CN100460066C - Process for preparing synthetic hydrocarbon catalyst of synthetic gas - Google Patents
Process for preparing synthetic hydrocarbon catalyst of synthetic gas Download PDFInfo
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- CN100460066C CN100460066C CNB2004100255153A CN200410025515A CN100460066C CN 100460066 C CN100460066 C CN 100460066C CN B2004100255153 A CNB2004100255153 A CN B2004100255153A CN 200410025515 A CN200410025515 A CN 200410025515A CN 100460066 C CN100460066 C CN 100460066C
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Abstract
The preparation process of catalyst for synthesizing synthetic gas to form hydrocarbon includes the following steps: adding sodium carbonate solution as precipitant into the mixed solution of ferric nitrate and copper nitrate, washing and filtering to obtain co-precipitated Fe-Cu filter cake; adding water solution of potassium silicate and silicon oxide into the co-precipitated Fe-Cu filter cake and pulping to obtain catalyst slurry; and drying and roasting to obtain the catalyst of the present invention. Compared with available technology, the present invention has the advantages of simple technological process and low catalyst producing cost, and the catalyst has the features of great processing amount, low power consumption, fast formation and being suitable for industrial production.
Description
Technical field
The present invention relates to a kind of Preparation of catalysts method, relate in particular to the preparation method of the synthetic hydrocarbon catalyst of a kind of synthesis gas.
Background technology
The synthetic hydrocarbon of synthesis gas is the indirect liquefaction of coal, is meant synthesis gas (CO+H
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 " TheFischer-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.
U.S. Mobil company discloses a kind of method that adopts the Fe-Cu-K fischer-tropsch synthetic catalyst of the low nitrogen content of continuous coprecipitation preparation in U.S. Pat P4617288, be specially: the ammonia spirit of the ferric nitrate of metered proportions and copper nitrate mixed solution and debita spissitudo is maintained the temperature at 80～90 ℃ with what pump squeezed into that a band stirs with water vapour, pH is at 6.6～6.8 head tank, the precipitation slurries import a subsider continuously, suction filtration, spend deionised water to there not being nitrate anion, add a certain amount of K again
2CO
3Solution, making beating, oven dry, 300 ℃ of roastings make the catalyst that nitrogen content is lower than 100ppm, and this method is fit to industrialization and produces continuously.But the employed cost of material of this method is expensive, causes the cost of catalyst to raise, and is on the high side.
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, need aerating oxygen in solution during dissolving, to reduce carbon monoxide content, the small amount of N O that overflows
2Remove with the absorption of KOH solution.Ammoniacal liquor is added in the nitrate mixed liquor of heat, PH is controlled at 7.4, obtains the precipitation slurries, then with the high-quality water washing of no chlorine to there not being ammonium nitrate, add solution of potassium carbonate subsequently, making beating, the weight percentage of catalyst in slurries is about 8～12%, use spray-drying then, remove most of moisture, obtaining rough is spherical catalyst granules, and diameter range is 5～50 μ m, last catalyst is heated to about 315 ℃ and removes residual moisture in air, make catalyst stabilising.It is too high that but this method yet exists cost, the defective that price is high.
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 iron 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.It is less and be continuous distributed that this preparation method makes the particle of catalyst, is unfavorable for starching separating of attitude bed reacting middle catalyst and wax.
U.S. Rentech company discloses a kind of preparation method of Fischer-Tropsch synthetic iron-based catalyst in U.S. Pat P5504118 and Chinese invention patent CN1113905, 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 rough is spherical catalyst granules, diameter range is 5～50 μ m, makes catalyst stabilising 315 ℃ of roastings at last, and is used for the syrup state bed Fischer Tropsch synthetic reaction.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., disclose a kind of Fe/Cu/K/SiO in 1990,29,1588～1599
2The Preparation of catalysts method is specially: add ammonia spirit and carry out continuous co-precipitation in ferric nitrate and copper nitrate mixed solution, washing and 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., will fill a prescription in 1999,38,3270～3275 is 100Fe/3Cu/4K/16SiO
2(weight meter) catalyst 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.
Summary of the invention
It is low that the technical issues that need to address of the present invention provide a kind of cost, and technology is simple and be applicable to the synthesis gas Synthin Preparation of catalysts method of industrial mass production.
Method of the present invention comprises the steps:
The mixed solution that the precipitating reagent sodium carbonate liquor is added ferric nitrate and copper nitrate, washing and filtering, obtain the co-precipitation filter cake of iron content copper, the potassium silicate and the silica aqueous solution are added the co-precipitation filter cake, making beating mixes, and makes catalyst pulp, dry, roasting, promptly obtain catalyst of the present invention, its weight ratio consists of: Fe: Cu: K: SiO
2=100: 1～8: 1～10: 6～25;
The molar concentration of the mixed solution of ferric nitrate and copper nitrate is 2～5mol/L, and wherein: the weight ratio of Fe and Cu is 100: 1～8, be preferably 100: 2～and 6;
Said precipitating reagent is selected from a kind of or its mixture that comprises in sodium carbonate, sodium acid carbonate or the NaOH, preferably adopting weight concentration is 10～25% sodium carbonate, sodium acid carbonate or sodium hydroxide solution, in the gross weight of iron and copper, the precipitating reagent addition is 100～105%;
In the gross weight of iron, the addition of potassium silicate is pressed Fe: K=100: 1～10, be preferably 100: 2～and 8;
In the gross weight of iron, the addition of silica solution is pressed Fe: SiO
2=100: 6～25, be preferably 100: 8～25;
Baking temperature is 100～130 ℃, is preferably 110 ℃;
Sintering temperature is 350～450 ℃, is preferably 400～450 ℃; Roasting time is 2～6 hours, is preferably 4 hours.
The analysis test method that the present invention is used:
1. the specific area of iron catalyst and pore volume are measured: adopt the disclosed low-temperature nitrogen adsorption methods of document such as old lock will, specific area is the BET specific area.
2. being determined in the fixed bed of the reactivity worth of catalyst carried out.
The present invention compared with prior art has following advantage:
(1) feature of the present invention is the wet iron content copper precipitation slurry that obtains, and direct disposable adding potassium silicate water glass solution has been simplified technological process, can further reduce the Catalyst Production cost effectively.
(2) the preparation force method of the synthetic hydrocarbon catalyst of synthesis gas provided by the present invention has that treating capacity is big, energy consumption is low, shaping of catalyst is rapid, is suitable for characteristic such as industrial continuous large-scale production.
Description of drawings
Fig. 1 is test period and C5+ yield relation.
Fig. 2 is test period and CO+H
2The conversion ratio relation.
The specific embodiment
Embodiment 1
Taking by weighing the 300g ferric nitrate is dissolved in the 1.5L deionized water, 4.72g copper nitrate is dissolved in the 20mL deionized water, both mix, pour in the 3L beaker, take by weighing the 120g natrium carbonicum calcinatum then and be dissolved in the 1160mL deionized water, both are put into water-bath make it to be heated to 85 ℃, and insulation is at 85 ℃, both are mixed, and high degree of agitation makes it to mix, be reflected at finish in several minutes after, with the gained solution left standstill, make precipitate aging, sediment is a rufous, leave standstill several hours after, carry out suction filtration and washing, suction filtration twice is with alkali and other soluble substance flush awaies; Take by weighing the 4.1g potassium silicate again and be dissolved in the 20mL deionized water, mix, take by weighing 4.75g left and right sides SiO again
2, pour both the filter cake of suction filtration gained into, add the making beating of 500mL deionized water again, stir; The gained slurry is a rufous, and the gained slurry evenly is laid in the pallet, puts into baking oven, forced air drying is 12 hours under 110 ℃ of conditions, pours the gained catalyst precursor into the 50mL crucible after the oven dry, puts into Muffle furnace, 430 ℃ of following roastings 5 hours, obtain 65g left and right sides catalyst.The proportioning of this catalyst activity component is: Fe:Cu:K:SiO
2=100:3:4:16, its leading indicator sees attached list 1.
Embodiment 2
Taking by weighing the 220g ferric nitrate is dissolved in the 1080mL deionized water, 2.31g copper nitrate is dissolved in the 20mL deionized water, both mix, pour in the 3L beaker, taking by weighing 100g NaOH then is dissolved in the 850mL deionized water, both are put into water-bath make it to be heated to 85 ℃, and insulation makes both mix at 85 ℃ then, and high degree of agitation makes it to mix, carry out coprecipitation reaction,, make precipitate aging the gained solution left standstill, sediment is a rufous, after leaving standstill several hours, carry out suction filtration and washing, with alkali and other soluble substance flush awaies; Take by weighing 2.g left and right sides potassium silicate again and 0.46g potash is dissolved in the 20mL deionized water, mix, pour the filter cake of suction filtration gained into, add the making beating of 200mL deionized water again, stir; The gained slurry is a rufous, and the gained slurry evenly is laid in the pallet, puts into baking oven, forced air drying is 12 hours under 110 ℃ of conditions, pours the gained catalyst precursor into the 50mL crucible after the oven dry, puts into Muffle furnace, 450 ℃ of following roastings 2 hours, obtain 50g left and right sides catalyst.
The proportioning of this catalyst activity component is: Fe:Cu:K:SiO
2=100:4:5:5,
Its leading indicator sees attached list 1.
Embodiment 3
Taking by weighing the 110g ferric nitrate is dissolved in the 540L deionized water, 1.52g copper nitrate is dissolved in the 20mL deionized water, both mix, pour in the 3L beaker, taking by weighing the 90g sodium acid carbonate then is dissolved in the 540mL deionized water, both are put into water-bath make it to be heated to 85 ℃, and insulation both are mixed, and high degree of agitation makes it to mix at 85 ℃, with the gained solution left standstill, make precipitate aging, sediment is a rufous, leave standstill two hours after, carry out suction filtration and washing, with alkali and other soluble substance flush awaies; Take by weighing 2.0g left and right sides potassium silicate again and be dissolved in the 20mL deionized water, mix, pour the filter cake of suction filtration gained into, add the making beating of 100mL deionized water again, stir; The gained slurry is a rufous, and the gained slurry evenly is laid in the pallet, puts into baking oven, forced air drying is 12 hours under 110 ℃ of conditions, pours the gained catalyst precursor into the 50mL crucible after the oven dry, puts into Muffle furnace, 400 ℃ of following roastings 6 hours, obtain 24g left and right sides catalyst.The proportioning of this catalyst activity component is: Fe:Cu:K:SiO
2=100:4:5:6, its leading indicator sees attached list 1.
Embodiment 4
Taking by weighing the 220g ferric nitrate is dissolved in the 1080L deionized water, 3.46g copper nitrate is dissolved in the 20mL deionized water, both mix, pour in the 3L beaker, taking by weighing the 90g natrium carbonicum calcinatum then is dissolved in the 850mL deionized water, both are put into water-bath make it to be heated to 85 ℃, and insulation both are mixed, and high degree of agitation makes it to mix at 85 ℃, with the gained solution left standstill, make precipitate aging, sediment is a rufous, leave standstill several hours after, carry out suction filtration and washing, with alkali and other soluble substance flush awaies; Take by weighing 6g left and right sides potassium silicate again and be dissolved in the 20mL deionized water, mix, pour the filter cake of suction filtration gained into, add the making beating of 200mL deionized water again, stir; The gained slurry is a rufous, and the gained slurry evenly is laid in the pallet, puts into baking oven, forced air drying is 12 hours under 110 ℃ of conditions, pours the gained catalyst precursor into the 50mL crucible after the oven dry, puts into Muffle furnace, 450 ℃ of following roastings 3 hours, obtain 45g left and right sides catalyst.The proportioning of this catalyst activity component is: Fe:Cu:K:SiO
2=100:3:8:10, its leading indicator sees attached list 1.
The described catalyst of subordinate list 1 embodiment gets performance indications
Adopt the catalyst of embodiment 2 in fixed bed, to test reaction condition: 280 ℃, 2.6MPa, 500h
-1, H
2/ CO charge ratio=2/3.Test period and C
5 +The yield relation is seen Fig. 1, test period and CO+H
2The conversion ratio relation is seen Fig. 2, and the weight percentage of each component (wt%) sees Table 2 in the hydrocarbon product.
Result of the test shows: it is high that this catalyst has stability, active good characteristics, and also the yield of its product reached higher level, compares with other catalyst, all can maintain an equal level or exceed.
The weight percentage of each component (wt%) in table 2 hydrocarbon product
Claims (3)
1. the preparation method of the synthetic hydrocarbon catalyst of a synthesis gas, it is characterized in that comprising the steps: precipitating reagent is added the mixed solution of ferric nitrate and copper nitrate, washing and filtering, obtain the co-precipitation filter cake of iron content copper, potassium silicate and silica suspension are added the co-precipitation filter cake, making beating, make catalyst pulp, dry, roasting, baking temperature is 100～130 ℃, and sintering temperature is 400 ℃-450 ℃, and roasting time is 2～6 hours, promptly obtain catalyst, its weight ratio consists of: Fe: Cu: K: SiO
2=100: 1～8: 1～10: 6～25;
Said precipitating reagent is selected from a kind of or its mixture in sodium carbonate, sodium acid carbonate or the NaOH;
In the gross weight of iron and copper, the precipitating reagent addition is 100～105%;
In the gross weight of iron, the addition of potassium silicate is Fe: K=100:1～10.
2. method according to claim 1 is characterized in that, the molar concentration of the mixed solution of ferric nitrate and copper nitrate is 2～5mol/L, and wherein: the weight ratio of Fe and Cu is 100: 1～8.
3. method according to claim 1 is characterized in that, precipitating reagent employing weight concentration is 10～25% sodium carbonate, sodium acid carbonate or sodium hydroxide solution.
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| CN100460066C true CN100460066C (en) | 2009-02-11 |
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| US10086365B2 (en) * | 2007-08-30 | 2018-10-02 | Res Usa, Llc | Strengthened iron catalyst for slurry reactors |
| CN102309967B (en) * | 2011-06-10 | 2013-06-05 | 浙江工业大学 | Catalyst for hydrocarbon synthesis by CO2 catalytic hydrogenation and preparation method thereof |
| CN108654654B (en) * | 2017-04-01 | 2021-09-03 | 国家能源投资集团有限责任公司 | Precipitated iron Fischer-Tropsch catalyst and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1395993A (en) * | 2001-07-12 | 2003-02-12 | 中国科学院山西煤炭化学研究所 | Fe-base catalyst for Fischer-Tropsch syuthesis and its preparing process |
| US20030158272A1 (en) * | 2002-02-19 | 2003-08-21 | Davis Burtron H. | Process for the production of highly branched Fischer-Tropsch products and potassium promoted iron catalyst |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1395993A (en) * | 2001-07-12 | 2003-02-12 | 中国科学院山西煤炭化学研究所 | Fe-base catalyst for Fischer-Tropsch syuthesis and its preparing process |
| US20030158272A1 (en) * | 2002-02-19 | 2003-08-21 | Davis Burtron H. | Process for the production of highly branched Fischer-Tropsch products and potassium promoted iron catalyst |
Non-Patent Citations (6)
| Title |
|---|
| Study on a new iron catalyst forslurryFischer-Tropschsynthesis. B Wu, L Tian, L Bai, et al.Catalysis Communications,Vol.5 No.5. 2004 |
| Study on a new iron catalyst forslurryFischer-Tropschsynthesis. B Wu, L Tian, L Bai, et al.Catalysis Communications,Vol.5 No.5. 2004 * |
| 廉价铁基催化剂F-T合成反应性能初探. 田磊，吴宝山，杨勇等.燃料化学学报，第31卷第1期. 2003 |
| 廉价铁基催化剂F-T合成反应性能初探. 田磊，吴宝山，杨勇等.燃料化学学报，第31卷第1期. 2003 * |
| 用于浆态床FT合成的Fe-Cu-K-Si催化剂的初步考察. 赵玉龙，苏晓丽，毕继诚，张荣.燃料化学学报，第30卷第4期. 2002 |
| 用于浆态床FT合成的Fe-Cu-K-Si催化剂的初步考察. 赵玉龙，苏晓丽，毕继诚，张荣.燃料化学学报，第30卷第4期. 2002 * |
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