CN1395992A - Process for preparing microspherical Fischer-Tropsch catalyst - Google Patents
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- CN1395992A CN1395992A CN 01120416 CN01120416A CN1395992A CN 1395992 A CN1395992 A CN 1395992A CN 01120416 CN01120416 CN 01120416 CN 01120416 A CN01120416 A CN 01120416A CN 1395992 A CN1395992 A CN 1395992A
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Abstract
A microspherical catalyst for Fischer-Tropsch synthesis is prepared through mixing the solution of iron nitrate (or sulfate) with the mixed solution of lanthanum nitrate and copper nitrate (or sulfate), adding sodium carbonate or ammonia aqeous solution, depositing to obtain a slurry containing La-Cu, washing and filtering the deposited slurry to obtain filter cake, adding the water glass solution of patassium silicate to the wet slurry, stirring, spray-drying and calcining. Its advantages are simple process and high speed.
Description
The invention belongs to a kind of Preparation of catalysts method, relate in particular to a kind of preparation method of microspherical Fischer-Tropsch catalyst.
Synthetic synthesis gas (the CO+H that is meant of Fischer-Tropsch
2) reaction of catalysis synthetic hydrocarbon liquid fuel on catalyst, from the fifties, realized that in South Africa Sasol company coal-based synthetic liquid fuel heavy industrialization (is published in Catalysis Today referring to Dry ME, paper on 1990,6 (3) 183～206 " The Fischer-Tropsch Process-Commercial Aspects ").What Fischer-Tropsch synthesized normal employing is ferrum-based catalyst, and the reactor of employing has fixed bed reactors, fluidized-bed reactor and paste state bed reactor.Because paste state bed reactor has higher production efficiency, catalyst is easy to loading and unloading and can directly uses low H
2The coal based synthetic gas of/CO ratio, and demonstrate bigger technical advantage, be the synthetic liquid fuel technology of giving priority in the world at present.Kott is at Oil and Gas Journal magazine 1997,95 (25), report in 16～21, the natural gas base synthesis gas synthetic mesophase fraction oil process industrialization that Sasol company in South Africa adopted ferrum-based catalyst and paste state bed reactor technology to realize 2500 barrel per days in 1993.
The ferrum-based catalyst that paste state bed reactor adopts need have a certain size particle and mar proof, with the ON-LINE SEPARATION that helps product wax and catalyst and the stability of catalyst runs.South Africa Sasol company discloses the preparation method of used for slurry bed Fischer-Tropsch synthetic iron-based catalyst in the WO99/49965 patent, be specially: the sedimentation type ferrum-based catalyst particle that will support certainly obtained less than the synthetic ferrum-based catalyst of using of the wear-resistant syrup state bed Fischer Tropsch of 45 μ m 360～390 ℃ of roastings in 0.5～4 hour.This preparation method does not relate to spray-drying, and the particle of catalyst is less and be continuous distributed, is unfavorable for starching separating of attitude bed reacting middle catalyst and wax.
U.S. Rentech company discloses a kind of preparation method who is used for the Fischer-Tropsch synthetic iron-based catalyst of paste state bed reactor in U.S. Pat P5504118 and Chinese invention patent CN1113905A, be specially: obtain ferrous nitrate with nitric acid dissolve metallic iron and copper, the mixed liquor of ferric nitrate and copper nitrate, then ammoniacal liquor is added in the nitrate mixed liquor of heat, the precipitation slurries, the washing back adds solution of potassium carbonate, making beating, the weight percentage of catalyst in slurries is about 8-12%, use the spray dryer spray-drying then, remove most of moisture, obtaining is spherical catalyst granules roughly, diameter range is 5-50 μ m, make catalyst stabilising 315 ℃ of roastings at last, and be used for the syrup state bed Fischer Tropsch synthetic reaction.This patent is not described concrete spray-drying installation and drying condition, and no anti abrasive SiO in the catalyst
2Binding agent, particle is little, is unfavorable for starching the wax under the operation of attitude bed and the ON-LINE SEPARATION of catalyst.
U.S. Texas A﹠amp; People such as the Burkur of M university are at magazine Ind.Eng.Chem.Res., and 1990,29, a kind of Fe/Cu/K/SiO is disclosed among the 1588-1599
2The Preparation of catalysts method is specially: add ammonia spirit and carry out continuous co-precipitation in ferric nitrate and copper nitrate mixed solution, behind washing and the suction filtration, add a certain amount of K
2SiO
3Solution, reslurry final vacuum drying is used a certain amount of KHCO again
3Solution impregnation is then at 5 hours Fe/Cu/K/SiO of 300 ℃ of roastings
2Catalyst, subsequently at Ind.Eng.Chem.Res., 1999,38, will fill a prescription among the 3270-3275 is 100Fe/3Cu/4K/16SiO
2The catalyst of (weight meter) sieves after pulverizing earlier, and the catalyst granules of getting 44～53 μ m is used for the syrup state bed Fischer Tropsch synthetic reaction, obviously, the required slurry attitude of this preparation method bed catalyst yield rate is too low, and it is too high to produce the catalyst cost, is not suitable for the industrial mass production catalyst.
People such as the Zhao of Univ. of Pittsburgh are at Ind.Eng.Chem.Res., and the preparation method of disclosed used for slurry bed ferrum-based catalyst is on 2001,40,1065～1075: at ferric nitrate, copper nitrate and Si (OC
2H
5)
4Add ammonia precipitation process in the mixed aqueous solution and obtain the precipitation slurry, in slurry, add KHCO again
3The aqueous solution further adds a certain amount of SiO
2Binding agent, spray-drying is carried out in making beating then under 250 ℃, and it is 100Fe/5Cu/4.2K/xSiO that the powder that drying obtains obtained the used for slurry bed prescription in 5 hours 300 ℃ of following roastings
2The catalyst of (x=3.85～21.6), the particle volume average diameter of these catalyst are 78～103 μ m.Use 15L/ minute air of catalyst, feeding of 5g 38～90 μ m particle sections to carry out wear test in jet cup, rear catalyst wearing and tearing best result was that the fine grained that is lower than 38 μ m accounts for 8.5wt% in 1 hour.This method adopts Si (OC
2H
5)
4For raw material can cause the catalyst cost higher, the preparation section that adds potassium and silicon is also more loaded down with trivial details, and the spray-drying condition that report is more not detailed, catalyst granules distribution and yield rate situation.
The purpose of this invention is to provide that a kind of cost is low, technology is simple and is suitable for the preparation method of the microspherical Fischer-Tropsch catalyst of industrial mass production.
The object of the present invention is achieved like this: ferric nitrate or ferrum sulfuricum oxydatum solutum and lanthanum nitrate and copper nitrate or copper sulphate mixed solution are mixed, add precipitating reagent sodium carbonate or ammonia spirit then, obtain the co-precipitation filter cake after the precipitation slurry washing of the iron content lanthanum copper that obtains filtered, potassium silicate water glass solution is directly added in the wet slurry of iron content lanthanum copper, making beating mixes and makes catalyst pulp, by spray-drying, roasting obtains the microspheroidal syrup state bed Fischer Tropsch synthesis iron base catalyst then.
Concrete preparation method of the present invention comprises the steps:
(1) consists of Fe: La: Cu: K: SiO by the catalyst weight ratio
2=100: 0.01～5: 0.5～15: 0.5～10: 5～30, ferric nitrate or ferric sulfate, lanthanum nitrate, copper nitrate or copper-bath are mixed, make the solution that total mole number is 1～5mol/L, add Na then
2CO
3Or ammoniacal liquor formation precipitation slurry, washing is filtered, and obtains the co-precipitation filter cake;
(2) in the co-precipitation filter cake, press catalyst and form adding SiO
2: K
2The O modulus is 1～10, SiO
2Concentration is that the potassium silicate water glass solution of 5～30wt% mixes, and adds deionized water and pulls an oar, and makes the catalyst pulp that solid content is 10～40wt%;
(3) catalyst pulp is sent in the centrifugal spray dryer,, carried out spray-drying under the condition that the wind exhausting outlet temperature is 100～180 ℃ 200～350 ℃ of hot-wind inlet temperature;
(4) powder after the spray-drying carries out roasting, and sintering temperature is 300～450 ℃, and roasting time is 2～12 hours, obtains the synthetic Fe/La/Cu/K/SiO of microspheroidal syrup state bed Fischer Tropsch
2Catalyst.
The weight ratio of aforesaid La is preferably 0.02～2.
The weight ratio of aforesaid Cu is preferably 1～8.
The weight ratio of aforesaid K is preferably 1～7.
Aforesaid SiO
2Weight ratio be preferably 8～27.
Aforesaid SiO
2: K
2The O modulus is preferably 2～5.
Aforesaid SiO
2Concentration be preferably 8～25wt%.
Solid content is preferably 20～30wt% in the aforesaid catalyst pulp.
Aforesaid hot-wind inlet temperature is preferably 220～280 ℃.
Aforesaid hot-blast outlet temperature is preferably 105～120 ℃.
Aforesaid sintering temperature is preferably 320～400 ℃.
Aforesaid roasting time is preferably 3～6 hours.
The roasting of the powder after the aforesaid spray-drying can be carried out in rotary kiln.The catalyst microsphere diameter that the present invention makes is that the yield rate of 50～120 mu m ranges reaches more than 92%, and abrasion index is 1～2.5% hour
-1, specific area is 120～280 meters
2/ gram, pore volume are 0.2～0.5 milliliter/gram.
The analysis test method that the present invention is used:
1. the mensuration of finished iron catalyst microballoon abrasion index: a certain amount of iron catalyst microballoon is put into the abrasion index determinator, under constant gas, blew mill 5 hours, except that the 1st hour, the percetage by weight that the fine powder sample less than 50 μ m that the back was produced in 4 hours accounts for raw catalyst is called the catalyst abrasion rate, claim abrasion index again, unit is % hour
-1
2. the specific area of iron catalyst and pore volume are measured: adopt low-temperature nitrogen adsorption method, specific area is the BET specific area.
3. catalyst granules distributes: adopt SEM method observation catalyst particle size and distribution situation, and stereoscan photograph is carried out graphical analysis acquisition particle size distribution.
The present invention compared with prior art has following advantage:
(1) feature of the present invention is the precipitation slurry of the wet iron content lanthanum copper that obtains, and the potassium silicate water glass solution of the different moduluses of direct disposable adding has been simplified technological process, can further reduce the Catalyst Production cost effectively.
(2) used spray-drying installation is a centrifugal spray dryer among the preparation method of fischer-tropsch synthetic catalyst provided by the present invention.Spray drying process has that treating capacity is big, energy consumption is low, shaping of catalyst is rapid, be suitable for characteristics such as industrial continuous large-scale production.
(3) the synthetic Fe/La/Cu/K/SiO that uses of said syrup state bed Fischer Tropsch in the method provided by the present invention
2The catalyst finished product, wherein the yield rate of microsphere diameter 50～120 mu m ranges reaches more than 92%, and abrasion index is 1～2.5% hour
-1, specific area is 120～280 meters
2/ gram, pore volume are 0.2～0.5 milliliter/gram, and the catalyst powder that makes can sieve, and can drop in the paste state bed reactor and use, and therefore can significantly reduce the cost of manufacture and the energy consumption of catalyst, are applicable to the extensive catalyst of making of industry.
The following examples will the present invention is described further, and protection scope of the present invention is not subjected to the restriction of these embodiment.
Embodiment 1
With 22KgFe (NO
3)
39H
2O is dissolved in the 108L deionized water, in addition with 232gCu (NO
3)
23H
2O and 4.8g La (NO
3)
36H
2O is dissolved in the 2L deionized water, again above-mentioned two solution are merged, other gets industrial natrium carbonicum calcinatum 8.8Kg and is dissolved in the 85L deionized water, above-mentioned solution is squeezed into continuously in the reactor of a high degree of agitation, carries out coprecipitation reaction, maintain the temperature at 85 ℃, after co-precipitation is finished, left standstill aging 2 hours the pH=7 of co-precipitation liquid～8.5, wash then and filter, until using AgNO
3Aqueous assay is less than Cl
-Till, it is 10 (wt) % that the gained filter cake adds 3.55Kg concentration, modulus is 3.45 K
2SiO
3Add the making beating of 16Kg deionized water after the aqueous solution is kneaded evenly again, the slurry of making solids content and be 20 (wt) % is used for spray-drying.Above-mentioned slurry carries out spray drying granulation 230 ℃ of control inlet hot blast temperatures under the condition that the outlet hot blast temperature is 100 ℃, and the gained dry microspheres promptly obtained the final catalyst of 4.8Kg in 4 hours 350 ℃ of following roastings in rotary kiln.The proportioning of this catalyst activity component is: Fe: La: Cu: K: SiO
2=100: 0.05: 2: 3: 8, its key technical indexes is seen attached list.
Embodiment 2
Press the method for embodiment 1, but catalyst filter cake and K
2SiO
3After kneading evenly, the aqueous solution adds the making beating of 4Kg deionized water again, making solids content is the slurry of 40 (wt) %, 260 ℃ of control inlet temperatures, carry out spray drying granulation under the condition that the outlet hot blast temperature is 120 ℃, thus obtained microsphere 300 ℃ of following roastings 6 hours, obtains the final catalyst of 4.8Kg in rotary kiln.
This catalyst is formed identical with embodiment 1, and all the other technical indicators are seen attached list.
Embodiment 3
With 34Kg Fe
2(SO
4)
3Be dissolved in the 29L deionized water, in addition with 1.98KgCu (NO
3)
23H
2O and 202g La (NO
3)
36H
2O is dissolved in the 3L deionized water, again above-mentioned two solution are merged, other gets industrial natrium carbonicum calcinatum 19.4Kg and is dissolved in the 46L deionized water, above-mentioned solution is squeezed into continuously in the reactor of a high degree of agitation, carries out coprecipitation reaction, maintain the temperature at 85 ℃, after co-precipitation is finished, left standstill aging 2 hours the pH=7 of co-precipitation liquid～8.5, wash then and filter, until using BaCl
2Aqueous assay is less than SO
4 2-Till, it is 30 (wt) % that the gained filter cake adds 4.34Kg concentration, modulus is 1.04 K
2SiO
3After the aqueous solution is kneaded evenly, add the making beating of 13.8Kg deionized water again, making solids content is the slurry of 40 (wt) %, at the inlet hot blast temperature is 230 ℃, the outlet hot blast temperature is to carry out spray drying granulation under 110 ℃ of conditions, thus obtained microsphere 330 ℃ of following roastings 5 hours, obtains the final catalyst of 11.3Kg in rotary kiln.This catalyst activity component proportioning is: Fe: La: Cu: K: SiO
2=100: 1: 8: 10: 8, all the other technical indicators are seen attached list.
Embodiment 4
With 210Kg Fe (NO
3)
39H
2O is dissolved in the 260L deionized water, in addition with 6.33KgCu (SO
4)
25H
2O and 1.81Kg La (NO
3)
36H
2O is dissolved in the 2L deionized water, again above-mentioned two solution are merged, other gets the ammonia spirit of 20 (wt) % of 70L, above-mentioned solution is squeezed into continuously in the reactor of a high degree of agitation, carries out coprecipitation reaction, maintain the temperature at 85 ℃, the pH=7 of co-precipitation liquid～8.5, after co-precipitation is finished, preposition aging 2 hours, wash then and filter, until using BaCl
2Aqueous assay is less than SO
4 2-Till, it is 25 (wt) % that the gained filter cake adds 34.38Kg concentration, modulus is 3.25 K
2SiO
3After the aqueous solution is kneaded evenly, add the 51.48Kg deionized water again, making solids content is the slurry of 40 (wt) %, at the inlet hot blast temperature is 250 ℃, the outlet hot blast temperature is to carry out spray drying granulation under 150 ℃ the condition, thus obtained microsphere 380 ℃ of following roastings 3 hours, obtains the final catalyst of 51.7Kg in rotary kiln.This catalyst component proportioning is: Fe: La: Cu: K: SiO
2=100: 2: 4: 8: 20, all the other technical indicators are seen attached list.
Embodiment 5
Press the method for embodiment 4, but the catalyst filter cake earlier with the mixed making beating of deionized water after again with K
2SiO
3Aqueous solution is even, making solids content is the slurry of 40 (wt) %, at the inlet hot blast temperature is 220 ℃, the outlet hot blast temperature is to carry out spray drying granulation under 110 ℃ of conditions, thus obtained microsphere in rotary kiln 320 ℃ of following roastings 6 hours, obtain the final catalyst of 51.7Kg, its component proportioning is identical with embodiment 4, and all the other technical indicators are seen attached list.
The performance indications catalyst of subordinate list embodiment 1～5 described catalyst is compiled size distribution (%) abrasion index BET specific area pore volume number (50～120 μ m ratio) (%h
-1) (m
2/ g) (ml/g) embodiment 1 93.5 1.3 150 0.32 embodiment 2 94.3 1.8 237 0.38 embodiment 3 92.5 2.2 127 0.24 embodiment 4 95.7 1.1 244 0.42 embodiment 5 96.0 1.0 252 0.44
Claims (13)
1. the preparation method of a microspherical Fischer-Tropsch catalyst is characterized in that the preparation method comprises the steps:
(1) consists of Fe: La: Cu: K: SiO by the catalyst weight ratio
2=100: 0.01～5: 0.5～15: 0.5～10: 5～30, ferric nitrate or ferric sulfate, lanthanum nitrate, copper nitrate or copper-bath are mixed, make the solution that total mole number is 1～5mol/L, add Na then
2CO
3Or ammoniacal liquor formation precipitation slurry, washing is filtered, and obtains the co-precipitation filter cake;
(2) in the co-precipitation filter cake, press catalyst and form adding SiO
2: K
2The O modulus is 1～10, SiO
2Concentration is that the potassium silicate water glass solution of 5～30wt% mixes, and adds deionized water and pulls an oar, and makes the catalyst pulp that solid content is 10～40wt%;
(3) catalyst pulp is sent in the centrifugal spray dryer,, carried out spray-drying under the condition that the wind exhausting outlet temperature is 100～180 ℃ 200～350 ℃ of hot-wind inlet temperature;
(4) powder after the spray-drying carries out roasting, and sintering temperature is 300～450 ℃, and roasting time is 2～12 hours, obtains the synthetic Fe/La/Cu/K/SiO of microspheroidal syrup state bed Fischer Tropsch
2Catalyst.
2. the preparation method of a kind of microspherical Fischer-Tropsch catalyst as claimed in claim 1, the weight ratio that it is characterized in that described La is 0.02～2.
3. the preparation method of a kind of microspherical Fischer-Tropsch catalyst as claimed in claim 1, the weight ratio that it is characterized in that described Cu is 1～8.
4. the preparation method of a kind of microspherical Fischer-Tropsch catalyst as claimed in claim 1, the weight ratio that it is characterized in that described K is 1～7.
5. the preparation method of a kind of microspherical Fischer-Tropsch catalyst as claimed in claim 1 is characterized in that described SiO
2Weight ratio be 8～27.
6. the preparation method of a kind of microspherical Fischer-Tropsch catalyst as claimed in claim 1 is characterized in that described SiO
2: K
2The O modulus is 2～5.
7. the preparation method of a kind of microspherical Fischer-Tropsch catalyst as claimed in claim 1 is characterized in that described SiO
2Concentration be 8～25wt%.
8. the preparation method of a kind of microspherical Fischer-Tropsch catalyst as claimed in claim 1 is characterized in that solid content is 20～30wt% in the described catalyst pulp.
9. the preparation method of a kind of microspherical Fischer-Tropsch catalyst as claimed in claim 1 is characterized in that described hot-wind inlet temperature is 220～280 ℃.
10. the preparation method of a kind of microspherical Fischer-Tropsch catalyst as claimed in claim 1 is characterized in that described hot-blast outlet temperature is 105～120 ℃.
11. the preparation method of a kind of microspherical Fischer-Tropsch catalyst as claimed in claim 1 is characterized in that described sintering temperature is 320～400 ℃.
12. the preparation method of a kind of microspherical Fischer-Tropsch catalyst as claimed in claim 1 is characterized in that described roasting time is 3～6 hours.
13. the preparation method of a kind of microspherical Fischer-Tropsch catalyst as claimed in claim 1 is characterized in that the roasting of the powder after the described spray-drying can be carried out in rotary kiln.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100434169C (en) * | 2005-08-22 | 2008-11-19 | 上海兖矿能源科技研发有限公司 | Microspherical iron-based catalyst for Fischer-Tropsch synthesis at high-temperature and production thereof |
| CN101884926A (en) * | 2010-07-02 | 2010-11-17 | 神华集团有限责任公司 | Precipitated iron catalyst for Fischer-Tropsch synthesis reaction, and preparation method and application thereof |
| CN101602000B (en) * | 2009-07-15 | 2011-10-05 | 神华集团有限责任公司 | Iron catalyst containing cobalt auxiliary agent for Fischer-Tropsch synthesis reaction and preparation method thereof |
| CN101811047B (en) * | 2009-02-20 | 2012-10-03 | 中科合成油技术有限公司 | Iron base catalyst used for Fischer-Tropsch synthesis and preparation method and application thereof |
| CN101735872B (en) * | 2008-11-12 | 2013-01-30 | 中科合成油技术有限公司 | Non-steady state reactor and method for producing synthesis gas |
| CN104874399A (en) * | 2007-09-14 | 2015-09-02 | Res美国有限责任公司 | Promoted, attrition resistant, silica supported precipitated iron catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100434169C (en) * | 2005-08-22 | 2008-11-19 | 上海兖矿能源科技研发有限公司 | Microspherical iron-based catalyst for Fischer-Tropsch synthesis at high-temperature and production thereof |
| CN104874399A (en) * | 2007-09-14 | 2015-09-02 | Res美国有限责任公司 | Promoted, attrition resistant, silica supported precipitated iron catalyst |
| US10086366B2 (en) | 2007-09-14 | 2018-10-02 | Res Usa, Llc | Promoted, attrition resistant, silica supported precipitated iron catalyst |
| CN101735872B (en) * | 2008-11-12 | 2013-01-30 | 中科合成油技术有限公司 | Non-steady state reactor and method for producing synthesis gas |
| CN101811047B (en) * | 2009-02-20 | 2012-10-03 | 中科合成油技术有限公司 | Iron base catalyst used for Fischer-Tropsch synthesis and preparation method and application thereof |
| CN101602000B (en) * | 2009-07-15 | 2011-10-05 | 神华集团有限责任公司 | Iron catalyst containing cobalt auxiliary agent for Fischer-Tropsch synthesis reaction and preparation method thereof |
| CN101884926A (en) * | 2010-07-02 | 2010-11-17 | 神华集团有限责任公司 | Precipitated iron catalyst for Fischer-Tropsch synthesis reaction, and preparation method and application thereof |
| CN101884926B (en) * | 2010-07-02 | 2012-12-05 | 神华集团有限责任公司 | Precipitated iron catalyst for Fischer-Tropsch synthesis reaction, and preparation method and application thereof |
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|---|---|
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Effective date of registration: 20070119 Address after: 030006, Taiyuan hi tech Zone, Shanxi, South Central Cyberport, port 4, 2, A and B Patentee after: Zhongke Synthetic Oil Technology Co., Ltd. Address before: 165 mailbox 030001, Shanxi City, Taiyuan Province Patentee before: Shanxi Institute of Coal Chemistry, Chinese Academy of Sciences |
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Denomination of invention: Process for preparing microspherical Fischer-Tropsch catalyst Effective date of registration: 20101206 Granted publication date: 20031126 Pledgee: China Development Bank Co Pledgor: Zhongke Synthetic Oil Technology Co., Ltd. Registration number: 2010990000994 |
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Address after: 101407 Beijing city Huairou District Yanqi Economic Development Zone C District No. 1 south two Street Park Patentee after: Zhongke Synthetic Oil Technology Co., Ltd. Address before: 030006, Taiyuan hi tech Zone, Shanxi, South Central Cyberport, port 4, 2, A and B Patentee before: Zhongke Synthetic Oil Technology Co., Ltd. |
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Date of cancellation: 20150807 Granted publication date: 20031126 Pledgee: China Development Bank Co Pledgor: Zhongke Synthetic Oil Technology Co., Ltd. Registration number: 2010990000994 |
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