CN1880288A - Process of methanol conversion for preparing arene and catalyst and catalyst preparation method - Google Patents
Process of methanol conversion for preparing arene and catalyst and catalyst preparation method Download PDFInfo
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- CN1880288A CN1880288A CNA2006100127031A CN200610012703A CN1880288A CN 1880288 A CN1880288 A CN 1880288A CN A2006100127031 A CNA2006100127031 A CN A2006100127031A CN 200610012703 A CN200610012703 A CN 200610012703A CN 1880288 A CN1880288 A CN 1880288A
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- methanol conversion
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- molecular sieve
- preparing arene
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract 57
- 238000000034 method Methods 0.000 title claims abstract 26
- 238000006243 chemical reaction Methods 0.000 title claims abstract 18
- 239000003054 catalyst Substances 0.000 title claims abstract 12
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims 19
- 238000002360 preparation method Methods 0.000 title claims 12
- 229930195733 hydrocarbon Natural products 0.000 claims abstract 8
- 239000002808 molecular sieve Substances 0.000 claims abstract 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract 8
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract 7
- 239000002994 raw material Substances 0.000 claims abstract 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract 3
- 239000007788 liquid Substances 0.000 claims abstract 3
- 238000000926 separation method Methods 0.000 claims abstract 3
- 239000000243 solution Substances 0.000 claims 7
- 239000013078 crystal Substances 0.000 claims 6
- 239000000047 product Substances 0.000 claims 6
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims 4
- 239000004215 Carbon black (E152) Substances 0.000 claims 3
- 239000011230 binding agent Substances 0.000 claims 3
- 239000012263 liquid product Substances 0.000 claims 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 2
- 241000282326 Felis catus Species 0.000 claims 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 2
- 229940044658 gallium nitrate Drugs 0.000 claims 2
- 239000012535 impurity Substances 0.000 claims 2
- 229910052746 lanthanum Inorganic materials 0.000 claims 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims 2
- 239000000463 material Substances 0.000 claims 2
- 239000000203 mixture Substances 0.000 claims 2
- 229910052710 silicon Inorganic materials 0.000 claims 2
- 239000010703 silicon Substances 0.000 claims 2
- 238000003756 stirring Methods 0.000 claims 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 1
- 229910021536 Zeolite Inorganic materials 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical group [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 239000008367 deionised water Substances 0.000 claims 1
- 229910021641 deionized water Inorganic materials 0.000 claims 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims 1
- 238000007598 dipping method Methods 0.000 claims 1
- 238000001125 extrusion Methods 0.000 claims 1
- 239000012530 fluid Substances 0.000 claims 1
- 229910052733 gallium Inorganic materials 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 claims 1
- 230000003068 static effect Effects 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 1
- -1 sulfuric acid amine Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 239000010457 zeolite Substances 0.000 claims 1
- 239000007791 liquid phase Substances 0.000 abstract 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 239000012071 phase Substances 0.000 abstract 1
- 238000011112 process operation Methods 0.000 abstract 1
Classifications
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Catalysts (AREA)
Abstract
一种甲醇转化制芳烃工艺是以甲醇为原料，以改性ZSM－5分子筛为催化剂，在操作压力为0.1～5.0Mpa，操作温度为300～460℃，原料液体空速为0.1～6.0h－1条件下催化转化为以芳烃为主的产物；经冷却分离将气相产物低碳烃与液相产物C5 +烃分离；液相产物C5 +烃经萃取分离，得到芳烃和非芳烃。本发明具有芳烃的总选择性高，工艺操作灵活的优点。A methanol conversion process for producing aromatics uses methanol as a raw material and modified ZSM-5 molecular sieve as a catalyst. The operating pressure is 0.1-5.0Mpa, the operating temperature is 300-460°C, and the liquid space velocity of the raw material is 0.1-6.0h - Catalytic conversion to aromatics-based products under the conditions of 1 ; the gas-phase product low-carbon hydrocarbons and liquid-phase product C 5 + hydrocarbons are separated by cooling and separation; the liquid-phase product C 5 + hydrocarbons is extracted and separated to obtain aromatics and non-aromatics. The invention has the advantages of high overall selectivity of aromatics and flexible process operation.
Description
Technical field
The invention belongs to a kind of is that raw material is produced the technology of aromatic hydrocarbons and used catalyzer and Preparation of catalysts method thereof with methyl alcohol.
Technical background
Methyl alcohol is a kind of abundant industrial raw material of originating, and is C
1The foundation stone of chemistry and chemical industry, the synthetic of methyl alcohol is a very active subject with transforming always.For improving the competitiveness, also towards maximization, energy-saving development, output continues to increase China's methanol production in recent years.At present, for methyl alcohol is used the good of prospect as automotive fuel, the methyl alcohol new device is also in continuous construction.Under the methyl alcohol situation bright as the automotive fuel unclear prospect, actively carry out the exploitation of Downstream Products of Methanol, crucial meaning (Shen Peizhi, chemical industry progress are arranged for the development of methanol industry, methyl alcohol market situation and scientific and technological development progress, NO1.vol22.2003).
Methyl alcohol is converted into hydro carbons under the effect of catalyzer be to study field comparatively widely.At first proposing to adopt the five-membered ring mesopore ZSM-5 molecular sieve catalyst of being made up of silicon-oxy tetrahedron that methyl alcohol is carried out height by Mobil company in early days selects to transform generation high-quality gasoline (United States Patent (USP) 4544781,4506106), makes oil mineral fuel such as Sweet natural gas and coal etc. in addition can become the effective energy.
Methanol conversion is that alkene (MTO) is the another one important directions of methanol conversion, and LURGI and Uop Inc. all have multinomial patent to describe this technology and corresponding catalyzer.Wherein, the technology of American UOP company and the cooperative development of Norway Norsk Hydro company, in more than 90 day process of operation, methanol conversion remains near 100%, ethene and propylene selectivity are respectively 55 (mol) % and 27 (mol) %, and the adjusting by severity can change ratio (Industrial Catalysis, 2001 between ethene and the propylene, 9 (4): 3-8), to satisfy the demand in market.The technology of LURGI mainly is to produce propylene, the selectivity of its propylene can greater than 70 (mol) % (refining of petroleum and chemical industry, 2001, vol32:58).Domestic Dalian Chemistry and Physics Institute has developed the technology of methyl alcohol through dme system alkene, has formed independent intellectual property right (ZL99127143), and this technology is just being prepared in Shaanxi at present and carried out the industrial demonstration test of ton.
An important problem is the Technological Economy problem in the methanol conversion technology.No matter be to be high-quality gasoline with methanol conversion at present, still be converted into alkene, the economy of process is all owing to the restriction of added value of product is hindered its industrialization process.
Aromatic hydrocarbons is important petrochemicals, has high added value.The aromatic hydrocarbons of China is mainly derived from petroleum resources, and the present situation of China's oil shortage of resources has determined the scarcity of aromatic hydrocarbon resource.From the direct preparing aromatic hydrocarbon by converting of resourceful methyl alcohol, for the shortage of alleviating aromatic hydrocarbons, improve the added value of Downstream Products of Methanol, prolong Coal Chemical Industry and gas chemical industry's industrial chain, have significant values.Methanol conversion is that description (chemistry world P406 is also arranged in the former document of the operational path of aromatic hydrocarbons, NO8,1996), but mostly be to carry out dimethyl ether by methanol dehydration earlier, continue dehydration by dme again and generate low-carbon alkene, low-carbon alkene then carries out reactions such as superimposed, isomerization, dehydrocyclization and forms stable hydrocarbon, aromatic hydrocarbons, alkene etc. then.But this operational path flow process more complicated, target product selectivity is not high yet.Also there is not at present a technology of directly producing aromatic hydrocarbons by methanol conversion.
Summary of the invention
The purpose of this invention is to provide a kind of methyl alcohol catalyzed conversion and produce the technology of aromatic hydrocarbons, and the catalyzer and the Preparation of catalysts method thereof of conversion process employing.
The technology (MTA) that methyl alcohol catalyzed conversion provided by the present invention is produced aromatic hydrocarbons comprises the steps:
1. being raw material with methyl alcohol, is catalyzer with the modified zsm-5 zeolite, is 0.1～5.0Mpa at working pressure, and service temperature is 300～460 ℃, and the raw material liq air speed is 0.1～6.0h
-1Under the condition, be converted into product based on aromatic hydrocarbons through one section catalytic reaction;
2. the product based on aromatic hydrocarbons passes through refrigerated separation, with gas-phase product lower carbon number hydrocarbons and liquid product C
5 +Hydrocarbon separates;
3. liquid product C
5 +Hydrocarbon obtains aromatic hydrocarbons and non-aromatics through extracting and separating.
In order to improve the overall selectivity of product aromatic hydrocarbons, the gas-phase product lower carbon number hydrocarbons that one section reaction generates also can further pass through second-stage reaction, under two sections operational conditions and two sections catalyst actions, is converted into aromatic hydrocarbons through aromatization.Concrete steps are as follows:
(1) the gas-phase product lower carbon number hydrocarbons enters second stage reactor, is 0.1～5.0Mpa at two sections working pressures, and two sections service temperatures are 250～500 ℃, and two sections air speeds are 50～2000h
-1, under two sections catalyzer existence conditions, obtain the second-stage reaction product;
(2) two sections products after gas-liquid separation, product liquid and one section liquid product C
5 +Hydrocarbon mixes.
Aforesaid one section working pressure the best is 0.1～3.5Mpa, and one section service temperature the best is 300～410 ℃, and one section raw material liq air speed the best is 0.4～2.0h
-1
Aforesaid two sections working pressure the bests are 0.1～3.5Mpa, 300～450 ℃ of two sections service temperature the bests, and two sections raw material liq air speed the bests are 100～1000h
-1
Aforesaid one section catalyzer is obtained by the ZSM-5 molecular sieve with small crystal grains modification.The weight percent of one section catalyzer consists of (wt%):
Little crystal grain HZSM-5:62.0～85.0
Ga： 0.5～2.0
La： 0.2～1.0
Binding agent: 14.0～34.0
The preparation method particularly of a section of conversion catalyst provided by the present invention comprises the steps:
(1) with nSiO
2/ nAl
2O
3Than being 20～100, preferred especially nSiO
2/ nAl
2O
3Than the ZSM-5 molecular sieve with small crystal grains that is 40～80, at 450～550 ℃, be preferably 490～530 ℃ of following roastings 1～10 hour, obtain removing the ZSM-5 molecular sieve with small crystal grains of impurity;
(2) ammonium nitrate or the sulfuric acid amine aqueous solution with 0.1～1.0mol/L exchanges 2 hours to the ZSM-5 molecular sieve with small crystal grains that removes impurity, filter, with deionized water wash 2～5 times, in 100～150 ℃ of baking ovens, dry, place stoving oven in 450～550 ℃ again, be preferably 490～530 ℃ and kept 3～6 hours down;
(3) molecular sieve and binding agent after the processing of (2) step are mixed in proportion, evenly grind;
(4) nitric acid is mixed with weight percent be 2～4% drips of solution add mix in the ground material of (3) step pinch after, extrusion molding is 100～150 ℃ of oven dry down;
Material after the oven dry of (5) (4) steps is preferably 490～550 ℃ of roastings 3～5 hours at 450～560 ℃;
(6) gallium nitrate is mixed with 0.2～3.0mol/L, is preferably the solution of 1.5～2.5mol/L, lanthanum nitrate is mixed with 0.01～1.0mol/L, is preferably the solution of 0.1～0.9mol/L; Two kinds of solution mix, and stir;
(7) molecular sieve with step (5) adds in the solution of step (6) preparation, carries out 1～10 hour dipping under 20～80 ℃ stirring;
(8) behind the steeping fluid evaporate to dryness, it was kept in 100～150 ℃ baking oven 3～8 hours, then at 350～450 ℃, be preferably 380～420 ℃ of roastings and made catalyzer in 2～8 hours.
Aforesaid binding agent is pseudo-boehmite, a gama-alumina or diatomite equimolecular sieve catalyst binding agent commonly used.
The raw material of one section catalyzer can be the ZSM-5 molecular sieve with small crystal grains that meets any source of above-mentioned condition, but the ZSM-5 molecular sieve with small crystal grains by Chinese patent 00109593.5 preparation is adopted in special recommendation of the present invention.
The preparation method of a section of conversion catalyst provided by the present invention adopts bimetal dipping upgrading method to obtain ZSM-5 molecular sieve with small crystal grains.The metal that bimetallic-modified adopts is gallium and lanthanum, improves the aromatization activity of molecular sieve by the introducing of gallium, and the introducing of lanthanoid metal strengthens the stability of molecular sieve, and with time modulation the acid matter of molecular sieve.Catalyzer prepared by this method has very high reactive behavior and selectivity of product.
Aforesaid two sections catalyzer are that the mol ratio with the silicon gallium of Chinese patent ZL0134776.4 preparation is 63-218, lanthanum content is 0.83-2.12wt%, total acid content is that the catalyzer of 0.468-0.672mmol/g.cat activates 1-20 hour in 360～480 ℃ high-temperature vapor, make catalyzer to the Static Adsorption amount of hexanaphthene within 0.073～0.079 gram/gram range of catalysts.
Chinese patent ZL0134776.4 Preparation of catalysts step is as follows:
(1) at first with the silicon gallium than carrying out mixed grinding for the 64-72Wt% of the acid type GaZSM-5 molecular sieve of 40-250 and the aluminum oxide of 28-36Wt%, the salpeter solution that drips 3-4V% then in the material that mixes mixes to be pinched suitably, by the banded extruder moulding and 100-130 ℃ of oven dry down, place retort furnace again in 540 ℃ of following roasting 6-8 hours;
(2) according to lanthanum: the molar ratio relation preparation lanthanum nitrate hexahydrate of nitric acid=1: 3.0-4.5, promptly at first taking by weighing mishmetal puts into beaker and adds nitric acid again and mix, then in 80-90 ℃ of heating until finish the fusing become clear solution till, be and be made into lanthanum nitrate reagent, and then add deionized water again according to desired concn and be mixed with the solution that volumetric molar concentration is 0.3-1.0;
(3) GaZSM-5 was flooded 3-5 hour down at 80-95 ℃ with different ratio heating with lanthanum nitrate hexahydrate, the cooling after-filtration is put into baking oven 100-120 ℃ of oven dry down with throw out;
(4) again the catalyzer of oven dry is inserted in the retort furnace and got final product in 300-350 ℃ of following roasting 3-5 hour.
With the molecular sieve catalyst of method for preparing 360～480 ℃ high-temperature vapor activation 1～20 hour, to adjust the character of catalyzer, make catalyzer to the Static Adsorption amount of hexanaphthene within 0.073～0.079 gram/gram range of catalysts.The variation of these basic structures has strengthened the type of selecting and the strong acid center of zeolite, has improved strong faintly acid synergy.The activity and the selectivity of one section gas-phase product aromatization of the present invention have been improved thus.
Aforesaid non-aromatics can be used as solvent oil or gasoline component uses.
Aforesaid gas phase part mainly is C
1～C
4Hydrocarbon, wherein existing stable hydrocarbon (alkane) also has unsaturated hydrocarbons (alkene).
The liquid product selectivity of one section conversion provided by the present invention is greater than 30% (methanol quality base), and the aromatic hydrocarbons mass content can reach more than 65% in the liquid product, can reach more than 80% under the optimal conditions.Lower carbon number hydrocarbons (the C of one section conversion
1～C
4) selectivity is less than 10% (methanol quality base), can be under top condition less than 5%.The transformation efficiency of one section methanol of reaction＞99%.
The gas-phase product lower carbon number hydrocarbons is through the further aromizing of second-stage reaction, and the mass yield of aromatic hydrocarbons can be greater than 60% under the optimal conditions greater than 40%.
Adopt two-stage method technology provided by the invention, C
5 +The liquid product total recovery is greater than 38% (methanol quality base), and the aromatic hydrocarbons total recovery is greater than 30% (methanol quality base).
The technology of methyl alcohol catalytic cracking aromatic hydrocarbons provided by the present invention has following characteristics:
1. adopt two sections conversion process to produce aromatic hydrocarbons, the overall selectivity of aromatic hydrocarbons is increased substantially by methanol conversion;
2. one section liquid air speed LHSV can be at 1.0～6.0h
-1Interior adjustment, technological operation handiness height;
3. liquid product separates aromatic hydrocarbons through extracting and separating with non-aromatics, obtains target product aromatic hydrocarbons.Non-aromatics can be used as solvent oil or gasoline component uses;
4. one section conversion ZSM-5 molecular sieve catalyst preparation method is simple; Have very high activity and selectivity.BTX aromatics content can be up to more than 65% in the liquid product, can be greater than 80% under the top condition;
5. two sections catalyzer have high arenes selectivity, long-life advantage.
Embodiment
Embodiment 1
1, one section Preparation of catalysts and sign
(1) gets nSiO
2/ nAl
2O
3Than being 30.28, median size is ZSM-5 molecular sieve with small crystal grains 30 grams of 0.1 μ m, 520 ℃ of following roastings 5 hours, to remove the impurity of its physical adsorption.The concrete preparation method of above-mentioned molecular sieve sees Chinese patent 00109593.5;
(2) amine nitrate solution with 0.5mol/L carries out ion-exchange 2 hours under boiling state, filters, and uses deionized water wash 3 times, dries in 120 ℃ of baking ovens, places stoving oven to keep 5 hours down in 540 ℃ again;
(3) get molecular sieve 20 grams that (2) step obtained, 7 gram γ-Al
2O
3, put into mortar and mix, evenly grind;
(4) 3% salpeter solution is dripped in the good material of mill, mix and pinch suitably, be squeezed into the bar column type of Ф 2, insert in the baking oven and dry down in 120 ℃ with the spiral banded extruder;
(5) the strip molecular sieve is crushed to 10～40 orders and puts into retort furnace and be warming up to 530 ℃ of roastings 5 hours,, treat that temperature is reduced to below 60 ℃ can take out to take off nitric acid and moisture;
(6) accurately take by weighing gallium nitrate 2.73g, add deionized water 15ml, be made into the solution of 0.5mol/L, be stirred to dissolving fully with glass stick;
(7) accurately take by weighing lanthanum nitrate 0.65g, add deionized water 15ml, the solution that is made into 0.1mol/L is stirred to dissolving fully with glass stick;
(8) (6), (7) two kinds of solution are merged, mix and stirred 10 minutes;
(9) take by weighing 10 molecular sieves that make of gram (5) step and put into the Erlenmeyer flask that fills prepared mixing solutions of (8) step, under 80 ℃, keeping 2 hours evaporate to dryness on the induction stirring well heater;
(10) again it is inserted keep 5 hours in 110 ℃ the baking oven after, put into retort furnace in 350 ℃, roasting made catalyzer in 3 hours and consists of (wt%):
Little crystal grain HZSM-5 69.12
Ga 1.33
La 0.34
Binding agent 29.21
Utilization NH
3-TPD characterizes strong, slightly acidic, and detailed process is as follows: the 0.2g catalyzer of packing in the stainless steel reactor of φ 8 * 1.5 * 300mm (20～40 order) is feeding high-purity N
2After be warming up to 500 ℃ and keep 1h, lowering the temperature then begins to switch absorption NH in 50 ℃
3Until saturated, switch to high-purity N again
2Purge 40min down at 50 ℃ and remove physical adsorption, the speed with 25 ℃/min is warming up to 600 ℃ of (high-purity N at last
2Flow velocity is 35ml/min) finish desorption.The suction of molecular sieve, desorption rate adopt TCD to detect, and data processing is calculated and got in conjunction with the HCl solution absorption titration of external standard method and 0.1M.With the desorption rate below 300 ℃ is the weak acid amount, and desorption rate is the strong acid amount more than 300 ℃.Table 2 is the acid characterization result of catalyzer.
In order to characterize the structural performance of catalyzer, catalyzer has been carried out the mensuration of adsorptive capacity.At first with the N of institute's test sample product at 300 ℃
2Dry purge under the atmospheric condition is evacuated to vacuum meter with adsorption unit then and is designated as 0.07Mpa, begins to adsorb selected adsorbate and keeps 3 hours, weighs then, calculates adsorptive capacity.Table 3 is the adsorptive capacity determination data of embodiment catalyzer to hexanaphthene, normal hexane.
2, MTA reaction
(1) with methyl alcohol being raw material, is 0.1Mpa at one section working pressure, and one section service temperature is 410 ℃, and one section raw material liq air speed is 6.0h
-1Under the condition, be converted into product based on aromatic hydrocarbons through one section catalyzer;
(2) product based on aromatic hydrocarbons passes through refrigerated separation, with gas-phase product lower carbon number hydrocarbons and liquid product C
5 +Hydrocarbon separates;
(3) liquid product C
5 +Hydrocarbon separates aromatic hydrocarbons through extracting and separating with non-aromatics, obtain target product aromatic hydrocarbons and non-aromatics part.Reaction result sees Table 1.
Embodiment 2
1, the preparation of a section of conversion catalyst
(1) gets nSiO
2/ nAl
2O
3Than being 40.12 ZSM-5 molecular sieve with small crystal grains, 30 grams 540 ℃ of following roastings 4 hours to remove the impurity of its physical adsorption;
(2) amine nitrate solution with 0.5mol/L carries out ion-exchange 2 hours under boiling state, filters, and uses deionized water wash 5 times, dries in 120 ℃ of baking ovens, places stoving oven to keep 5 hours down in 520 ℃ again, obtains little crystal grain HZSM-5 molecular sieve;
(3) 14 mol sieve is restrained γ-Al with 6
2O
3Put into mortar simultaneously and mix, evenly grind;
(4) 3% salpeter solution is dripped in the good material of mill, mix and pinch suitably, be squeezed into the bar column type of Ф 2, insert in the baking oven and dry down in 110 ℃ with the spiral banded extruder;
(5) again the strip molecular sieve is crushed to 10～40 orders and puts into retort furnace and be warming up to 510 ℃ of roastings 3 hours,, treat that temperature is reduced to below 60 ℃ can take out to take off nitric acid and moisture;
(6) accurately take by weighing 4.36 gram gallium nitrates, add deionized water, shake up to the solution that 15ml is mixed with 0.8mol/L;
(7) accurately take by weighing 1.30 lanthanum nitrates and add deionized water, shake up to the solution that 15ml is mixed with 0.2mol/L;
(8) (6), (7) two kinds of solution are merged, mix and stirred 10 minutes;
(9) get the molecular sieve that 10 gram (5) steps made, put into the Erlenmeyer flask that fills prepared mixing solutions of (8) step, under 80 ℃, keeping 2 hours evaporate to dryness on the induction stirring well heater;
(10) it is inserted keep 7 hours in 105 ℃ the baking oven after, put into retort furnace in 400 ℃ of roastings 3 hours.Obtain catalyzer (wt%) composed as follows:
Little crystal grain HZSM-5 69.0
Ga 0.73
La 0.24
Binding agent 30.03
2, MTA reaction
The methanol conversion reaction conditions: one section working pressure is 0.5Mpa; One section service temperature is 340 ℃; One section operation air speed is 0.6h
-1, all the other are with embodiment 1.Reaction result sees Table 1.
Embodiment 3
1, preparation a section of conversion catalyst
(1) with nSiO
2/ nAl
2O
3Than being 54.36 ZSM-5 molecular sieve with small crystal grains, 30 grams 540 ℃ of following roastings 5 hours to remove the impurity of its physical adsorption;
(2) the sulfuric acid amine aqueous solution with 0.5mol/L carries out ion-exchange 2 hours under boiling state, filters, and uses deionized water wash 4 times, dries in 120 ℃ of baking ovens, places stoving oven to keep 5 hours down in 530 ℃ again, obtains little crystal grain HZSM-5 molecular sieve;
(3) 14.4 mol sieve is put into mortar simultaneously with the thin water aluminum oxide of 5.6 gram plans and mix, evenly grind;
(4) 3% salpeter solution is dripped in the good material of mill, mix and pinch suitably, be squeezed into the bar column type of Ф 2, insert in the baking oven and dry down in 115 ℃ with the spiral banded extruder;
(5) the strip molecular sieve is crushed to 10～40 orders and puts into retort furnace and be warming up to 520 ℃ of roastings 3 hours,, treat that temperature is reduced to below 60 ℃ can take out to take off nitric acid and moisture;
(6) accurately take by weighing 8.19 gram gallium nitrates, add deionized water, shake up to the solution that 15ml is mixed with 1.5mol/L;
(7) accurately take by weighing 1.95 lanthanum nitrates and add deionized water, shake up to the solution that 15ml is mixed with 0.3mol/L;
(8) triangular flask is put in solution merging in (6), (7) two, mixed and stirred 10 minutes;
(9) get 10 molecular sieves that make of gram (5) step and put into the Erlenmeyer flask that fills prepared mixing solutions of (8) step, under 80 ℃, keeping 2 hours evaporate to dryness on the induction stirring well heater;
(10) after it is inserted and keeps 7 hours in 105 ℃ the baking oven, put into retort furnace and promptly obtained catalyzer in 3 hours in 400 ℃ of roastings.Obtain catalyzer (wt%) composed as follows:
Little crystal grain HZSM-5 71.02
Ga 1.45
La 0.24
Binding agent 27.29
2, MTA reaction
The methanol conversion reaction conditions: one section working pressure is 3.5Mpa; One section service temperature is 320 ℃; One section operation air speed is 1.0h
-1, all the other are with embodiment 1.Reaction result sees Table 1.
Embodiment 4
1, preparation a section of conversion catalyst
(1) SiO
2/ nAl
2O
3Than being 65.38 ZSM-5 molecular sieve with small crystal grains, 30 grams 530 ℃ of following roastings 4 hours to remove the impurity of its physical adsorption;
(2) the sulfuric acid amine aqueous solution with 0.5mol/L carries out ion-exchange 2 hours under boiling state, filters, and uses deionized water wash 5 times, dries in 120 ℃ of baking ovens, places stoving oven to keep 5 hours down in 530 ℃ again, obtains little crystal grain HZSM-5 molecular sieve;
(3) the little crystal grain HZSM-5 molecular sieve of 12.8 grams is restrained γ-Al with 7.2
2O
3Put into mortar simultaneously and mix, evenly grind;
(4) 3% salpeter solution is dripped in the good material of mill, mix and pinch suitably, be squeezed into the bar column type of Ф 2, insert in the baking oven and dry down in 120 ℃ with the spiral banded extruder;
(5) again the strip molecular sieve is crushed to 10～40 orders and puts into retort furnace and be warming up to 520 ℃ of roastings 3 hours,, treat that temperature is reduced to below 60 ℃ to take out to take off nitric acid and moisture;
(6) accurately take by weighing 9.83 gram gallium nitrates, add deionized water, shake up to the solution that 15ml is mixed with 1.8mol/L;
(7) accurately take by weighing 2.60 lanthanum nitrates and add deionized water, shake up to the solution that 15ml is mixed with 0.4mol/L;
(8) triangular flask is put in (6), (7) two kinds of solution merging, mixed and stirred 10 minutes;
(9) take by weighing 10 molecular sieves that make of gram (5) step and put into the Erlenmeyer flask that fills prepared mixing solutions of (8) step, under 80 ℃, keeping 2 hours evaporate to dryness on the induction stirring well heater;
(10) it is inserted keep 6 hours in 120 ℃ the baking oven after, put into retort furnace and made catalyzer in 3 hours in 350 ℃ of roastings.Obtain catalyzer (wt%) composed as follows:
Little crystal grain HZSM-5 64.12
Ga 1.80
La 0.38
Binding agent 33.70
2, MTA reaction
The methanol conversion reaction conditions: one section working pressure is 4.0Mpa; One section service temperature is 340 ℃; One section operation air speed is 1.0h
-1, all the other are with embodiment 1.Reaction result sees Table 1.
Embodiment 5
1, the preparation of a section of conversion catalyst
(1) with nSiO
2/ nAl
2O
3Than being 76.92 ZSM-5 molecular sieve with small crystal grains, 30 grams 520 ℃ of following roastings 5 hours to remove the impurity of its physical adsorption;
(2) the sulfuric acid amine aqueous solution with 0.5mol/L carries out ion-exchange 2 hours under boiling state, filters then, uses deionized water wash 5 times, dries in 120 ℃ of baking ovens, places stoving oven to keep 5 hours down in 510 ℃ again, obtains little crystal grain HZSM-5 molecular sieve;
(3) get the little crystal grain HZSM-5 molecular sieve of 14.0 grams and put into mortar simultaneously and mix, evenly grind with 6.0 gram diatomite;
(4) 3% salpeter solution is dripped in the good raw material of mill, mix and pinch suitably, be squeezed into the bar column type of Ф 2, insert in the baking oven and dry down in 120 ℃ with the spiral banded extruder;
(5) the strip molecular sieve is crushed to 10～40 orders and puts into retort furnace and be warming up to 530 ℃ of roastings 5 hours,, treat that temperature is reduced to below 60 ℃ can take out to take off nitric acid and moisture;
(6) accurately take by weighing 1.92 gram gallium nitrates, add deionized water, shake up to the solution that 15ml is mixed with 2.0mol/L;
(7) accurately take by weighing 3.25 lanthanum nitrates and add deionized water, shake up to the solution that 15ml is mixed with 0.5mol/L;
(8) triangular flask is put in solution merging in (6), (7) two, mixed and stirred 10 minutes;
(9) take by weighing 10 molecular sieves that make of gram (5) step and put into the Erlenmeyer flask that fills prepared mixing solutions of (8) step, under 60 ℃, keeping 2 hours evaporate to dryness on the induction stirring well heater;
(10) after it is inserted and keeps 5 hours in 110 ℃ the baking oven, put into retort furnace and made catalyzer in 3 hours in 400 roastings.Obtain catalyzer (wt%) composed as follows:
Little crystal grain HZSM-5 69.12
Ga 1.83
La 0.44
Binding agent 28.61
2, MTA reaction
The methanol conversion reaction conditions: one section working pressure is 2.0Mpa; One section service temperature is 380 ℃; One section operation air speed is 0.6h
-1, all the other are with embodiment 1.Reaction result sees Table 1.
Table 1 reaction result
The acid characterization result of table 2 catalyzer
The adsorptive capacity of table 3 catalyzer characterizes
Embodiment 6-10
1, one section Preparation of catalysts is with embodiment 1-5
2, two sections Preparation of catalysts
Five prepared among the embodiment 1 to embodiment 5 with Chinese patent 00134776.4 catalyzer carry out steam activation under differing temps, obtain the catalyzer of five embodiment.The Preparation of Catalyst condition and the composition that are adopted see Table 4.
3, MTA reaction
One section of using of embodiment 6-10 and two sections catalyst combination see Table 5.The concrete operations step of embodiment 6-10 is as follows:
(1) with methyl alcohol be raw material, at one section working pressure, one section service temperature under one section raw material liq air speed condition, is converted into product based on aromatic hydrocarbons through one section catalyzer;
(2) product based on aromatic hydrocarbons passes through refrigerated separation, with gas-phase product lower carbon number hydrocarbons and liquid product C
5 +Hydrocarbon separates;
(3) the gas-phase product lower carbon number hydrocarbons continues to enter second stage reactor, at two sections working pressures, and two sections service temperatures, two sections operation raw material liq air speeds under two sections catalyzer existence conditions, obtain two sections gas-liquid products; One section and second-stage reaction condition and reaction result see Table 6.
Two sections Preparation of Catalyst conditions of table 4 and composition, acid amount
| Embodiment | Soak time (hour) | Activation temperature ℃ | Lanthanum content wt% | Silicon-gallium molar ratio | Total acid content mmol/g.cat |
| 6 | 5 | 360 | 1.25 | 63 | 0.670 |
| 7 | 10 | 380 | 0.91 | 88 | 0.588 |
| 8 | 1 | 390 | 1.34 | 124 | 0.660 |
| 9 | 20 | 410 | 1.38 | 144 | 0.628 |
| 10 | 15 | 430 | 0.83 | 183 | 0.589 |
One section and two sections catalyst combination of table 5
| Embodiment | One section catalyzer | Two sections catalyzer |
| 6 | Embodiment 5 | Embodiment 6 |
| 7 | Embodiment 3 | Embodiment 7 |
| 8 | Embodiment 1 | Embodiment 8 |
| 9 | Embodiment 2 | Embodiment 9 |
| 10 | Embodiment 4 | Embodiment 10 |
Table 6 embodiment 6～10 reaction results
| Embodiment | One section reaction conditions | The second-stage reaction condition | Oil phase total recovery % (methyl alcohol weight base) | Aromatic hydrocarbons total recovery % (methyl alcohol weight base) | Aromatic hydrocarbons overall selectivity % (aromatic hydrocarbons/oil phase) | ||||
| Temperature (℃) | Pressure (MPa) | Air speed (h -1) | Temperature (℃) | Pressure (MPa) | Air speed (h 1) | ||||
| Embodiment 6 | 410 | 0.1. | 0.6 | 410 | 0.1 | 192 | 39.5 | 31.5 | 79.7 |
| Embodiment 7 | 340 | 0.5 | 1.0 | 350 | 0.5 | 320 | 41.1 | 33.0 | 80.4 |
| Embodiment 8 | 320 | 3.5 | 6.0 | 300 | 3.5 | 1920 | 40.2 | 33.8 | 83.9 |
| Embodiment 9 | 340 | 4.0 | 0.6 | 310 | 4.0 | 192 | 40.1 | 32.2 | 80.3 |
| Embodiment 10 | 380 | 2.0 | 1.0 | 380 | 2.0 | 320 | 39.7 | 33.2 | 83.7 |
Claims (15)
1. process of methanol conversion for preparing arene, it is characterized in that comprising the steps: that (1) is raw material with methyl alcohol, is catalyzer with the modified zsm-5 zeolite, is 0.1～5.0Mpa at working pressure, service temperature is 300～460 ℃, and the raw material liq air speed is 0.1～6.0h
-1Under the condition, be converted into product based on aromatic hydrocarbons through one section catalytic reaction;
(2) product based on aromatic hydrocarbons passes through refrigerated separation, with gas-phase product lower carbon number hydrocarbons and liquid product C
5 +Hydrocarbon separates;
(3) liquid product C
5 +Hydrocarbon obtains aromatic hydrocarbons and non-aromatics through extracting and separating.
2, a kind of process of methanol conversion for preparing arene as claimed in claim 1 is characterized in that described one section working pressure is 0.1～3.5Mpa, and one section service temperature is 300～410 ℃, and one section raw material liq air speed is 0.4～2.0h
-1
3, a kind of process of methanol conversion for preparing arene as claimed in claim 1 or 2 is characterized in that also comprising the steps:
(1) the gas-phase product lower carbon number hydrocarbons enters second stage reactor, is 0.1～5.0Mpa at two sections working pressures, and two sections service temperatures are 250～500 ℃, and two sections air speeds are 50～2000h
-1, under two sections catalyzer existence conditions, obtain the second-stage reaction product;
(2) two sections products after gas-liquid separation, product liquid and one section liquid product C
5 +Hydrocarbon mixes.
4, a kind of process of methanol conversion for preparing arene as claimed in claim 3 is characterized in that described two sections working pressures are 0.1～3.5Mpa, 300～450 ℃ of two sections service temperatures, and two sections raw material liq air speeds are 100～1000h
-1
5, as one section used catalyzer of each described a kind of process of methanol conversion for preparing arene of claim 1-4, it is characterized in that the weight percent of described one section catalyzer consists of:
Little crystal grain HZSM-5:62.0～85.0
Ga： 0.5～2.0
La： 0.2～1.0
Binding agent: 14.0～34.0
6, the used Preparation of catalysts method of a kind of process of methanol conversion for preparing arene as claimed in claim 5 is characterized in that comprising the steps:
(1) with nSiO
2/ nAl
2O
3Than the ZSM-5 molecular sieve with small crystal grains that is 20～100,, obtain removing the ZSM-5 molecular sieve with small crystal grains of impurity 450～550 ℃ of following roastings of maturing temperature 1～10 hour;
(2) ammonium nitrate or the sulfuric acid amine aqueous solution with 0.1～1.0mol/L exchanges 2 hours to the ZSM-5 molecular sieve with small crystal grains that removes impurity, filter, with deionized water wash 2～5 times, in 100～150 ℃ of baking ovens, dry, place stoving oven to keep 3～6 hours down again in 450～550 ℃;
(3) molecular sieve and binding agent after the processing of (2) step are mixed in proportion, evenly grind;
(4) nitric acid is mixed with weight percent be 2～4% drips of solution add mix in the ground material of (3) step pinch after, extrusion molding is 100～150 ℃ of oven dry down;
Material after the oven dry of (5) (4) steps was 450～560 ℃ of roastings of maturing temperature 3～5 hours;
(6) gallium nitrate is mixed with the solution of 0.2～3.0mol/L, lanthanum nitrate is mixed with the solution of 0.01～1.0mol/L; Two kinds of solution mix, and stir;
(7) molecular sieve with step (5) adds in the solution of step (6) preparation, carries out 1～10 hour dipping under 20～80 ℃ stirring;
(8) behind the steeping fluid evaporate to dryness, it was kept in 100～150 ℃ baking oven 3～8 hours, then 350～450 ℃ of maturing temperatures, be preferably 380～420 ℃ of roastings and made catalyzer in 2～8 hours.
7, the used Preparation of catalysts method of a kind of process of methanol conversion for preparing arene as claimed in claim 6 is characterized in that described binding agent is pseudo-boehmite, gama-alumina or diatomite.
8, the used Preparation of catalysts method of a kind of process of methanol conversion for preparing arene as claimed in claim 6 is characterized in that described nSiO
2/ nAl
2O
3Than being 40～80.
9, the used Preparation of catalysts method of a kind of process of methanol conversion for preparing arene as claimed in claim 6 is characterized in that described step (1) or step (2) maturing temperature are 490～530 ℃.
10, the used Preparation of catalysts method of a kind of process of methanol conversion for preparing arene as claimed in claim 6 is characterized in that described step (5) maturing temperature is 490～550 ℃.
11, the used Preparation of catalysts method of a kind of process of methanol conversion for preparing arene as claimed in claim 6 is characterized in that described gallium nitrate is mixed with the solution of 1.5～2.5mol/L, and lanthanum nitrate is mixed with the solution of 0.1～0.9mol/L.
12, the used Preparation of catalysts method of a kind of process of methanol conversion for preparing arene as claimed in claim 6 is characterized in that described maturing temperature is 380～420 ℃.
13, the used Preparation of catalysts method of a kind of process of methanol conversion for preparing arene as claimed in claim 6 is characterized in that described ZSM-5 molecular sieve with small crystal grains is the ZSM-5 molecular sieve with small crystal grains that adopts by Chinese patent 00109593.5 preparation.
14, as two sections used catalyzer of each described a kind of process of methanol conversion for preparing arene of claim 1-4, it is characterized in that the mol ratio that described two sections catalyzer are silicon galliums is 63-218, lanthanum content is 0.83-2.12wt%, total acid content is that the catalyzer of 0.468-0.672mmol/g.cat activates 1-20 hour in 360～480 ℃ high-temperature vapor, and making catalyzer is 0.073～0.079 gram/gram catalyzer to the Static Adsorption amount of hexanaphthene.
15, two sections used Preparation of catalysts methods of a kind of process of methanol conversion for preparing arene as claimed in claim 14, it is characterized in that it being that mol ratio with the silicon gallium is 63-218, lanthanum content is 0.83-2.12wt%, and total acid content is that the catalyzer of 0.468-0.672mmol/g.cat activates 1-20 hour in 360～480 ℃ high-temperature vapor.
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