CN1139430C - Zeolite catalyst for directly synthesizing aromatic hydrocarbon by using methane and its preparation method - Google Patents
Zeolite catalyst for directly synthesizing aromatic hydrocarbon by using methane and its preparation method Download PDFInfo
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- CN1139430C CN1139430C CNB991019245A CN99101924A CN1139430C CN 1139430 C CN1139430 C CN 1139430C CN B991019245 A CNB991019245 A CN B991019245A CN 99101924 A CN99101924 A CN 99101924A CN 1139430 C CN1139430 C CN 1139430C
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- zeolite
- methane
- zsm
- arene
- catalyst
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Abstract
The present invention belongs to a zeolite catalyst used for directly synthesizing arene from methane and a preapring method thereof. The basic chemical composition of the catalyst is aA/Hn<AlnSiyOx>, wherein A is an active component, <AlnSiyOx> represents the skeleton of ZSM series zeolite, a is mass percentage content, n=1 to 20, and y/n=1 to 100. The preparing method comprises the following steps: synthesizing zeolite raw powder by using a hydrothermal crystallization method; converting the zeolite raw powder into hydrogen type zeolite by calcination and ion exchanging; carrying the active component by using methods of immersion, etc. Auxiliary agent can be added in the catalyst, and the catalyst can be used for directly synthesizing arene from methane under the condition of no oxygen. At the temperature of 650 to 750 DEG C, the maximum conversion rate is 11.5%, and the maximum selectivity of benzene is 90%.
Description
The present invention relates to zeolite catalyst of a kind of methane directly synthetic aromatic hydrocarbons under oxygen free condition and preparation method thereof.
Occurring in nature storage has a large amount of carbon resources such as Sweet natural gas (its main component is a methane), though they can be used as fuel, its use value is lower, if be translated into important chemical material such as benzene, then can bring tangible economic benefit; In addition, Sweet natural gas often is stored in remote districts, is translated into aromatic hydrocarbons, also can reduce the expense of transporting greatly.
Common methane directly changes into aromatic hydrocarbons under oxygen free condition need just can carry out under very high temperature.The methane technology that is converted into aromatic hydrocarbons is seen Chinese patent " catalyzer of direct synthesis of arene with methane and the application in building-up reactions thereof " at a lower temperature, and application number is 93115889.3.The disclosed catalyzer of this application for a patent for invention is with ZnO, Ga
2O
3, Cr
2O
3Or MoO
3-xThe HZSM-5 zeolite of modification, wherein X between 0～1, the SiO of HZSM-5
2/ Al
2O
3Be 30～60, it forms content is (weight percent) active ingredient/HZSM-5=(1～12): (99～88).And active ingredient is preferably MoO
3-x, MoO
3-xOptimum content be 2～4.The Preparation of catalysts method that discloses this Mo/HZSM-5 in this patent specification can be divided into synthetic ammonium type zeolite---support the process of active ingredient-roasting moulding.Wherein the synthetic of ammonium type zeolite is to get NaZSM-5 molecular sieve NH
4NO
3Aqueous solution exchange obtains NH
4ZSM-5 is 110 ℃ of oven dry down.Support is to flood or carry out ion-exchange or mechanically mixing with the nitrate solution that contains required active ingredient or with containing soluble metal complex acid salts solution.At last with prepared catalyst sample 110 ℃ of oven dry, 500～700 ℃ of roastings 2 hours.The catalyzer that uses the HZSM-5 zeolite to support active ingredient can be realized direct synthesis of arene with methane between 680～720 ℃ of temperature of reaction under the oxygen free condition, transformation efficiency is up to 7.2%.But the stability of this catalyzer is high not enough, and methane conversion is lower, and prior art does not relate to the application aspect catalyzer of the ZSM series Si-Al zeolite of other structure beyond the ZSM-5 zeolite yet.
The present invention for overcoming the deficiencies in the prior art, provides novel zeolite framework exactly, supports the catalyzer of active ingredient, selects the content of suitable active ingredient, reaches the purpose that improves transformation efficiency and stability.
The zeolite catalyst of direct synthesis of arene with methane of the present invention is a skeleton with the ZSM series zeolite, supports active ingredient, and general formula is:
AA/H
n[Al
nSi
yO
z] wherein A be active ingredient, H is a hydrogen ion, [Al
nSi
yO
z] represent ZSM series zeolite skeleton, SiO is arranged in the skeleton in molar ratio
2/ Al
2O
3=10～60, n=1～20, y/n=1～100, Z is the integer that satisfies each component valency requirement.In the general formula, press mass ratio a=1～15.Said active component A is MoO
3-δ, δ=0～1 or MoC
2-ε, ε=0～2, said zeolite framework comprise ZSM-5 ,-8 ,-11 ,-12.-18 ,-25 ,-35 ,-38 ,-48, and their mixed crystal zeolite.
ZSM series zeolite skeleton is best zeolite framework with ZSM-11, and the mixed crystal zeolite of ZSM-5 and ZSM-11 is best mixed crystal zeolite framework.SiO in zeolite framework
2/ Al
2O
3, be best proportioning at=20～29 o'clock.In the case, methane conversion is not less than 8.5%.
Active ingredient in the catalyzer has certain influence to the aromatization of methane.Experiment shows, MoO
3Content is lower than 1% by mass percentage, or is higher than 8%, and methane conversion is all extremely low.And be the optimum activity component concentration 3.1～5.5%.Active ingredient is when 4.1～5.1% scope, and methane conversion is more than 8.4%.
Add auxiliary agent the aromizing performance of methane is further improved, can use WO
3, Cr
2O
3, ZnO, Ga
2O
3, In
2O
3, V
2O
3, V
2O
4Deng metal oxide or La
2O
3Deng precious metals such as rare earth oxide or Pt, Re as auxiliary agent.The content of auxiliary agent is proper with 0.1～2.0%.
The zeolite catalyst preparation method of direct synthesis of arene with methane of the present invention also is the synthetic h-type zeolite of experience-the support process of active ingredient-moulding.Said synthetic h-type zeolite process is to adopt the former powder of hydrothermal crystallization method synthetic zeolite, obtains h-type zeolite through roasting and ion-exchange again; The said active component that supports is to contain active ingredient meltability salt or to contain active ingredient and the soluble salt of auxiliary agent supports on the zeolite framework carrier by pickling process, or supports on the carrier by mechanical mixing; Said moulding process is straight forming or adds the tackiness agent aftershaping.
Synthetic h-type zeolite is one of feature of the present invention.Detailed process can be, with organic amine or phosphine is template, with silicon-containing compound, as white carbon black, water glass or water glass, ethyl silicate etc. is the silicon source, with aluminum contained compound, be the aluminium source as Tai-Ace S 150, sodium metaaluminate, boehmite etc., in alkaline medium, become glue under the violent stirring, pack in the stainless steel cauldron, at 85～200 ℃ of former powder of hydrothermal crystallizing synthetic zeolite; Crystallization time 2～7 days; Again with zeolite powder 500～600 ℃ of following roastings in air, remove organic formwork agent after, change it into h-type zeolite by ion-exchange.
Above-mentioned organic amine, organic phosphine are template, can be TPAOH (TPA), tetraethyl ammonium hydroxide (TEAOH), TBAH (TBAOH), methyl triethyl brometo de amonio (MTEABr), three---quaternary ammonium hydroxide (TQA), tetramethyleneimine, choline, 1,6-be diamines etc.
In moulding process, be after supporting active ingredient, 500～550 ℃ of following roastings straight forming after 2～5 hours in air, or after roasting, add tackiness agent, as aluminum oxide, boehmite, silica gel reshaping, make finished catalyst.
Use catalyzer of the present invention under the anaerobic situation, by direct synthesis of arene with methane, its process and reaction conditions are as follows: catalyzer is loaded in the fixed-bed reactor of continuously feeding, by air-activated, feed methane then and carry out aromatization, temperature of reaction is 650～750 ℃, normal pressure, and the unstripped gas air speed is 500～2000h
-1
Synthesizing of embodiment 1 ZSM-11 type zeolite
Template adopts TBA
+Or TBP
+Bromide and oxyhydroxide, the mole proportioning of raw material is Na
2O/TBA
+/ Al
2O
3/ SiO
2/ H
2O=(0～0.7)/0.02～0.2/0.05～0.1/1.0/10～100,85～200 ℃ of crystallization temperatures, crystallization time 1.5～4 days.
Synthesizing of the h-type zeolite (carrier) of embodiment 2 different structures
The method of synthetic h-type zeolite all is the former powder of hydrothermal crystallization method elder generation's synthetic zeolite, obtains h-type zeolite through roasting and ion-exchange again.Different structures adopts different template, proportioning raw materials and different crystallization conditions.Specifically see Table 1.
Table 1 molecular sieve template gel is formed crystallization temperature, time ZSM-5 TPAOH (rPA) SiO
2/ Al
2O
3=10～100, OH
-/ SiO
2=0.1～0.8,160 ℃, 3 days
H
2O/OH
-=10～300, TPA
+/ (TPA
++ Na
+)=0.4～0.9ZSM～8 tetraethyl ammonium hydroxides (TEAOH) SiO
2/ Al
2O
3=10～100, Na
2O/SiO
2=0.3～0.5 160 ℃, 4 days
H
2O/Na
2O=120～150, TEAOH/SiO
2=0.1～0.2ZSM-12 methyl triethyl brometo de amonio (MTEABr) SiO
2/ Al
2O
3=10～150, Na
2O/SiO
2=0.05～0.10 150 ℃, 7 days
H
2O/Na
2O=420～450, MTEABr/SiO
2=0.15～0.2ZSM-18 three-quaternary ammonium hydroxide (TQA) SiO
2/ Al
2O
3=10～30, Na
2O/SiO
2=0.05～0.2 60～150 ℃, 7 days
H
2O/Al
2O
3=200～1500, TQA//Al
2O
3=1～10ZSM-35 tetramethyleneimine SiO
2/ Al
2O
3=8.8～200, OH
-/ SiO
2=0.05～0.5,150 ℃, 3 days
H
2O/OH
-=41～500, R
+/ (R
++ Na
+)=0.2～1.0ZSM-48 1,6-hexanediamine (HMDA) SiO
2/ Al
2O
3=50～∞, OH
-/ SiO
2=0～0.25,160 ℃, 2～3 days
H
2O/OH
-＝10～400，R/SiO
2＝0.01～2.0
The aromizing performance of the catalyzer of embodiment 3 different carriers structures
When the catalyzer of following each carrier structure carries out aromatization, be the result's (institute's column data is not all considered coking) who under 700 ℃ of normal pressures, methane air speed 1400～1600ml/h condition, obtains.
Table 2 carrier structure affects zeolite type methane conversion (%) arenes selectivity (%) H-ZSM-5 7.5 92.5H-ZSM-8 6.7 89.8H-ZSM-11 8.5 93.6 H-ZSM-48 4.7 78.9 to reactivity worth
By the visible HZSM-11 zeolite of table 2 is the catalyzer of carrier, is that the methane conversion or the selectivity of aromatic hydrocarbons all are best catalyzer.Experiment proves that also ZSM-6 and the mixed crystal zeolite of ZSM-11 are that the catalyst effect of carrier is identical with ZSM-5 or better.
Embodiment 4 different SiO
2/ Al
2O
3The reactivity worth of the catalyzer of ratio
In fixed-bed reactor, adorn 1gMoO
3Under/H-ZSM-11 the catalyzer, 700 ℃ and normal pressure, the methane air speed is to carry out aromatization, result such as table 3 under 1400～1600ml/h.
Table 3 silica alumina ratio is to catalyst reaction Effect on Performance SiO
2/ Al
2O
3Methane conversion (%) arenes selectivity (%) 20 8.8 92.330 8.5 93.640 8.2 95.250 7.9 91.4
As seen, when other condition is identical, SiO
2/ Al
2O
3=20～29 scopes, methane conversion are more than 8.6%, and the selectivity of benzene hydrocarbon is also than higher.In following examples, SiO
2/ Al
2O
3Get 30.
Embodiment 5 reactivity worth are with the variation in reaction times
Condition by embodiment 4 is carried out methane aromatization, result such as table 4.
Table 4 reaction times to catalyst performance influence reaction times (branch) 10 30 60 90 120 150 180 240 methane conversions (%) 6.4 7.5 8.5 8.4 8.2 8.0 7.8 6.8 benzene selectives (%) 87.8 90.5 93.6 93.8 92.6 92.0 90.4 88.3 as shown in Table 4 the reaction times at 60～100 minutes for best.
The reactivity worth of embodiment 6 different activities component concentration catalyzer
Carry out the aromatization of methane by the reaction conditions of embodiment 4, the results are shown in the table 5.
Table 5 MoO
3Content to reactivity worth influence MoO3 content (%) methane conversion (%) arenes selectivity (%) 1 5.8 87.63 8.0 92.55 8.5 93.67 8.2 92.210 4.7 82.9 when active ingredient best at 4.1～6% reaction effects.
The reactivity worth of catalyzer under embodiment 7 differing tempss
Except that temperature of reaction, all the other conditions are with example 4.Aromatization the results are shown in table 6.
Table 6 temperature to reactivity worth influence temperature of reaction (℃) methane conversion (%) arenes selectivity (%) 650 4.2 95.4700 8.5 93.6750 11.5 86.5
The aromizing performance of catalyzer under the embodiment 8 different methane air speeds
Except that the methane air speed, all the other conditions are with example 4.The results are shown in Table 7.
Table 7 methane air speed influences methane air speed (ml/h) methane conversion (%) arenes selectivity (%) 500 8.9 95.61500 8.5 93.62000 7.3 90.1 to reactivity worth
The zeolite catalyst of direct synthesis of arene with methane of the present invention owing to selected suitable carriers zeolite and active ingredient for use, is significantly improved methane conversion, and the selectivity of aromatic hydrocarbons is more than 90%.Because pore passage structure comprises the differences such as the useful space of sinuousness, infall, cause the difference of products distribution, to compare with HZSM-5, catalytic effect is better.The surperficial coke content of catalyzer reduces than Mo/HZSM-5, and stability also improves greatly.MoO
3Loading is in 3.1～5.5 scopes, and the Mo catalyzer has produced a kind of new middle strong acidity position, and it plays an important role for the aromizing of methane.
Claims (5)
1, a kind of zeolite catalyst of direct synthesis of arene with methane is frame supported active ingredient with ZSM zeolite, and general formula is:
AA/H
n[Al
nSi
yO
z] wherein A represent active ingredient, [Al
nSi
yO
z] represent the skeleton of ZSM zeolite, n=1～20, y/n=1～100, z is the integer that satisfies each component valency requirement, and in the general formula, a is the content of active component A, it is characterized in that, and the content of said active component A is 4.1～6%; Said zeolite framework is the mixed crystal zeolite of ZSM-11 or ZSM-5 and ZSM-11; In the skeleton, SiO is arranged in molar ratio
2/ Al
2O
3=20～29.
According to the zeolite catalyst of the described direct synthesis of arene with methane of claim 1, it is characterized in that 2, said active ingredient is MoC
2-ε, ε=0～2.
According to the zeolite catalyst of claim 1 or 2 described direct synthesis of arene with methane, it is characterized in that 3, said zeolite catalyst contains Ga
2O
3, In
2O
3, La
2O
3, Pt, Re be as auxiliary agent, auxiliary agent content is 0.1～2.0%.
4, a kind of preparation method of zeolite catalyst of direct synthesis of arene with methane of claim 1, the synthetic h-type zeolite one of experience supports the process of active ingredient one moulding, it is characterized in that, said synthetic h-type zeolite process is to adopt the former powder of hydrothermal crystallization method synthetic zeolite, be template promptly with organic amine or organic phosphine, with the silicon-containing compound is the silicon source, with the aluminum contained compound is the aluminium source, violent stirring becomes glue in alkaline medium, pack in the stainless steel cauldron, at 85～200 ℃ of former powder of hydrothermal crystallizing synthetic zeolite, crystallization time 2～7 days, again with zeolite powder 500～600 ℃ of following roastings in air, remove organic formwork agent after, change it into h-type zeolite by ion-exchange; Said moulding is to add the tackiness agent moulding after the roasting, and tackiness agent is aluminum oxide or boehmite or silica gel.
According to the preparation method of the zeolite catalyst of the described direct synthesis of arene with methane of claim 4, it is characterized in that 5, template adopts Tetrabutyl amonium bromide or TBAH or tetrabutylammonium hydroxide phosphine, the feed molar proportioning is Na
2O/TBA
+Or TBP
+/ Al
2O
3/ SiO
2/ H
2O=0～0.7/0.02～0.2/0.05～0.1/1.0/10～100, under 85～200 ℃ of situations of crystallization temperature, crystallization 1.5～4 days makes ZSM-11 type zeolite.
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|---|---|---|---|
| CNB991019245A CN1139430C (en) | 1999-01-29 | 1999-01-29 | Zeolite catalyst for directly synthesizing aromatic hydrocarbon by using methane and its preparation method |
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|---|---|---|---|
| CNB991019245A CN1139430C (en) | 1999-01-29 | 1999-01-29 | Zeolite catalyst for directly synthesizing aromatic hydrocarbon by using methane and its preparation method |
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|---|---|
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| CN1139430C true CN1139430C (en) | 2004-02-25 |
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| CN107892308B (en) * | 2017-12-12 | 2021-07-27 | 太原理工大学 | ZSM-5 molecular sieve and preparation method thereof |
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