CN108484346A - A kind of method that waste cooking oils aromatisation prepares light aromatics - Google Patents
A kind of method that waste cooking oils aromatisation prepares light aromatics Download PDFInfo
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- CN108484346A CN108484346A CN201810377575.3A CN201810377575A CN108484346A CN 108484346 A CN108484346 A CN 108484346A CN 201810377575 A CN201810377575 A CN 201810377575A CN 108484346 A CN108484346 A CN 108484346A
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- C07—ORGANIC CHEMISTRY
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- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
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- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
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- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C07C2529/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
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- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
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- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
- C07C2529/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65 containing iron group metals, noble metals or copper
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Abstract
The invention discloses a kind of methods that waste cooking oils aromatisation prepares light aromatics, include the following steps：(1) by waste cooking oils, or waste cooking oils are mixed with solvent, is sent into the fixed bed reactors for being filled with catalyst and is reacted after preheating vaporization；(2) reaction product condensation, the separation obtained step (1), obtains aromatic hydrocarbons.It is exactly largely aromatic hydrocarbons in aromatization products obtained by method provided by the invention, only micro oxygenatedchemicals, oxygen atom in grease molecules is substantially all the form for being converted into water or carbon dioxide, therefore it only needs to remove moisture using solvent extraction or extractive distillation method, it can be obtained aromatic product, and belongs to continuous operation, be suitable for industrialization large-scale production.
Description
Technical field
The present invention relates to a kind of method preparing light aromatics, more particularly to a kind of waste cooking oils aromatisation prepares lightweight
The method of aromatic hydrocarbons.
Background technology
Edible oil is indispensable in people's diet, but will necessarily generate quite a lot discarding after use and eat
Oil.According to statistics, the yield of Chinese waste cooking oils is also up to 5,000,000 tons/year.Currently, the whole world does not form waste cooking oils
It efficiently uses, this causes under the stimulation of economic interests, has many people to learn " making the best use of everything ", by local method skill that its is heavy
It is processed as edible oil, reaches the degree mixed the genuine with the fictitious, seriously endangers the health of the mankind.In addition, waste cooking oils can also be with
It municipal drainage network and enters rivers and lakes, organic matter is promoted largely to grow, cause the problem of environmental pollutions such as cyanobacterial bloom.It utilizes
New process, new technology convert waste cooking oils to high valuable chemicals, can carry out waste utilization to waste cooking oils, subtract
Few its enters environmental pollution and the harm to people's health caused by the ecosystem.
Aromatic hydrocarbons, especially benzene,toluene,xylene (abbreviation BTX) are the base stocks of organic chemical industry, and industrial chain runs through people
The various aspects such as food, clothing, housing and transportation.Continuous with world population increases and the rapid raising of the Eastern Hemisphere industrialization degree,
The expansion of the aromatic hydrocarbons downstream industry production capacity such as engineering plastics, rubber antioxidant, dyestuff, polyester, has driven the demand to aromatic hydrocarbons swift and violent
Increase.Now aromatic hydrocarbons originate from mostly the catalytic reforming of petroleum path, Hydrocracking extracting, with petroleum resources peter out with
The aggravation of crude oil degree of heaviness is caused crude oil price constantly soaring, is received using crude oil as the traditional handicraft of raw material fierce
It attacks.In addition, easily causing the environmental pollutions such as acid rain, greenhouse effects, waste residue, waste water to ask in traditional petrochemical production process
Topic.Therefore, seek new, sustainable, clean aromatics production path for improving global aromatic hydrocarbons production capacity and alleviating environment dirt
Dye problem all has important strategic importance.
In recent years, technology of aromatization research both domestic and external is concentrated mainly on lower carbon number hydrocarbons and methanol, and catalyst is then with modification
HZSM-5 molecular sieves are main study subject.Patent CN 102030605A disclose a kind of low-carbon hydrocarbon aromatization method, and raw material is low
Carbon hydrocarbon successively by the reaction zone containing HZSM-5 molecular sieves and h-mordenite aromatized catalyst respectively, is not reducing virtue
Under the premise of Auditory steady-state responses, hence it is evident that improve the content of utility value high benzene and dimethylbenzene.Patent CN 104098418A are disclosed
A kind of aromatization of methanol technique, material benzenemethanol are introduced into reactor tube side, and modified ZSM-5 molecular sieve is catalyzed production obtained by the reaction
Object enters back into shell side, is equally contacted with Modified HZSM-5 Zeolite Catalyst, and the product liquid for converting gained is isolated to virtue
Hydrocarbon.Although lower carbon number hydrocarbons and methanol aromatic hydrocarbons technology make some progress, the main source of lower carbon number hydrocarbons is oil and natural
Gas, methanol mostly come from coal.However oil is during use, can discharge a large amount of harmful substances, such as carbon dioxide, nitrogen
The hydrocarbon of the carcinogens such as compound, sulfide, especially benzene all can cause prodigious prestige to human body and natural environment
The side of body；The exploitation and utilization of coal equally cause serious ecological disruption and environmental pollution, such as surface subsidence, the stream of water and soil resources
It loses and pollution, the pollution etc. of atmospheric environment.
In addition, with the continuous improvement of living standards, the size of population is continuously increased, the demand of the energy is higher and higher,
And non-renewable oil and coal are relied on simply, it is unfavorable for the sustainable development in the whole world.Furthermore in lower carbon number hydrocarbons or methanol
In aromatization, it need to be designed as the reaction of multisection type mostly, can just effectively improve the content of aromatic hydrocarbons in product, technological process ratio
It is cumbersome.And the aromatization category endothermic reaction of lower carbon number hydrocarbons, need under higher reaction temperature (600~1000 DEG C) ability
It carries out.
Patent CN106281404A discloses a kind of method that grease vacuum pyrolysis gas phase is prepared by recombinant aromatic compound, will
Raw oil material is fitted into be placed in the reaction unit of catalyst in advance, is heated up under vacuum with 10-50 DEG C/min heating rates
To 500-800 DEG C, 10~30min of catalytic reforming reaction, condensed liquid of the acquisition containing aromatic compound of pyrolysis gas are then carried out
Product.The patent has the following defects：(1) it is vacuum thermal cracking technique, belongs to intermittently operated, is often produced after a kettle product just
It must cool down and add raw material after separating catalyst, then heat up, not be suitable for being mass produced.(2) it was reacting
Waste grease and catalyst contact time are long in journey, it is easy to lead to the further coking life carbon of the aromatic hydrocarbons generated, reduce virtue
Also the service life of catalyst is shortened while hydrocarbon yield.(3) operated under vacuum, narrow application range, energy consumption also compared with
It is high.(4) gaseous product obtained by the reaction is not followed and is badly utilized, but direct emission, aromatics yield on the one hand can be reduced, it is another
Aspect also be easy to cause environmental pollution.(5) its directly will liquid phase grease and solid catalyst mix after heat react again (it is cold into
Material), it can cause to contain a large amount of oxygenatedchemicals in aromatization products, the oxygen atom in grease molecules is substantially to contain oxycarbide
Form stayed in liquid product, cause aromatics yield relatively low.
Invention content
Goal of the invention：In order to solve the above-mentioned problems in the prior art, the present invention provides a kind of waste cooking oils
The method that aromatisation prepares light aromatics.
Technical solution：The method that waste cooking oils aromatisation of the present invention prepares light aromatics, includes the following steps：
(1) by waste cooking oils, or waste cooking oils are mixed with solvent, is sent into after preheating vaporization and is filled with catalyst
Fixed bed reactors in reacted；
(2) reaction product condensation, the separation obtained step (1), obtains aromatic hydrocarbons.
In step (1), when waste cooking oils are mixed with solvent, the solvent is the mixture of water, alcohol or both.
Preferably, the alcohol is one or more of methanol, ethyl alcohol, normal propyl alcohol, isopropanol or isobutanol.
In step (1), when waste cooking oils are mixed with solvent, waste cooking oils are dense by waste cooking oils quality with solvent
Degree is more than or equal to 1%, and the ratio less than 100% mixes.Preferably, waste cooking oils mass concentration is 5%~95%, more preferably
Ground, waste cooking oils mass concentration are 5%~30%.
In step (1), preheating temperature is 150~500 DEG C, preferably 350~500 DEG C.
In step (1), the catalyst is HZSM-5, H β, HY, H-SAPO-34, H-SAPO-11, HZSM-35, NKF-
One or more of 5A, NKF-13X, SBA-15, MCM-41 or MCM-22 zeolite is compound, preferably H β, HY, HZSM-35,
One or more of NKF-5A is compound.
In step (1), the catalyst be with HZSM-5, H β, HY, H-SAPO-34, H-SAPO-11, HZSM-35,
One or more of NKF-5A, NKF-13X, SBA-15, MCM-41 or MCM-22 zeolite be carrier, with zinc, lanthanum, silver, magnesium,
One or more of potassium, vanadium, aluminium, rhenium, terbium, cerium, iron, gallium, molybdenum, nickel, manganese, chromium, copper, tin, platinum or cobalt are urging for active component
Agent, wherein the ratio that active component accounts for total catalyst weight is to be less than or equal to 30%, preferably 1%~10% more than 0.It is preferred that
Ground, for the catalyst using HZSM-5 as carrier, one or more of zinc, tin, gallium are active component.
In step (1), reaction temperature is 300~600 DEG C, and reaction pressure is 0.01~10.0MPa, mass space velocity 0.01
~10.0h-1。
In step (2), the condensed isolated gas-phase product of reaction product that step (1) is obtained, liquid phase oil-phase product
And liquid phase water, liquid phase oil-phase product is through solvent extraction or the isolated aromatic hydrocarbons of extractive distillation method and non-aromatics.
Solvent used in the solvent extraction or extractive distillation method be diethylene glycol (DEG), sulfolane, N- methyl pyrrole networks alkanone,
One or more of N- N-formyl morpholine Ns.
The reaction was continued back to reactor for non-aromatics ingredient in the gas-phase product and liquid phase oil-phase product.
Advantageous effect：The present invention compared with the prior art, has the following advantages：
(1) method provided by the invention is fixed bed continuous catalysis technique, belongs to continuous operation, by the way that original is ceaselessly added
The continual production aromatic hydrocarbon product of material energy is suitable for industrializing extensive life without ceaselessly cooling, heating and washing catalyst
Production.
(2) method provided by the invention can carry out under normal pressure, decompression, pressurized state, and the scope of application is wider, energy consumption phase
To relatively low.
(3) method provided by the invention carries out obtained gaseous product in reaction process to follow bad utilization, on the one hand subtracts
Environmental pollution caused by having lacked it, the alkane being on the other hand also beneficial in gas-phase product, alkene are further converted into aromatic hydrocarbons
To improve final aromatics yield.Further, since alkane aromatization needs to be carried out at a higher temperature (such as CN103539620A institutes
State), and the waste cooking oils aromatization described in present patent application is exothermic reaction, the heat released can just be used for
Carry out recycling for product --- alkane aromatization, thereby saving energy consumption.
(4) method charge raw material provided by the invention is grease and water, the mixture of ethyl alcohol or methanol equal solvent.Alcohols is molten
Agent is conducive to cooperate with aromatisation effect with grease formation, improves aromatics yield, can make after alcohols is mixed with waste cooking oils in addition
The H/C ratios for obtaining raw material entirety increase, and catalyst inactivation slows down, and is more advantageous to the progress of reaction.And on the one hand water can reduce oil
The partial pressure of fat, be conducive to improve aromatic hydrocarbons Equilibrium yield, another aspect water can also with the coke gasification reaction in reaction process, to reduce
Carbon is given birth in catalyst coking, extends catalyst service life.
(5) method provided by the invention is grease-solvent gaseous mixture charging (hot feed), with liquid phase feeding (cold feed) phase
Than gas-phase feed (hot feed) can not only increase the contact area of reaction raw materials and catalyst, accelerate reaction rate, and it is anti-
The yield of the pilot process and product answered can all have a certain difference.Big portion in aromatization products obtained by hot feed of the present invention
It is exactly aromatic hydrocarbons to divide, only micro oxygenatedchemicals, and the oxygen atom in grease molecules, which is substantially all, is converted into water or carbon dioxide
Form, therefore only need to remove moisture using solvent extraction or extractive distillation method, you can obtain aromatic product.
(6) present invention is using waste cooking oils as the raw material of aromatisation, and with the common aromatisation raw material such as methanol or alkane
Compared to having a clear superiority：First, aromatization of low carbon hydrocarbon is the endothermic reaction, more demanding to reaction temperature, and waste cooking oils
Aromatisation is exothermic reaction, and reaction temperature is reduced to 600 DEG C hereinafter, energy consumption of reaction can be reduced effectively by 600~1000 DEG C.
Secondly, the main source of lower carbon number hydrocarbons and methanol is respectively oil and coal, during the utilization of the two, can be caused to environment sternly
The pollution of weight, and the two is non-renewable.However waste cooking oils come from reproducible bioenergy, not only clean pollution is small,
And it is sustainable energy.In addition, waste cooking oils aromatization step is less, reaction condition is mild, and technological process is easy,
Raw material is cheap and abundant, and production cost is low, and environmental pollution is small, and feed stock conversion is high, and purpose product yield is higher, final discarded food
With oily conversion ratio up to 95~100%, light aromatics yield is up to 40~80%.Both traditional BTX production lines had been changed to oil
The dependence of work raw material, and can prevent waste cooking oils from putting on the dining table the harm to people's health again, moreover it is possible to reduce blue algae water
The problem of environmental pollutions such as China have preferable economy and social benefit.
Specific implementation mode
Embodiment 1：
1) by after the preheating of 350 DEG C of pure waste cooking oils by be pumped into be filled with HZSM-5 molecular sieve catalysts fixed bed it is anti-
Answer in device, normal pressing operation, reaction temperature be 500 DEG C, mass space velocity 1.20h-1Under conditions of reacted, through catalysis turn
Turn to the product based on aromatic hydrocarbons；
2) the condensed isolated gas-phase product of the above reaction product, liquid phase oil-phase product and liquid phase water, liquid phase oil phase
Product is through the isolated aromatic hydrocarbons of diethylene glycol (DEG) extractive distillation and non-aromatics, and non-aromatics ingredient in gas-phase product and oil phase is back to anti-
Answering device, the reaction was continued.
Embodiment 2：
1) waste cooking oils are pressed into waste cooking oils matter with water, methanol, ethyl alcohol, normal propyl alcohol, isopropanol and isobutanol respectively
A concentration of 15% ratio mixing is measured, is filled with the fixation of HZSM-5 molecular sieve catalysts after 350 DEG C of heating and gasifyings by being pumped into
Bed reactor in, normal pressing operation, reaction temperature be 500 DEG C, mass space velocity 1.20h-1Under conditions of reacted, through urging
Change the product being converted into based on aromatic hydrocarbons；
2) the condensed isolated gas-phase product of the above reaction product, liquid phase oil-phase product and liquid phase water, liquid phase oil phase
Product distills isolated aromatic hydrocarbons and non-aromatics through sulfolane extraction, and the non-aromatics ingredient in gas-phase product and oil phase is back to instead
Answering device, the reaction was continued.
Embodiment 1 and the reaction result of embodiment 2 are shown in Table 1.
Table 1
By table 1 as it can be seen that waste cooking oils conversion ratio after the process is high, water, alcohols equal solvent addition energy
Significantly improve aromatics yield.
Embodiment 3：
1) waste cooking oils and isopropanol are mixed in the ratio that waste cooking oils mass concentration is 20%, 400 DEG C of preheatings
Afterwards by being pumped into the fixed bed reactors for being filled with H β, HY, HZSM-35, NKF-5A, MCM-41 molecular sieve catalyst respectively,
Normal pressing operation, reaction temperature be 500 DEG C, mass space velocity 1.00h-1Under conditions of reacted, through be catalytically conveted to
Product based on aromatic hydrocarbons；
2) the condensed isolated gas-phase product of the above reaction product, liquid phase oil-phase product and liquid phase water, liquid phase oil phase
Product is through the isolated aromatic hydrocarbons of N- methyl pyrrole network alkanone extractive distillations and non-aromatics, the non-aromatics ingredient in gas-phase product and oil phase
Back to reactor, the reaction was continued.
Reaction result comparison is shown in Table 2.
Table 2
As can be seen from Table 2, conversion ratio and aromatics yield of the waste cooking oils under H β, HY, HZSM-35, NKF-5A catalysis are equal
It is higher.The hole of MCM-41 is mesoporous, and HZSM-35 is micropore, and micropore is easier to shape-selective generation aromatic hydrocarbons relative to MCM-41.
Embodiment 4：
1) waste cooking oils and isobutanol are mixed in the ratio that waste cooking oils mass concentration is 25%, 500 DEG C of preheatings
Afterwards by being pumped into the fixed bed reactors for being filled with HZSM-5 molecular sieve catalysts, normal pressing operation is distinguished in reaction temperature
It is 350 DEG C, 500 DEG C, 600 DEG C, mass space velocity 1.50h-1Under conditions of reacted, through being catalytically conveted to based on aromatic hydrocarbons
Product；
2) the condensed isolated gas-phase product of the above reaction product, liquid phase oil-phase product and liquid phase water, liquid phase oil phase
Product obtains aromatic hydrocarbons and non-aromatics through N- N-formyl morpholine N solvent extraction and separations, and the non-aromatics ingredient in gas-phase product and oil phase returns
To reactor, the reaction was continued.
Reaction result comparison is shown in Table 3.
Table 3
By table 3 as it can be seen that reaction temperature can influence final aromatics yield.
Embodiment 5：
1) waste cooking oils and ethyl alcohol are mixed in the ratio that waste cooking oils mass concentration is 40%, after 450 DEG C of preheatings
By being pumped into the fixed bed reactors for being filled with HZSM-5 composite molecular sieve catalysts, normal pressing operation, in reaction temperature point
Wei not be 500 DEG C, mass space velocity is respectively 0.68h-1、1.20h-1、2.05h-1Under conditions of reacted, through be catalytically conveted to
Product based on aromatic hydrocarbons；
2) the condensed isolated gas-phase product of the above reaction product, liquid phase oil-phase product and liquid phase water, liquid phase oil phase
Product is through diethylene glycol (DEG)/isolated aromatic hydrocarbons of sulfolane complex solvent extraction and non-aromatics, the non-aromatics in gas-phase product and oil phase
The reaction was continued back to reactor for ingredient.
Reaction result comparison is shown in Table 4.
Table 4
By table 4 as it can be seen that Feed space velocities can influence final aromatics yield.
Embodiment 6：
1) waste cooking oils and methanol are pressed to the ratio that waste cooking oils mass concentration is 50%, 40%, 30%, 20% respectively
Example mixing is grasped by being pumped into the fixed bed reactors for being filled with HZSM-5 molecular sieve catalysts after 350 DEG C of preheatings under normal pressure
Make, is respectively 500 DEG C in reaction temperature, mass space velocity is respectively 1.20h-1Under conditions of reacted, through be catalytically conveted to
Product based on aromatic hydrocarbons；
2) the condensed isolated gas-phase product of the above reaction product, liquid phase oil-phase product and liquid phase water, liquid phase oil phase
Through solvent extraction or the isolated aromatic hydrocarbons of extractive distillation method and non-aromatics, the non-aromatics ingredient in gas-phase product and oil phase returns product
Returning to reactor, the reaction was continued.
Embodiment 6 and the comparison of 2 reaction result of embodiment are shown in Table 5.
Table 5
By table 5 as it can be seen that the content of waste cooking oils and solvent can influence final aromatics yield in charging mixed liquor.
Embodiment 7：
1) waste cooking oils and methanol are mixed in the ratio that waste cooking oils mass concentration is 60%, after 350 DEG C of preheatings
By the fluidized-bed reaction for being pumped into the HZSM-5 molecular sieve catalysts for being filled with 1%, 3%, 5%, 10% Zn-ef ficiency of load respectively
In device, normal pressing operation is respectively 500 DEG C in reaction temperature, and mass space velocity is respectively 1.20h-1Under conditions of reacted, pass through
It is catalytically conveted to the product based on aromatic hydrocarbons；
2) the condensed isolated gas-phase product of the above reaction product, liquid phase oil-phase product and liquid phase water, liquid phase oil phase
Product distills isolated aromatic hydrocarbons and non-aromatics, gas-phase product and oil through N- methyl pyrrole networks alkanone/N- N-formyl morpholine N compound extractings
The reaction was continued back to reactor for non-aromatics ingredient in phase.
Embodiment 8：
1) waste cooking oils and methanol are mixed in the ratio that waste cooking oils mass concentration is 70%, after 350 DEG C of preheatings
By being pumped into the fluidized-bed reactor for the HZSM-5 molecular sieve catalysts for being filled with 3% tin element of load respectively, grasped under normal pressure
Make, is respectively 500 DEG C in reaction temperature, mass space velocity is respectively 1.20h-1Under conditions of reacted, through be catalytically conveted to
Product based on aromatic hydrocarbons；
2) the condensed isolated gas-phase product of the above reaction product, liquid phase oil-phase product and liquid phase water, liquid phase oil phase
Product is through the isolated aromatic hydrocarbons of diethylene glycol (DEG) extractive distillation and non-aromatics, and non-aromatics ingredient in gas-phase product and oil phase is back to anti-
Answering device, the reaction was continued.
Embodiment 9：
1) waste cooking oils and methanol are mixed in the ratio that waste cooking oils mass concentration is 80%, after 350 DEG C of preheatings
By being pumped into the fluidized-bed reactor for the HZSM-5 molecular sieve catalysts for being filled with 3% silver element of load respectively, grasped under normal pressure
Make, is respectively 500 DEG C in reaction temperature, mass space velocity is respectively 1.20h-1Under conditions of reacted, through be catalytically conveted to
Product based on aromatic hydrocarbons；
2) the condensed isolated gas-phase product of the above reaction product, liquid phase oil-phase product and liquid phase water, liquid phase oil phase
Through the isolated aromatic hydrocarbons of the sulfolane extraction way of distillation and non-aromatics, the non-aromatics ingredient in gas-phase product and oil phase returns to product
The reaction was continued for reactor.
Embodiment 10：
1) waste cooking oils and methanol are mixed in the ratio that waste cooking oils mass concentration is 90%, after 350 DEG C of preheatings
By being pumped into the fixed bed reactors for the HZSM-5 molecular sieve catalysts for being filled with 3% gallium element of load respectively, grasped under normal pressure
Make, is respectively 500 DEG C in reaction temperature, mass space velocity is respectively 1.20h-1Under conditions of reacted, through be catalytically conveted to
Product based on aromatic hydrocarbons；
2) the condensed isolated gas-phase product of the above reaction product, liquid phase oil-phase product and liquid phase water, liquid phase oil phase
Product distills isolated aromatic hydrocarbons and non-aromatics, gas-phase product and oil phase through diethylene glycol (DEG)/sulfolane/N- N-formyl morpholine N compound extractings
In non-aromatics ingredient the reaction was continued back to reactor.
Embodiment 11：
1) waste cooking oils and methanol are mixed in the ratio that waste cooking oils mass concentration is 95%, after 350 DEG C of preheatings
By the fixed bed reactors for being pumped into the HZSM-5 molecular sieve catalysts for being filled with 2% Zn-ef ficiency of load and 1% tin element respectively
Interior, normal pressing operation is respectively 500 DEG C in reaction temperature, and mass space velocity is respectively 1.20h-1Under conditions of reacted, through urging
Change the product being converted into based on aromatic hydrocarbons；
2) the condensed isolated gas-phase product of the above reaction product, liquid phase oil-phase product and liquid phase water, liquid phase oil phase
Product distills isolated aromatic hydrocarbons and non-aromatics through sulfolane/N- N-formyl morpholine N compound extractings, non-in gas-phase product and oil phase
The reaction was continued back to reactor for aromatic fractions.
Embodiment 12：
1) waste cooking oils and methanol are mixed in the ratio that waste cooking oils mass concentration is 5%, after 350 DEG C of preheatings by
It is pumped into the fixed bed reactors for the HZSM-5 molecular sieve catalysts for being filled with 2% Zn-ef ficiency of load and 1% gallium element respectively,
Normal pressing operation is respectively 500 DEG C in reaction temperature, and mass space velocity is respectively 1.20h-1Under conditions of reacted, through catalysis
It is converted into the product based on aromatic hydrocarbons；
2) the condensed isolated gas-phase product of the above reaction product, liquid phase oil-phase product and liquid phase water, liquid phase oil phase
Product distills isolated aromatic hydrocarbons and non-aromatics through sulfolane/N- N-formyl morpholine N compound extractings, non-in gas-phase product and oil phase
The reaction was continued back to reactor for aromatic fractions.
The reaction result comparison of embodiment 7~12 is shown in Table 6.
Table 6
By table 6 as it can be seen that the introducing of active metal can further increase aromatics yield.
Embodiment 13：
1) waste cooking oils and methanol are mixed in the ratio that waste cooking oils mass concentration is 15%, after 350 DEG C of preheatings
By being pumped into the fixed bed reactors for the MCM-41 molecular sieve catalysts for being filled with load cobalt element and copper respectively,
In, the load capacity of two kinds of metals accounts for the 0.1% and 0.2% of MCM-41 mass respectively, and normal pressing operation is respectively in reaction temperature
500 DEG C, mass space velocity is respectively 1.20h-1Under conditions of reacted, the product through being catalytically conveted to based on aromatic hydrocarbons.
2) the condensed isolated gas-phase product of the above reaction product, liquid phase oil-phase product and liquid phase water, liquid phase oil phase
Product distills isolated aromatic hydrocarbons and non-aromatics through sulfolane extraction, and the non-aromatics ingredient in gas-phase product and oil phase is back to instead
Answering device, the reaction was continued.
Reaction result：Feed stock conversion 97.2%, aromatic hydrocarbons total recovery 47.94% in gross product, BTX yields 35.06%,
Middle benzene 8.96%, toluene 15.51%, dimethylbenzene 10.59%.
Claims (10)
1. a kind of method that waste cooking oils aromatisation prepares light aromatics, which is characterized in that include the following steps：
(1) by waste cooking oils, or waste cooking oils are mixed with solvent, is sent into after preheating vaporization and is filled with consolidating for catalyst
It is reacted in fixed bed reactor；
(2) reaction product condensation, the separation obtained step (1), obtains aromatic hydrocarbons.
2. according to the method described in claim 1, it is characterized in that, in step (1), when waste cooking oils are mixed with solvent,
The solvent is the mixture of water, alcohol or both.
3. according to the method described in claim 1, it is characterized in that, in step (1), when waste cooking oils are mixed with solvent,
Waste cooking oils are more than or equal to 1% with solvent by waste cooking oils mass concentration, and the ratio less than 100% mixes.
4. according to the method described in claim 1, it is characterized in that, in step (1), preheating temperature is 150~500 DEG C.
5. according to the method described in claim 1, it is characterized in that, in step (1), the catalyst be HZSM-5, H β,
One in HY, H-SAPO-34, H-SAPO-11, HZSM-35, NKF-5A, NKF-13X, SBA-15, MCM-41 or MCM-22 zeolite
Kind is several compound.
6. according to the method described in claim 1, it is characterized in that, in step (1), the catalyst be with HZSM-5, H β,
One in HY, H-SAPO-34, H-SAPO-11, HZSM-35, NKF-5A, NKF-13X, SBA-15, MCM-41 or MCM-22 zeolite
Kind or it is several be carrier, with zinc, lanthanum, silver, magnesium, potassium, vanadium, aluminium, rhenium, terbium, cerium, iron, gallium, molybdenum, nickel, manganese, chromium, copper, tin, platinum or cobalt
One or more of be active component catalyst, wherein active component account for total catalyst weight ratio be more than 0, it is small
In equal to 30%.
7. according to the method described in claim 1, it is characterized in that, in step (1), reaction temperature is 300~600 DEG C, reaction
Pressure is 0.01~10.0MPa, and mass space velocity is 0.01~10.0h-1。
8. according to the method described in claim 1, it is characterized in that, in step (2), the reaction product that step (1) is obtained passes through
Condensation separation obtains gas-phase product, liquid phase oil-phase product and liquid phase water, and liquid phase oil-phase product is through solvent extraction or extractive distillation
The isolated aromatic hydrocarbons of method and non-aromatics.
9. according to the method described in claim 8, it is characterized in that, molten used in the solvent extraction or extractive distillation method
Agent is one or more of diethylene glycol (DEG), sulfolane, N- methyl pyrrole networks alkanone, N- N-formyl morpholine Ns.
10. according to the method described in claim 8, it is characterized in that, non-in the gas-phase product and liquid phase oil-phase product
The reaction was continued back to reactor for aromatic fractions.
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