CN108689806A - A kind of method of cresols product rectifying still raffinate recycling cresols - Google Patents
A kind of method of cresols product rectifying still raffinate recycling cresols Download PDFInfo
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- CN108689806A CN108689806A CN201810423806.XA CN201810423806A CN108689806A CN 108689806 A CN108689806 A CN 108689806A CN 201810423806 A CN201810423806 A CN 201810423806A CN 108689806 A CN108689806 A CN 108689806A
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- cresols
- cracking
- rectifying still
- phenol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms
- C07C37/52—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms by splitting polyaromatic compounds, e.g. polyphenolalkanes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L5/00—Solid fuels
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A method of the cresols rectifying still raffinate of efficient, cleaning and environmental protection recycles cresols.Cresols rectifying still raffinate is first de- light through distilling, then is cracked in the presence of a catalyst, and valuable product is recycled.
Description
Technical field
The present invention relates to a kind of cresols product rectifying still raffinate high efficiente callback utilization technologies.
Technical background
Cresols is important fine-chemical intermediate, is widely used in pesticide, medicine, fragrance, dyestuff, antioxidant, inhibition
The fields such as agent, rubber chemicals, coating.In recent years since the development of product downstream is very fast, paracresol product demand increases very
Soon.Currently, obtaining there are mainly two types of the methods of cresols, one is being obtained by chemical synthesis, another kind is carried from coal tar
It takes.But either which kind of method, the cresols product that obtain high-purity are required for detaching by rectifying.Due to cresols chemical property
Relatively active, cresols is easy to happen condensation in rectifying tower reactor in distillation process, coking life is polymerizeing phenol and colloid, asphalitine,
Cause heavy constituent in tower reactor to increase, not only influence rectifying, also results in waste and increase.Up to now, the residual object of cresols rectifying still is still
Suitable applications are not so found, currently more common method of disposal is that fuel oil is directly burnt up or be added to as fuel by it
Middle burn-up, but since a large amount of ash and penetrating odor can be formed when burning, to which ecological, environmental protective problem can be caused.Institute
With a kind of method recycling valuable cresols product from the residual object of cresols rectifying still to the maximum extent will have very big value.
Invention content
Purpose of the present invention is to be directed to disadvantage present in background technology and problem to be improved and innovated, provide a kind of high
The method of the cresols rectifying still raffinate recycling cresols of effect, cleaning and environmental protection.Invention technician is carrying out cresols rectifying research
Shi Faxian, cresols is heated in rectifying still easily occurs dimerization reaction formation cresols conjugate, this cresols conjugate
It is unstable, it can further occur to crack when heated and polymerize, therefore generating cresols and cresols polymer can be polymerize with cresols
The mode of object thermal cracking recycles the cresols product of high added value, while also can get coke product.In addition, researcher also sends out
Existing, when cresols polymer carries out thermal cracking, the cresols of generation only accounts for the 40%~50% of cracking product, and the coke being cracked to form accounts for
30%~40%, if a certain amount of catalytic cracking is added in cracking(FCC)Poising agent makees catalyst, and it is reachable to be cracked to form cresols
To the 60%~70% of cracking product, the amount of coke of generation can be down to 20% or so, and the coke quality generated is loose, be easy clear
Reason, thus this method has very high practical value.
The technical solution adopted by the present invention is:
The residual object composition of cresols rectifying still is made of cresols, cresols conjugate, colloid and asphalitine, and kettle raffinate first subtracts through evaporator
After pressure-off removes cresols, a certain amount of catalytic cracking is added in remaining heavy constituent(FCC)Equilibrium catalyst is re-fed into continous way cracking
Reactor is cracked under certain temperature and pressure, and cracker overhead material is sent into cresols rectifying column and is detached back
All kinds of cresols products are received, coke product is discharged in cracker slag-drip opening.
In technical solution the method, cresols includes monomethyl phenol, dimethyl phenol, trimethyl phenol and four
Sylvan, cresols conjugate include that general structure is(N=1,2,3)
Cresols dimer.
In technical solution the method, the residual object group of cresols rectifying still becomes cresols mass fraction 5%~30%, cresols conjugate
Mass fraction 60%~90%, resin and asphalt mass fraction 2%~15%.
In technical solution the method, rectifying still raffinate be evaporated under reduced pressure removing cresols when vacuum degree control -0.05MPa with
On, vapo(u)rizing temperature is controlled at 220 DEG C or less.
In technical solution the method, when rectifying still raffinate cracks, using FCC equilibrium catalysts as catalyst for cracking,
Its mass percent being added is 0.5~10%.
In technical solution the method, cracking reaction temperature is 250 DEG C~500 DEG C.
In technical solution the method, cracking reaction absolute pressure is 0.05MPa~0.2MPa.
In technical solution the method, material residence time in cracker is 30min~120min.
It is an advantage of the invention that valuable product recovery utilization rate is high, pyrolysis product is simple in structure, easily separated, the coke of generation
Charcoal easy to clean.
Specific implementation mode
Embodiment 1
1000kg cresols rectifying still raffinates, consisting of cresols 13%, cresols conjugate 78%, resin and asphalt 9%, through charging
It after pump boosting, then through heat exchanger being preheated to 180 DEG C, is sent into falling film evaporator and is evaporated under reduced pressure, control vacuum degree is-
0.09MPa, overhead return cresols rectifying column and carry out separation and purification, and 3% FCC equilibrium catalysts are added in the heavy constituent of bottom
Afterwards, it is sent into continous way cracker to be cracked, control cracking temperature is 400 DEG C, absolute pressure 0.1MPa, is evaporated at the top of cracker
Go out material feeding cresols rectifying column to carry out separating and recovering all kinds of cresols products, coke product, cracking knot is discharged in cracker slag-drip opening
Fruit is shown in Table 1.
Embodiment 2
1000kg cresols rectifying still raffinates, processing procedure is same as Example 1, but kettle raffinate group becomes cresols 21%, cresols
Conjugate 74%, resin and asphalt 5%, 200 DEG C of evaporating temperature, evaporation in vacuo degree are -0.08MPa, the addition of FCC equilibrium catalysts
Amount is 1%, and cracking temperature is 500 DEG C, and absolute pressure 0.2MPa the results are shown in Table 1.
Embodiment 3
1000kg cresols rectifying still raffinates, processing procedure is same as Example 1, but kettle raffinate group becomes cresols 7%, cresols
Conjugate 81%, resin and asphalt 12%, 160 DEG C of evaporating temperature, evaporation in vacuo degree are -0.098MPa, and FCC equilibrium catalysts add
Dosage is 10%, and cracking temperature is 300 DEG C, and absolute pressure 0.07MPa the results are shown in Table 1.
Embodiment 4
1000kg cresols rectifying still raffinates, processing procedure is same as Example 1, but kettle raffinate group becomes cresols 29%, cresols
Conjugate 64%, resin and asphalt 7%, 220 DEG C of evaporating temperature, evaporation in vacuo degree are -0.06MPa, the addition of FCC equilibrium catalysts
Amount is 5%, and cracking temperature is 400 DEG C, and absolute pressure 0.12MPa the results are shown in Table 1.
Embodiment 5
1000kg cresols rectifying still raffinates, processing procedure is same as Example 1, but kettle raffinate group becomes cresols 18%, cresols
Conjugate 73%, resin and asphalt 9%, 220 DEG C of evaporating temperature, evaporation in vacuo degree are -0.06MPa, the addition of FCC equilibrium catalysts
Amount is 5%, and cracking temperature is 450 DEG C, and absolute pressure 0.12MPa the results are shown in Table 1.
Embodiment 6
1000kg cresols rectifying still raffinates, processing procedure is same as Example 1, but kettle raffinate group becomes cresols 6%, cresols
Conjugate 82%, resin and asphalt 12%, 180 DEG C of evaporating temperature, evaporation in vacuo degree are -0.09MPa, and FCC equilibrium catalysts add
Dosage is 8%, and cracking temperature is 350 DEG C, and absolute pressure 0.09MPa the results are shown in Table 1.
Embodiment 7
Comparative example 1, processing method is same as Example 1, but is not added with FCC equilibrium catalysts.Cracking the results are shown in Table 1.
1 cresols rectifying still raffinate of table cracks handling result
The above, is specific embodiments of the present invention, and the present invention is not limited by above example.It is any to understand, is ripe
The technical staff of the industry is known, without departing from the scope of the present invention, is done when using the technology contents of the disclosure above
Go out a little change or be modified to the equivalent embodiment of equivalent variations, as long as being without departing from technical solution of the present invention content, according to this
The technical spirit of invention to any simple modification made by above example, is equal within the spirit and principles in the present invention
Replace and improve etc., still fall within the protection domain of technical solution of the present invention.
Claims (8)
1. a kind of method of cresols product rectifying still raffinate recycling cresols, it is characterised in that:The residual object composition of cresols rectifying still is by first
Phenol, cresols conjugate, colloid and asphalitine composition, kettle is residual after evaporator removed under reduced pressure cresols first, in remaining heavy constituent
A certain amount of catalytic cracking is added(FCC)Equilibrium catalyst is re-fed into continous way cracking reactor, under certain temperature and pressure into
Row cracking, cracker overhead material are sent into cresols rectifying column and carry out separating and recovering all kinds of cresols products, cracker slag-drip opening
Coke product is discharged.
2. according to claim 1, cresols includes monomethyl phenol, dimethyl phenol, trimethyl phenol and four
Sylvan, cresols conjugate include that general structure is(N=1,2,3)Cresols
Dimer.
3. according to claim 1, the residual object group of cresols rectifying still becomes cresols mass fraction 5%~30%, cresols is coupled substance
Measure score 60%~90%, resin and asphalt mass fraction 2%~15%.
4. according to claim 1, rectifying still raffinate be evaporated under reduced pressure removing cresols when vacuum degree control more than -0.05MPa,
Vapo(u)rizing temperature is controlled at 220 DEG C or less.
5. method according to claim 1, using FCC equilibrium catalysts as catalyst for cracking, the quality percentage being added
Than being 0.5~10%.
6. method according to claim 1, cracking reaction temperature is 250 DEG C~500 DEG C.
7. method according to claim 1, cracking reaction absolute pressure is 0.05MPa~0.3MPa.
8. method according to claim 1, material residence time in cracker is 30min~120min.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810423806.XA CN108689806A (en) | 2018-05-06 | 2018-05-06 | A kind of method of cresols product rectifying still raffinate recycling cresols |
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| CN201810423806.XA CN108689806A (en) | 2018-05-06 | 2018-05-06 | A kind of method of cresols product rectifying still raffinate recycling cresols |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022068800A1 (en) * | 2020-09-29 | 2022-04-07 | 天津大学 | Treatment method for phenolic rectification kettle residues |
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| CN105214740A (en) * | 2015-09-30 | 2016-01-06 | 广西大学 | Interior evaporation plavini regenerating and modifying FCC Induction refining and application thereof |
| CN107252692A (en) * | 2017-07-27 | 2017-10-17 | 黎帮华 | The rejuvenation method of FCC dead catalyst |
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- 2018-05-06 CN CN201810423806.XA patent/CN108689806A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1053080A (en) * | 1989-12-29 | 1991-07-17 | 切夫尔昂研究和技术公司 | Two-pack cracking catalyst and be used for the method for catalytically crack hydrocarbons |
| CN1868992A (en) * | 2005-05-28 | 2006-11-29 | 淄博万昌科威化工有限公司 | Alkylphenol coproduction technology |
| CN1974516A (en) * | 2006-12-08 | 2007-06-06 | 鞍钢股份有限公司 | Process of producing 3,5-xylenol |
| CN101204666A (en) * | 2006-12-19 | 2008-06-25 | 石大卓越科技股份有限公司 | Catalytic cracking propylene-increasing catalyst and preparation method thereof |
| CN101168137A (en) * | 2007-12-10 | 2008-04-30 | 北京立诚石化技术有限公司 | System and method for regenerating reactivating and recovering FCC balance catalyst |
| CN101757944A (en) * | 2008-12-25 | 2010-06-30 | 中国石油化工股份有限公司 | Cracking additive for increasing production of liquid gas and preparation method thereof |
| CN102837863A (en) * | 2012-09-24 | 2012-12-26 | 北京立诚石化技术有限公司 | Catalyst unpacking and conveying and dust removing system and method for FCC (Fluid Catalytic Cracking) device |
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| CN105214740A (en) * | 2015-09-30 | 2016-01-06 | 广西大学 | Interior evaporation plavini regenerating and modifying FCC Induction refining and application thereof |
| CN107252692A (en) * | 2017-07-27 | 2017-10-17 | 黎帮华 | The rejuvenation method of FCC dead catalyst |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2022068800A1 (en) * | 2020-09-29 | 2022-04-07 | 天津大学 | Treatment method for phenolic rectification kettle residues |
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Application publication date: 20181023 |