CN108130127A - A kind of processing method of olefine aldehydr vapor phase method synthesis isoprene reactor off-gas - Google Patents
A kind of processing method of olefine aldehydr vapor phase method synthesis isoprene reactor off-gas Download PDFInfo
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- 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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
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Abstract
The invention belongs to field of environment protection more particularly to a kind of processing methods of olefine aldehydr vapor phase method synthesis isoprene reactor off-gas.This method includes the following steps：A) exhaust gas is provided；Remaining ingredient after the gaseous mixture progress separating isoprene that the exhaust gas is isobutene and formaldehyde gas phase reaction obtains；B) exhaust gas and hydrogen carry out hydrogenation deoxidation reaction, obtain the product gas after hydrogenation deoxidation；C) the product gas carries out rectifying, collects the fraction that boiling range is 60~180 DEG C.The present invention after olefine aldehydr reaction product is isolated exhaust gas, after hydrogenated deoxidation and rectifying, collects the fraction that boiling range is 60 DEG C~180 DEG C for the composition of olefine aldehydr vapor phase method synthesis isoprene reactor off-gas.Due to having carried out hydrogenation deoxidation, the fraction compositions that the present invention obtains are alkane, can be used as fuel oil.Method provided by the invention, which is not only realized, to turn waste into wealth, but also can effectively reduce the discharge of olefine aldehydr vapor phase method synthesis isoprene reactor off-gas, environment friendliness.
Description
Technical field
The invention belongs to the processing sides of field of environment protection more particularly to a kind of olefine aldehydr vapor phase method synthesis isoprene reactor off-gas
Method.
Background technology
Isoprene is the essential raw material of natural man-made rubber, particularly in terms of specific rubber product is synthesized
Using being that other industrial chemicals are irreplaceable.At present, the main method for producing isoprene is divided into physical partition method and chemistry
Synthetic method.Physical partition method is to extract its C5 fraction by naphtha pyrolysis ethylene, and this method is limited by market fluctuation
System, and against the continuous development of rubber industry, increasingly increase severely to high-performance natural man-made rubber demand, this is to traditional physics
Divide and propose huge challenge, thus develop chemical synthesis synthesis isoprene and provide new approaches to solve this problem.Change
Method mainly includes isobutene-formaldehyde method, acetylene acetone method and propylene dimerization, wherein using C4 resources, with isobutene and first
Aldehyde as raw material gas-phase one-step method it is simple for process, investment is small, cost of material is relatively low the advantages of, there is considerable economic effect
Benefit.The technology is under 150~400 DEG C of normal pressures, formaldehyde and isobutene mixing gasifying is passed through reactor, in the effect of catalyst
Lower dehydrating condensation prepares isoprene, and this method has the characteristics that flow is short, product is easily separated, easy to operate, investment is small,
It receives significant attention in the industry.
At present, the catalyst involved by the technology mainly has phosphorus series catalysts, Cu-series catalyst, molecular sieve catalyst, silver
Series catalysts etc., the RU2354450C1 as disclosed in Russ P, RU2421441C1, Chinese Academy of Sciences's Changchun applied chemistry are ground
Study carefully disclosed CN201610161038.6, CN201610944377.1.The technology can also generate while producing isoprene
Large quantity of exhaust gas is discharged into air, and the main composition of these exhaust gas is hydrocarbon carbon compound.The excess emissions of hydrocarbon can cause
Atmosphere pollution, this kind of compound, which enters air, to carry out photochemical reaction with oxynitrides, generate strong oxidizer acetaldehyde and PAN
Deng generating serious harm to human body and plant, such as《Industry public hazards》Air caused by the hydrocarbon of the volume report of page 17 3 is dirty
Dye.And the discharge of limiting carbon hydrogen compound becomes environmental protection effective means already.Therefore, while Chemical Manufacture is carried out,
Reduce hydrocarbon discharge or be transformed into other useful products, be current research personnel widely focus of attention it
One.
Invention content
In view of this, the purpose of the present invention is to provide a kind of processing of olefine aldehydr vapor phase method synthesis isoprene reactor off-gas
Method, method provided by the invention can be by fuel oil of the exhaust gas conversion for high added value.
The present invention provides a kind of processing method of olefine aldehydr vapor phase method synthesis isoprene reactor off-gas, including following step
Suddenly：
A), exhaust gas is provided；The exhaust gas carries out separation isoamyl two for the gaseous mixture that isobutene and formaldehyde gas phase reaction obtain
Remaining ingredient after alkene；
B), the exhaust gas and hydrogen carry out hydrogenation deoxidation reaction in the presence of a catalyst, obtain the product after hydrogenation deoxidation
Gas；
The active component of the catalyst includes one or more in Ru, Pd, Pt, Co, Ni and Ir；
C), the product gas after the hydrogenation deoxidation carries out rectifying, collects the fraction that boiling range is 60~180 DEG C.
Preferably, in step b), the catalyst is loaded catalyst, and the active component is supported on the support type
On the carrier of catalyst, the carrier includes SBA-15, ZSM-5, X-type molecular sieve, Y type molecular sieve, beta-molecular sieve, SAPO molecules
Sieve, Al/SiO2、Al2O3、Zr/SiO2And ZrO2In it is one or more.
Preferably, the activity component load quantity of the loaded catalyst is 0.1~5wt%.
Preferably, in step b), the volume ratio of the exhaust gas and hydrogen is (5~100)：1.
Preferably, in step b), the temperature of the reaction is 200~400 DEG C；The pressure of the reaction is 0~5MPa；Institute
The time of contact for stating exhaust gas and hydrogen and the catalyst is 0.4~1.5s.
Preferably, in step b), before being reacted, first the catalyst is activated using hydrogen.
Preferably, the temperature of the activation is 200~400 DEG C, and the time of the activation is 0.5~2h.
Preferably, in step c), the product gas after the hydrogenation deoxidation is before rectifying is carried out, first to the hydrogenation deoxidation
Product gas washed.
Preferably, in step c), the fraction of 180 DEG C of boiling range ＞ is also collected.
Preferably, the ingredient of the exhaust gas includes 2- butylene, isobutene, 1- butylene, 2,4,4- trimethyl -1- amylenes, 5,
5- dimethyl -2- hexenes, 2,5- dimethyl -3- hexenes, 2,4,4- trimethyl -2- amylenes, 2,3,4- trimethyl -2- amylenes, 2,
3- dimethyl -1- hexenes, 3,4- dimethyl -3- hexenes, 2,4- dimethyl -2- hexenes, 3,4- dimethyl -2- hexenes, 2,5- bis-
Methyl-1-hexene, 2,4- dimethyl-1- hexenes, 2,6- dimethyl-1- hexenes, 2,4,4- trimethyl-2- amylenes, 2,3,4- tri-
Methyl -2- amylenes, 3,3- dimethyl -1- hexenes, 2,5- dimethyl -2- hexenes, 2,4,4- trimethyl -2- amylenes, 2,3,4- tri-
Methyl -2- amylenes, 2,3- dimethyl -2- hexenes, 3- methyl -4- methylene-hexane, 3,4- dimethyl -2- hexenes, 1,2,4,4-
Tetramethyl-ring amylene, 6,6- dimethyl -2,4- heptadiene, 2,6- dimethyl -2,4- heptadiene, 3,5,5- trimethyl cyclohex alkene,
1,6,6- trimethyl cyclohex alkene, 3,5,5- trimethyl cyclohexenes, 3,4,4- trimethyl cyclohexenes, 2,3,5- trimethyls 1,3- oneself
Diene, 2,6- dimethyl -2,4- heptadiene, dimethyl -3- octynes, cis-1,4- dimethyl -2- vinyl cyclohexanes, 2,4- bis-
Methyl heptane, cis-1,4- dimethyl -2- vinyl cyclohexanes, 1,2,3- trimethylbenzenes, 1,3,5- trimethylbenzenes, 1,2,4- tri-
It is one or more in methylbenzene, 1- ethyls -4- methyl-benzene, 1,2,3- trimethylbenzenes and 1,3,5- trimethylbenzenes.
Compared with prior art, the present invention provides a kind of processing sides of olefine aldehydr vapor phase method synthesis isoprene reactor off-gas
Method.Method provided by the invention includes the following steps：A), exhaust gas is provided；The exhaust gas is obtained for isobutene and formaldehyde gas phase reaction
The gaseous mixture arrived carries out the remaining ingredient after separating isoprene；B), the exhaust gas and hydrogen are added in the presence of a catalyst
Hydrogen deoxygenation obtains the product gas after hydrogenation deoxidation；The active component of the catalyst includes Ru, Pd, Pt, Co, Ni and Ir
In it is one or more；C), the product gas after the hydrogenation deoxidation carries out rectifying, collects the fraction that boiling range is 60~180 DEG C.This
Invention for olefine aldehydr vapor phase method synthesis isoprene reactor off-gas composition, after olefine aldehydr reaction product is isolated exhaust gas, through Ru,
The catalyst to catalyzing hydrogenating deoxidation such as Pd, Pt, Co, Ni, Ir using rectifying, collects the fraction that boiling range is 60 DEG C~180 DEG C.By
In having carried out hydrogenation deoxidation processing, therefore the fraction compositions that the present invention obtains are alkane, can be used as fuel oil.The present invention
The method of offer, which is not only realized, to turn waste into wealth, but also can effectively reduce the row of olefine aldehydr vapor phase method synthesis isoprene reactor off-gas
It puts, it is environment friendliness.The experimental results showed that be alkane using the fraction compositions that method provided by the invention obtains, sulfur-bearing
Amount≤0.1wt%, without mechanical admixture, boiling range meets the boiling range requirement of light fuel oil.
Description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention, for those of ordinary skill in the art, without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is the chromatogram that the embodiment of the present invention 1 provides.
Specific embodiment
The technical solution in the embodiment of the present invention is clearly and completely described below, it is clear that described embodiment
Only part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel all other embodiments obtained without making creative work belong to the model that the present invention protects
It encloses.
The present invention provides a kind of processing method of olefine aldehydr vapor phase method synthesis isoprene reactor off-gas, including following step
Suddenly：
A), exhaust gas is provided；The exhaust gas carries out separation isoamyl two for the gaseous mixture that isobutene and formaldehyde gas phase reaction obtain
Remaining ingredient after alkene；
B), the exhaust gas and hydrogen carry out hydrogenation deoxidation reaction in the presence of a catalyst, obtain the product gas of hydrogenation deoxidation；
The active component of the catalyst includes one or more in Ru, Pd, Pt, Co, Ni and Ir；
C), the product gas of the hydrogenation deoxidation carries out rectifying, collects the fraction that boiling range is 60~180 DEG C.
In the present invention, exhaust gas is provided first, the exhaust gas for the gaseous mixture that isobutene and formaldehyde gas phase reaction obtain into
Remaining ingredient after row separating isoprene.In the present invention, do not have to the detailed process of the isobutene and formaldehyde gas phase reaction
It is particularly limited to, isobutene and formaldehyde is preferably passed through in the fixed bed reactors of catalyst filling, isobutene and formaldehyde are being urged
It is reacted in the presence of agent, obtains the gaseous mixture containing isoprene.Wherein, the catalyst, which has, may be selected ZSM-5；
The molar ratio of the isobutene and formaldehyde is preferably (2~9)：1, concretely 2:1、3:1、4:1、5:1、6:1、7:1、8:1 or
9:1；The temperature of the reaction is preferably 150~400 DEG C, concretely 150 DEG C, 200 DEG C, 210 DEG C, 220 DEG C, 230 DEG C, 240
℃、250℃、260℃、270℃、280℃、290℃、300℃、310℃、320℃、330℃、340℃、350℃、360℃、
370 DEG C, 380 DEG C or 390 DEG C；The pressure of the reaction is preferably normal pressure；In reaction process, the isobutene and formaldehyde and catalysis
The time of contact of agent is preferably 0.3~1.5s, concretely 0.3s, 0.4s, 0.5s, 0.6s, 0.7s, 0.8s, 0.9s, 1s,
1.1s, 1.2s, 1.3s, 1.4s or 1.5s.After obtaining the gaseous mixture containing isoprene, to the isoprene in the gaseous mixture
It is detached.In the present invention, it is preferred to refrigerated separation is carried out according to the boiling point difference of other components in isoprene and gaseous mixture,
Gaseous mixture is cooled down at 35 DEG C, respectively obtains gas (main component is isoprene) and liquid.Later to described
Liquid is heated, you can obtains exhaust gas of the present invention.In one embodiment provided by the invention, the exhaust gas into
Point include 2- butylene, isobutene, 1- butylene, 2,4,4- trimethyl -1- amylenes, 5,5- dimethyl -2- hexenes, 2,5- dimethyl -
3- hexenes, 2,4,4- trimethyl -2- amylenes, 2,3,4- trimethyl -2- amylenes, 2,3- dimethyl -1- hexenes, 3,4- dimethyl -
3- hexenes, 2,4- dimethyl -2- hexenes, 3,4- dimethyl -2- hexenes, 2,5- dimethyl -1- hexenes, 2,4- dimethyl -1- oneself
Alkene, 2,6- dimethyl -1- hexenes, 2,4,4- trimethyl -2- amylenes, 2,3,4- trimethyl -2- amylenes, 3,3- dimethyl -1- oneself
Alkene, 2,5- dimethyl -2- hexenes, 2,4,4- trimethyl -2- amylenes, 2,3,4- trimethyl -2- amylenes, 2,3- dimethyl -2- oneself
Alkene, 3- methyl -4- methylene-hexane, 3,4- dimethyl -2- hexenes, 1,2,4,4- tetramethyl-rings amylene, 6,6- dimethyl -2,
4- heptadiene, 2,6- dimethyl -2,4- heptadiene, 3,5,5- trimethyl cyclohex alkene, 1,6,6- trimethyl cyclohex alkene, 3,5,5-
Trimethyl cyclohexene, 3,4,4- trimethyl cyclohexenes, 2,3,5- trimethyl 1,3- hexadienes, 2,6- dimethyl -2,4- heptadiene,
Dimethyl -3- octynes, cis-1,4- dimethyl -2- vinyl cyclohexanes, 2,4- dimethyl heptanes, cis-1,4- dimethyl -2-
Vinyl cyclohexane, 1,2,3- trimethylbenzenes, 1,3,5- trimethylbenzenes, 1,2,4- trimethylbenzenes, 1- ethyls -4- methyl-benzene, 1,
It is one or more in 2,3- trimethylbenzenes and 1,3,5- trimethylbenzenes.
After obtaining exhaust gas, the exhaust gas and hydrogen are subjected to hydrogenation deoxidation reaction in the presence of a catalyst.Wherein, it is described to urge
The active component of agent includes one or more in Ru, Pd, Pt, Co, Ni and Ir.In one embodiment provided by the invention
In, the catalyst is loaded catalyst, and the active component is supported on the carrier of the loaded catalyst, the load
Body includes SBA-15, ZSM-5, X-type molecular sieve, Y type molecular sieve, beta-molecular sieve, SAPO molecular sieve, Al/SiO2、Al2O3、Zr/
SiO2And ZrO2In it is one or more.It is described in embodiment of the catalyst provided by the invention for loaded catalyst
Activity component load quantity is preferably 0.1~5wt%, concretely 0.5wt%, 0.8wt%, 1.2wt%, 1.5wt%, 2wt%,
2.5wt%, 3wt%, 3.5wt%, 4wt% or 4.5wt%.In the present invention, it before being reacted, is first urged using hydrogen described
Agent is activated.Wherein, the temperature of the activation is preferably 200~400 DEG C, concretely 200 DEG C, 250 DEG C, 300 DEG C,
350 DEG C or 400 DEG C；The time of the activation is preferably 0.5~2h, concretely 0.5h, 1h, 1.5h or 2h.In the present invention,
The volume ratio of the exhaust gas and hydrogen is preferably (5~100)：1, concretely 10:1、20:1、30:1、40:1、50:1、60:1、
70:1、80:1 or 90:1；The temperature of the reaction is preferably 200~400 DEG C, concretely 250 DEG C, 260 DEG C, 270 DEG C, 280
DEG C, 290 DEG C, 300 DEG C, 310 DEG C, 320 DEG C, 330 DEG C, 340 DEG C, 350 DEG C, 360 DEG C, 370 DEG C, 380 DEG C or 390 DEG C；It is described anti-
The pressure answered is preferably 0~5MPa, concretely 0.8MPa, 1MPa, 1.5MPa, 2MPa, 2.2MPa, 2.5MPa, 2.8MPa,
3MPa or 3.5MPa；The time of contact of the exhaust gas and hydrogen and the catalyst is preferably 0.4~1.5s, concretely
0.4s, 0.5s, 0.6s, 0.7s, 0.8s, 0.9s, 1s, 1.1s, 1.2s, 1.3s, 1.4s or 1.5s；The device of the reaction is preferred
For fixed bed reactors.After exhaust gas and hydrogen are reacted in the presence of a catalyst, the product gas after hydrogenation deoxidation is obtained.
The product gas after hydrogenation deoxidation is obtained, rectifying is carried out to the product gas after the hydrogenation deoxidation.In the present invention, it is excellent
It is selected in before the progress rectifying of the product gas after the hydrogenation deoxidation, first the product gas after the hydrogenation deoxidation is washed.Its
In, the washing is preferably distilled water or deionized water with water.In the present invention, boiling range 60~180 is collected in distillation process
DEG C fraction, also preferably relate to the fraction of 180 DEG C of boiling range ＞.Wherein, the fraction of 60~180 DEG C of boiling range can make as light fuel oil
With the fraction that 180 DEG C of boiling range ＞ can be used as heavy fuel oil.In the present invention, the rectifying is preferably set in tower height direction
There are three being carried out in the rectifying column of rectifying mouth, wherein rectifying mouth in bottom is used to collect the fraction of 180 DEG C of boiling range ＞, intermediate rectifying mouth
For collecting the fraction that boiling range is 60~180 DEG C, top fractionation mouth is used to collect the fraction of 60 DEG C of boiling range ＜.
The present invention isolates olefine aldehydr reaction product useless for the composition of olefine aldehydr vapor phase method synthesis isoprene reactor off-gas
After gas, through the catalyst to catalyzing hydrogenating deoxidation such as Ru, Pd, Pt, Co, Ni, Ir, using rectifying, it is 60 DEG C~180 DEG C to collect boiling range
Fraction.Due to having carried out hydrogenation deoxidation processing, the fraction compositions that the present invention obtains are alkane, can be made as fuel oil
With.Method provided by the invention, which is not only realized, to turn waste into wealth, but also can effectively reduce the synthesis isoprene reaction of olefine aldehydr vapor phase method
The discharge of exhaust gas, it is environment friendliness.The experimental results showed that it is alkane using the fraction compositions that method provided by the invention obtains
Hydrocarbon, sulfur content≤0.1wt%, without mechanical admixture, boiling range meets the boiling range requirement of light fuel oil.
For the sake of becoming apparent from, it is described in detail below by following embodiment.
The present embodiments relate to source exhaust gas it is as follows：
2.0g ZSM-5 are synthesized into isoprene for olefine aldehydr vapor phase method, reaction condition is：Under normal pressure in fixed bed,
At 270 DEG C, using nitrogen (10ml/min) as internal standard, it is 6 to keep isobutene and formaldehyde mole ratio：1, catalyst contact time is
0.7s.In reaction process, the gas of generation is cooled down at 35 DEG C, and gaseous state is reverted to after the liquid cooled down is heated,
Pending exhaust gas as of the invention.
Gas chromatography-mass spectrum (GC-MS) is carried out to the exhaust gas to analyze, (5975 gas chromatograph-mass spectrometer of Agilent), as a result such as
Shown in table 1：
1 exhaust gas constituents table of table
Embodiment 1
(1) 2g catalyst Ru/SBA-15 (Ru load capacity 0.8wt%) is taken to be packed into fixed bed reactors, is first passed through before reaction
H2After activating 1h at 300 DEG C, it is 300 DEG C to keep reaction temperature, cuts olefine aldehydr reactor off-gas, adjusts exhaust gas and hydrogen flowing quantity,
It is 20 to keep the mixed proportion of exhaust gas and hydrogen, time of contact 0.8s, pressure 1.5MPa；
(2) after hydrogenated deoxygenation, reaction gas is passed through rectifier unit after washing in a manner of bubbling；
(3) set each zone temperatures of rectifier unit, respectively from upper, middle and lower end collect less than 60 DEG C fractions, 60~180 DEG C
Fraction and 180 DEG C or more fractions.
Gas chromatography-mass spectrum (GC-MS) is carried out to 60~180 DEG C of fractions of collection to analyze, (5975 gas chromatography mass spectrometry of Agilent
Instrument), wherein it is as shown in Figure 1 to obtain chromatography.Fig. 1 is the chromatogram that the embodiment of the present invention 1 provides.GC-MS analysis results show 60
It is alkane without alkenes substance in~180 DEG C of fractions.
Embodiment 2
(1) 2g catalyst Pd/ [Zr/SiO are taken2] (Pd load capacity 3wt%) loading fixed bed reactors, it is first passed through before reaction
H2After activating 1h at 300 DEG C, reaction temperature is set as 280 DEG C, cuts olefine aldehydr reactor off-gas, adjusts exhaust gas and hydrogen flowing quantity,
It is 30 to keep the mixed proportion of exhaust gas and hydrogen, time of contact 1.2s, pressure 2.5MPa；
(2) after hydrogenated deoxygenation, reaction gas is passed through rectifier unit after washing in a manner of bubbling；
(3) set each zone temperatures of rectifier unit, respectively from upper, middle and lower end collect less than 60 DEG C fractions, 60~180 DEG C
Fraction and 180 DEG C or more fractions.
GC-MS analyses are carried out to 60~180 DEG C of fractions to collection using the analysis method of embodiment 1, the results showed that, 60
It is alkane without alkenes substance in~180 DEG C of fractions.
Embodiment 3
(1) 2g catalyst Ir/ZSM-5 (Ir load capacity 1.5wt%) is taken to be packed into fixed bed reactors, H is first passed through before reaction2
After activating 1h at 300 DEG C, reaction temperature is set as 320 DEG C, cuts olefine aldehydr reactor off-gas, adjusts exhaust gas and hydrogen flowing quantity, is protected
The mixed proportion for holding exhaust gas and hydrogen is 50, time of contact 1.1s, pressure 3.5MPa；
(2) after hydrogenated deoxygenation, reaction gas is passed through rectifier unit after washing in a manner of bubbling；
(3) set each zone temperatures of rectifier unit, respectively from upper, middle and lower end collect less than 60 DEG C fractions, 60~180 DEG C
Fraction and 180 DEG C or more fractions.
GC-MS analyses are carried out to 60~180 DEG C of fractions to collection using the analysis method of embodiment 1, the results showed that, 60
It is alkane without alkenes substance in~180 DEG C of fractions.
Embodiment 4
(1) 2g catalyst Co/ [Al/SiO are taken2] (Co load capacity 3.0wt%) loading fixed bed reactors, first lead to before reaction
Enter H2After activating 1h at 300 DEG C, reaction temperature is set as 360 DEG C, cuts olefine aldehydr reactor off-gas, adjusts exhaust gas and hydrogen stream
Amount, it is 70 to keep the mixed proportion of exhaust gas and hydrogen, time of contact 0.7s, pressure 0.8MPa；
(2) after hydrogenated deoxygenation, reaction gas is passed through rectifier unit after washing in a manner of bubbling；
(3) set each zone temperatures of rectifier unit, respectively from upper, middle and lower end collect less than 60 DEG C fractions, 60~180 DEG C
Fraction and 180 DEG C or more fractions.
GC-MS analyses are carried out to 60~180 DEG C of fractions to collection using the analysis method of embodiment 1, the results showed that, 60
It is alkane without alkenes substance in~180 DEG C of fractions.
Embodiment 5
(1) 2g catalyst ns i/SAPO (Ni load capacity 3.0wt%) is taken to be packed into fixed bed reactors, H is first passed through before reaction2
After activating 1h at 300 DEG C, reaction temperature is set as 250 DEG C, cuts olefine aldehydr reactor off-gas, adjusts exhaust gas and hydrogen flowing quantity, is protected
The mixed proportion for holding exhaust gas and hydrogen is 70, time of contact 1.2s, pressure 2.2MPa；
(2) after hydrogenated deoxygenation, reaction gas is passed through rectifier unit after washing in a manner of bubbling；
(3) set each zone temperatures of rectifier unit, respectively from upper, middle and lower end collect less than 60 DEG C fractions, 60~180 DEG C
Fraction and 180 DEG C are with fraction.
GC-MS analyses are carried out to 60~180 DEG C of fractions to collection using the analysis method of embodiment 1, the results showed that, 60
It is alkane without alkenes substance in~180 DEG C of fractions.
Embodiment 6
(1) 2g catalyst Pts/ZrO is taken2(Pt load capacity 1.2wt%) is packed into fixed bed reactors, and H is first passed through before reaction2
After activating 1h at 300 DEG C, reaction temperature is set as 330 DEG C, cuts olefine aldehydr reactor off-gas, adjusts exhaust gas and hydrogen flowing quantity, is kept
The mixed proportion of exhaust gas and hydrogen is 40, time of contact 0.6s, pressure 2.8MPa；
(2) after hydrogenated deoxygenation, reaction gas is passed through rectifier unit after washing in a manner of bubbling；
(3) set each zone temperatures of rectifier unit, respectively from upper, middle and lower end collect less than 60 DEG C fractions, 60~180 DEG C
Fraction and 180 DEG C or more fractions.
GC-MS analyses are carried out to 60~180 DEG C of fractions to collection using the analysis method of embodiment 1, the results showed that, 60
It is alkane without alkenes substance in~180 DEG C of fractions.
Embodiment 7
60~180 DEG C of fractions collected to Examples 1 to 6 are detected detection, and the results are shown in Table 2：
The analysis testing result of 2 60~180 DEG C of fractions of table
It can be seen from Table 2 that 60~180 DEG C of fraction sulfur content≤0.1wt% that the embodiment of the present invention is collected, without machine
Tool impurity and moisture, boiling range meet the boiling range requirement of light fuel oil.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of processing method of olefine aldehydr vapor phase method synthesis isoprene reactor off-gas, includes the following steps：
A), exhaust gas is provided；After the gaseous mixture progress separating isoprene that the exhaust gas is isobutene and formaldehyde gas phase reaction obtains
Remaining ingredient；
B), the exhaust gas and hydrogen carry out hydrogenation deoxidation reaction in the presence of a catalyst, obtain the product gas after hydrogenation deoxidation；
The active component of the catalyst includes one or more in Ru, Pd, Pt, Co, Ni and Ir；
C), the product gas after the hydrogenation deoxidation carries out rectifying, collects the fraction that boiling range is 60~180 DEG C.
2. processing method according to claim 1, which is characterized in that in step b), the catalyst is supported catalyst
Agent, the active component are supported on the carrier of the loaded catalyst, and the carrier includes SBA-15, ZSM-5, X-type point
Sub- sieve, Y type molecular sieve, beta-molecular sieve, SAPO molecular sieve, Al/SiO2、Al2O3、Zr/SiO2And ZrO2In it is one or more.
3. processing method according to claim 2, which is characterized in that the activity component load quantity of the loaded catalyst
For 0.1~5wt%.
4. processing method according to claim 1, which is characterized in that in step b), the volume ratio of the exhaust gas and hydrogen
For (5~100)：1.
5. processing method according to claim 1, which is characterized in that in step b), the temperature of the reaction for 200~
400℃；The pressure of the reaction is 0~5MPa；The time of contact of the exhaust gas and hydrogen and the catalyst for 0.4~
1.5s。
6. processing method according to claim 1, which is characterized in that in step b), before being reacted, first using hydrogen pair
The catalyst is activated.
7. processing method according to claim 6, which is characterized in that the temperature of the activation is 200~400 DEG C, described
The time of activation is 0.5~2h.
8. processing method according to claim 1, which is characterized in that in step c), the product gas after the hydrogenation deoxidation
Before rectifying is carried out, first the product gas of the hydrogenation deoxidation is washed.
9. processing method according to claim 1, which is characterized in that in step c), also collect evaporating for 180 DEG C of boiling range ＞
Point.
10. according to claim 1~9 any one of them processing method, which is characterized in that the ingredient of the exhaust gas includes 2- fourths
Alkene, isobutene, 1- butylene, 2,4,4- trimethyl -1- amylenes, 5,5- dimethyl -2- hexenes, 2,5- dimethyl -3- hexenes, 2,4,
4- trimethyl -2- amylenes, 2,3,4- trimethyl -2- amylenes, 2,3- dimethyl -1- hexenes, 3,4- dimethyl -3- hexenes, 2,4-
Dimethyl -2- hexenes, 3,4- dimethyl -2- hexenes, 2,5- dimethyl -1- hexenes, 2,4- dimethyl -1- hexenes, 2,6- diformazans
Base -1- hexenes, 2,4,4- trimethyl -2- amylenes, 2,3,4- trimethyl -2- amylenes, 3,3- dimethyl -1- hexenes, 2,5- diformazans
Base -2- hexenes, 2,4,4- trimethyl -2- amylenes, 2,3,4- trimethyl -2- amylenes, 2,3- dimethyl -2- hexenes, 3- methyl -4-
Methylene-hexane, 3,4- dimethyl -2- hexenes, 1,2,4,4- tetramethyl-rings amylene, 6,6- dimethyl -2,4- heptadiene, 2,6-
Dimethyl -2,4- heptadiene, 3,5,5- trimethyl cyclohex alkene, 1,6,6- trimethyl cyclohex alkene, 3,5,5- trimethyl cyclohexenes,
3,4,4- trimethyl cyclohexenes, 2,3,5- trimethyl 1,3- hexadienes, 2,6- dimethyl -2,4- heptadiene, dimethyl -3- are pungent
Alkynes, cis-1,4- dimethyl -2- vinyl cyclohexanes, 2,4- dimethyl heptanes, cis-1,4- dimethyl -2- vinyl cyclohexyls
Alkane, 1,2,3- trimethylbenzenes, 1,3,5- trimethylbenzenes, 1,2,4- trimethylbenzenes, 1- ethyls -4- methyl-benzene, 1,2,3- trimethyls
It is one or more in benzene and 1,3,5- trimethylbenzenes.
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