CN102513142A - Preparation method for preparing gasoline catalyst with methanol - Google Patents
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- CN102513142A CN102513142A CN2011103278161A CN201110327816A CN102513142A CN 102513142 A CN102513142 A CN 102513142A CN 2011103278161 A CN2011103278161 A CN 2011103278161A CN 201110327816 A CN201110327816 A CN 201110327816A CN 102513142 A CN102513142 A CN 102513142A
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Abstract
The invention relates to a preparation method for preparing a gasoline catalyst with methanol. The preparation method is characterized by comprising the following steps of: before molding the catalyst, performing aluminum-removing and silicon replenishing treatment on a catalyst matrix nanoscale ZSM-5 molecular sieve with an acid solution to adjusting the acidic property of the molecular sieve; and after the catalyst is molded, pretreating the catalyst by using a hydrothermal aging device to enhance the gasoline selectivity and stability of the catalyst. When the catalyst prepared with the method is applied to a reaction for preparing gasoline with methanol on a section of fixed bed, the gasoline yield is up to 36-37 percent.
Description
Technical field
The invention belongs to methyl alcohol deep process technology field, what be specifically related to is a kind of preparing gasoline by methanol Preparation of catalysts method.
Background technology
In recent years, under the high-order operation of oil price background, coal system oil (CTL) research constantly heats up, and preparing gasoline by methanol (MTG), as one of core technology of CTL second half section, is also favored once more.MTG technology be the methyl alcohol in Mobil company exploitation on the basis that is converted into aromatic hydrocarbons on the ZSM-5 molecular sieve, develop and---making the raw material production synthesis gas with coal or natural gas, again with synthesising gas systeming carbinol, is high-knock rating gasoline with thick methanol conversion at last.US3928483; US3931349, US4035430, US4579999 are the early stage methyl alcohol system hydro carbons patents of Mobil company; Adopt two sections fixed-bed process; Wherein first section is preparing dimethyl ether by dewatering methanol, and first section dimethyl ether that comes out, water and unreacted methanol mixture get into second section reactor, under the effect of ZSM-5 molecular sieve catalyst, transforms Generation Liquid gasification and gasoline.
In the last few years, the MTG technology had had very big progress, and CN1923366A has disclosed a kind of one-step method preparing gasoline by methanol new technology, and methyl alcohol directly generates gasoline and liquefied gas through first stage reactor.This technology is by the research and development of Shanxi coalification research institute, and coalification group has obtained industrial Demonstration Application in Yunnan.Compare with two-stage method technology, the technological process of one-step method preparing gasoline by methanol is short, invest low, thereby make the economy of MTG obtain raising.
The conversion of methyl alcohol on the ZSM-5 molecular sieve belongs to typical acid catalyzed reaction; So catalyst need have a certain amount of acid site; But too much acid amount or too high acid can aggravate the generation of side reaction such as cracking by force again, cause yield of gasoline to reduce, and the accessory substance liquefied gas yield rises.Therefore, adopt the acid amount and the acid strength of various method of modifying modulation molecular sieves usually, and then improve the stability and the gasoline selective of molecular sieve catalyst.
Disclose among patent US4402867 and the US4480145, deposit amorphous silicon can promote the stability of catalyst on the ZSM-5 molecular sieve, but can stop up the part duct of molecular sieve.Patent EP0571090; Disclose among US5545791 and the US5723401, carried metal or metal ion on phosphorous carrier can promote the gasoline selective of catalyst; Metal comprises transition metal, alkali metal and alkaline-earth metal; Carrier is compounds such as aluminum phosphate, trbasic zinc phosphate and magnesium phosphate, but high through the catalyst cost of this method preparation, is prone to coking and deactivation.Disclose among patent CN85100759A and the CN10186813A; In sieve synthesis procedure, add one or more metal mixtures; Add the binding agent moulding again after molecular sieve is synthetic and promptly prepare catalyst; Though this method simple and fast, the catalyst metal components of preparation is disperseed inhomogeneous, poor stability.
Summary of the invention
The purpose of this invention is to provide a kind of preparing gasoline by methanol Preparation of catalysts method, it is characterized in that:
Catalyst Precursors is selected nanoscale HZSM-5 molecular sieve for use; At first the molecular sieve parent is handled 0.5～6h through the acid solution of 0.01～5.0mol/L down at 50～150 ℃; Silica alumina ratio is promoted to 30～100 by 25; Molecular sieve and binding agent were with 9: 1～3: 7 butt weight ratio moulding then, and the catalyst of last moulding is handled 0.5～10h at 400～700 ℃ of following hydrothermal agings;
Processing step comprises:
(1) preparation hydrogen proton concentration is the acid solution of 0.01～5.0mol/L; Be selected from one or more mixed solution of hydrochloric acid solution, sulfuric acid solution, salpeter solution, silicate fluoride solution, acetic acid solution, oxalic acid solution, citric acid solution; Handle nanoscale HZSM-5 molecular sieve with this; 50～150 ℃ of treatment temperatures, processing time 0.5～6h;
(2) nanoscale HZSM-5 molecular sieve after acid solution is handled and binding agent were with 9: 1～3: 7 butt weight ratio moulding, and binding agent is selected from aluminium oxide, boehmite, Ludox or diatomite; Through 120 ℃ of dryings, behind 550 ℃, 0.5～4h roasting; Carry out hydrothermal aging again and handle 400～700 ℃ of treatment temperatures, processing time 0.5～10h, steam quality air speed 0.5～5.0;
According to Preparation of catalysts method of the present invention, its preferred version is characterised in that:
Catalyst Precursors is selected nanoscale HZSM-5 molecular sieve for use; At first the molecular sieve parent is handled 1～5h through the acid solution of 0.05～4.0mol/L down at 60～120 ℃; Silica alumina ratio is promoted to 43～96 by 25; Molecular sieve and binding agent were with 8: 2～4: 6 butt weight ratio moulding then, and the catalyst of last moulding is handled 1～8h at 450～650 ℃ of following hydrothermal agings;
Processing step comprises:
(1) preparation hydrogen proton concentration is the acid solution of 0.05～4.0mol/L; Be selected from one or more mixed solution of hydrochloric acid solution, sulfuric acid solution, salpeter solution, silicate fluoride solution, acetic acid solution solution, handle nanoscale HZSM-5 molecular sieve with this, 60～120 ℃ of treatment temperatures, processing time 1～5h;
(2) nanoscale HZSM-5 molecular sieve after acid solution is handled and binding agent were with 8: 2～4: 6 butt weight ratio moulding, and binding agent is selected from aluminium oxide, boehmite or Ludox; Through 120 ℃ of dryings, behind 550 ℃, 1～3h roasting; Carry out hydrothermal aging and handle 450～650 ℃ of treatment temperatures, processing time 1～8h, steam quality air speed 0.8～4.5;
The catalyst of the present invention's preparation is metallic components not, therefore has higher specific surface area and pore volume, and this helps reducing the diffusional resistance of hydrocarbon molecules, reduces the generation of degree of depth side reaction product durene (1,2,4, the 5-durol).In addition, low through the catalyst cost of the present invention's preparation, gasoline selective is high, and the one way life-span is long, can be applied to one-step method, two-stage method preparing gasoline by methanol technology.
Description of drawings:
Fig. 1 catalyst life evaluation result:
(a) methanol conversion of ZC-2-550; (b) methanol conversion of KC-X;
(c) yield of gasoline of ZC-2-550; (d) yield of gasoline of KC-X.
Specific embodiments:
Below through embodiment and Comparative Examples the present invention is further described, but therefore do not limit content of the present invention.
At first; Adopt hydrothermal synthesis method to prepare the former powder of sodium type of micron and nano-ZSM-5 molecular sieve respectively, respectively two kinds of former powder of sodium type are prepared into Hydrogen micron molecular sieve H-M and Hydrogen nano molecular sieve Z-N through the ammonium exchange then, wherein; The H-M silica alumina ratio is 44, and the Z-N silica alumina ratio is 25.
Comparative Examples 1
Micron molecular sieve H-M and aluminium oxide are mixed with the butt mass ratio at 8: 2, add 10% mixed the pinching of salpeter solution then, at last extruded moulding on the twin-screw banded extruder.Strip catalyst is dried down at 120 ℃, 550 ℃ of following roasting 4h, and be labeled as HC-M.
Embodiment 1
At first dispose the silicate fluoride solution 2.5L of 0.06mol/L, take by weighing 300g molecular sieve Z-N then, silicate fluoride solution is slowly added in the molecular sieve, then 60 ℃ of processing 2h under stirring condition.After processing finished, with the slurries suction filtration, washing obtained modified molecular screen Z-1 after 120 ℃ of following dryings.
Embodiment 2
Repeat embodiment 1, but the silicate fluoride solution concentration of configuration is 1.0mol/L, 80 ℃ of treatment temperatures, processing time 3h, the modified molecular screen that accordingly processing is obtained is labeled as Z-2.
Embodiment 3
Repeat embodiment 1, but the silicate fluoride solution concentration of configuration is 3.0mol/L, 100 ℃ of treatment temperatures, processing time 4h, the modified molecular screen that accordingly processing is obtained is labeled as Z-3.
Embodiment 4
Nano molecular sieve Z-N and aluminium oxide are mixed with the butt mass ratio at 8: 2, add 10% mixed the pinching of salpeter solution then, at last extruded moulding on the twin-screw banded extruder.Strip catalyst is dried down at 120 ℃, 550 ℃ of following roasting 4h, and be labeled as ZC-N.
Repeat embodiment 4, but molecular sieve adopts Z-1, Z-2, Z-3 successively, the catalyst with preparation is labeled as ZC-1, ZC-2, ZC-3 accordingly.
Embodiment 6
Take by weighing the ZC-2 catalyst 30g of preparation among the embodiment 5, be loaded on the hydrothermal aging device, under 450 ℃, utilize 100% steam treatment 4h then, steam feeding amount is 2.0g/min, and the catalyst with modification is labeled as ZC-2-450 accordingly.
Embodiment 7
Repeat embodiment 6, but the hydrothermal aging temperature is 550 ℃, the catalyst with modification is labeled as ZC-2-550 accordingly.
Embodiment 8
Repeat embodiment 6, but the hydrothermal aging temperature is 650 ℃, the catalyst with modification is labeled as ZC-2-650 accordingly.
Catalyst characterization example 1
NH
3-TPD carries out on AutoChem II 2920, and the filling granularity of catalyst is 20～40 orders, and loadings is about 0.15g.In the characterization, sample is reduced to 200 ℃ afterwards and is advanced NH earlier at 600 ℃ of following preliminary treatment 2h
3-He gas adsorbs saturated laggard high-purity Ar and purges to baseline to walk surely.Speed with 10 ℃/min is warming up to 600 ℃ of completion desorptions, and desorption rate adopts the TCD detector to detect, and characterization result is as shown in table 1, and wherein KC-X is commercially available one-step method preparing gasoline by methanol catalyst.
The acid matter of catalyst before and after table 1 modification
| Catalyst | The molecular sieve silica alumina ratio | T?at?Max(℃) | Acid concentration (mmol/g) |
| HC-M | 44 | 418.1 | 0.317 |
| KC-X | 65 | 402.3 | 0.265 |
| ZC- |
25 | 392.6 | 0.349 |
| ZC-1 | 43 | 385.7 | 0.328 |
| ZC-2 | 68 | 385.2 | 0.303 |
| ZC-3 | 96 | 385.0 | 0.273 |
| ZC-2-450 | 68 | 383.3 | 0.286 |
| ZC-2-550 | 68 | 381.4 | 0.215 |
| ZC-2-650 | 68 | 326.5 | 0.120 |
Catalyst characterization example 2
Adopt Micromeritics ASAP2420 type to adsorb specific area, pore volume and the pore size distribution that appearance is measured catalyst automatically, wherein, as adsorbing medium, liquid nitrogen is a cold-trap with high purity nitrogen, and adsorption temp is-196 ℃, relative pressure P/P
0Be 0～0.995, characterization result is as shown in table 2.
The pore structure character of table 2 catalyst
| Catalyst | Specific area (m 2/g) | Pore volume (cm 3/g) | Average pore size (nm) |
| HC-M | 298.3 | 0.255 | 3.31 |
| KC-X | 295.6 | 0.279 | 3.52 |
| ZC-N | 346.8 | 0.383 | 4.46 |
| ZC-1 | 334.4 | 0.371 | 4.41 |
| ZC-2 | 328.7 | 0.366 | 4.39 |
| ZC-3 | 320.5 | 0.351 | 4.27 |
| ZC-2-450 | 322.1 | 0.356 | 4.35 |
| ZC-2-550 | 312.4 | 0.351 | 4.15 |
| ZC-2-650 | 303.3 | 0.343 | 4.21 |
Evaluating catalyst example 1
The catalyst of preparation is loaded on one section fixed-bed reactor of 20ml, and at 300 ℃ of following preliminary treatment 1h, begins pump then and advance methyl alcohol, reaction condition is as shown in table 3.
The reaction condition of table 3 evaluating catalyst
| Bed temperature/℃ | 360～420 |
| Pressure/MPa | 1.0 |
| WHSV/h -1 | 3.0 |
| Nitrogen: methyl alcohol (mol ratio) | 1∶1 |
| Sample time/h | 3.0 |
The composition of gasoline adopts the Agilent6820 gas-chromatography to analyze in the product, and the result who analyzes and estimate is as shown in table 4.Wherein, the computational methods of yield of gasoline and methanol conversion are following:
The composition of table 4 evaluating catalyst result and product gasoline
Can find out by table 4; Before the hydrothermal aging modification, be that the ZC-2 catalyst of 68 nano-class molecular sieve preparation has the highest yield of gasoline by silica alumina ratio, subsequently; The hydrothermal aging modification further promotes the reactivity worth of catalyst again, is included in two aspects of ratio of yield of gasoline and accessory substance durene.
Evaluating catalyst example 2
The ZC-2-550 catalyst is loaded on one section fixed-bed reactor of 100ml, and at 300 ℃ of following preliminary treatment 2h, begins pump then and advance methyl alcohol, investigate life of catalyst, reaction condition is as shown in table 5.With the life-span of same procedure investigation contrast medium KC-X, the result who analyzes and estimate is as shown in Figure 1.
The reaction condition that table 5 catalyst life is estimated
| Bed temperature/℃ | 360～420 |
| Pressure/MPa | 2.0 |
| WHSV/h -1 | 1.5 |
| Circulating air: methyl alcohol (mol ratio) | 9∶1 |
Claims (2)
1. preparing gasoline by methanol Preparation of catalysts method is characterized in that:
Catalyst Precursors is selected nanoscale HZSM-5 molecular sieve for use; At first the molecular sieve parent is handled 0.5～6h through the acid solution of 0.01～5.0mol/L down at 50～150 ℃; Silica alumina ratio is promoted to 30～100 by 25; Molecular sieve and binding agent were with 9: 1～3: 7 butt weight ratio moulding then, and the catalyst of last moulding is handled 0.5～10h at 400～700 ℃ of following hydrothermal agings;
Processing step comprises:
(1) preparation hydrogen proton concentration is the acid solution of 0.01～5.0mol/L; Be selected from one or more mixed solution of hydrochloric acid solution, sulfuric acid solution, salpeter solution, silicate fluoride solution, acetic acid solution, oxalic acid solution, citric acid solution; Handle nanoscale HZSM-5 molecular sieve with this; 50～150 ℃ of treatment temperatures, processing time 0.5～6h;
(2) nanoscale HZSM-5 molecular sieve after acid solution is handled and binding agent were with 9: 1～3: 7 butt weight ratio moulding, and binding agent is selected from aluminium oxide, boehmite, Ludox or diatomite; Through 120 ℃ of dryings, behind 550 ℃, 0.5～4h roasting; Carry out hydrothermal aging again and handle 400～700 ℃ of treatment temperatures, processing time 0.5～10h, steam quality air speed 0.5～5.0;
2. according to the described method of claim 1, it is characterized in that:
Catalyst Precursors is selected nanoscale HZSM-5 molecular sieve for use; At first the molecular sieve parent is handled 1～5h through the acid solution of 0.05～4.0mol/L down at 60～120 ℃; Silica alumina ratio is promoted to 43～96 by 25; Molecular sieve and binding agent were with 8: 2～4: 6 butt weight ratio moulding then, and the catalyst of last moulding is handled 1～8h at 450～650 ℃ of following hydrothermal agings;
Processing step comprises:
(1) preparation hydrogen proton concentration is the acid solution of 0.05～4.0mol/L; Be selected from one or more mixed solution of hydrochloric acid solution, sulfuric acid solution, salpeter solution, silicate fluoride solution, acetic acid solution solution, handle nanoscale HZSM-5 molecular sieve with this, 60～120 ℃ of treatment temperatures, processing time 1～5h;
(2) nanoscale HZSM-5 molecular sieve after acid solution is handled and binding agent were with 8: 2～4: 6 butt weight ratio moulding, and binding agent is selected from aluminium oxide, boehmite or Ludox; Through 120 ℃ of dryings, behind 550 ℃, 1～3h roasting; Carry out hydrothermal aging and handle 450～650 ℃ of hydrothermal aging treatment temperatures, processing time 1～8h, steam quality air speed 0.8～4.5.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103506150A (en) * | 2013-10-18 | 2014-01-15 | 中国科学院上海高等研究院 | Water vapor modified catalyst for preparing gasoline from methanol, and preparation method and application of water vapor modified catalyst |
| CN104209139A (en) * | 2013-06-04 | 2014-12-17 | 中国石油天然气集团公司 | Catalyst for producing gasoline by methanol conversion and giving consideration to propylene yield and preparation method thereof |
| CN104353446A (en) * | 2014-11-24 | 2015-02-18 | 湖南省馨盛能源开发有限责任公司 | Preparing process of catalyst for preparing gasoline from methyl alcohol |
| CN105413735A (en) * | 2015-12-31 | 2016-03-23 | 易高环保能源研究院有限公司 | Catalyst for reaction of preparing gasoline from methanol, preparation method and applications thereof |
| CN106732754A (en) * | 2017-01-23 | 2017-05-31 | 东南大学 | The sour dealuminzation method for preparing catalyst of hydro carbons yield is improved for biomass pyrolytic |
| CN110882717A (en) * | 2019-12-03 | 2020-03-17 | 新榕能源(福建)有限公司 | Simple synthesis method and application of catalyst for preparing oil from methanol under normal pressure |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104209139A (en) * | 2013-06-04 | 2014-12-17 | 中国石油天然气集团公司 | Catalyst for producing gasoline by methanol conversion and giving consideration to propylene yield and preparation method thereof |
| CN103506150A (en) * | 2013-10-18 | 2014-01-15 | 中国科学院上海高等研究院 | Water vapor modified catalyst for preparing gasoline from methanol, and preparation method and application of water vapor modified catalyst |
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| CN105413735A (en) * | 2015-12-31 | 2016-03-23 | 易高环保能源研究院有限公司 | Catalyst for reaction of preparing gasoline from methanol, preparation method and applications thereof |
| CN106732754A (en) * | 2017-01-23 | 2017-05-31 | 东南大学 | The sour dealuminzation method for preparing catalyst of hydro carbons yield is improved for biomass pyrolytic |
| CN110882717A (en) * | 2019-12-03 | 2020-03-17 | 新榕能源(福建)有限公司 | Simple synthesis method and application of catalyst for preparing oil from methanol under normal pressure |
| CN110882717B (en) * | 2019-12-03 | 2022-08-16 | 新榕能源(福建)有限公司 | Simple synthesis method and application of catalyst for preparing oil from methanol under normal pressure |
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Address after: 100010 Chaoyangmen North Street, Dongcheng District, Dongcheng District, Beijing Co-patentee after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE CO., LTD. Patentee after: China Offshore Oil Group Co., Ltd. Address before: 100010 Chaoyangmen North Street, Dongcheng District, Dongcheng District, Beijing Co-patentee before: CNOOC Tianjin Chemical Research & Design Institute Patentee before: China National Offshore Oil Corporation |