CN103030500B - The method of propylene preparation through methanol conversion - Google Patents
The method of propylene preparation through methanol conversion Download PDFInfo
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- CN103030500B CN103030500B CN201110300260.7A CN201110300260A CN103030500B CN 103030500 B CN103030500 B CN 103030500B CN 201110300260 A CN201110300260 A CN 201110300260A CN 103030500 B CN103030500 B CN 103030500B
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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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- 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
Abstract
The present invention relates to the method for propylene preparation through methanol conversion, mainly in solution prior art, there is the problem that the selectivity of object product propylene is low.The present invention is by adopting a kind of method of propylene preparation through methanol conversion, and taking industrial methanol as raw material, is 400 ~ 600 DEG C in temperature of reaction, and reaction pressure is 0 ~ 0.15MPa, and liquid phase weight air speed is 0.5 ~ 3.0 hour
-1, water and methanol molar ratio are under the condition of 0.5 ~ 3.0, and raw material and catalyst exposure generate the technical scheme of propylene, solve this problem preferably, can be used for methanol conversion and produce in the industrial production of propylene.
Description
Technical field
The present invention relates to a kind of method of propylene preparation through methanol conversion.
Background technology
The demand of the basic chemical raw materials such as propylene, ethene constantly increases, and propylene, ethene are mainly derived from naphtha steam cracking and catalytic cracking at present, main raw material is still petroleum hydrocarbon, because petroleum resources are more and more deficienter, price is more and more expensive, brings propylene and ethylene imbalance between supply and demand to become increasingly conspicuous.Therefore, developing the light olefin techniques such as economically viable Non oil-based route propylene enhancing, an ethene is that commercial company of various countries is urgently pursued.By coal, Sweet natural gas, even biomass are through the mature production technology of synthesising gas systeming carbinol, and the technology of the light olefins such as Methanol ethylene, propylene has large quantifier elimination, as MTO, MTP, and existing a large amount of report.
On the other hand, mixed c 4 and above alkene, alkane are the by-product of ethylene plant, refinery FCC apparatus and methanol-to-olefins, gasoline apparatus, usually can only as low value-added products such as liquefied gas as fuel, be propylene and ethylene product by its further deep processing, useful economically and technical be also feasible.
The technique being generally used for olefin cracking has: CN1284109A discloses a kind of technique for carbon more than four olefin cracking preparation of propylene, ethene, its catalyzer used is the hydrothermal modification ZSM-5 molecular sieve that a kind of silica alumina ratio is greater than 200, in embodiment 3, etherificate carbon four cracking transformation efficiency is 54%, propene yield is only 29%, only has the operation data of 160 hours.
EPA0109059 discloses the method for carbon more than four olefin cracking preparation of propylene, ethene, ZSM-5 or the ZSM-11 molecular sieve being less than 360 with silica alumina ratio is catalyzer, reaction must be carried out under the high-speed of 50 hours-1, higher propene yield could be obtained, and the example illustrates reaction only several hours, thus can not meet macrocyclic industrial application.
US6307117 discloses a kind of catalyzer, and its active ingredient is almost without protonic acid, the ZSM-5 molecular sieve of argentiferous, this processing requirement reaction velocity (16 ~ 39 hours-1), temperature higher (~ 600 DEG C).High temperature makes the energy consumption of product high, and the requirement of mechanical strength of high-speed to catalyzer is high, otherwise easily efflorescence, cause bed pressure drop to increase, device is difficult to long-term operation.
Have with the method for methyl alcohol preparing propone, ethene: US Patent No. 6534692B1 and US2002/0147376A1, US6,995,111, US 6,844,291 etc., the aluminium silicophosphate molecular sieve SAPO-34 or its modifier that use aperture are catalyzer main active ingredient, greatly can limit the generation of macromole product, thus there is propylene, feature that ethene selectivity of light olefin is high, and its ethylene ratio propylene be high usually.Simultaneously because its molecular sieve small structure is easily by the coking and blocking that reaction is produced, the very fast inactivation of catalyzer, causes practical art complicated.
US7,015,369 and CN1431982 disclose a kind of technique by methanol production propylene, use three reactors of connecting, and in order to make full use of reaction heat, between the reactor of series connection, carry out sectional feeding, and the ethene that reaction generates, butylene return charging after initial gross separation, result is a reactor outlet in the end, and in the product of generation, the content of propylene is 20 ~ 50%.This patent embodiment adopts the ZSM-5 molecular sieve catalyzer with 460M2 specific surface area, and catalyzer is less than the modification of 0.05% through ZnO+CdO.
Patent US2006229482, JP2006008655, WO2005056504 (A1) provides a kind of technique of producing propylene, the ethene that reaction generates is turned back in the mixture of methanol/dimethyl ether, react under catalyst action, by controlling the amount of ethene, the yield of propylene is made to be greater than 40mol%.Used catalyst is solid acid catalyst, the crystallizable silicate zeolite of the porous as modification or thin layer zeolite.Invention JP2005281254 provides a kind of method of producing propylene, has very high productive rate and selectivity, meanwhile, by reacting, the ethene in product and methyl alcohol and dme to improve the ratio of propylene/ethylene under catalyzer further.
Patent US 4,499,314 provides a kind of methyl alcohol under Si-Al zeolite catalyst action, reacts the hydrocarbon products that production is primary product with ethene and propylene.Catalyzer can be faujusite, mordenite, ZSM-5 etc., and stablely at 250 DEG C ~ 500 DEG C has carried out hydrothermally stable process, and reaction process adds aromatic hydroxy compound as the promotor of preparing alkene.Patent US4767886 discloses a kind of method that methyl alcohol or dme produce low charcoal alkene, at 0.1 ~ 20h
-1air speed, under 300 ~ 650 DEG C of temperature, 0.1 ~ 100 atmospheric pressure, use a kind of through alkali-earth metal modified boracic al silicate molecular sieve as its catalyzer, but the concrete classification of undeclared molecular sieve.
CN1489563 discloses and relates to one by being contacted at oxygenatedchemicals zone of transformation with oxygenatedchemicals by molecular sieve catalyst, makes a part of oxygenatedchemicals be converted into olefin product; Catalyzer is separated with olefin product, and revivifier sent into by a catalyzer part separated; Regenerated catalyst is contacted in alcohol zone of action with the alcohol being selected from methyl alcohol, ethanol, 1-propyl alcohol, n-butyl alcohol or their mixture; The process of oxygenatedchemicals zone of transformation is delivered to prepare the technique of ethene, propylene and butylene from alcohol zone of action with the catalyzer after being contacted by alcohol.
It is containing C by methyl alcohol or dimethyl ether conversion that CN1352627 provides a kind of
2~ C
4the method of olefin product, the method comprises the step that the material containing methyl alcohol or dme is contacted with the catalyzer containing zeolite, its mesolite has 10 ring intersecting channels, as ZSM-5, and work as at 120 DEG C and 2, the pressure of 2-dimethylbutane is that the diffusion parameter of zeolite to 2,2-dimethylbutane is less than 100 seconds when measuring under 8KPA
-1.Contact procedure be 370 ~ 480 DEG C, methanol partial pressure is 30 ~ 150psia, and the per pass conversion of methyl alcohol is less than 95%.
CN1084431 discloses a kind of method of methanol/dimethyl ether being produced alkene, use a kind of definitely heat fixation bed bioreactor technique, catalyzer be with lanthanum, phosphorous modified ZSM-5 molecular sieve active ingredient and ~ 35% silicon-dioxide for binding agent, embodiment disclose only reaction gas phase C
2~ C
4olefin yields is greater than 85%, and the regeneration period of catalyzer only 24 hours strong.
In sum, the catalyzer that preparing olefin by conversion of methanol technology uses is porous molecular sieve materials, as ZSM-5/ZSM-11, SAPO-34 equimolecular sieve.It is favourable to reaction generation ethylene, propylene that reaction process adds thinner, thinner can be the inert substances such as nitrogen, but utilize water vapour as thinner in Technology be all optimal economically, it can not only make response light olefine selective improve, delay catalyzer coking----extending catalyst the regeneration period, and be cheaply easy to get.
Summary of the invention
Technical problem to be solved by this invention is the problem that the object product propylene selectivity that exists in prior art is low.There is provided a kind of method of propylene preparation through methanol conversion, the method is used in preparing propylene from methanol reaction, has the advantage that the selectivity of propylene is higher.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of propylene preparation through methanol conversion, take industrial methanol as raw material, is 400 ~ 600 DEG C in temperature of reaction, and reaction pressure is 0 ~ 0.15MPa, and liquid phase weight air speed is 0.5 ~ 3.0 hour
-1, water and methanol molar ratio are under the condition of 0.5 ~ 3.0, and raw material and catalyst exposure generate propylene, and wherein, used catalyst, with weight parts, comprises following component:
A) SiO of 50 ~ 95 parts
2/ Al
2o
3silica alumina ratio is the ZSM-48 type molecular sieve of 100 ~ 1000,
B) binding agent being selected from least one in aluminum oxide or silicon oxide of 5 ~ 50 parts.
In technique scheme, preferred technical scheme catalyzer is also containing phosphoric, and in catalyst weight number, phosphorus element content preferable range is 0.1 ~ 2.0 part, and more preferably scope is 0.2 ~ 0.5 part.Before preferred technical scheme charging reaction, catalyzer 100% steam-treated 24 ~ 72h, temperature of reaction preferable range is 450 ~ 550 DEG C; Weight space velocity preferable range is 0.7 ~ 2.0 hour
-1.
The catalyst preparation process used in the inventive method is mainly as follows:
The synthesis of ZSM-48 molecular screen primary powder: by 1200 grams of water, 12 grams of sodium hydroxide, 174 gram 1,6-hexanediamine and 500 grams of silicon sol add in 2000 ml beakers according to a definite sequence, aging 4 hours of stirring at room temperature, then 115 ~ 170 DEG C of variable temperature crystallizations three days in 2 liters of reactors, obtain high-silicon ZSM-5-48.When synthesizing Si-Al is than relatively low ZSM-48, add high-silicon ZSM-5-48 as crystal seed, centrifugal after Different Silicon aluminum ratio ZSM-48 crystallization completes, wash and be less than 9.0 to solution pH value, then dry and obtain ZSM-48 molecular screen primary powder.
ZSM-48 shaping of catalyst: mixed with aluminum oxide or silicon oxide by ZSM-48 molecular screen primary powder, adds dust technology and is adjusted to suitable humidity, is extruded into strip after making beating evenly.Dust technology ammonium solution is adopted to be exchanged for ammonium type after burn off template.
Hydrothermal aging process: if needed, can by the catalyzer of the inventive method through 100% water vapor original position 450 ~ 550 DEG C process 24 ~ 72 hours, more caducous framework aluminum atom is deviate from, in advance with the activity of rugged catalyst.
For improving the hydrothermal stability of catalyzer, also can add phosphoric in catalyzer and carry out modification, phosphorus source generally can adopt phosphoric acid, ammonium di-hydrogen phosphate or Secondary ammonium phosphate.The optimum content of phosphorus is generally 0.1 ~ 2.0%.ZSM-48 catalyst modification method is: configure certain density solution containing phosphate as required, joins in the ammonium type ZSM-48 catalyzer of forming and floods a few hours, last vacuumizing and drying, make phosphorus distribute in the catalyst so more even.
In the present invention, methyl alcohol used is industrial methanol, adds thinner in reactor feed gas, can reduce raw material and the olefin product dividing potential drop of logistics, shortens the alkene residence time on a catalyst, can reduce hydrogen transfer reactions and coking, thus is beneficial to the selectivity increasing propylene.Thinner can be nitrogen, methane, propane, water vapor, but the thinner using water (steam) as reaction, have be easy to get, inexpensive, after condensation easily with the advantage such as gas, hydrocarbon product are separated, and water vapour can delay coke to be formed on a catalyst, the regeneration period of extending catalyst.
The present invention is by adopting with ZSM-48 molecular sieve as catalyzer, ZSM-48 has the pore passage structure of 10 rings, orifice diameter is 0.6nm, close with ZSM-5 molecular sieve, but the duct of ZSM-48 is two-dimentional non-penetrating linear channels, and ZSM-5 is the three-dimensional open-framework that straight nibs road intersects with Z-type duct.The difference of their performances in preparing propylene by methanol transformation may be caused just because of the two difference on pore passage structure.Produce propylene for methanol conversion, methyl alcohol adopts distilled water to dilute, and makes the weight ratio of first alcohol and water be 0.5 ~ 3: 1.Temperature of reaction preferable range is 450 ~ 550 DEG C, and liquid phase air speed preferable range is 0.5 ~ 2.0 hour
-1, ZSM-48 molecular sieve silica alumina ratio (SiO
2/ Al
2o
3) preferable range be 200 ~ 600, in this technical scheme, methanol conversion is greater than 99%, and Propylene Selectivity can reach more than 46%, achieves good technique effect.
Below by embodiment, the invention will be further elaborated.
Embodiment
[embodiment 1]
By 1200 grams of water, 12 grams of sodium hydroxide, 174 gram 1,6-hexanediamine and 500 grams of silicon sol add in 2000 ml beakers according to a definite sequence, aging 4 hours of stirring at room temperature, then 115 ~ 170 DEG C of variable temperature crystallizations three days in 2 liters of reactors, obtain ZSM-48, product through washing, dry after as crystal seed.
By 1200 grams of water, 12 grams of sodium hydroxide, 174 gram 1,6-hexanediamine, 500 grams of silicon sol, 2.22 grams of Tai-Ace S 150 (containing 18 crystal water), 10 grams of high-silicon ZSM-5-48 crystal seeds add in 2000 ml beakers according to a definite sequence, aging 4 hours of stirring at room temperature, then 115 ~ 170 DEG C of variable temperature crystallizations three days in 2 liters of reactors, obtain the former powder of ZSM-48.
By 20 grams of ZSM-48 molecular sieves after crystallization after washing, oven dry, roasting, be placed in 400 milliliters, 5% weight NH
4nO
3in solution, at 85 ~ 90 DEG C of temperature, exchange 2 hours, repeat 3 times.Through washing, drying the ZSM-48 molecular sieve obtaining ammonium type after exchange.The ZSM-5 molecular sieve of 10 grams of ammonium type adds 2.78 gram of 40% silicon sol as binding agent, extrusion moulding.Again through 120 DEG C of oven dry, obtained catalyst A after 550 DEG C of roastings.Reaction procatalyst A is 480 DEG C, activation 2 hours under nitrogen atmosphere.The raw material used in experiment from industrial methanol, and adds a certain amount of distilled water, makes the weight ratio of water and methyl alcohol be 1: 1.Temperature of reaction 480 DEG C, the weight space velocity of methyl alcohol is 0.73h
-1, pressure 0.05Mpa, reaction result is in table 1.
[comparative example 1]
The ZSM-5 molecular sieve of identical silica alumina ratio is carried out shaping according to the method that embodiment 1 is identical and evaluates at identical conditions.Reaction result is as shown in table 1.
Table 1
[embodiment 2 ~ 3]
Change the SiO of ZSM-48
2/ Al
2o
3ratio, synthesizes the former powder of ZSM-48 according to the method identical with embodiment 1, shaping, obtained catalyst B (SiO
2/ Al
2o
3=600) and catalyzer C (SiO
2/ Al
2o
3=400), and evaluate at identical conditions, reaction result is as shown in table 1.
[embodiment 4 ~ 6]
The catalyzer ammonium dibasic phosphate solution being numbered C is flooded modification, makes phosphorus content be 0.1 ~ 0.5% (weight fraction).After room temperature immersion a few hours, rise to 60 DEG C of vacuumizing and drying, 550 DEG C of roastings 4 hours, obtain catalyzer D (phosphorus content 0.1%), catalyzer E (phosphorus content 0.3%) and catalyzer F (phosphorus content 0.7%).All phosphorus-containing catalysts are original position 100% steam-treated 48h before charging reaction.The reactivity worth of catalyzer is in table 1.
[embodiment 7 ~ 12]
Adopt the catalyzer E identical with embodiment 5, temperature of reaction temperature 450 ~ 550 DEG C, carry out the evaluation of preparing propylene from methanol reaction under the condition of pressure 0 ~ 0.5Mpa, the results are shown in Table 2.
Table 2
[embodiment 13]
The catalyzer identical by embodiment 7 and reaction conditions, carry out catalyst life test, and its result is as follows:
Claims (1)
1. the method for a propylene preparation through methanol conversion, by 1200 grams of water, 12 grams of sodium hydroxide, 174 gram 1,6-hexanediamine and 500 grams of silicon sol add in 2000 ml beakers according to a definite sequence, aging 4 hours of stirring at room temperature, then 115 ~ 170 DEG C of variable temperature crystallizations three days in 2 liters of reactors, obtain ZSM-48, product through washing, dry after as crystal seed;
By 1200 grams of water, 12 grams of sodium hydroxide, 174 gram 1,6-hexanediamine, 500 grams of silicon sol, 2.22 grams of Tai-Ace S 150 containing 18 crystal water, 10 grams of high-silicon ZSM-5-48 crystal seeds add in 2000 ml beakers according to a definite sequence, aging 4 hours of stirring at room temperature, then 115 ~ 170 DEG C of variable temperature crystallizations three days in 2 liters of reactors, obtain the former powder of ZSM-48;
By 20 grams of ZSM-48 molecular sieves after crystallization after washing, oven dry, roasting, be placed in 400 milliliters, 5% weight NH
4nO
3in solution, at 85 ~ 90 DEG C of temperature, exchange 2 hours, repeat 3 times; Through washing, drying the ZSM-48 molecular sieve obtaining ammonium type after exchange; The ZSM-5 molecular sieve of 10 grams of ammonium type adds 2.78 gram of 40% silicon sol as binding agent, extrusion moulding; Again through 120 DEG C of oven dry, obtained catalyst A after 550 DEG C of roastings; Reaction procatalyst A is 480 DEG C, activation 2 hours under nitrogen atmosphere; The raw material used in experiment from industrial methanol, and adds a certain amount of distilled water, makes the weight ratio of water and methyl alcohol be 1:1; Temperature of reaction 480 DEG C, the weight space velocity of methyl alcohol is 0.73h
-1, pressure 0.05Mpa, reaction result: methanol conversion 99.9%, ethylene selectivity 7.4%, Propylene Selectivity 39.4%, carbon four selectivity 24.4%, carbon five selectivity 12.0%.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1506343A (en) * | 2002-12-11 | 2004-06-23 | 中国石油化工股份有限公司 | Propylene producing process |
| WO2009016153A2 (en) * | 2007-07-31 | 2009-02-05 | Total Petrochemicals Research Feluy | Phosphorus modified molecular sieves, their use in conversion of organics to olefins |
| CN101429085A (en) * | 2007-11-07 | 2009-05-13 | 中国石油化工股份有限公司 | Method for producing propylene, ethylene light olefin hydrocarbon |
| CN101801848A (en) * | 2007-09-18 | 2010-08-11 | 埃克森美孚研究工程公司 | Synthesizing of high activity ZSM-48 |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1506343A (en) * | 2002-12-11 | 2004-06-23 | 中国石油化工股份有限公司 | Propylene producing process |
| WO2009016153A2 (en) * | 2007-07-31 | 2009-02-05 | Total Petrochemicals Research Feluy | Phosphorus modified molecular sieves, their use in conversion of organics to olefins |
| CN101801848A (en) * | 2007-09-18 | 2010-08-11 | 埃克森美孚研究工程公司 | Synthesizing of high activity ZSM-48 |
| CN101429085A (en) * | 2007-11-07 | 2009-05-13 | 中国石油化工股份有限公司 | Method for producing propylene, ethylene light olefin hydrocarbon |
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