CN101422743A - Catalyst for direct synthesis of arene by synthesis gas and production method and use thereof - Google Patents
Catalyst for direct synthesis of arene by synthesis gas and production method and use thereof Download PDFInfo
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Abstract
The invention discloses a catalyst for directly synthesizing aromatic hydrocarbon by synthesis gas, which has the composition with following weight ratio: HNKF-5:aluminophosphate molecular sieve:Ga2O3:ZnO:BaO equal to 1:1-3:0.01-0.3:0.01-0.3:0.01-0.3. The invention has the advantages of simple technical process, medium catalyst acidity of aromatic hydrocarbon synthesis, better aromatization performance, and high aromatic hydrocarbon content.
Description
Technical field
The present invention relates to a kind of synthesis gas directly catalyst and the preparation method and the application of synthetic aromatic hydrocarbons, relate in particular to a kind of catalyst and preparation method and application by synthesis gas through methanol, the synthetic aromatic hydrocarbons of dimethyl ether.
Background technology
Benzene,toluene,xylene (being called for short BTX) is important Organic Chemicals, is mainly used in chemical products such as producing chemical fibre, plastics and rubber.In recent years, along with production of polyester in the global range continues to enlarge, the demand that drives PTA (terephthalic acid (TPA)) and PX (paraxylene) rapidly increased.Aromatic hydrocarbon resource is mainly derived from catalytic reforming and generates oil, drippolene and coal tar.Along with the development of petroleum refining industry, be that the shared ratio of aromatic hydrocarbons of raw material progressively increases with the oil, account for more than 98% domestic accounting for more than 85% abroad.Though China's aromatic hydrocarbons production capacity increases by a fairly big margin [domestic and international petrochemical industry wall bulletin, 36 (9): 27, (2006)] in recent years, and reaches certain scale, but still can not satisfy the actual market demand.Aromatic hydrocarbons is China's oil chemical industry major product, and aromatic hydrocarbons and ethene are all the tap of two product chains of petrochemical industry.According to statistics, China's benzene yield in 2005 reaches 3,060,000 tons.Before 2004,, therefore can satisfy the demands substantially, and section port is arranged because domestic benzene downstream product production capacity is less.But China's benzene downstream product production capacity increased comparatively fast over the past two years, and especially along with a large amount of construction of process units such as styrene, phenol, aniline, cyclohexanone, the benzene market demand heightens.Therefore since 2004, China became pure importer by the exported country of benzene, and import volume reached 25.5 ten thousand tons in 2005.Domestic benzene still can't satisfy the downstream market demand to estimate the coming years.2005, China's paraxylene output was 2,230,000 tons, and import volume reaches 1,600,000 tons, had become the importer of world's paraxylene maximum.Estimate 2010, China's paraxylene import volume will reach 2,500,000 tons.
China is the oil-poor country of rich coal, and in order to guarantee the energy security of country, it is vital opening up from the route of coal system aromatic hydrocarbons.From the process route of methyl alcohol, dimethyl ether system aromatic hydrocarbons [Chinese patent 200610012703, EP0090284, EP0005287], existing people explores, but this technology is subjected to the restriction of methyl alcohol market fluctuation easily, opens up that directly to make the technology of aromatic hydrocarbons from coal extremely urgent.This work bibliographical information is few, as N.Guan[Catalysis Today, 30 (1-3): 207-213,1996] etc. with Cu-Fe/MnO+HZSM-5 and the synthetic aromatic hydrocarbons of GaZSM-5 catalyst; [catalysis journal such as Wang Desheng, 23 (4): 333-335,2002] the lower carbon number hydrocarbons intermediate that utilizes the Fe/MnO-ZnZSM-5 catalyst that synthesis gas is generated in Fischer-Tropsch reaction directly is converted into aromatic hydrocarbons on molecular sieve, and the arenes selectivity of this process is low, only reaches about 53%; [Journal of Catalysis, 87 (1): 136-143,1984] such as Kaoru Fujimoto utilize Pd/SiO
2+ H-ZSM-5or H-mordenite catalyst is through the synthetic aromatic hydrocarbons of the route of methyl alcohol, alkene, aromatic hydrocarbons, and arenes selectivity is low, only reaches about 50%.
Summary of the invention
The purpose of this invention is to provide a kind of arenes selectivity high catalyst and preparation method and application by the directly synthetic aromatic hydrocarbons of synthesis gas.
The weight ratio of catalyst of the present invention consists of:
HNKF-5: aluminium phosphate molecular sieve: Ga
2O
3: ZnO:BaO is:
1:1-3:0.01-0.3:0.01-0.3:0.01-0.3。
Preparation method's following steps of the present invention:
(1) preparation H NKF-5: the NKF-5 molecular sieve is exchanged with hydrochloric acid, become hydrogen type molecular sieve H NKF-5;
(2) prepare aluminium phosphate molecular sieve: undertaken by the method shown in the CN1132781C, be prepared as follows:
The formation of colloidal sol: add aluminium isopropoxide, phosphoric acid, diethylamine, rhodamine B, ethanol, water in order successively, wherein, the mol ratio of aluminium isopropoxide and phosphoric acid is 0.6-1.5, the mol ratio of rhodamine B and diethylamine is 0.3-0.6, and the mol ratio of ethanol and water is 0.4-0.7, and the mol ratio of rhodamine B and phosphoric acid is 0.2-0.5, the mol ratio of water and phosphoric acid is 30-70, mix, stirred 24-50 hour, form colloidal sol;
Hydro-thermal is synthetic: the colloidal sol of above-mentioned formation adds in the reactor, and synthesis temperature is 120-200 ℃, reaction time 3-7 days, makes aluminium phosphate molecular sieve;
(3) with Ga
2O
3, ZnO, BaO nitrate be mixed with the aqueous solution of 0.1-0.8M respectively;
(4) natrium carbonicum calcinatum is mixed with the aqueous solution of 0.1-0.8M;
(5) synthetic arenes catalytic agent: press HNKF-5: aluminium phosphate molecular sieve: Ga
2O
3: ZnO:BaO is the weight ratio of 1:1-3:0.01-0.3:0.01-0.3:0.01-0.3, the aqueous solution of gallium nitrate, zinc nitrate, barium nitrate, adds H NKF-5 and aluminium phosphate molecular sieve again and stirs evenly, and uses Na
2CO
3The aqueous solution is 60-80 ℃ of following precipitation, and precipitation is finished the pH value of back control solution between 6-8, wash, suction filtration, and 50-100 ℃ of dry 10-24 hour, 300-450 ℃ roasting 3-6 hour, moulding is crushed to the 20-60 order, obtains catalyst.
Application of the present invention is as follows:
Mix composition dimethyl ether catalyst (one section catalyst), the first stage reactor of packing into being crushed to 20-60 purpose methanol synthesis catalyst and methanol dehydration catalyst with the weight ratio of 1-5:1; The 20-60 purpose synthesize arenes catalytic agent (two sections catalyst) with the dimethyl ether catalyst volume ratio be that the ratio of 1-3:1 is packed in the second stage reactor, under the normal pressure, feed H
2: (H
2+ N
2) the dilution hydrogen of volume ratio 5-20:100 carries out temperature programmed reduction to one section catalyst, reducing program is: be warmed up to 250-260 ℃ with 3-6 ℃/min heating rate from room temperature, constant temperature 2-5 hour;
After having reduced, feed H
2The unstripped gas of/CO=1-5:1 mol ratio, at 2.0-5.0MPa, gas space velocity: 1000-5000h
-1, 260-300 ℃ of first stage reactor temperature, the aromatic hydrocarbons synthetic reaction takes place down in the reaction condition that the second-stage reaction actuator temperature is 320-360 ℃.
Aforesaid methanol synthesis catalyst is the DC207 that the big auspicious Fine Chemical Co., Ltd in Linqu produces, and methanol dehydration catalyst is γ-Al that Changling Refinery Chemical Industry Co., Ltd.'s catalyst plant is produced
2O
3
The invention advantage:
This technology is the directly synthetic aromatic hydrocarbons of raw material with synthesis gas (comprising coal based synthetic gas, biomass synthesis gas, natural gas synthesis gas etc.), and raw material range is wide, and technological process is simple, and aromatic hydrocarbons synthetic catalyst acidity is moderate, and the aromatisation performance is good, the arene content height.
The specific embodiment
Embodiment one
Methanol synthesis catalyst (DC207 that the big auspicious Fine Chemical Co., Ltd in Linqu produces), methanol dehydration catalyst (γ-Al that Changling Refinery Chemical Industry Co., Ltd.'s catalyst plant is produced
2O
3) be crushed to the 20-30 order respectively, press DC207/ γ-Al
2O
3Volume ratio is that the ratio of 1:1 is mixed, and forms one section catalyst.
The catalyst of two sections synthetic aromatic hydrocarbons prepares in the following manner:
(1) the NKF-5 molecular sieve of Catalyst Factory, Nankai Univ production exchanges with hydrochloric acid, becomes hydrogen type molecular sieve H NKF-5;
(2) aluminium phosphate molecular sieve is undertaken by the method shown in the CN1132781C, detailed process:
In the beaker of 100ml, add aluminium isopropoxide 2.042 grams successively, phosphoric acid (85%) 1.153 gram, rhodamine B 1.360 grams, diethylamine 0.451 gram, water 40 grams, ethanol 26 grams mix, and stir 24 hours under the room temperature, form relatively uniform sol.Above-mentioned colloidal sol is added polytetrafluoroethylene (PTFE) do in the stainless steel cauldron of lining, sealing, 170 ℃ were reacted 7 days down, make aluminium phosphate molecular sieve.
(3) modified component Ga
2O
3, ZnO, BaO nitrate be mixed with the solution of 0.1M respectively.
(4) natrium carbonicum calcinatum is mixed with the solution of 0.1M.
(5) synthetic arenes catalytic agent: press H NKF-5: aluminium phosphate molecular sieve: Ga
2O
3: ZnO:BaO is the weight ratio of 1:1:0.3:0.01:0.01, the 0.1M aqueous solution of gallium nitrate, zinc nitrate, barium nitrate is added in the beaker mix, and adds H NKF-5 again, aluminium phosphate molecular sieve stirs evenly, with the Na of 0.1M
2CO
3Solution precipitates down at 80 ℃, and the pH value of control solution was 7 after precipitation was finished.Washing, suction filtration, 50 ℃ of down dry 24 hours, 500 ℃ following roastings 5 hours, moulding was crushed to 20 ~ 30 orders, obtains catalyst.
One section catalyst of 20 ~ 30 purposes, in the first stage reactor of packing into; The synthetic arenes catalytic agent of 20 ~ 30 purposes is to pack in the second stage reactor than the ratio that is 1:1 with one section catalyst volume.Under the normal pressure, feed 5% dilution H
2(H
2/ (H
2+ N
2) volume ratio) one section catalyst is carried out temperature programmed reduction, reducing program is: be warmed up to 260 ℃ with 6 ℃/min heating rate from room temperature, constant temperature 5 hours.
After having reduced, feed H
2The unstripped gas of/CO (mol ratio)=2, at 3.0MPa, gas space velocity: 1000h
-1, 300 ℃ of one section temperature under the reaction condition that two sections temperature are 360 ℃, are carried out synthetic reaction.Reaction result is as shown in table 1.
Embodiment two
Methanol synthesis catalyst (DC207 that the big auspicious Fine Chemical Co., Ltd in Linqu produces), methanol dehydration catalyst (γ-Al that Changling Refinery Chemical Industry Co., Ltd.'s catalyst plant is produced
2O
3) be crushed to the 40-60 order respectively, press DC207/ γ-Al
2O
3Volume ratio is that the ratio of 2:1 is mixed, and forms one section catalyst.
The catalyst of two sections synthetic aromatic hydrocarbons prepares in the following manner:
(1) the NKF-5 molecular sieve of Catalyst Factory, Nankai Univ production exchanges with hydrochloric acid, becomes hydrogen type molecular sieve H NKF-5;
(2) aluminium phosphate molecular sieve is undertaken by the method shown in the CN1132781C, detailed process:
In the beaker of 100ml, add aluminium isopropoxide 3.065 grams successively, phosphoric acid (85%) 1.736 gram, rhodamine B 2.505 grams, diethylamine 0.678 gram, water 60 grams, ethanol 45 grams mix, and stir 48 hours under the room temperature, form relatively uniform sol.Above-mentioned colloidal sol is added polytetrafluoroethylene (PTFE) do in the stainless steel cauldron of lining, sealing, 170 ℃ were reacted 5 days down, make aluminium phosphate molecular sieve.
(3) modified component Ga
2O
3, ZnO, BaO nitrate be mixed with the solution of 0.5M respectively.
(4) natrium carbonicum calcinatum is mixed with the solution of 0.5M.
(5) synthetic arenes catalytic agent: press H NKF-5: aluminium phosphate molecular sieve: Ga
2O
3: ZnO:BaO is the weight ratio of 1:3:0.1:0.3:0.15, the 0.5M aqueous solution of gallium nitrate, zinc nitrate, barium nitrate is added in the beaker mix, and adds H NKF-5 again, aluminium phosphate molecular sieve stirs evenly, with the Na of 0.5M
2CO
3Solution precipitates down at 70 ℃, and the pH value of control solution was 6 after precipitation was finished.Washing, suction filtration, 80 ℃ of down dry 10 hours, 600 ℃ following roastings 3 hours, moulding was crushed to 40 ~ 60 orders, obtains catalyst.
One section catalyst of 40 ~ 60 purposes, in the first stage reactor of packing into; The synthetic arenes catalytic agent of 40 ~ 60 purposes is to pack in the second stage reactor than the ratio that is 1.5:1 with one section catalyst volume.Under the normal pressure, feed 10% dilution H
2(H
2/ (H
2+ N
2) volume ratio) one section catalyst is carried out temperature programmed reduction, reducing program is: be warmed up to 250 ℃ with 3 ℃/min heating rate from room temperature, constant temperature 2 hours.
After having reduced, feed H
2The unstripped gas of/CO (mol ratio)=3, at 4.0MPa, gas space velocity: 3000h
-1, 260 ℃ of one section temperature under 320 ℃ of reaction conditions of two sections temperature, are carried out synthetic reaction.Reaction result is as shown in table 1.
Embodiment three
Methanol synthesis catalyst (DC207 that the big auspicious Fine Chemical Co., Ltd in Linqu produces), methanol dehydration catalyst (γ-Al that Changling Refinery Chemical Industry Co., Ltd.'s catalyst plant is produced
2O
3) be crushed to the 30-40 order respectively, press DC207/ γ-Al
2O
3Volume ratio is that the ratio of 5:1 is mixed, and forms one section catalyst.
The catalyst of two sections synthetic aromatic hydrocarbons prepares in the following manner:
(1) the NKF-5 molecular sieve of Catalyst Factory, Nankai Univ production exchanges with hydrochloric acid, becomes hydrogen type molecular sieve H NKF-5;
(2) aluminium phosphate molecular sieve is undertaken by the method shown in the CN1132781C, detailed process:
In the beaker of 100ml, add aluminium isopropoxide 4.084 grams successively, phosphoric acid (85%) 2.289 gram, rhodamine B 3.664 grams, diethylamine 0.995 gram, water 146 grams, ethanol 65 grams mix, and stir 50 hours under the room temperature, form relatively uniform sol.Above-mentioned colloidal sol is added polytetrafluoroethylene (PTFE) do in the stainless steel cauldron of lining, sealing, 170 ℃ were reacted 7 days down, make aluminium phosphate molecular sieve.
(3) modified component Ga
2O
3, ZnO, BaO nitrate be mixed with the solution of 0.8M respectively.
(4) natrium carbonicum calcinatum is mixed with the solution of 0.8M.
(5) synthetic arenes catalytic agent: press H NKF-5: aluminium phosphate molecular sieve: Ga
2O
3/: ZnO:BaO is the weight ratio of 1:2:0.2:0.15:0.3, the 0.8M aqueous solution of gallium nitrate, zinc nitrate, barium nitrate is added in the beaker mix, and adds H NKF-5 again, aluminium phosphate molecular sieve stirs evenly, with the Na of 0.8M
2CO
3Solution precipitates down at 60 ℃, and the pH value of control solution was 8 after precipitation was finished.Washing, suction filtration, 50 ℃ of down dry 15 hours, 550 ℃ following roastings 4 hours, moulding was crushed to 30 ~ 40 orders, obtains catalyst.
One section catalyst of 30 ~ 40 purposes, in the first stage reactor of packing into; The synthetic arenes catalytic agent of 30 ~ 40 purposes is to pack in the second stage reactor than the ratio that is 2:1 with one section catalyst volume.Under the normal pressure, feed 15% dilution H
2(H
2/ (H
2+ N
2) volume ratio) one section catalyst is carried out temperature programmed reduction, reducing program is: be warmed up to 255 ℃ with 5 ℃/min heating rate from room temperature, constant temperature 3 hours.
After having reduced, feed H
2The unstripped gas of/CO (mol ratio)=4, at 2.0MPa, gas space velocity: 2000h
-1, 280 ℃ of one section temperature under the reaction condition that two sections temperature are 340 ℃, are carried out synthetic reaction.Reaction result is as shown in table 1.
Embodiment four
Methanol synthesis catalyst (DC207 that the big auspicious Fine Chemical Co., Ltd in Linqu produces), methanol dehydration catalyst (γ-Al that Changling Refinery Chemical Industry Co., Ltd.'s catalyst plant is produced
2O
3) be crushed to 30 ~ 40 orders respectively, press DC207/ γ-Al
2O
3Volume ratio is that the ratio of 4:1 is mixed, and forms one section catalyst.
The catalyst of two sections synthetic aromatic hydrocarbons prepares in the following manner:
(1) the NKF-5 molecular sieve of Catalyst Factory, Nankai Univ production exchanges with hydrochloric acid, becomes hydrogen type molecular sieve H NKF-5;
(2) aluminium phosphate molecular sieve is undertaken by the method shown in the CN1132781C, detailed process:
In the beaker of 100ml, add aluminium isopropoxide 2.042 grams successively, phosphoric acid (85%) 1.153 gram, rhodamine B 1.360 grams, diethylamine 0.451 gram, water 40 grams, ethanol 26 grams mix, and stir 36 hours under the room temperature, form relatively uniform sol.Above-mentioned colloidal sol is added polytetrafluoroethylene (PTFE) do in the stainless steel cauldron of lining, sealing, 170 ℃ were reacted 7 days down, make aluminium phosphate molecular sieve.
(3) modified component Ga
2O
3, ZnO, BaO nitrate be mixed with the solution of 0.6M respectively.
(4) natrium carbonicum calcinatum is mixed with the solution of 0.6M.
(5) synthetic arenes catalytic agent: press H NKF-5: aluminium phosphate molecular sieve: Ga
2O
2: ZnO:BaO is the weight ratio of 1:1:0.01:0.2:0.1, the 0.6M aqueous solution of gallium nitrate, zinc nitrate, barium nitrate is added in the beaker mix, and adds H NKF-5 again, aluminium phosphate molecular sieve stirs evenly, with the Na of 0.6M
2CO
3Solution precipitates down at 70 ℃, and the pH value of control solution was 7 after precipitation was finished.Washing, suction filtration, 100 ℃ of down dry 10 hours, 550 ℃ following roastings 6 hours, moulding was crushed to 30 ~ 40 orders, obtains catalyst.
One section catalyst of 30 ~ 40 purposes, in the first stage reactor of packing into; The synthetic arenes catalytic agent of 30 ~ 40 purposes is to pack in the second stage reactor than the ratio that is 2:1 with one section catalyst volume.Under the normal pressure, feed 20% dilution H
2(H
2/ (H
2+ N
2) volume ratio) one section catalyst is carried out temperature programmed reduction, reducing program is: be warmed up to 250 ℃ with 4 ℃/min heating rate from room temperature, constant temperature 4 hours.
After having reduced, feed H
2The unstripped gas of/CO (mol ratio)=1, at 5.0MPa, gas space velocity: 4000h
-1, 270 ℃ of one section temperature under the reaction condition that two sections temperature are 330 ℃, are carried out synthetic reaction.Reaction result is as shown in table 1.
Embodiment five
Methanol synthesis catalyst (DC207 that the big auspicious Fine Chemical Co., Ltd in Linqu produces), methanol dehydration catalyst (γ-Al that Changling Refinery Chemical Industry Co., Ltd.'s catalyst plant is produced
2O
3) be crushed to 30 ~ 40 orders respectively, press DC207/ γ-Al
2O
3Volume ratio is that the ratio of 3:1 is mixed, and forms one section catalyst.
The catalyst of two sections synthetic aromatic hydrocarbons prepares in the following manner:
(1) the NKF-5 molecular sieve of Catalyst Factory, Nankai Univ production exchanges with hydrochloric acid, becomes hydrogen type molecular sieve H NKF-5;
(2) aluminium phosphate molecular sieve is undertaken by the method shown in the CN1132781C, detailed process:
In the beaker of 100ml, add aluminium isopropoxide 2.042 grams successively, phosphoric acid (85%) 1.153 gram, rhodamine B 1.360 grams, diethylamine 0.451 gram, water 40 grams, ethanol 26 grams mix, and stir 30 hours under the room temperature, form relatively uniform sol.Above-mentioned colloidal sol is added polytetrafluoroethylene (PTFE) do in the stainless steel cauldron of lining, sealing, 170 ℃ were reacted 7 days down, make aluminium phosphate molecular sieve.
(3) modified component Ga
2O
3, ZnO, BaO nitrate be mixed with the solution of 0.5M respectively.
(4) natrium carbonicum calcinatum is mixed with the solution of 0.5M.
(5) synthetic arenes catalytic agent: press H NKF-5: aluminium phosphate molecular sieve: Ga
2O
3: ZnO:BaO is the weight ratio of 1:1:0.1:0.1:0.1, the 0.5M aqueous solution of gallium nitrate, zinc nitrate, barium nitrate is added in the beaker mix, and adds H NKF-5 again, aluminium phosphate molecular sieve stirs evenly, with the Na of 0.5M
2CO
3Solution precipitates down at 70 ℃, and the pH value of control solution was 7 after precipitation was finished.Washing, suction filtration, 80 ℃ of down dry 15 hours, 550 ℃ following roastings 5 hours, moulding was crushed to the 30-40 order, obtains catalyst.
One section catalyst of 30-40 purpose, in the first stage reactor of packing into; The synthetic arenes catalytic agent of 30-40 purpose is to pack in the second stage reactor than the ratio that is 3:1 with one section catalyst volume.Under the normal pressure, feed 18% dilution H
2(H
2/ (H
2+ N
2) volume ratio) one section catalyst is carried out temperature programmed reduction, reducing program is: be warmed up to 252 ℃ with 3 ℃/min heating rate from room temperature, constant temperature 4 hours.
After having reduced, feed H
2/ CO (mol ratio)=5 unstripped gas, at 5.0MPa, gas space velocity: 5000h
-1, 290 ℃ of one section temperature under the reaction condition that two sections temperature are 350 ℃, are carried out synthetic reaction.Reaction result is as shown in table 1.
Table 1 reaction result
Claims (4)
1, a kind of catalyst by the directly synthetic aromatic hydrocarbons of synthesis gas is characterized in that the weight ratio of catalyst consists of: HNKF-5: aluminium phosphate molecular sieve: Ga
2O
3: ZnO::BaO=
1：1～3：0.01～0.3：0.01～0.3：0.01～0.3。
2, a kind of Preparation of catalysts method of directly synthesizing aromatic hydrocarbons by synthesis gas as claimed in claim 1 is characterized in that comprising the steps:
(1) preparation H NKF-5: the NKF-5 molecular sieve is exchanged with hydrochloric acid, become hydrogen type molecular sieve HNKF-5;
(2) prepare aluminium phosphate molecular sieve: undertaken by the method shown in the CN1132781C, be prepared as follows:
The formation of colloidal sol: add aluminium isopropoxide, phosphoric acid, diethylamine, rhodamine B, ethanol, water in order successively, wherein, the mol ratio of aluminium isopropoxide and phosphoric acid is 0.6～1.5, the mol ratio of rhodamine B and diethylamine is 0.3～0.6, and the mol ratio of ethanol and water is 0.4～0.7, and the mol ratio of rhodamine B and phosphoric acid is 0.2～0.5, the mol ratio of water and phosphoric acid is 30～70, mix, stirred 24～50 hours, form colloidal sol;
Hydro-thermal is synthetic: the colloidal sol of above-mentioned formation adds in the reactor, and synthesis temperature is 120～200 ℃, in 3～7 days reaction time, makes aluminium phosphate molecular sieve;
(3) with Ga
2O
3, ZnO, BaO nitrate be mixed with the aqueous solution of 0.1～0.8M respectively;
(4) natrium carbonicum calcinatum is mixed with the aqueous solution of 0.1～0.8M;
(5) synthetic arenes catalytic agent: press HNKF-5: aluminium phosphate molecular sieve: Ga
2O
3: ZnO:BaO is the weight ratio of 1:1～3:0.01～0.3:0.01～0.3:0.01～0.3, the aqueous solution of gallium nitrate, zinc nitrate, barium nitrate, adds H NKF-5 and aluminium phosphate molecular sieve again and stirs evenly, and uses Na
2CO
3The aqueous solution is 60～80 ℃ of following precipitations, and precipitation is finished the pH value of back control solution between 6～8, wash, suction filtration, and 10～24 hours, 300～450 ℃ roastings of 50～100 ℃ of dryings 3～6 hours, moulding is crushed to 20～60 orders, obtains catalyst.
3, a kind of Application of Catalyst of directly synthesizing aromatic hydrocarbons by synthesis gas as claimed in claim 1 is characterized in that:
Mix composition dimethyl ether catalyst, the first stage reactor of packing into being crushed to 20～60 purpose methanol synthesis catalysts and methanol dehydration catalyst with the weight ratio of 1～5:1; The synthetic arenes catalytic agent of 20～60 purposes with the dimethyl ether catalyst volume ratio be that the ratio of 1～3:1 is packed in the second stage reactor, under the normal pressure, feed H
2: (H
2+ N
2) the dilution hydrogen of volume ratio 5～20:100 carries out temperature programmed reduction to one section catalyst, reducing program is: be warmed up to 250～260 ℃ with 3～6 ℃/min heating rate from room temperature, constant temperature 2～5 hours;
After having reduced, feed H
2The unstripped gas of/CO=1～5:1 mol ratio, at 2.0～5.0MPa, gas space velocity: 1000～5000h
-1, 260～300 ℃ of first stage reactor temperature, the aromatic hydrocarbons synthetic reaction takes place down in the reaction condition that the second-stage reaction actuator temperature is 320～360 ℃.
4, a kind of Application of Catalyst of directly synthesizing aromatic hydrocarbons by synthesis gas as claimed in claim 3, it is characterized in that described methanol synthesis catalyst is the DC207 that the big auspicious Fine Chemical Co., Ltd in Linqu produces, methanol dehydration catalyst is γ-Al that Changling Refinery Chemical Industry Co., Ltd.'s catalyst plant is produced
2O
3
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| CN106540740A (en) * | 2016-10-28 | 2017-03-29 | 厦门大学 | Catalyst by synthesis gas high selectivity light aromatics and preparation method thereof |
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| CN107262142A (en) * | 2017-07-10 | 2017-10-20 | 清华大学 | The catalyst and its application process and preparation method of a kind of one-step synthesis aromatic hydrocarbons |
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2008
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