CN107760358A - Reform oil-off olefin process for refining process - Google Patents
Reform oil-off olefin process for refining process Download PDFInfo
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- CN107760358A CN107760358A CN201610708967.4A CN201610708967A CN107760358A CN 107760358 A CN107760358 A CN 107760358A CN 201610708967 A CN201610708967 A CN 201610708967A CN 107760358 A CN107760358 A CN 107760358A
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- oil
- olefin
- refining process
- molecular sieve
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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
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
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- Oil, Petroleum & Natural Gas (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to one kind to reform oil-off olefin process for refining process, and multinuclear aromatic ring macromolecule impurity increase in product after the reaction of oil-off olefin technology reaction product is reformed before mainly solving, causes high-boiling-point impurity to increase, the problem of influenceing subsequent technique and equipment.The present invention uses as shown in figure 1, reaction raw materials reformate 1 enters reactor containing molecular sieve catalyst 2 reacts, and after product 3 enters colloid scavenger tower 4, method that final material 5 enters down-stream system preferably solves problem, can be applied to the industrial production of deolefination.
Description
Technical field
The invention belongs to reform oil-off olefin technical process, and in particular to a kind of deolefination method for removing impurity in products.
Background of invention
The present invention relates to reform oil-off olefin technique.
Catalytic reforming is the main manufacturing process of the industrial chemicals such as benzene,toluene,xylene.With entering for catalytic reforming technology
Step and material composition change, the exploitation of new reforming catalyst, the reaction severity of reformation are improving, and ultralow pressure operating technology is general
All over using, the problem of bringing therewith is that the olefin(e) centent in catalytic reforming generation oil further increases.In catalytic reforming generation oil
Rich in aromatic hydrocarbons and solvent naphtha, qualified aromatic hydrocarbons and solvent naphtha are produced, it is necessary to remove alkene therein.Reformed oil it is a small amount of
Alkene, the corrosion for causing extraction system equipment can be polymerize in extraction solvent.
Domestic and international device removes the alkene in reformed oil using the methods of activated particle carclazyte, molecular sieve catalyst
Hydrocarbon, also there is the olefin(e) centent that reformate is reduced using hydrofinishing process.
Atlapulgite is to carry out a kind of acidified modified obtained bentonite modified product to bentonite by inorganic acid, and acidifying changes
Property can improve bentonitic whiteness, specific surface area, acid strength etc., and obtained atlapulgite has the work(such as adsorption bleaching, catalysis
Energy.Granular carclazyte process for refining, which exists, easily to be inactivated, is difficult to regenerate, changes the shortcomings of frequent and pollution environment.It is anti-with reforming
Severity more and more higher is answered, causes carclazyte inactivation to be accelerated, just needs the carclazyte more renewed, some devices even one general some months
Zhou Genghuan is once.
The method of Hydrobon removing alkene is containing base metal (such as Co-Mo or Ni-Mo/Al2O3) or your gold
Belong to (Pt, Pd/Al2O3) catalyst action under alkene in selective hydrogenation saturation reformed oil.The reaction that the former needs
Temperature is higher (typically at 300 DEG C~330 DEG C or so), and high energy consumption, aromatic hydrocarbons loss are larger.And use noble metal catalyst selectivity
The alkene that hydrogenation and removing benzene is rich in into xylene fraction, can (90~150 DEG C) progress under the process conditions more relaxed
Hydrogenation reaction, aromatic hydrocarbons loss is smaller, but expensive catalyst, and the presulfurization generation sulfide of catalyst causes environment pollution.
There is non-hydrogenated molecule sieve catalyst for refining the catalyst single trip use life-span can reach 8 times of granular carclazyte at present
More than, while can regenerate repeatedly.But when catalyst for reforming and generating oil-off olefin directly reacts, olefin(e) centent is higher and the later stage
When catalyst runs, more polynuclear aromatic hydrocarbons impurity is generated, long-term operating causes subsequent handling and equipment operation problem, makes
Production cost improves.
In CN103184067A, using atlapulgite and the compound packing method of molecular sieve catalyst for refining, catalysis is extended
Agent service life, but can not solve the problems, such as that higher boiling impurity in products increases in catalyst operation.
The invention aims to overcome catalyst reaction impurity in products removing problem, impurity is generated after reaction, is led
The problem of causing production cost too high.The present invention carries out reforming the life of oil-off olefin technique by using the method for successive links removing tower
Production, preferably solves the problem.
The content of the invention
The technical problems to be solved by the invention are that reaction product higher boiling impurity in products increases in olefinic hydrocarbon expelling catalyzer operation
A kind of the problem of more, there is provided reformation oil-off olefin technique of new removing impurity in products.This method is anti-for reforming oil-off olefin
Should, have technique simple, remove the advantages of facilitating.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：One kind reforms oil-off olefin process for refining
Process, such as Fig. 1, reaction raw materials reformate 1 enter reactor containing molecular sieve catalyst 2 and reacted, and the product 3 for removing alkene enters colloid
Scavenger tower 4, after removing higher boiling impurity in products, final material 5 enters down-stream system.
In above-mentioned technical proposal, reform oil-off olefin finishing reactor rear impurity removing tower in scavenger can be carclazyte,
Atlapulgite, activated carbon, adsorbent of molecular sieve, dimethylbenzene adsorption tower adsorbent are one or more of.Scavenger material by when,
Adsorbing contaminant, purify material.
In above-mentioned technical proposal, using the method that adsorptive reactor is added after reactor.
In above-mentioned technical proposal, the deolefination reactor catalyst before removing tower is USY, Y or NaY molecular sieve catalyst
At least one of, olefin-containing raw material forms the product of higher molecular weight after being eliminated by catalyst reaction double bond.Due to for solid-liquid
Phase reaction, macromolecule diffusion is slower, easily continues reaction and generates higher molecule.
In above-mentioned technical proposal, mixed material enters the process conditions of impurity removal tower：0.1~5.0MPa of reaction pressure, instead
Answer 30~250 DEG C of temperature, 0.1~30.0h of volume space velocity-1。
In above-mentioned technical proposal, removing impurities matter some processes can be when olefinic hydrocarbon expelling catalyzer operates initial stage, normal operating, behaviour
Make the later stage to apply respectively.
In above-mentioned technical proposal, when impurity content is higher, double removing tower switchings can be used to use.
In above-mentioned technical proposal, heat exchanger can be increased after molecular sieve catalyst reactor to improve abjection multinuclear high score
Sub- impurity.Adsorbent adsorbing contaminant temperature is different, therefore can reach optimal reaction by way of exchanging heat or heating
Effect.
In above-mentioned technical proposal, material 3 can directly enter material 5 according to product characteristicses partial material.In material 3 in impurity
When relatively low, partial material can be delivered directly to behind removing tower.
During catalyst deolefination, high content olefin feedstock can produce higher boiling impurity in products, will by adsorption tower
The problem of these impurity are removed, and impurity is generated after preferably resolving reaction, and long-term operating influences production.
Below by embodiment, the invention will be further elaborated.
Brief description of the drawings
In Fig. 1,1 is reaction raw materials reformate, and 2 be reactor containing molecular sieve catalyst, and 3 is remove the product of alkene, and 4 are
Colloid scavenger tower, 5 be the final material into downstream.
Embodiment
Following examples are used for illustrating invention by some specific scopes, and these embodiments are not entirely included invention
It is required that claim scope.It is conventional technology category in other parameters technique change, and the technology of the present invention embodies.
【Embodiment 1】
The bromine index 2305 for the reformate fresh feed that this process example uses, in 180 DEG C, 2.0MPa, 3.0h-1Under,
The product bromine index 30 after the reaction of deolefination USY hydrogen-catalyst reactors.20g adsorbents are taken to be evaluated.Latter embodiments are same.
Using such as Fig. 1 technological process.
Gum level is 13.0mg/100ml materials 3 in 130 DEG C, 2.0MPa, 3.0h-1Under the conditions of, enter clay impurities absorption
Tower, the gum level of material 5 is 1.5mg/100ml.
【Embodiment 2】
Gum level be 13.0mg/100ml after the heat exchange material 3 in 30 DEG C, 0.1MPa, 3.0h-1Under the conditions of, enter molecule
Impurity absorption tower is sieved, 20% material directly mixes with the material after removing impurities matter, and the gum level of the material 5 of formation is 4.0mg/
100ml。
【Embodiment 3】
Gum level be 13mg/100ml after olefinic hydrocarbon expelling catalyzer mid-term heat exchange material 3 180 DEG C, 1.5MPa,
30.0h-1Under the conditions of, enter atlapulgite impurity absorption tower, the gum level of material 5 is 0.8mg/100ml.
【Embodiment 4】
Gum level be 35mg/100ml after the heat exchange of olefinic hydrocarbon expelling catalyzer later stage material 3 250 DEG C, 5.0MPa,
2.0h-1Under the conditions of, enter atlapulgite impurity absorption tower, the gum level of material 5 is 4.2mg/100ml.
【Embodiment 5】
Gum level be 35mg/100ml after the last phase heat exchange of olefinic hydrocarbon expelling catalyzer material 3 200 DEG C, 3.0MPa,
0.1h-1Under the conditions of, enter atlapulgite (50% weight of material 3) and activated carbon (50% weight of material 3) impurity absorption tower, thing
The gum level of material 5 is 1.1mg/100ml.
【Embodiment 6】
Gum level be 35mg/100ml after the last phase heat exchange of olefinic hydrocarbon expelling catalyzer material 3 170 DEG C, 2.0MPa,
1.2h-1Under the conditions of, enter PX adsorbent impurity absorption towers, the gum level of material 5 is 1.0mg/100ml.
【Embodiment 6】
Gum level be 35mg/100ml after olefinic hydrocarbon expelling catalyzer latter stage heat exchange material 3 170 DEG C, 2.0MPa,
1.2h-1Under the conditions of, wherein, 1/3 weight of material 3 enters atlapulgite adsorption tower, 1/3 weight of material 3 enters activated carbon adsorber
Enter Ca-USY adsorbent of molecular sieve impurity absorption towers with 1/3 weight of material 3, the gum level of material 5 is 1.2mg/
100ml。
Claims (10)
1. one kind reforms oil-off olefin process for refining process, it is characterised in that reaction raw materials reformate (1) enters containing molecular sieve catalytic
Agent reactor (2) reacts, and after product (3) enters colloid scavenger tower (4), final material (5) enters down-stream system.
2. oil-off olefin process for refining process is reformed according to claim 1, it is characterised in that adsorbent in reactor, be selected from
One or more in carclazyte, atlapulgite, activated carbon, adsorbent of molecular sieve, dimethylbenzene adsorption tower adsorbent.
3. oil-off olefin process for refining process is reformed according to claim 1, it is characterised in that olefinic hydrocarbon expelling catalyzer is selected from USY
At least one of molecular sieve catalyst, Y molecular sieve catalyst or NaY molecular sieve catalyst.
4. oil-off olefin process for refining process is reformed according to claim 1, it is characterised in that mixed material enters reactor work
Skill condition：0.1~5.0MPa of reaction pressure, 30~250 DEG C of reaction temperature, 0.1~30.0h of volume space velocity-1。
5. oil-off olefin process for refining process is reformed according to claim 1, it is characterised in that technique is in olefinic hydrocarbon expelling catalyzer
When operation initial stage, normal operating, the operation later stage applies respectively.
6. oil-off olefin process for refining process is reformed according to claim 1, it is characterised in that inhaled using being added after reactor
The method of reaction enclosure device.
7. oil-off olefin process for refining process is reformed according to claim 1, it is characterised in that make using double removing tower switchings
With.
8. reforming oil-off olefin process for refining process according to claim 1, increase after molecular sieve catalyst reactor and change
Hot device improves abjection multinuclear macromolecule impurity.
9. oil-off olefin process for refining process is reformed according to claim 1, it is characterised in that material (3) is according to product characteristicses
Partial material directly enters material (5).
10. oil-off olefin process for refining process is reformed according to claim 1, it is characterised in that olefin(e) centent in reaction raw materials
Applied when higher.
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| CN201610708967.4A CN107760358A (en) | 2016-08-23 | 2016-08-23 | Reform oil-off olefin process for refining process |
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| CN201610708967.4A CN107760358A (en) | 2016-08-23 | 2016-08-23 | Reform oil-off olefin process for refining process |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108192663A (en) * | 2018-01-22 | 2018-06-22 | 盱眙恒信粘土科技有限公司 | A kind of method for combining catalysis method removing trace amounts of alkenes in reformate |
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| CN103012036A (en) * | 2012-11-28 | 2013-04-03 | 浙江工业大学 | Aromatic hydrocarbon purifying method |
| CN103184067A (en) * | 2012-08-23 | 2013-07-03 | 中国海洋石油总公司 | Method for prolonging service life of reformate molecular sieve refined catalyst |
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| CN1220300A (en) * | 1997-12-16 | 1999-06-23 | 中国石油化工总公司 | Adsorption refining method of synthetic hydrocarbon oil |
| US20030032850A1 (en) * | 1999-10-28 | 2003-02-13 | Brown Stephen H. | Process for BTX purification |
| CN101591212A (en) * | 2009-06-25 | 2009-12-02 | 中国石油化工集团公司 | A kind of process for refining and removing olefin from aromatic hydrocarbon |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108192663A (en) * | 2018-01-22 | 2018-06-22 | 盱眙恒信粘土科技有限公司 | A kind of method for combining catalysis method removing trace amounts of alkenes in reformate |
| CN108192663B (en) * | 2018-01-22 | 2019-11-12 | 盱眙恒信粘土科技有限公司 | A method of combination catalysis method removes trace amounts of alkenes in reformate |
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