CN109321267A - A kind of liquid oil and preparation method thereof rich in aromatic compound - Google Patents
A kind of liquid oil and preparation method thereof rich in aromatic compound Download PDFInfo
- Publication number
- CN109321267A CN109321267A CN201811189433.0A CN201811189433A CN109321267A CN 109321267 A CN109321267 A CN 109321267A CN 201811189433 A CN201811189433 A CN 201811189433A CN 109321267 A CN109321267 A CN 109321267A
- Authority
- CN
- China
- Prior art keywords
- rich
- liquid oil
- aromatic compound
- pyrolysis
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
-
- 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
- C10G2300/80—Additives
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to biomass economy fields, and specifically disclose a kind of liquid oil and preparation method thereof rich in aromatic compound, specifically use following steps to prepare: being dried after biomass powder is broken to 80-120 mesh particle to obtain pyrolysis feed；By pyrolysis feed and burnt calcium based additives after mixing as in fixed bed reactors, pyrolytic reaction is carried out under an inert atmosphere, wherein pyrolysis temperature is 450-750 DEG C, reaction time 10-20min, and the volatile matter for being pyrolyzed generation is reformed by mutually synthermal catalyst bed；The volatile matter after the reformation of acquisition is cooled down using mixture of ice and water, collecting liquid product is the liquid oil product for being rich in arene compound.The present invention has low in cost, simple process, the advantage of a large amount of rich arene liquid oil of energy continuous high-efficient preparation.
Description
Technical field
The invention belongs to biomass economy field, more particularly, to a kind of liquid oil rich in aromatic compound and its
Preparation method.
Background technique
Aromatic hydrocarbons (including benzene,toluene,xylene, naphthalene etc.) is basic Organic Ingredients, and a variety of staple products can be spread out by aromatic hydrocarbons
Life obtains, and is widely used in fields such as synthetic resin, synthetic fibers monomer, coating, medicine and fine chemicals.
Current aromatics production both at home and abroad relies primarily on petroleum resources, by addition catalyst under high-temperature and high-pressure conditions by plus hydrogen, again
The processes such as whole, aromatic hydrocarbons conversion, separation obtain aromatic compound.But this method and process, equipment are sufficiently complex, and petroleum is limited
It is that leading chemical engineering industry cost is constantly soaring that reserves, which are resulted in petroleum,.In addition to this, it can be generated during oil refining big
Measure environmentally harmful by-product.Biomass can give birth to as unique reproducible carbon source, rich reserves and by rationally conversion
A variety of organic chemicals and fuel are produced, is received significant attention.Containing there are many aromatic hydrocarbon objects in the bio oil that biomass pyrolytic obtains
Matter, but its relative amount is lower and pyrolysis oil in oxygen content it is higher, be unfavorable for subsequent application, therefore, it is novel, high to be badly in need of exploitation
The method of selective production of aryl hydrocarbon compound.
In order to improve the content of arene substance in liquid oil, at present mainly by way of catalytic pyrolysis, commonly
Catalyst has: soluble inorganic matter, metal oxide, zeolite molecular sieve etc., wherein zeolite molecular sieve is in pyrolysis oil deoxidation effectiveness
It is good that aspect performance is produced with aromatic hydrocarbon.HZSM-5, can be to a high degree because having regular pore characteristic and suitable acidity
Removing pyrolysis oil in oxygen, become production the most effective molecular sieve catalyst of aromatic hydrocarbon.But HZSM-5 pore size is limited, resistance
The diffusion of aromatic hydrocarbon in pyrolytic process is hindered, easy carbon deposit causes the yield of bio oil lower.In order to which the catalysis for promoting HZSM-5 is special
Property, the methods of alkali process method, chemical vapour deposition technique, carried metal modified by nano particles are developed, but these method and processes are multiple
Miscellaneous, higher cost and there is certain harm to environment.And use calcium based additives as catalyst when, can higher degree reservation give birth to
Hydrogen atom in object oil, promotes the hydrogen-carbon ratio of bio oil, but its deoxidation effectiveness is relatively low, the bio oil being pyrolyzed still cannot
Directly use.
Therefore, it needs to develop a kind of novel method for preparing rich arene liquid oil using catalytic pyrolysis of biomass, it can
Meet easy to operate, low in cost, environmentally friendly and the energy continuous high-efficient a large amount of liquid oils rich in aromatic hydrocarbon substance of preparation want
It asks.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the present invention provides a kind of liquid rich in aromatic compound
Oil and preparation method thereof is intended to using biomass mild deoxidation coupling ex situ depth deoxidation preparation in situ rich in aromatic hydrocarbons chemical combination
The liquid oil of object realizes that catalytic pyrolysis of biomass prepares high added value aromatic hydrocarbon substance, promotes the added value of bio oil, be pyrolyzed
It is not necessarily to corrosive catalysts in journey, reduces the harm to equipment and environment, there is low in cost, simple process, it can be continuous high
The advantage of a large amount of rich arene liquid oil of effect preparation.
To achieve the above object, according to one aspect of the present invention, a kind of liquid oil rich in aromatic compound is proposed
Preparation method, which comprises the steps of:
S1 is dried after biomass powder is broken to 80-120 mesh particle to obtain pyrolysis feed；
S2 by pyrolysis feed and burnt calcium based additives after mixing as in fixed bed reactors, in indifferent gas
Pyrolytic reaction is carried out under atmosphere, wherein pyrolysis temperature is 450-750 DEG C, and reaction time 10-20min is pyrolyzed the volatile matter of generation
It is reformed by mutually synthermal molecular sieve catalyst bed；
Volatile matter after the reformation that S3 obtains step S2 using mixture of ice and water cools down, and collects liquid product and is
Liquid oil product rich in arene compound.
As it is further preferred that biomass in the step S1 is corncob, rice straw, chestnut shell, one in bamboo scraps
Kind is a variety of.
As it is further preferred that drying temperature in the step S1 is 100 DEG C~105 DEG C, drying time be 12h~
24h。
As it is further preferred that calcium based additives are through 850 DEG C of calcining 4h, molecular sieve catalyst warp in the step S2
600 DEG C of calcining 2h.
As it is further preferred that the heating rate of pyrolysis feed is 10 in biomass pyrolysis process in the step S2
DEG C/s~100 DEG C/s.
As it is further preferred that in the step S2, the mass ratio of pyrolysis feed and calcium based additives is 1:2~1:5,
The mass ratio of pyrolysis feed and molecular sieve catalyst is 1:4.
As it is further preferred that pyrolysis temperature is preferably 600 DEG C in the step S2, the reaction time is preferably
15min。
As it is further preferred that calcium based additives are preferably dolomite powder, molecular sieve catalyst in the step S2
Preferably HZSM-5 molecular sieve catalyst.
It is another aspect of this invention to provide that providing a kind of liquid oil rich in aromatic compound, the method is used
Preparation.
As it is further preferred that including benzene, toluene in the liquid oil of the richness compound fragrant hydrocarbon, to toluene, naphthalene
With 2- methyl naphthalene.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, mainly have below
Technological merit:
1. the present invention carries out thermochemical study preparation to biomass using situ catalytic coupling ex situ catalytic pyrolysis technology
The liquid oil product rich in aromatic hydrocarbon substance of high added value, has many advantages, such as that the operation is simple and convenient, continuous high-efficient.
2. the present invention can be real by adjusting pyrolysis feed, calcium based additives, the amount of catalyst and reaction heating rate
Arene compounds, calcium based catalysts used in the present invention and the recyclable recycling of molecular sieve catalyst are now efficiently prepared,
Avoid the problem of resource waste in conventional catalyst pyrolytic process.
3. the present invention has achieved the purpose that continuous high-efficient prepares aromatic compound, while operating letter using biomass as raw material
Just, the cost for preparing aromatic hydrocarbon substance is reduced.
4. the arene compounds that the present invention obtains include benzene,toluene,xylene, naphthalene, 2- methyl naphthalene etc., higher selection
Property create good condition for subsequent separating-purifying, realize the higher value application of biomass resource.
5. the present invention is also studied and designed to the proportion of raw material each in pyrolytic reaction, so that pyrolysis feed and calcium base
The mass ratio of additive is 1:2~1:5, and the mass ratio of catalyst and pyrolysis feed is 4:1, to obtain high level in the product
Aromatic hydrocarbon substance, and retain toluene, the substances such as naphthalene as far as possible.
6. the present invention is also studied and designed to the concrete technology of pyrolytic reaction, optimal pyrolytic process is obtained, heat
Solving temperature is 450-750 DEG C, reaction time 10-20min, and preferably 600 DEG C of+15min promote various aromatic hydrocarbon substances with this
Yield.
7. the present invention is also studied and has been designed to the calcine technology of calcium based additives and molecular sieve catalyst, so that calcium
The calcine technology of based additive is 850 DEG C of calcining 4h, and the calcine technology of molecular sieve catalyst is 600 DEG C of calcining 2h, sufficiently with this
The moisture in calcium based additives and molecular sieve catalyst is removed, reaction efficiency, protection consersion unit is promoted, can also reduce in product
Oxygen content.
Detailed description of the invention
Fig. 1 is a kind of flow chart of liquid oil preparation method rich in aromatic compound provided in an embodiment of the present invention；
Corncob catalytic thermal when different calcium base catalyst loading when Fig. 2 is 10 DEG C/s of heating rate in the embodiment of the present invention
Solve the relative amount comparison diagram of the aromatic hydrocarbon substance of preparation.
Corncob is catalyzed when different calcium base catalyst loading when Fig. 3 is 100 DEG C/s of heating rate in the embodiment of the present invention
It is pyrolyzed the relative amount comparison diagram of the aromatic hydrocarbon substance of preparation.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
As shown in Figure 1, a kind of liquid oil preparation method rich in aromatic compound provided in an embodiment of the present invention, utilizes
Biomass mild deoxidation coupled molecule sieve catalyst ex situ depth deoxidation preparation in situ is rich in the liquid oil of aromatic compound,
Include the following steps:
S1 prepares pyrolysis feed
After biomass powder to be broken to the particle of 80-120 mesh, it is dried to obtain pyrolysis feed, wherein will be biological
Matter is crushed to 80-120 mesh, increases the heating surface area of biological particles, promotes reaction rate, guarantees that reaction sufficiently carries out, biology
Matter can be for corncob, rice straw, chestnut shell, bamboo scraps etc., and drying temperature is 100 DEG C~105 DEG C, and drying time is 12h~for 24 hours,
The moisture in calcium based additives and molecular sieve catalyst can be sufficiently removed under above-mentioned drying process, promote reaction efficiency, protection instead
Equipment is answered, the oxygen content in product can be also reduced.
S2 carries out pyrolytic reaction
Pyrolysis feed and burnt calcium based additives (such as dolomite powder) is anti-as for fixed bed after mixing
It answers in device, carries out pyrolytic reaction under inert atmosphere (such as nitrogen, argon gas etc.), wherein pyrolysis temperature is 450-750 DEG C, instead
Be 10-20min between seasonable, be pyrolyzed the volatile matter of generation by mutually synthermal catalyst bed (i.e. identical as pyrolysis temperature) into
Row is reformed, and pyrolysis temperature is preferably 600 DEG C, and the reaction time is preferably 15min, under above-mentioned pyrolytical condition, help to obtain compared with
The aromatic hydrocarbon substance of high yield；Specifically, calcium based additives, through 850 DEG C of calcining 4h, the catalyst in catalyst bed passes through in advance
600 DEG C of calcining 2h promote reaction efficiency and reduce product sufficiently to remove the moisture in calcium based additives and molecular sieve catalyst
In oxygen content；In pyrolytic process the heating rate of pyrolysis feed be 10 DEG C/s~100 DEG C/s, with separately verify slow pyrolysis with
The influence that fast pyrogenation is distributed product；The mass ratio of pyrolysis feed and calcium based additives is 1:5-1:2, and catalyst and pyrolysis are former
The mass ratio of material is that 4:1 so that there is the aromatic hydrocarbon substance of high level in product, and retains as far as possible under above-mentioned mass ratio
The components such as toluene, naphthalene；Specifically, catalyst is molecular sieve catalyst, preferably HZSM-5 molecular sieve catalyst, HZSM-5 has
The pore characteristic of rule and suitable acidity, can oxygen in the removing pyrolysis oil of higher degree；
S3 collects liquid product
The volatile matter after the reformation obtained in step S2 is cooled down using mixture of ice and water, cooling obtained liquid produces
Object is the required liquid oil product rich in arene compound, include in the richness compound fragrant hydrocarbon liquid oil benzene,
Toluene, to toluene, naphthalene and 2- methyl naphthalene etc..
The principle of the above inventive concept of the present invention is: the volatilization that calcium based catalysts are pyrolyzed after mixing with biomass material
Divide and reformed under the catalysis of molecular sieve catalyst, greatly improves the content of aromatic hydrocarbon substance in bio oil.It acts on former
Reason is: the addition of calcium based catalysts can promote bio oil with compared with reasonable manner deoxidation, and largely retain in bio oil
Hydrogen atom, promote bio oil hydrogen-carbon ratio, but its deoxidation effectiveness is lower, and the removing of molecular sieve catalyst energy greater efficiency is biological
Oxygen in oil passes through the non-of the mild deoxidation coupled molecule sieve catalyst in the original position of calcium based catalysts in biomass material pyrolytic process
The higher biological oil product of arene content can be obtained in depth deoxidation in situ.
In the method for the present invention, pass through mildly deoxidation and the depth deoxidation of molecular sieve catalyst ex situ in situ by calcium based catalysts
Coupling, can significantly improve the content of aromatic hydrocarbon substance in liquid oil, the content of aromatic compound is up to 60% in liquid oil, institute
Aromatic hydrocarbons is obtained after separating-purifying, can be used for the fields such as synthetic resin, synthetic fibers monomer, coating, medicine and fine chemicals.
The method of the present invention not only extends the purposes of biomass, but also opens wide prospect for the later use of bio oil.
For more detailed description the method for the present invention, further illustrated below with reference to specific embodiment.
Embodiment 1
The embodiment of the present invention illustrates a kind of de- using biomass mild deoxidation coupled molecule catalyst ex situ depth in situ
The method of liquid oil of the oxygen preparation rich in aromatic compound, specifically comprises the following steps:
Corncob crushing is sized to 80~120 mesh by S1, is placed in 100 DEG C~105 DEG C baking ovens and is dried, drying time
12h~for 24 hours；
S2 carries out catalytic pyrolysis using fixed bed reactors, and reactor is heated to specified temperature with the heating rate of 10 DEG C/s
After 600 DEG C of degree, catalytic pyrolysis, the matter of calcium based catalysts and pyrolysis feed are carried out to the mixture of pyrolysis feed and calcium based catalysts
Amount is than being 1:10, reaction time 15min；The HZSM-5 molecular sieve of the identical temperature of volatilization lease making (i.e. 600 DEG C) after pyrolysis is urged
The mass ratio of agent progress catalytic reforming, HZSM-5 molecular sieve catalyst and pyrolysis feed is 4:1；
S3 volatiles are brought into condenser by mixed gas, are become through mixture of ice and water is cooling rich in aromatic compound
Liquid oil product, wherein aromatic compound mainly includes benzene,toluene,xylene, naphthalene, 2- methyl naphthalene etc..
Embodiment 2
The present embodiment is same as Example 1, and only calcium based catalysts and the mass ratio of pyrolysis feed are 1:5.
Embodiment 3
The present embodiment is same as Example 1, and only calcium based catalysts and the mass ratio of pyrolysis feed are 3:10.
Embodiment 4
The present embodiment is same as Example 1, and only calcium based catalysts and the mass ratio of pyrolysis feed are 2:5.
Embodiment 5
The present embodiment is same as Example 1, and only calcium based catalysts and the mass ratio of pyrolysis feed are 1:2.
Embodiment 6
The present embodiment is same as Example 1, does not add calcium based catalysts only, is only pyrolyzed biomass material, gained volatilization
Condensation obtains liquid oil after lease making molecular sieve catalyst carries out catalytic reforming.
Embodiment 7
The present embodiment is same as Example 1, and only heating rate is 100 DEG C/s, the matter of calcium based catalysts and pyrolysis feed
Amount is than being 1:2.
Embodiment 8
The present embodiment is same as Example 7, and only calcium based catalysts and the mass ratio of pyrolysis feed are 1:1.
Embodiment 9
The present embodiment is same as Example 7, does not add calcium based catalysts only, is only pyrolyzed biomass material, gained volatilization
Condensation obtains liquid oil after lease making molecular sieve catalyst carries out catalytic reforming.
Corncob is catalyzed when Fig. 2 is different calcium base catalyst loading when heating rate is 10 DEG C/s in the embodiment of the present invention
It is pyrolyzed the relative amount comparison diagram of the aromatic hydrocarbon substance of preparation, shows the experimental result of embodiment 1-6.As shown in Fig. 2, corn
Core raw material at 600 DEG C after calcium based catalysts deoxidation coupling HZSM-5 molecular sieve catalyst ex situ depth deoxidation in situ mild,
Compare be not added calcium based catalysts as a result, toluene, dimethylbenzene, naphthalene, 2- methyl naphthalene content have a rising in pyrolysis oil, increase calcium base
The yield of catalyst ratio aromatic hydrocarbon substance increases, and the yield of polycyclic aromatic hydrocarbon is apparently higher than mononuclear aromatics.Work as calcium based catalysts
When with the mass ratio of biomass material being 1:2 in pyrolysis oil aromatic hydrocarbon substance yield highest.
Corncob is catalyzed when different calcium base catalyst loading when Fig. 3 is 100 DEG C/s of heating rate in the embodiment of the present invention
It is pyrolyzed the relative amount comparison diagram of the aromatic hydrocarbon substance of preparation, shows the experimental result of embodiment 7-9.As shown in figure 3, working as calcium
When base catalyst and corncob mass ratio are not more than 1, the ratio for increasing calcium based catalysts can increase the total yield of aromatic hydrocarbons product
Amount.
Facilitate to promote hydrogen-carbon ratio and molecular sieve catalyst in bio oil pyrolysis oil present invention utilizes calcium based additives
The feature for facilitating oxygen content in reduction biomass pyrolysis oil, has many advantages, such as that the operation is simple and convenient, continuous high-efficient, heat
The selectivity of aromatic compound is high in the liquid oil that solution obtains, can be used for being widely used in synthetic resin, fiber monomer and coating,
The fields such as fuel, medicine, fine chemicals are conducive to prepare aromatic compound for biomass and provide a new potential way
Diameter.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of liquid oil preparation method rich in aromatic compound, which comprises the steps of:
S1 is dried after biomass powder is broken to 80-120 mesh particle to obtain pyrolysis feed；
S2 by pyrolysis feed and burnt calcium based additives after mixing as in fixed bed reactors, under an inert atmosphere
Pyrolytic reaction is carried out, wherein pyrolysis temperature is 450-750 DEG C, reaction time 10-20min, and the volatile matter for being pyrolyzed generation passes through
Mutually synthermal molecular sieve catalyst bed is reformed；
Volatile matter after the reformation that S3 obtains step S2 using mixture of ice and water cools down, and collecting liquid product is to be rich in
The liquid oil product of arene compound.
2. the liquid oil preparation method according to claim 1 rich in aromatic compound, which is characterized in that the step S1
In biomass be one of corncob, rice straw, chestnut shell, bamboo scraps or a variety of.
3. the liquid oil preparation method according to claim 1 rich in aromatic compound, which is characterized in that the step S1
In drying temperature be 100 DEG C~105 DEG C, drying time is 12h~for 24 hours.
4. the liquid oil preparation method according to claim 1 rich in aromatic compound, which is characterized in that the step S2
Middle calcium based additives are through 850 DEG C of calcining 4h, and molecular sieve catalyst is through 600 DEG C of calcining 2h.
5. the liquid oil preparation method according to claim 1 rich in aromatic compound, which is characterized in that the step S2
The heating rate of pyrolysis feed is 10 DEG C/s~100 DEG C/s in middle biomass pyrolysis process.
6. the liquid oil preparation method according to claim 1 rich in aromatic compound, which is characterized in that the step S2
In, the mass ratioes of pyrolysis feed and calcium based additives is 1:2~1:5, and the mass ratio of pyrolysis feed and molecular sieve catalyst is 1:
4。
7. the liquid oil preparation method according to claim 1-6 rich in aromatic compound, which is characterized in that institute
It states in step S2, pyrolysis temperature is preferably 600 DEG C, and the reaction time is preferably 15min.
8. the liquid oil preparation method according to claim 1-7 rich in aromatic compound, which is characterized in that institute
It states in step S2, calcium based additives are preferably dolomite powder, and molecular sieve catalyst is preferably HZSM-5 molecular sieve catalyst.
9. a kind of liquid oil rich in aromatic compound, which is characterized in that use the method according to claim 1
Preparation.
10. the liquid oil according to claim 9 rich in aromatic compound, which is characterized in that the richness arene
Close in the liquid oil of object includes benzene, toluene, to toluene, naphthalene and 2- methyl naphthalene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811189433.0A CN109321267B (en) | 2018-10-12 | 2018-10-12 | Liquid oil rich in aromatic hydrocarbon compounds and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811189433.0A CN109321267B (en) | 2018-10-12 | 2018-10-12 | Liquid oil rich in aromatic hydrocarbon compounds and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109321267A true CN109321267A (en) | 2019-02-12 |
| CN109321267B CN109321267B (en) | 2020-02-21 |
Family
ID=65261388
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811189433.0A Active CN109321267B (en) | 2018-10-12 | 2018-10-12 | Liquid oil rich in aromatic hydrocarbon compounds and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109321267B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104357076A (en) * | 2014-11-10 | 2015-02-18 | 东南大学 | Double-stage catalytic reaction method for enhancing quality of biomass pyrolysis oil |
| CN107652998A (en) * | 2017-11-06 | 2018-02-02 | 南昌大学 | A kind of method using biomass controlled syntheses aviation kerosine aromatic component |
-
2018
- 2018-10-12 CN CN201811189433.0A patent/CN109321267B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104357076A (en) * | 2014-11-10 | 2015-02-18 | 东南大学 | Double-stage catalytic reaction method for enhancing quality of biomass pyrolysis oil |
| CN107652998A (en) * | 2017-11-06 | 2018-02-02 | 南昌大学 | A kind of method using biomass controlled syntheses aviation kerosine aromatic component |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109321267B (en) | 2020-02-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Foong et al. | Progress in waste valorization using advanced pyrolysis techniques for hydrogen and gaseous fuel production | |
| Wu et al. | Microwave-assisted pyrolysis of waste cooking oil for hydrocarbon bio-oil over metal oxides and HZSM-5 catalysts | |
| Zhang et al. | Microwave-assisted pyrolysis of biomass for bio-oil production | |
| Wang et al. | Ex-situ catalytic fast pyrolysis of soapstock for aromatic oil over microwave-driven HZSM-5@ SiC ceramic foam | |
| CN107083252A (en) | A kind of chemical chain pyrolysis deoxidization technique that can reduce biomass pyrolysis oil oxygen content and system | |
| JP6752399B2 (en) | Method and apparatus for producing aromatic hydrocarbons and olefins by coupling of catalytic hydrogenation and catalytic cracking of biological oils | |
| Valizadeh et al. | Production of aromatics fuel additives from catalytic pyrolysis of cow manure over HZSM-5, HBeta, and HY zeolites | |
| Abdul Mutalib et al. | SiO 2-Rich sugar cane bagasse ash catalyst for transesterification of palm oil | |
| CN102886274B (en) | Hydrogenation catalyst for coal tar and ethylene tar and preparation method thereof | |
| Sun et al. | Development of a bimetallic dolomite based tar cracking catalyst | |
| CN104479717A (en) | Method used for improving bio oil quality via co-catalysis of waste polyolefin plastic with biomass | |
| Liu et al. | Promotion of monocyclic aromatics by catalytic fast pyrolysis of biomass with modified HZSM-5 | |
| Jiang et al. | Integrating pyrolysis and ex-situ catalytic reforming by microwave heating to produce hydrocarbon-rich bio-oil from soybean soapstock | |
| Zeng et al. | Microwave-assisted catalytic pyrolysis of corn cobs with Fe-modified Choerospondias axillaris seed-based biochar catalyst for phenol-rich bio-oil | |
| Kim et al. | CO2-cofed catalytic pyrolysis of tea waste over Ni/SiO2 for the enhanced formation of syngas | |
| CN111229237B (en) | Preparation method and application of novel metal-biochar-based hydrogenation catalyst | |
| Yu et al. | Microwave-assisted catalytic pyrolysis of Chinese tallow kernel oil for aromatic production in a downdraft reactor | |
| Xu et al. | Ex-situ catalytic upgrading of biomass pyrolysis volatiles over thermal-decomposition products of spent lithium-ion batteries for bio-oil deoxygenation and hydrogen-rich syngas production | |
| CN105175205B (en) | A kind of bio-oil prepares the method that carboxylate methyl ester catalytic aromatization prepares aromatic hydrocarbons | |
| Du et al. | Investigation of the catalytic performance of coal gangue char on biomass pyrolysis in a thermogravimetric analyzer and a fixed bed reactor | |
| Liu et al. | Co-production of upgraded bio-oils and H2-rich gas from microalgae via chemical looping pyrolysis | |
| Amin et al. | In situ catalytic pyrolysis of low‐rank coal for the conversion of heavy oils into light oils | |
| Li et al. | Pyrolysis behaviors of biomass tar-related model compounds catalyzed by Ni-modified HZSM-5 molecular sieve | |
| Hu et al. | One-pot cogeneration of phenol-rich bio-oil, hydrogen-rich gas and solid carbon degradation material from reed | |
| CN112973747B (en) | Preparation method of transition metal carbide catalyst and application of transition metal carbide catalyst in preparation of high value-added synthesis gas from biomass solid waste |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |