CN1398951A - Co/TiO2 catalyst for Fischer-Tropsch synthesis of heavy hydrocarbon and its prepn - Google Patents
Co/TiO2 catalyst for Fischer-Tropsch synthesis of heavy hydrocarbon and its prepn Download PDFInfo
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- CN1398951A CN1398951A CN 02126614 CN02126614A CN1398951A CN 1398951 A CN1398951 A CN 1398951A CN 02126614 CN02126614 CN 02126614 CN 02126614 A CN02126614 A CN 02126614A CN 1398951 A CN1398951 A CN 1398951A
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Abstract
A Co/TiO2 catalyst for Fischer-Tropsch synthesis of heavy hydrocarbon consists of: Co 8-15 wt% and carrier 85-92 wt% and the carrier comprises ZrO2 and TiO2 in the weight ratio of 0-10 to 100. The present invention also provides the carrier crystal phase controlling method for preparing the Fischer-Tropsch syinthesis catalyst with low cost and high performance.
Description
Affiliated field:
The invention belongs to a kind of fischer-tropsch synthetic catalyst and preparation method, relate in particular to a kind of Co/TiO that is used for Fischer-Tropsch synthesis of heavy hydrocarbon
2Catalyzer and preparation method
Background technology:
The technology (fischer-tropsch is synthetic) that Sweet natural gas, coal-seam gas is converted into power fuel and high quality chemical product under the effect of catalyzer is the emphasis of present international C-1 chemistry research.Based on fischer-tropsch synthetic reaction mechanism as can be known CO hydrogenation process be an oligomerisation dynamic process, distribution of reaction products not only is subjected to reaction conditions, but also is subjected to catalysts influence.Cobalt-base catalyst is owing to have advantages of high catalytic activity, C
5 +Selectivity, low water-gas shift activity become the most promising class Fischer-Tropsch catalyst.Yet because cobalt catalyst expensive with respect to iron catalyst makes the application of cobalt catalyst be subjected to certain restriction, so the development of load type cobalt-base catalyst and exploitation become fischer-tropsch synthetic research emphasis.Some large-scale International Petroleum Companys have been developed Co/SiO in succession
2, Co/TiO
2, Co/Al
2O
3Deng catalyst system.Because gas making expense portion is the highest in the synthetic oil technology, and the synthetic gas of new gas making technology production contains the N of a great deal of
2, in the case, adopting the one way high conversion, tail gas not round-robin operating method will strengthen the economy of process significantly.But, the common catalytic activity of existing catalyzer, C
5 +Selectivity is lower, is difficult to satisfy processing requirement, thereby is necessary to develop optionally new catalyst of high reactivity, high heavy hydrocarbon.
Co/TiO
2Catalyzer is existing many in the patent documentation of Exxon company.Mostly general patent documentation is at TiO
2The inorganic oxide caking agent is added on the low surface of carrier targetedly, improves the charge capacity of cobalt metal, thereby improves the reactivity worth of catalyzer; Or add auxiliary agent and second metal component disperses and reducing property to improve catalyzer, for the Co/TiO of the adding noble metal of having reported
2Catalyzer has improved the reactive behavior and the C of catalyzer significantly
5 +Selectivity.For example in United States Patent (USP) 275252, propose at Co (12%)/TiO
2The CO transformation efficiency is increased to 85% by 67% behind the Re of (rutile 53%) catalyzer adding 0.5%.Yet, make the exploitation of this type of catalyzer and application all be subjected to certain restriction because the introducing of heavy metal auxiliary agent will cause the cost increase of catalyzer.United States Patent (USP) 4568663 utilizes the P-25 roasting preparation of Deguss company to contain the titania support of rutile in addition, finds for Co (12%)/TiO
2Rutile content is 53% o'clock in the support of the catalyst, and the CO transformation efficiency only has 67%, and rutile content is 100% o'clock, and the CO transformation efficiency is 79%.The crystalline phase that shows titania support has decisive action for the reactivity worth of controlling cobalt-base catalyst, and the carrier that therefore prepares high-rutile content just becomes the emphasis of this type of catalyst research.Yet mostly the preparation about support of the catalyst on the document is to obtain the preparation cost height from commercial P-25 roasting.
Summary of the invention:
The purpose of this invention is to provide the low Co/TiO that is used for Fischer-Tropsch synthesis of heavy hydrocarbon of a kind of cost
2Catalyzer and preparation method
The present invention adopts anion surfactant or neutral organic polymer as template, and utilizes sol-gel method to prepare titania support; Or to adopt tetravalent salt of titanium be TiO 2 precursor, prepares the titanium oxide of high-rutile content as precipitation agent with alkali.Catalyzer adopts the preparation of equal-volume wet impregnation, utilizes pure hydrogen in-situ reducing afterwards.
Catalyst weight per-cent of the present invention consists of:
Co:8-15wt% carrier: 85-92wt%
Described carrier is that weight ratio is ZrO
2: TiO
2=0-10: 100 material is preparation method one of the present invention comprise the steps:
(1) Ti (OH)
4The preparation of colloidal sol
Tensio-active agent, tetrabutyl titanate, ethanol are mixed with solution A, and weight ratio is 1: (8-20): (1: 10) is formulated as solution B with water and ethanol, and its weight ratio is 1: (2-4) Ti in above-mentioned two kinds of solution
4+: H
2The mol ratio of O is strict controlled in mixes at 1: 4, and reaction generates precipitation under the 283-373K temperature, and aging 12-150h obtains Ti (OH) under the 293-403K temperature
4Colloidal sol;
(2) preparing carriers
Press ZrO
2: TiO
2Weight proportion is 0-10: 100 are dissolved in above-mentioned Ti (OH) with zirconium nitrate
4Colloidal sol in, after the 373-403K drying,, make carrier then at 773-1173K roasting 2-8h;
(3) Preparation of Catalyst
Compound concentration is the cobalt nitrate solution of 0.14-0.25M, presses the Co:8-15wt% carrier: 85-92wt% equal-volume wet method, flood above-mentioned carrier with cobalt nitrate solution.Catalyzer is after the 393-403K drying, in 573-873K roasting 6-10h.
Preparation method two of the present invention comprises the steps
(1) Ti (OH)
4The preparation of colloidal sol.
Under vigorous stirring, the 0.1-10M alkaline solution is added dropwise to 0.1-10M TiCl
4In the solution, in the 293-333K temperature, pH generates precipitation under the condition of 1-7;
(2) preparation of carrier
Press ZrO
2: TiO
2Weight proportion is 0-10: 100, zirconium nitrate is dissolved in above-mentioned Ti (OH)
4Colloidal sol in, then after the 373-403K drying, at 773-1173K roasting 2-6h;
(3) Preparation of Catalyst
Compound concentration is the cobalt nitrate solution of 0.14-0.25M, presses the Co:8-15wt% carrier: 85-92wt% equal-volume wet method, flood above-mentioned carrier with cobalt nitrate solution.Catalyzer is after the 393-403K drying, in 573-873K roasting 6-10h.
Aforesaid alkali is ammoniacal liquor, yellow soda ash, salt of wormwood.Catalyzer application conditions of the present invention is: temperature of reaction 483-523K, reaction pressure 1-5MPa, air speed 300-200h
-1, unstripped gas proportioning H
2/ CO=1: 10-10: 1.The present invention compared with prior art has following advantage;
1. cost low 2. provides the method for control carrier crystalline phase.3. prepared a kind of high-performance fischer-tropsch synthetic catalyst.
Embodiment:
Embodiment 1:
Taking by weighing 34g tetrabutyl titanate (TBOT) pours into and is dissolved with 3g C
12H
30(EO)
30-50g ethanol (ETOH) solution stirs 1h under the room temperature, is dropwise adding 7.2g water-16g ethanolic soln.Obtain mixing solutions and consist of TBOT: C
12H
30(EO)
30: H
2O: EtOH=1: 0.02: 4: 15.The at room temperature static 72h of this mixing solutions filters, and dries by the fire 12h under 393K in baking oven, and roasting 6h under 923K promptly makes required titania support.With 2.15g Cobaltous nitrate hexahydrate incipient impregnation 5g titania support, leave standstill 24h, 393K is dried, and promptly makes the Co/TiO of 8wt% in 673K roasting 6h
2Catalyzer.At temperature of reaction 490K, pressure 2MPa, air speed 500h
-1, H
2/ CO=2 conditioned response the results are shown in table 1 embodiment 2:
Take by weighing 34g tetrabutyl titanate (TBOT) and pour into and be dissolved with 0.55g cetyl trimethylammonium bromide-50g ethanolic soln, stir 1h under the room temperature, dropwise adding 7.2g water-16g ethanolic soln.Obtain mixing solutions and consist of TBOT: C
19H
42BrN: H
2O: EtOH=1: 0.02: 4: 15.The at room temperature static 72h of this mixing solutions filters, under 393K in baking oven dry 12h, at 923K roasting 6h, promptly make required titania support.With 2.74g Cobaltous nitrate hexahydrate incipient impregnation 5g titania support, leave standstill 24h, 393K is dried, and promptly makes the Co/TiO of 10wt% in 673K roasting 6h
2Catalyzer.Reaction conditions is with embodiment 1.
Embodiment 3:
Taking by weighing 34g tetrabutyl titanate (TBOT) pours into and is dissolved with 3g C
12H
30(EO)
30Stir 1h under the-50g ethanolic soln, room temperature, dropwise add 7.2g water-16g ethanolic soln again.Obtain mixing solutions and consist of TBOT: C
12H
30(EO)
30: H
2O: EtOH=1: 0.02: 4: 15.The at room temperature static 72h of this mixing solutions filters the back with 2.1g zirconium nitrate solution dipping, dries by the fire 12h in the 393K baking oven, at 923K roasting 6h, promptly makes required zirconium and oozes assorted titania support 5%ZrO
2/ TiO
2Cobaltous nitrate hexahydrate incipient impregnation 5gZrO with 3.37g
2/ TiO
2Carrier leaves standstill 24h, in the 393K oven dry, promptly makes the Co/ZrO of 12wt% in 673K roasting 6h
2/ TiO
2Catalyzer.Reaction conditions is with embodiment 1.
Embodiment 4:
Taking by weighing 34g tetrabutyl titanate (TBOT) pours into and is dissolved with 3gC
12H
30(EO)
30Stir 1h under the-50g ethanolic soln, room temperature, dropwise adding 7.2g water-16g ethanolic soln.Obtain mixing solutions and consist of TBOT: C
12H
30(EO)
30: H
2O: EtOH=1: 0.02: 4: 15.The at room temperature static 72h of this mixing solutions filters, and dries by the fire 12h under 393K in baking oven, at 923K roasting 6h, promptly makes required titania support.With 4.36g.2M Cobaltous nitrate hexahydrate incipient impregnation 5g titania support leaves standstill 24h, and 393K is dried, and promptly makes the Co/TiO of 15wt% in 673K roasting 6h
2Catalyzer.Reaction conditions together
Embodiment 1.
Embodiment 5:
Adopt sol-gel method to prepare full rutile TiO
2Carrier.Take by weighing 34g tetrabutyl titanate (TBOT) and pour into and be dissolved in the 50g ethanol, stir 1h under the room temperature, dropwise adding 7.2g water-16g ethanolic soln.Obtain mixing solutions and consist of TBOT: H
2O: EtOH=1: 4: 15.The at room temperature static 72h of this mixing solutions filters, and dries by the fire 12h under 393K in baking oven, takes out 923K roasting 6h in muffle furnace, promptly makes required titania support.4.36g Cobaltous nitrate hexahydrate incipient impregnation 5g titania support with preparing leaves standstill 24h, in the 393K oven dry, promptly makes the Co/TiO of 15wt% in 673K roasting 6h
2Catalyzer.Reaction conditions is with embodiment 1.
Embodiment 6:
Adopt coprecipitation method to prepare full rutile TiO
2Carrier.Measure 40mlTiCl
4Pour in the distilled water of 273K, stir 1h under the room temperature, 25% the ammonia soln for preparing is added dropwise to TiCl
4In the aqueous solution, the pH of final solution is controlled at 1.The at room temperature static 24h of this mixing solutions filters, and dries by the fire 12h under 393K in baking oven, and taking-up 923K roasting 6h in muffle furnace promptly makes required titania support.Cobaltous nitrate hexahydrate (4.36g) incipient impregnation titania support (5g) with preparing leaves standstill 24h, and 393K is dried, and promptly makes the Co/TiO of 15wt% in 673K roasting 6h
2Catalyzer.Reaction conditions is with embodiment 1.
Table 1 Co/TiO
2The reaction result of catalyzer
Temperature inversion rate products distribution catalyzer
(℃) (％) C
1 C
2-4 C
5 +
220 78.8 9.2 6.0 84.8
Embodiment 1
230 92.8 8.8 5.3 85.9
220 82.3 10.4 7.3 82.3
Embodiment 2
230 91.1 11.6 7.9 80.5
220 47.8 17.2 12.5 70.3
Embodiment 3
230 69.1 18.8 12.9 68.3
220 71.6 13.2 10.1 76.7
Embodiment 4
230 88.2 11.8 9.1 79.1
220 48.1 11.1 11.1 77.8
Embodiment 5
230 70.5 12.4 12.2 75.4
220 80.5 7.7 7.8 84.5
Embodiment 6
230 94.2 13.4 16.1 70.5
Claims (4)
1. Co/TiO who is used for Fischer-Tropsch synthesis of heavy hydrocarbon
2Catalyzer is characterized in that catalyst weight per-cent consists of:
Co:8-15wt% carrier: 85-92wt%
Described carrier is that weight ratio is ZrO
2: TiO
2=0-10: 100 material
2. a kind of Co/TiO that is used for Fischer-Tropsch synthesis of heavy hydrocarbon as claimed in claim 1
2Method for preparing catalyst is characterized in that comprising the steps:
(1) Ti (OH)
4The preparation of colloidal sol
With tensio-active agent, tetrabutyl titanate, ethanol is 1 by weight ratio: 8-12: 1-10 is mixed with solution A, and be 1 by weight ratio with water and ethanol: 2-4 is mixed with solution B, and solution A and solution B are pressed Ti in the solution
4+: the mol ratio of water is
1: 4Mix, reaction generates precipitation under the 283-373K temperature, and aging 12-150h obtains Ti (OH) under the 293-403K temperature
4Colloidal sol;
(2) preparing carriers
Press ZrO
2: TiO
2Weight proportion is 0-10: 100 are dissolved in above-mentioned Ti (OH) with zirconium nitrate
4
Colloidal sol in, then after the 373-403K drying, at 773-1173K roasting 2-8h,
Make carrier;
(3) Preparation of Catalyst
Compound concentration is the cobalt nitrate solution of 0.14-0.25M, presses the Co:8-15wt% carrier: 85-92wt% equal-volume wet method, flood above-mentioned carrier with cobalt nitrate solution.Catalyzer is after the 393-403K drying, in 573-873K roasting 6-10h.
3. a kind of Co/TiO that is used for Fischer-Tropsch synthesis of heavy hydrocarbon as claimed in claim 1
2Method for preparing catalyst is characterized in that comprising the steps:
(1) Ti (OH)
4The preparation of colloidal sol.
Under vigorous stirring, the 0.1-10M alkaline solution is added dropwise to 0.1-10M TiCl
4In the solution, in the 293-333K temperature, pH generates precipitation under the condition of 1-7;
(2) preparation of carrier
Press ZrO
2: TiO
2Weight proportion is 0-10: 100, zirconium nitrate is dissolved in above-mentioned Ti (OH)
4Colloidal sol in, then after the 373-403K drying, at 773-1173K roasting 2-6h;
(3) Preparation of Catalyst
Compound concentration is the cobalt nitrate solution of 0.14-0.25M, presses the Co:8-15wt% carrier: 85-92wt% equal-volume wet method, flood above-mentioned carrier with cobalt nitrate solution.Catalyzer is after the 393-403K drying, in 573-873K roasting 6-10h.
4. a kind of Co/TiO that is used for Fischer-Tropsch synthesis of heavy hydrocarbon as claimed in claim 3
2Method for preparing catalyst is characterized in that aforesaid alkali is ammoniacal liquor, yellow soda ash, salt of wormwood.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02126614 CN1198682C (en) | 2002-07-19 | 2002-07-19 | Co/TiO2 catalyst for Fischer-Tropsch synthesis of heavy hydrocarbon and its prepn |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02126614 CN1198682C (en) | 2002-07-19 | 2002-07-19 | Co/TiO2 catalyst for Fischer-Tropsch synthesis of heavy hydrocarbon and its prepn |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1398951A true CN1398951A (en) | 2003-02-26 |
| CN1198682C CN1198682C (en) | 2005-04-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02126614 Expired - Lifetime CN1198682C (en) | 2002-07-19 | 2002-07-19 | Co/TiO2 catalyst for Fischer-Tropsch synthesis of heavy hydrocarbon and its prepn |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101134164B (en) * | 2006-08-31 | 2010-12-22 | 中国石油化工股份有限公司 | Co-based fischer-tropsch synthesis catalyst and method for preparing the same |
| CN105597772A (en) * | 2014-11-04 | 2016-05-25 | 中国科学院上海高等研究院 | Cobalt-based catalyst having core-shell structure, and preparation method thereof |
| CN107854999A (en) * | 2017-11-23 | 2018-03-30 | 成都新柯力化工科技有限公司 | A kind of catalysis fibre material and preparation method for purification of air |
| CN109289864A (en) * | 2018-09-29 | 2019-02-01 | 中国科学院上海高等研究院 | A kind of high-performance cobalt-base catalyst and its preparation method and application |
| WO2023060707A1 (en) * | 2021-10-11 | 2023-04-20 | 国家能源投资集团有限责任公司 | Fischer-tropsch synthesis catalyst, preparation method therefor, and application thereof |
-
2002
- 2002-07-19 CN CN 02126614 patent/CN1198682C/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101134164B (en) * | 2006-08-31 | 2010-12-22 | 中国石油化工股份有限公司 | Co-based fischer-tropsch synthesis catalyst and method for preparing the same |
| CN105597772A (en) * | 2014-11-04 | 2016-05-25 | 中国科学院上海高等研究院 | Cobalt-based catalyst having core-shell structure, and preparation method thereof |
| CN107854999A (en) * | 2017-11-23 | 2018-03-30 | 成都新柯力化工科技有限公司 | A kind of catalysis fibre material and preparation method for purification of air |
| CN109289864A (en) * | 2018-09-29 | 2019-02-01 | 中国科学院上海高等研究院 | A kind of high-performance cobalt-base catalyst and its preparation method and application |
| CN109289864B (en) * | 2018-09-29 | 2022-08-30 | 中国科学院上海高等研究院 | High-performance cobalt-based catalyst and preparation method and application thereof |
| WO2023060707A1 (en) * | 2021-10-11 | 2023-04-20 | 国家能源投资集团有限责任公司 | Fischer-tropsch synthesis catalyst, preparation method therefor, and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1198682C (en) | 2005-04-27 |
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Granted publication date: 20050427 |