CN102372548A - Method for preparing low-carbon olefin through methanol dehydration - Google Patents
Method for preparing low-carbon olefin through methanol dehydration Download PDFInfo
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Abstract
The invention relates to a method for preparing low-carbon olefin through methanol dehydration, and mainly solves the problems that the activity of a catalyst and the yield of the low-carbon olefin are low in the conventional technology for preparing the low-carbon olefin through catalytic pyrolysis. In the invention, methanol which is taken as a raw material is contacted with an adhesive-free molecular sieve catalyst through a catalyst bed to generate the low-carbon olefin under the conditions that the reaction temperature is 400 to 600 DEG C, the gauge pressure of the reaction is 0.001 to 0.5MPa, the weight space velocity of the reaction is 0.1 to 4h<-1> and the weight ratio of water to methanol is (0.1-3):1, wherein the pore volume, the average aperture and porosity of the adhesive-free molecular sieve catalyst are tested by mercury porosimetry, the pore volume is 0.31 to 0.5ml/g, the average aperture is 71 to 100nm, and the porosity is 31 to 40 percent. Through the technical scheme, the problems are better solved. The method can be used for the industrial production of the low-carbon olefin through methanol dehydration.
Description
Technical field
The present invention relates to a kind of method of methanol dehydration producing light olefins.
Technical background
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.More than 100,000,000 ton of ethene is produced in the whole world per year at present, is raw material with petroleum naphtha (or ethane) mainly, adopts steam heat cracking technique (under the temperature about 800 ℃) production, and its output surpasses 90% of ultimate production.But steam cracking needs high temperature of reaction, and energy consumption is big, needs expensive high-temperature alloy steel molecular sieve, and the operational cycle is short, and the boiler tube life-span is low, discharge great amount of carbon dioxide, and yield of light olefins is lower, has restricted further developing of ethylene industry.
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.
Zeolite molecular sieve has good shape selective catalysis performance and absorption property owing to have evenly regular pore passage structure, bigger specific surface area and higher thermostability, is applied in field of petrochemical industry widely.Because molecular sieve in use need add the sticker moulding, in the catalyzer after the moulding, because sticker parcel molecular sieve; Caused the effective rate of utilization of molecular sieve to descend, caused the specific surface area of catalyzer lower, activity is also lower; Again because sticker does not have regular pore passage structure; Reaction raw materials and product are in catalyzer diffusion difficulty, and carbon deposit has certain influence to life of catalyst easily.Be converted into the active principle molecular sieve to the sticker in the catalyzer and then can overcome above problem, improve activity of such catalysts and diffusion.
The binder free zeolite catalyst is exactly the active principle that changes into the sticker that is added in the zeolite [molecular sieve moulding process in molecular sieve, makes not contain the sticker composition in the whole catalyzer, keeps the good intensity of catalyzer simultaneously.Be converted into the molecular sieve composition fully owing to sticker in the binder free catalyzer; So just improved the content of molecular sieve in the per volume of catalyst; Make activity of such catalysts higher, treatment capacity is bigger, simultaneously owing to no longer include sticker in the catalyzer; Solved sticker parcel molecular sieve and reduced the effective rate of utilization of molecular sieve and the problem that sticker stops up molecular sieve pore passage, the effective rate of utilization of molecular sieve and carbon accumulation resisting ability are improved greatly.
General binder free zeolite [molecular sieve refers in the catalyzer binder content smaller or equal to 5%.
General coexisting molecular sieve is Powdered, no intensity through the preparation of hydro-thermal synthetic method; Be prone to run off, can not directly use, even compression molding; Intensity also is lower than 20 newton, need add sticker when industry or laboratory applications and carry out extrusion or spray shaping.In the general sieve catalyst moulding process, the weight that add sticker is no less than 40% of total catalyst weight, though the moulding rear catalyst has had intensity, the effective rate of utilization of catalyzer reduces, active and diffusion variation.
All use organic formwork agent to promote that the commentaries on classics of sticker is brilliant in the process of prior art for preparing binder free catalyzer.
Chinese patent CN101347742 has reported a kind of catalyzer that hydrocarbon raw material prepares light aromatics and light paraffins that is used for; Mainly solve the content that sticker in the dual-function catalyst of Zeolite support preparation that available technology adopting contains sticker can reduce active principle; Cause adsorptive capacity to descend; Effective surface area is reduced, and the activity that therefore causes is lower, the technical problem of less stable.The present invention comprises following component through adopting by weight percentage: a) 0.01～0.8% be selected among Pt or the Pd at least a; B) the surplus technical scheme that is selected from least a preparation dual-function catalyst in mordenite, y-type zeolite, Y zeolite, ZSM-5 or the ZSM-11 zeolite of binder free has solved this problem preferably, can be used in the industrial production that hydrocarbon raw material prepares light aromatics and light paraffins.Also used template in the process of wherein prepared binder free y-type zeolite.
Chinese patent 200510028782 has reported that the present invention of small crystal grain without bonding agent prepare zeolite method is a main raw material through adopting with zeyssatite or WHITE CARBON BLACK; Add the crystal seed directed agents; And with silicon sol or water glass as the sticker moulding; Handle the technical scheme that is converted into integrated little crystal grain with organic amine mutually with the water vapor gas-solid then; Mainly solve the zeolite powder and in practical application, have difficult recovery, be prone to inactivation and accumulative weakness, and the adding sticker can cause that effective surface area reduces the problem that influences with diffusional limitation in the moulding process.But the preparation process is used organic amine and crystal seed directed agents.
Chinese patent 200510029462 has been reported the preparation method of ZSM-type molecular sieve without binding agent.Through adopting content is the mixture that the former powder of 5～50 weight % sticker silicon oxide and ZSM type molecule forms; In the aqueous solution that contains halogenation organic amine and alkyl diamine or steam; Be converted into the technical scheme of integrated ZSM type molecular sieve through hydrothermal treatment consists, mainly solved and add sticker in the sieve catalyst moulding process and can cause that effective surface area reduces the problem with the diffusional limitation influence.
In the binder free Preparation of catalysts method of existing report, all need add organic amine or crystal seed directed agents as template or directed agents.Adopt the preparation cost of template high, the organic amine of interpolation is poisoned big to human body, and environmental pollution is serious, reclaims difficulty, adopts the method for roasting to remove usually, and required energy consumption is big, and environment is also had pollution; Prepare the method that adds crystal seed or directed agents in the process, building-up process is very complicated comparatively.No template does not have the method that crystal seed directly prepares the binder free catalyzer can avoid the problems referred to above, and corresponding optimization synthesis step, has tangible economic worth and social value.At present, the method for not using template to prepare the binder free catalyzer is not seen report.
Because molecular sieve in use need add the sticker moulding, in the catalyzer after the moulding, because sticker parcel molecular sieve; Caused the effective rate of utilization of molecular sieve to descend, caused the specific surface area of catalyzer lower, activity is also lower; Again because sticker does not have regular pore passage structure; Reaction raw materials and product are in catalyzer diffusion difficulty, and carbon deposit has certain influence to life of catalyst easily.Be converted into the active principle molecular sieve to the sticker in the catalyzer and then can overcome above problem, improve activity of such catalysts and diffusion.
Chinese patent 200510028782 has reported that the present invention of small crystal grain without bonding agent ZSM-5 prepare zeolite method is a main raw material through adopting with zeyssatite or WHITE CARBON BLACK; Add the crystal seed directed agents; And with silicon sol or water glass as the sticker moulding; Handle the technical scheme that is converted into integrated small-grain ZSM-5 with organic amine mutually with the water vapor gas-solid then.Mainly solve the zeolite powder and in practical application, have difficult recovery, be prone to inactivation and accumulative weakness, and the adding sticker can cause that effective surface area reduces the problem that influences with diffusional limitation in the moulding process.But the preparation process is used organic amine and crystal seed directed agents.
Chinese patent 200510029462 has been reported the preparation method of ZSM-type molecular sieve without binding agent.Through adopting content is the mixture that the former powder of 5～50 weight % sticker silicon oxide and ZSM type molecule forms; In the aqueous solution that contains halogenation organic amine and alkyl diamine or steam; Be converted into the technical scheme of integrated ZSM type molecular sieve through hydrothermal treatment consists, mainly solved and add sticker in the sieve catalyst moulding process and can cause that effective surface area reduces the problem with the diffusional limitation influence.But the preparation process also uses organic amine to make template.
In the binder free Preparation of catalysts method of existing report, all need add organic amine or crystal seed directed agents as template or directed agents.Adopt the preparation cost of template high, the organic amine of interpolation is poisoned big to human body, and environmental pollution is serious, reclaims difficulty, adopts the method for roasting to remove usually, and required energy consumption is big, and environment is also had pollution; Prepare the method that adds crystal seed or directed agents in the process, building-up process is very complicated comparatively.No template does not have the method that crystal seed directly prepares the binder free catalyzer can avoid the problems referred to above, and corresponding optimization synthesis step, has tangible economic worth and social value.
Summary of the invention
Technical problem to be solved by this invention is that the catalyzer use temperature that exists in the prior art is high, and the problem that the yield of low-carbon alkene is low provides a kind of method of new methanol dehydration producing light olefins.This method has the catalyst activity height, the high characteristics of yield of light olefins.
For solving the problems of the technologies described above; The technical scheme that the present invention adopts is following: a kind of method of methanol dehydration producing light olefins is a raw material with methyl alcohol, is 400～600 ℃ in temperature of reaction; The reaction gauge pressure is 0.001MPa～0.5MPa, and the reaction weight space velocity is 0.1～4 hour
-1, water/methyl alcohol weight ratio is under 0.1～3: 1 the condition, and raw material is through beds, and reaction generates low-carbon alkene, and catalyst system therefor is the binder free catalyzer, and pore volume is 0.31～0.5 a milliliter/gram, and mean pore size is 71～100nm, and voidage is 31～40%; Binder content is 0～5%; Catalyst strength behind the shaping and roasting is 50～180 newton.
In the technique scheme, the molecular sieve preferred version is at least a in ZSM-5, ZSM-23, ZSM-11, mordenite, Y zeolite, β zeolite, MCM-22, MCM-49, MCM-56, ZSM-5/ mordenite, ZSM-5/ β zeolite, ZSM-5/Y, MCM-22/ mordenite, ZSM-5/Magadiite, ZSM-5/ β zeolite/mordenite, ZSM-5/ β zeolite/Y zeolite, the ZSM-5/Y zeolite/mordenite.The temperature of reaction preferable range is 430～580 ℃; The reaction pressure preferable range is 0.01MPa～0.2Mpa; Reaction weight space velocity preferable range is 0.2～2 hour
-1Water/methyl alcohol weight ratio preferable range is 0.2～2: 1.
The Preparation of catalysts method comprises following several steps:
A) in the catalyst weight behind the shaping and roasting; After the compound of the molecular sieve 10～70%, 0.1～20% alkaline matter, 0～20% aluminium and 20～80% silicon oxide mixing, moulding, the drying; Obtain preformed catalyst precursor mixture I, the compound weight content of mixture aluminium is less than the weight content of silicon oxide in the mixture I;
B) the mixture I is placed put into water vapor, carry out obtaining binder free zeolite catalyst precursor after crystallization handles 10～300 hours at 100～200 ℃;
C) catalyst precursor 400～700 ℃ of following roastings 1～10 hour, obtains the binder free zeolite [molecular sieve through super-dry;
Wherein, salts solution is selected from least a in carbonate, supercarbonate, oxalate, Citrate trianion and the ammonium salt of periodic table of elements I A or II A element; The compound of aluminium is at least a in the oxyhydroxide of hydrous oxide or aluminium of oxide compound, aluminium of aluminium salt, aluminium, and binder content is 0～5% in the binder free catalyzer that makes.
I A family element preferred version is at least a in sodium or the potassium; II A family element preferred version is at least a in magnesium or the calcium; The ammonium salt preferred version is for being selected from volatile salt, bicarbonate of ammonia, at least a in ammonium citrate, ammonium oxalate, ammonium sulfate, monoammonium sulfate, ammonium sulphite, ammonium bisulfite, ammonium phosphate, ammonium hydrogen phosphate, the Secondary ammonium phosphate.In the catalyst weight behind the shaping and roasting, the consumption preferable range of molecular sieve is 20～70%; The consumption preferable range of alkaline matter is 0.5～10%; The compound preferred version of aluminium is hydroxide species at least a of hydrous oxide or aluminium of oxide compound, the aluminium of aluminium salt, aluminium, and the consumption preferable range is 1～15%; The weight percentage preferable range of silicon oxide is 30～70%; The crystallization temperature preferable range is 120～200 ℃, and the crystallization time preferable range is 20～100 hours.
In the characterization method of binder free catalyzer, with the contained thing of XRD test mutually and the content of each thing phase, change the pattern of molecular sieve of situation and the generation of crystalline substance with the scanning electron microscopic observation sticker.Change brilliant back binder content through the XRD thing mutually quantitatively and in the stereoscan photograph content of sticker confirm.The catalyzer silica alumina ratio is confirmed with chemico-analytic method.The strength test method of catalyzer is the crushing strength of the catalyzer after test roasting on the pressure testing machine; Every of the catalyzer of surveying is of a size of 1.5 millimeters of diameters; 5 millimeters of length; Be disposed across on the trier, suffered peak pressure when measuring catalyst breakage is got its MV after testing 10 catalyzer crushing strengths.The mercury penetration method test is adopted in catalyzer pore volume, mean pore size and porosity test.
The present invention is through adding crystal seed in preformed catalyst, control is suitable for the alkaline environment and the material proportion of zeolite growth, makes sticker inducing jointly down at zeolite seed crystal and alkali ion; In the environment of water vapor, can carry out nucleation and growth, sticker changes into zeolite effective constituent; Obtain the binder free zeolite catalyst; Molecular sieve content is higher in its unit volume, and therefore, active site is also more.The content of sticker can reach below 2% in the binder free type zeolite catalyst that makes; Even do not contain sticker; All be zeolite in the catalyzer, owing to change the staggered growth of the binder free catalyst zeolite crystal grain that obtains behind the crystalline substance, intercrystalline combines closely; So the intensity of catalyzer is also higher, can reach 180 newton/more than.It is more that the present invention has in the unit volume active site through employing, and the pore volume of catalyzer is bigger, and mean pore size and porosity are bigger; Catalyst activity and diffusion be the binder free catalyzer preferably, has improved the quantity of active site in the unit volume, and open grain can contact raw material with active site rapidly; Reaction product can diffuse out rapidly, has reduced the generation of carbon distribution and other side reactions, has improved the selectivity of low-carbon alkene; Higher pore volume has also increased the appearance carbon ability of catalyzer, makes life of catalyst longer, and the catalyzer that makes is used in the reaction of methanol dehydration producing light olefins; The diene yield reaches 80%, has obtained better technical effect.
Through specific embodiment the present invention being done a nearly step below sets forth.
Embodiment
[embodiment 1]
Get silica alumina ratio (molecular ratio, down with) and be 30 ZSM-5 molecular sieve 60 grams, add weight percentage and be 40% silicon sol 40 grams, after the mixing and stirring; 10 milliliters of sodium hydrogen carbonate solutions that add 1 mol again, mixing and stirring, agent bar moulding then, preformed catalyst was 80 ℃ of oven dry 3 hours; Put into the aqueous autoclave of inner bag bottom then, catalyzer does not contact with liquid water, puts into baking oven after the autoclave sealing; 180 ℃ of crystallization were taken out after 60 hours, washed then 2 times, put into 120 ℃ of oven dry of baking oven 3 hours; Putting into the 400 ℃ of roastings 2 hours that heat up of retort furnace internal program, 550 ℃ of roastings 3 hours make the adhesiveless ZSM-5 catalyzer.The XRD figure spectrum of the catalyzer that makes is shown as pure ZSM-5 thing phase.The ESEM picture of the catalyzer that makes is shown as pure ZSM-5 crystal grain, has the sticker of unformed state hardly, and the binder content of unformed state is 0.2%.The withstand voltage broken intensity of detecting catalyst sample be 145 newton/.With the mercury penetration method test, pore volume is 0.38 a milliliter/gram, and mean pore size is 82nm, and voidage is 36%.
[embodiment 2]
Preparing silica alumina ratio by the method for Chinese patent CN101428233A is 40 ZSM-5/ β zeolite mixed crystal molecular sieve.Get ZSM-5/ β zeolite 60 gram, add weight percentage and be 40% silicon sol 40 grams, after the mixing and stirring, add 20 milliliters of the ammonium citrate solutions of 1 mol again; Mixing and stirring, agent bar moulding then, preformed catalyst was 80 ℃ of oven dry 3 hours; Put into the aqueous autoclave of inner bag bottom then, catalyzer does not contact with liquid water, puts into baking oven after the autoclave sealing; 165 ℃ of crystallization were taken out after 80 hours, washed then 2 times, put into 120 ℃ of oven dry of baking oven 3 hours; Putting into the 400 ℃ of roastings 2 hours that heat up of retort furnace internal program, 550 ℃ of roastings 3 hours, it is as shown in table 1 to make adhesiveless ZSM-5/beta-zeolite catalyst.The withstand voltage broken intensity of detecting catalyst sample be 160 newton/, the binder content of unformed state is 0.6%.With the mercury penetration method test, pore volume is 0.37 a milliliter/gram, and mean pore size is 80nm, and voidage is 35%.
[embodiment 3～16]
Get silica alumina ratio respectively and be 20 mordenite, silica alumina ratio and be 10 Y zeolite 60 grams, silica alumina ratio and be 40 MCM-22 molecular sieve, silica alumina ratio and be 20 ZSM-5/ mercerization zeolite symbiosis molecular screen, silica alumina ratio and be 40 ZSM-5/ β zeolite/Y zeolite coexisting molecular sieve, silica alumina ratio and be 20 ZSM-5/Y zeolite/mercerization zeolite symbiosis molecular screen, silica alumina ratio and be 20 ZSM-23, silica alumina ratio and be 30 ZSM-11, silica alumina ratio and be 40 MCM-49, silica alumina ratio and be 60 MCM-56, silica alumina ratio and be 20 ZSM-5/Y coexisting molecular sieve, silica alumina ratio and be 40 MCM-22/ mordenite, silica alumina ratio and be 200 ZSM-5/Magadiite, silica alumina ratio and be ZSM-5/ β zeolite/mordenite of 30; Proportioning raw materials such as table 1; Method according to embodiment 1; Make the binder free mordenite catalyst, as shown in table 3.
[embodiment 17～22]
Select the used molecular sieve of embodiment 3～8 respectively, according to the method for embodiment 1, other condition is constant; In moulding process, add expanding agents such as 2.0 gram sesbania powder, methylcellulose gum, Zulkovsky starch, Z 150PH, it is as shown in table 2 that raw material is formed proportioning, mixing and stirring; Extrusion, moulding; Press the method for embodiment 1 again, process the binder free zeolite catalyst, the result is as shown in table 3.
[embodiment 23]
Get the binder free catalyzer that embodiment 1 makes; Using concentration is 5% ammonium nitrate solution, is 1: 10 ratio in the solid-to-liquid ratio of catalyzer and ammonium nitrate solution, exchanges three times at 90 ℃; 550 ℃ of roastings made the Adhesive-free Molecular Sieve catalyzer of Hydrogen after 3 hours then.With methyl alcohol is raw material, and the use diameter is 12 millimeters fixed-bed reactor, at 450 ℃, 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 29%, the propylene weight yield reaches 49%, diene weight total recovery is 78%.
[embodiment 24]
Method according to embodiment 1 makes the adhesiveless ZSM-5 catalyzer, and use concentration is 5% ammonium nitrate solution, twice of 70 ℃ of exchange; 550 ℃ of roastings are 3 hours then, after twice of the repeated exchanged, make Hydrogen ZSM-5 sieve catalyst again; Break into pieces then, sieve, get 20～40 purpose particles and put into fixed-bed reactor, the employing dme is a raw material; Examination activity of such catalysts, use diameter are 12 millimeters fixed-bed reactor normal pressure examination down, and range of reaction temperature is 480 ℃; 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 32%, and the propylene weight yield is 49%, and diene weight total recovery is 81%.
Table 3
[comparative example 1]
Preparing silica alumina ratio by the method for Chinese patent CN101428233A is 40 ZSM-5/ β zeolite mixed crystal molecular sieve; Method by embodiment 23 is processed hydrogen type molecular sieve; Then mixed crystal molecular sieve direct compression, break into pieces, sieve, do not contained 20～40 purpose granules of catalyst of sticker, put into fixed-bed reactor; Press the method examination of embodiment 23, the result sees table 4.
[comparative example 2]
Preparing silica alumina ratio by the method for Chinese patent CN101428233A is 40 ZSM-5/ β zeolite mixed crystal molecular sieve; Method by embodiment 23 is processed hydrogen type molecular sieve; And then, obtain containing the ZSM-5/ β zeolite mixed crystal sieve catalyst of sticker according to the method extruded moulding of embodiment 1, put into fixed-bed reactor; Press the method examination of embodiment 23, the result sees table 4.
[comparative example 3]
The silica alumina ratio of getting the production of Oil of Shanghai Petrochemical Company research institute is 40 ZSM-5 molecular sieve; Method by embodiment 23 is processed hydrogen type molecular sieve; Then ZSM-5 molecular sieve direct compression, break into pieces, sieve, do not contained 20～40 purpose granules of catalyst of sticker, put into fixed-bed reactor; Press the method examination of embodiment 23, the result sees table 4.
[comparative example 4]
The silica alumina ratio of getting the production of Oil of Shanghai Petrochemical Company research institute is 40 β zeolite; Method by embodiment 23 is processed hydrogen type molecular sieve; Then β zeolite direct compression, break into pieces, sieve, do not contained 20～40 purpose granules of catalyst of sticker, put into fixed-bed reactor; Press the method examination of embodiment 23, the result sees table 4.
[comparative example 5]
The silica alumina ratio that Oil of Shanghai Petrochemical Company research institute produces is 40 ZSM-5 molecular sieve; Method by embodiment 23 is processed hydrogen type molecular sieve; And then, obtain containing the ZSM-5 sieve catalyst of sticker according to the method extruded moulding of embodiment 1, put into fixed-bed reactor; Press the method examination of embodiment 23, the result sees table 4.
[comparative example 6]
The silica alumina ratio of getting the production of Oil of Shanghai Petrochemical Company research institute is 40 β zeolite; Method by embodiment 23 is processed hydrogen type molecular sieve; And then, obtain containing the beta zeolite coexisting sieve catalyst of sticker according to the method extruded moulding of embodiment 1, put into fixed-bed reactor; Press the method examination of embodiment 23, the result sees table 4.
[comparative example 7]
The silica alumina ratio of getting the production of Oil of Shanghai Petrochemical Company research institute is 40 ZSM-5, and silica alumina ratio is 40 β zeolite, is mixed into mechanical mixture at 1: 1 according to weight ratio; Method by embodiment 23 is processed hydrogen type molecular sieve; And then, obtain containing the ZSM-5 of sticker and the catalyzer of β zeolite mechanical mixture according to the method extruded moulding of embodiment 23, put into fixed-bed reactor; Press the method examination of embodiment 23 again, the result sees table 4.
[comparative example 8]
Preparing silica alumina ratio by the method for Chinese patent CN101428233A is 40 ZSM-5/ β zeolite mixed crystal molecular sieve.Get ZSM-5/ β zeolite 60 grams, the adding weight percentage is 40% silicon sol 40 grams, after the mixing and stirring; After pressing the method extrusion, moulding, oven dry of embodiment 2; Put into then the inner bag bottom moisture with the tetraethylammonium bromide mass ratio be 200 milliliters autoclave of 1: 1 mixing solutions 40 gram, catalyzer does not contact with liquid water, autoclave is put into baking oven after sealing; Press the method for embodiment 2 again and change brilliant processing; Make adhesiveless ZSM-5/beta zeolite coexisting sieve catalyst, the withstand voltage broken intensity of detecting catalyst sample be 150 newton/, the binder content of unformed state is 0.7%.Method by embodiment 23 is processed hydrogen type molecular sieve, puts into fixed-bed reactor, presses the method examination of embodiment 23 again, and the result sees table 4.
Table 4
[embodiment 25～28]
Getting the binder free catalyzer of embodiment 1,2,3 and 4 preparations respectively, make hydrogen type catalyst by the method for embodiment 20, press the examining method of embodiment 20, 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 5.
[embodiment 29～32]
Getting the binder free catalyzer of embodiment 5,6,7 and 8 preparations respectively, make hydrogen type catalyst by the method for embodiment 20, press the examining method of embodiment 20, is that 3: 1, weight space velocity are 0.5 hour in water/dme weight ratio
-1, temperature of reaction is followed successively by 400 ℃ respectively; 430 ℃; Check and rate under the condition of 550 ℃ and 600 ℃, the result sees table 5.
[embodiment 33～36]
Getting the binder free catalyzer of embodiment 9,10,11 and 12 preparations respectively, make hydrogen type catalyst by the method for embodiment 20, press the examining method of embodiment 20, is 0.5 hour at weight space velocity
-1, temperature is that 650 ℃, 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 5.
[embodiment 37～40]
Getting the binder free catalyzer of embodiment 13,14,15 and 16 preparations respectively, make hydrogen type catalyst by the method for embodiment 20, press the examining method of embodiment 20, is 0.5 hour at weight space velocity
-1, temperature of reaction be 480 ℃, water/methanol quality than 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 5.
Table 5
| Embodiment | Yield of ethene (weight %) | Propene yield (weight %) | Diene yield (weight %) |
| Embodiment 25 | 29.7 | 46.4 | 76.1 |
| Embodiment 26 | 25.3 | 46.0 | 71.3 |
| Embodiment 27 | 26.0 | 47.4 | 73.4 |
| Embodiment 28 | 28.1 | 47.3 | 75.4 |
| Embodiment 29 | 25.1 | 44.6 | 69.7 |
| Embodiment 30 | 23.2 | 44.5 | 67.7 |
| Embodiment 31 | 29.4 | 48.2 | 77.6 |
| Embodiment 32 | 30.2 | 45.2 | 75.4 |
| Embodiment 33 | 28.8 | 48.7 | 77.5 |
| Embodiment 34 | 28.7 | 48.8 | 77.5 |
| Embodiment 35 | 28.6 | 45.8 | 74.4 |
| Embodiment 36 | 27.1 | 42.6 | 69.7 |
| Embodiment 37 | 29.5 | 47.2 | 76.7 |
| Embodiment 38 | 28.3 | 48.2 | 76.5 |
| Embodiment 39 | 28.2 | 47.4 | 76.6 |
| Embodiment 40 | 27.5 | 47.3 | 74.8 |
Claims (3)
1. the method for a methanol dehydration producing light olefins is a raw material with methyl alcohol, 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 weight ratio is under 0.1～3: 1 the condition, raw material contacts with catalyzer through beds; Reaction generates low-carbon alkene, and used catalyzer is the Adhesive-free Molecular Sieve catalyzer, and pore volume is 0.31～0.5 a milliliter/gram; Mean pore size is 71～100nm, and voidage is 31～40%; Binder content is 0～5%; Catalyst strength behind the shaping and roasting is 50～180 newton.
2. the method for methanol dehydration producing light olefins according to claim 1 is characterized in that molecular sieve described in the Adhesive-free Molecular Sieve catalyzer comprises at least a in ZSM-5, ZSM-23, ZSM-11, mordenite, Y zeolite, β zeolite, MCM-22, MCM-49, MCM-56, ZSM-5/ mordenite, ZSM-5/ β zeolite, ZSM-5/Y, MCM-22/ mordenite, ZSM-5/Magadiite, ZSM-5/ β zeolite/mordenite, ZSM-5/ β zeolite/Y zeolite, the ZSM-5/Y zeolite/mordenite.
3. the method for methanol dehydration producing light olefins according to claim 1 is characterized in that temperature of reaction is 430～580 ℃; Reaction pressure is 0.01MPa～0.2Mpa; The reaction weight space velocity is 0.2～2 hour
-1Water/methyl alcohol weight ratio is 0.2～2: 1.
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| CN104096590A (en) * | 2013-04-10 | 2014-10-15 | 上海碧科清洁能源技术有限公司 | Hybrid molecular sieve catalyst and its preparation method and application |
| WO2014166372A1 (en) * | 2013-04-10 | 2014-10-16 | 上海碧科清洁能源技术有限公司 | Mixed molecular sieve catalyst and preparation method and use thereof |
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| US20180022611A1 (en) * | 2015-02-12 | 2018-01-25 | Basf Se | Process for the preparation of a dealuminated zeolitic material having the bea framework structure |
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| US10556801B2 (en) * | 2015-02-12 | 2020-02-11 | Basf Se | Process for the preparation of a dealuminated zeolitic material having the BEA framework structure |
| CN107282096A (en) * | 2016-04-01 | 2017-10-24 | 中触媒新材料股份有限公司 | A kind of SSZ-13 molecular sieve catalysts and preparation method and application |
| CN107973678A (en) * | 2016-10-21 | 2018-05-01 | 中国科学院大连化学物理研究所 | A kind of method of olefine selective in raising MTO reactions |
| CN107973678B (en) * | 2016-10-21 | 2021-01-19 | 中国科学院大连化学物理研究所 | Method for improving olefin selectivity in MTO reaction |
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