CN108192663A - A kind of method for combining catalysis method removing trace amounts of alkenes in reformate - Google Patents
A kind of method for combining catalysis method removing trace amounts of alkenes in reformate Download PDFInfo
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- CN108192663A CN108192663A CN201810058281.4A CN201810058281A CN108192663A CN 108192663 A CN108192663 A CN 108192663A CN 201810058281 A CN201810058281 A CN 201810058281A CN 108192663 A CN108192663 A CN 108192663A
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- trace amounts
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- hydrogen peroxide
- oil
- alkenes
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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
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
- C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
- C10G53/14—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one oxidation step
-
- 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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
Abstract
The invention discloses a kind of methods for combining catalysis method removing trace amounts of alkenes in reformate, this method adds in ammonium persulfate in reformed oil, industrial hydrogen peroxide organic acid soln is added dropwise again, heating stirring is reacted, oligomerization and epoxidation reaction are occurred to remove the trace amounts of olefin in reformed oil by the trace amounts of olefin in catalytic reforming generation oil under conditions of non-hydrogen, the deolefination process warm and, reaction temperature is low, it is simple for process, the oligomeric oligomeric epoxy olefins for reoxidizing reaction and forming certain molecular weight of trace amounts of olefin, can centrifuge or natural subsidence after separated together with ammonium persulfate and hydrogen peroxide etc., treated, and reformed oil can meet following process bromine index<The requirement of 100 mgBr/100g oil.
Description
Technical field
The present invention relates to the technical fields of removing trace amounts of alkenes in reformate, and in particular to a kind of combination catalysis method removing
The method of trace amounts of alkenes in reformate, i.e., by ammonium persulfate, hydrogen peroxide catalytic reforming generation oil in trace amounts of olefin it is oligomeric,
Epoxidation reaction removes the trace amounts of olefin in reformed oil.
Background technology
Contain a small amount of olefin impurity in reformed oil, these olefin impurity properties are very active, it is easy to which polymerization is formed
Colloid influences the quality of aromatic hydrocarbon product, and following process process can be had adverse effect on olefin(e) centent is very low.For
Ensure being smoothed out for subsequent technique, it is necessary to by olefin removal a small amount of in reformed oil.
Reforming and generating oil-off olefin technique has following 4 kinds at present：It is clay-filtered；Hydrogenation catalyst refines；Molecular sieve
Catalytic refining；4. group technology.Wherein methodWithIt is maturation process, is industrially applied, clay-filtered master
If it adsorbs on carclazyte by alkene or polymerize to remove trace amounts of olefin on a small quantity；Hydrofinishing is in hydro condition, is catalyzed hydrogen
Gas and olefine reaction make alkene saturation, so as to remove alkene, but generate oil for long distillate, ineffective.Molecular sieve catalytic essence
System is the catalytic action by molecular sieve, and alkene is made to be alkylated with the aromatic hydrocarbons in generation oil and is reacted, therein micro- to remove
Measure alkene；Group technology is that physical absorption removes trace amounts of olefin with reference to chemical reaction, and latter two technique is the hot spot of exploitation.
He Yaxian etc.（Development [J] the Speciality Petrochemicals progress of refined aromatic hydrocarbons granular carclazyte, 2001,2 (6)：15-
22）Using X x ray diffractions, pore-size distribution test and deolefination evaluation test, determine good carclazyte mineral resources, have studied acidification
The influence of condition, binding agent and calcination temperature to granular carclazyte performance, is prepared for good granular carclazyte.
Wang Ming etc.（Industrial Evaluation of Particulate Clay for Aromatic Refining [J] fine-chemical intermediates, 2004,34 (4)：66-
72.）By industrial side line evaluation test, under the conditions of device technique, to 4 kinds of Emathlites in oil-off olefin processing is reformed
Effect is evaluated, and makes technical economic analysis.
Weng Weidong etc.（A kind of ammonium fluoride is modified the method for preparing de- olefin of reforming oil catalyst, ZL
201510004450.2）Disclose a kind of for modification clay catalyst of deolefination and preparation method thereof, which is used for
Remove the trace amounts of olefin in reformed oil.Preparation method is：First clay is disperseed, reaming and acidification；Then lead to
It crosses ultrasound and infusion process has loaded rare earth element and heteropoly acid double activated component；The clay of load active component is put into aluminium again
In solution, pass through the method for heating stirring so that the predecessor of aluminium is coated on the outer surface of clay, is obtained finally by high-temperature calcination
To catalyst.This catalyst has very high initial activity and service life, and this catalyst loses for environmentally friendly compared with industrial carclazyte
It can regenerate and be recycled for multiple times after work.Experiment, which shows to recycle 4 times, still the activity higher than fresh activity carclazyte.
Invention content
The present invention is higher for existing Emathlite adsorbing and removing alkene temperature（180~210℃）, short life（2 ~ 3 months）、
The technical issues of solid waste is more and catalytic alkylation and the technical issues of complicated hydrogenation catalyst preparation process, provide a kind of mistake
Ammonium sulfate, hydrogen peroxide combination Catalytic processes, the method for catalytic eliminating trace amounts of alkenes in reformate, catalyst are easy to get, and price is just
Preferably, treated, and reformed oil meets industrial requirements, does not have harmful effect, high conversion rate to following process.
The invention is realized by the following technical scheme：
A kind of method for combining catalysis method removing trace amounts of alkenes in reformate,
Step（1）：Ammonium persulfate is added in into reformed oil, heating stirring reaction makes alkene that oligomeric consecutive reaction occur, greatly
Vivo reaction type is：
R1, R2, R3, R4,=H, CH3-,CH3CH2-,CH3CH2CH2-,….
R5, R6, R7, R8,=other alkane
Step（2）：Industrial hydrogen peroxide organic acid soln is added dropwise into above-mentioned reactant, after being added dropwise, is stirred under heating catalysis
Alkene and lower polyolefins carry out epoxidation reaction,
By taking acetic acid as an example, acetic acid first reacts generation Peracetic acid with hydrogen peroxide, Peracetic acid again with the insatiable hunger in reformed oil
Epoxidation reaction occurs with double bond, reaction equation is such as：
,
Natural subsidence separation is centrifuged or keeps the temperature while hot after reaction, removal persulfuric acid is pressed, hydrogen peroxide, organic acid and micro
Epoxidation reaction forms the oligomeric epoxy olefins of certain molecular weight to olefin oligomerization again, the reformed oil that obtains that treated.
The present invention is further improved scheme, step（1）The ammonium persulfate addition is to reform generation oil quality
0.01% ~ 0.1%, heating temperature is 80 DEG C ~ 100 DEG C, 0.5 ~ 2h of reaction time, and pressure is saturated vapor pressure at this temperature.
Further improvement project is step to the present invention（2）The hydrogen peroxide organic acid soln is industrial hydrogen peroxide with having
Machine acid mixes, and 8 hours standing times or more, is more advantageous to the generation of organic peroxide acid, wherein hydrogen peroxide：The mass ratio of organic acid
It is 20:1~5:1.
Further improvement project is step to the present invention（2）The organic acid is formic acid or acetic acid.
Further improvement project is step to the present invention（2）The hydrogen peroxide organic acid soln dripping quantity is generated to reform
The 0.1% ~ 5% of oil quality, 60 DEG C ~ 80 DEG C of dropping temperature, pressure are saturated vapor pressure at this temperature, are added dropwise, and are reheated
0.5 ~ 2h is reacted, reaction temperature is 60 DEG C ~ 80 DEG C.
This bright advantageous effect：
It is of the invention that ammonium persulfate, industrial hydrogen peroxide etc. is used to be used to be catalyzed except alkene generation is oligomeric in reformed oil for catalyst
Reaction or epoxidation reaction, lower polyolefins or oligomeric epoxy olefins of the product for certain molecular weight, by centrifuging or keeping the temperature nature
The methods of sedimentation, detaches.Treated reformed oil, bromine index<100mgBr/100g oil meets post processing requirement, to rear
Continuous processing is also without harmful effect.This combination Catalytic processes reaction condition is mild, and catalyst is ammonium persulfate, hydrogen peroxide is easy to get,
It is cheap.
Specific embodiment
The particular content of the present invention has been illustrated in following embodiments and comparative example, and but it is not limited to this：
Embodiment 1：Weigh industrial hydrogen peroxide（Content 30%）It is for use to be uniformly mixed 8 hours standing times or more by 100g, formic acid 5g；
Weigh 100 grams of reformed oils（Bromine index is 2531mgBr/100g oil）, add in ammonium persulfate 0.01g, in a sealed container 80
0.5h is stirred to react at DEG C, reaction was completed；60 DEG C are cooled to, then above-mentioned hydrogen peroxide formic acid solution is added dropwise, is added dropwise, at 60 DEG C
1h is stirred to react, after reaction, centrifugation or natural subsidence separating reformed oil while hot are removal additive ammonium persulfate, double
Oxygen water, formic acid and micro lower polyolefins and oligomeric epoxy hydrocarbon.
Treated reformed oil sampling analysis, bromine index are:87mgBr/100g oil, meets industrial requirements<
100mgBr/100g oil, conversion ratio 96.56%.
Embodiment 2：Weigh industrial hydrogen peroxide（Content 30%）100g, formic acid 20g are uniformly mixed 8 hours standing times or more
For use；Weigh 100 grams of reformed oils（Bromine index is 2531mgBr/100g oil）, ammonium persulfate 0.1g is added in, in sealing container
In be stirred to react 2h at 100 DEG C, reaction was completed；It is cooled at 80 DEG C and above-mentioned hydrogen peroxide formic acid solution is added dropwise, be added dropwise, 80
2h is stirred to react at DEG C, after reaction, centrifugation or natural subsidence separating reformed oil, remove additive persulfuric acid while hot
Ammonium, hydrogen peroxide, formic acid and micro lower polyolefins and oligomeric epoxy hydrocarbon.
Treated reformed oil sampling analysis, bromine index are 27mgBr/100g oil, meet industrial requirements<
100mgBr/100g oil, conversion ratio 98.93%.
Embodiment 3：Weigh industrial hydrogen peroxide（Content 30%）100g, acetic acid 10g are uniformly mixed 8 hours standing times or more
For use；Weigh 100 grams of reformed oils（Bromine index is 2531mgBr/100g oil）, ammonium persulfate 0.05g is added in, is held in sealing
1h is stirred to react at 90 DEG C in device, reaction was completed；60 DEG C are cooled to, then above-mentioned hydrogen peroxide acetic acid solution is added dropwise, is added dropwise, is risen
Temperature is to 1h is stirred to react at 80 DEG C, and after reaction, centrifugation or natural subsidence separating reformed oil, remove additive mistake while hot
Ammonium sulfate, hydrogen peroxide, formic acid and micro lower polyolefins and oligomeric epoxy hydrocarbon.
Treated reformed oil sampling analysis, bromine index are 83mgBr/100g oil, meet industrial requirements<
100mgBr/100g oil, conversion ratio 96.72%.
Embodiment 4：Weigh industrial hydrogen peroxide（Content 30%）100g, acetic acid 5g are uniformly mixed 8 hours standing times or more
For use；Weigh 100 grams of reformed oils（Bromine index is 2531mgBr/100g oil）, ammonium persulfate 0.02g is added in, is held in sealing
1h is stirred to react at 80 DEG C in device, reaction was completed；At 80 DEG C, then above-mentioned hydrogen peroxide acetic acid solution is added dropwise, is added dropwise, stir
React 1h, after reaction, centrifugation or natural subsidence separating reformed oil while hot, removal additive ammonium persulfate, hydrogen peroxide,
Formic acid and micro lower polyolefins and oligomeric epoxy hydrocarbon.
Treated reformed oil sampling analysis, bromine index are 72mgBr/100g oil, meet industrial requirements<
100mgBr/100g oil, conversion ratio 97.15%.
Comparative example 1：Weigh 100 grams of reformed oils（Bromine index is 2531mgBr/100g oil）, add in ammonium persulfate
0.1g is stirred to react 2h at 100 DEG C in a sealed container, and reaction was completed；80 DEG C are cooled to, is stirred for reaction 2h（It is not added with dioxygen
Water beetle acid solution）, after reaction, centrifugation while hot or natural subsidence separating reformed oil and ammonium persulfate.
Treated reformed oil sampling analysis, bromine index are 962mgBr/100g oil, are unsatisfactory for industrial requirements<
100mgBr/100g oil, conversion ratio is only 61.99%.
Comparative example 2：Weigh industrial hydrogen peroxide（Content 30%）100g, formic acid 20g are uniformly mixed 8 hours standing times or more
For use；Weigh 100 grams of reformed oils（Bromine index is 2531mgBr/100g oil）, it is stirred to react at 100 DEG C in a sealed container
2h（It is not added with ammonium persulfate）, reaction was completed；It is cooled at 80 DEG C and above-mentioned hydrogen peroxide formic acid solution is added dropwise, be added dropwise, at 80 DEG C
2h is stirred to react, after reaction, centrifugation while hot or natural subsidence separating reformed oil and hydrogen peroxide, formic acid.
Treated reformed oil sampling analysis, bromine index are 672mgBr/100g oil, are unsatisfactory for industrial requirements<
100mgBr/100g oil, conversion ratio is only 73.45%.
Claims (5)
- A kind of 1. method for combining catalysis method removing trace amounts of alkenes in reformate, it is characterised in that：Step（1）：Ammonium persulfate is added in into reformed oil, heating stirring reaction makes alkene that oligomeric consecutive reaction occur；Step（2）：Industrial hydrogen peroxide organic acid soln is added dropwise into above-mentioned reactant, after being added dropwise, is stirred under heating catalysis Alkene and lower polyolefins carry out epoxidation reaction, centrifuge or keep the temperature while hot after reaction natural subsidence separation, remove persulfuric acid Press, hydrogen peroxide, organic acid and the oligomeric epoxidation reaction again of trace amounts of olefin form the oligomeric epoxy olefins of certain molecular weight, obtain Treated reformed oil.
- 2. a kind of method for combining catalysis method removing trace amounts of alkenes in reformate according to claim 1, feature exist In：Step（1）The ammonium persulfate addition is reform generation oil quality 0.01% ~ 0.1%, and heating temperature is 80 DEG C ~ 100 DEG C, 0.5 ~ 2h of reaction time, pressure is saturated vapor pressure at this temperature.
- 3. a kind of method for combining catalysis method removing trace amounts of alkenes in reformate according to claim 1, feature exist In：Step（2）The hydrogen peroxide organic acid soln is that industrial hydrogen peroxide is mixed with organic acid, 8 hours standing times or more, wherein Hydrogen peroxide：The mass ratio of organic acid is 20:1~5:1.
- 4. a kind of method for combining catalysis method removing trace amounts of alkenes in reformate according to claim 3, feature exist In：Step（2）The organic acid is formic acid or acetic acid.
- 5. a kind of method for combining catalysis method removing trace amounts of alkenes in reformate according to claim 1, feature exist In：Step（2）The hydrogen peroxide organic acid soln dripping quantity is to reform generate oil quality 0.1% ~ 5%, dropping temperature 60 DEG C ~ 80 DEG C, pressure is saturated vapor pressure at this temperature, is added dropwise, and reheats 0.5 ~ 2h of reaction, and reaction temperature is 60 DEG C ~ 80 DEG C.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2845372A1 (en) * | 2002-10-08 | 2004-04-09 | Inst Francais Du Petrole | Recovery of hydrogen from a hydrocarbon-rich effluent comprises removing olefins, using the hydrogen to hydrogenate unsaturated compounds and dehydrogenating the product |
| CN103007996A (en) * | 2011-09-28 | 2013-04-03 | 中国石油化工股份有限公司 | Catalyst for removing olefin in reformed oil and preparation method of catalyst |
| CN104588089A (en) * | 2015-01-07 | 2015-05-06 | 盱眙恒信粘土科技有限公司 | Reformate olefin-removal catalyst preparation method by ammonium fluoride modification |
| CN106076308A (en) * | 2016-06-07 | 2016-11-09 | 常州大学 | A kind of method for preparing catalyst removing trace amounts of alkenes in reformate and application |
| CN107760358A (en) * | 2016-08-23 | 2018-03-06 | 中国石油化工股份有限公司 | Reform oil-off olefin process for refining process |
-
2018
- 2018-01-22 CN CN201810058281.4A patent/CN108192663B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2845372A1 (en) * | 2002-10-08 | 2004-04-09 | Inst Francais Du Petrole | Recovery of hydrogen from a hydrocarbon-rich effluent comprises removing olefins, using the hydrogen to hydrogenate unsaturated compounds and dehydrogenating the product |
| CN103007996A (en) * | 2011-09-28 | 2013-04-03 | 中国石油化工股份有限公司 | Catalyst for removing olefin in reformed oil and preparation method of catalyst |
| CN104588089A (en) * | 2015-01-07 | 2015-05-06 | 盱眙恒信粘土科技有限公司 | Reformate olefin-removal catalyst preparation method by ammonium fluoride modification |
| CN106076308A (en) * | 2016-06-07 | 2016-11-09 | 常州大学 | A kind of method for preparing catalyst removing trace amounts of alkenes in reformate and application |
| CN107760358A (en) * | 2016-08-23 | 2018-03-06 | 中国石油化工股份有限公司 | Reform oil-off olefin process for refining process |
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