CN103864559B - C3 fraction selective hydrogenation method - Google Patents
C3 fraction selective hydrogenation method Download PDFInfo
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- CN103864559B CN103864559B CN201410084274.3A CN201410084274A CN103864559B CN 103864559 B CN103864559 B CN 103864559B CN 201410084274 A CN201410084274 A CN 201410084274A CN 103864559 B CN103864559 B CN 103864559B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The present invention relates to a kind of C3 fraction selective hydrogenation method, mainly solve in prior art reactor size compared with the problem big, loaded catalyst is many, regeneration gas consumption is big.The present invention is by using a kind of C3 fraction selective hydrogenation method, propine and the C3 fraction of allene molar concentration≤25000ppm and hydrogen enter two fixed bed reactors of at least a part of which in the response system including at least three fixed bed reactors in parallel, contact with selective hydrocatalyst, obtain propine molar concentration≤5ppm, the C3 fraction of allene molar concentration≤10ppm, remaining fixed bed reactors preferably solve the problems referred to above for standby or catalyst regeneration technical scheme, can be used in C3 fraction hydrogenation.
Description
Technical field
The present invention relates to a kind of C3 fraction selective hydrogenation method.
Background technology
Existing low-carbon alkene segregation apparatus, either large-scale ethylene plant, or large-scale methanol-to-olefins (MTO) device, its
Reaction generates the removing of propine/allene in gas, when need not reclaim propine/allene, and general employing catalytic hydrogenation method.
Under certain process conditions, spent hydroprocessing catalyst, propine and allene (being referred to as MAPD) is made to be hydrogenated to accordingly
Carbon alkatrienes, thus reach to remove the purpose of propine/allene.Number of patent application is 200910092097.2 to relate to a kind of carbon
Three fraction selective hydrogenation methods, employing carrier is Al2O3Pd and Ag catalyst removal C3 fraction in MAPD.Work as carbon
After three selective hydrogenation catalysts use certain time, its selectivity declines and is difficult to maintain normal operating, needs at by regeneration
Reason recovers its activity.Number of patent application is 01139822.1 ex-situ regeneration technique relating to hydrogenation catalyst, describes a kind of stone
The outer high temperature of catalyst device used in oil refining plant burns process process engineering for regenerating.Number of patent application is 201110027356
Relate to the renovation process of a kind of novel hydrogenation catalyst, be a kind of conventional coke burning regeneration and chemistry combines adds
The method of hydrogen catalyst ex-situ regeneration.
In prior art, " one opens one for ethylene unit and MTO device C 3 fraction selective hydrogenation and catalyst regeneration flow process employing
Standby " technological process, one be used for hydrogenation reaction, another for regeneration or standby, every hydrogenation reactor catalyst
Loadings is 100%, in regenerative process, needs to consume the regeneration gas of 100%, there is catalyst for hydrogenation loadings many,
The problems such as regeneration gas consumption is big.
The present invention solves the problems referred to above targetedly.
Summary of the invention
The technical problem to be solved be in prior art reactor size compared with big, loaded catalyst is many, regeneration gas
The problem that consumption is big, it is provided that a kind of new C3 fraction selective hydrogenation method.This technique is hydrogenated with for C3 fraction
In, there is reactor size compared with advantage little, that loaded catalyst is few, regeneration gas consumption is little.
For solving the problems referred to above, the technical solution used in the present invention is as follows: a kind of C3 fraction selective hydrogenation method,
The C3 fraction of MAPD molar concentration≤25000ppm and hydrogen enter and include the anti-of at least three fixed bed reactors in parallel
Answer two fixed bed reactors of at least a part of which in system, contact with selective hydrocatalyst, it is thus achieved that propine molar concentration
The C3 fraction of≤5ppm, allene molar concentration≤10ppm, remaining fixed bed reactors are for standby or catalyst again
Raw.
In technique scheme, it is preferable that in described selective hydrocatalyst, active component comprises Pd and Ag, carrier is
Al2O3。
In technique scheme, it is preferable that described C3 fraction and hydrogen enter the reaction system of three fixed bed reactors in parallel
Wherein two fixed bed reactors in system, another fixed bed reactors are used for regenerating, anti-for two fixed beds of hydrogenation
The operation pressure answering device is 1.00～3.40MPaG, and operation temperature is 10～100 DEG C, the liquid in every fixed bed reactors
Volume space velocity is 40～100h-1。
In technique scheme, it is highly preferred that the described operation pressure of two fixed bed reactors for hydrogenation be 1.55～
2.85MPaG, operation temperature is 20～80 DEG C.
In technique scheme, most preferably, the described operation pressure of two fixed bed reactors for hydrogenation be 1.85～
2.55MPaG, operation temperature is 30～60 DEG C.
In technique scheme, it is preferable that when remaining fixed bed reactors regenerate for catalyst, operate pressure
Being 0.4～1.4MPaG, operation temperature is 90～510 DEG C, gas space velocity 200h-1。
In technique scheme, it is highly preferred that when remaining fixed bed reactors regenerate for catalyst, operation pressure
Power is 0.6～1.0MPaG, and operation temperature is 100～510 DEG C.
The technological process of " one open one standby " of prior art is improved at least the technological process of " two open standby " by the present invention,
Separate unit reactor size is reduced, and loaded catalyst declines 25%, and regeneration gas consumption reduces by 50% the most accordingly, obtains
Preferable technique effect.
Below by embodiment, the invention will be further elaborated, but is not limited only to the present embodiment.
Detailed description of the invention
[embodiment 1]
The one energy-saving low-carbon alkene segregation apparatus C_3 hydrogenation reaction regeneration technique that the present invention relates to for production scale is
800000 tons/year of ethylene units.Response system includes that three fixed bed reactors, C3 fraction and hydrogen enter two therein,
Another regenerates for catalyst.In C 3 fraction selective hydrogenation catalysts, active component is Pd and Ag, and carrier is
Al2O3, model is that the mass fraction of BC-L-80, load P d and Ag is respectively 0.2%, 1.4%；Hydrogenation reactor import
C3 fraction contained by MAPD molar concentration≤25000ppm, hydrogenation reactor outlet C3 fraction contained by propine mole dense
Degree ＜ 5ppm, allene molar concentration ＜ 10ppm.Hydrogenation operation pressure is 1.00MPaG, and initial stage operation temperature is
10 DEG C, final operation temperature is 60 DEG C, liquid volume air speed 40h-1；Catalyst regenerative operation pressure is 0.4PaG, the initial stage
Operation temperature is 90 DEG C, and maximum allowable operating temperature (M.A.O.T.) is 510 DEG C, and regeneration gas volume space velocity is 200h-1.Every hydrogenation reactor chi
Very little Ф 900 × 4630mm, the loaded catalyst of three reactors is 6.18m3, regeneration nitrogen flow is 4000kg/h.
[embodiment 2]
According to the condition described in embodiment 1, production scale changes 1,000,000 tons/year of ethylene units into, and simply operating condition changes.
In C 3 fraction selective hydrogenation catalysts, active component is Pd and Ag, and carrier is Al2O3, model is BC-L-83, negative
The mass fraction carrying Pd and Ag is respectively 0.3%, 0.8%；Contained by the C3 fraction of hydrogenation reactor import MAPD mole
Concentration≤25000ppm, hydrogenation reactor outlet C3 fraction contained by propine molar concentration ＜ 5ppm, allene mole is dense
Degree ＜ 10ppm.Hydrogenation operation pressure is 3.40MPaG, and initial stage operation temperature is 30 DEG C, and final operation temperature is
100 DEG C, liquid volume air speed 100h-1；Catalyst regenerative operation pressure is 1.4PaG, and initial stage operation temperature is 100 DEG C,
High Operating Temperature is 510 DEG C, and regeneration gas volume space velocity is 200h-1.Every hydrogenation reactor a size of Ф 1600 × 7650mm,
The loaded catalyst of three reactors is 32.3m3, regeneration nitrogen flow is 5000kg/h.
[embodiment 3]
The one energy-saving low-carbon alkene segregation apparatus C_3 hydrogenation reaction regeneration technique that the present invention relates to for production scale is
600000 tons/year of MTO devices.In C 3 fraction selective hydrogenation catalysts, active component is Pd and Ag, and carrier is Al2O3,
Model is that the mass fraction of BC-L-83, load P d and Ag is respectively 0.5%, 0.2%；The carbon three of hydrogenation reactor import evaporates
Divide contained MAPD molar concentration≤25000ppm, propine molar concentration ＜ contained by the C3 fraction of hydrogenation reactor outlet
5ppm, allene molar concentration ＜ 10ppm.Hydrogenation operation pressure is 2.80MPaG, and initial stage operation temperature is 20 DEG C,
Final operation temperature is 60 DEG C, liquid volume air speed 60h-1；Catalyst regenerative operation pressure is 0.8PaG, initial stage operation temperature
Degree is 100 DEG C, and maximum allowable operating temperature (M.A.O.T.) is 510 DEG C, and regeneration gas volume space velocity is 200h-1.Every hydrogenation reactor is a size of
Ф 2400 × 4970mm, the loaded catalyst of three reactors is 47.2m3, regeneration nitrogen flow is 6000kg/h.
[comparative example 1]
According to the condition described in embodiment 1, use " one open one standby " technique of prior art, the carbon of hydrogenation reactor import
MAPD molar concentration≤25000ppm contained by three fractions, hydrogenation reactor outlet C3 fraction contained by propine molar concentration ＜
5ppm, allene molar concentration ＜ 10ppm.Every hydrogenation reactor a size of Ф 1200 × 5200mm, three reactors
Loaded catalyst is 8.23m3, regeneration nitrogen flow is 8000kg/h.
[comparative example 2]
According to the condition described in embodiment 2, use " one open one standby " technique of prior art, the carbon of hydrogenation reactor import
MAPD molar concentration≤25000ppm contained by three fractions, hydrogenation reactor outlet C3 fraction contained by propine molar concentration ＜
5ppm, allene molar concentration ＜ 10ppm.Every hydrogenation reactor a size of Ф 2000 × 9800mm, three reactors
Loaded catalyst is 43.1m3, regeneration nitrogen flow is 10000kg/h.
[comparative example 3]
According to the condition described in embodiment 3, use " one open one standby " technique of prior art, the carbon of hydrogenation reactor import
MAPD molar concentration≤25000ppm contained by three fractions, hydrogenation reactor outlet C3 fraction contained by propine molar concentration ＜
5ppm, allene molar concentration ＜ 10ppm.Every hydrogenation reactor a size of Ф 2800 × 7300mm, three reactors
Loaded catalyst is 62.9m3, regeneration nitrogen flow is 12000kg/h.
Claims (7)
1. a C3 fraction selective hydrogenation method, propine and the C3 fraction of allene molar concentration≤25000ppm and hydrogen enter two fixed bed reactors of at least a part of which in the response system including at least three fixed bed reactors in parallel, contact with selective hydrocatalyst, obtaining propine molar concentration≤5ppm, the C3 fraction of allene molar concentration≤10ppm, remaining fixed bed reactors are for standby or catalyst regeneration.
The most according to claim 1, C3 fraction selective hydrogenation method, it is characterised in that in described selective hydrocatalyst, active component comprises Pd and Ag, carrier is Al2O3。
C3 fraction selective hydrogenation method the most according to claim 1, it is characterized in that described C3 fraction and hydrogen enter wherein two fixed bed reactors in the response system of three fixed bed reactors in parallel, another fixed bed reactors are used for regenerating, operation pressure for two fixed bed reactors of hydrogenation is 1.00～3.40MPaG, operation temperature is 10～100 DEG C, and the liquid volume air speed in every fixed bed reactors is 40～100h-1。
The most according to claim 3, C3 fraction selective hydrogenation method, it is characterised in that the described operation pressure for two fixed bed reactors of hydrogenation is 1.55～2.85MPaG, operation temperature is 20～80 DEG C.
The most according to claim 4, C3 fraction selective hydrogenation method, it is characterised in that the described operation pressure for two fixed bed reactors of hydrogenation is 1.85～2.55MPaG, operation temperature is 30～60 DEG C.
C3 fraction selective hydrogenation method the most according to claim 1, it is characterised in that when remaining fixed bed reactors regenerate for catalyst, operation pressure is 0.4～1.4MPaG, and operation temperature is 90～510 DEG C, gas space velocity 200h-1。
C3 fraction selective hydrogenation method the most according to claim 6, it is characterised in that when remaining fixed bed reactors regenerate for catalyst, operation pressure is 0.6～1.0MPaG, and operation temperature is 100～510 DEG C.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1974375A (en) * | 2006-12-07 | 2007-06-06 | 中国石油化工股份有限公司 | Fixed bed adsorption reinforced methane water vapor reforming hydrogen producing process and apparatus |
| CN101906015A (en) * | 2009-09-15 | 2010-12-08 | 中国石油天然气股份有限公司 | Carbon three-fraction selective hydrogenation method |
| CN102206132A (en) * | 2011-04-07 | 2011-10-05 | 中国石油天然气股份有限公司 | Carbon three-fraction selective hydrogenation method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1974375A (en) * | 2006-12-07 | 2007-06-06 | 中国石油化工股份有限公司 | Fixed bed adsorption reinforced methane water vapor reforming hydrogen producing process and apparatus |
| CN101906015A (en) * | 2009-09-15 | 2010-12-08 | 中国石油天然气股份有限公司 | Carbon three-fraction selective hydrogenation method |
| CN102206132A (en) * | 2011-04-07 | 2011-10-05 | 中国石油天然气股份有限公司 | Carbon three-fraction selective hydrogenation method |
Non-Patent Citations (1)
| Title |
|---|
| 烷基化反应器单台运行改并联运行在乙苯生产工艺上的应用与推广;唐继育等;《沈阳化工学院学报》;20010630;第15卷(第2期);第116-120页 * |
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