CN1176748C - Catalyst with molecular sieve carrier for synthesizing high-grade diesel oil - Google Patents
Catalyst with molecular sieve carrier for synthesizing high-grade diesel oil Download PDFInfo
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- CN1176748C CN1176748C CNB021434921A CN02143492A CN1176748C CN 1176748 C CN1176748 C CN 1176748C CN B021434921 A CNB021434921 A CN B021434921A CN 02143492 A CN02143492 A CN 02143492A CN 1176748 C CN1176748 C CN 1176748C
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Abstract
The present invention relates to a Fischer-Tropsch reaction catalyst prepared from a molecular sieve and metallic cobalt, wherein the molecular sieve is a Y-type molecular sieve, a Beta molecular sieve or an MOR molecular sieve. The catalyst is prepared from 3 wt% to 10 wt% of cobalt and a surplus quantity of molecular sieve, and the silica alumina ratio n of the molecular sieve is from 5 to 200. The catalyst is prepared with an impregnation method, and the conversion rate of synthetic gas in the reaction process is nearly remained unchanged under appropriate reaction conditions; the selectivity of hydrocarbons from C10 to C20 is higher than 35% under suitable reaction conditions when a molecular sieve with the pore diameter of larger than 0.7 nm is used as a carrier and the cobalt carrying capacity is appropriate; the selectivity of straight chain paraffin from C10 to C20 exceeds 50% when the MOR molecular sieve in a one-dimensional pore canal structure is used as the carrier. In addition, the phenomenon of the carbon deposition of the catalyst is avoided or reduced at a relatively high reaction temperature (higher than 250DEG C) so that the continuous running of the catalyst is guaranteed.
Description
Technical field
The present invention relates to a kind of Fischer-Tropsch reaction catalyst.
Background technology
Natural gas is converted into synthesis gas earlier, again through the technology of Fischer-Tropsch reaction synthesizing liquid hydrocarbon (GTL), for the conversion of natural gas utilization provides a practicable approach.Companies such as Shell, Sasol, Exxon, Syntroleum, Energe International have all developed GTL patented technology and new technology separately respectively.Liquid product in the GTL product is made up of straight-chain hydrocarbons, alkene basically, has characteristics such as no sulphur, no nitrogen, no metal, no aromatic hydrocarbons, is environment amenable fuel oil and chemicals.The GTL technology can be by the regulation and control of catalyst, adapt to multiple demand, product is from cleaning high-quality oil product (as aviation kerosine, diesel oil, lubricating oil) to chemicals (as higher olefins, light olefin and oxygenatedchemicals), has very high added value, middle-size and small-size gas field for the dispersion of development and utilization outlying district, particularly the natural gas of oil gas symbiosis is of great significance.
Recent bibliographical information (Scholten J J F, Xu X D, Von Der Decken C-B et al.Int J EnergRes, 1994,18,185) consisting of of business-like typical cobalt-based Fischer-Tropsch catalyst: (alkali metal, rare earth metal and transition metal oxide are as ZrO for second kind of metal (being generally noble metal), the oxides additive of cobalt, trace
2Deng) and a kind of carrier (Al
2O
3, SiO
2, TiO
2, ZSM etc.).It is that the novel Fischer-Tropsch catalyst of carrier can be produced linear mixing saturated hydrocarbons by synthesis gas with Si, Al, Zr, Sn, Mg or oxides such as rare earth, Ti that European patent EP 800 864 discloses a kind of.CN1052844 discloses a kind of catalyst that synthesis gas is converted into hydrocarbon that is used for, and its component mainly comprises Co and Zn.CN 1084153 discloses a kind of catalyst that is used to prepare higher hydrocarbon, comprises Co/Al
2O
3With to the insensitive second kind of metal of load capacity, product mainly is the mixture that contains alkane.U.S. Pat 5545674 is by the outer surface spraying cobalt metal active top layer of spraying process at inorganic oxide carrier, add auxiliary agent (as rhenium, zirconium, hafnium, cerium, thorium and uranium or its mixture) simultaneously, to improve the selectivity of activity of such catalysts, power of regeneration and liquid hydrocarbon, the reacting middle catalyst inactivation is slow, the distillate productive rate that contains linear alkane and alkene is very high, product basic composition is C
10+Hydro carbons.From patent and bibliographical information as seen, although use above-mentioned catalyst can obtain low CH
4Selectivity and higher C
5+The conversion ratio of selectivity and synthesis gas, however its product distribute and accord with F-S-A and distribute, this makes diesel component (C in the product
10～C
20) selectivity generally lower.In addition, reaction temperature is generally all below 250 ℃, and the heavy carbon hydrocarbon of reaction generation easily is trapped on the catalyst like this, and the duct of blocking catalyst makes activity of such catalysts and selectivity change.
Summary of the invention
Purpose of the present invention aim to provide a kind of with molecular sieve as catalyst carrier, have higher C
10～C
20Hydrocarbon-selective and can avoid or reduce catalyst generation carbon distribution is made the cobalt-base catalyst of high-grade diesel oil from synthesis gas.
The said catalyst of the present invention is made up of molecular sieve and metallic cobalt, and the chemical composition of catalyst is
xCo/Na
2O·Al
2O
3·nSiO
2
Wherein x is the weight percentage of Co in catalyst, Na
2OAl
2O
3NSiO
2Be the chemical expression formula of molecular sieve, n is the SiO of molecular sieve
2With Al
2O
3Mol ratio.Said molecular sieve is sodium type faujasite molecular sieve Y, sodium type mordenite molecular sieve (MOR) and sodium type beta-molecular sieve (Beta).Catalyst the ratio of each component is cobalt (percentage by weight) 3%～10%, is preferably 5%, and surplus is a molecular sieve, the SiO of molecular sieve
2With Al
2O
3Mol ratio n be 5～200.
Preparation of catalysts adopts immersion process for preparing, and its step is as follows:
1) take by weighing cobalt salt by the catalytic component proportioning, adding deionized water, to be mixed with concentration expressed in percentage by weight be 2%～5% solution, and said cobalt salt is cobalt nitrate, cobalt acetate or acetylacetone cobalt;
2) take by weighing molecular sieve by the catalytic component proportioning, join in the cobalt liquor that has prepared, after stir (2h), place 24h;
3) with above-mentioned mixed liquor evaporate to dryness in 50～80 ℃ of water-baths, then at 40～100 ℃ of vacuum drying 24h;
4) dried solid is fully ground after, in 300～800 ℃ of roasting 4～10h;
5) with the pressed powder moulding after the roasting, sieve is got the presoma of 30～60 purpose components as catalyst;
6) presoma of catalyst reduces 12～20h in 400～500 ℃ hydrogen atmosphere, Fischer-Tropsch catalyst.
The evaluation of catalyst is carried out (tube inner diameter 8mm) in fixed bed stainless steel high pressure microreactor.Reaction condition is that unstripped gas is formed H
2/ CO/Ar=64: 32: 4,250～260 ℃ of reaction temperatures, reaction pressure 2.0MPa, air speed 1.5～6.0Lg
-1h
-1The gas-phase product that reaction generates (is analyzed Ar, CH by GC-950 type gas chromatograph 5A molecular sieve column
4, CO), Porapak-Q post (Analysis for CO+CH
4, CO
2, C
2H
4, C
2H
6, C
3H
6, C
3H
8Deng), the TCD on-line analysis.Liquid product is collected the back by cold-trap and is analyzed by GC-112 type gas chromatograph AT PONA quartz capillary column, FID.Catalyst of the present invention is under proper reaction conditions, and the synthesis gas conversion ratio almost remains unchanged in course of reaction; The aperture is the above molecular sieve of 0.7nm when being carrier, under suitable cobalt load capacity, suitable reaction condition, and C
10～C
20The selectivity of hydrocarbon is more than 35%; When the MOR molecular sieve with one-dimensional tunnel structure is carrier, C
10～C
20The selectivity of linear paraffin surpass 50%.In addition, the present invention uses higher relatively reaction temperature (more than 250 ℃), avoids or reduces catalyst generation carbon distribution phenomenon, thereby guarantee the continuous operation of catalyst.
Description of drawings
Fig. 1 is the conversion ratio graph of a relation over time of embodiment 1CO.
Fig. 2 is the conversion ratio graph of a relation over time of embodiment 2CO.
Fig. 3 is the conversion ratio graph of a relation over time of embodiment 3CO.
The specific embodiment
The present invention will be further described below by embodiment.
Embodiment 1: weighing Co (NO
3)
26H
2O 5.20g adds the 200g deionized water dissolving, takes by weighing SiO
2With Al
2O
3Mol ratio n be 18.5 MOR 20g, join in the above-mentioned solution, place 24h after stirring 2h; With above-mentioned mixed liquor evaporate to dryness in 70～80 ℃ of water-baths, then 60 ℃ of vacuum drying one day, after dried solid fully ground, in 550 ℃ of roasting 6h, with the pressed powder moulding after the roasting, sieve is got 30～60 purpose components as catalyst precarsor, and catalyst precarsor is reduced 16h in 400 ℃ hydrogen atmosphere, the 5wt%Co/MOR Fischer-Tropsch catalyst.Mordenite molecular sieve MOR adopts the hydrothermal synthesis method preparation, and table 1 is its chemical composition and some physicochemical properties.
The chemical composition of table 1 MOR and physicochemical properties
| Title | Na-Mordenite | ||
| Outward appearance | Powdery | ||
| Chemical composition | SiO 2 | wt％ | 87.0 |
| Al 2O 3 | wt％ | 7.99 | |
| Na 2O | wt％ | 5.03 | |
| Fe | wt％ | 0.03 | |
| Ig.Loss | wt％ | 8.9 | |
| SiO 2/Al 2O 3Ratio | 18.5 | ||
| Rerum natura | Particle diameter | μm | 0.1～0.5 |
| Proportion | g/cc | 0.29 | |
| Specific area | m 2/g | 340 | |
Catalytic reaction is carried out (tube inner diameter 8mm) in fixed bed stainless steel high pressure microreactor, take by weighing presoma (30～60 order) 0.8g of 5wt%Co/MOR, pack in the reaction tube, logical hydrogen under the normal pressure, (4 ° of heating rates/min) to 400 ℃ of reduction 16h, hydrogen flowing quantity is 30ml/min in temperature programming; After the presoma reduction, be cooled to below 40 ℃, press unstripped gas and form H
2/ CO/Ar=64: 32: 4,250 ℃ of reaction temperatures, reaction pressure 2.0MPa, air speed 1.5Lg
-1h
-1Reaction condition, switch synthesis gas, adjusting synthesis gas pressure is 2.0MPa, flow is 20ml/min, after treating the pressure and stability of flow of system, temperature programming (4 ° of heating rates/min) react to 250 ℃, reaction operation 12h, and the gas-phase product that reaction generates (is analyzed Ar, CH by GC-950 type gas chromatograph 5A molecular sieve column
4, CO), Porapak-Q post (Analysis for CO+CH
4, CO
2, C
2H
4, C
2H
6, C
3H
6, C
3H
8Deng), the TCD on-line analysis.Liquid product is collected the back by cold-trap and is analyzed by GC-112 type gas chromatograph AT PONA quartz capillary column, FID.
The catalytic perfomance evaluation is listed in the table 2.Be no more than 30% by gaseous product selectivity in the product of the visible 5wt%Co/MOR catalyst of table 2, and product liquid is based on high-grade diesel oil and lightweight wax.Diesel component (C in the product liquid
10～C
20) be about about 75wt%, and product is based on positive structure hydrocarbon, and alkene and isohydrocarbon only are about 10wt%.Thousands of h of catalyst continuously-running and activity change does not take place.
The reactivity worth of table 2 5wt%Co/MOR catalyst
| CO conversion ratio (%) | 42.8 |
| CH 4Selectivity (%) | 17.6 |
| Gaseous hydrocarbon (C 2～C 4) selectivity (%) | 4.3 |
| Liquid light hydrocarbon (C 5～C 9) selectivity (%) | 8.6 |
| Diesel component (C 10～C 20) selectivity (%) | 57.1 |
| The selectivity (%) of positive structure hydrocarbon in the diesel component | 50.3 |
| Wax phase (C 21+) selectivity (%) | 9.7 |
Fig. 1 concerns over time that for the conversion ratio of CO the 5wt%Co/MOR catalyst is under proper reaction conditions as we know from the figure, and the synthesis gas conversion ratio almost keeps constant substantially in course of reaction.
Embodiment 2: weighing Co (No
3)
26H
2O 5.20g adds the 200g deionized water dissolving, takes by weighing SiO
2With Al
2O
3Mol ratio n be 5.6 NaY 20g, join in the above-mentioned solution, place 24h after stirring 2h, with above-mentioned mixed liquor evaporate to dryness in 70～80 ℃ of water-baths, then 60 ℃ of vacuum drying one day, after dried solid fully ground, in 550 ℃ of roasting 6h, with the pressed powder moulding after the roasting, sieve is got 30～60 purpose components as catalyged precursor, catalyst precarsor reduces 16h in 400 ℃ hydrogen atmosphere, the 5wt%Co/NaY Fischer-Tropsch catalyst.The NaY molecular sieve adopts the hydrothermal synthesis method preparation in experiment, table 3 is its chemical composition and some physicochemical properties.
Chemical composition and the physicochemical properties of table 3NaY
| Title | NaY | ||
| Outward appearance | Powdery | ||
| Chemical composition | SiO 2 | wt％ | 67.3 |
| Al 2O 3 | wt％ | 20.3 | |
| Na 2O | wt％ | 12.4 | |
| Ig.Loss | wt％ | 20.7 | |
| SiO 2/Al 2O 3Ratio | 5.6 | ||
| Rerum natura | Particle diameter | μm | 0.2～0.6 |
| Proportion | g/cc | 0.33 | |
| Specific area | m 2/g | 660 | |
Catalytic reaction is carried out (tube inner diameter 8mm) in fixed bed stainless steel high pressure microreactor, take by weighing presoma (30～60 order) 0.8g of 5wt%Co/NaY, and in the reaction tube of packing into, reaction condition and product analysis are with embodiment 1.
The reactivity worth of 5wt%Co/NaY is listed in the table 4.Be no more than 30% by gaseous product selectivity in the product of the visible 5wt%Co/NaY catalyst of table 4, and product liquid is based on diesel oil and lightweight wax.Diesel component (C in the product liquid
10～C
20) be about about 66wt%, product is a hydrocarbon mixture, positive structure hydrocarbon is about 66wt%.The 5wt%Co/NaY catalyst is under this reaction condition as shown in Figure 2, and the synthesis gas conversion ratio begins to increase with the reaction time in course of reaction, reaches maximum behind the 3h and reduces gradually subsequently, almost remains unchanged behind the 8h.
The reactivity worth of table 4 5wt%Co/NaY catalyst
| CO conversion ratio (%) | 47.0 |
| CH 4Selectivity (%) | 21.4 |
| Gaseous hydrocarbon (C 2～C 4) selectivity (%) | 6.5 |
| Liquid light hydrocarbon (C 5～C 9) selectivity (%) | 17.9 |
| Diesel component (C 10～C 20) selectivity (%) | 46.9 |
| The selectivity (%) of positive structure hydrocarbon in the diesel component | 31.3 |
| Wax phase (C 21+) selectivity (%) | 5.6 |
Embodiment 3: weighing Co (NO
3)
26H
2O 5.20g adds the 200g deionized water dissolving, takes by weighing SiO
2With Al
2O
3Mol ratio n be 25 Beta 20g, join in the above-mentioned solution, place 24h after stirring 2h, with above-mentioned mixed liquor evaporate to dryness in 70～80 ℃ of water-baths, then 60 ℃ of vacuum drying one day, after dried solid fully ground, in 550 ℃ of roasting 6h, with the pressed powder moulding after the roasting, sieve is got 30～60 purpose components as catalyged precursor, catalyst precarsor reduces 16h in 400 ℃ hydrogen atmosphere, the 5wt%Co/Beta Fischer-Tropsch catalyst.The Beta molecular sieve adopts the hydrothermal synthesis method preparation in experiment, table 5 is its chemical composition and some physicochemical properties.
Chemical composition and the physicochemical properties of table 5Beta
| Title | Beta | ||
| Outward appearance | Powdery | ||
| Chemical composition | SiO 2 | wt％ | 93.54 |
| Al 2O 3 | wt％ | 6.28 | |
| Na | wt％ | 0.15 | |
| Fe | wt％ | 0.03 | |
| Ig.Loss | wt％ | 10 | |
| SiO 2/Al 2O 3Ratio | 25 | ||
| Rerum natura | Specific area | m 2/g | 500 |
Catalytic reaction is carried out (tube inner diameter 8mm) in fixed bed stainless steel high pressure microreactor, take by weighing presoma (30～60 order) 0.8g of 5wt%Co/Beta, and in the reaction tube of packing into, reaction condition and product analysis are with embodiment 1.
The reactivity worth of 5wt%Co/Beta is listed in the table 6.Be no more than 35% by gaseous product selectivity in the product of the visible 5wt%Co/Beta catalyst of table 6, and product liquid is based on diesel oil.Diesel component (C in the product liquid
10～C
20) be about about 72wt%, product is a hydrocarbon mixture, positive structure hydrocarbon only is about 20wt%.The 5wt%Co/Beta catalyst is under this reaction condition as shown in Figure 3, and the synthesis gas conversion ratio begins to increase in time in course of reaction, reaches maximum behind the 3h and reduces gradually subsequently, almost remains unchanged behind the 8h.
The reactivity worth of table 6 5wt%Co/Beta catalyst
| CO conversion ratio (%) | 46.9 |
| CH 4Selectivity (%) | 28.1 |
| Gaseous hydrocarbon (C 2～C 4) selectivity (%) | 6.6 |
| Liquid light hydrocarbon (C 5～C 9) selectivity (%) | 24.4 |
| Diesel component (C 10～C 20) selectivity (%) | 39.1 |
| The selectivity (%) of positive structure hydrocarbon in the diesel component | 8.0 |
| Wax phase (C 21+) selectivity (%) | Trace |
Embodiment 4: weighing Co (NO
3)
26H
2O 4.58g adds the 300g deionized water dissolving.Take by weighing MOR 30g, join in the above-mentioned solution, place 24h behind the stirring 2h, all the other operating procedures get the 3wt%Co/MOR Fischer-Tropsch catalyst with embodiment 1.The performance evaluation of catalyst the results are shown in table 7 with embodiment 1.
The reactivity of table 7 3wt%Co/MOR catalyst
| CO conversion ratio (%) | 26.0 |
| CH 4Selectivity (%) | 23.0 |
| Gaseous hydrocarbon (C 2～C 4) selectivity (%) | 5.0 |
| Liquid light hydrocarbon (C 5～C 9) selectivity (%) | 12.6 |
| Diesel component (C 10～C 20) selectivity (%) | 49.1 |
| The selectivity (%) of positive structure hydrocarbon in the diesel component | 43.7 |
| Wax phase (C 21+) selectivity (%) | 10.4 |
Embodiment 5: weighing Co (NO
3)
26H
2O16.5g adds the 200g deionized water dissolving.Take by weighing MOR30g, join in the above-mentioned solution, place 24h behind the stirring 2h, all the other operating procedures get the 10wt%Co/MOR Fischer-Tropsch catalyst with embodiment 1.The performance evaluation of catalyst the results are shown in table 8 with embodiment 1.
The reactivity worth of table 8 10wt%Co/MOR catalyst
| CO conversion ratio (%) | 64.3 |
| CH 4Selectivity (%) | 10.5 |
| Gaseous hydrocarbon (C 2～C 4) selectivity (%) | 3.0 |
| Liquid light hydrocarbon (C 5～C 9) selectivity (%) | 9.8 |
| Diesel component (C 10～C 20) selectivity (%) | 43.0 |
| The selectivity (%) of positive structure hydrocarbon in the diesel component | 37.0 |
| Wax phase (C 21+) selectivity (%) | 30.3 |
Claims (2)
1. molecular sieve is the catalyst of the combined diesel oil of carrier, it is characterized in that described catalyst is made up of molecular sieve and metallic cobalt, and the chemical composition of catalyst is xCo/[M
1] OAl
2O
3NSiO
2, wherein x is the weight percentage of Co in catalyst, [M
I] OAl
2O
3NSiO
2Be the chemical expression formula of molecular sieve, M
IBe Na, n is the SiO of molecular sieve
2With Al
2O
3Mol ratio, the percentage by weight proportioning of each component of catalyst is a cobalt 3%～10%, surplus is a molecular sieve, the SiO of molecular sieve
2With Al
2O
3Mol ratio n be 5～25, described molecular sieve is sodium type faujasite molecular sieve Y, sodium type mordenite molecular sieve MOR or sodium type beta-molecular sieve Beta;
Preparation of catalysts adopts immersion process for preparing, and its step is as follows:
1) take by weighing cobalt salt by the catalytic component proportioning, adding deionized water, to be mixed with concentration expressed in percentage by weight be 2%～5% solution, and described cobalt salt is cobalt nitrate, cobalt acetate or acetylacetone cobalt;
2) take by weighing molecular sieve by the catalytic component proportioning, join in the cobalt liquor that has prepared, after stirring, place 24h;
3) with above-mentioned mixed liquor evaporate to dryness in 50～80 ℃ of water-baths, then at 40～100 ℃ of vacuum drying 24h;
4) dried solid is fully ground after, in 300～800 ℃ of roasting 4～10h;
5) with the pressed powder moulding after the roasting, sieve is got the presoma of 30～60 purpose components as catalyst;
6) presoma of catalyst reduces 12～20h in 400～500 ℃ hydrogen atmosphere, Fischer-Tropsch catalyst.
2. molecular sieve as claimed in claim 1 is the catalyst of the combined diesel oil of carrier, and the weight percent content that it is characterized in that cobalt in the described catalyst is 5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021434921A CN1176748C (en) | 2002-09-30 | 2002-09-30 | Catalyst with molecular sieve carrier for synthesizing high-grade diesel oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021434921A CN1176748C (en) | 2002-09-30 | 2002-09-30 | Catalyst with molecular sieve carrier for synthesizing high-grade diesel oil |
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| Publication Number | Publication Date |
|---|---|
| CN1403536A CN1403536A (en) | 2003-03-19 |
| CN1176748C true CN1176748C (en) | 2004-11-24 |
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ID=4750478
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|---|---|---|---|
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101890361B (en) * | 2010-07-27 | 2013-04-24 | 万华实业集团有限公司 | Preparation method of catalyst for use in highly selective preparation of gasoline fractions from synthesis gas |
| CN104148107B (en) * | 2014-08-08 | 2016-03-16 | 厦门大学 | A kind of Catalysts and its preparation method being transformed diesel oil distillate processed by synthesis gas one step |
| CN107847862B (en) * | 2015-06-18 | 2020-12-18 | 庄信万丰股份有限公司 | NH3Overdose tolerant SCR catalyst |
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