CN102872761B - Production device of low-carbon olefins - Google Patents
Production device of low-carbon olefins Download PDFInfo
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- CN102872761B CN102872761B CN201110193474.9A CN201110193474A CN102872761B CN 102872761 B CN102872761 B CN 102872761B CN 201110193474 A CN201110193474 A CN 201110193474A CN 102872761 B CN102872761 B CN 102872761B
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
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Abstract
The invention relates to a production device of low-carbon olefins, mainly solving the problem of low yield of low-carbon olefins in the prior art. The device disclosed herein mainly comprises a first riser 5, a second riser 7, a first disengager 4, a second disengager 8, and a regenerator 15, wherein the outlet of the first riser 5 is connected with the first disengager 4; the top of the first disengager is provided with a product gas outlet, and the bottom is provided with a catalyst outlet which is connected with the second riser7; the outlet of the second riser 7 is connected with the second disengager 8, the top of the second disengager is provided with a product gas outlet, and the bottom is provided with a catalyst outlet which is connected with the regenerator 15; the top of the regenerator 15 is provided with a smoke outlet 17, and the bottom is provided with a catalyst outlet which is connected with the first riser 5 through a regeneration inclined pipe 14. The device disclosed herein well solves the problem and can be used in the industrial production of low-carbon olefins.
Description
Technical field
The present invention relates to a kind of process units of low-carbon alkene.
Technical background
Low-carbon alkene, i.e. ethene and propylene, be two kinds of important basic chemical industry raw materials, its demand is in continuous increase.Usually, ethene, propylene are produced by petroleum path, but due to the limited supply of petroleum resources and higher price, produce ethene by petroleum resources, the cost of propylene constantly increases.In recent years, people start to greatly develop the technology that alternative materials transforms ethene processed, propylene.Wherein, the important alternative materials for light olefin production of one class is oxygenatedchemicals, such as alcohols (methyl alcohol, ethanol), ethers (dimethyl ether, ethyl methyl ether), ester class (dimethyl carbonate, methyl formate) etc., these oxygenatedchemicals can be transformed by coal, natural gas, living beings equal energy source.Some oxygenatedchemicals can reach fairly large production, and as methyl alcohol, can be obtained by coal or natural gas, technique is very ripe, can realize the production scale of up to a million tonnes.Due to the popularity in oxygenatedchemicals source, add the economy transforming and generate light olefin technique, so by the technique of oxygen-containing compound conversion to produce olefine (OTO), be particularly subject to increasing attention by the technique of preparing olefin by conversion of methanol (MTO).
Naphtha is a kind of light-end products, is cut corresponding cut by crude distillation or oil secondary operations and is obtained.Its boiling spread is determined according to need, is generally wider boiling range, as 20-220 DEG C.Naphtha is pyrolysis in tubular furnace preparing ethylene, and propylene and catalytic reforming produce the important source material of benzene,toluene,xylene.As cracking stock, in requiring naphtha to form, the content of alkane and cycloalkane is not less than 70% (volume).Naphtha catalytic pyrolysis preparing low-carbon alkene is then under catalyst existent condition, carries out cracking to obtain the production process of low-carbon alkene to petroleum hydrocarbon.Compare with traditional tube furnace steam heat cracking, this process reaction temperature is about lower than steam cracking reaction 50 ~ 200 DEG C, and energy consumption significantly reduces; Cracking furnace pipe inwall coking rate also can reduce, thus can prolong operation cycle, increases the boiler tube life-span; CO2 emission simultaneously also can reduce, and alleviates pollution, and can adjust the product mix flexibly.
Technology and reactor that a kind of oxygenate conversion is low-carbon alkene is disclosed in US6166282, adopt fast fluidized bed reactor, gas phase is after the lower Mi Xiangfanyingqu of gas speed has reacted, after rising to the fast subregion that internal diameter diminishes rapidly, special gas-solid separation equipment initial gross separation is adopted to go out most entrained catalyst.Due to reaction afterproduct gas and catalyst quick separating, effectively prevent the generation of secondary response.Through analog computation, compared with traditional bubbling fluidization bed bioreactor, needed for this fast fluidized bed reactor internal diameter and catalyst, reserve all greatly reduces.
The multiple riser reaction unit disclosed in CN1723262 with central catalyst return is low-carbon alkene technique for oxygenate conversion, this covering device comprises multiple riser reactor, gas solid separation district, multiple offset components etc., each riser reactor has the port of injecting catalyst separately, be pooled to the Disengagement zone of setting, catalyst and gas product are separated.But there is the lower shortcoming of yield of light olefins in the method.
Disclose a kind of method of methanol production propylene in EP0448000 and EP0882692, first methyl alcohol be converted into DME and water, then mixture is transported to First reactor, and add steam in this reactor.In the first reactor, methyl alcohol and (or) dimethyl ether or its mixture and catalyst exposure react, catalyst adopts the special ZSM-5 catalyst containing ZnO and CdO, reaction temperature 280 ~ 570 DEG C, pressure 0.01 ~ 0.1MPa, preparing with propylene is the product of main hydro carbons.Heavier product is as C
5 +hydrocarbon continues to carry out reacting the hydro carbons be converted into based on propylene in second reactor, after cooling, send separator back to.Product is compressed, refining further after can obtain the chemical grade propylene that purity is 97%.But adopt multiple fixed bed reactors in this technique, because the activity of catalyst limits, therefore need frequent handover operation, and heat-obtaining problem is also very complicated.
US 20070083071 discloses the process that a kind of hydrocarbon catalytic pyrolysis produces ethene, propylene, hydrocarbon feed is converted into the product comprising low-carbon alkene in catalytic cracker, then product stream is separated into C2 ~ C3 alkane, C2 ~ C3 alkene, the three kinds of logistics of C4+ hydrocarbon by series of process, C2 ~ C3 alkane is returned tube cracking furnace and carries out thermal cracking, C4+ hydrocarbon returns catalytic cracker and carries out catalytic pyrolysis, finally obtains the ethene of higher yields, propylene product.The method adopts riser reactor, and reactant residence time is shorter, and low-carbon alkene product once through yield is lower.
Due to naphtha catalytic cracking and preparing olefin by conversion of methanol react object product---low-carbon alkene is identical, and key component kind separately in product is roughly the same, the catalyst system adopted is also roughly the same, and from reaction mechanism angle, all there is the process being cracked into Small molecular hydro carbons by large molecule hydrocarbon or intermediate, therefore these two kinds of technologies are had ready conditions and are coupled.Prior art is still not good to be coupled two kinds of technology.The present invention solves this problem targetedly.
Summary of the invention
Technical problem to be solved by this invention is the problem that the yield of light olefins that exists in prior art is not high, provides a kind of process units of new low-carbon alkene.This device is used for, in the production of low-carbon alkene, having the advantage that yield of light olefins is higher.
For solving the problem, the technical solution used in the present invention is as follows: a kind of process units of low-carbon alkene, mainly comprise the first riser 5, second riser 7, first settler 4, second settler 8, regenerator 15, first riser 5 exports and is connected with the first settler 4, first settler 4 top has product gas outlet, bottom has catalyst outlet and is connected with the second riser 7, second riser 7 exports and is connected with the second settler 8, second settler 8 top has product gas outlet, bottom has catalyst outlet and is connected with regenerator 15, regenerator 15 top has exhanst gas outlet 17, bottom is had catalyst outlet and is connected with the first riser 5 by regenerator sloped tube 14.
In technique scheme, described catalyst comprises ZSM-5 molecular sieve; Described first settler 4, second settler 8 bottom is equipped with stripping zone; Gas product in described first settler 4, second settler 8 shares a centrifugal station by cross-line 6; Described catalyst flow is controlled by guiding valve or plug valve.
ZSM-5 molecular sieve of the present invention can adopt method known in the field, as hydrothermal synthesis method, be prepared, described molecular sieve catalyst optionally load can have the metal of dehydrogenation functionality, the metal of dehydrogenation functionality is selected from least one in IB, IIB, VB, VIB, VIIB in the periodic table of elements or VIII, and the method for the Metal Supported of dehydrogenation functionality on ZSM-5 molecular sieve can be adopted method known in the field, as infusion process or coprecipitation.After the ZSM-5 molecular sieve of load dehydrogenation functionality metal prepares, add binding agent, make mixed slurry, adopt spray drying process to carry out drying and moulding, then the catalyst fines after shaping is placed in roaster and carries out roasting, after cooling, obtain catalyst sample.Binding agent can select SiO
2, Al
2o
3deng.
Adopt device of the present invention, two risers are set, it is low-carbon alkene that first riser is mainly used in naphtha catalytic cracking, second riser is mainly used in converting methanol, and in the first riser, naphtha contact high temperature, highly active regenerated catalyst, transforms and generate low-carbon alkene, simultaneously pre-carbon distribution on a catalyst, the catalyst of pre-carbon distribution enters the second riser after the first settler, contacts with methyl alcohol, the generation low-carbon alkene of high selectivity.In first riser, naphtha pyrolysis also reduces the temperature of regenerated catalyst simultaneously, is conducive to ensureing that methyl alcohol reacts under suitable reaction temperature.Therefore, adopt device of the present invention, not only realize energy-optimised, and methyl alcohol and convert naphtha are prepared low-carbon alkene be coupled, reach the object improving yield of light olefins.
Adopt technical scheme of the present invention: described catalyst comprises ZSM-5 molecular sieve; Described first settler 4, second settler 8 bottom is equipped with stripping zone; Gas product in described first settler 4, second settler 8 shares a centrifugal station by cross-line 6; Described catalyst flow is controlled by guiding valve or plug valve, and low-carbon alkene carbon base absorption rate can reach 58.05% weight, achieves good technique effect.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of device of the present invention.
In Fig. 1,1 is naphtha feed pipeline; 2 is methanol feed line; 3 is the first settler fluidizing agent feeding line; 4 is the first settler; 5 is the first riser; 6 is cross-line; 7 is the second riser; 8 is the second settler; 9 is the second settler gas product pipeline; 10 is the first settler gas product pipeline; 11 is that the first settler catalyst enters the second riser pipeline; 12 is that the second settler catalyst enters regenerator pipeline; 13 is the first settler fluidizing agent feeding line; 14 is regenerator sloped tube; 15 is regenerator; 16 is regenerating medium entrance; 17 is exhanst gas outlet.
The raw material comprising naphtha enters the first riser 5, with catalyst exposure, the product stream generated and catalyst enter the first settler 4, catalyst in first settler 4 enters the second riser 7, with the contact raw being mainly methyl alcohol, the product stream generated and catalyst enter the second settler 8, catalyst in second settler 8 enters regenerator 15 and regenerates, the regenerated catalyst formed returns the first riser 5 through regenerator sloped tube 14, gaseous products logistics in first settler 4 and the second settler 8 enters centrifugal station, obtains the product comprising low-carbon alkene.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Detailed description of the invention
[embodiment 1]
In reaction unit as shown in Figure 1, catalyst is ZSM-5, SiO
2/ Al
2o
3mol ratio is 10, and in catalyst, binding agent mass content is 45%, and ZSM-5 molecular sieve mass content is 45%, loaded Cu/Zn/Co, and the percentage that carried metal quality accounts for catalyst quality is Cu:5.53; Zn:2.76; Co:1.68.The raw material comprising naphtha enters the first riser, with catalyst exposure, the product stream generated and catalyst enter the first settler, catalyst in first settler enters the second riser, contact with methanol feedstock, the product stream generated and catalyst enter the second settler, catalyst in second settler enters regenerator regeneration, the regenerated catalyst formed returns the first riser, gaseous products logistics in first settler and the second settler enters centrifugal station, obtains the product comprising low-carbon alkene.Described first settler 4, second settler (8) bottom is equipped with stripping zone; Gas product in described first settler 4, second settler 8 shares a centrifugal station by cross-line 6; Described catalyst flow is controlled by guiding valve or plug valve.Described regenerated catalyst coke content mass fraction is 0.01%.Naphtha composition is in table 1.In first riser, reaction condition is: reaction temperature is 570 DEG C, and reaction pressure counts 0.01MPa with gauge pressure, and gas phase linear speed is 4 meter per seconds; In second riser, reaction condition is: reaction temperature is 440 DEG C, and reaction pressure counts 0.01MPa with gauge pressure, and gas phase linear speed is 4 meter per seconds.Methyl alcohol and naphtha feed weight ratio are 1: 1.Keep the stability that catalyst flowing controls, gas product adopts online gas chromatographic analysis, and low-carbon alkene carbon base absorption rate is 46.65% weight.
Naphtha typical case composition described in table 1
| Initial boiling point, DEG C | 40 |
| The end point of distillation, DEG C | 162 |
| Positive structure and isoparaffin, % by weight | 65.18 |
| Alkene, % by weight | 0.17 |
| Cycloalkane, % by weight | 28.44 |
| Aromatic hydrocarbons, % by weight | 6.21 |
[embodiment 2]
According to the condition described in embodiment 1 and step, catalyst is ZSM-5, SiO
2/ Al
2o
3mol ratio is 100, loaded Cu/Zn/Co, and the percentage that carried metal quality accounts for catalyst quality is Cu:5.53; Zn:2.76; Co:1.68.Described regenerated catalyst coke content mass fraction is 0.5%.In first riser, reaction condition is: reaction temperature is 670 DEG C, and reaction pressure counts 0.01MPa with gauge pressure, and gas phase linear speed is 10 meter per seconds; In second riser, reaction condition is: reaction temperature is 520 DEG C, and reaction pressure counts 0.01MPa with gauge pressure, and gas phase linear speed is 10 meter per seconds.Methyl alcohol and naphtha feed weight ratio are 2: 1.Keep the stability that catalyst flowing controls, gas product adopts online gas chromatographic analysis, and low-carbon alkene carbon base absorption rate is 51.15% weight.
[embodiment 3]
According to the condition described in embodiment 1 and step, catalyst is ZSM-5, SiO
2/ Al
2o
3mol ratio is 50, loaded Cu/Zn/Co, and the percentage that carried metal quality accounts for catalyst quality is Cu:5.53; Zn:2.76; Co:1.68.Described regenerated catalyst coke content mass fraction is 0.15%.In first riser, reaction condition is: reaction temperature is 640 DEG C, and reaction pressure counts 0.01MPa with gauge pressure, and gas phase linear speed is 7 meter per seconds; In second riser, reaction condition is: reaction temperature is 480 DEG C, and reaction pressure counts 0.01MPa with gauge pressure, and gas phase linear speed is 6 meter per seconds.Methyl alcohol and naphtha feed weight ratio are 3: 1.Keep the stability that catalyst flowing controls, gas product adopts online gas chromatographic analysis, and low-carbon alkene carbon base absorption rate is 58.05% weight.
[embodiment 4]
According to the condition described in embodiment 1 and step, catalyst is ZSM-5, SiO
2/ Al
2o
3mol ratio is 70, loaded Cu/Zn/Co, and the percentage that carried metal quality accounts for catalyst quality is Cu:5.53; Zn:2.76; Co:1.68.Described regenerated catalyst coke content mass fraction is 0.1%.In first riser, reaction condition is: reaction temperature is 650 DEG C, and reaction pressure counts 0.3MPa with gauge pressure, and gas phase linear speed is 5 meter per seconds; In second riser, reaction condition is: reaction temperature is 480 DEG C, and reaction pressure counts 0.3MPa with gauge pressure, and gas phase linear speed is 5 meter per seconds.Methyl alcohol and naphtha feed weight ratio are 2: 1.Keep the stability that catalyst flowing controls, gas product adopts online gas chromatographic analysis, and low-carbon alkene carbon base absorption rate is 50.02% weight.
[embodiment 5]
According to the condition described in embodiment 1 and step, catalyst is ZSM-34, SiO
2/ Al
2o
3mol ratio is 50.Keep the stability that catalyst flowing controls, gas product adopts online gas chromatographic analysis, and low-carbon alkene carbon base absorption rate is 29.65% weight.
[comparative example 1]
According to the condition described in embodiment 3 and step, just the first settler catalyst does not enter the second riser and enters regenerator, and regenerated catalyst 50% enters the first riser, and 50% enters the second riser, and low-carbon alkene carbon base absorption rate is 52.55% weight.
Obviously, adopt device of the present invention, the object improving yield of light olefins can be reached, there is larger technical advantage, can be used in the industrial production of low-carbon alkene.
Claims (3)
1. the production method of a low-carbon alkene, its process units mainly comprises the first riser (5), second riser (7), first settler (4), second settler (8), regenerator (15), first riser (5) outlet is connected with the first settler (4), first settler (4) top has product gas outlet, bottom has catalyst outlet and is connected with the second riser (7), second riser (7) outlet is connected with the second settler (8), second settler (8) top has product gas outlet, bottom has catalyst outlet and is connected with regenerator (15), regenerator (15) top has exhanst gas outlet (17), bottom is had catalyst outlet and is connected with the first riser (5) by regenerator sloped tube (14),
The raw material of naphtha enters the first riser (5), with catalyst exposure, the product stream generated and catalyst enter the first settler (4), catalyst in first settler (4) enters the second riser (7), with the contact raw of methyl alcohol, the product stream generated and catalyst enter the second settler (8), catalyst in second settler (8) enters regenerator (15) regeneration, the regenerated catalyst formed returns the first riser (5) through regenerator sloped tube (14), gaseous products logistics in first settler (4) and the second settler (8) enters centrifugal station, obtain the product comprising low-carbon alkene, first settler (4), the second settler (8) bottom are equipped with stripping zone,
Wherein, catalyst comprises ZSM-5 molecular sieve, and on molecular sieve catalyst, load has the metal of dehydrogenation functionality, and the metal of dehydrogenation functionality is selected from least one in I B in the periodic table of elements, II B, V B, VI B, VII B or VIII race.
2. the production method of low-carbon alkene according to claim 1, is characterized in that the gas product in described first settler (4), the second settler (8) shares a centrifugal station by cross-line (6).
3. the production method of low-carbon alkene according to claim 1, is characterized in that described catalyst flow is controlled by guiding valve or plug valve.
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| US4012455A (en) * | 1974-07-31 | 1977-03-15 | Mobil Oil Corporation | Upgrading refinery light olefins with hydrogen contributor |
| CN1029407C (en) * | 1992-07-16 | 1995-08-02 | 中国石油化工总公司 | Catalytic cracking method for adaptable multieffect hydrocarbons |
| CN101367699B (en) * | 2007-10-31 | 2012-05-09 | 陕西煤化工技术工程中心有限公司 | Preparation of propylene |
| CN101941874A (en) * | 2009-07-06 | 2011-01-12 | 中国石油化工股份有限公司上海石油化工研究院 | Method for producing low-carbon olefins |
| CN102039107A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Parallel cyclic reaction-regeneration device with embedded riser |
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