CN103539613B - The production method of propylene - Google Patents
The production method of propylene Download PDFInfo
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- CN103539613B CN103539613B CN201210240011.8A CN201210240011A CN103539613B CN 103539613 B CN103539613 B CN 103539613B CN 201210240011 A CN201210240011 A CN 201210240011A CN 103539613 B CN103539613 B CN 103539613B
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Abstract
The present invention relates to a kind of production method of propylene, mainly solve the problem needing consumption of ethylene existed in conventional art.The present invention is by adopting the material comprising 1-butylene, 2-butylene, Trimethylmethane and normal butane to be carbon four raw material, carbon four raw material obtains the technical scheme of product propylene respectively through disproportionation reactor, de-ethylene column and depropenizer and extraction procedure, can be used for the industrial production of carbon four propylene processed.
Description
Technical field
The present invention relates to a kind of production method of propylene.
Background technology
Traditional ethene coproduction and refinery's Propylene recovery method are obviously difficult to meet growing propylene demand, adopt olefin metathesis technology can digest C while not reducing naphtha cracking severity
4cut, and can propylene enhancing, thus the research and development of preparing propylene through olefin disproportionation technology is not only to the output improving propylene, simultaneously to the low value-added C of promotion
4the comprehensive utilization of cut all has great significance, and butylene disproportionation wherein involved in the present invention is produced third and rarely made a kind of up-and-coming technique.
Olefin dismutation reaction is also called olefinic double bonds replacement(metathesis)reaction, it is a kind of conversion of olefines phenomenon found the sixties in 20th century, olefin dismutation reaction just becomes a class significant process of conversion of olefines since then, utilizes olefin dismutation reaction some comparatively cheap, abundant olefin feedstocks can be converted into the higher olefin product of multiple added value.Olefin dismutation reaction process can be represented with following formula:
Wherein R and R ' represents alkyl or hydrogen atom.The simplest olefin dismutation reaction is that propylene disproportionation generates ethene and butene-2.
WO2005009929 reports a kind of working method of the C4 olefin stream for maximum production of propylene, does not add ethene in this method, comprises conventional metathesis reaction and automatic replacement(metathesis)reaction.
WO2006052688 reports the Catalyst And Method of a kind of ethene and butylene metathesis production propylene, and the method makes described charging and contact ethylene production propylene under metathesis reaction conditions in the replacement(metathesis)reaction district containing metathesis catalyst.
CN97121426 reports a kind of preparation method of propylene, and the method is included under metathesis catalyst exists and makes 2-amylene and ethylene reaction, and above-mentioned catalyzer at least contains a kind of element, the compound of the VIth b, VII b or VIII group 4 transition metal in periodictable.
When propylene reaction processed for carbon four, all there is the problem needing consumption of ethylene in the method in above document.
Summary of the invention
Technical problem to be solved by this invention is the problem needing consumption of ethylene existed in prior art, provides a kind of new propylene production.When the method is reacted for carbon four propylene processed, there is the advantage not needing consumption of ethylene.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of production method of propylene, to contain 1-butylene, 2-butylene, the carbon four of normal butane and Trimethylmethane is raw material, comprises the following steps: (a) carbon four raw material obtains being rich in the logistics I of 2-butylene after isomerization reactor reaction; B () logistics I and disproportionation catalyst contact reacts obtain the logistics II containing product ethylene, propylene, carbon four and carbon five; C () logistics II enters de-ethylene column, tower top obtains ethene, and tower reactor obtains the logistics III containing propylene, carbon four, carbon five; D () logistics III enters depropenizer, tower top obtains product propylene, and the carbon four that tower reactor obtains obtains butene stream after extraction procedure removing Trimethylmethane wherein and normal butane.
In technique scheme, the catalyzer in the isomerization reactor described in step (a) is Ni/Al
2o
3, the charge capacity of Ni is 5 ~ 20%, operational condition: temperature of reaction 40 ~ 60 DEG C, reaction pressure in absolute pressure 1 ~ 2MPa, the mass space velocity 1 ~ 8h of carbon four
-1; The preferred version of disproportionation catalyst described in step (b) is WO
3/ SiO
2, WO
3charge capacity be 4 ~ 15%, the preferred version of operational condition is temperature of reaction 250 ~ 350 DEG C, reaction pressure in absolute pressure 1 ~ 4MPa, the mass space velocity 1 ~ 8h of carbon four
-1; The preferred version of de-ethylene column operational condition: theoretical plate number 100 ~ 120 pieces, tower pressure 1.8 ~ 2.2MPa, tower top temperature-35 ~-30 DEG C, bottom temperature-10 ~-5 DEG C; The preferred version of depropenizer operational condition: theoretical plate number 160 ~ 180 pieces, tower pressure 1.7 ~ 1.9MPa, tower top temperature 40 ~ 45 DEG C, bottom temperature 50 ~ 55 DEG C; In extraction procedure, the preferred version of extraction agent used is the mixed solvent of n-formylmorpholine and methylethylketone, and both weight ratios are 1:1
The present invention is by increasing extraction procedure by alkene and alkane separation after middle depropenizer, effectively can improve the utilization ratio of C 4 olefin and rationally reclaim butane, compare and do not adopt the technique propylene weight yield of extraction procedure to improve 5%, in disproportionation reactor, 1-butylene and 2-butylene disproportionation reaction generate propylene and amylene simultaneously, under the identical amount propylene condition of production, do not need ethene as reaction raw materials, improve economic benefit, achieve good technique effect.
Accompanying drawing explanation
Fig. 1 is the schema of the technological system of the present invention of C 4 materials for the production of propylene.
In Fig. 1,1 is carbon four raw material, and 2 is mixed c 4 raw material, and 3 for being rich in carbon four logistics of 2-butylene, 4 is reaction product, and 5 is ethene, and 6 is de-ethylene column tower reactor logistics, 7 is propylene, and 8 for containing butylene and butane logistics, and 9 is carbon five logistics, 10 is Trimethylmethane and normal butane, and 11 is circulation butylene, and 21 is isomerization reactor, 22 is disproportionation reactor, 23 is de-ethylene column, and 24 is depropenizer, and 25 is extraction procedure.
With reference to Fig. 1, method of the present invention is briefly stated in flow charts.
As shown in Figure 1, carbon four raw material 1 and circulation butylene 11 are mixed to get cyclic carbon 42, logistics 2 is obtained by reacting carbon four logistics 3 being rich in 2-butylene through isomerization reactor 21, logistics 3 and disproportionation catalyst contact reacts, be obtained by reacting target product propylene, carbon four and carbon five logistics, reaction product 4 is through de-ethylene column, the ethene 5 that tower top obtains, the component 6 that tower reactor obtains enters depropenizer process, tower top obtains polymerization-grade propylene 7, the carbon four that tower reactor obtains and carbon five, carbon five can be used as liquefied gas and uses, carbon four removes through extraction procedure 25 the circulation butylene obtained after Trimethylmethane and normal butane and can be used as reaction raw materials recycling.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
By the technical process shown in Fig. 1, the catalyzer in isomerization reactor is 12%Ni/Al
2o
3, operational condition: temperature of reaction 50 DEG C, reaction pressure in absolute pressure 1.5MPa, the mass space velocity 2h of carbon four
-1; Disproportionation catalyst in disproportionation reactor is 8%WO
3/ SiO
2, operational condition is: temperature of reaction 300 DEG C, reaction pressure in absolute pressure 3MPa, the mass space velocity 2h of carbon four
-1; Extraction agent is the mixed solvent of n-formylmorpholine and methylethylketone, and weight ratio is 1:1.The operational condition of de-ethylene column and depropenizer is as shown in table 1, and the operational condition of extraction procedure is as shown in table 2, reaction conditions and reaction result as shown in table 3.
[embodiment 2 ~ 6]
React by each condition of embodiment 1 and step, just change different operating parameterss, the operational condition of de-ethylene column and depropenizer is as shown in table 1, and the operational condition of extraction procedure is as shown in table 2, reaction conditions and reaction result as shown in table 3.
[comparative example 1]
By the technical process shown in Fig. 1, just not through extraction procedure.Disproportionation catalyst preferred version in disproportionation reactor is 8%WO
3/ SiO
2, operational condition is: temperature of reaction 300 DEG C, reaction pressure in absolute pressure 3MPa, the mass space velocity 2h of carbon four
-1.The operational condition of de-ethylene column and depropenizer is as shown in table 1, reaction conditions and reaction result as shown in table 3.
[comparative example 2]
By the technical process shown in Fig. 1, extraction agent is the mixed solvent of n-formylmorpholine and methylethylketone, and weight ratio is 1:1; Disproportionation catalyst in disproportionation reactor is 4%WO
3/ SiO
2, operational condition is: temperature of reaction 350 DEG C, reaction pressure in absolute pressure 2MPa, the mass space velocity 4h of carbon four
-1, the mol ratio of ethene and carbon four is 2:1.The operational condition of extraction procedure is as shown in table 1, and the operational condition of de-ethylene column and depropenizer is as shown in table 1, reaction conditions and reaction result as shown in table 3.
[comparative example 3]
By the technical process shown in Fig. 1, extraction agent is the mixed solvent of n-formylmorpholine and methylethylketone, and weight ratio is 1:1; Disproportionation catalyst in disproportionation reactor is 12%WO
3/ SiO
2, operational condition is: temperature of reaction 400 DEG C, reaction pressure in absolute pressure 4MPa, the mass space velocity 1h of carbon four
-1, the mol ratio of ethene and carbon four is 1:1.The operational condition of extraction procedure is as shown in table 1, and the operational condition of de-ethylene column and depropenizer is as shown in table 1, reaction conditions and reaction result as shown in table 3.
Table 1
Table 2
Table 3
Note: the data of disproportionation catalyst are all the mass percentage of active ingredient.
Claims (1)
1. a production method for propylene, to contain 1-butylene, 2-butylene, the carbon four of normal butane and Trimethylmethane is raw material, comprises the following steps:
A () carbon four raw material obtains the logistics I being rich in 2-butylene after isomerization reactor reaction;
B () logistics I and disproportionation catalyst contact reacts obtain the logistics II containing product ethylene, propylene, carbon four and carbon five;
C () logistics II enters de-ethylene column, tower top obtains ethene, and tower reactor obtains the logistics III containing propylene, carbon four, carbon five;
D () logistics III enters depropenizer, tower top obtains product propylene, and the carbon four that tower reactor obtains obtains butene stream after extraction procedure removing Trimethylmethane wherein and normal butane;
Catalyzer in isomerization reactor described in step (a) is Ni/Al
2o
3, the charge capacity of Ni is 5 ~ 20%, operational condition: temperature of reaction 40 ~ 60 DEG C, reaction pressure in absolute pressure 1 ~ 2MPa, the mass space velocity 1 ~ 8h of carbon four
-1;
Disproportionation catalyst described in step (b) is WO
3/ SiO
2, WO
3charge capacity be 4 ~ 15%, operational condition is: temperature of reaction 300 ~ 450 DEG C, reaction pressure in absolute pressure 1 ~ 4MPa, the mass space velocity 1 ~ 8h of carbon four
-1;
The operational condition of described de-ethylene column: theoretical plate number 100 ~ 120 pieces, tower pressure 1.8 ~ 2.2MPa, tower top temperature-35 ~-30 DEG C, bottom temperature-10 ~-5 DEG C; The operational condition of depropenizer: theoretical plate number 160 ~ 180 pieces, tower pressure 1.7 ~ 1.9MPa, tower top temperature 40 ~ 45 DEG C, bottom temperature 50 ~ 55 DEG C;
In extraction procedure, extraction agent used is the mixed solvent of n-formylmorpholine and methylethylketone, and both weight ratios are 1:1.
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|---|---|---|---|
| CN201210240011.8A CN103539613B (en) | 2012-07-12 | 2012-07-12 | The production method of propylene |
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|---|---|
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| CN103539613B true CN103539613B (en) | 2016-04-13 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1358697A (en) * | 2000-12-29 | 2002-07-17 | 烟台大学 | Process for separating butane and butylene by methyl-ethyl ketone mixing solvent |
| CN1852878A (en) * | 2003-07-15 | 2006-10-25 | Abb拉默斯环球有限公司 | Processing C4 olefin streams for the maximum production of propylene |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6743958B2 (en) * | 1999-12-24 | 2004-06-01 | Institut Francais Du Petrole | Process for selective production of propylene from hydrocarbon fractions with four carbon atoms |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1358697A (en) * | 2000-12-29 | 2002-07-17 | 烟台大学 | Process for separating butane and butylene by methyl-ethyl ketone mixing solvent |
| CN1852878A (en) * | 2003-07-15 | 2006-10-25 | Abb拉默斯环球有限公司 | Processing C4 olefin streams for the maximum production of propylene |
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