CN102373070B - Method for producing light olefins by light oil catalytic cracking - Google Patents
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Abstract
The invention relates to a method for producing light olefins by light oil catalytic cracking, and mainly solves the problem of poor wear resistance of fluidized bed catalysts in present technologies for producing light olefins by catalytic cracking. By the adoption of the method provided by the invention, C4-C10 hydrocarbon light oil is used as a raw material to contact with a catalyst through acatalyst bed, wherein the reaction temperature if 600-700 DEG C, the reaction surface pressure is 0.001MPa-0.5MPa, the reaction weight space velocity is 0.1-4 h<-1>, the weigh ratio of water to lightoil is 0.1-4: 1, and the catalyst used is the fluidized bed catalyst with good wear resistance. The technical scheme provided by the invention greatly solves the problem and can be used in the industrial production of producing light olefins by light oil catalytic cracking.
Description
Technical field
The present invention relates to a kind of method of preparing low-carbon olefin by catalytic pyrolysis light oil.
Background technology
Ethylene, propylene industry has very important status as the tap of petrochemical industry in the national economic development.Along with the development of society, the market requirement of China's ethylene, propylene sharply increases, and the import volume of ethylene, propylene and derived product thereof increases year by year, and the home products share of market is less than half.Ethene and propylene can be used for producing plastics and other Chemicals, are important Organic Chemicals, and along with progress and the development of modern society, its demand is increasing.Ethylene yield more than 98% comes from steam cracking technology in the world at present, and production of propylene mainly produces the joint product of ethene with steam cracking and two kinds of forms of byproduct of refinery catalytic cracking obtain.
Molecular sieve is widely used in field of petrochemical industry owing to having good shape selective catalysis performance and thermostability preferably.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 is lower than 20 newton, is difficult to be shaped to the catalyzer that directly applies to commercial run.The manufacturing cost of molecular sieve is generally higher, if adopt 100% molecular sieve as commercial catalysts, with so that the operating cost of commercial run increase.Commercial run general requirement catalyzer possesses certain shape and intensity to be adapted to industrial reactor.For fixed-bed reactor, catalyzer need not mobile after installing, but catalyzer need possess certain crush strength, to prevent in dress agent process that catalyzer is hit and damaged, and prevents from being installed in the catalyzer of lower floor owing to bearing pressure and breakage.The damaged efflorescence of catalyzer may cause the rising of device Pressure Drop, and reflex action may occur unusually, and the product composition changes, and is unfavorable for the goal response process.For fluidized-bed reactor, because this constantly circulates catalyzer 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 the transport pipe wall and collision all can make catalyzer levigate and damaged, final form effusion reactive system with fine powder.These fine powders pollute the environment, and the use cost of catalyzer is risen.Therefore, no matter be that molecular sieve is applied to fixed-bed reactor, still be applied to fluidized-bed reactor, all need pass through molecular sieve and solid support material the effect formation molecular sieve catalyst composition of binding agent; This combination of molecular sieve can have catalytic activity, selectivity, stability, shape and intensity concurrently simultaneously, thereby satisfies commercial run to the requirement of catalyzer.
The US6509290 patent discloses a kind of method for preparing molecular 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 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 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 US6153552 patent research a kind of method for preparing molecular sieve catalyst, the method comprises molecular sieve and alumina sol is mixed together, this alumina sol prepares in solution and remains under 2～10 the pH value, and this mixture of spraying drying and high-temperature roasting makes wear-resistant catalyst.
The CN1791463 patent discloses a kind of method for preparing molecular sieve catalyst, and the method comprises that the molecular sieve catalyst with molecular sieve, liquid and effective large drying of hardening capacity is mixed together the formation slurry, and 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, needs further to improve.
Summary of the invention
Technical problem to be solved by this invention is the relatively poor problem of molecular sieve fluid bed catalyst wear resisting property of using in the existing preparing low-carbon olefin by catalytic pyrolysis light oil technology, a kind of method of new preparing low-carbon olefin by catalytic pyrolysis light oil 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: a kind of method of preparing low-carbon olefin by catalytic pyrolysis light oil, and with C
4～C
10The light oil of hydrocarbon is raw material, is 600～700 ℃ 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/light oil weight ratio is under 0.1～4: 1 the condition, and raw material is by beds, and reaction generates low-carbon alkene, and used catalyzer is a kind of binder free catalyzer, in the finished catalyst weight percentage after the roasting, comprises that following material forms:
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 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, glass fibre, the Wollastonite, length-to-diameter ratio preferable range bar-shaped or needle-like material is 5～10, and with the finished catalyst weighing scale 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, with the finished catalyst weighing scale after the roasting, the molecular sieve content preferable range is 20～50%; The binding agent preferred version is to be selected from least a in silicon sol or the aluminium colloidal sol, and with the finished catalyst weighing scale 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, diatomite, wilkinite, the carclazyte, and with the finished catalyst weighing scale after the roasting, the matrix material content preferable range is 10～50%.The temperature of reaction preferable range is 630～680 ℃; 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, binding agent, substrate material, expanding agent, dispersion agent and liquid medium Uniform Dispersion are formed suspension, the 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) add anti-wear agent in suspension, restir is even; (d) this suspension 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, polyvinyl alcohol, sesbania powder, Zulkovsky starch, the CNT (carbon nano-tube), with contained molecular sieve weighing scale 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 with contained molecular sieve weighing scale in the finished catalyst weight after the 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%; 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 kg/hour; The catalyzer of spraying drying preparation is through after the 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; Binding agent accounts for 10～40 % by weight in the catalyzer that makes; Molecular sieve accounts for 10～50 % by weight; Body material accounts for 10～80 % by weight.
In the technical scheme of the present invention, the catalyzer that adopts is in preparation process, special be selected from bar-shaped or the needle inorganic material by adding, its length-to-diameter ratio is 2～20 anti-wear agent, after emulsify at a high speed is sheared, slurry is even, each component Uniform Dispersion in the catalyzer, be difficult for reuniting, suspension liquid is difficult for layering or precipitation, and the catalyst surface of preparing is smooth, sphericity is high, each component, can combine closely between each material, the finished catalyst that obtains has higher abrasive wear resistance, its abrasion index can reach 0.001 % by weight/hour, catalyzer is used in naphtha catalytic pyrolysis preparing ethylene and the propylene reaction, be 680 ℃ at range of reaction temperature, reaction pressure is 0.02MPa, and weight space velocity is 1 hour
-1, water/stock oil weight ratio is 1: 1 time examination, and obtaining the weight ethylene yield is 27%, and the propylene weight yield is 22%, and diene weight total recovery is 49%, has obtained preferably technique effect.
The invention will be further elaborated below by embodiment, but be not limited only to the 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 distilled water, with high-speed shearing machine high speed shear 30 minutes, then add 400 gram sial molecular ratios and be 30 ZSM-5 molecular sieve, high speed shear is 30 minutes again, then aluminium colloidal sol 500 grams that add salic 20 % by weight, continued high speed shear 30 minutes, add again 1 gram 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 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 kg/hour.Particle behind the spray shaping adopts temperature-programmed calcination, burns 3 hours at 400 ℃, and then 650 ℃ were burnt 3 hours.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 instrument mensuration 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 makes fluidized bed catalyst performance as shown in table 1 for containing silicon-dioxide 40 % by weight.
[embodiment 11]
The methods of getting 200 gram embodiment 1 make fluidized-bed ZSM-5 catalyzer, put into internal diameter and be 50 millimeters fluidized-bed reactor, and the component that adopts Shanghai Gaoqiao petro-chemical corporation to produce is C
4～C
10Light oil be raw material (the raw material physical index sees Table 3), the examination catalyzer activity, range of reaction temperature is 680 ℃, reaction pressure is 0.02MPa, weight space velocity is 1 hour
-1, water/stock oil weight ratio is 1: 1 time examination, and products distribution sees Table 4, and obtaining the weight ethylene yield is 27%, and the propylene weight yield is 22%, diene weight total recovery is 49%.
Table 3 light oil raw material index
| Project | Data |
| Density (20 ℃) kg/m 3 | 704.6 |
| Boiling range is boiling range ℃ just | 40 |
| Whole boiling range ℃ | 160 |
| Saturated vapor pressure (20 ℃) kPa | 50.2 |
| Alkane % (% by weight) | 65.2 |
| Naphthenic hydrocarbon % (% by weight) | 28.4 |
| Alkene % (% by weight) | 0.2 |
| Aromatic hydrocarbons % (% by weight) | 6.2 |
Table 4
| Products distribution | Product weight yield (%) |
| Methane | 6.2 |
| Ethane | 7.1 |
| Ethene | 27.0 |
| Propane | 7.5 |
| Propylene | 22.0 |
| Butane | 8.7 |
| Butylene | 8.6 |
| Carbon five above cuts | 9.8 |
| Other | 3.1 |
[embodiment 12～15]
Getting respectively the catalyzer of embodiment 1,2,3 and 4 preparations, press the examining method of embodiment 11, is that 650 ℃, water/stock oil weight ratio are that 3: 1, weight space velocity are 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 results are shown in Table 5.
[embodiment 16～19]
Getting respectively the catalyzer of embodiment 5,6,7 and 8 preparations, press the examining method of embodiment 11, is that 3: 1, weight space velocity are 0.5 hour in water/stock oil weight ratio
-1, temperature of reaction is followed successively by respectively 600 ℃; 630 ℃; Check and rate under the condition of 680 ℃ and 700 ℃, the results are shown in Table 5.
[embodiment 20～23]
Getting respectively the catalyzer of embodiment 9,10,1 and 2 preparations, press the examining method of embodiment 11, is 0.5 hour at weight space velocity
-1, temperature is that 650 ℃, water/stock oil mass ratio are followed successively by respectively 4: 1; 2: 1; 0.5: 1 and condition under check and rate at 0.1: 1, the results are shown in Table 5.
[embodiment 24～27]
Getting respectively the catalyzer of embodiment 3,4,5 and 6 preparations, press the examining method of embodiment 11, is 05 hour at weight space velocity
-1, temperature of reaction is 650 ℃, water/stock oil mass ratio 3: 1, reaction pressure is followed successively by respectively 0.01MPa; 0.05MPa; 0.1MPa and check and rate under the condition of 0.2MPa, the results are shown in Table 5.
Table 5
| Embodiment | Yield of ethene (% by weight) | Propene yield (% by weight) | Diene yield (% by weight) |
| Embodiment 12 | 26 | 22 | 48 |
| Embodiment 13 | 25 | 21 | 46 |
| Embodiment 14 | 24 | 22 | 46 |
| Embodiment 15 | 23 | 21 | 43 |
| Embodiment 16 | 22 | 22 | 44 |
| Embodiment 17 | 23 | 20 | 43 |
| Embodiment 18 | 28 | 20 | 48 |
| Embodiment 19 | 27 | 20 | 47 |
| Embodiment 20 | 25 | 20 | 45 |
| Embodiment 21 | 22 | 20 | 42 |
| Embodiment 22 | 29 | 20 | 49 |
| Embodiment 23 | 23 | 19 | 42 |
| Embodiment 24 | 25 | 18 | 43 |
| Embodiment 25 | 27 | 16 | 43 |
| Embodiment 26 | 23 | 18 | 41 |
| Embodiment 27 | 26 | 20 | 46 |
Claims (1)
1. the method for a preparing low-carbon olefin by catalytic pyrolysis light oil, take by weighing 500 gram kaolin, sesbania powder 2 grams and length-to-diameter ratio are 8 wollastonite 20 grams, after mixing, add 2000 gram distilled water, with high-speed shearing machine high speed shear 30 minutes, then add 400 gram sial molecular ratios and be 30 ZSM-5 molecular sieve, high speed shear is 30 minutes again, then aluminium colloidal sol 500 grams that add salic 20 % by weight, continue high speed shear 30 minutes, and added again 1 gram 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 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 kg/hour; Particle behind the spray shaping adopts temperature-programmed calcination, burns 3 hours at 400 ℃, and then 650 ℃ were burnt 3 hours; 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 is 0.9 grams per milliliter, adopt abrasion instrument measure wear index be 0.001 % by weight/hour;
Get 200 gram aforesaid methods and make fluidized-bed ZSM-5 catalyzer, put into internal diameter and be 50 millimeters fluidized-bed reactor, the component that adopts Shanghai Gaoqiao petro-chemical corporation to produce is C
4～C
10Light oil be raw material, the raw material physical index is as follows:
Density in the time of 20 ℃: 704.6 kg/ms
3, 40 ℃ of first boiling ranges, 160 ℃ of whole boiling ranges, saturated vapor pressure in the time of 20 ℃: 50.2 kPas, alkane 65.2 % by weight, naphthenic hydrocarbon 28.4 % by weight, alkene 0.2 % by weight, aromatic hydrocarbons 6.2 % by weight;
The activity of examination catalyzer, temperature of reaction is 680 ℃, and reaction pressure is 0.02MPa, and weight space velocity is 1 hour
-1, water/stock oil weight ratio is 1: 1 time examination, products distribution is as follows:
Methane weight yield 6.2%, ethane weight yield 7.1%, weight ethylene yield 27.0%, propane weight yield 7.5%, propylene weight yield 22.0%, butane weight yield 8.7%, butylene weight yield 8.6%, carbon five above cut weight yields 9.8%, other product weight yields 3.1%; The diene weight total recovery that obtains ethene and propylene is 49%.
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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 |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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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