CN108130127B - Treatment method of reaction waste gas generated in synthesis of isoprene by olefine aldehyde gas phase method - Google Patents
Treatment method of reaction waste gas generated in synthesis of isoprene by olefine aldehyde gas phase method Download PDFInfo
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Abstract
The invention belongs to the field of environmental protection, and particularly relates to a treatment method of reaction waste gas generated in synthesis of isoprene by an olefine aldehyde gas phase method. The method comprises the following steps: a) providing an exhaust gas; the waste gas is the residual component after isoprene is separated from the mixed gas obtained by the gas-phase reaction of isobutene and formaldehyde; b) carrying out hydrodeoxygenation reaction on the waste gas and hydrogen to obtain hydrodeoxygenated product gas; c) and rectifying the product gas, and collecting fractions with the distillation range of 60-180 ℃. Aiming at the composition of reaction waste gas generated in the synthesis of isoprene by an olefine aldehyde gas phase method, after the waste gas is separated from an olefine aldehyde reaction product, the olefine aldehyde reaction product is subjected to hydrodeoxygenation and rectification, and then fraction with the distillation range of 60-180 ℃ is collected. Because of the hydrodeoxygenation, all the components of the fraction obtained by the method are alkanes, and the fraction can be used as fuel oil. The method provided by the invention not only changes waste into valuable, but also can effectively reduce the emission of reaction waste gas generated in the synthesis of isoprene by an olefine aldehyde gas phase method, and is environment-friendly and economical.
Description
Technical Field
The invention belongs to the field of environmental protection, and particularly relates to a treatment method of reaction waste gas generated in synthesis of isoprene by an olefine aldehyde gas phase method.
Background
Isoprene is an indispensable raw material for synthesizing natural rubber, and particularly, the application of isoprene in synthesizing special rubber products is irreplaceable in other chemical raw materials. Currently, the main methods for producing isoprene are divided into physical separation methods and chemical synthesis methods. The physical separation method is used for extracting the C-V fraction of ethylene by naphtha cracking, is limited by market fluctuation, and has increasingly increased demand for high-performance synthetic natural rubber aiming at the continuous development of the rubber industry, which provides great challenge for the traditional physical separation, so that a new idea is provided for solving the problem by developing a chemical synthesis method for synthesizing isoprene. The chemical method mainly comprises an isobutene-formaldehyde method, an acetylene acetone method and a propylene dimerization method, wherein the advantages of simple gas phase one-step method process, small investment and relatively low raw material cost are achieved by utilizing a C4 resource and taking isobutene and formaldehyde as raw materials, and the method has considerable economic benefit. The technology is characterized in that formaldehyde and isobutene are mixed, gasified and introduced into a reactor at the normal pressure of 150-400 ℃, and are dehydrated and condensed under the action of a catalyst to prepare isoprene.
At present, the catalysts related to the technology mainly comprise phosphorus catalysts, copper catalysts, molecular sieve catalysts, silver catalysts and the like, such as RU2354450C1 and RU2421441C1 disclosed in russian patent, CN201610161038.6 and CN201610944377.1 disclosed in changchun applied chemistry research institute of chinese academy of sciences. The technology produces isoprene and simultaneously produces a large amount of waste gas to be discharged into the atmosphere, and the main composition of the waste gas is hydrocarbon compounds. Excessive emission of hydrocarbons can cause atmospheric pollution, and the compounds enter the atmosphere and can carry out photochemical reaction with oxynitrides to generate strong oxidants of acetaldehyde, PAN and the like, thereby causing serious harm to human bodies and plants, such as atmospheric pollution caused by the hydrocarbons reported in paper 17 page 3 of the Industrial public hazard. And limiting hydrocarbon emissions has long been an effective means for environmental protection. Therefore, reducing the emission of hydrocarbons or converting them into other useful products while performing chemical production is one of the focuses of current researchers.
Disclosure of Invention
In view of the above, the present invention provides a method for treating reaction waste gas from the synthesis of isoprene by an olefine aldehyde gas phase method, which can convert the waste gas into fuel oil with high added value.
The invention provides a method for treating reaction waste gas generated in synthesis of isoprene by an olefine aldehyde gas phase method, which comprises the following steps:
a) providing an exhaust gas; the waste gas is the residual component after isoprene is separated from the mixed gas obtained by the gas-phase reaction of isobutene and formaldehyde;
b) carrying out hydrodeoxygenation reaction on the waste gas and hydrogen in the presence of a catalyst to obtain hydrodeoxygenated product gas;
the active component of the catalyst comprises one or more of Ru, Pd, Pt, Co, Ni and Ir;
c) and rectifying the hydrodeoxygenated product gas, and collecting fractions with the distillation range of 60-180 ℃.
Preferably, in step b), theThe catalyst is a supported catalyst, the active component is supported on a carrier of the supported catalyst, and the carrier comprises SBA-15, ZSM-5, X-type molecular sieve, Y-type molecular sieve, beta molecular sieve, SAPO molecular sieve and Al/SiO2、Al2O3、Zr/SiO2And ZrO2One or more of (a).
Preferably, the loading amount of the active component of the supported catalyst is 0.1-5 wt%.
Preferably, in the step b), the volume ratio of the waste gas to the hydrogen is (5-100): 1.
preferably, in the step b), the reaction temperature is 200-400 ℃; the reaction pressure is 0-5 MPa; and the contact time of the waste gas and the hydrogen with the catalyst is 0.4-1.5 s.
Preferably, in step b), the catalyst is activated with hydrogen before the reaction is carried out.
Preferably, the activation temperature is 200-400 ℃, and the activation time is 0.5-2 h.
Preferably, in step c), the hydrodeoxygenated product gas is washed with water before being rectified.
Preferably, in step c), a fraction having a distillation range of > 180 ℃ is also collected.
Preferably, the composition of the exhaust gas comprises 2-butene, isobutene, 1-butene, 2,4, 4-trimethyl-1-pentene, 5-dimethyl-2-hexene, 2, 5-dimethyl-3-hexene, 2,4, 4-trimethyl-2-pentene, 2, 3-dimethyl-1-hexene, 3, 4-dimethyl-3-hexene, 2, 4-dimethyl-2-hexene, 3, 4-dimethyl-2-hexene, 2, 5-dimethyl-1-hexene, 2, 4-dimethyl-1-hexene, 2, 6-dimethyl-1-hexene, 2, 4-dimethyl-2-pentene, 2, 4-dimethyl-1-pentene, 2, 4-dimethyl-, 2,4, 4-trimethyl-2-pentene, 2,3, 4-trimethyl-2-pentene, 3-dimethyl-1-hexene, 2, 5-dimethyl-2-hexene, 2,4, 4-trimethyl-2-pentene, 2, 3-dimethyl-2-hexene, 3-methyl-4-methylene-hexane, 3, 4-dimethyl-2-hexene, 1,2,4, 4-tetramethylcyclopentene, 6-dimethyl-2, 4-heptadiene, 2, 6-dimethyl-2, 4-heptadiene, 3,5, 5-trimethyl-cyclohexene, 2,3, 4-dimethylheptene, 2, 4-heptadiene, 2,5, 5-trimethyl-cyclohexene, 2-pentene, 2,3,4-, 1,6, 6-trimethyl-cyclohexene, 3,5, 5-trimethylcyclohexene, 3,4, 4-trimethylcyclohexene, 2,3, 5-trimethyl-1, 3-hexadiene, 2, 6-dimethyl-2, 4-heptadiene, dimethyl-3-octyne, cis-1, 4-dimethyl-2-vinylcyclohexane, 2, 4-dimethylheptane, cis-1, 4-dimethyl-2-vinylcyclohexane, 1,2, 3-trimethylbenzene, 1,3, 5-trimethylbenzene, 1,2, 4-trimethylbenzene, 1-ethyl-4-methyl-benzene, 1,2, 3-trimethylbenzene and 1,3, 5-trimethylbenzene.
Compared with the prior art, the invention provides a method for treating reaction waste gas generated in the synthesis of isoprene by an olefine aldehyde gas phase method. The method provided by the invention comprises the following steps: a) providing an exhaust gas; the waste gas is the residual component after isoprene is separated from the mixed gas obtained by the gas-phase reaction of isobutene and formaldehyde; b) carrying out hydrodeoxygenation reaction on the waste gas and hydrogen in the presence of a catalyst to obtain hydrodeoxygenated product gas; the active component of the catalyst comprises one or more of Ru, Pd, Pt, Co, Ni and Ir; c) and rectifying the hydrodeoxygenated product gas, and collecting fractions with the distillation range of 60-180 ℃. Aiming at the composition of reaction waste gas generated in the synthesis of isoprene by an olefine aldehyde gas phase method, olefine aldehyde reaction products are separated to form the waste gas, and then are subjected to catalytic hydrodeoxygenation by catalysts such as Ru, Pd, Pt, Co, Ni and Ir, and then are rectified to collect fractions with the distillation range of 60-180 ℃. Because of the hydrodeoxygenation treatment, all the components of the fraction obtained by the method are alkanes, and the fraction can be used as fuel oil. The method provided by the invention not only changes waste into valuable, but also can effectively reduce the emission of reaction waste gas generated in the synthesis of isoprene by an olefine aldehyde gas phase method, and is environment-friendly and economical. Experimental results show that all the components of the distillate obtained by the method provided by the invention are alkane, the sulfur content is less than or equal to 0.1 wt%, no mechanical impurity is contained, and the distillation range meets the distillation range requirement of light fuel oil.
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In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a chromatogram provided in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a method for treating reaction waste gas generated in synthesis of isoprene by an olefine aldehyde gas phase method, which comprises the following steps:
a) providing an exhaust gas; the waste gas is the residual component after isoprene is separated from the mixed gas obtained by the gas-phase reaction of isobutene and formaldehyde;
b) carrying out hydrodeoxygenation reaction on the waste gas and hydrogen in the presence of a catalyst to obtain hydrodeoxygenated product gas;
the active component of the catalyst comprises one or more of Ru, Pd, Pt, Co, Ni and Ir;
c) and rectifying the hydrodeoxygenated product gas, and collecting fractions with the distillation range of 60-180 ℃.
In the invention, firstly, waste gas is provided, and the waste gas is the residual component after isoprene is separated from mixed gas obtained by gas-phase reaction of isobutene and formaldehyde. In the present invention, the specific process of the gas phase reaction of isobutylene and formaldehyde is not particularly limited, but preferably isobutylene and formaldehyde are introduced into a fixed bed reactor filled with a catalyst, and isobutylene and formaldehyde react in the presence of the catalyst to obtain an isoprene-containing mixed gas. Wherein the catalyst has optional ZSM-5; the molar ratio of the isobutene to the formaldehyde is preferably (2-9): 1, specifically 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1 or 9: 1; the reaction temperature is preferably 150-400 ℃, and specifically can be 150 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃, 360 ℃, 370 ℃, 380 ℃ or 390 ℃; the pressure of the reaction is preferably normal pressure; in the reaction process, the contact time of the isobutene and the formaldehyde with the catalyst is preferably 0.3-1.5 s, and specifically can be 0.3s, 0.4s, 0.5s, 0.6s, 0.7s, 0.8s, 0.9s, 1s, 1.1s, 1.2s, 1.3s, 1.4s or 1.5 s. After the mixed gas containing isoprene is obtained, separating the isoprene in the mixed gas. In the present invention, it is preferable to perform cooling separation based on the difference in boiling points between isoprene and other components in the mixed gas, that is, to cool the mixed gas at 35 ℃ to obtain a gas (isoprene as a main component) and a liquid, respectively. And then heating the liquid to obtain the waste gas. In one embodiment provided by the present invention, the composition of the off-gas comprises 2-butene, isobutene, 1-butene, 2,4, 4-trimethyl-1-pentene, 5-dimethyl-2-hexene, 2, 5-dimethyl-3-hexene, 2,4, 4-trimethyl-2-pentene, 2, 3-dimethyl-1-hexene, 3, 4-dimethyl-3-hexene, 2, 4-dimethyl-2-hexene, 3, 4-dimethyl-2-hexene, 2, 5-dimethyl-1-hexene, 2, 4-dimethyl-1-hexene, 2, 6-dimethyl-1-hexene, 2,4, 4-trimethyl-2-pentene, 2,3, 4-trimethyl-2-pentene, 3-dimethyl-1-hexene, 2, 5-dimethyl-2-hexene, 2,4, 4-trimethyl-2-pentene, 2, 3-dimethyl-2-hexene, 3-methyl-4-methylene-hexane, 3, 4-dimethyl-2-hexene, 1,2,4, 4-tetramethylcyclopentene, 6-dimethyl-2, 4-heptadiene, 2, 6-dimethyl-2, 4-heptadiene, 3,5, 5-trimethyl-cyclohexene, 1,6, 6-trimethyl-cyclohexene, 3,5, 5-trimethylcyclohexene, 3,4, 4-trimethylcyclohexene, 2,3, 5-trimethyl-1, 3-hexadiene, 2, 6-dimethyl-2, 4-heptadiene, dimethyl-3-octyne, cis-1, 4-dimethyl-2-vinylcyclohexane, 2, 4-dimethylheptane, cis-1, 4-dimethyl-2-vinylcyclohexane, 1,2, 3-trimethylbenzene, 1,3, 5-trimethylbenzene, 1,2, 4-trimethylbenzene, 1-ethyl-4-methyl-benzene, 1,2, 3-trimethylbenzene and 1,3, 5-trimethylbenzene.
After obtaining the waste gas, carrying out hydrodeoxygenation reaction on the waste gas and hydrogen in the presence of a catalyst. Wherein, theThe active component of the catalyst comprises one or more of Ru, Pd, Pt, Co, Ni and Ir. In one embodiment provided by the invention, the catalyst is a supported catalyst, the active component is supported on a carrier of the supported catalyst, and the carrier comprises SBA-15, ZSM-5, X-type molecular sieve, Y-type molecular sieve, beta molecular sieve, SAPO molecular sieve, Al/SiO molecular sieve2、Al2O3、Zr/SiO2And ZrO2One or more of (a). In an embodiment where one of the catalysts provided by the present invention is a supported catalyst, the active component loading amount is preferably 0.1 to 5wt%, and specifically may be 0.5 wt%, 0.8 wt%, 1.2 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, or 4.5 wt%. In the present invention, the catalyst is activated with hydrogen before the reaction is carried out. Wherein the activation temperature is preferably 200-400 ℃, and specifically can be 200 ℃, 250 ℃, 300 ℃, 350 ℃ or 400 ℃; the activation time is preferably 0.5-2 h, and specifically can be 0.5h, 1h, 1.5h or 2 h. In the invention, the volume ratio of the waste gas to the hydrogen is preferably (5-100): 1, specifically 10:1, 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1 or 90: 1; the reaction temperature is preferably 200-400 ℃, and specifically can be 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃, 360 ℃, 370 ℃, 380 ℃ or 390 ℃; the reaction pressure is preferably 0-5 MPa, and specifically can be 0.8MPa, 1MPa, 1.5MPa, 2MPa, 2.2MPa, 2.5MPa, 2.8MPa, 3MPa or 3.5 MPa; the contact time of the waste gas and the hydrogen with the catalyst is preferably 0.4-1.5 s, and specifically can be 0.4s, 0.5s, 0.6s, 0.7s, 0.8s, 0.9s, 1s, 1.1s, 1.2s, 1.3s, 1.4s or 1.5 s; the apparatus for the reaction is preferably a fixed bed reactor. Reacting the waste gas with hydrogen in the presence of a catalyst to obtain hydrodeoxygenated product gas.
Obtaining hydrodeoxygenated product gas, and rectifying the hydrodeoxygenated product gas. In the present invention, it is preferable that the hydrodeoxygenated product gas is washed with water before the hydrodeoxygenated product gas is rectified. Wherein, the water for washing the water is preferably distilled water or deionized water. In the invention, the fraction with the distillation range of 60-180 ℃ is collected in the rectification process, and preferably the fraction with the distillation range of more than 180 ℃ is also involved. Wherein, the fraction with the distillation range of 60-180 ℃ can be used as light fuel oil, and the fraction with the distillation range of more than 180 ℃ can be used as heavy fuel oil. In the invention, the rectification is preferably carried out in a rectification tower provided with three rectification ports in the tower height direction, wherein the bottom rectification port is used for collecting the fraction with the distillation range of more than 180 ℃, the middle rectification port is used for collecting the fraction with the distillation range of 60-180 ℃, and the top rectification port is used for collecting the fraction with the distillation range of less than 60 ℃.
Aiming at the composition of reaction waste gas generated in the synthesis of isoprene by an olefine aldehyde gas phase method, olefine aldehyde reaction products are separated to form the waste gas, and then are subjected to catalytic hydrodeoxygenation by catalysts such as Ru, Pd, Pt, Co, Ni and Ir, and then are rectified to collect fractions with the distillation range of 60-180 ℃. Because of the hydrodeoxygenation treatment, all the components of the fraction obtained by the method are alkanes, and the fraction can be used as fuel oil. The method provided by the invention not only changes waste into valuable, but also can effectively reduce the emission of reaction waste gas generated in the synthesis of isoprene by an olefine aldehyde gas phase method, and is environment-friendly and economical. Experimental results show that all the components of the distillate obtained by the method provided by the invention are alkane, the sulfur content is less than or equal to 0.1 wt%, no mechanical impurity is contained, and the distillation range meets the distillation range requirement of light fuel oil.
For the sake of clarity, the following examples are given in detail.
The waste gas sources related to the embodiment of the invention are as follows:
2.0g of ZSM-5 was used for the gas phase synthesis of isoprene from enal under the following reaction conditions: on a fixed bed at atmospheric pressure, at 270 ℃ and with nitrogen (10ml/min) as internal standard, a molar ratio of isobutene to formaldehyde of 6:1, the catalyst contact time is 0.7 s. In the reaction process, the generated gas is cooled at 35 ℃, and the liquid obtained by cooling is heated and then returns to be gaseous, namely the waste gas to be treated.
The off-gas was subjected to gas chromatography-mass spectrometry (GC-MS), (agilent 5975 gas chromatograph-mass spectrometer), and the results are shown in table 1:
TABLE 1 exhaust gas composition Table
Example 1
(1) 2g of catalyst Ru/SBA-15(Ru load 0.8 wt%) is loaded into a fixed bed reactor, and H is introduced before reaction2After activation for 1h at 300 ℃, keeping the reaction temperature at 300 ℃, cutting in olefine aldehyde reaction waste gas, adjusting the flow of the waste gas and hydrogen, keeping the mixing ratio of the waste gas and the hydrogen at 20, the contact time at 0.8s and the pressure at 1.5 MPa;
(2) after the hydrodeoxygenation reaction, reaction gas is washed by water in a bubbling mode and then is introduced into a rectifying device;
(3) setting the temperature of each section of the rectifying device, and collecting fractions below 60 ℃, fractions below 60 ℃ and fractions above 180 ℃ from the upper end, the middle end and the lower end respectively.
And (3) carrying out gas chromatography-mass spectrometry (GC-MS) analysis on the collected fractions at 60-180 ℃ (Agilent 5975 gas chromatograph-mass spectrometer), wherein the obtained chromatogram is shown in figure 1. FIG. 1 is a chromatogram provided in example 1 of the present invention. GC-MS analysis results show that the 60-180 ℃ fractions contain no alkene substances and are all alkanes.
Example 2
(1) 2g of catalyst Pd/[ Zr/SiO ] was taken2](Pd loading 3 wt%) was charged into a fixed bed reactor, and H was introduced before the reaction2After activation for 1h at 300 ℃, setting the reaction temperature to be 280 ℃, cutting in olefine aldehyde reaction waste gas, adjusting the flow of the waste gas and hydrogen, keeping the mixing ratio of the waste gas and the hydrogen to be 30, the contact time to be 1.2s and the pressure to be 2.5 MPa;
(2) after the hydrodeoxygenation reaction, reaction gas is washed by water in a bubbling mode and then is introduced into a rectifying device;
(3) setting the temperature of each section of the rectifying device, and collecting fractions below 60 ℃, fractions below 60 ℃ and fractions above 180 ℃ from the upper end, the middle end and the lower end respectively.
GC-MS analysis of the collected 60-180 ℃ fractions by the analysis method of example 1 shows that the 60-180 ℃ fractions contain no alkene substances and are all alkanes.
Example 3
(1) 2g of catalyst Ir/ZSM-5(Ir load 1.5 wt%) is loaded into a fixed bed reactor, and H is introduced before reaction2After activation for 1h at 300 ℃, setting the reaction temperature to be 320 ℃, cutting in the olefine aldehyde reaction waste gas, adjusting the flow of the waste gas and hydrogen, keeping the mixing ratio of the waste gas and the hydrogen to be 50, the contact time to be 1.1s and the pressure to be 3.5 MPa;
(2) after the hydrodeoxygenation reaction, reaction gas is washed by water in a bubbling mode and then is introduced into a rectifying device;
(3) setting the temperature of each section of the rectifying device, and collecting fractions below 60 ℃, fractions below 60 ℃ and fractions above 180 ℃ from the upper end, the middle end and the lower end respectively.
GC-MS analysis of the collected 60-180 ℃ fractions by the analysis method of example 1 shows that the 60-180 ℃ fractions contain no alkene substances and are all alkanes.
Example 4
(1) 2g of Co/[ Al/SiO ] catalyst was taken2](Co loading 3.0 wt.%) was charged into a fixed bed reactor and H was introduced before reaction2After activation for 1h at 300 ℃, setting the reaction temperature to be 360 ℃, cutting in olefine aldehyde reaction waste gas, adjusting the flow of the waste gas and hydrogen, keeping the mixing ratio of the waste gas and the hydrogen to be 70, the contact time to be 0.7s and the pressure to be 0.8 MPa;
(2) after the hydrodeoxygenation reaction, reaction gas is washed by water in a bubbling mode and then is introduced into a rectifying device;
(3) setting the temperature of each section of the rectifying device, and collecting fractions below 60 ℃, fractions below 60 ℃ and fractions above 180 ℃ from the upper end, the middle end and the lower end respectively.
GC-MS analysis of the collected 60-180 ℃ fractions by the analysis method of example 1 shows that the 60-180 ℃ fractions contain no alkene substances and are all alkanes.
Example 5
(1) 2g of catalyst Ni/SAPO (Ni loading 3.0 wt%) was loaded into a fixed bedA reactor, H is introduced before reaction2After activation for 1h at 300 ℃, setting the reaction temperature to be 250 ℃, cutting in olefine aldehyde reaction waste gas, adjusting the flow of the waste gas and hydrogen, keeping the mixing ratio of the waste gas and the hydrogen to be 70, the contact time to be 1.2s and the pressure to be 2.2 MPa;
(2) after the hydrodeoxygenation reaction, reaction gas is washed by water in a bubbling mode and then is introduced into a rectifying device;
(3) setting the temperature of each section of the rectifying device, and collecting fractions below 60 ℃, fractions at 60-180 ℃ and fractions at 180 ℃ from the upper end, the middle end and the lower end respectively.
GC-MS analysis of the collected 60-180 ℃ fractions by the analysis method of example 1 shows that the 60-180 ℃ fractions contain no alkene substances and are all alkanes.
Example 6
(1) 2g of catalyst Pt/ZrO was taken2(Pt loading 1.2 wt%) was charged into a fixed bed reactor and H was introduced before the reaction2After activation for 1h at 300 ℃, setting the reaction temperature to be 330 ℃, cutting in olefine aldehyde reaction waste gas, adjusting the flow of the waste gas and hydrogen, keeping the mixing ratio of the waste gas and the hydrogen to be 40, the contact time to be 0.6s and the pressure to be 2.8 MPa;
(2) after the hydrodeoxygenation reaction, reaction gas is washed by water in a bubbling mode and then is introduced into a rectifying device;
(3) setting the temperature of each section of the rectifying device, and collecting fractions below 60 ℃, fractions below 60 ℃ and fractions above 180 ℃ from the upper end, the middle end and the lower end respectively.
GC-MS analysis of the collected 60-180 ℃ fractions by the analysis method of example 1 shows that the 60-180 ℃ fractions contain no alkene substances and are all alkanes.
Example 7
The 60-180 ℃ fractions collected in examples 1-6 were tested and the results are shown in Table 2:
analytical test results of fractions at 260-180 ℃ in Table
As can be seen from Table 2, the sulfur content of the fraction collected at 60-180 ℃ in the embodiment of the invention is less than or equal to 0.1 wt%, the fraction does not contain mechanical impurities and water, and the distillation range meets the distillation range requirement of light fuel oil.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (6)
1. A treatment method of reaction waste gas generated in synthesis of isoprene by an olefine aldehyde gas phase method comprises the following steps:
a) providing an exhaust gas; the waste gas is the residual component after isoprene is separated from the mixed gas obtained by the gas-phase reaction of isobutene and formaldehyde;
the composition of the exhaust gas includes 2-butene, isobutene, 1-butene, 2,4, 4-trimethyl-1-pentene, 5-dimethyl-2-hexene, 2, 5-dimethyl-3-hexene, 2,4, 4-trimethyl-2-pentene, 2, 3-dimethyl-1-hexene, 3, 4-dimethyl-3-hexene, 2, 4-dimethyl-2-hexene, 3, 4-dimethyl-2-hexene, 2, 5-dimethyl-1-hexene, 2, 4-dimethyl-1-hexene, 2, 6-dimethyl-1-hexene, hexene, 2,4, 4-trimethyl-2-pentene, 2,3, 4-trimethyl-2-pentene, 3-dimethyl-1-hexene, 2, 5-dimethyl-2-hexene, 2,4, 4-trimethyl-2-pentene, 2, 3-dimethyl-2-hexene, 3-methyl-4-methylene-hexane, 3, 4-dimethyl-2-hexene, 1,2,4, 4-tetramethylcyclopentene, 6-dimethyl-2, 4-heptadiene, 2, 6-dimethyl-2, 4-heptadiene, 3,5, 5-trimethyl-cyclohexene, 2,3, 4-dimethylheptene, 2, 4-heptadiene, 2,5, 5-trimethyl-cyclohexene, 2-pentene, 2,3,4-, 1,6, 6-trimethyl-cyclohexene, 3,5, 5-trimethylcyclohexene, 3,4, 4-trimethylcyclohexene, 2,3, 5-trimethyl 1, 3-hexadiene, 2, 6-dimethyl-2, 4-heptadiene, dimethyl-3-octyne, cis-1, 4-dimethyl-2-vinylcyclohexane, 2, 4-dimethylheptane, cis-1, 4-dimethyl-2-vinylcyclohexane, 1,2, 3-trimethylbenzene, 1,3, 5-trimethylbenzene, 1,2, 4-trimethylbenzene, 1-ethyl-4-methyl-benzene, 1,2, 3-trimethylbenzene and 1,3, 5-trimethylbenzene;
b) carrying out hydrodeoxygenation reaction on the waste gas and hydrogen in the presence of a catalyst to obtain hydrodeoxygenated product gas;
the catalyst is Ru/SBA-15, Pd/[ Zr/SiO ]2]Ir/ZSM-5 or Pt/ZrO2；
The volume ratio of the waste gas to the hydrogen is (20-50): 1;
c) and sequentially washing and rectifying the hydrodeoxygenated product gas, and collecting fractions with the distillation range of 60-180 ℃.
2. The treatment method according to claim 1, wherein the catalyst has an active component loading of 0.1 to 5 wt%.
3. The treatment method according to claim 1, wherein in the step b), the reaction temperature is 200-400 ℃; the reaction pressure is 0-5 MPa; and the contact time of the waste gas and the hydrogen with the catalyst is 0.4-1.5 s.
4. The process of claim 1, wherein the catalyst is activated with hydrogen before the reaction in step b).
5. The treatment method according to claim 4, wherein the temperature of the activation is 200 to 400 ℃, and the time of the activation is 0.5 to 2 hours.
6. The process according to claim 1, characterized in that in step c) fractions with a distillation range > 180 ℃ are also collected.
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