CN102417431A - N-butene fixed bed catalytic isomerization method - Google Patents
N-butene fixed bed catalytic isomerization method Download PDFInfo
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- CN102417431A CN102417431A CN2011103126347A CN201110312634A CN102417431A CN 102417431 A CN102417431 A CN 102417431A CN 2011103126347 A CN2011103126347 A CN 2011103126347A CN 201110312634 A CN201110312634 A CN 201110312634A CN 102417431 A CN102417431 A CN 102417431A
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- butene
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/584—Recycling of catalysts
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Abstract
The invention provides an n-butene fixed bed catalytic isomerization method. The method comprises the following steps of: exchanging heat between an n-butene raw material and an isobutene-containing raw material till the temperature is 160-400 DEG C, heating to 300-500 DEG C by using a heating furnace, undergoing an n-butene isomerization reaction in the presence of an isomerization catalyst, exchange isomerization reaction heat of n-butene to 40-650 DEG C by using a deep heat exchanger, and compressing with a compressor for separating a product to obtain an isobutene-containing product; and after the n-butene isomerization reaction is undergone for a preset period of time, burning and regenerating a coking catalyst. In the method, n-butenes such as butene-1, maleic, trans-butene and the like in C4 are transformed into isobutene, so that the temperature of a reaction product can be controlled effectively, and the product added value and plant liquid yield of n-butene can be increased effectively; and the method has wide application prospect.
Description
Technical field
The invention provides a kind of n-butene fixed-bed catalytic isomery method, belong to n-butene isomery technical field.
Background technology
Refinery's liquefied gas, C4 behind the ether of ether-based device (MTBE), generally as the liquefied gas commodity, how the n-butene during it is formed utilizes, and has been subjected to increasing concern.
In existing industriallization n-butene fixed-bed catalytic isomery method; Reaction feed and product are through two parallelly connected vertical heat exchanger heat exchange; Because there is the bias current problem in the vertical heat exchanger of two parallel connections, cause temperature higher (general 110 ℃) after the reaction product heat exchange.High-temperature reaction product will adopt the lifting of boosting of high temperature compressed machine, and the volumetric flow rate of compressor is bigger, and the equipment heatproof requires high, and facility investment is big, and process cost is high.
Summary of the invention
The objective of the invention is n-butene to be converted into iso-butylene through fixed-bed catalytic isomery method; Adopt the weldering plate-type heat exchanger simultaneously; And, solve the too high problem of reaction product temperature, and then a kind of n-butene fixed-bed catalytic isomery method is provided through degree of depth heat transfer technology.
The objective of the invention is to realize through following technical scheme:
A kind of n-butene fixed-bed catalytic isomery method comprises:
With n-butene raw material warp and raw material heat exchange to 160～400 of containing iso-butylene ℃,
After process furnace is heated to 300～500 ℃ in the presence of isomerization catalyst; Carry out the n-butene isomerization reaction; Said n-butene isomerization reaction heat is carried out product through compressor compresses again and is separated through after the degree of depth interchanger heat exchange to 40～65 ℃, obtains containing the isomerized products of iso-butylene;
Through after the scheduled time, coked catalyst is carried out coke burning regeneration at said n-butene isomerization reaction.
N-butene fixed-bed catalytic isomery method provided by the invention; N-butenes such as the butene-1 among the C4, maleic and anti-butylene are converted into iso-butylene; Ether-based device is returned in recycling; Can effectively control the temperature of reaction product, and can effectively improve added value of product and factory's liquid receipts of n-butene, be with a wide range of applications.
Description of drawings
Fig. 1 is the schematic flow sheet of the n-butene fixed-bed catalytic isomery method that provides of the specific embodiment of the invention; Label 1 expression feed exchanger among Fig. 1, label 2 expression charging process furnace, label 3 expression reactor drums, flow container is divided in label 4 expression isomerized products suctions port of compressor, label 5 expression isomerized products compressors.
Embodiment
The specific embodiment of the invention provides a kind of n-butene fixed-bed catalytic isomery method, and as shown in Figure 1, this method specifically comprises:
C4 was as raw material after the n-butene fixed-bed catalytic isomery method of this embodiment adopted MTBE ether, and this raw material is formed as follows:
| Title | Content |
| Propylene | 0.5 |
| Propane | 0.02 |
| Trimethylmethane | 6.76 |
| Normal butane | 7.00 |
| Iso-butylene | 0.54 |
| 1-butylene | 22.44 |
| Maleic | 26.4 |
| Anti-butylene | 35.86 |
| |
0.49 |
| Add up to | 100 |
Employed catalyzer is a sieve catalyst, and this catalyzer has following character:
| Character | Index |
| Shape or outward appearance | Bar shaped |
| Main active component | Molecular sieve |
| Size, mm | Φ2～Φ3 |
| Pore volume, ml/g | ＞0.35 |
| Specific surface area, m 2/g | ＞198 |
| Crushing strength, kg/cm2 | ＞220 |
| Bulk density, g/cm3 | 0.5～0.6 |
| Length, cm | 2.0～3.0 |
The catalytic isomerization operational condition that this embodiment is main:
| Condition | The reaction operating mode |
| The warm end temperature difference of interchanger 1 | 141 |
| Process furnace 2 temperature ins | 275 |
| Reactor drum 3 temperature ins, ℃ | 400 |
| The cold-end temperature difference of interchanger 1 | 11 |
| Temperature after the reaction product heat exchange, ℃ | 51 |
The composition of reaction completion product is following:
| Raw material | Present embodiment |
| Ethene | 0.02 |
| Ethane | 0.01 |
| Propylene | 0.81 |
| Propane | 0.02 |
| Trimethylmethane | 6.99 |
| Normal butane | 6.89 |
| Iso-butylene | 27.2 |
| 1-butylene | 12.86 |
| Maleic | 16.02 |
| Anti-butylene | 22.14 |
| More than carbon five reaches | 7.04 |
| Add up to | 100 |
| Conversion rate of products | 40.2％ |
| Selectivity | 79.5％ |
Conversion rate of products and selectivity are calculated based on following formula:
The comparative example:
Adopt the raw material identical with embodiment, reach under the situation of analogous products composition, reaction conditions is following:
| Condition | The reaction operating mode |
| The warm end temperature difference of interchanger 1 | 180 |
| Process furnace 2 temperature ins | 236 |
| Reactor drum 3 temperature ins, ℃ | 400 |
| The cold-end temperature difference of interchanger 1 | 70 |
| Temperature after the reaction product heat exchange, ℃ | 110 |
Because the optimization of reaction conditions is compared with the comparative example after the employing inventive embodiments:
Result in the analytical table, improved n-butene fixed-bed catalytic isomerization processes has been compared following advantage with comparative example's n-butene isomery device:
1, adopt in the claim 4 behind the weldering plate-type heat exchanger, compressor inlet temperature reduces by 59 ℃, and comparison is than the little 104m of suction port of compressor flow of embodiment
3/ min, facility investment is little;
2, adopt in the claim 4 behind the weldering plate-type heat exchanger, compressor inlet temperature reduces by 59 ℃, and the suction port of compressor flow is wanted little 104m
3/ min, the little 520kW of shaft power saves process cost;
3, according to improved method in the claim 4,5, the process furnace temperature in raises 39 ℃, reduces process furnace load 2500kW, can save standard fuel 215kg/h.
The condition of in reactor drum, carrying out catalyst regeneration is following:
When reaction conversion ratio＜35%, need carry out the catalyzer coke burning regeneration.
The nitrogen that contains 0.2% oxygen and 99.8% is warming up to 600 ℃ from 220 ℃ always, and corresponding oxygen level brings up to 10% gradually, carries out the degree of depth and burns.
Burning process generally needs 2～3 days.
The mode mode that turnover has been reacted with reactant flow of burning air turnover reactor drum is identical, all adopts the enterprising mode that goes out down, does not exist reactor bed to blow the problem of turning over, and reactor drum need not be provided with to be prevented blowing cover plate, and the internals simplicity of design is effectively practiced thrift investment.
The technical scheme that adopts present embodiment to provide; Through n-butenes such as the butene-1 among the C4, maleic and anti-butylene are converted into iso-butylene; Ether-based device is returned in recycling; Can effectively control the temperature of reaction product, and can effectively improve added value of product and factory's liquid receipts of n-butene, be with a wide range of applications.
The above; Be merely the preferable embodiment of the present invention, but protection scope of the present invention is not limited thereto, any technician who is familiar with the present technique field is in the technical scope that the present invention discloses; The variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.
Claims (10)
1. a n-butene fixed-bed catalytic isomery method is characterized in that, comprising:
With n-butene raw material warp and raw material heat exchange to 160～400 of containing iso-butylene ℃;
After process furnace is heated to 300～500 ℃ in the presence of isomerization catalyst; Carry out the n-butene isomerization reaction; Said n-butene isomerization reaction heat is carried out product through compressor compresses again and is separated through after the degree of depth interchanger heat exchange to 40～65 ℃, obtains containing the isomerized products of iso-butylene;
Through after the scheduled time, coked catalyst is carried out coke burning regeneration at said n-butene isomerization reaction.
2. method according to claim 1 is characterized in that, described n-butene raw material is refinery's liquefied gas, C4 behind the ether of ethene cracking gas or MTBE ether-based device, and wherein iso-butylene content is less than 1%, n-butene content＞10%.
3. method according to claim 1 is characterized in that described isomerization reaction carries out in isomerization reactor; Said isomerization reactor comprises two or three axial flow reactors, and when adopting two axial flow reactors, an axial flow reactor is used for isomerization reaction; An axial flow reactor is used for catalyst regeneration; When adopting three axial flow reactors, two axial flow reactors are used for isomerization reaction, and an axial flow reactor is used for catalyst regeneration.
4. method according to claim 3 is characterized in that, after said isomerization reaction was through 3～30 days, switches and uses another said axial flow reactor, and catalyzer is regenerated.
5. method according to claim 1 is characterized in that, described heat exchange is carried out heat exchange for adopting the weldering plate-type heat exchanger, and the cold-end temperature difference scope is 5～20 ℃ after the heat exchange, and the compressor inlet temperature scope is 45～65 ℃, and adopts the cold conditions compressor.
6. method according to claim 5 is characterized in that, in the process that adopts said weldering plate-type heat exchanger, the hot junction temperature range is 130～160 ℃ after the reaction feed heat exchange.
7. method according to claim 1 is characterized in that, the burnt O that contains 0.2～10%mol that adopts of said coke burning regeneration
2N with 90～99.8%mol
2Burn.
8. method according to claim 1, the temperature when it is characterized in that said coke burning regeneration is 220～600 ℃.
9. according to any described method in the claim 1 to 8; It is characterized in that; In the process of carrying out the catalyzer coke burning regeneration, resurgent gases gets into from reactor head, and regeneration product goes out and identical with the mode of when reaction reactant flow turnover reactor drum from reactor bottom.
10. method according to claim 1 is characterized in that, said catalyzer adopts the molecular sieve catalyst series, and the reaction velocity scope is 0.5～10h
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103755513A (en) * | 2013-12-24 | 2014-04-30 | 山东滨州裕华化工厂有限公司 | Process for recovering C4 from etherified liquefied gas |
| CN103755512A (en) * | 2013-12-24 | 2014-04-30 | 山东滨州裕华化工厂有限公司 | Process for separating C4 fraction from etherified liquefied gas |
| CN105585411A (en) * | 2014-10-21 | 2016-05-18 | 中国石油化工股份有限公司 | Hydrogenation method of butadiene extraction tail gas |
| CN103755511B (en) * | 2013-12-24 | 2016-09-14 | 山东滨州裕华化工厂有限公司 | The technique that after ether, liquefied gas produces and separates C 4 fraction |
| CN109851465A (en) * | 2017-11-30 | 2019-06-07 | 中国石油化工股份有限公司 | A kind of method and device of n-butene isomerization |
| CN109851464A (en) * | 2017-11-30 | 2019-06-07 | 中国石油化工股份有限公司 | A kind of method and device of n-butene isomerization |
| CN110105158A (en) * | 2018-10-12 | 2019-08-09 | 新疆寰球工程公司 | After a kind of ether in carbon four n-butene isomerization processing method |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103755513A (en) * | 2013-12-24 | 2014-04-30 | 山东滨州裕华化工厂有限公司 | Process for recovering C4 from etherified liquefied gas |
| CN103755512A (en) * | 2013-12-24 | 2014-04-30 | 山东滨州裕华化工厂有限公司 | Process for separating C4 fraction from etherified liquefied gas |
| CN103755513B (en) * | 2013-12-24 | 2016-06-15 | 山东滨州裕华化工厂有限公司 | Liquefied gas restoring C4 technique after a kind of ether |
| CN103755511B (en) * | 2013-12-24 | 2016-09-14 | 山东滨州裕华化工厂有限公司 | The technique that after ether, liquefied gas produces and separates C 4 fraction |
| CN105585411A (en) * | 2014-10-21 | 2016-05-18 | 中国石油化工股份有限公司 | Hydrogenation method of butadiene extraction tail gas |
| CN109851465A (en) * | 2017-11-30 | 2019-06-07 | 中国石油化工股份有限公司 | A kind of method and device of n-butene isomerization |
| CN109851464A (en) * | 2017-11-30 | 2019-06-07 | 中国石油化工股份有限公司 | A kind of method and device of n-butene isomerization |
| CN109851465B (en) * | 2017-11-30 | 2021-11-19 | 中国石油化工股份有限公司 | Method and device for isomerizing n-butene |
| CN109851464B (en) * | 2017-11-30 | 2021-11-19 | 中国石油化工股份有限公司 | Method and device for isomerizing n-butene |
| CN110105158A (en) * | 2018-10-12 | 2019-08-09 | 新疆寰球工程公司 | After a kind of ether in carbon four n-butene isomerization processing method |
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Application publication date: 20120418 |