CN105694944A - Method for preparing diesel distillates by means of catalytically hydrogenating stearic acid or waste oil - Google Patents

Method for preparing diesel distillates by means of catalytically hydrogenating stearic acid or waste oil Download PDF

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CN105694944A
CN105694944A CN201610232265.3A CN201610232265A CN105694944A CN 105694944 A CN105694944 A CN 105694944A CN 201610232265 A CN201610232265 A CN 201610232265A CN 105694944 A CN105694944 A CN 105694944A
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waste oil
hydrogen
stearic acid
oil
reaction
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CN105694944B (en
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李志霞
李福威
黄振涛
丁世磊
黎跃
陈丛瑾
胡华宇
黄祖强
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Guangxi University
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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
    • C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
    • 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
    • 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
    • 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
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1003—Waste materials
    • C10G2300/1007—Used oils
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil
    • 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

Abstract

The invention discloses a method for preparing diesel distillates by means of catalytically hydrogenating stearic acid or waste oil. Tetrahydronaphthalene is used as a hydrogen donor. The method includes technological steps of mixing the stearic acid or the treated waste oil with the tetrahydronaphthalene according to a mass ratio of 1:4 to obtain mixtures, vulcanizing NiMo/gamma-Al2O3-beta-molecular sieve composite solid-acid catalysts in a reaction kettle, then adding the mixtures into the reaction kettle, filling the reaction kettle with hydrogen under the hydrogen pressures of 0.8-5 MPa under the control, carrying out reaction at the reaction temperatures of 300-350 DEG C for 1-4 h and collecting liquid products to obtain the diesel distillates. The weight of the catalysts accounts for 1.67% of the total mass of the mixtures. The method has the advantages that diversified utilization of the waste oil can be broadened, the tetrahydronaphthalene is used as the hydrogen donor, catalytic hydrogenation and deoxidation reaction of the stearic acid or the waste oil in the hydrogen donor and the hydrogen donation activity of the hydrogen donor during catalytic hydrogenation reaction are investigated, accordingly, the hydrogen donor can be partially or completely replace the hydrogen to be used as a source of active hydrogen, the method is favorable for reducing the usage of the hydrogen, and the cost can be saved.

Description

A kind of method that stearic acid or waste oil catalytic hydrogenation prepare diesel oil distillate
Technical field
The present invention relates to bio oil catalytic hydrogenation and prepare technical field of fuel oil, be specifically related to a kind of stearic acid or method that waste oil catalytic hydrogenation prepares diesel oil distillate。
Background technology
The energy is the material base of the human society survival and development, along with the fast development of China's economic and increasing rapidly of population, the demand of the energy is increasing, and energy resource consumption is significantly increased, traditional energy resource reduces day by day, can not meet the needs of the national economic development。Meanwhile, traditional energy consuming the deterioration of the ecological environment caused and day by day manifest, China meets domestic growing energy-consuming demand in the urgent need to new forms of energy, reduces greenhouse gas emission, built environment friendly country。The reserves of biomass energy are extremely abundant, are the key components of regenerative resource, are also the regenerative resources having industrialization and scale prospect most, occupy critical role in the energy resource structure of various countries。Biomass are also a kind of unique reproducible carbon sources, can change into the solid-state of routine, liquid and fuel gas。
The annual edible vegetable oil of Chinese and animal oil are about 22,500,000 t, and every annual meeting produces the waste oil of about 4,000,000 t, and these waste oil are used for manufacturing biodiesel except part, and also some comes back to dining table, form pollution of dining table。On the other hand, these waste oil are again bio oil, are reproducible environmentally friendly bio-fuel-oils, are the succedaneum of Fossil fuel most potential quality。For the shortcoming such as overcome bio oil oxygen content high and calorific value is low, being that core reduces bio oil oxygen content, the process route that improves its calorific value arises at the historic moment with Catalytic Hydrogenation Techniques, up to now, hydrogen is the main hydrogen source of Catalytic Hydrogenation Techniques。Consumption hydrogen is more, and investing higher is the main weak point of these techniques。
Hydrogen Energy is to clean reproducible secondary energy sources, is absent from hydrogen, it is necessary to obtain from the material containing hydrogen, and the preparation expense of hydrogen source is too high, largely limit popularization and the application of hydrogen addition technology in nature, and this promotes people to develop the novel hydrogen source material of searching。Hydrogen donor is a kind of compound that can provide active hydrogen free radical, is also referred to as hydrogen supply agent。Reactant, as reaction dissolvent, is not only played the scattered effect of dissolving by liquid hydrogen supply agent, and being alternatively arranged as hydrogen supply agent provides and transfer activity hydrogen, and to the reaction intermediate generated, free radical plays stable and protective effect；Also promoting the hydrogenation degradation reaction of oils and fats, the hydrogen generated under high temperature can also capture Active Radicals Produced produced by oil splitting, terminates the transmission of cracking reaction chain, it is suppressed that cracking, reduces polymerization secondary response, thus efficiently reducing deposition。Hydrogen supply agent, as the use of novel hydrogen source, is expected to carry forward vigorously the process that waste oil catalytic hydrogenation converts, the range of application that extension waste oil is recycled to bio-fuel-oil。
Up to now, also do not seen that the research having the catalytic hydrogenation reaction that liquid hydrogen supply agent joins fatty acid or waste oil was reported。Due to the complicated component of waste oil, except containing substantial amounts of triglyceride, possibly together with a small amount of free fatty。The catalytic hydrogenation of waste oil is also complex, hydrogenolysis and two processes of hydrogenation deoxidation need to be experienced, fatty acid is the initial stage product of triglyceride generation hydrogenolysis, and fatty acid is a kind of raw material of more difficult hydrogenation deoxidation reduction, accordingly, it can be said that the effect of catalyzing glycerol three ester through hydrogenation deoxidation is mainly determined by the hydrogenation deoxidation effect of fatty acid。
Summary of the invention
It is an object of the invention to overcome consumption hydrogen in conventional catalyst hydrogen addition technology more, relatively costly weak point, for the shortage of current fossil resources, bio-fuel-oil exploitation has recyclability and eco-friendly feature, propose a kind of with stearic acid or waste oil for raw material, using naphthane as hydrogen supply agent, converted stearic acid or method that waste oil is diesel oil distillate product by Catalytic Hydrogenation Techniques, partly or entirely substitute the hydrogen source as reactive hydrogen realizing liquid hydrogen supply agent。
The present invention solves above-mentioned technical problem with following technical scheme:
A kind of method that stearic acid or waste oil catalytic hydrogenation prepare diesel oil distillate, naphthane is as hydrogen supply agent, and processing step is as follows: stearic acid or pretreated waste oil are mixed with naphthane 1:4 in mass ratio, by NiMo/ γ-Al2O3-β-molecular sieve composite solid-acid catalyst is placed in reactor after sulfuration, said mixture is added in reactor, catalyst accounts for the 1.67% of mixture gross mass, pass into hydrogen, and to control Hydrogen Vapor Pressure be 0.8～5MPa, reaction temperature is 300～350 DEG C, collects product liquid and get final product after reaction 1～4h。
Described waste oil is the one in restaurant waste edible oil, waste vegetable oil, animal oil, waste oil or hogwash fat or mixing。
Described waste oil is with stearic acid for model compound。
The preprocess method of described waste oil is: waste oil and saturated aqueous common salt are mixed by the mass ratio of 1:2,3h removing glue is stirred at 80 DEG C, stratification obtains oils and fats, grease obtained middle addition quality is the activated carbon of waste oil quality 2% and distilled water that quality is waste oil quality 5 times, stirs 3h, rotating speed 700rpm at 80 DEG C, sucking filtration while hot again, gained liquid stratification, gained oil reservoir puts into Rotary Evaporators evacuation 1h at 100 DEG C, then dries。
Described NiMo/ γ-Al2O3The preparation method of-β-molecular sieve composite solid-acid catalyst is: by γ-Al2O3Weighing with β-molecular sieve 3:2 in mass ratio, add water stirring mixing, adding the water yield is γ-Al2O3With 15 times of β-molecular sieve quality sum, with magnetic stirring apparatus 90 DEG C of heated and stirred to moisture major part remove, mixing speed 400rpm, the solid product obtained 105 DEG C dry after in Muffle furnace 450 DEG C calcining 2h, prepare complex carrier；On gained complex carrier, active component Ni and Mo is supported by infusion process, Ni and Mo mol ratio is 3:7, active component is with its metal-oxide mass percent content meter, account for the 20% of described catalyst gross mass, after dipping, gained catalyst powder compressing machine carries out tabletting, then 380 DEG C of calcining 5h in Muffle furnace, obtain NiMo/ γ-Al2O3-β-molecular sieve composite solid acid catalyst。
Described infusion process is add water dissolving after Nickelous nitrate hexahydrate and Ammonium Molybdate Tetrahydrate 1:1.425 in mass ratio mixing, the addition water yield is 40 times of Nickelous nitrate hexahydrate and Ammonium Molybdate Tetrahydrate quality sum, then press complex carrier quality 10% adds citric acid, form metal salt solution, again by described complex carrier and above-mentioned metal salt solution in mass ratio 1: 16.4 mix after heating in vacuum on a rotary evaporator, heating means are 40 DEG C of heating 30min, 50 DEG C of heating remove to most of moisture, then 60 DEG C of heating 30min, are evaporated to moisture。
Described NiMo/ γ-Al2O3The vulcanization process of-β-molecular sieve composite solid-acid catalyst is: add described catalyst in autoclave, seals, H2Leak detection, adds dimethyl disulfides by the 1.5 of catalyst quality times, then passes into the hydrogen of 1.5MPa, be warming up to 320 DEG C with 2 DEG C/min, then Hydrogen Vapor Pressure brought up to 5MPa, vulcanize 3h at 320 DEG C。
Compared with existing catalytic hydrogenation method, the method have the advantages that:
(1) the inventive method uses waste oil to be raw material, is fuel oil by waste oil Efficient Conversion, improves the utilization rate of waste oil, has opened up extensively waste oil diversification utilization。
(2), when using naphthane as hydrogen supply agent catalytic hydroconversion stearic acid, operating condition is gentle, it is not necessary to higher H2Pressure, just can reach higher conversion ratio, and hydrogenation products is mainly the diesel oil distillate materials such as alkane and the alkene of C15～C18。Reaction temperature 350 DEG C, H2Pressure 0.8MPa (only uses H before reaction2Emptying reactor, initial H2Pressure is only 0.1MPa) response time 2h, stearic acid is made solvent conversion rate and is reached 90%, and reacts under equal conditions, uses dodecane to make solvent, and conversion ratio only reaches 17%；Work as H2Pressure from 0.8MPa increase to 5MPa time, naphthalene value gradually decreases down 0.23 from 1.14, illustrates that naphthane is at relatively low H2Its excellent hydrogen supply effect can be played under pressure condition, the hydrogen source as reactive hydrogen can be substituted。
(3) when using naphthane as hydrogen supply agent catalytic hydroconversion waste oil, at 350 DEG C, H2Pressure 4～5MPa reacts 3h, and the hydrogenolysis rate of waste oil and conversion ratio have all reached more than 98%, and hydrogenation products is mainly the diesel oil distillate materials such as alkane and the alkene of C15～C18；Compared with conventional reaction dissolvent dodecane, at relatively low H2Under pressure (< 3MPa) condition, the present invention adopts naphthane to obtain higher conversion ratio as solvent。As at 350 DEG C, H2Pressure 2MPa reacts 3h, and it is 72% that naphthane makes conversion ratio during solvent, and when adopting dodecane to make solvent, conversion ratio is only 54%。When naphthane makes hydrogen supply agent, along with H2Pressure increases 5MPa from 2MPa, and the naphthalene value of hydrogenation products gradually decreases to 0.1 from 0.8, it was shown that when relatively low hydrogen pressure, and naphthane can play good hydrogen supply effect。
Detailed description of the invention
Embodiment 1:
(1) raw material prepares
Making hydrogen supply agent with naphthane, with the stearic acid (the being commonly called as stearic acid) model compound as waste oil, the catalyst of selection is NiMo/ γ-Al2O3-β-molecular sieve composite solid-acid catalyst。
Catalyst preparing and vulcanization process:
First by 3.0g γ-Al2O3Join in 75ml water stirring mixing with 2.0g β-molecular sieve, with 90 DEG C of heated and stirred of magnetic stirring apparatus, mixing speed 400rpm, evaporate to moisture major part, gained solid product dry at 105 DEG C after in Muffle furnace 450 DEG C of calcining 2h, prepare complex carrier；On complex carrier, support active component Ni and Mo by infusion process, make metal-oxide NiO and MoO3Quality sum account for the 20% of catalyst gross mass, the mol ratio of Ni and Mo is 3:7；After dipping, gained catalyst powder compressing machine carries out tabletting, and then 380 DEG C of calcining 5h in Muffle furnace, finally prepare NiMo/ γ-Al2O3-β-molecular sieve composite solid acid catalyst。
Above-mentioned infusion process is: be first dissolved in a certain amount of water by 0.87g Nickelous nitrate hexahydrate and 1.24g Ammonium Molybdate Tetrahydrate, the addition water yield is 40 times of Nickelous nitrate hexahydrate and Ammonium Molybdate Tetrahydrate quality sum, add 0.5g citric acid and prepare metal salt solution, 5.0g complex carrier is mixed with above-mentioned metal salt solution, heating in vacuum on a rotary evaporator, heating means are: 40 DEG C of heating 30min, and 50 DEG C of heating remove to moisture major part, then 60 DEG C of heating 30min, are evaporated to moisture。
The vulcanization process of catalyst: add the above-mentioned catalyst of 0.1g in the autoclave of volume 20ml, seal, H2Leak detection, adds 0.15g dimethyl disulfide, passes into the hydrogen of 1.5MPa, with 2 DEG C/min temperature programming to 320 DEG C。When temperature arrives 320 DEG C, Hydrogen Vapor Pressure is brought up to 5MPa, vulcanize 3h at 320 DEG C。The effect of sulfuration is the hydrogenation activity and the heat stability that improve catalyst, moreover it is possible to avoid it to inactivate。
(2) preparation method
With naphthane for hydrogen supply agent, stearic acid and naphthane, as model compound, are mixed by stearic acid with mass ratio 1:4, after described catalyst 0.1g vulcanizes in reactor, adding in reactor by stearic acid-naphthane mixed solution 6.0g immediately, controlling reaction temperature is 350 DEG C, H2Pressure is 5MPa, and being respectively provided with the response time is 1h, 2h, 3h, is respectively combined above-mentioned reaction condition and is prepared experiment。
Interpretation: after reaction terminates, stop heating, reactor is allowed to naturally cool to room temperature, slowly open air bleeding valve to be emptied by incoagulable gas, after question response still inside and outside air pressure balance, open reactor lid, solidliquid mixture is poured out from reactor, sample analysis, the response time on stearic acid hydrogenation deoxidation affect result and dominant response product is shown in Table 1。Test result indicate that, at 350 DEG C and 5MPaH2When, along with the response time is increased to 3h by 1h, stearic conversion ratio is increased to 100% by 88%, product isomerisation degree is increased to 38% by 20%, meanwhile, product naphthalene value increases to 0.41 from 0.22, and this illustrates that the reaction of stearic hydrogenation deoxidation and isomerization reaction carry out simultaneously, when reaction carries out to 2-3h, the dehydrogenation reaction of naphthane is strengthened, and hydrogen supply effect strengthens。
Embodiment 2
(1) raw material prepares: with embodiment 1。
(2) preparation method:
Using naphthane as hydrogen supply agent, stearic acid is as model compound, stearic acid and naphthane are mixed with mass ratio 1:4, after described catalyst 0.1g vulcanizes in reactor, being added in reactor by stearic acid-naphthane mixed solution 6.0g immediately, the control response time is 2h, and being respectively provided with Hydrogen Vapor Pressure is 3MPa and 5MPa, reaction temperature is respectively set to 300 DEG C, 320 DEG C, 350 DEG C, is respectively combined above-mentioned reaction condition and is prepared experiment。
Interpretation: reaction temperature on stearic acid hydrogenation deoxidation affect result and reaction primary product as shown in table 1。Test result indicate that: react when two kinds of Hydrogen Vapor Pressures, along with temperature increases to 350 DEG C from 300 DEG C, stearic conversion ratio, product isomerisation degree and naphthalene value all raise along with temperature and improve；And, at identical temperature conditions, 5MPaH2The naphthalene value of gained product liquid is reacted well below 3MPaH under pressure2React the naphthalene value of products therefrom under pressure, this imply that at relatively low H2Under pressure condition, naphthane has higher activity, and hydrogen supply capacity is stronger。At 350 DEG C, when two kinds of Hydrogen Vapor Pressures, the isomerisation degree of product is more or less the same。
Embodiment 3
(1) raw material prepares: with embodiment 1。
(2) preparation method:
Using naphthane as hydrogen supply agent, stearic acid is as model compound, stearic acid and naphthane are mixed with mass ratio 1:4, after described catalyst 0.1g vulcanizes in reactor, being added in reactor by stearic acid-naphthane mixed solution 6.0g immediately, the response time is 2h, and controlling reaction temperature respectively is 310 DEG C, 350 DEG C, reaction pressure is 0.8MPa, 3MPa, 5MPa respectively, is respectively combined above-mentioned reaction condition and is prepared experiment。
Interpretation: reaction pressure on stearic acid catalytic hydrodeoxygenation affect result and reaction primary product as shown in table 1。Test result indicate that, when reaction temperature is 310 DEG C, along with H2Pressure increases to 5MPa from 0.8MPa, and stearic acid conversion ratio increases to 72% from 30%, and naphthalene value reduces to 0.07 from 0.53。And when reaction temperature is 350 DEG C, with H2The increase of pressure, conversion ratio is kept at more than 90%, and naphthalene value increases with pressure and reduces。Especially as the initial H of reactor2Stuffing pressure is only 0.1MPa (when arriving 350 DEG C, pressure is 0.8MPa) time, stearic acid conversion ratio still reaches 90%, and now naphthalene value reaches maximum 1.14, this illustrates that naphthane has very strong hydrogen supply capacity when 350 DEG C of low hydrogen pressures, can partly or entirely substitute the hydrogen source as reactive hydrogen。H2The isomerisation degree of product is affected little by pressure, and product isomerisation degree maintains between 25～40%。
Embodiment 4
(1) pretreatment of waste oil
Take 50g waste oil sample, add 100ml saturated aqueous common salt at 80 DEG C, stir 3h removing glue, pour stratification 12h in separatory funnel into, take upper strata oils and fats, then in oils and fats, add 1.0g activated carbon and 250ml distilled water stirs 3h depigmentation at 80 DEG C, rotating speed 700rpm, while hot sucking filtration, pour stratification 12h in separatory funnel into by liquid, take oil reservoir and put in Rotary Evaporators, at 100 DEG C, evacuation 1h dewaters, and then oils and fats is put into 105 DEG C of dry 12h of baking oven, seals and preserves。
Catalyst preparing and vulcanization process are with embodiment 1。
(2) preparation method:
With naphthane for hydrogen supply agent, to mix with mass ratio 1:4 with hydrogen supply dissolvent through above-mentioned pretreated waste oil, after described catalyst 0.1g vulcanizes in reactor, immediately waste oil-naphthane mixed solution 6.0g be added in reactor, reaction temperature is 350 DEG C, H2Pressure is 5MPa, and the response time is respectively set to 1h, 2h, 3h and 4h, is respectively combined above-mentioned reaction condition and is prepared experiment。
Interpretation: the response time on waste oil hydrogenation deoxidation affect result and reaction primary product as shown in table 2。Test result indicate that, when the response time is 2h, the hydrogenolysis rate of waste oil reaches 93%, and conversion ratio only reaches 80%, and hydrogenolysis rate reaches 100% when being 3h between when reacted, conversion ratio reaches 98%, this illustrates that waste oil is first carry out hydrogenation degradation reaction to produce fatty acid in this reaction system, then carries out the catalytic hydrogenating reduction reaction of fatty acid, and hydrogenolysis speed is more than rate of reduction。Increasing to 4h from 1h over time, product isomerisation degree is increased to 5.5% by 3.9%, and therefore the response time is little on the impact of product isomerisation degree。
Embodiment 5
(1) pretreatment of waste oil, catalyst preparing and vulcanization process are all with embodiment 4。
(2) preparation method:
Using naphthane as hydrogen supply dissolvent, to mix with mass ratio 1:4 with hydrogen supply dissolvent through pretreated waste oil, after described catalyst 0.1g vulcanizes in reactor, immediately waste oil-naphthane mixed solution 6.0g is added in reactor, controlling reaction temperature respectively is 300 DEG C, 325 DEG C and 350 DEG C, H2Pressure is 5MPa, and the response time is 3h, is respectively combined above-mentioned reaction condition and is prepared experiment。
Interpretation: reaction temperature on waste oil hydrogenation deoxidation affect result and reaction primary product as shown in table 2。Test result indicate that, along with temperature increases to 350 DEG C from 300 DEG C, the hydrogenolysis rate of waste oil increases to 100% from 80%, and the conversion ratio of waste oil increases to 100% from 45%。It can thus be seen that the hydrogenation that reaction temperature 300 DEG C can promote waste oil preferably is degraded, but the catalytic hydrodeoxygenation reaction of fatty acid can not be effectively facilitated。When temperature is lower than 325 DEG C, the isomerisation degree of product is 0, and when temperature reaches 350 DEG C, product isomerisation degree reaches 4%, it was shown that higher temperature can promote that the isomerization level of product improves。Compared with stearic catalytic hydrogenation product, the catalytic hydrogenation product isomerisation degree of waste oil is relatively low, this reactive hydrogen being likely to be due to naphthane offer is mainly consumed in the hydrogenation degradation reaction of oils and fats, and meanwhile, the by-product glycerin of hydrogenation degradation reaction is likely to the isomerization process affecting product。
Embodiment 6
(1) pretreatment of waste oil, with embodiment 4。
(2) preparation method
Using naphthane as hydrogen supply agent, to mix with mass ratio 1:4 with hydrogen supply dissolvent through pretreated waste oil, after described catalyst 0.1g vulcanizes in reactor, adding in reactor by waste oil-naphthane mixed solution 6.0g immediately, controlling reaction temperature is 350 DEG C；Response time is 3h, and being respectively provided with reaction pressure is 2MPa, 3MPa, 4MPa and 5MPa。It is respectively combined above-mentioned reaction condition and is prepared experiment。
Interpretation: reaction pressure on waste oil hydrogenation deoxidation affect result and reaction primary product as shown in table 2。Along with pressure rises to 5MPa from 2MPa, waste oil hydrogenolysis rate maintains more than 95%, and conversion ratio increases to 98% from 72%, and the isomerisation degree of product maintains 4～17%, and the naphthalene value of product drops to 0.1 from 0.8, and higher H is described2Pressure, contributes to waste oil and converts to Hydrocarbon, but be as H2The hydrogen activity that supplies increasing naphthane of pressure decreases。Compared with stearic catalytic hydrogenation reaction, at reaction temperature 350 DEG C, H2Pressure 2MPa, reacts 2h, and stearic acid conversion ratio reaches 96%, and product naphthalene value is 1, and waste oil is at same temperature and H2Under pressure condition, reaction 3h, conversion ratio but only has 73%, product naphthalene value is 0.8, this illustrates in catalyzed conversion waste oil process, the reactive hydrogen that naphthane provides mainly is consumed in the hydrogenation degradation reaction of waste oil, and the by-product glycerin hydrogenating degradation reaction is probably and the interfering material of fatty acid contention hydrogen source, and these all have impact on the transformation efficiency for hydrogen activity and waste oil of naphthane。
The analysis result of stearic acid catalytic hydrodeoxygenation product when table 1 differential responses
-: represent concentrations less than 1%；
The mensuration of conversion ratio: product liquid is carried out acid value measuring, takes 1.0g product liquid and adds 50ml isopropanol, add 1ml10g/L phenolphthalein-dehydrated alcohol indicator, with the KOH-dehydrated alcohol titration that concentration is 0.05mol/L。Remaining stearic quality in product is calculated by product acid number。
m1: stearic acid initial mass (g)；M2: product liquid remains stearic quality (g)。
The calculating of naphthalene value: because the product after naphthane dehydrogenation is naphthalene, result is analyzed according to gas chromatograph-mass spectrometer (GC-MS), calculate the ratio (also referred to as naphthalene value) of naphthalene and other non-fat acids product (including Hydrocarbon, alcohols and the aldehydes) content generated in product, naphthane hydrogen supply effect is evaluated。The implication of naphthalene value is in that in product to generate the quality of naphthalene produced by 1.0g hydrogenating reduction product (alkane, alkene, alcohols and aldehydes), and the naphthalene of generation more many explanations naphthane participates in reaction and hydrogen supply is more many。
Isomerization calculates: the ratio (%) of the content of isoparaffin and all hydrocarbons content in product liquid gas chromatographic analysis。
The analysis result of waste oil catalytic hydrodeoxygenation product when table 2 differential responses
-: represent concentrations less than 1%；
The mensuration of conversion ratio (T) in table 2: analyze through GC-MS after product liquid esterification, not waste oil catalytic hydrogenation product (alkane, alkene, alcohols and aldehydes) percentage (product composition does not comprise naphthane) in product composition。
The definition of hydrogenolysis rate in table 2: after hydrogenation degradation reaction occurs waste oil, originally free fatty acid is generated, the fatty acid part generated is transformed to Hydrocarbon and the reduzate such as alcohols, aldehydes (this Partial Conversion ratio can use conversion ratio T to replace) through catalytic hydrogenation, and another part is likely to still with free fatty acid form existence。Can be calculated by acid value measuring with the oils and fats ratio that free fatty acid form exists。First product liquid is carried out acid value measuring, acid number calculate the content of product free fatty acid, then occurred hydrogenation degraded to form the oils and fats ratio (Ra) of these fatty acids by the cubage of fatty acid。Namely hydrogenolysis rate comprises two parts: a part is to be converted into the oil fraction of hydrogenating reduction product (alkane, alkene, alcohols and aldehydes), and another part is the oil fraction existed with fatty acid form。Hydrogenolysis rate (%)=T+Ra。

Claims (7)

1. the method that a stearic acid or waste oil catalytic hydrogenation prepare diesel oil distillate, it is characterised in that naphthane is as hydrogen supply agent, and processing step is as follows: stearic acid or pretreated waste oil are mixed with naphthane 1:4 in mass ratio, by NiMo/ γ-Al2O3-β-molecular sieve composite solid-acid catalyst is placed in reactor after sulfuration, said mixture is added in reactor, catalyst accounts for the 1.67% of mixture gross mass, pass into hydrogen, and to control Hydrogen Vapor Pressure be 0.8～5MPa, reaction temperature is 300～350 DEG C, collects product liquid and get final product after reaction 1～4h。
2. the method that a kind of stearic acid as claimed in claim 1 or waste oil catalytic hydrogenation prepare diesel oil distillate, it is characterised in that described waste oil is the one in restaurant waste edible oil, waste vegetable oil, animal oil, waste oil or hogwash fat or mixing。
3. the method that a kind of stearic acid as claimed in claim 1 or waste oil catalytic hydrogenation prepare diesel oil distillate, it is characterised in that described waste oil is with stearic acid for model compound。
4. the method that a kind of stearic acid as claimed in claim 1 or waste oil catalytic hydrogenation prepare diesel oil distillate, it is characterized in that, the preprocess method of described waste oil is: waste oil mixes by the mass ratio of 1:2 with saturated aqueous common salt, 3h removing glue is stirred at 80 DEG C, stratification obtains oils and fats, grease obtained middle addition quality is the activated carbon of waste oil quality 2% and the distilled water that quality is waste oil quality 5 times stirs 3h at 80 DEG C, rotating speed 700rpm, sucking filtration while hot again, gained liquid stratification, gained oil reservoir puts into Rotary Evaporators evacuation 1h at 100 DEG C, dry again。
5. the method that a kind of stearic acid as claimed in claim 1 or waste oil catalytic hydrogenation prepare diesel oil distillate, it is characterised in that described NiMo/ γ-Al2O3The preparation method of-β-molecular sieve composite solid-acid catalyst is: by γ-Al2O3Weighing with β-molecular sieve 3:2 in mass ratio, add water stirring mixing, adding the water yield is γ-Al2O3With 15 times of β-molecular sieve quality sum, with magnetic stirring apparatus 90 DEG C of heated and stirred to moisture major part remove, mixing speed 400rpm, the solid product obtained 105 DEG C dry after in Muffle furnace 450 DEG C calcining 2h, prepare complex carrier；On gained complex carrier, active component Ni and Mo is supported by infusion process, Ni and Mo mol ratio is 3:7, active component is with its metal-oxide mass percent content meter, account for the 20% of described catalyst gross mass, after dipping, gained catalyst powder compressing machine carries out tabletting, then 380 DEG C of calcining 5h in Muffle furnace, obtain NiMo/ γ-Al2O3-β-molecular sieve composite solid acid catalyst。
6. the method that a kind of stearic acid as claimed in claim 5 or waste oil catalytic hydrogenation prepare diesel oil distillate, it is characterized in that, described infusion process is be dissolved in water after Nickelous nitrate hexahydrate and Ammonium Molybdate Tetrahydrate 1:1.425 in mass ratio mixing, the addition water yield is 40 times of Nickelous nitrate hexahydrate and Ammonium Molybdate Tetrahydrate quality sum, then press complex carrier quality 10% adds citric acid, form metal salt solution, again by described complex carrier and above-mentioned metal salt solution in mass ratio 1: 17.4 mix after heating in vacuum on a rotary evaporator, heating means are 40 DEG C of heating 30min, 50 DEG C of heating remove to most of moisture, then 60 DEG C of heating 30min, it is evaporated to moisture。
7. the method that a kind of stearic acid as claimed in claim 1 or waste oil catalytic hydrogenation prepare diesel oil distillate, it is characterised in that described NiMo/ γ-Al2O3The vulcanization process of-β-molecular sieve composite solid-acid catalyst is: add described catalyst in autoclave, seals, H2Leak detection, adds dimethyl disulfides by the 1.5 of catalyst quality times, then passes into the hydrogen of 1.5MPa, be warming up to 320 DEG C with 2 DEG C/min, then Hydrogen Vapor Pressure brought up to 5MPa, vulcanize 3h at 320 DEG C。
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CN111135857A (en) * 2019-12-30 2020-05-12 广西中医药大学 Preparation method and application of reduced catalyst
CN111298799A (en) * 2019-12-30 2020-06-19 广西中医药大学 Preparation method and application of reduced NiMo bifunctional catalyst

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