CN104211556B - A kind of preparation method of low-carbon alkene - Google Patents
A kind of preparation method of low-carbon alkene Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of low-carbon alkene.The method comprises: under the oxi-chlorination condition of methane, mixed gas containing methane, hydrogenchloride and oxygen source and the first catalyzer are carried out the first contact reacts, and the first contact reacts gained mixture and the second catalyzer are carried out the second contact reacts, described second catalyzer is one or more in aluminum oxide, Si-Al molecular sieve and silicoaluminophosphamolecular molecular sieves.The method preparation technology is simple, does not need the separating step through removing water, higher to the selectivity of low-carbon alkene, and can carry out under lower temperature of reaction.
Description
Technical field
The present invention relates to a kind of preparation method of low-carbon alkene.
Background technology
World today's energy system is mainly based upon on Sweet natural gas, coal and oil these three kinds flammable fossil resource bases.Methane is the main component in Sweet natural gas.Therefore, develop methane conversion is have high value-added product reality as great in low-carbon alkene, oxygenatedchemicals etc. have and strategic importance.
Methane can be divided into three kinds for the method for low-carbon alkene, namely utilizes methane directly to prepare low-carbon alkene, take synthetic gas as Intermediate Preparation low-carbon alkene and be intermediate producing light olefins with methyl halide.
The method utilizing methane directly to prepare low-carbon alkene comprises methane pyrolytic decomposition and methane oxidation coupling two kinds of approach.The product of methane pyrolytic decomposition is based on acetylene, and temperature of reaction is very high.The shortcoming one of Catalyst for Oxidative Coupling of Methane is that temperature of reaction is still higher, and two is also do not have efficient catalyzer at present, and yield of ethene is still lower, does not also have industrial application value.
Fischer-Tropsch (Fischer-Tropsch) synthesis and MTO(MethanoltoOlefin) method is all be that low-carbon alkene prepared by raw material with synthetic gas.These two kinds of methods need first to change methane into synthetic gas, and whole process flow is long, and energy consumption, material consumption are all higher.
CN101659595A and CN100582064C discloses a kind of method being prepared monobromethane, high-carbon hydrocarbon, methyl alcohol or dme by methane oxygen bromination, and methane is at SiO
2precious metal Ru, Rh, Pd, Pt upper generation oxygen bromination reaction of load generates methyl bromide, and methyl bromide reaction under ZnO, MgO or CuO of the load of second stage catalyst molecule sieve exist generates high-carbon hydrocarbon.But methane oxygen bromination reaction needs using expensive precious metal as catalyst activity component, and temperature of reaction higher (600-700 DEG C).
The process that methane prepares low-carbon alkene through monochloro methane generally includes two-step reaction, and namely for methane and chlorine source oxi-chlorination occur and prepare monochloro methane and monochloro methane converts low-carbon alkene under certain condition again.
The catalyzer of methane oxi-chlorination has two classes usually, is namely the catalyzer of active ingredient with transition metal and take rare earth element as the catalyzer of active ingredient.Conventional transition metal has Cu(EP0720975A1, US4039596, US5240398), Fe(US3172915, US3819732), Co(US5019652).Conventional rare earth element has La(CN1206196C, US6984763, US20040097767), Ce(Angew.Chem.Int.Ed.2012,51,2438-2442, CN102344339A).For taking rare earth element as the catalyzer of active ingredient, take transition metal as the maximum advantage of the catalyzer of active ingredient be low price.
US4513092 discloses a kind of preparation method of composite catalyst, makes methane by directly obtaining low-carbon alkanes after beds, and catalyzer used is that load Deacon catalyzer on alumina and H-ZSM-5 are composited.Composite catalyst requires higher to the selection of reaction conditions, and such as, in methane oxi-chlorination, temperature raises the conversion being conducive to methane; And changing in the reaction of low-carbon alkene at monochloro methane, temperature raises meeting accelerator activator inactivation, and can affect the selectivity of product, and the selection of end reaction temperature will be compromise result, and two-step reaction so just cannot be made to occur all in the best condition.
US4769504 discloses a kind of by the method for methane for low-carbon alkene, and catalyzer used is silicon dioxide carried CuCl, KCl and LaCl
3and H-ZSM-5.But in the method, except the selectivity of above-mentioned H-ZSM-5 to ethene, propylene is lower, between the catalyzed reaction in two stages, also add a step-down temperature drying step to remove the water produced in first stage reaction, this will inevitably cause extending process time, and production cost increases.
Therefore, develop that a kind of temperature of reaction is low, processing step simple and to selectivity of light olefin high be still for the method for low-carbon alkene the problem that is needed badly solution by methane.
Summary of the invention
The object of the invention is to overcome in prior art and utilize methane for the above-mentioned defect existed in the process of low-carbon alkene, a kind of preparation method of low-carbon alkene is provided.
The invention provides a kind of preparation method of low-carbon alkene, wherein, the method comprises: under the oxi-chlorination condition of methane, mixed gas containing methane, hydrogenchloride and oxygen source and the first catalyzer are carried out the first contact reacts, and the first contact reacts gained mixture and the second catalyzer are carried out the second contact reacts, described second catalyzer is one or more in aluminum oxide, Si-Al molecular sieve and silicoaluminophosphamolecular molecular sieves.
The preparation method of low-carbon alkene provided by the invention, methane is utilized to prepare low-carbon alkene by two-step reaction, preparation method is simple, do not need the separating step through removing water, and adopt specific second catalyzer, make the selectivity of method provided by the invention to low-carbon alkene (ethene and propylene) higher.Particularly, the selectivity of ethene is the highest can reach more than 40%, and the selectivity of propylene is the highest can reach more than 15%, and the overall selectivity of ethene and propylene is the highest can reach more than 55%.
In addition, the preparation method of low-carbon alkene provided by the invention can carry out under lower temperature of reaction (particularly, being less than 500 DEG C).
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of preparation method of low-carbon alkene, wherein, the method comprises: under methane oxi-chlorination condition, mixed gas containing methane, hydrogenchloride and oxygen source and the first catalyzer are carried out the first contact reacts, and the first contact reacts gained mixture and the second catalyzer are carried out the second contact reacts, described second catalyzer is one or more in aluminum oxide, Si-Al molecular sieve and silicoaluminophosphamolecular molecular sieves.
According to the present invention, to the mol ratio of methane, hydrogenchloride and oxygen source, there is no particular limitation, can change in wider scope, as long as enable methane that oxi-chlorination occur generate monochloro methane.Under preferable case, the mol ratio of methane, hydrogenchloride and oxygen source is 2-75:2-8:1, and under further preferable case, the mol ratio of methane, hydrogenchloride and oxygen source is 5-10:4-8:1.
According to the present invention, to the weight ratio of described first catalyzer and the second catalyzer, there is no particular limitation, can change in wider scope.But consider that the first catalyzer plays the effect of the oxi-chlorination of catalytic methane and the second catalyzer plays the effect making monochloro methane generate low-carbon alkene, under preferable case, the weight ratio of described first catalyzer and the second catalyzer is 1:0.5-5, under further preferable case, the weight ratio of described first catalyzer and the second catalyzer is 1:1-3, under most preferred case, the weight ratio of described first catalyzer and the second catalyzer is 1:2-3.
In the present invention, described first catalyzer is the catalyzer that catalytic methane generation oxi-chlorination generates monochloro methane; Described second catalyzer is make monochloro methane transform the catalyzer generating the reaction of the low-carbon alkene such as ethene, propylene.
It should be noted that, " first " and " second " in first catalyzer described in the present invention and described second catalyzer does not have special implication, just represent that described first catalyzer and described second catalyzer are different catalyzer, but do not limit the first catalyzer and the second catalyzer.
According to the present invention, with the volume of described first catalyzer for benchmark, the volume space velocity of described mixed gas is 900-3500h
-1, be preferably 1500-1700h
-1.
In the present invention, volume space velocity is the volume by the mixed gas of per volume of catalyst in the unit time.Relatively described first catalyzer, the volume space velocity of described mixed gas is the ratio of the flow velocity of mixed gas and the volume of described first catalyzer.
In the present invention, the volume of described first catalyzer is the bulk density of quality divided by described first catalyzer of described first catalyst loading.
According to the present invention, described oxygen source can be oxygen or mixed gas oxygenous arbitrarily, such as, can be oxygen or air.
In the present invention, under preferable case, available diluent gas dilutes mixture of feed body, to contribute to the generation removed heat and reduce side reaction from reactor.Described diluent gas can for can not disturb the first contact reacts and the second catalytic gas, such as, can be one or more in nitrogen, argon gas and helium.Described diluent gas can enter in reactor with the mixed gas containing methane, hydrogenchloride and oxygen source simultaneously.The consumption of described diluent gas according to not affecting the first contact reacts and the second catalytic principle is reasonably selected, can not repeat them here.
According to the present invention, the catalyzer of the various catalytic methane oxi-chlorinations that described first catalyzer can be well known to those skilled in the art.Under preferable case, described first catalyzer contains carrier and load active ingredient on the carrier, described active ingredient comprises main active ingredient and helps active ingredient, described main active ingredient is copper component, described in help active ingredient to be alkaline components and/or alkaline earth metal component and rare earth component.
According to the present invention, to the content of the described carrier in described first catalyzer and load active ingredient on the carrier, there is no particular limitation, can at wider range changing.Under preferable case, with the gross weight of described first catalyzer for benchmark, the content of described carrier is 70-97 % by weight, the content of described active ingredient is 3-30 % by weight, and with elemental metal, the content of copper component is 1-10 % by weight, and the content of rare earth component is 1-10 % by weight, and the content of alkaline components and/or alkaline earth metal component is 1-10 % by weight.Under further preferable case, with the gross weight of described first catalyzer for benchmark, the content of described carrier is 75-95 % by weight, the content of described active ingredient is 5-17 % by weight, and with elemental metal, the content of copper component is 3-8 % by weight, and the content of rare earth component is 1-4 % by weight, and the content of alkaline components and/or alkaline earth metal component is 1-5 % by weight.
It should be noted that, the content of described alkaline components and/or alkaline earth metal component refers to the one in the content of the content of alkaline components, alkaline earth metal component and the content of alkaline components and alkaline earth metal component total amount.
According to the present invention, the carrier of what described carrier can be well known to those skilled in the art be applicable to catalytic methane catalyst in oxychlorination reaction, such as, can be one or more in aluminum oxide, silicon-dioxide and titanium oxide, be preferably silicon-dioxide.
According to the present invention, described copper component exists with the form of water-soluble mantoquita, and under preferable case, described water-soluble mantoquita is cupric chloride.
According to the present invention, described rare earth component be preferably in lanthanum component, cerium component, neodymium component, praseodymium component and yttrium component one or more.Further in preferred situation, described rare earth component is lanthanum component.
According to the present invention, described rare earth component exists with the form of water-solubility rare-earth metal-salt.Under preferable case, described rare earth component is water soluble lanthanum salt.Described water soluble lanthanum salt preferably exists with the form of the hydrochloride of rare earth metal (i.e. the muriate of rare earth metal), also be, lanthanum component preferably exists with the form of Lanthanum trichloride, cerium component preferably exists with the form of Cerium II Chloride, neodymium component preferably exists with the form of Neodymium trichloride, praseodymium component preferably exists with the form of praseodymium chloride, and yttrium component preferably exists with the form of Yttrium trichloride.In most preferred situation, described rare earth component exists with the form of Lanthanum trichloride.
According to the present invention, described alkaline components is preferably lithium component and/or potassium component; Described alkaline earth metal component is preferably magnesium component.Further in preferred situation, described alkaline components is potassium component, and described alkaline earth metal component is preferably magnesium component.
In the present invention, described alkaline components and/or alkaline earth metal component exist with the form of the salt of basic metal and/or alkaline-earth metal.Under preferable case, described basic metal and/or alkaline earth metal component exist with the form of the hydrochloride (i.e. the muriate of basic metal and/or alkaline-earth metal) of basic metal and/or alkaline-earth metal, also namely, potassium component and/or magnesium component preferably exist with the form of Repone K and/or magnesium chloride.
A preferred embodiment of the invention, described copper component is water-soluble mantoquita, and described rare earth component is water soluble lanthanum salt, and described alkaline components is sylvite.In further preferred embodiment, described copper component is cupric chloride, and described rare earth component is Lanthanum trichloride, and described alkaline components is Repone K.
According to the present invention, the preparation method of described first catalyzer is conventionally known to one of skill in the art, such as, adopt pickling process.As long as the first catalyzer of preparing of described dipping method can the oxi-chlorination of catalytic methane, those skilled in the art reasonably can select the condition of described dipping method according to mentioned above principle.
According to the present invention, described second catalyzer is one or more in aluminum oxide, Si-Al molecular sieve and silicoaluminophosphamolecular molecular sieves, is preferably Si-Al molecular sieve and silicoaluminophosphamolecular molecular sieves, is more preferably silicoaluminophosphamolecular molecular sieves.Described second catalyzer preferably has vesicular structure, and its aperture can be 1-3nm, and pore volume can be 0.15-1.5cm
3/ g, specific surface area can be 200-700m
2/ g, particle diameter can be 0.25-2mm, considers that the second catalyzer has better catalytic effect, and under preferable case, the aperture of described second catalyzer is 1.5-2.5nm, and pore volume is 0.25-1.2cm
3/ g, specific surface area is 250-650m
2/ g, particle diameter is 0.45-0.90mm.
It should be noted that, in the present invention, the backbone element in Si-Al molecular sieve is Silicified breccias and the Sauerstoffatom with its coordination, such as H-ZSM-5, and silicoaluminophosphamolecular molecular sieves is Al or P that Si part replaces in aluminium phosphate molecular sieve skeleton, such as SAPO-34.
The preparation method of low-carbon alkene provided by the invention, prepares low-carbon alkene by two-step reaction, does not need the separating step through removing water, and adopts specific second catalyzer to make the selectivity of method provided by the invention to low-carbon alkene higher.
According to the present invention, the various conditions of the oxi-chlorination of the methane that described first catalytic condition can be well known to those skilled in the art, under preferable case, described first catalytic condition comprises: reaction pressure is 0.08-1MPa, is preferably 0.09-0.2MPa; Temperature of reaction is 300-600 DEG C, is preferably 350-450 DEG C.
It should be noted that, the reaction pressure in the present invention refers to absolute pressure.
According to the present invention, what described second catalytic condition can be well known to those skilled in the art makes monochloro methane change into the various reaction conditionss of low-carbon alkene, under preferable case, described second catalytic condition comprises: reaction pressure is 0.08-1MPa, is preferably 0.09-0.2MPa; Temperature of reaction is 300-600 DEG C, is preferably 350-450 DEG C.
It should be noted that, " first " and " second " in first contact reacts described in the present invention and described second contact reacts does not have special implication, just represent that described first contact reacts and described second contact reacts are different reactions, but do not limit the first contact reacts and the second contact reacts.
In the present invention, described first contact reacts and described second contact reacts can be carried out continuously in same reactor, also can carry out continuously in two independently reactor respectively.Under preferable case, described first contact reacts and described second contact reacts are carried out continuously in same reactor.
According to the present invention, described first catalytic condition can be identical or different with the condition of described second reaction contacted, namely described first catalytic pressure and described second catalytic pressure can be identical or different, and described first catalytic temperature and described second catalytic temperature can be identical or different.
In the preferred embodiment of the present invention, described first contact reacts and the second contact reacts are carried out in same reactor, and described first catalytic condition is identical with described second catalytic condition.
In the present invention, low-carbon alkene refers to C
2-C
3alkene.
Below will be described the present invention by embodiment.
In following preparation example, the specific surface area of catalyzer, aperture and pore volume adopt Micromeritics company ASAP-2020 specific surface and pore distribution determinator to measure.Described aperture, pore volume and specific surface area are measured by nitrogen adsorption-detachment assays.By sample at 350 DEG C degassed 4 hours before measuring.The mensuration of the physical properties of catalyzer comprises: the bulk density of catalyzer adopts graduated cylinder method of masurement to measure; Ultimate analysis in catalyzer adopts PANalyticalBV company Axios-Advanced wavelength dispersion X-ray fluorescence spectrometer to measure.
In following examples, methane conversion, ethylene selectivity and Propylene Selectivity are recorded by gas chromatography.Concrete operations will be for reacting products therefrom after overcooling removing water and partial oxidation hydrogen, with gas chromatograph (the Agilent company being furnished with FID and TCD detector, model is 6890) carry out on-line analysis, with HP-PLOTQ chromatographic column separating hydrocarbons compound and chloroparaffin, with HP-PLOTQ and HPPLOTMolesieve chromatographic column combined separation CO, CO
2and CH
4, with CH
4associate.Methane conversion, ethylene selectivity and Propylene Selectivity calculate according to following calculation formula respectively.
(1) calculation formula of methane conversion:
Wherein:
that alkane, alkene, methyl chloride, oxycarbide and methanol phase are for CH respectively
4mole correction factor;
the peak area of alkane, alkene, methyl chloride, oxycarbide, methyl alcohol and methane respectively.
(2) calculation formula of ethylene selectivity:
Wherein:
that ethene is relative to CH
4mole correction factor,
the peak area of ethene and methane respectively.
(3) calculation formula of Propylene Selectivity:
Wherein:
that propylene is relative to CH
4mole correction factor,
the peak area of propylene and methane respectively.
Preparation example 1
This preparation example is for illustration of the preparation method of the first catalyzer and the second catalyzer.
Take 0.4gCuCl
22H
2o, 0.34gKCl, 0.41gLaCl
37H
2o is dissolved in 25mL water, and (specific surface area is 650m to add 3g silica supports
2/ g, aperture is 8nm, identical below), stirring is spent the night, water bath method at 80 DEG C, dry at 120 DEG C, in atmosphere with the ramp to 550 of 5 DEG C/min DEG C roasting 5 hours, be cooled to compressing tablet after room temperature, pulverize, sieve, get the part between 20-40 order, gained catalyzer is labeled as A1.
By silicoaluminophosphamolecular molecular sieves SAPO-34(purchased from Tianjin Kai Meisite Science and Technology Ltd., aperture is 1.6nm, and pore volume is 0.26cm
3/ g, specific surface area is 623.96m
2/ g, (Al+P)/Si(mol ratio)=3) carry out compressing tablet, pulverize, sieve, get the part between 20-40 order (0.45-0.90mm), gained catalyzer is labeled as B1.
By H-ZSM-5(purchased from Tianjin Kai Meisite Science and Technology Ltd., aperture is 2.5nm, and pore volume is 0.23cm
3/ g, specific surface area is 367.83m
2/ g, Si/Al(mol ratio)=100) carry out compressing tablet, pulverize, sieve, get the part between 20-40 order (0.45-0.90mm), gained catalyzer is labeled as B2.
Preparation example 2
This preparation example is for illustration of the preparation method of the first catalyzer.
Take 0.51gCuCl
22H
2o, 0.23gKCl, 0.25gLaCl
37H
2o is dissolved in 25mL water, add 3g silica supports, stirring is spent the night, water bath method at 80 DEG C, dry at 120 DEG C, in atmosphere with the ramp to 550 of 5 DEG C/min DEG C roasting 5 hours, be cooled to compressing tablet after room temperature, pulverize, sieve, get the part between 20-40 order, gained catalyzer is labeled as A2.
Preparation example 3
This preparation example is for illustration of the preparation method of the first catalyzer.
Take 0.81gCuCl
22H
2o, 0.09gKCl, 0.12gLaCl
37H
2o is dissolved in 25ml water, add 3g silica supports, stirring is spent the night, water bath method at 80 DEG C, dry at 120 DEG C, in atmosphere with the ramp to 550 of 5 DEG C/min DEG C roasting 5 hours, be cooled to compressing tablet after room temperature, pulverize, sieve, get the part between 20-40 order, gained catalyzer is labeled as A3.
Preparation example 4
This preparation example is for illustration of the preparation method of the first catalyzer.
Prepare the first catalyzer according to the method for preparation example 1, difference is, in the process of preparation first catalyzer, replaces silica supports, obtain catalyst A 4 with the titanium dioxide carrier of identical weight.
Preparation example 5
This preparation example is for illustration of the preparation method of the first catalyzer.
Prepare the first catalyzer according to the method for preparation example 1, difference is, in the process of preparation first catalyzer, replaces silica supports, obtain catalyst A 5 with the alumina supporter of identical weight.
Preparation example 6
This preparation example is for illustration of the preparation method of the first catalyzer.
Prepare the first catalyzer according to the method for preparation example 1, difference is, in the process of preparation first catalyzer, uses CeCl
37H
2o replaces LaCl
37H
2o, keeps the content of each component in catalyzer constant, obtains catalyst A 6.
Preparation example 7
This preparation example is for illustration of the preparation method of the first catalyzer.
Prepare the first catalyzer according to the method for preparation example 1, difference is, in the process of preparation first catalyzer, replaces Repone K with calcium chloride, keeps the content of each component in catalyzer constant, obtains catalyst A 7.
Embodiment 1
The present embodiment is for illustration of the preparation method of low-carbon alkene provided by the invention.
In silica glass pipe reactor (internal diameter is 8mm), adding 0.25g catalyst A 1(bulk density is successively 0.334g/mL) and 0.50g catalyst B 1, the upper and lower filled stone sand of catalyzer (20-40 order).Pass into nitrogen (21mL/min), with the ramp to 450 DEG C of 5 DEG C/min, switch to feeding gas after activation 30min, flow velocity is 21mL/min, and it consists of methane 23.8%, hydrogenchloride 19%, molecular oxygen 4.8%, and all the other are nitrogen.Under the pressure of 0.09MPa, feeding gas and catalyst A 1 are reacted, then reacts with catalyst B 1.By gas chromatography determination methane conversion, ethylene selectivity and Propylene Selectivity, test result is in table 1.
Comparative example 1
Low-carbon alkene is prepared according to the method for embodiment 1, unlike, after feeding gas and catalyst A 1 are reacted, the water in reaction gained mixture, again through cold hydrazine (circulating liquid-4 ° of C), is removed, and then is reacted with ZSM-5 by cooling.By gas chromatography determination methane conversion, ethylene selectivity and Propylene Selectivity, test result is as shown in table 1.
Comparative example 2
Low-carbon alkene is prepared according to the method for embodiment 1, unlike, first catalyst A 1 and catalyst B 1 are carried out mixing then compressing tablet and become composite catalyst, feeding gas is contacted with this composite catalyst.By gas chromatography determination methane conversion, ethylene selectivity and Propylene Selectivity, test result is as shown in table 1.
Embodiment 2
The present embodiment is for illustration of the preparation method of low-carbon alkene provided by the invention.
In silica glass pipe reactor (internal diameter is 8mm), adding 0.25g catalyst A 3(bulk density is successively 0.333g/mL) and 0.75g catalyst B 1, the upper and lower filled stone sand of catalyzer (20-40 order).Pass into nitrogen (21mL/min), with the ramp to 350 DEG C of 5 DEG C/min, switch to feeding gas after activation 30min, flow velocity is 21mL/min, and it consists of methane 48%, hydrogenchloride 38.4%, molecular oxygen 4.8%, and all the other are nitrogen.Under the pressure of 0.2MPa, feeding gas and catalyst A 3 are reacted, then reacts with catalyst B 1.By gas chromatography determination methane conversion, ethylene selectivity and Propylene Selectivity, test result is in table 1.
Embodiment 3
In silica glass pipe reactor (internal diameter is 8mm), adding 0.25g catalyst A 2(bulk density is successively 0.33g/mL) and 0.63g catalyst B 1, the upper and lower filled stone sand of catalyzer (20-40 order).Pass into nitrogen (21mL/min), with the ramp to 400 DEG C of 5 DEG C/min, switch to feeding gas after activation 30min, flow velocity is 21mL/min, and it consists of methane 33.0%, hydrogenchloride 28%, molecular oxygen 4.7%, and all the other are nitrogen.Under the pressure of 0.2MPa, feeding gas and catalyst A 2 are reacted, then reacts with catalyst B 1.By gas chromatography determination methane conversion, ethylene selectivity and Propylene Selectivity, test result is in table 1.
Embodiment 4
The present embodiment is for illustration of the preparation method of low-carbon alkene provided by the invention.
In silica glass pipe reactor (internal diameter is 8mm), adding 0.25g catalyst A 1(bulk density is successively 0.334g/mL) and 0.75g catalyst B 2, the upper and lower filled stone sand of catalyzer (20-40 order).Pass into nitrogen (21mL/min), with the ramp to 400 DEG C of 5 DEG C/min, switch to feeding gas after activation 30min, flow velocity is 21mL/min, and it consists of methane 23.8%, hydrogenchloride 19%, molecular oxygen 4.8%, and all the other are nitrogen.Under the pressure of 0.1MPa, feeding gas and catalyst A 1 are reacted, then reacts with catalyst B 2.By gas chromatography determination methane conversion, ethylene selectivity and Propylene Selectivity, test result is in table 1.
Embodiment 5
The present embodiment is for illustration of the preparation method of low-carbon alkene provided by the invention.
In silica glass pipe reactor (internal diameter is 8mm), adding 0.25g catalyst A 4(bulk density is successively 0.663g/mL) and 0.50g catalyst B 1, the upper and lower filled stone sand of catalyzer (20-40 order).Pass into nitrogen (21mL/min), with the ramp to 450 DEG C of 5 DEG C/min, switch to feeding gas after activation 30min, flow velocity is 21mL/min, and it consists of methane 23.8%, hydrogenchloride 19%, molecular oxygen 4.8%, and all the other are nitrogen.Under the pressure of 0.1MPa, feeding gas and catalyst A 4 are reacted, then reacts with catalyst B 1.By gas chromatography determination methane conversion, ethylene selectivity and Propylene Selectivity, test result is in table 1.
Embodiment 6
The present embodiment is for illustration of the preparation method of low-carbon alkene provided by the invention.
In silica glass pipe reactor (internal diameter is 8mm), adding 0.25g catalyst A 5(bulk density is successively 0.617g/mL) and 0.50g catalyst B 1, the upper and lower filled stone sand of catalyzer (20-40 order).Pass into nitrogen (21mL/min), with the ramp to 450 DEG C of 5 DEG C/min, switch to feeding gas after activation 30min, flow velocity is 21mL/min, and it consists of methane 23.8%, hydrogenchloride 19%, molecular oxygen 4.8%, and all the other are nitrogen.Under the pressure of 0.1MPa, feeding gas and catalyst A 5 are reacted, then reacts with catalyst B 1.By gas chromatography determination methane conversion, ethylene selectivity and Propylene Selectivity, test result is in table 1.
Embodiment 7
The present embodiment is for illustration of the preparation method of low-carbon alkene provided by the invention.
In silica glass pipe reactor (internal diameter is 8mm), adding 0.25g catalyst A 6(bulk density is successively 0.334g/mL) and 0.50g catalyst B 1, the upper and lower filled stone sand of catalyzer (20-40 order).Pass into nitrogen (21mL/min), with the ramp to 450 DEG C of 5 DEG C/min, switch to feeding gas after activation 30min, flow velocity is 21mL/min, and it consists of methane 23.8%, hydrogenchloride 19%, molecular oxygen 4.8%, and all the other are nitrogen.Under the pressure of 0.1MPa, feeding gas and catalyst A 6 are reacted, then reacts with catalyst B 1.By gas chromatography determination methane conversion, ethylene selectivity and Propylene Selectivity, test result is in table 1.
Embodiment 8
The present embodiment is for illustration of the preparation method of low-carbon alkene provided by the invention.
In silica glass pipe reactor (internal diameter is 8mm), adding 0.25g catalyst A 7(bulk density is successively 0.335g/mL) and 0.50g catalyst B 2, the upper and lower filled stone sand of catalyzer (20-40 order).Pass into nitrogen (21mL/min), with the ramp to 450 DEG C of 5 DEG C/min, switch to feeding gas after activation 30min, flow velocity is 21mL/min, and it consists of methane 23.8%, hydrogenchloride 19%, molecular oxygen 4.8%, and all the other are nitrogen.Under the pressure of 0.1MPa, feeding gas and catalyst A 7 are reacted, then reacts with catalyst B 2.By gas chromatography determination methane conversion, ethylene selectivity and Propylene Selectivity, test result is in table 1.
Table 1
| Embodiment is numbered | Methane conversion (%) | Ethylene selectivity (%) | Propylene Selectivity (%) |
| Embodiment 1 | 24.8 | 44.9 | 14.6 |
| Comparative example 1 | 19.2 | 40.1 | 12.1 |
| Comparative example 2 | 10.6 | 8.4 | 2.7 |
| Embodiment 2 | 23.0 | 45.8 | 16.5 |
| Embodiment 3 | 23.6 | 45.0 | 13.9 |
| Embodiment 4 | 19.8 | 41.0 | 12.8 |
| Embodiment 5 | 20.2 | 40.5 | 13.0 |
| Embodiment 6 | 22.4 | 42.2 | 13.5 |
| Embodiment 7 | 22.5 | 43.8 | 13.4 |
| Embodiment 8 | 21.7 | 40.5 | 12.3 |
Can be found out by the data of embodiment 1-8 and comparative example 1 and comparative example 2, the ethene adopting method provided by the invention to obtain and the selectivity of propylene higher, particularly, the selectivity of ethene is the highest can reach more than 40%, the selectivity of propylene is the highest can reach more than 15%, and the overall selectivity of ethene and propylene is the highest can reach more than 55%; And the method preparation is simple, do not need the step through removing water.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (14)
1. the preparation method of a low-carbon alkene, it is characterized in that, the method comprises: under the oxi-chlorination condition of methane, mixed gas containing methane, hydrogenchloride and oxygen source and the first catalyzer are carried out the first contact reacts, and the first contact reacts gained mixture and the second catalyzer are carried out the second contact reacts, described second catalyzer is silicoaluminophosphamolecular molecular sieves; Wherein, described first catalyzer contains carrier and load active ingredient on the carrier, described active ingredient comprises main active ingredient and helps active ingredient, described main active ingredient is copper component, the described active ingredient that helps is alkaline components and/or alkaline earth metal component and rare earth component, and described low-carbon alkene refers to C
2-C
3alkene.
2. preparation method according to claim 1, wherein, the mol ratio of methane, hydrogenchloride and oxygen source is 2-75:2-8:1.
3. preparation method according to claim 1, wherein, the weight ratio of described first catalyzer and the second catalyzer is 1:0.5-5.
4. preparation method according to claim 1, wherein, the weight ratio of described first catalyzer and the second catalyzer is 1:1-3.
5. preparation method according to claim 1 and 2, wherein, described oxygen source is oxygen or air.
6. preparation method according to claim 1, wherein, with the gross weight of described first catalyzer for benchmark, the content of described carrier is 70-97 % by weight, the content of described active ingredient is 3-30 % by weight, and with elemental metal, the content of copper component is 1-10 % by weight, the content of rare earth component is 1-10 % by weight, and the content of alkaline components and/or alkaline earth metal component is 1-10 % by weight.
7. preparation method according to claim 6, wherein, described carrier is one or more in aluminum oxide, silicon-dioxide and titanium oxide.
8. preparation method according to claim 7, wherein, described carrier is silicon-dioxide.
9. preparation method according to claim 6, wherein, described copper component is water-soluble mantoquita; Described rare earth component is water-solubility rare-earth metal-salt; Described alkaline components and/or alkaline earth metal component are the salt of basic metal and/or alkaline-earth metal.
10. preparation method according to claim 9, wherein, described rare earth component is water soluble lanthanum salt.
11. preparation methods according to claim 9, wherein, described alkaline components and/or alkaline earth metal component are sylvite and/or the magnesium salts of basic metal and/or alkaline-earth metal.
12. preparation methods according to claim 1, wherein, described first catalytic condition comprises: reaction pressure is 0.08-1MPa, and temperature of reaction is 300-600 DEG C; Described second catalytic condition comprises: reaction pressure is 0.08-1MPa, and temperature of reaction is 300-600 DEG C.
13. preparation methods according to claim 12, wherein, described first catalytic condition comprises: reaction pressure is 0.09-0.2MPa, and temperature of reaction is 350-450 DEG C.
14. preparation methods according to claim 12, wherein, described second catalytic condition comprises: reaction pressure is 0.09-0.2MPa, and temperature of reaction is 350-450 DEG C.
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| US4769504A (en) * | 1987-03-04 | 1988-09-06 | The United States Of America As Represented By The United States Department Of Energy | Process for converting light alkanes to higher hydrocarbons |
| CN1525950A (en) * | 2001-05-21 | 2004-09-01 | Oxidative halogenation of C* hydrocarbons to halogenated C* hydrocarbons and integrated processes related thereto |
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| CN1525950A (en) * | 2001-05-21 | 2004-09-01 | Oxidative halogenation of C* hydrocarbons to halogenated C* hydrocarbons and integrated processes related thereto |
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