CN103030509A - Method for preparing propylene by C4 and ethylene - Google Patents
Method for preparing propylene by C4 and ethylene Download PDFInfo
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- CN103030509A CN103030509A CN2011103011413A CN201110301141A CN103030509A CN 103030509 A CN103030509 A CN 103030509A CN 2011103011413 A CN2011103011413 A CN 2011103011413A CN 201110301141 A CN201110301141 A CN 201110301141A CN 103030509 A CN103030509 A CN 103030509A
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Abstract
The invention relates to a method for preparing propylene by C4 and ethylene, and mainly solves the problem of the prior art that the utilization ratio of C4 olefin is not high. The method disclosed by the invention has the technical scheme that the C4 and the ethylene are used as raw materials, the raw material C4 is respectively subjected to an extraction process and an isomerization reactor to obtain a butene material flow rich in 2-butene, the butene material flow is mixed with fresh ethylene to obtain a feed material flow, and the product propylene and unreacted materials ethylene and C4 which can be circulated are obtained through a disproportionation reactor, an ethylene removing tower and a propylene removing tower. The method can be used for the industrial production of the propylene prepared by the C4 and the ethylene.
Description
Technical field
The present invention relates to the method for a kind of carbon four and ethene propylene processed.
Background technology
Traditional ethene coproduction and refinery's Propylene recovery method obviously are difficult to satisfy growing propylene demand, adopt the olefin metathesis technology can digest C when not reducing the naphtha cracking severity
4Cut, but and propylene enhancing, thereby the research and development of preparing propylene through olefin disproportionation technology is not only to improving the output of propylene, simultaneously to promoting low value-added C
4The comprehensive utilization of cut all has great significance, and wherein butylene disproportionation involved in the present invention is produced third and rarely made a kind of up-and-coming technique.
Olefin dismutation reaction is called again the olefinic double bonds replacement(metathesis)reaction, it is a kind of conversion of olefines phenomenon of finding the sixties in 20th century, olefin dismutation reaction just becomes a class significant process of conversion of olefines since then, utilizes olefin dismutation reaction to be converted into the higher olefin product of multiple added value by the olefin feedstock that some are comparatively cheap, abundant.Can represent the olefin dismutation reaction process with following formula:
Wherein R and R ' represent alkyl or hydrogen atom.The simplest olefin dismutation reaction is that propylene disproportionation generates ethene and butene-2.
WO2005009929 has reported a kind of working method of the C4 olefin stream for maximum production of propylene, does not add ethene in this method, comprises conventional replacement(metathesis)reaction and automatic replacement(metathesis)reaction.
WO2006052688 has reported the Catalyst And Method of a kind of ethene and butylene metathesis production propylene, and the method makes described charging contact with ethene in the replacement(metathesis)reaction district of containing metathesis catalyst under metathesis reaction conditions and produces propylene.
CN97121426 has reported a kind of preparation method of propylene, and the method is included under the metathesis catalyst existence and makes 2-amylene and ethylene reaction, and above-mentioned catalyzer contains a kind of element at least, the compound of VIb, VIIb or VIII group 4 transition metal in the periodictable.
All there is the not high problem of C 4 olefin utilization ratio in method in the above document when being used for the propylene reaction processed of carbon four and ethene.
Summary of the invention
Technical problem to be solved by this invention is the not high problem of C 4 olefin utilization ratio that exists in the prior art, and a kind of new carbon four and the method for ethene propylene processed are provided.When the method is used for carbon four and ethene propylene reaction processed, has the high advantage of C 4 olefin utilization ratio.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: the method for a kind of carbon four and ethene propylene processed take carbon four and ethene as raw material, may further comprise the steps:
(a) carbon four raw materials obtain olefin stream I after extraction procedure is removed Trimethylmethane in the raw material and normal butane;
(b) olefin stream I and isomerization catalyst contact reacts obtain being rich in the stream I I of 2-butylene;
(c) fresh ethylene outside stream I I and the battery limit (BL) is mixed by obtaining stream I II after the sorbent treatment;
(d) stream I II and disproportionation catalyst contact reacts obtain containing the stream I V of product propylene, unreacted ethene and carbon four;
(e) stream I V enters and takes off ethylene column, and cat head obtains ethene, and tower reactor obtains containing the logistics V of propylene and carbon four;
(f) logistics V enters depropenizer, and cat head obtains the product propylene, and tower reactor obtains carbon four.
In the technique scheme, described in the step (a) in the extraction procedure preferred version of used extraction agent be the mixed solvent of n-formylmorpholine and methylethylketone, both weight ratios are 1: 1; The preferred version of the isomerization catalyst described in the step (b) is Ni/Al
2O
3, the charge capacity of Ni is 5～20%, and the preferred version of operational condition is 40～60 ℃ of temperature of reaction, and reaction pressure is in absolute pressure 1～2MPa, the mass space velocity 1～8h of carbon four
-1The preferred version of sorbent material is BASFSelexsorb CD and COS described in the step (c), and the weight ratio of BASF Selexsorb CD and COS is 2: 1; The preferred version of disproportionation catalyst is WO described in the step (d)
3/ SiO
2, WO
3Charge capacity be 4～15%, the preferred version of operational condition is 250～350 ℃ of temperature of reaction, reaction pressure is in absolute pressure 1～4MPa, the mass space velocity 1～8h of carbon four
-1Take off the preferred version of ethylene column operational condition: 100～120 of theoretical plate numbers, tower are pressed 1.8～2.2MPa, tower top temperature-35～-30 ℃, tower reactor temperature-10～-5 ℃; The preferred version of depropenizer operational condition: 160～180 of theoretical plate numbers, tower is pressed 1.7～1.9MPa, 40～45 ℃ of tower top temperatures, 50～55 ℃ of tower reactor temperature.
The present invention is by increasing extraction procedure with alkene and alkane separation before reactor, the utilization ratio of energy Effective Raise C 4 olefin and the reasonable butane that reclaims, by getting the Balancing Analysis of Charges that uses the extraction cells front and back, produce the required mixed c 4 raw material of identical output propylene and can reduce by 7%, improve the utilization ratio of carbon four raw materials, obtained preferably technique effect.
Description of drawings
Fig. 1 is the schema for the production of the technological system of the present invention of the C 4 olefin material of propylene.
1 is carbon four raw materials among Fig. 1, and 2 is Trimethylmethane and normal butane, and 3 is C 4 olefin, and 4 for being rich in the C 4 olefin of 2-butylene, 5 fresh ethylene, 6 is mixing raw material, and 7 is the impurity of removing, and 8 is the raw material feed stream, 9 is reaction product, and 10 is ethene tail gas, and 11 is propylene product, 12 is carbon fourth officer product, and 13 is that cyclic carbon four, 14 is cyclic ethylene, 21 is extraction procedure, and 22 is isomerizing reactor, and 23 is the impurity treater, 24 is disproportionation reactor, and 25 for taking off ethylene column, and 26 is depropenizer.
With reference to Fig. 1, method of the present invention briefly is expressed in the schema.
As shown in Figure 1, carbon four raw materials 1 obtain alkene C 4 olefin logistics 3 after extraction procedure is removed Trimethylmethane in the raw material and normal butane 2, olefin stream 3 and isomerization catalyst contact reacts obtain being rich in the C 4 olefin logistics 4 of 2-butylene, after mixing, fresh ethylene outside material 4 and the battery limit (BL) forms mixing raw material 6, mixing raw material is removed the impurity 7 in the raw material after sorbent treatment, impurity comprises water, alcohol, ether isopolarity material, pretreated material 8 and disproportionation catalyst contact reacts, reaction obtains target product propylene and unreacted ethene and C 4 olefin, reaction product 9 is through taking off ethylene column, most ethene that cat head obtains reuse as reaction raw materials with the form of cyclic ethylene 14, all the other are with the ethene exhaust emissions, the component that tower reactor obtains enters depropenizer and processes, cat head obtains polymerization-grade propylene, the carbon four that tower reactor obtains mainly reuses as reaction raw materials with the form of cyclic carbon 4 13, and remaining carbon fourth officer product can be used as liquefied gas and uses.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
By technical process shown in Figure 1, extraction agent is the mixed solvent of n-formylmorpholine and methylethylketone, and weight ratio is 1: 1; Catalyzer in the isomerization reactor is 12%Ni/Al
2O
3, operational condition: 50 ℃ of temperature of reaction, reaction pressure be in absolute pressure 1.5MPa, the mass space velocity 2h of carbon four
-1Sorbent material in the impurity treater is BASF Selexsorb CD and COS, and both weight ratios are 2: 1, and the disproportionation catalyst in the disproportionation reactor is 8%WO
3/ SiO
2, operational condition is: 300 ℃ of temperature of reaction, reaction pressure be in absolute pressure 3MPa, the mass space velocity 2h of carbon four
-1The material balance of reaction is as shown in table 2.
[embodiment 2～6]
Each condition and step by embodiment 1 are reacted, and just change different operating parameterss, and its reaction conditions is listed in table 1, and the material balance of reaction is as shown in table 2.
Annotate: the data of isomerization catalyst and disproportionation catalyst all are the quality percentage composition of active ingredient
[comparative example 1]
By technical process shown in Figure 1, just do not pass through extraction procedure.Catalyzer in the isomerization reactor is 12%Ni/Al
2O
3, operational condition: 50 ℃ of temperature of reaction, reaction pressure be in absolute pressure 1.5MPa, the mass space velocity 2h of carbon four
-1Sorbent material in the impurity treater is BASF Selexsorb CD and COS, and both weight ratios are 2: 1, and the disproportionation catalyst preferred version in the disproportionation reactor is 8%WO
3/ SiO
2, operational condition is: 300 ℃ of temperature of reaction, reaction pressure be in absolute pressure 3MPa, the mass space velocity 2h of carbon four
-1The material balance of reaction is as shown in table 2.
Table 2 material balance
Claims (7)
1. the method for a carbon four and ethene propylene processed take carbon four and ethene as raw material, may further comprise the steps:
(a) carbon four raw materials obtain olefin stream I after extraction procedure is removed Trimethylmethane in the raw material and normal butane;
(b) olefin stream I and isomerization catalyst contact reacts obtain being rich in the stream I I of 2-butylene;
(c) fresh ethylene outside stream I I and the battery limit (BL) is mixed by obtaining stream I II after the sorbent treatment;
(d) stream I II and disproportionation catalyst contact reacts obtain containing the stream I V of product propylene, unreacted ethene and carbon four;
(e) stream I V enters and takes off ethylene column, and cat head obtains ethene, and tower reactor obtains containing the logistics V of propylene and carbon four;
(f) logistics V enters depropenizer, and cat head obtains the product propylene, and tower reactor obtains carbon four.
2. the method for carbon four according to claim 1 and ethene propylene processed is characterized in that described in the step (a) that used extraction agent is the mixed solvent of n-formylmorpholine and methylethylketone in the extraction procedure, and both weight ratios are 1: 1.
3. the method for carbon four according to claim 1 and ethene propylene processed is characterized in that the isomerization catalyst described in the step (b) is Ni/Al
2O
3, the charge capacity of Ni is 5～20%, operational condition: 40～60 ℃ of temperature of reaction, reaction pressure be in absolute pressure 1～2MPa, the mass space velocity 1～8h of carbon four
-1
4. the method for carbon four according to claim 1 and ethene propylene processed is characterized in that the sorbent material described in the step (c) is BASF Selexsorb CD and COS, and the weight ratio of BASF Selexsorb CD and COS is 2: 1.
5. the method for carbon four according to claim 1 and ethene propylene processed is characterized in that disproportionation catalyst is WO described in the step (d)
3/ SiO
2, WO
3Charge capacity be 4～15%, operational condition is: 250～350 ℃ of temperature of reaction, reaction pressure be in absolute pressure 1～4MPa, the mass space velocity 1～8h of carbon four
-1
6. the method for carbon four according to claim 1 and ethene propylene processed is characterized in that the ethene and the carbon four that obtain in step (e) and the step (f) utilize as reaction raw materials again with the form of cyclic ethylene and cyclic carbon four.
7. the method for carbon four according to claim 1 and ethene propylene processed, the operational condition that it is characterized in that taking off ethylene column: 100～120 of theoretical plate numbers, tower is pressed 1.8～2.2MPa, tower top temperature-35～-30 ℃, tower reactor temperature-10～-5 ℃; The operational condition of depropenizer: 160～180 of theoretical plate numbers, tower is pressed 1.7～1.9MPa, 40～45 ℃ of tower top temperatures, 50～55 ℃ of tower reactor temperature.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105585401A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Method for producing propylene |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1235947A (en) * | 1998-03-27 | 1999-11-24 | Basf公司 | Preparation of olefins |
| CN1465435A (en) * | 2002-06-21 | 2004-01-07 | 中国科学院大连化学物理研究所 | Catalyst for preparing propene at low temp. from ethylene and butylene, proparation process and use thereof |
| 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 |
| CN101679146A (en) * | 2007-06-14 | 2010-03-24 | 利安德化学技术有限公司 | Propylene production |
| CN101827804A (en) * | 2007-10-15 | 2010-09-08 | 巴斯夫欧洲公司 | Method for isomerizing olefins |
-
2011
- 2011-09-29 CN CN201110301141.3A patent/CN103030509B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1235947A (en) * | 1998-03-27 | 1999-11-24 | Basf公司 | Preparation of olefins |
| CN1465435A (en) * | 2002-06-21 | 2004-01-07 | 中国科学院大连化学物理研究所 | Catalyst for preparing propene at low temp. from ethylene and butylene, proparation process and use thereof |
| 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 |
| CN101679146A (en) * | 2007-06-14 | 2010-03-24 | 利安德化学技术有限公司 | Propylene production |
| CN101827804A (en) * | 2007-10-15 | 2010-09-08 | 巴斯夫欧洲公司 | Method for isomerizing olefins |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105585401A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Method for producing propylene |
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