CN102372534B - 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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- CN102372534B CN102372534B CN201010261529.0A CN201010261529A CN102372534B CN 102372534 B CN102372534 B CN 102372534B CN 201010261529 A CN201010261529 A CN 201010261529A CN 102372534 B CN102372534 B CN 102372534B
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- 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
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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, as the tap of petrochemical industry, has very important status in the national economic development.Along with social development, 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 home products share of market is less than half.
Preparing light olefins from methanol refers to the Technology of utilizing methyl alcohol to generate the low-carbon alkene such as ethene, propylene under catalyst action.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, owing to having good shape selective catalysis performance and good thermostability, is widely used in field of petrochemical industry.When molecular sieve is applied to Industrial Catalysis, generally can not adopt 100% molecular sieve to become catalyzer to be applied to commercial run.Self cohesiveness of molecular sieve is poor, and self granularity is too tiny, even compression molding, intensity, also lower than 20 newton, is difficult to be shaped to the catalyzer that directly applies to commercial run.For fluidized-bed reactor, due to catalyzer, this constantly circulates or turbulence in reactor, friction between granules of catalyst and particle, catalyzer and wall of reactor, catalyzer and revivifier wall, catalyzer and heat collector wall, catalyzer and transport pipe wall and collision all can make catalyzer levigate and damaged, the final form effusion reactive system with fine powder.Fluid catalyst should have certain intensity and wear resistance, thereby meets the requirement of commercial run to catalyzer.
US6509290 patent discloses a kind of method of preparing molecular sieve catalyst, contains molecular sieve and grind particle and initial molecule sieve in this catalyzer.This grinds particle mainly from the broken particle of Catalyst Production technique and reactive system recirculation.The method comprises molecular sieve, original binding agent 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 finished product granules of catalyst.In order to increase the intensity of granules of catalyst, this grinds particle and does not basically contain coke.
CN1791463 patent discloses a kind of method of preparing molecular sieve catalyst, the method comprise by molecular sieve, liquid and effectively the large dry molecular sieve catalyst of hardening capacity be mixed together formation slurry, roasting after 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 preparation process needs further to reduce.
Summary of the invention
Technical problem to be solved by this invention is the poor problem of molecular sieve fluid bed catalyst wear resisting property using in existing converting oxygen-containing compound to low-carbon olefins technology, a kind of method of new converting oxygen-containing compound to low-carbon olefins is provided, and the catalyzer that the method is used has advantages of that abrasive wear resistance is high.
For addressing the above problem, the technical solution used in the present invention is as follows: taking methyl alcohol or dme as raw material, be 400～600 DEG C in temperature of reaction, reaction gauge pressure is 0.001MPa～0.5MPa, and reaction weight space velocity is 0.1～4 hour
-1, water/methyl alcohol or dme weight ratio are that under 0.1～3: 1 condition, raw material contacts with catalyzer by beds, reaction generates low-carbon alkene, catalyzer used is a kind of binder free catalyzer, in the finished catalyst weight percentage after roasting, comprises following material composition:
A.10～60% molecular sieve;
B.10～40% binding agent;
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 with the finished catalyst weighing scale after roasting, anti-wear agent content is 0.5～20%.
In technique scheme, anti-wear agent preferred version is the one being selected from asbestos, ceramic fiber, glass fibre, Wollastonite, length-to-diameter ratio preferable range bar-shaped or needle-like material is 5～10, and with the finished catalyst weighing scale after roasting, anti-wear agent content preferable range is 1～15%; Molecular sieve preferred version is at least one being selected from ZSM-5, mordenite, β zeolite, Y zeolite, MCM-22, ZSM-5/ mordenite, ZSM-5/ β zeolite, 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, with the finished catalyst weighing scale after roasting, molecular sieve content preferable range is 20～50%; Binding agent preferred version is at least one being selected from silicon sol or aluminium colloidal sol, and with the finished catalyst weighing scale after roasting, binder content preferable range is 5～20%; Substrate material preferred version is at least one being selected from kaolin, calcined kaolin, diatomite, wilkinite, carclazyte, and with the finished catalyst weighing scale after roasting, matrix material content preferable range is 10～50%.Temperature of reaction preferable range is 450～600 DEG C; Reaction pressure preferable range is 0.01MPa～0.2Mpa; Reaction weight space velocity preferable range is 0.2～2 hour
-1; Water/light oil weight ratio preferable range is 0.2～2: 1.
The preparation method of the fluid catalyst that the present invention uses, comprises the following steps: (a) by dispersed to molecular sieve, binding agent, material, expanding agent, dispersion agent and liquid medium formation suspension, suspension solids content is 10～50%; (b) adopt in the method control suspension of high speed shear or circulating emulsion raw meal particle size between 0.5～5um; (c) in suspension, add anti-wear agent, then stir; (d) dry this suspension of spraying forms microspherical catalyst; (e) this microspherical catalyst of roasting forms finished catalyst.
In technique scheme, expanding agent preferred version is at least one being selected from methylcellulose gum, polyvinyl alcohol, sesbania powder, Zulkovsky starch, CNT (carbon nano-tube), with contained molecular sieve weighing scale in the finished catalyst weight after roasting, the consumption preferable range of expanding agent is 0.1～10%; Dispersion agent preferred version is at least one being selected from Triammonium citrate, ammonium oxalate, volatile salt, bicarbonate of ammonia, and with contained molecular sieve weighing scale in the finished catalyst weight after roasting, the consumption preferable range of dispersion agent is 0.01～10%; Adopt the middle material particular diameter preferable range of method control step (b) of high speed shear or circulating emulsion between 0.1～2um; (a) step suspension solids content preferable range is 10～50%; Spray shaping condition is 180～300 DEG C of inlet temperatures, 100～160 DEG C of temperature outs, and 5000～15000 revs/min of centrifugal rotational speeds, exit whirlwind pressure reduction is 0.5～1.0KPa, input speed is 0.5～5 kg/hour; The catalyzer of the dry preparation of spraying is after high-temperature roasting, the median size of particle 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 % by weight/hour; In the catalyzer making, binding agent accounts for 10～40 % by weight; Molecular sieve accounts for 10～50 % by weight; Body material accounts for 10～80 % by weight.
In technical scheme of the present invention, the catalyzer adopting is in preparation process, by adding the special bar-shaped or needle inorganic material that is selected from, its length-to-diameter ratio is 2～20 anti-wear agent, after emulsify at a high speed is sheared, slurry is even, in catalyzer, each component is dispersed, be difficult for reuniting, suspension liquid is difficult for layering or precipitation, and the catalyst surface of preparing is smooth, sphericity is high, between each component, each material, can combine closely, the finished catalyst obtaining has higher abrasive wear resistance, its abrasion index can reach 0.001 % by weight/hour.Taking methyl alcohol as raw material, at 480 DEG C, weight space velocity 1h
-1, check and rate under water/methyl alcohol weight ratio 1: 1, the pressure condition that is 0.02MPa, weight ethylene yield reaches 25%, propylene weight yield reaches 50%, diene weight total recovery is 75%, has obtained good technique effect.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
Take 20 grams of the wollastonites that 500 grams of kaolin, 2 grams, sesbania powder and length-to-diameter ratio are 8, after mixing, add 2000 grams of distilled water, by high-speed shearing machine high speed shear 30 minutes, then add the ZSM-5 molecular sieve that 400 grams of sial molecular ratios are 30, high speed shear 30 minutes again, then add 500 grams of the aluminium colloidal sols of salic 20 % by weight, continue high speed shear 30 minutes, add again 1 gram of Triammonium citrate, continue high speed shear after 30 minutes, measure the granularity of this suspension with laser particle analyzer, its median size is 2 microns.Use spray-drier spray shaping, spray shaping condition is: 240 DEG C of inlet temperatures, and 120 DEG C of temperature outs, 10000 revs/min of centrifugal rotational speeds, exit whirlwind pressure reduction is 0.7KPa, input speed is 1 kg/hour.Particle after spray shaping adopts temperature-programmed calcination, burns 3 hours at 400 DEG C, and then 650 DEG C are burnt 3 hours.The catalyzer obtaining after 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 is at 0.9 grams per milliliter, adopt abrasion instrument measure wear index be 0.001 % by weight/hour.
[embodiment 2～10]
According to the method for embodiment 1, adopt batching and the preparation condition of table 1, wherein silicon sol, for containing silicon-dioxide 40 % by weight, makes fluidized bed catalyst performance as shown in table 1.
[embodiment 11]
The method of getting 200 grams of embodiment 1 makes fluidized-bed ZSM-5 catalyzer, puts into internal diameter and be the fluidized-bed reactor of 50 millimeters, taking methyl alcohol as raw material, at 480 DEG C, weight space velocity 1h
-1, check and rate under water/methyl alcohol weight ratio 1: 1, the pressure condition that is 0.02MPa, weight ethylene yield reaches 25%, propylene weight yield reaches 50%, products distribution is in 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 |
| The above cut of carbon five | 4.8 |
| Other | 2.1 |
[embodiment 12]
Make ZSM-5/ beta zeolite coexisting molecular sieve catalyst according to the method for embodiment 9, employing dme is raw material, and range of reaction temperature is 480 DEG C, and reaction pressure is 0.02MPa, and weight space velocity is 1 hour
-1, water/methyl alcohol weight ratio is 1: 1, and obtaining weight ethylene yield is 29%, and propylene weight yield is 48%, and diene weight total recovery is 77%.
[embodiment 13～16]
Getting respectively the catalyzer of embodiment 1,2,3 and 4 preparation, by the examining method of embodiment 11, is that 480 DEG C, water/methyl alcohol weight ratio are that 3: 1, weight space velocity are followed successively by respectively 2 hours in temperature of reaction
-1; 1 hour
-1; 0.8 hour
-1with 0.25 hour
-1condition under check and rate, the results are shown in Table 4.
[embodiment 17～20]
Getting respectively the catalyzer of embodiment 5,6,7 and 8 preparation, by 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 respectively 400 DEG C; 450 DEG C; Under the condition of 550 DEG C and 600 DEG C, check and rate, the results are shown in Table 4.
[embodiment 21～24]
The catalyzer of getting respectively embodiment 9,10,1 and 2 preparations, by the examining method of embodiment 11, is 0.5 hour at weight space velocity
-1, temperature is that 480 DEG C, water/methanol quality are followed successively by 4: 1 than respectively; 2: 1; Within 0.5: 1 and 0.1: 1, under condition, check and rate, the results are shown in Table 4.
[embodiment 25～28]
The catalyzer of getting respectively embodiment 3,4,5 and 6 preparations, by the examining method of embodiment 11, is 0.5 hour at weight space velocity
-1, temperature of reaction is 450 DEG C, water/dme weight ratio 3: 1, reaction pressure is followed successively by respectively 0.01MPa; 0.05MPa; Under the condition of 0.1MPa and 0.2MPa, check and rate, the results are shown in Table 4.
Table 4
| Embodiment | Yield of ethene (% by weight) | Propene yield (% by weight) | Diene yield (% by 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 (1)
1. the method for a converting oxygen-containing compound to low-carbon olefins, take 500 grams of kaolin, 20 grams of the wollastonites that 2 grams, sesbania powder and length-to-diameter ratio are 8, after mixing, add 2000 grams of distilled water, by high-speed shearing machine high speed shear 30 minutes, then add the ZSM-5 molecular sieve that 400 grams of sial molecular ratios are 30, high speed shear 30 minutes again, then add 500 grams of the aluminium colloidal sols of salic 20 % by weight, continue high speed shear 30 minutes, add again 1 gram of Triammonium citrate, continue high speed shear after 30 minutes, measure the granularity of this suspension with laser particle analyzer, its median size is 2 microns, use spray-drier spray shaping, spray shaping condition is: 240 DEG C of inlet temperatures, and 120 DEG C of temperature outs, 10000 revs/min of centrifugal rotational speeds, exit whirlwind pressure reduction is 0.7KPa, input speed is 1 kg/hour, particle after spray shaping adopts temperature-programmed calcination, burns 3 hours at 400 DEG C, and then 650 DEG C are burnt 3 hours, the catalyzer obtaining after 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 is 0.9 grams per milliliter, adopt abrasion instrument measure wear index be 0.001 % by weight/hour,
Get 200 grams of aforesaid methods and make fluidized-bed ZSM-5 catalyzer, put into internal diameter and be the fluidized-bed reactor of 50 millimeters, taking methyl alcohol as raw material, at 480 DEG C, weight space velocity 1h
-1, check and rate under water/methyl alcohol weight ratio 1: 1, the pressure condition that is 0.02MPa, weight ethylene yield reaches 25%, propylene weight yield reaches 50%, diene weight total recovery is 75%, products distribution is as follows:
Methane weight yield is 5.2%,
Ethane weight yield is 2.1%,
Weight ethylene yield is 25.0%,
Propane weight yield is 3.5%,
Propylene weight yield is 50.0%,
Butane weight yield is 3.7%,
Butylene weight yield is 3.6%,
The above cut of carbon five is 4.8%,
Other composition weight yields are 2.1%.
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| CN103962169B (en) * | 2013-01-31 | 2017-04-05 | 上海碧科清洁能源技术有限公司 | It is a kind of for preparing catalyst of alkene and preparation method thereof by methanol in fluid bed |
| CN103962170A (en) | 2013-01-31 | 2014-08-06 | 上海碧科清洁能源技术有限公司 | Methanol-to-olefin catalyst with high C4 olefin selectivity and preparation method thereof |
| US20160257625A1 (en) * | 2013-10-31 | 2016-09-08 | Shell Oil Company | Process for converting oxygenates to olefins |
| 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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| CN1704163A (en) * | 2004-05-28 | 2005-12-07 | 中国石油化工股份有限公司 | Molecular screen microspherical catalyst |
| CN101172242A (en) * | 2006-10-31 | 2008-05-07 | 中国石油化工股份有限公司 | Catalytic cracking catalyst and its preparation |
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| CN101612592A (en) * | 2009-07-21 | 2009-12-30 | 上海化工研究院 | A kind of preparation method of low abrasion microsphere catalyst produced in situ |
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| CN1704163A (en) * | 2004-05-28 | 2005-12-07 | 中国石油化工股份有限公司 | Molecular screen microspherical catalyst |
| CN101172242A (en) * | 2006-10-31 | 2008-05-07 | 中国石油化工股份有限公司 | Catalytic cracking catalyst and its preparation |
| CN101422728A (en) * | 2008-12-18 | 2009-05-06 | 哈尔滨工业大学 | Catalyst for denitration of power plant soot fume SCR and preparation method thereof |
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