CN108192663B - A method of combination catalysis method removes trace amounts of alkenes in reformate - Google Patents
A method of combination catalysis method removes trace amounts of alkenes in reformate Download PDFInfo
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- CN108192663B CN108192663B CN201810058281.4A CN201810058281A CN108192663B CN 108192663 B CN108192663 B CN 108192663B CN 201810058281 A CN201810058281 A CN 201810058281A CN 108192663 B CN108192663 B CN 108192663B
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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
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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
- 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
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- Oil, Petroleum & Natural Gas (AREA)
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- General Chemical & Material Sciences (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a kind of methods of combination catalysis method removing trace amounts of alkenes in reformate, ammonium persulfate is added in reformed oil in this method, industrial hydrogen peroxide organic acid soln is added dropwise again, heating stirring reaction, 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, simple process, the oligomeric oligomeric epoxy olefins for reoxidizing reaction and forming certain molecular weight of trace amounts of olefin, can be centrifuged or natural subsidence after separated together with ammonium persulfate and hydrogen peroxide etc., treated, and reformed oil can satisfy the requirement of following process bromine index < 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 generate oil in trace amounts of olefin it is oligomeric,
Epoxidation reaction removes the trace amounts of olefin in reformed oil.
Background technique
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, can have adverse effect on to following process process olefin(e) centent is very low.For
Guarantee going on smoothly 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 purification；Molecular sieve
Catalytic refining；4. group technology.Wherein methodWithIt is mature technology, is industrially applied, clay-filtered master
If being adsorbed on carclazyte by alkene or a small amount of polymerization being to remove trace amounts of olefin；Hydrofinishing is to be catalyzed hydrogen in hydro condition
Gas and olefine reaction, are saturated alkene, to remove alkene, but generate oil for long distillate, ineffective.Molecular sieve catalytic essence
System is the catalytic action by molecular sieve, is alkylated alkene with the aromatic hydrocarbons generated in oil and reacts, therein micro- to remove
Measure alkene；Group technology is that physical absorption removes trace amounts of olefin in conjunction with chemical reaction, and latter two technique is the hot spot of exploitation.
(development [J] the Speciality Petrochemicals progress of purification aromatic hydrocarbons granular carclazyte, 2001,2 (6): 15- such as He Yaxian
22) it using X x ray diffraction, pore-size distribution test and deolefination evaluation test, determines good carclazyte mineral resources, has studied acidification
The influence of condition, binder and maturing temperature to granular carclazyte performance, is prepared for good granular carclazyte.
(Industrial Evaluation of Particulate Clay for Aromatic Refining [J] fine-chemical intermediate, 2004,34 (4): 66- such as Wang Ming
72.) by industrial side line evaluation test, under the conditions of device technique, to 4 kinds of Emathlites in reforming oil-off olefin processing
Effect is evaluated, and makes technical economic analysis.
(a kind of modified method for preparing de- olefin of reforming oil catalyst of ammonium fluoride, the ZL such as Weng Weidong
201510004450.2) a kind of modification clay catalyst and preparation method thereof for deolefination is disclosed, which is used for
Remove the trace amounts of olefin in reformed oil.The preparation method comprises the following steps: first clay is dispersed, 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, obtained so that the predecessor of aluminium is coated on the outer surface of clay finally by high-temperature calcination by the method for heating stirring
To catalyst.This catalyst be it is environmentally friendly, compare very high initial activity and service life with industry carclazyte, and the mistake of this catalyst
It can regenerate and be recycled for multiple times after work.Experiment, which shows to be recycled 4 times, still the activity higher than fresh activity carclazyte.
Summary of the invention
The present invention be directed to existing Emathlite adsorbing and removing alkene temperature higher (180 ~ 210 DEG C), the service life short (2 ~ 3 months),
The technical problem of technical problem and catalytic alkylation and hydrogenation catalyst preparation process complexity more than solid waste, provides a kind of mistake
Ammonium sulfate, hydrogen peroxide combine Catalytic processes, the method for catalytic eliminating trace amounts of alkenes in reformate, and catalyst is easy to get, and price is just
Preferably, treated, and reformed oil meets industrial requirements, does not have adverse effect, high conversion rate to following process.
The invention is realized by the following technical scheme:
A method of combination catalysis method removes trace amounts of alkenes in reformate,
Step (1): ammonium persulfate being added into reformed oil, and heating stirring reaction makes alkene that oligomeric consecutive occur anti-
It answers, big vivo reaction type are as follows:
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 in Xiang Shangshu reactant, after being added dropwise, is stirred under heating
Catalyzed alkene and lower polyolefins carry out epoxidation reaction,
By taking acetic acid as an example, acetic acid is first reacted with hydrogen peroxide generates Peracetic acid, and Peracetic acid is again and in reformed oil
Epoxidation reaction occurs for unsaturated double-bond, and reaction equation is such as are as follows:
,
After reaction while hot be centrifuged or keep the temperature natural subsidence separation, removal persulfuric acid press, hydrogen peroxide, organic acid, and
The oligomeric epoxidation reaction again of trace amounts of olefin forms the oligomeric epoxy olefins of certain molecular weight, the reformed oil that obtains that treated.
The present invention is further improved scheme, and step (1) the ammonium persulfate additional amount is to reform to generate 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 the present invention, and step (2) the hydrogen peroxide organic acid soln is industrial hydrogen peroxide and have
Machine acid-mixed is closed, and standing time 8 hours or more, is more advantageous to the generation of organic peroxide acid, wherein hydrogen peroxide: the mass ratio of organic acid
For 20:1 ~ 5:1.
Further improvement project is the present invention, and step (2) organic acid is formic acid or acetic acid.
Further improvement project is the present invention, and step (2) the hydrogen peroxide organic acid soln dripping quantity is to reform to generate
The 0.1% ~ 5% of oil quality, 60 DEG C ~ 80 DEG C of dropping temperature, pressure is saturated vapor pressure at this temperature, is added dropwise, and is reheated
0.5 ~ 2h is reacted, reaction temperature is 60 DEG C ~ 80 DEG C.
This it is bright the utility model has the advantages that
It is catalyst for being catalyzed except alkene occurs in reformed oil that the present invention, which uses ammonium persulfate, industrial hydrogen peroxide etc.,
Oligomerization or epoxidation reaction, product is the lower polyolefins or oligomeric epoxy olefins of certain molecular weight, by being centrifuged or keeping the temperature
The separation of the methods of natural subsidence.Treated reformed oil, bromine index < 100mgBr/100g oil, meets post-processing and requires,
To following process also without adverse effect.This combination Catalytic processes reaction condition is mild, and catalyst is ammonium persulfate, hydrogen peroxide is easy
, it is cheap.
Specific embodiment
Particular content of the invention has been illustrated in following embodiments and comparative example, and but it is not limited to this:
Embodiment 1: weighing industrial hydrogen peroxide (content 30%) 100g, formic acid 5g, is uniformly mixed 8 hours standing times or more
For use；100 grams of reformed oils (bromine index is 2531mgBr/100g oil) is weighed, ammonium persulfate 0.01g is added, holds in sealing
It is stirred to react 0.5h at 80 DEG C in device, reaction was completed；60 DEG C are cooled to, then above-mentioned hydrogen peroxide formic acid solution is added dropwise, is added dropwise,
1h is stirred to react at 60 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 as follows: 87mgBr/100g oil, meet industrial requirements <
100mgBr/100g oil, conversion ratio 96.56%.
Embodiment 2: weighing industrial hydrogen peroxide (content 30%) 100g, formic acid 20g, is uniformly mixed 8 hours standing times or more
For use；100 grams of reformed oils (bromine index is 2531mgBr/100g oil) is weighed, ammonium persulfate 0.1g is added, 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: weighing industrial hydrogen peroxide (content 30%) 100g, acetic acid 10g, is uniformly mixed 8 hours standing times or more
For use；100 grams of reformed oils (bromine index is 2531mgBr/100g oil) is weighed, ammonium persulfate 0.05g is added, holds in sealing
It is stirred to react 1h 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: weighing industrial hydrogen peroxide (content 30%) 100g, acetic acid 5g, is uniformly mixed 8 hours standing times or more
For use；100 grams of reformed oils (bromine index is 2531mgBr/100g oil) is weighed, ammonium persulfate 0.02g is added, holds in sealing
It is stirred to react 1h 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, stirs
React 1h, after reaction, while hot centrifugation or natural subsidence separating reformed oil, 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: 100 grams of reformed oils (bromine index is 2531mgBr/100g oil) is weighed, ammonium persulfate is added
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, reaction 2h(is stirred for and dioxygen is not added
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, be unsatisfactory for industrial requirements <
100mgBr/100g oil, conversion ratio is only 61.99%.
Comparative example 2: weighing industrial hydrogen peroxide (content 30%) 100g, formic acid 20g, is uniformly mixed 8 hours standing times or more
For use；100 grams of reformed oils (bromine index be 2531mgBr/100g oil) is weighed, is stirred to react at 100 DEG C in a sealed container
Ammonium persulfate is not added in 2h(), 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
It is stirred to react 2h, 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, be unsatisfactory for industrial requirements <
100mgBr/100g oil, conversion ratio is only 73.45%.
Claims (5)
1. a kind of method of combination catalysis method removing trace amounts of alkenes in reformate, it is characterised in that:
Step (1): ammonium persulfate being added into reformed oil, and heating stirring reaction makes alkene that oligomeric consecutive reaction occur；
Step (2): industrial hydrogen peroxide organic acid soln is added dropwise in Xiang Shangshu reactant, after being added dropwise, is stirred under heating catalysis
Alkene and lower polyolefins carry out epoxidation reaction, are centrifuged or keep the temperature while hot after reaction natural subsidence separation, remove persulfuric acid
Ammonium, 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 of combination catalysis method removing trace amounts of alkenes in reformate according to claim 1, feature exist
In: step (1) the ammonium persulfate additional amount is to reform generate 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 of combination catalysis method removing trace amounts of alkenes in reformate according to claim 1, feature exist
It is that industrial hydrogen peroxide is mixed with organic acid in: step (2) the hydrogen peroxide organic acid soln, standing time 8 hours or more, wherein
Hydrogen peroxide: the mass ratio of organic acid is 20:1 ~ 5:1.
4. a kind of method of combination catalysis method removing trace amounts of alkenes in reformate according to claim 3, feature exist
In: step (2) organic acid is formic acid or acetic acid.
5. a kind of method of combination 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 0.5 ~ 2h of reaction is reheated, 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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