CN102372534A - Method for preparing light olefins through conversion of oxygen-containing compounds - Google Patents
Method for preparing light olefins through conversion of oxygen-containing compounds Download PDFInfo
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- CN102372534A CN102372534A CN2010102615290A CN201010261529A CN102372534A CN 102372534 A CN102372534 A CN 102372534A CN 2010102615290 A CN2010102615290 A CN 2010102615290A CN 201010261529 A CN201010261529 A CN 201010261529A CN 102372534 A CN102372534 A CN 102372534A
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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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective 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 method for preparing light olefins through conversion of oxygen-containing compounds and mainly aims to solve the problem of poor wear resistance of a fluidized bed catalyst in conventional preparation processes for light olefins through conversion of oxygen-containing compounds. A technical scheme for the invention is as follows: methanol or dimethyl ether is used as a raw material; under the conditions of a reaction temperature of 400 to 600 DEG C, reaction gauge pressure of 0.001 MPa to 0.5 MPa, reaction weight space velocity of 0.1 to 4/h and a weight ratio of water to methanol or dimethyl ether of 0.1-3:1, raw materials contact with a catalyst through a catalyst bed layer, and light olefins are produced by reaction of the raw materials with the catalyst; the catalyst used therein is a fluidized bed catalyst containing a wear-resisting agent. Utilization of the technical scheme enables the problem mentioned above to be well overcome, and the invention is applicable to industrial production of light olefins through conversion of oxygen-containing compounds.
Description
Technical field
The present invention relates to a kind of method of converting oxygen-containing compound to low-carbon olefins.
Background technology
Low-carbon alkene industry has critical role as the tap of petrochemical industry in the national economic development.Along with the development of society, the market requirement of China's low-carbon alkene sharply increases, and the import volume of low-carbon alkene and derived product thereof increases year by year, and the home products share of market is less than half the.
Preparing light olefins from methanol is meant the Technology of utilizing methyl alcohol under catalyst action, to generate low-carbon alkenes such as ethene, propylene.The preparing light olefins from methanol technology is the new technology route that non-oil resource is produced Chemicals, has become one of new forms of energy resource technical study exploitation focus.
Molecular sieve is applied in field of petrochemical industry widely owing to have good shape selective catalysis performance and thermostability preferably.When molecular sieve is applied to Industrial Catalysis, generally can not adopt 100% molecular sieve to be prepared into catalyst applications in commercial run.Self cohesiveness of molecular sieve is poor, and self granularity is too tiny, even compression molding, intensity also is lower than 20 newton, is difficult to be shaped to the catalyzer that directly applies to commercial run.For fluidized-bed reactor; Because catalyst themselves constantly circulates in reactor drum or turbulence; Friction between granules of catalyst and particle, catalyzer and wall of reactor, catalyzer and revivifier wall, catalyzer and heat collector wall, catalyzer and the transport pipe wall and collision all can make catalyzer levigate and damaged, final form effusion reactive system with fine powder.Fluid catalyst should have certain intensity and wear resistance, thereby satisfies the requirement of commercial run to catalyzer.
The US6509290 patent discloses a kind of method for preparing sieve catalyst, contains molecular sieve in this catalyzer and grinds particle and initial molecule sieve.This grinds particle mainly from the broken particle of Catalyst Production technology and reactive system recycling.This method comprises molecular sieve, original sticker and filler, spray-diredly grinds particle or agglomerate and be mixed together from the non-original particle that grinds of reaction unit.This mixture is dry, form the finished product granules of catalyst.In order to increase the intensity of granules of catalyst, this grinds particle and is substantially free of coke.
The CN1791463 patent discloses a kind of method for preparing sieve catalyst, this method comprise with molecular sieve, liquid and effectively the big exsiccant sieve catalyst of hardening capacity be mixed together the formation slurry, roasting behind dry this slurry forms wear-resistant catalyst.
Although more existing patents have related to the preparation method of fluid catalyst, the abrasive wear resistance of fluid catalyst is lower, and the energy consumption in the preparation process needs further to reduce.
Summary of the invention
Technical problem to be solved by this invention is the relatively poor problem of using in the existing converting oxygen-containing compound to low-carbon olefins technology of molecular sieve fluid bed catalyst wear resisting property; A kind of method of new converting oxygen-containing compound to low-carbon olefins is provided, and the catalyzer that this method is used has the high advantage of abrasive wear resistance.
For addressing the above problem, the technical scheme that the present invention adopts is following: with methyl alcohol or dme is raw material, is 400～600 ℃ in temperature of reaction, and the reaction gauge pressure is 0.001MPa～0.5MPa, and the reaction weight space velocity is 0.1～4 hour
-1, water/methyl alcohol or dme weight ratio are under 0.1～3: 1 the condition, raw material contacts with catalyzer through beds; Reaction generates low-carbon alkene; Used catalyzer is a kind of binder free catalyzer, in the finished catalyst weight percentage after the roasting, comprises following material composition:
A.10～60% molecular sieve;
B.10～40% sticker;
C.10～60% matrix;
D.0.1～30% anti-wear agent;
Wherein, anti-wear agent is for being selected from bar-shaped or needle-like material, and its length-to-diameter ratio is 2～20, and in the finished catalyst weight after the roasting, anti-wear agent content is 0.5～20%.
In the technique scheme; The anti-wear agent preferred version is to be selected from a kind of in asbestos, ceramic fiber, spun glass, the wollastonite mineral; Length-to-diameter ratio preferable range bar-shaped or needle-like material is 5～10, and in the finished catalyst weight after the roasting, anti-wear agent content preferable range is 1～15%; The molecular sieve preferred version is to be selected from least a in ZSM-5, mordenite, β zeolite, Y zeolite, MCM-22, ZSM-5/ mordenite, ZSM-5/ β zeolite, the ZSM-5/Y zeolite; The crystal particle diameter preferable range of molecular sieve is between 0.1～5um; The density preferable range of molecular sieve is at 0.5～2 grams per milliliter; In the finished catalyst weight after the roasting, the molecular sieve content preferable range is 20～50%; The sticker preferred version is to be selected from least a in silicon sol or the aluminium colloidal sol, and in the finished catalyst weight after the roasting, the binder content preferable range is 5～20%; The substrate material preferred version is to be selected from least a in kaolin, calcined kaolin, zeyssatite, wilkinite, the carclazyte, and in the finished catalyst weight after the roasting, the matrix material content preferable range is 10～50%.The temperature of reaction preferable range is 450～600 ℃; The reaction pressure preferable range is 0.01MPa～0.2Mpa; Reaction weight space velocity preferable range is 0.2～2 hour
-1Water/light oil weight ratio preferable range is 0.2～2: 1.
The preparation method of the fluid catalyst that the present invention uses may further comprise the steps: (a) molecular sieve, sticker, material, expanding agent, dispersion agent and liquid medium homodisperse are formed suspension-s, the suspension-s solids content is 10～50%; (b) adopt in the method control suspension-s of high speed shear or circulating emulsion raw meal particle size between 0.5～5um; (c) in suspension-s, add anti-wear agent, restir is even; (d) this suspension-s of spraying drying forms microspherical catalyst; (e) this microspherical catalyst of roasting forms finished catalyst.
In the technique scheme; The expanding agent preferred version is to be selected from least a in methylcellulose gum, Z 150PH, sesbania powder, Zulkovsky starch, the CNT; In contained molecular sieve weight in the finished catalyst weight after the roasting, the consumption preferable range of expanding agent is 0.1～10%; The dispersion agent preferred version is to be selected from least a in Triammonium citrate, ammonium oxalate, volatile salt, the bicarbonate of ammonia, and in contained molecular sieve weight in the finished catalyst weight after the roasting, the consumption preferable range of dispersion agent is 0.01～10%; The middle material particular diameter preferable range of method controlled step (b) that adopts high speed shear or circulating emulsion is between 0.1～2um; (a) step suspension-s solids content preferable range is 10～50%; The spray shaping condition is 180～300 ℃ of inlet temperatures, 100～160 ℃ of temperature outs, and 5000～15000 rev/mins of centrifugal rotational speeds, exit whirlwind pressure reduction is 0.5～1.0KPa, input speed is 0.5～5 kilogram/hour; The catalyzer of spraying drying preparation is through after the high-temperature roasting; The particulate median size is between 50～90um, and specific surface area is between 100～300, and mean pore size is between 1～20nm; Density between 0.6～1.2 grams per milliliter, abrasion index 0.01～1.2 weight %/hour; Sticker accounts for 10～40 weight % in the catalyzer that makes; Molecular sieve accounts for 10～50 weight %; Body material accounts for 10～80 weight %.
In the technical scheme of the present invention, the catalyzer of employing special is selected from bar-shaped or the needle inorganic material through adding in the preparation process; Its length-to-diameter ratio is 2～20 anti-wear agent, and after emulsify at a high speed was sheared, slurry was even; Each component homodisperse in the catalyzer is difficult for reuniting, and suspension liquid is difficult for layering or deposition; The catalyst surface of preparing is smooth, and sphericity is high, can combine closely between each component, each material; The finished catalyst that obtains has higher abrasive wear resistance, its abrasion index can reach 0.001 weight %/hour.With methyl alcohol is raw material, at 480 ℃, weight space velocity 1h
-1, water/methyl alcohol weight ratio 1: 1, pressure is to check and rate under the condition of 0.02MPa, the weight ethylene yield reaches 25%, the propylene weight yield reaches 50%, diene weight total recovery is 75%, has obtained better technical effect.
Through embodiment the present invention is done further elaboration below, but be not limited only to present embodiment.
Embodiment
[embodiment 1]
Take by weighing 500 gram kaolin, sesbania powder 2 grams and length-to-diameter ratio and be 8 wollastonite 20 grams, after mixing, add 2000 gram zero(ppm) water; With high-speed shearing machine high speed shear 30 minutes, add 400 gram sial molecular ratios then and be 30 ZSM-5 molecular sieve, high speed shear is 30 minutes again; Aluminium colloidal sol 500 grams that add salic 20 weight % then; Continue high speed shear 30 minutes, and added 1 gram Triammonium citrate again, continue high speed shear after 30 minutes; With the granularity of this suspension-s of laser particle analyzer mensuration, its median size is 2 microns.Use the spray-drier spray shaping, the spray shaping condition is: 240 ℃ of inlet temperatures, and 120 ℃ of temperature outs, 10000 rev/mins of centrifugal rotational speeds, exit whirlwind pressure reduction is 0.7KPa, input speed is 1 kilogram/hour.Particle behind the spray shaping adopts temperature-programmed calcination, burns 3 hours at 400 ℃, and 650 ℃ were burnt 3 hours then.The catalyzer that obtains after the roasting is measured granularity with laser particle analyzer, and its median size is 68 microns, and specific surface area is 305m
2/ gram, mean pore size is 3.2nm, density of catalyst be at 0.9 grams per milliliter, adopt abrasion appearance mensuration wear index be 0.001 weight %/hour.
[embodiment 2～10]
According to the method for embodiment 1, adopt the batching and the preparation condition of table 1, wherein silicon sol is for containing silicon-dioxide 40 weight %, and it is as shown in table 1 to make the fluid catalyst performance.
[embodiment 11]
The method of getting 200 gram embodiment 1 makes fluidized-bed ZSM-5 catalyzer, puts into internal diameter and be 50 millimeters fluidized-bed reactor, is raw material with methyl alcohol, at 480 ℃, weight space velocity 1h
-1, water/methyl alcohol weight ratio 1: 1, pressure is to check and rate under the condition of 0.02MPa, the weight ethylene yield reaches 25%, the propylene weight yield reaches 50%, products distribution is seen table 3, diene weight total recovery is 75%.
Table 3
| Products distribution | Product weight yield (%) |
| Methane | 5.2 |
| Ethane | 2.1 |
| Ethene | 25.0 |
| Propane | 3.5 |
| Propylene | 50.0 |
| Butane | 3.7 |
| Butylene | 3.6 |
| Carbon five above cuts | 4.8 |
| Other | 2.1 |
[embodiment 12]
Method according to embodiment 9 makes ZSM-5/ beta zeolite coexisting sieve catalyst, and the employing dme is a raw material, and range of reaction temperature is 480 ℃, and reaction pressure is 0.02MPa, and weight space velocity is 1 hour
-1, water/methyl alcohol weight ratio is 1: 1, and obtaining the weight ethylene yield is 29%, and the propylene weight yield is 48%, and diene weight total recovery is 77%.
[embodiment 13～16]
Getting the catalyzer of embodiment 1,2,3 and 4 preparations respectively, press the examining method of embodiment 11, is that 480 ℃, water/methyl alcohol weight ratio are that 3: 1, weight space velocity were followed successively by respectively 2 hours in temperature of reaction
-11 hour
-10.8 hour
-1With 0.25 hour
-1Condition under check and rate, the result sees table 4.
[embodiment 17～20]
Getting the catalyzer of embodiment 5,6,7 and 8 preparations respectively, press the examining method of embodiment 12, is that 3: 1, weight space velocity are 0.5 hour in water/methyl alcohol weight ratio
-1, temperature of reaction is followed successively by 400 ℃ respectively; 450 ℃; Check and rate under the condition of 550 ℃ and 600 ℃, the result sees table 4.
[embodiment 21～24]
Getting the catalyzer of embodiment 9,10,1 and 2 preparations respectively, press the examining method of embodiment 11, is 0.5 hour at weight space velocity
-1, temperature is that 480 ℃, water/methanol quality were followed successively by 4: 1 than respectively; 2: 1; 0.5: 1 and condition under check and rate at 0.1: 1, the result sees table 4.
[embodiment 25～28]
Getting the catalyzer of embodiment 3,4,5 and 6 preparations respectively, press the examining method of embodiment 11, is 0.5 hour at weight space velocity
-1, temperature of reaction is 450 ℃, water/dme weight ratio 3: 1, reaction pressure is followed successively by 0.01MPa respectively; 0.05MPa; 0.1MPa with check and rate under the condition of 0.2MPa, the result sees table 4.
Table 4
| Embodiment | Yield of ethene (weight %) | Propene yield (weight %) | Diene yield (weight %) |
| Embodiment 13 | 26.1 | 45.3 | 71.4 |
| Embodiment 14 | 25.3 | 47.0 | 72.3 |
| Embodiment 15 | 26.0 | 47.8 | 73.8 |
| Embodiment 16 | 27.1 | 49.3 | 76.4 |
| Embodiment 17 | 24.2 | 41.6 | 65.8 |
| Embodiment 18 | 25.3 | 43.5 | 68.8 |
| Embodiment 19 | 30.5 | 45.2 | 75.7 |
| Embodiment 20 | 31.2 | 42.2 | 73.4 |
| Embodiment 21 | 26.5 | 48.8 | 74.3 |
| Embodiment 22 | 27.6 | 46.5 | 74.1 |
| Embodiment 23 | 25.4 | 46.3 | 71.7 |
| Embodiment 24 | 25.1 | 44.8 | 69.9 |
| Embodiment 25 | 27.5 | 45.2 | 72.7 |
| Embodiment 26 | 27.8 | 46.3 | 74.1 |
| Embodiment 27 | 27.2 | 46.5 | 73.7 |
| Embodiment 28 | 28.7 | 47.2 | 75.9 |
Claims (6)
1. the method for a converting oxygen-containing compound to low-carbon olefins is a raw material with methyl alcohol or dme, is 400～600 ℃ in temperature of reaction, and the reaction gauge pressure is 0.001MPa～0.5MPa, and the reaction weight space velocity is 0.1～4 hour
-1, water/raw material weight ratio is under 0.1～3: 1 the condition, raw material contacts with catalyzer through beds; Reaction generates low-carbon alkene; Used catalyzer is the fluidized-bed sieve catalyst, and in the finished catalyst weight percentage after the roasting, catalyzer comprises following material composition:
A.10～60% molecular sieve;
B.2～40% sticker;
C.10～60% matrix;
D.0.1～30% anti-wear agent;
Wherein, anti-wear agent is for being selected from bar-shaped or the needle inorganic material, and its length-to-diameter ratio is 2～20.
2. the method for converting oxygen-containing compound to low-carbon olefins according to claim 1; It is characterized in that anti-wear agent is to be selected from a kind of in asbestos, ceramic fiber, spun glass, the wollastonite mineral; Length-to-diameter ratio bar-shaped or needle-like material is 3～10; In the finished catalyst weight after the roasting, anti-wear agent content is 1～15%.
3. the method for converting oxygen-containing compound to low-carbon olefins according to claim 1; It is characterized in that at least a in ZSM-5, mordenite, β zeolite, Y zeolite, MCM-22, ZSM-5/ mordenite, ZSM-5/ β zeolite or ZSM-5/Y zeolite of molecular screening; The crystal particle diameter of molecular sieve is between 0.1～20um; The density of molecular sieve is at 0.5～2 grams per milliliter, and in the finished catalyst weight after the roasting, molecular sieve content is 20～50%.
4. the method for converting oxygen-containing compound to low-carbon olefins according to claim 1; It is characterized in that substrate material is to be selected from least a in kaolin, calcined kaolin, zeyssatite, wilkinite, carclazyte or the clay; In the finished catalyst weight after the roasting, matrix material content is 10～50%; Sticker is to be selected from least a in silicon sol or the aluminium colloidal sol, and in the finished catalyst weight after the roasting, binder content is 5～20%.
5. the method for converting oxygen-containing compound to low-carbon olefins according to claim 1; The median size that it is characterized in that granules of catalyst is between 50～90um; Specific surface area is between 100～300; Mean pore size between 1～20nm, density between 0.7～1.4 grams per milliliter, abrasion index 0.001～1.0 weight %/hour.
6. the method for converting oxygen-containing compound to low-carbon olefins according to claim 1 is characterized in that temperature of reaction is 450～600 ℃; Reaction pressure is 0.01MPa～0.2Mpa; The reaction weight space velocity is 0.1～2 hour
-1Water/raw material weight ratio is 0.1～2: 1.
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Cited By (4)
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| WO2014117740A1 (en) * | 2013-01-31 | 2014-08-07 | 上海碧科清洁能源技术有限公司 | Catalyst with high c4 olefin selectivity for preparing olefin from methanol and preparation method thereof |
| WO2014117735A1 (en) * | 2013-01-31 | 2014-08-07 | 上海碧科清洁能源技术有限公司 | Catalyst for preparing olefin from methanol in fluidized bed and preparation method thereof |
| CN105722807A (en) * | 2013-10-31 | 2016-06-29 | 国际壳牌研究有限公司 | Process for converting oxygenates to olefins |
| CN111450874A (en) * | 2020-04-09 | 2020-07-28 | 中国石油大学(北京) | Metal modified mordenite, preparation method thereof and application of metal modified mordenite in preparation of ethylene by catalyzing dimethyl ether |
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| CN111450874A (en) * | 2020-04-09 | 2020-07-28 | 中国石油大学(北京) | Metal modified mordenite, preparation method thereof and application of metal modified mordenite in preparation of ethylene by catalyzing dimethyl ether |
| CN111450874B (en) * | 2020-04-09 | 2021-08-20 | 中国石油大学(北京) | Metal modified mordenite, preparation method thereof and application of metal modified mordenite in preparation of ethylene by catalyzing dimethyl ether |
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