CN106607079A - Methanol-to-aromatic hydrocarbon catalyst and uses tehreof - Google Patents
Methanol-to-aromatic hydrocarbon catalyst and uses tehreof Download PDFInfo
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Abstract
The present invention relates to a methanol-to-aromatic hydrocarbon catalyst and uses thereof. A purpose of the present invention is mainly to solve the problems of low selectivity and poor catalyst stability in the conversion of methanol into aromatic hydrocarbons in the prior art. The technical scheme of the present invention comprises that a modified mesoporous and microporous compounded molecular sieve is adopted as a catalyst, methanol is adopted as a raw material, and the raw material is subjected to an aromatization reaction at a reaction temperature of 360-500 DEG C under a reaction pressure of 0-1.0 MPa at a raw material mass space velocity of 0.4-8 h<-1> under the effect of the catalyst. With the technical scheme, the problems in the prior art are well solved. The catalyst of the present invention can be used for the industrial production of methanol-to-aromatic hydrocarbon.
Description
Technical field
The present invention relates to a kind of catalyst of methanol aromatic hydrocarbons and application thereof.
Background technology
Aromatic hydrocarbons is important basic chemical industry raw material, be widely used in garment material, electric equipment products, agricultural production,
The various fields such as transportation, the annual aromatic hydrocarbons consumption of China is more than 20,000,000 tons.The production master of current aromatic hydrocarbons
Oil is derived from, the techniques such as the catalytic reforming of oil product, pyrolysis gasoline hydrogenation extracting are depended on.Due to me
State's petroleum resources shortage, causes the external dependence degree of benzene, toluene and dimethylbenzene very big.In view of China richness coal, lack
The current resources situation of oil, few gas, exploitation is had great importance based on the methanol aromatic hydrocarbons technology of coal resources.
Methanol aromatic hydrocarbons refers to methanol in the presence of catalyst, through the chemical reaction of series of complex, finally
It is converted into the process of aromatic hydrocarbons.Because reaction is accompanied by many by-products, it usually needs three tons or so of methanol ability
One ton of BTX (benzene, toluene and the dimethylbenzene that refer in aromatic hydrocarbons) is obtained, the catalyst having been reported that at present mostly is and changes
The micropore ZSM-5 catalyst of property.
Patent CN1880288A describes the technique and catalyst of a kind of methanol conversion for preparing arene, the catalyst
With ZSM-5 molecular sieve with small crystal grains as carrier, a part of La and Ga is loaded as metal-modified component, pass through
Two-stage reaction technique, converts methanol into aromatic hydrocarbons.Patent CN102372535B is described using various different
Micro porous molecular sieve, such as by ZSM-5, ZSM-11, MCM-22 carries out mixed-forming, by zinc supported and nickel
Deng aromatization of methanol catalyst prepared by element, at 480 DEG C, reaction pressure is 0.1MPa, and feed space velocity is
0.5h-1Under conditions of, efficient can convert methanol into aromatic hydrocarbons.Patent CN102416342B provides one
The catalyst that methanol high selectivity prepares aromatic hydrocarbons is planted, the catalyst includes two kinds of components A and B, component A bag
Include the element modified mixed type micro porous molecular sieve such as Cr, Mo, Cu, Zn, such as SAPO-11 and ZSM-5,
B component includes aluminium oxide or silica supported thulium and halogen.Patent CN101550051B
Be also to employ a kind of ZSM-5 catalyst that the metallic elements such as Ga, Zn are modified, for fixed bed or
Flotation bed, in 0.1～3.5MPa of pressure, at 380～500 DEG C, liquid air speed is in 0.1～10h for temperature-1, nitrogen
Air speed is in 120～800h-1Under, convert methanol into aromatic hydrocarbons.Current work all concentrates on the metal to carrier
On modified, carrier used is all the molecular sieve with microcellular structure.Due to microporous molecular mesh size it is less, no
Beneficial to the diffusion of reactant and product, mass-transfer efficiency is converted into the reaction of macromole aromatic hydrocarbons than relatively low in methanol
During, hole is easy to be generated thing blocking inactivation, causes the life-span shorter.When micro porous molecular sieve is through metal-modified
Afterwards, its aperture may be less, also poor to the selectivity of macromole product.
The content of the invention
The technical problem to be solved is methanol arenes catalytic agent stability present in prior art
The not high problem of difference, BTX selectivitys；A kind of catalyst of new methanol conversion for preparing arene, the catalysis are provided
Agent is used for methanol aromatic hydrocarbons when reacting, and with aromatics yield height, BTX selectivitys are good, catalyst stability is good
Advantage.
To solve above-mentioned technical problem, the technical solution used in the present invention is as follows：A kind of catalysis of methanol aromatic hydrocarbons
Agent, catalyst is in terms of parts by weight, including following components：A.30 the molecule that～80 part mesoporous and micropore is combined
Sieve；B.0.5～12 part zinc element or its oxide；C.20～60 part binding agent.
In above-mentioned technical proposal, it is preferred that catalyst is also selected from the B of the periodic table of elements the IVth containing 0.5～5 part
At least one or its oxide in race's element；It is furthermore preferred that in the B races element of the periodic table of elements the IVth at least
A kind of or its oxide is at least one or its oxide in Ti and Zr.
In above-mentioned technical proposal, it is preferred that binding agent is aluminium oxide or silicon oxide.
In above-mentioned technical proposal, it is preferred that molecular sieve is mesoporous type ZSM 5 molecular sieve, with catalyst weight
Number meter, its consumption is 40～80 parts；It is furthermore preferred that the silica alumina ratio SiO of mesoporous ZSM-5 molecular sieve2/Al2O3
For 20～160.
In above-mentioned technical proposal, it is preferred that the macropore diameter of mesoporous ZSM-5 molecular sieve between 10～20nm,
Between 4～6nm, average pore size is 7～10nm to micropore size；It is furthermore preferred that mesoporous ZSM-5 molecular sieve
Total specific surface area be 350～490m2/ g, wherein mesopore surface area account for total specific surface area 20～60%.
In above-mentioned technical proposal, it is preferred that mesoporous ZSM-5 molecular sieve is synthesized by following method：1) will
Template R, sodium hydroxide and silicon source are dissolved in and formed in deionized water mixed solution A；2) by tetraethyl orthosilicate,
Sodium hydroxide and additive M dissolve in formation mixed solution B in deionized water；3) by the mixed solution of A and B
In being transferred to rustless steel crystallizing kettle, hydrothermal treatment consists 20～70 hours at a temperature of 160～200 DEG C；4) crystalline substance is treated
Change is filtrated to get white powder after terminating, and deionized water cyclic washing is to neutrality；5) this white powder is done
Dry, roasting obtains molecular sieve, is repeatedly dried afterwards with ammonium nitrate solution ion exchange, to obtain Hydrogen after roasting mesoporous
ZSM-5 molecular sieve；Template R used be 4-propyl bromide, TPAOH, ethylenediamine and
At least one of n-butylamine, source of aluminium is aluminum isopropylate. or sodium metaaluminate, and silicon source used is methyl silicate
Or tetraethyl orthosilicate, additive therefor M is Brij30 and/or polyvinyl alcohol.
In above-mentioned technical proposal, it is preferred that the mol ratio of each component is (15～120) SiO2：(0.8～4.1)
R：(2.0～6.7) NaOH：1Al2O3：(60～480) C2H5OH：(0～0.30) M：(200～5000)
H2O。
The using method of above-mentioned catalyst is as follows：A kind of catalyst of methanol aromatic hydrocarbons, with methanol as raw material,
360～500 DEG C of reaction temperature, reaction pressure is 0～1.0MPa, raw materials quality 0.4～8h of air speed-1Under the conditions of, make
Raw material obtains aromatic hydrocarbons with generation aromatization on above-mentioned catalyst.
In above-mentioned technical proposal, it is preferred that reaction temperature is 380～480 DEG C.
In above-mentioned technical proposal, it is preferred that reaction pressure is 0～0.8MPa.
In above-mentioned technical proposal, it is preferred that methanol quality air speed is 0.8～5h-1。
Mesoporous ZSM-5 molecular sieve used in the present invention, includes mesoporous and microcellular structure, and its specific surface area is adopted
Calculated with the adsorption desorption isothermal curve of nitrogen, sample processes 12 hours in 350 DEG C of evacuation first, so
Carry out nitrogen adsorption desorption experiment at -196 DEG C afterwards, take measure pressure and atmospheric pressure ratio in the range of 0.05～0.25
Isothermal curve, calculate its specific surface area with BET methods, determine mesoporous pore-size distribution with BJH methods,
The volume of micropore is determined with t-plot methods.
The present invention compared with prior art, has the following advantages that and beneficial effect：
1. the catalyst for being provided using the present invention, in the reaction of methanol conversion for preparing arene, with aromatics yield
Height, with carbon-based calculating, more than 60%, wherein BTX selectivitys are more than 70% for its yield；Urge containing Zn
Agent does not typically have higher stability, but the present invention is conventional by being substituted using mesoporous ZSM-5 molecular sieve
ZSM-5 molecular sieve, effectively increases the stability containing Zn catalyst；
2. the mesoporous ZSM-5 molecular sieve carrier that the present invention is used, with uniform mesoporous distribution, higher ratio
Surface area, average pore size is larger, and compared with the molecular sieve carrier in traditional single duct, it is in longer time
Interior energy keeps higher reactivity, and catalyst inactivation is slow；
3. the method for methanol conversion for preparing arene provided by the present invention, gentle with reaction condition, operable model
The characteristics of enclosing wide, technological process is simple.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
【Embodiment 1】
19 grams of 4-propyl bromides, 3.3 grams of sodium hydroxide, 9.8 grams of aluminum isopropylate. are added into 180 grams of deionizations
In water, hydrolyze 6 hours in room temperature strong agitation, obtain solution A.By 127 grams of tetraethyl orthosilicates, 1.2g hydrogen
Sodium oxide, 5.3 grams of polyoxyethylene laurel ethers are added in 120 grams of water, and strong agitation 5 hours obtains solution B.
It is stirred at room temperature after A is mixed with B 6 hours, the mixed solution for obtaining is transferred to rustless steel crystallizing kettle
In, at a temperature of 180 DEG C, hydrothermal treatment consists 50 hours.After crystallization is complete, by the white powder mistake for obtaining
Filter, deionized water cyclic washing is to neutrality.This white powder is dried under 110 degree, at 550 DEG C
The molecular sieve that roasting 8h the is obtained ammonium nitrate ion exchange three times of 0.5mol/L, according to above the step of be dried
After roasting, the mesoporous ZSM-5 molecular sieve of Hydrogen that silica alumina ratio is 30 is just obtained.The test of Jing specific surface areas is obtained,
Total specific surface area of mesoporous ZSM-5 molecular sieve is 428m2/ g, wherein mesopore surface area are 159m2/ g, puts down
Aperture is 8.9nm.
Take 20 mole to sieve, 1.2 grams of sesbania powders, 6.8 grams of aluminium oxidies are 5% with 15.6 gram mass concentration
After the abundant kneading of aqueous solution of nitric acid, extruded moulding makes catalyst carrier I after drying roasting.Take 15 grams
Carrier I, in impregnated in 11 milliliters of zinc nitrate solutions containing 0.31 gram of Zinc Oxide, is stored at room temperature 24 hours,
Drying, 560 DEG C of roastings 4 hours, makes catalyst A.
By the catalyst for the reaction of methanol aromatic hydrocarbons, in continuous fixed bed reactors, normal pressure, 390 DEG C of temperature,
Weight space velocity 2h-1Under the conditions of, its reaction result is listed in table 1.
【Embodiment 2】
Using the carrier I of embodiment 1,15 grams of carriers I are taken, impregnated in 11 milliliters containing 1.1 grams of Zinc Oxide
In zinc nitrate solution, it is stored at room temperature 24 hours, drying, catalyst B is made in 560 DEG C of roastings 4 hours.
Reaction condition is same as Example 1.
【Embodiment 3】
7.8 grams of n-butylamines, 2.3 grams of sodium hydroxide, 6.0 grams of sodium metaaluminates are added in 150 grams of deionized waters,
Hydrolyze 5 hours in room temperature strong agitation, obtain solution A.By 127 grams of tetraethyl orthosilicates, 1.5 grams of hydroxides
Sodium, 6.2 grams of polyvinyl alcohol are added in 120 grams of water, and strong agitation 7 hours obtains solution B.By A and B
It is stirred at room temperature after being mixed 4 hours, the mixed solution for obtaining.Other conditions are same as Example 1.Jing
Specific surface area test is obtained, and total specific surface area of mesoporous ZSM-5 molecular sieve is 415m2/ g, its intermediary hole compares table
Area is 125m2/ g, average pore size is 7.7nm.
20 mole sieve, 1.2 grams of sesbania powders are taken, 24 gram mass concentration are after the 40% abundant kneading of Ludox,
Extruded moulding, makes catalyst carrier II after drying roasting.15 grams of carriers II are taken, 11 milliliters is impregnated in and is contained
In the solution of zinc sulfate of 0.89 gram of Zinc Oxide, it is stored at room temperature 24 hours, drying, 560 degree of roastings 4 hours,
Make catalyst C.Reaction condition is same as Example 1.
【Embodiment 4】
According to the method for embodiment 1, by the amount for adjusting aluminum isopropylate., prepare silica alumina ratio be 60 it is mesoporous
ZSM-5 molecular sieve, and the method according to embodiment one prepares catalyst carrier III.15 grams of carriers III are taken, is soaked
Stain is stored at room temperature 24 hours, drying, 560 in 11 milliliters of zinc nitrate solutions containing 0.51 gram of Zinc Oxide
Degree roasting 4 hours, makes catalyst D.Reaction condition is same as Example 1.The test of Jing specific surface areas is obtained,
Total specific surface area of mesoporous ZSM-5 molecular sieve is 440m2/ g, wherein mesopore surface area are 176m2/ g, puts down
Aperture is 9.1nm.
【Embodiment 5】
Adopt the silica alumina ratio of the synthesis of embodiment 4 for 60 mesoporous ZSM-5, take 20 mole sieve, 1.2 grams of fields
After cyanines powder, 15 grams of aluminium oxidies and the abundant kneading of aqueous solution of nitric acid that 21 gram mass concentration are 5%, extruded moulding,
Catalyst carrier IV is made after drying roasting.15 grams of carriers IV are taken, 11 milliliters is impregnated in containing 0.97 gram of oxygen
In changing the solution of zinc sulfate of zinc, it is stored at room temperature 24 hours, drying, 560 degree of roastings 4 hours are made and urged
Agent E.Reaction condition is identical with embodiment one.
【Embodiment 6】
According to the method for embodiment 3, by the amount for adjusting sodium metaaluminate, prepare silica alumina ratio be 100 it is mesoporous
ZSM-5 molecular sieve.The test of Jing specific surface areas is obtained, and total specific surface area of mesoporous ZSM-5 molecular sieve is
431m2/ g, wherein mesopore surface area are 159m2/ g, average pore size is 9.3nm.
Take 20 mole sieve, 1.2 grams of sesbania powders, 26.5 grams of Ludox for containing 40%, extrusion after abundant kneading
Molding, makes catalyst carrier V after drying roasting.15 grams of carriers V are taken, 11 milliliters is impregnated in containing 0.89
In the zinc nitrate solution of gram Zinc Oxide, it is stored at room temperature 24 hours, drying, 550 DEG C of degree roasting 4 hours,
Make catalyst F.Reaction condition is same as Example 1.
【Embodiment 7】
Using the catalyst carrier I prepared by embodiment 1.15 grams of carriers I are taken, 11 milliliters is impregnated in and is contained
In the mixed solution of 1.42 grams of zinc nitrates and 0.7 gram of zirconium nitrate, it is stored at room temperature 24 hours, drying, 560 DEG C
Roasting 4 hours, makes catalyst G.
By the catalyst for the reaction of methanol aromatic hydrocarbons, in continuous fixed bed reactors, normal pressure, 390 DEG C of temperature,
Weight space velocity 2h-1Under the conditions of, its reaction result is listed in table 1.
【Embodiment 8】
Using the catalyst carrier I prepared by embodiment 1.15 grams of carriers I are taken, 11 milliliters is impregnated in and is contained
In the mixed solution of 1.4 grams of zinc nitrates and 1.67 grams of Titanium Nitrates, it is stored at room temperature 24 hours, drying, 560 DEG C
Roasting 4 hours, makes catalyst H.
By the catalyst for the reaction of methanol aromatic hydrocarbons, in continuous fixed bed reactors, normal pressure, 390 DEG C of temperature,
Weight space velocity 2h-1Under the conditions of, its reaction result is listed in table 1.
【Embodiment 9】
Using the catalyst B of embodiment 2, reaction condition is changed to into mass space velocity for 3h-1, temperature is 460 DEG C,
Reaction pressure is 0.2MPa.Reaction result is listed in table 2.
【Embodiment 10】
Using the catalyst B of embodiment 3, reaction condition is changed to into air speed for 1.5h-1, temperature is 420 DEG C, instead
Pressure is answered to be 0.4MPa.Reaction result is listed in table 2.
【Embodiment 11】
Using the catalyst B of embodiment 4, reaction condition is changed to into air speed for 3.8h-1, temperature is 440 DEG C, instead
Pressure is answered to be 0.3MPa.Reaction result is listed in table 2.
【Comparative example 1】
Adopt silica alumina ratio for 30 commercial ZSM-5 molecular sieve, as described in Example 1, make catalyst I.
By the catalyst for the reaction of methanol aromatic hydrocarbons, in continuous fixed bed reactors, normal pressure, 390 DEG C of temperature,
Weight space velocity 2h-1Under the conditions of, its reaction result is listed in table 1.
【Comparative example 2】
10 grams of commercial ZSM-5 molecular sieves for taking that silica alumina ratio is 30 and 10 grams of MCM-41 molecular sieves, 2.5 grams
Sesbania powder, after 6.8 grams of aluminium oxidies, with the abundant kneading of aqueous solution of nitric acid that 18 gram mass concentration are 5%, extrusion
Molding, makes catalyst carrier VI after drying roasting.15 grams of carriers VI are taken, 11 milliliters is impregnated in containing 0.51
In the zinc nitrate solution of gram Zinc Oxide, it is stored at room temperature 24 hours, drying, 560 DEG C of roastings 4 hours, system
Into catalyst J.
By the catalyst for the reaction of methanol aromatic hydrocarbons, in continuous fixed bed reactors, normal pressure, 390 DEG C of temperature,
Weight space velocity 2h-1Under the conditions of, its reaction result is listed in table 1.
【Comparative example 3】
Adopt silica alumina ratio for 30 commercial ZSM-5 molecular sieve, weigh 30 mole sieve, use 50ml concentration
For the sodium hydroxide solution of 0.05mol/L, process 7 hours at 60 degree, be then washed with deionized into
Property, it is dried.Take the molecular sieve after 20 grams of alkali process, 1.2 grams of sesbania powders, 6.8 grams of aluminium oxidies, with 16 grams of matter
Amount concentration is that extruded moulding makes carrier VII after the 5% abundant kneading of aqueous solution of nitric acid after drying roasting.
15 grams of carriers VII are taken, in impregnated in 11 milliliters of zinc nitrate solutions containing 0.51 gram of Zinc Oxide, 24 is stored at room temperature
Hour, catalyst K is made in drying, 560 DEG C of roastings 4 hours.
By the catalyst for the reaction of methanol aromatic hydrocarbons, in continuous fixed bed reactors, normal pressure, 390 DEG C of temperature,
Weight space velocity 2h-1Under the conditions of, its reaction result is listed in table 1.
Table 1
Table 2
Claims (10)
1. a kind of catalyst of methanol aromatic hydrocarbons, catalyst is in terms of parts by weight, including following components：A.30～
80 parts of mesoporous molecular sieves being combined with micropore；B.0.5～12 part zinc element or its oxide；～60 part c.20
Binding agent.
2. the catalyst of methanol aromatic hydrocarbons according to claim 1, it is characterised in that catalyst also contains
0.5～5 part of at least one or its oxide in the B races element of the periodic table of elements the IVth.
3. the catalyst of methanol aromatic hydrocarbons according to claim 1, it is characterised in that binding agent be aluminium oxide or
Person's silicon oxide.
4. the catalyst of methanol aromatic hydrocarbons according to claim 1, it is characterised in that molecular sieve used
For mesoporous type ZSM 5 molecular sieve, in terms of catalyst weight number, its consumption is 40～80 parts.
5. the catalyst of methanol aromatic hydrocarbons according to claim 4, it is characterised in that mesoporous ZSM-5 point
The silica alumina ratio SiO of son sieve2/Al2O3For 10～200.
6. the catalyst of methanol aromatic hydrocarbons according to claim 4, it is characterised in that mesoporous ZSM-5 point
Between 10～20nm, between 4～6nm, average pore size is 7～10nm to micropore size to the macropore diameter of son sieve.
7. the catalyst of methanol aromatic hydrocarbons according to claim 4, it is characterised in that mesoporous ZSM-5 point
Total specific surface area of son sieve is 350～490m2/ g, wherein mesopore surface area account for total specific surface area 20～60%.
8. the catalyst of methanol aromatic hydrocarbons according to claim 1, it is characterised in that mesoporous ZSM-5 point
Son sieve is synthesized by following method：1) template R, sodium hydroxide and silicon source are dissolved in into shape in deionized water
Into mixed solution A；2) tetraethyl orthosilicate, sodium hydroxide and additive M are dissolved in be formed in deionized water and is mixed
Close solution B；3) mixed solution of A and B is transferred in rustless steel crystallizing kettle, in 160～200 DEG C of temperature
The lower hydrothermal treatment consists of degree 20～70 hours；4) white powder is filtrated to get after crystallization terminates, deionized water is repeatedly
Wash to neutrality；5) this white powder is dried, roasting obtains molecular sieve, uses ammonium nitrate solution ion exchange
After repeatedly, after dry, roasting the mesoporous ZSM-5 molecular sieve of Hydrogen is obtained；Template R used is tetrapropyl
At least one of ammonium bromide, TPAOH, ethylenediamine and n-butylamine, source of aluminium be aluminum isopropylate. or
Sodium metaaluminate or aluminum sulfate, silicon source used is methyl silicate or tetraethyl orthosilicate, and additive therefor M is
Brij30 and/or polyvinyl alcohol.
9. the catalyst of methanol aromatic hydrocarbons according to claim 8, it is characterised in that mesopore molecular sieve
The mol ratio of gel each component is (15～120) SiO2：(0.8～4.1) R：(2.0～6.7) NaOH：1Al2O3：
(60～480) C2H5OH：(0～0.30) M：(200～5000) H2O。
10. a kind of method of methanol aromatic hydrocarbons, with methanol as raw material, in 360～500 DEG C of reaction temperature, reaction pressure
Power is 0～1.0MPa, raw materials quality 0.4～8h of air speed-1Under the conditions of, make raw material and any one of claim 1～9
Aromatic hydrocarbons obtained and aromatization in described catalyst there is.
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| CN113019433A (en) * | 2021-03-23 | 2021-06-25 | 兰州理工大学 | Preparation method of HZSM-5 zeolite catalyst |
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| CN113751055A (en) * | 2021-09-24 | 2021-12-07 | 大连理工大学 | A kind of in-situ preparation method of high stability molecular sieve supported metal catalyst |
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| CN113019433A (en) * | 2021-03-23 | 2021-06-25 | 兰州理工大学 | Preparation method of HZSM-5 zeolite catalyst |
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