A kind of method that adopts unvulcanised Preparation of Catalyst biofuel of the present invention specifically may further comprise the steps:
Step 1: with being immersed on the carrier after the transition metal salt dissolving, dipping adopts equal-volume or excessive pickling process, dipping 1～5h, and dry back roasting 2～8h in 300～700 ℃ retort furnace, obtaining containing massfraction is 5～25%MoO 3Or WO 3Bimetallic catalyst with 1～10%NiO;
Step 2: adopt substep equal-volume or excessive pickling process; The bimetallic catalyst that step 1 is obtained is immersed in the solution that contains Secondary ammonium phosphate or rare earth metal salt; Dipping 1～5h, dry back roasting 2～8h in 300～700 ℃ retort furnace, obtaining containing massfraction is 1～10%P 2O 5Or 0.5～5%La 2O 3And CeO 2Multimetallic catalyst;
Step 3: the multimetallic catalyst that step 2 obtains is put into reactor drum; Keep hydrogen dividing potential drop 1～7MPa in the reactor drum, flow velocity 20～200ml/min, reductase 12～8h under 200～700 ℃ of conditions of temperature; Then vegetables oil is added in the reactor drum; At hydrogen dividing potential drop 1～7MPa, hydrogen-oil ratio 500～1500, air speed 0.5～5h -1, react under 200～400 ℃ of conditions of temperature.
Wherein, be that activated alumina, silicon-dioxide or activated alumina and silicon-dioxide mix for two kinds at the carrier described in the step 1.
Wherein, be that in curcas oil, rapeseed oil, VT 18, peanut oil, Viscotrol C, plam oil, the sunflower seed oil one or more mix at the vegetables oil described in the step 3.
The invention has the advantages that:
1, a kind of method that adopts unvulcanised Preparation of Catalyst biofuel of proposing of the present invention need not sulfuration in this method technological process, avoids hydrogen sulfide to corrosion on Equipment, to the pollution of environment and to the harm of human body.
2, a kind of method that adopts unvulcanised Preparation of Catalyst biofuel of the present invention's proposition, the catalyzer of this method preparation is through elements such as interpolation rare earth metals, and strong to the suitability of raw material, transformation efficiency is high, product yield height, good stability.
3, a kind of method that adopts unvulcanised Preparation of Catalyst biofuel of the present invention's proposition; The product of this method preparation is the alkane of carbon number between 15 to 18, has higher cetane value, has good burning performance; Heteroatoms such as sulfur-bearing oxygen has not improved the quality of fuel oil product.
4, a kind of method that adopts unvulcanised Preparation of Catalyst biofuel of the present invention's proposition, this method is in harmonious proportion through the product ratio on demand of different catalysts preparation, can reduce the zero pour of green diesel, improves its low-temperature fluidity.
5, a kind of method that adopts unvulcanised Preparation of Catalyst biofuel of the present invention's proposition, this method can be used as biogasoline, biological kerosene and green diesel through the product of different catalysts preparation.
(4) description of drawings
Fig. 1: a kind of process flow sheet that adopts the method for unvulcanised Preparation of Catalyst biofuel that the present invention proposes.
(5) embodiment
Below in conjunction with accompanying drawing and specific embodiment technical characterstic of the present invention is described in detail, as shown in Figure 1.
Embodiment 1:
A kind of method that adopts unvulcanised Preparation of Catalyst biofuel of the present invention specifically may further comprise the steps:
Step 1: with being immersed on the carrier after the transition metal salt dissolving, dipping adopts equi-volume impregnating, dipping 5h, and dry back roasting 4h in 400 ℃ retort furnace, obtaining containing massfraction is 15%MoO 3Bimetallic catalyst with 5%NiO.
Described carrier is an activated alumina.
Step 2: adopt excessive pickling process, the bimetallic catalyst that step 1 is obtained is immersed in the solution that contains rare earth metal salt, dipping 2h, and dry back roasting 4h in 400 ℃ retort furnace, obtaining containing massfraction is 3%La 2O 3And CeO 2Multimetallic catalyst.
Step 3: the multimetallic catalyst that step 2 obtains is put into reactor drum, keep hydrogen dividing potential drop 4MPa in the reactor drum, flow velocity 100ml/min; Reduce 4h under 400 ℃ of conditions of temperature, then vegetables oil is added in the reactor drum, at hydrogen dividing potential drop 3MPa; Hydrogen-oil ratio 1000, air speed 2h -1, react under 300 ℃ of conditions of temperature.
Described vegetables oil is curcas oil, rapeseed oil and VT 18.
Reaction result shows, more than 80%, product is mainly the normal paraffin of carbon number 17 and 18 to this unvulcanised catalyzer to the transformation efficiency of vegetables oil.
Embodiment 2:
A kind of method that adopts unvulcanised Preparation of Catalyst biofuel of the present invention specifically may further comprise the steps:
Step 1: with being immersed on the carrier after the transition metal salt dissolving, dipping adopts equi-volume impregnating, dipping 3h, and dry back roasting 5h in 700 ℃ retort furnace, obtaining containing massfraction is 10%MoO 3Bimetallic catalyst with 10%NiO.
Described carrier is a silicon-dioxide.
Step 2: adopt the substep equi-volume impregnating, the bimetallic catalyst that step 1 is obtained is immersed in earlier in the solution that contains Secondary ammonium phosphate, dipping 3h, and dry back roasting 5h in 700 ℃ retort furnace, obtaining containing massfraction is 10%P 2O 5Catalyzer, again with this catalyst soakage in containing the solution of rare earth metal salt, dipping 3h, dry back roasting 5h in 700 ℃ retort furnace, obtaining containing massfraction is 1%La 2O 3Multimetallic catalyst.
Step 3: the multimetallic catalyst that step 2 obtains is put into reactor drum, keep hydrogen dividing potential drop 5MPa in the reactor drum, flow velocity 50ml/min, reductase 12 h under 500 ℃ of conditions of temperature adds vegetables oil in the reactor drum then, at hydrogen dividing potential drop 4MPa, hydrogen-oil ratio 800, air speed 1h -1, react under 200 ℃ of conditions of temperature.
Described vegetables oil is a curcas oil.
Reaction result shows, more than 70%, product is mainly the normal paraffin of carbon number 17 to this unvulcanised catalyzer to the transformation efficiency of vegetables oil.
Embodiment 3:
A kind of method that adopts unvulcanised Preparation of Catalyst biofuel of the present invention specifically may further comprise the steps:
Step 1: with being immersed on the carrier after the transition metal salt dissolving, dipping adopts excessive pickling process, dipping 2h, and dry back roasting 6h in 600 ℃ retort furnace, obtaining containing massfraction is 20%WO 3Bimetallic catalyst with 8%NiO.
Described carrier is that activated alumina and silicon-dioxide mix for two kinds.
Step 2: adopt equi-volume impregnating, the bimetallic catalyst that step 1 is obtained is immersed in the solution that contains Secondary ammonium phosphate, dipping 5h, and dry back roasting 6h in 600 ℃ retort furnace, obtaining containing massfraction is 5%P 2O 5Multimetallic catalyst.
Step 3: the multimetallic catalyst that step 2 obtains is put into reactor drum, keep hydrogen dividing potential drop 2MPa in the reactor drum, flow velocity 150ml/min; Reduce 6h under 300 ℃ of conditions of temperature, then vegetables oil is added in the reactor drum, at hydrogen dividing potential drop 6MPa; Hydrogen-oil ratio 1300, air speed 4h -1, react under 400 ℃ of conditions of temperature.
Described vegetables oil is curcas oil and Viscotrol C.
Reaction result shows; This unvulcanised catalyzer to the transformation efficiency of vegetables oil more than 90%; Product is mainly the isoparaffin of small molecules alkane and carbon number 15 to 18, can the small molecules cut be done biogasoline, and the cut of carbon number ten to 14 can be made biological kerosene; The product of the cut of carbon number 15 to 18 and embodiment 1 or embodiment 2 gained is in harmonious proportion and uses, to improve the low-temperature fluidity of green diesel.

Claims (3)

1. a method that adopts unvulcanised Preparation of Catalyst biofuel is characterized in that, this method specifically may further comprise the steps:
Step 1: with being immersed on the carrier after the transition metal salt dissolving, dipping adopts equal-volume or excessive pickling process, dipping 1～5h, and dry back roasting 2～8h in 300～700 ℃ retort furnace, obtaining containing massfraction is 5～25%MoO 3Or WO 3Bimetallic catalyst with 1～10%NiO;
Step 2: adopt substep equal-volume or excessive pickling process; The bimetallic catalyst that step 1 is obtained is immersed in the solution that contains Secondary ammonium phosphate or rare earth metal salt; Dipping 1～5h, dry back roasting 2～8h in 300～700 ℃ retort furnace, obtaining containing massfraction is 1～10%P 2O 5Or 0.5～5%La 2O 3And CeO 2Multimetallic catalyst;
Step 3: the multimetallic catalyst that step 2 obtains is put into reactor drum; Keep hydrogen dividing potential drop 1～7MPa in the reactor drum, flow velocity 20～200ml/min, reductase 12～8h under 200～700 ℃ of conditions of temperature; Then vegetables oil is added in the reactor drum; At hydrogen dividing potential drop 1～7MPa, hydrogen-oil ratio 500～1500, air speed 0.5～5h -1, react under 200～400 ℃ of conditions of temperature.
2. a kind of method that adopts unvulcanised Preparation of Catalyst biofuel according to claim 1 is characterized in that: at the carrier described in the step 1 is that activated alumina, silicon-dioxide or activated alumina and silicon-dioxide mix for two kinds.
3. a kind of method that adopts unvulcanised Preparation of Catalyst biofuel according to claim 1 is characterized in that: at the vegetables oil described in the step 3 is that in curcas oil, rapeseed oil, VT 18, peanut oil, Viscotrol C, plam oil and the sunflower seed oil one or more mix.
CN2011103211123A 2011-10-20 2011-10-20 Method for preparing bio-fuel by unsulfurized catalyst Pending CN102433148A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107303489A (en) * 2016-04-19 2017-10-31 中国石油天然气股份有限公司 Double-bond saturation and hydrodeoxygenation catalyst and preparation method and application thereof
CN114250080A (en) * 2021-12-31 2022-03-29 中国林业科学研究院林产化学工业研究所 Method for preparing hydrocarbon-rich biofuel by catalyzing grease deoxidation
CN117691131A (en) * 2024-02-01 2024-03-12 新乡学院 MoO for lithium air battery 2 /CeO 2 Nanosphere composite material and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107303489A (en) * 2016-04-19 2017-10-31 中国石油天然气股份有限公司 Double-bond saturation and hydrodeoxygenation catalyst and preparation method and application thereof
CN107303489B (en) * 2016-04-19 2020-09-04 中国石油天然气股份有限公司 Double-bond saturation and hydrodeoxygenation catalyst and preparation method and application thereof
CN114250080A (en) * 2021-12-31 2022-03-29 中国林业科学研究院林产化学工业研究所 Method for preparing hydrocarbon-rich biofuel by catalyzing grease deoxidation
CN117691131A (en) * 2024-02-01 2024-03-12 新乡学院 MoO for lithium air battery 2 /CeO 2 Nanosphere composite material and preparation method thereof

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Application publication date: 20120502