CN105013524B - It is a kind of to be used to prepare molecular sieve catalyst containing cadmium and manganese of aromatic hydrocarbons and preparation method thereof using methanol as raw material - Google Patents
It is a kind of to be used to prepare molecular sieve catalyst containing cadmium and manganese of aromatic hydrocarbons and preparation method thereof using methanol as raw material Download PDFInfo
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Abstract
The invention provides a kind of molecular sieve catalyst for being used to prepare using methanol as raw material the manganese containing cadmium of aromatic hydrocarbons, the catalyst includes cadmium, manganese and the molecular sieves of ZSM 5, and the silica alumina ratio in the catalyst is SiO2/Al2O3=10 200, counted in the form of CdO, gross weight based on the catalyst, the percentage by weight of cadmium in the catalyst is 0.1 10%, counted in the form of MnO, based on the gross weight of the catalyst, the percentage by weight of manganese in the catalyst is 0.01 3%, and the percentage by weight of the molecular sieves of ZSM 5 in the catalyst is 87% 99.89%.Present invention also offers a kind of method for being used for preparing the method for the catalyst and preparing aromatic hydrocarbons by methanol using the catalyst, this method can effectively improve aromatics yield, particularly improve BTX yield.
Description
Technical field
The present invention relates to chemical industry synthesis field, is more particularly to a kind of ZSM-5 molecular sieve catalyst containing cadmium and manganese, this is urged
The preparation method of agent, and the method for preparing aromatic hydrocarbons by methanol for raw material using the catalyst.
Background technology
Aromatic hydrocarbons with benzene,toluene,xylene (being denoted as BTX below) for representative is that to be only second to ethene, one kind of propylene high attached
Value added large petrochemicals, it all has and had been widely used in fuel, chemical industry, plastics, rubber, medicine and other fields.Closely
As the scarcity of petroleum resources, the price of aromatic hydrocarbons also remain high over year.Under this background, how from the alternate resources of oil
Aromatic hydrocarbons is obtained in inexpensive manner, becomes the focus of people's research.Methanol is a kind of very sufficient chemical products of supply, can
Easily to obtain methanol by coal or biomass resource.Resourceful methanol is converted into aromatic hydrocarbons is one has very much
The alternative route of value, the concern that people are increasingly extensive is caused.
The earliest report of methanol aromatic hydrocarbons sees the technology of the preparing gasoline by methanol of Mobil companies of U.S. exploitation, its vapour
It is aromatic hydrocarbons to have 30% in oil product.Thereafter people have made extensive and intensive studies to this technique, with various metals or non-gold
Category element is doped or loaded modified to zeolite catalyst, in the hope of improving the catalytic performance of catalyst, is improved in aromatic product
BTX selectivity and yield.Doping way is mainly mixed into dipping, ion exchange, solid abrasive used by people at present
It is main.Specifically, it is to synthesize required molecular sieve catalyst, such as ZSM-5, ZSM-10 by modes such as hydro-thermal methods first,
Then it is placed in the solution comprising nonmetallic or metal-doped component or dispersion and is impregnated or ion exchange, can also
Doping component is ground or extruded with ZSM molecular sieve, so as to which the catalyst of required modification be made.
It is relatively cumbersome low but above-described molecular sieve doped modification mode is required for operating procedures more than two steps
Effect, and these catalyst can not often realize preferable aromatic hydrocarbons (BTX) yield.
In view of this, it is necessary to a kind of new catalyst is developed, this catalyst can be prepared by simple method,
And the yield of aromatic hydrocarbons can be further lifted in the reaction of methanol aromatic hydrocarbons, while improve the content of BTX in aromatic hydrocarbons.
The content of the invention
In order to solve the problem, the invention provides it is a kind of be used for using methanol as raw material prepare aromatic hydrocarbons containing cadmium and manganese
ZSM-5 molecular sieve catalyst, the aromatic product yield of methanol aromatics process can be effectively improved using the catalyst,
The content of BTX in aromatic product is improved simultaneously.The catalyst includes the cadmium and manganese and ZSM-5 molecular sieve as modified metal,
Silica alumina ratio in the catalyst is SiO2/Al2O3=10-200, is counted in the form of CdO, the gross weight based on catalyst,
The percentage by weight of cadmium in the catalyst is 0.1-10%, is counted in the form of MnO, and based on the gross weight of the catalyst, manganese exists
Percentage by weight in catalyst is 0.01-3%, and the percentage by weight of ZSM-5 molecular sieve in the catalyst is 87%-
99.89%.
The second aspect of the invention, which provides, a kind of to be used for preparing the ZSM-5 molecular sieve of the present invention containing cadmium and manganese and urging
The method of agent, it is characterised in that the described method comprises the following steps：(1) by silicon source, silicon source, template, cadmium source, manganese source, water
Raw slurry is mixed to form with optional pH adjusting agent；(2) aging is carried out to the raw slurry；(3) by the institute after aging
State raw slurry crystallization under hydrothermal conditions.
In an embodiment of the invention, the aging is carried out 1-10 hours at room temperature, more preferably 1-5 hours；
The temperature of the hydrothermal condition be 120-200 DEG C, more preferably 140-180 DEG C, the crystallization 1-120 hours under the hydrothermal condition, more
It is preferred that 1-96 hours；After step (3), also product made from step (3) is washed, dried, is calcined, sintering temperature is
300-650 DEG C, preferably 400-600 DEG C, roasting time are 1-72 hours, preferably 5-48 hours.
In the preferred embodiment of the present invention, in the raw slurry, the mol ratio of various components is as follows：
SiO2/Al2O3=10-250:1；
Na2O/SiO2=0.1-0.8:1；
Template/SiO2=0.05-0.5；
H2O/SiO2=5-50；
CdO/SiO2=0.001-0.5；
MnO/SiO2=0.001-0.3；
The pH value of raw slurry is 11-13, preferably 12-13 made from the step (1).
In an embodiment of the invention, the silicon source is selected from：Tetraethyl orthosilicate, Ludox, waterglass, hard charcoal
It is black, and its any combination.Source of aluminium is selected from：Aluminium isopropoxide, aluminum sulfate, boehmite, aluminum nitrate, aluminium chloride, and its appoint
Meaning combination.The template is the organic formwork agent selected from following compound：N-butylamine, triethylamine, ethylenediamine, tetrapropyl hydrogen-oxygen
Change ammonium, 4-propyl bromide, and its any combination.The cadmium source is selected from：Cadmium nitrate, cadmium sulfate, caddy, formic acid cadmium, acetic acid
Cadmium and its any combination.The manganese source is selected from：Manganese nitrate, manganese chloride, manganese sulfate, manganese acetate and its any combination.It is excellent at one
In the embodiment of choosing, the pH adjusting agent is selected from NaOH, KOH, Na2CO3、NaHCO3And its any combination.
The third aspect of the invention provides a kind of method by methanol aromatic hydrocarbons, and methods described includes, in reaction bar
Under part so that methanol vapor contacts with the catalyst of the present invention, so as to generate aromatic product.In a preferred embodiment
In, methods described is carried out in fixed bed reactors or fluidized-bed reactor, and the reaction condition is as follows：Reaction temperature is 100-
550 DEG C, preferably 250-500 DEG C, more preferably 300-450 DEG C；Reaction pressure is 0.1-5.0MPa；Methanol feed liquid air speed is
0.1-20 hours-1, preferably 0.1-10 hours-1, more preferably 0.1-5 hours-1。
Brief description of the drawings
Fig. 1 shows the XRD spectra of catalyst made from one embodiment of the present invention.
Embodiment
" scope " disclosed herein is represented in the form of lower and upper limit.Can be respectively one or more lower limits, and
One or more upper limits.Given range is defined by selecting a lower limit and a upper limit.Selected lower limit and upper
Define the border of special scope.All scopes that can be defined by this way are to include end value and can be mutually combined
, i.e., any lower limit can combine to form a scope with any upper limit.For example, for special parameter list 60-120 and
80-110 scope, the scope for being interpreted as 60-110 and 80-120 are also what is expected.If the in addition, minimum zone value listed
1 and 2, and list maximum magnitude value 3,4 and 5, then following scope can be expected all：1-3、1-4、1-5、2-3、2-4
And 2-5.
In the present invention, unless otherwise indicated, number range " a-b " represents the contracting of any real combinings between a to b
Sketch form shows that wherein a and b are real numbers.Such as number range " 0-5 " represents all to have listed herein between " 0-5 "
Whole real numbers, " 0-5 " are that the breviary of these combinations of values represents.
If be not specifically stated, the term " two kinds " used in this specification refers to " at least two ".
In the present invention, if without particularly illustrating, all embodiments mentioned in this article and the side of being preferable to carry out
Formula can be mutually combined to form new technical scheme.
In the present invention, if without particularly illustrating, all technical characteristics and preferred feature mentioned in this article can
New technical scheme is formed to be mutually combined.
In the present invention, if without particularly illustrating, all steps mentioned in this article can be carried out sequentially, can also
It is random to carry out, it is preferred that being that order is carried out.For example, methods described includes step (a) and (b), represent that methods described can wrap
The step of order is carried out (a) and (b) are included, the step of order is carried out (b) and (a) can also be included.For example, described mention the side
Method may also include step (c), represent that step (c) can be added to methods described with random order, for example, methods described can include
Step (a), (b) and (c), step (a), (c) and (b) are may also comprise, step (c), (a) and (b) etc. can also be included.
In the present invention, if without particularly illustrating, " comprising " mentioned in this article represents open or envelope
Enclosed.For example, the " comprising " can represent that the other elements do not listed can also be included, it can also only include the member listed
Part.
The method of the present invention is the fabricated in situ ZSM-5 under conditions of it cadmium source/manganese source be present, so as to obtaining containing cadmium metal and
The ZSM-5 molecular sieve catalyst of manganese.Specifically, the present invention is used for preparing the method tool for the ZSM-5 molecular sieve that cadmium and manganese are modified
Body comprises the following steps：
(1) silicon source, silicon source, template, cadmium source, manganese source, water and optional pH adjusting agent are mixed to form raw slurry；
(2) aging is carried out to the raw slurry；
(3) by the crystallization under hydrothermal conditions of the raw slurry after aging；
(4) wash, dry, roasting, the ZSM-5 molecular sieve catalyst that obtained cadmium and manganese are modified.
The silicon source that the present invention uses can be silicon-containing material commonly used in the art, and it is molten to be preferably selected from tetraethyl orthosilicate, silicon
Glue, waterglass, white carbon, and its any combination.Ludox is that silicon dioxide microparticle is suspended in the colloid formed in water, its granularity
Can be 10-100 nanometers, the solids content in colloid reaches as high as 40 weight %.Waterglass is the hydration of alkali silicate
Thing, its molecular formula can write R2O·n SiO2, R in formula2O is alkali metal oxide, and n is silica and alkali metal oxide
The ratio of molal quantity, most common alkali metal are sodium.White carbon is white powder amorphous silica and silicate product
General name, be primarily referred to as precipitated silica, aerosil, superfine silicon dioxide gel etc..White carbon is porous
Material, its composition can use SiO2·nH2O expressions, wherein nH2O is present in the form of surface hydroxyl.
The silicon source that the present invention uses can be any salt containing aluminium, be preferably selected from aluminium isopropoxide, boehmite, sulfuric acid
Aluminium, aluminum nitrate, aluminium chloride, and its any combination.Other silicon sources known in the art can also be used as needed.
The organic formwork agent that the present invention uses can include aminated compounds and/or organic ammonium class compound.Preferably, institute
State organic formwork agent and be selected from n-butylamine, triethylamine, ethylenediamine, TPAOH, 4-propyl bromide, and its any group
Close.By properly selecting the species and content of organic formwork agent, can have to the microcosmic pore passage structure of obtained zeolite
The regulation and control of effect.
Cadmium source used in the present invention can be the cadmium salt of any valence state, be preferably selected from cadmium nitrate, cadmium sulfate, caddy,
Formic acid cadmium, cadmium acetate and its any combination.Used manganese source preferably be selected from manganese nitrate, manganese chloride, manganese sulfate, manganese acetate and its
Any combination.
PH adjusting agent used in the present invention can be any acid or alkaline reagent well known in the art, preferably
NaOH、KOH、Na2CO3、NaHCO3And its any combination.
By controlling the dosage of silicon source and silicon source in raw material, can effectively adjust in final mixed molecular sieve catalyst
The silica alumina ratio in ratio and ZSM-5 molecular sieve shared by ZSM-5 molecular sieve.In one preferred embodiment, the step
(1) there is the raw slurry prepared in following mol ratio to form：
SiO2/Al2O3=10-250:1；
Na2O/SiO2=0.1-0.8:1；
Template/SiO2=0.05-0.5；
H2O/SiO2=5-50；
CdO/SiO2=0.001-0.5；
MnO/SiO2=0.001-0.3；
The pH value of the raw slurry is 11-13, preferably 12-13.
At this it is important to note that SiO in above scale relation2、Al2O3、Na2O and CdO, MnO are to represent
The various elements included in silicon source, silicon source, sodium source, cadmium source, manganese source and optional pH adjusting agent are converted into accordingly
The form of oxide represents that these elements may also exist in the form of various salt, hydroxide etc., such a to be expressed as oxide
The way of form is the conventional practice of molecular sieve art.
In some embodiments, can be with by selecting the composition and dosage of the raw materials such as silicon source, silicon source, cadmium source, manganese source
So that obtained raw slurry has required pH value, in the case, without adding pH adjusting agent.In other embodiment party
In formula, it is also necessary to pH adjusting agent is it is possible to additionally incorporate, to cause raw slurry that there is required pH value.
The Na included in the raw slurry2O can derive from silicon source, silicon source and pH adjusting agent.It is for example, excellent at one
In the embodiment of choosing, when the silicon sources containing sodium such as the waterglass using appropriate composition and concentration, it can be carried simultaneously with silicon source
For required silicon and sodium.In another preferred embodiment, by it is possible to additionally incorporate NaOH into the raw slurry, so as to
Introduce sodium.
Water in the raw slurry may also originate from silicon source, silicon source, cadmium from not only the water being individually added into
Source, the aqueous solvent of manganese source, the crystallization water and the water generated as the product of the reactions such as decomposition, neutralization.
In embodiments of the present invention, it is to accelerate gelatinization by the effect of the raw slurry prepared progress aging.
In the ageing process, active gel, convenient follow-up crystallization steps are formed.Preferably, the Aging Step is at room temperature
Carry out.It is highly preferred that the aging lasting 1-10 hours, most preferably 1-5 hours.
Hydrothermal crystallizing operation is in the reactor of sealing, is carried out under high-temperature and high-pressure conditions.Under hydrothermal conditions
In crystallization process, the silicon source, silicon source form the crystal unit structure of ZSM-5 molecular sieve, the water in the presence of template
The temperature of heat condition is 120-200 DEG C, and more preferably 140-180 DEG C, the crystallization duration is 1-120 hours, and more preferably 1-96 is small
When.
The roasting is at a temperature of 300-650 DEG C, preferably 400-600 DEG C, is carried out in heating furnace 1-72 hours, excellent
Select 5-48 hours.The step such as washing, dry and roasting, removes and is included on catalyst surface and within pore passage structure more than
Template and various impurity.
The catalyst of the present invention can be used for preparing aromatic hydrocarbons product by the course shown in following formula using methanol as raw material, should
Reaction is also referred to as " aromatization of methanol reaction "：
nCH3OH→CnH2n-6(aromatic hydrocarbons)+nH2O
In the present invention, the product of above reaction is based on benzene, toluene and dimethylbenzene.
In the preferred embodiment of the present invention, before aromatization of methanol reaction is carried out, in advance with acid molten
Liquid carries out ion exchange to the catalyst of the present invention so that the counter cation of catalyst surface connection is substituted by hydrogen ion, so
It is used for carrying out the reaction that the methanol prepares aromatic product again afterwards.
The preferred embodiment of the present invention is further illustrated below by specific embodiment, but the guarantor of the present invention
Shield scope is not limited only to this.Can by carrying out various changes or combination to the preferred embodiment of the present invention, without departing from
On the premise of the protection domain that claims of the present invention limits, the other embodiments of the present invention are obtained, can still be realized
Similar technique effect.
Embodiment
In the examples below, unless otherwise indicated, the water otherwise used is deionized water, and the chemical reagent used is equal
It is pure to analyze.Ludox be silica concentration be 30 weight % aqueous silica sol, 18 nanometers of solid particle average grain diameter, pH
Value 9.0；Dioxide-containing silica in white carbon>99.9 weight %.
Embodiment 1
According to following molar ratio raw slurry：SiO2:Al2O3:Na2O:N-butylamine:CdO:MnO:H2O=1:0.033:
0.50:0.16:0.04:0.02:45.1.35 grams of aluminium isopropoxides are weighed, 40 ml deionized waters is dissolved in, adds thereto
1.17 grams of n-butylamines and 4.0 grams of sodium hydroxides are simultaneously mixed evenly, wiring solution-forming A；Then 20.83 grams of positive silicic acid second are weighed
Ester, add 20 ml deionized waters, wiring solution-forming B；B is added in A, and is uniformly mixed, obtains colloid C, continues to stir
Mix 0.5 hour.Then 1.07 grams of cadmium acetates and 0.72 gram of manganese nitrate are weighed, are dissolved in 12ml deionized water wiring solution-formings, so
The solution is added in colloid C afterwards, aging 1.5 hours at room temperature under conditions of being kept stirring for, is then transferred to material
In stainless steel cauldron, the reactor is sealed, is heated to 180 DEG C, crystallization 72 hours under this hydrothermal condition, quick cooling afterwards
To room temperature, product is centrifuged, is washed with water to the pH value of supernatant<8, transferred product is entered in infrared baking oven, at 120 DEG C
Then lower processing is transferred the sample into Muffle furnace, is calcined 12 hours under 550 DEG C of air atmosphere to be baked to for 6 hours.
XRD signs are carried out to the sample, gained XRD spectrums are close with Fig. 1, wherein being observed in 2 θ=23.19,24.04,24.53 etc.
The characteristic diffraction peak signal of ZSM-5 molecular sieve, it was demonstrated that synthesis has obtained ZSM-5.The content of cadmium in the product is measured by ICP
(CdO meters) is 1.5 weight % (being counted on the basis of the gross weight of catalyst), and the content (MnO meters) of manganese is 0.6%.
Embodiment 2
According to following molar ratio raw slurry：SiO2:Al2O3:Na2O:TPAOH:CdO:MnO:H2O=
1:0.028:0.45:0.10:0.05:0.02:40.1.87 grams of aluminum sulfate are weighed, are dissolved in 30 ml deionized waters, it is molten to this
8.13 gram 25% of the TPAOH aqueous solution and 3.6 grams of sodium hydroxides is added in liquid, these materials are mixed equal
It is even, wiring solution-forming A；Then 20 grams of Ludox are weighed, add 25 ml deionized waters thereto, are made into slurries B；B is added to A
In be uniformly mixed, obtain colloid C, colloid C continue stirring 0.5 hour.Then 1.28 grams of cadmium sulfates and 0.31 gram are weighed
Manganese chloride, 10ml deionized waters are dissolved in, be then added in colloid C, the aging at room temperature under conditions of being kept stirring for
1.5 hours, it is transferred in stainless steel cauldron, seals the reactor, is heated to 180 DEG C, crystallization 72 hours under this hydrothermal condition,
Room temperature is quickly cooled to afterwards, product is centrifuged, and is washed with water to the pH value of supernatant<8, transferred product is entered into infrared baking
In case, 6 hours are handled at 120 DEG C to be baked to, is then transferred the sample into Muffle furnace, in 550 DEG C of air atmosphere
Lower roasting 12 hours.To the sample carry out XRD signs, gained spectrogram as shown in figure 1, wherein 2 θ=23.19,24.04,
24.53 etc. observe the characteristic diffraction peak signal of ZSM-5 molecular sieve, it was demonstrated that synthesis has obtained ZSM-5.This is measured by ICP
The content (CdO meters) of cadmium is 1.4 weight % (being counted on the basis of the gross weight of catalyst) in product, and the content (MnO meters) of manganese is
0.5%.
Embodiment 3
According to following molar ratio raw slurry：SiO2:Al2O3:Na2O:N-butylamine:CdO:MnO:H2O=1:0.035:
0.54:0.15:0.07:0.04:50 dispensings.2.33 grams of aluminum sulfate are weighed, 40 ml deionized waters is dissolved in, adds thereto
1.10 grams of n-butylamines and 4.32 grams of sodium hydroxides simultaneously mix, and stir, wiring solution-forming A；Then 6.0 grams of white carbons are weighed, are added
Enter 40 ml deionized waters, be made into suspension B；B is added in A and is uniformly mixed, obtains colloid C, it is small to continue stirring 0.5
When.Then 2.16 grams of cadmium nitrates and 1.0 grams of manganese acetates are weighed, are dissolved in 10ml deionized waters, wiring solution-forming is then molten by this
Liquid is added in colloid C, and under conditions of being kept stirring for, aging 1.5 hours, stainless steel cauldron is transferred to by material at room temperature
In, the reactor is sealed, is heated to 175 DEG C, crystallization 96 hours, are quickly cooled to room temperature afterwards under this hydrothermal condition, will produce
Product centrifuge, and are washed with water to the pH value of supernatant<8, transferred product is entered in infrared baking oven, handled 6 hours at 120 DEG C
To be baked to, then transfer the sample into Muffle furnace, be calcined 12 hours under 550 DEG C of air atmosphere.The sample is entered
Row XRD is characterized, and gained spectrogram is similar with Fig. 1, wherein observing ZSM-5 molecular sieve in 2 θ=23.19,24.04,24.53 etc.
Characteristic diffraction peak signal, it was demonstrated that synthesis obtained ZSM-5.The content (CdO meters) that cadmium in the product is measured by ICP is 2.1
Weight % (is counted) on the basis of the gross weight of catalyst, and the content (MnO meters) of manganese is 0.9%.
Embodiment 4
According to following molar ratio raw slurry：SiO2:Al2O3:Na2O:4-propyl bromide:CdO:MnO:H2O=1:
0.04:0.50:0.10:0.08:0.04:50 dispensings.2.66 grams of aluminum sulfate are weighed, are dissolved in 40 ml deionized waters, Xiang Qi
2.66 grams of 4-propyl bromides of middle addition and 4.0 grams of sodium hydroxides simultaneously mix, and stir, wiring solution-forming A；Then 6.0 are weighed
Gram white carbon, 40 ml deionized waters are added, are made into suspension B；B is added in A and is uniformly mixed, obtains colloid C, after
Continuous stirring 0.5 hour.Then 2.47 grams of cadmium nitrates and 1.43 grams of manganese nitrates are weighed, are dissolved in 10ml deionized waters, are made into molten
Liquid, then the solution is added in colloid C, under conditions of being kept stirring for, aging 1.5 hours, material is turned at room temperature
Enter in stainless steel cauldron, seal the reactor, be heated to 175 DEG C, crystallization 96 hours under this hydrothermal condition, fast quickly cooling afterwards
But to room temperature, product is centrifuged, is washed with water to the pH value of supernatant<8, transferred product is entered in infrared baking oven, 120
6 hours are handled at DEG C to be baked to, is then transferred the sample into Muffle furnace, it is small that 12 are calcined under 550 DEG C of air atmosphere
When.XRD signs are carried out to the sample, gained spectrogram is similar with Fig. 1, wherein in 2 θ=23.19,24.04,24.53 etc. observations
To the characteristic diffraction peak signal of ZSM-5 molecular sieve, it was demonstrated that synthesis has obtained ZSM-5.The content of cadmium in the product is measured by ICP
(CdO meters) is 2.3 weight % (being counted on the basis of the gross weight of catalyst), and the content (MnO meters) of manganese is 1.2%.
For above-described embodiment 1-4, because cadmium therein, manganese content are relatively low, it is impossible to embodied in XRD.
Embodiment 5
Ion exchange is carried out to catalyst made from embodiment 1-4 first.Concretely comprise the following steps at 80 DEG C, use 0.1mol/L
Ammonium nitrate solution according to solid-liquid weight than 1:10 pairs of catalyst ions exchange 2 hours, filtering, repeat exchange 3 times.Last
After primary ions exchange, filtered sample, transferred product is entered in infrared baking oven, 6 hours are handled at 120 DEG C to be dried
It is dry, then transfer the sample into Muffle furnace, be calcined 6 hours under 500 DEG C of air atmosphere.
It is 20-40 mesh by the catalyst breakage screening after roasting.
8 grams of Catalyst packings are weighed to enter in the stainless steel fixed bed reactors that internal diameter is 10mm, at reaction conditions, Xiang Qi
In be passed through methanol vapor, to be reacted.Specifically reaction condition is：Reaction temperature：450 DEG C, pressure：0.5Mpa, methanol liquid
Air speed：3.0h-1.Methanol enters preheater by constant-flux pump in liquid form, and the temperature of preheater is 300 DEG C, and methanol is pre- at this
Gasification forms methanol vapor in hot device, is then incubated into reactor and reacts.Product uses gas phase under conditions of insulation
Chromatogram carries out on-line analysis, and gas-chromatography uses PLOT Q capillary columns and hydrogen flame detector, and the temperature in gas chromatograph is
180℃。
Comparative example 1
Catalyst is prepared according to the step described in embodiment 3, difference is not add cadmium and manganese.XRD is carried out to the sample
Characterize, gained spectrogram is similar with Fig. 1, wherein observing the feature of ZSM-5 molecular sieve in 2 θ=23.19,24.04,24.53 etc.
Diffraction peak-to-peak signal, it was demonstrated that synthesis has obtained ZSM-5.And the step described according to embodiment 5, by the obtained catalysis of the comparative example 1
Agent is used for the reaction of methanol aromatic hydrocarbons.
Comparative example 2 is to comparative example 6
In comparative example 2 into comparative example 6, repeat embodiment 3 described in step, differ only in using Zn, Ga, Ag, Cd,
The respective nitrate of Mn replaces the combination of cadmium salt and manganese salt, so as to prepare the ZSM-5 catalyst with these element dopings.To being made
Each sample carry out XRD signs, gained spectrogram is similar with Fig. 1, wherein being observed in 2 θ=23.19,24.04,24.53 etc.
The characteristic diffraction peak signal of ZSM-5 molecular sieve, it was demonstrated that synthesis has obtained ZSM-5.Being characterized by ICP proves, comparative example 2 is finally made
ZnO content in the catalyst obtained is 1.8%；The final Ga in obtained catalyst of comparative example 32O3Content be 1.3%；It is right
The final Ag in obtained catalyst of ratio 42O content is 0.8%；Finally CdO in obtained catalyst contains comparative example 5
Measure as 1.7%；The final MnO in obtained catalyst of comparative example 6 content is 1.5%.And the step described according to embodiment 5
Suddenly, catalyst made from these comparative examples is used for the reaction of methanol aromatic hydrocarbons.
Comparative example 7
The step of repeating above example 3, but use the nickel nitrate of equimolar amounts to replace manganese acetate, so as to which Cd- be made
The catalyst product of Ni doping.To obtained each sample carry out XRD signs, gained spectrogram is similar with Fig. 1, wherein 2 θ=
23.19th, 24.04,24.53 etc. the characteristic diffraction peak signal for observing ZSM-5 molecular sieve, it was demonstrated that synthesis has obtained ZSM-5.It is logical
Crossing ICP and characterizing proves, finally the CdO contents in obtained catalyst are 1.9% to comparative example 7；NiO contents are 0.5%.And according to
Step described in embodiment 5, catalyst made from comparative example 7 to be used for the reaction of methanol aromatic hydrocarbons.
Comparative example 8
The step of repeating above example 3, but use the gallium nitrate of equimolar amounts to replace cadmium nitrate, so as to which Ga- be made
The catalyst product of Mn doping.To obtained each sample carry out XRD signs, gained spectrogram is similar with Fig. 1, wherein 2 θ=
23.19th, 24.04,24.53 etc. the characteristic diffraction peak signal for observing ZSM-5 molecular sieve, it was demonstrated that synthesis has obtained ZSM-5.It is logical
Crossing ICP and characterizing proves, the final Ga in obtained catalyst of comparative example 72O3Content is 1.6%；MnO contents are 0.7%.
According to the step described in embodiment 5, catalyst made from comparative example 8 is used for the reaction of methanol aromatic hydrocarbons.
As a result collect and be listed in the table below.
Table 1
* note：The quality * 100 of quality/methanol of aromatics yield=aromatic hydrocarbons
It can see from the result of upper table, compared with the molecular sieve catalyst of the comparative example 1-4 not containing cadmium metal and manganese, this
The catalyst of invention can significantly improve aromatics yield when the reaction for methanol aromatic hydrocarbons, in addition in gained aromatic hydrocarbons
BTX content also obtain significant raising.Compared with only including the comparative example 5-6 of cadmium metal or manganese, aromatics yield and BTX
Content is also significantly increased.As can be seen here, the catalyst of bimetal-doped of the invention and the molecular sieve of other monometallics doping
Catalyst is compared, and the ZSM-5 catalyst of the bimetal-doped of the invention effect in terms of aromatics yield and BTX yields is improved is more aobvious
Write, its reason may be that cadmium and manganese generate cooperative effect in the catalyst, and dehydrogenation is stronger, so as to be advantageous to the shape of aromatic hydrocarbons
Into.
In addition, the present inventors have additionally discovered that, ZSM-5 is doped when the combination using Cd and Ni combination, Ga and Mn
When, the aromatic hydrocarbons and BTX product yields of gained do not show Cd and Mn and combine embodied catalytic effect, and this shows only originally
The catalyst of invention can just realize the effect of above-mentioned collaboration.
Claims (14)
1. a kind of catalyst for being used to prepare aromatic hydrocarbons using methanol as raw material, the catalyst include cadmium and manganese and ZSM-5 molecular sieve,
Silica alumina ratio in the catalyst is SiO2/Al2O3=10-200, is counted in the form of CdO, based on the total of the catalyst
Weight, the percentage by weight of cadmium in the catalyst are 0.1-10%, are counted in the form of MnO, based on the gross weight of the catalyst,
The percentage by weight of manganese in the catalyst is 0.01-3%, and the percentage by weight of ZSM-5 molecular sieve in the catalyst is 87%-
99.89%；
The catalyst is prepared by the method comprised the following steps：
(1) silicon source, silicon source, template, cadmium source, manganese source, water and optional pH adjusting agent are mixed to form raw slurry；
(2) aging is carried out to the raw slurry；
(3) by the crystallization under hydrothermal conditions of the raw slurry after aging.
A kind of 2. method for preparing catalyst as claimed in claim 1, it is characterised in that methods described includes following step
Suddenly：
(1) silicon source, silicon source, template, cadmium source, manganese source, water and optional pH adjusting agent are mixed to form raw slurry；
(2) aging is carried out to the raw slurry；
(3) by the crystallization under hydrothermal conditions of the raw slurry after aging.
3. method as claimed in claim 2, it is characterised in that the aging carries out 1-10 hours at room temperature；The hydro-thermal
The temperature of condition is 120-200 DEG C, the crystallization 1-120 hours under the hydrothermal condition；After step (3), also step (3) is made
The product obtained is washed, dried, is calcined, and sintering temperature is 300-650 DEG C, and roasting time is 1-72 hours.
4. method as claimed in claim 2, it is characterised in that the aging carries out 1-5 hours at room temperature；The hydro-thermal bar
The temperature of part is 140-180 DEG C, the crystallization 1-96 hours under the hydrothermal condition；After step (3), also step (3) is made
Product washed, dried, be calcined, sintering temperature be 400-600 DEG C, roasting time is 5-48 hours.
5. method as claimed in claim 2, it is characterised in that in the raw slurry, the mol ratio of various components is as follows：
SiO2/Al2O3=10-250:1；
Na2O/SiO2=0.1-0.8:1；
Template/SiO2=0.05-0.5；
H2O/SiO2=5-50；
CdO/SiO2= 0.001-0.5；
MnO/SiO2=0.001-0.3；
The pH value of the raw slurry made from step (1) is 11-13.
6. method as claimed in claim 5, it is characterised in that the pH value of the raw slurry made from step (1) is 12-
13。
7. method as claimed in claim 2, it is characterised in that the silicon source is selected from：Waterglass, tetraethyl orthosilicate, Ludox,
White carbon, and its any combination.
8. method as claimed in claim 2, it is characterised in that source of aluminium is selected from：Aluminium isopropoxide, boehmite, sulfuric acid
Aluminium, aluminum nitrate, aluminium chloride, and its any combination.
9. method as claimed in claim 2, it is characterised in that the template is the organic formwork selected from following compound
Agent：N-butylamine, triethylamine, ethylenediamine, TPAOH, 4-propyl bromide, and its any combination.
10. method as claimed in claim 2, it is characterised in that the cadmium source is selected from：Cadmium nitrate, cadmium sulfate, formic acid cadmium, second
Sour cadmium, caddy and its any combination；The manganese source is selected from：Manganese nitrate, manganese chloride, manganese sulfate, manganese acetate and its any combination；
The pH adjusting agent is selected from NaOH, KOH, Na2CO3、NaHCO3And its any combination.
11. a kind of method by methanol aromatic hydrocarbons, methods described includes, at reaction conditions so that methanol vapor will with right
The catalyst described in 1 or the catalyst prepared by the method any one of claim 2-10 is asked to contact, so as to raw
Into aromatic product.
12. method as claimed in claim 11, it is characterised in that methods described is in fixed bed reactors or fluidized-bed reactor
Middle progress, the reaction condition are as follows：Reaction temperature is 100-550 DEG C；Reaction pressure is 0.1-5.0MPa；Methanol feed liquid
Air speed is 0.1-20 hours-1。
13. method as claimed in claim 11, it is characterised in that methods described is in fixed bed reactors or fluidized-bed reactor
Middle progress, the reaction condition are as follows：Reaction temperature is 250-500 DEG C；Reaction pressure is 0.1-5.0MPa；Methanol feed liquid
Air speed is 0.1-10 hours-1。
14. method as claimed in claim 11, it is characterised in that methods described is in fixed bed reactors or fluidized-bed reactor
Middle progress, the reaction condition are as follows：Reaction temperature is 300-450 DEG C；Reaction pressure is 0.1-5.0MPa；Methanol feed liquid
Air speed is 0.1-5 hours-1。
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2014
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