CN1586715A - Preparation and use of samarium oxide catalyst - Google Patents
Preparation and use of samarium oxide catalyst Download PDFInfo
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- CN1586715A CN1586715A CN 200410062736 CN200410062736A CN1586715A CN 1586715 A CN1586715 A CN 1586715A CN 200410062736 CN200410062736 CN 200410062736 CN 200410062736 A CN200410062736 A CN 200410062736A CN 1586715 A CN1586715 A CN 1586715A
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- oxide catalyst
- samarium oxide
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Abstract
The present invention belongs to the field of catalyst preparation in chemical technology. The samarium nitrate or samarium chloride is prepared into the samarium oxide catalyst through the steps of dissolving in deionized water, dropping into ammonia water solution as precipitant, ageing, washing, drying and roasting to obtain the samarium oxide catalyst of Sm2O3-B, Sm2O3-C, Sm2O3-D, Sm2O3-B*, Sm2O3-D* or Sm2O3-E*. The catalyst is used in the isomerized synthesis with mixed CO and H2 material under heating and pressurized condition in a fixed bed reactor to obtain isomerized C4 hydrocarbon product. It has CO converting rate of 3-8 %, isomerized C4 hydrocarbon mixture gas selectivity of 42-69 %, the ratio between the C4 hydrocarbon to isomerized C4 hydrocarbon mixture gas of 35-77 %, and the ratio of isobutylene and isobutane to isomerized C4 hydrocarbon of 44-100 %.
Description
Technical field
The invention belongs to catalyst preparation field in the Chemical Engineering Technology, particularly a kind of preparation of samarium oxide catalyst and application.
Background technology
Isobutene and iso-butane are important Organic Chemicals.Can prepare chemical products such as isobutanol, methyl tertiary butyl ether(MTBE), methacrylic acid, tert-butylamine, di-tert-butylphenol, tert-butyl mercaptan, methacrylonitrile from isobutene, wherein isobutanol still is the gasoline additive of function admirable.Isobutene oligomerisation obtains the isooctene repeated hydrogenation can obtain isooctane, and isooctane can improve the octane number of gasoline as gasoline additive.Dehydrogenation of isobutane can make isobutene.Current, isobutene mainly obtains from the C-4-fraction of naphtha steam cracking process of producing ethylene and catalytic cracking process by-product.The strong growth of the market demand makes isobutene, and supply falls short of demand, and petroleum reserves is limited, makes the supply of isobutene face immense pressure.China is the country of primary energy based on coal, through the synthesis gas preparation isobutene, is a technology path that the supply that overcomes isobutene relies on petroleum resources from coal or natural gas.
With synthesis gas (mixed air of carbon monoxide, hydrogen) is raw material, through catalytic reaction, can obtain hydrocarbon compounds such as isobutene and iso-butane and (abbreviate isomery C as
4Hydrocarbon).It is synthetic that this course of reaction is also referred to as isomery.Report in the document " Brennst.Chem., 1949,30:13～22 ": early stage isomery is synthetic to be to carry out under the reaction condition (10～100MPa, 400～450 ℃) in harshness, and the catalyst of use is to have radioactive thorium oxide.Report: La in document " Chem.Soc., Chem.Commun., 1983,763～764 "
2O
3, CeO
2Also can be used as the iso-synthesis catalyst Deng metal oxide, but the reactivity of these catalyst and selectively very low.In document " Chem.Lett.1984,747 ~ 748; J.Catal.1990,109:284～297; J.Catal.1994,145:126 ~ 131 " middle report: ZrO
2Catalyst demonstrates good performance in the isomery synthetic reaction.But isomery C
4The selectivity of hydrocarbon is also not really high.Iso-synthesis can regard that also a kind of directed Fischer-Tropsch is synthetic as.Mostly the synthetic used catalyst of Fischer-Tropsch is metallic catalyst such as Fe, Co etc. (such as Chinese patent CN1395993, CN1398669 and CN1417291), and the used catalyst of iso-synthesis is metal oxide catalyst mostly, such as ZrO
2, La
2O
3, CeO
2In the isomery synthetic catalyst of present bibliographical information, purpose product isomery C
4The selectivity of hydrocarbon is also not really high, and accessory substance CO
2Also many.Invent novel isomery synthetic catalyst, improve isomery C
4The selectivity of hydrocarbon is that the isomery synthetic technology is moved towards one of key of practical application.
Summary of the invention
The purpose of this invention is to provide a kind of preparation and application of samarium oxide catalyst; It is characterized in that: described preparation samarium oxide catalyst is with samaric nitrate (Sm (NO
3)
36H
2O) or samarium trichloride (SmCl
36H
2O) be raw material, be dissolved in deionized water, being mixed with concentration is the 0.1-0.3mol/L aqueous solution, is added drop-wise in 10% (volume ratio) aqueous solution of 20-30wt% concentration ammoniacal liquor, and ageing 2-3h makes Sm (OH)
3Hydrogel.Obtain filter cake with the abundant agitator treating of ionized water, suction filtration then, with filter cake at 110 ℃ of lower air or N
2Dry 5-24h in the gas atmosphere, dried sample is at 500-600 ℃ of lower Muffle furnace Air or N
2Roasting 3-8h in the gas atmosphere, the samarium oxide catalyst that makes is designated as Sm
2O
3-B, Sm
2O
3-C, Sm
2O
3-D, Sm
2O
3-B*, Sm
2O
3-D* or Sm
2O
3-E*.
Described with samarium oxide catalyst prepare isobutene and iso-butane technology be: the mixed air that uses carbon monoxide and hydrogen carries out in the presence of samarium oxide catalyst, on fixed-bed reactor as the synthetic raw material of isomery; Used fixed bed reactors are stainless steel tubes of liner quartz ampoule, unstripped gas is a carbon monoxide: hydrogen=1: 1 (volume ratio) gaseous mixture, filter through 5A molecular sieve and activated carbon are housed purifies earlier before entering reactor, to remove the trace iron carbonyl compound and the moisture that may contain in the unstripped gas; Samarium oxide catalyst is seated in the crystal reaction tube middle part, and reaction procatalyst elder generation is at the N of 400 ℃ of temperature current downflow
2In preliminary treatment 3 hours, then under 350～500 ℃ of reaction temperatures from N
2Switch to the synthetic reaction unstripped gas, the flow that air velocity is controlled at unstripped gas is 12ml/min, and the pressure of synthesis gas is generally 4～6MPa by counterbalance valve and pressure maintaining valve control, carries out the isomery synthetic reaction, obtains containing isomery C at reactor outlet
4Hydrocarbon products; And with the product of gas chromatographic analysis reactor outlet.
The invention has the beneficial effects as follows compared with prior art the samarium oxide (Sm that the present invention makes with different samarium salt raw materials
2O
3) catalyst, manufacture craft is simple, and stable performance is used for heating to depress in the presence of samarium oxide catalyst, in fixed-bed reactor and carrying out with the mixed air of carbon monoxide and the hydrogen isomery synthetic reaction as raw material, obtains isomery C
4Hydrocarbon products; The conversion ratio of its carbon monoxide is 3～8%, isomery C
4The hydrocarbon products selectivity is 42～69%, C
4Hydrocarbon accounts for isomery C
4The ratio of hydrocarbon products is 35～77%, and isobutene and iso-butane account for isomery C
4The ratio of hydrocarbon is 44～100%.
The specific embodiment
The invention provides a kind of preparation and application of samarium oxide catalyst; The above preparation samarium oxide catalyst is with samaric nitrate (Sm (NO
3)
36H
2O) or samarium trichloride (SmCl
36H
2O) be raw material, be dissolved in deionized water, be mixed with the aqueous solution that concentration is 0.1-0.3mol/L, the ammoniacal liquor that is added drop-wise to concentration and is 20-30wt% accounts in the aqueous solution of 10% (volume ratio), and ageing 2-3h makes Sm (OH)
3Hydrogel.Obtain filter cake with the abundant agitator treating of ionized water, suction filtration then, with filter cake at 110 ℃ of lower air or N
2Dry 5-24h in the gas atmosphere, dried sample is at 500-600 ℃ of lower Muffle furnace Air or N
2Roasting 3-8h in the gas atmosphere, the samarium oxide catalyst that makes is designated as Sm
2O
3-B, Sm
2O
3-C, Sm
2O
3-D, Sm
2O
3-B*, Sm
2O
3-D* or Sm
2O
3-E*.
Described application samarium oxide catalyst prepare isobutene and iso-butane technology be: the mixed air that uses carbon monoxide and hydrogen carries out in the presence of samarium oxide catalyst, on fixed-bed reactor as the synthetic raw material of isomery; Used fixed bed reactors are stainless steel tubes of liner quartz ampoule, unstripped gas is a carbon monoxide: hydrogen=1: 1 (volume ratio) gaseous mixture, filter through 5A molecular sieve and activated carbon are housed purifies earlier before entering reactor, to remove the trace iron carbonyl compound and the moisture that may contain in the unstripped gas; Samarium oxide catalyst is seated in the crystal reaction tube middle part, and reaction procatalyst elder generation is at the N of 400 ℃ of temperature current downflow
2In preliminary treatment 3 hours, then under 350～500 ℃ of reaction temperatures from N
2Switch to the synthetic reaction unstripped gas, the flow that air velocity is controlled at unstripped gas is 12ml/min, and the pressure of synthesis gas is generally 4～6MPa by counterbalance valve and pressure maintaining valve control, carries out the isomery synthetic reaction, obtains containing isomery C at reactor outlet
4The gaseous mixture of hydrocarbon; And with the gaseous mixture of gas chromatographic analysis reactor outlet.
Above-mentioned samarium oxide (Sm
2O
3) be prepared as follows:
(1) Sm
2O
3The preparation of-B:
Step 1: take by weighing 22.50gSm (NO
3)
36H
2O is dissolved in the 300ml deionized water, and being mixed with concentration is the Sm (NO of 0.17mol/L
3)
3The aqueous solution; Measure 25wt% ammoniacal liquor 100ml, be diluted to 1000ml as precipitating reagent with deionized water again; Under agitation, with the Sm (NO for preparing
3)
3The aqueous solution is added drop-wise in the precipitating reagent ammoniacal liquor, and after dropwising, ageing 2 hours makes Sm (OH)
3Hydrogel;
Step 2: the Sm (OH) that step 1 is obtained
3Use the normal temperature deionised water behind the hydrogel suction filtration.Add deionized water at normal temperature 2000ml, fully behind the agitator treating, suction filtration adds deionized water at normal temperature 2000ml again, repeats above-mentioned washing step 4 times, with the hydrogel suction filtration, obtains filter cake;
Step 3: filter cake is dry 24h in 110 ℃ of lower air atmospheres, and dried sample is roasting 3h in 550 ℃ of lower Muffle furnace Air atmosphere, and prepared samarium oxide catalyst is denoted as Sm
2O
3-B.
(2) Sm
2O
3The preparation of-C:
Step 1: with Sm
2O
3The preparation process 1 of-B is identical.
Step 2: with Sm
2O
3The preparation process 2 of-B is identical.
Step 3: the gained filter cake washs displacement moisture wherein with 100mL absolute ethyl alcohol (AR), and the ethanol washing repeats 8 times, with Sm (OH)
3The alcogel suction filtration obtains filter cake.
Step 4: the gained filter cake is at the N of 110 ℃ of current downflow
2Dry 5h in the atmosphere, dried sample is at the N of 550 ℃ of current downflow
2Roasting 8h in the atmosphere.Prepared samarium oxide catalyst is denoted as Sm
2O
3-C.
(3) Sm
2O
3The preparation of-D:
Step 1: with Sm
2O
3The preparation process 1 of-C is identical.
Step 2: with Sm
2O
3The preparation process 2 of-C is identical.
Step 3: with Sm
2O
3The preparation process 3 of-C is identical.
Step 4: the gained filter cake is dry 24h in 110 ℃ of following air atmospheres, and dried sample is roasting 3h in 550 ℃ of following air atmospheres.Prepared samarium oxide catalyst is denoted as Sm
2O
3-D.
(4) Sm
2O
3The preparation of-B*:
Preparation process and Sm
2O
3The preparation process of-B is identical, is used samarium raw material salt difference.(use 18.61gSmCl
36H
2O replaces 22.50gSm (NO
3)
36H
2O is configured to the SmCl that concentration is 0.17mol/L
3The aqueous solution.)
(5) Sm
2O
3The preparation of-D*:
Preparation process and Sm
2O
3The preparation process of-D is identical, just uses SmCl
36H
2O replaces Sm (NO
3)
36H
2O is as Sm
2O
3Raw material.
(6) Sm
2O
3The preparation of-E*:
Step 1: take by weighing 18.61gSmCl
36H
2O is dissolved in the 300ml deionized water, is mixed with the SmCl that concentration is 0.17mol/L
3The aqueous solution.Measure 100ml ammoniacal liquor (25wt%), be diluted to 1000ml as precipitating reagent with deionized water.Under agitation, with the SmCl for preparing
3The aqueous solution is added drop-wise in the precipitating reagent ammoniacal liquor, and after dropwising, ageing 2 hours makes Sm (OH)
3Hydrogel.
Step 2: the Sm (OH) that step 1 is obtained
3After the supernatant liquor of hydrogel is outwelled, with the deionized water washing of boiling.Add deionization boiling water 2000ml, fully behind the agitator treating, it is 8-9 that dropping ammonia is regulated pH, leave standstill certain hour after, supernatant liquor is outwelled, add deionization boiling water 2000ml once more, repeat above-mentioned washing step 4 times, with the hydrogel suction filtration, obtain filter cake.
Step 3: filter cake is dry 24h in 110 ℃ of following air atmospheres, dried sample roasting 3h in the air atmosphere in 550 ℃ of following Muffle furnaces.Prepared samarium oxide catalyst is denoted as Sm
2O
3-E*.
Exemplify below above-mentioned samarium oxide catalyst be applied to prepare isobutene and iso-butane concrete technology the present invention is further specified.
Embodiment 1
Use the Sm of said method preparation
2O
3-B is as the iso-synthesis catalyst, and catalyst amount 500mg uses CO/H
2Mixed air (CO: H
2=1: 1) be reactor feed gas, the flow of unstripped gas is 12ml/min, at stagnation pressure 5.0MPa, carries out the iso-synthesis reaction under 425 ℃ of the reaction temperatures.Analytical reactions tail gas, the conversion ratio that obtains carbon monoxide is 4.4%, and the total hydrocarbon product selectivity is 56.0%, and isobutene and iso-butane account for C
4The ratio of hydrocarbon is 85.0%.Analysis result is listed in table 1.
Embodiment 2
Except the Sm that uses the said method preparation
2O
3-C is as outside the catalyst, and other operates with embodiment 1.Analysis result is listed in table 1.
Embodiment 3
Except the Sm that uses the said method preparation
2O
3-D is as outside the catalyst, and other operates with embodiment 1.Analysis result is listed in table 1.
Embodiment 4
Except the Sm that uses the said method preparation
2O
3-B* is as outside the catalyst, and other operates with embodiment 1.Analysis result is listed in table 1.
Embodiment 5
Except the Sm that uses the said method preparation
2O
3-D* is as outside the catalyst, and other operates with embodiment 1.Analysis result is listed in table 1.
Embodiment 6
Except reaction temperature is 450 ℃, other operates with embodiment 5.Analysis result is listed in table 1.
Embodiment 7
Except reaction temperature is 475 ℃, other operates with embodiment 5.Analysis result is listed in table 1.
Embodiment 8
Except reaction temperature is 500 ℃, other operates with embodiment 5.Analysis result is listed in table 1.
Embodiment 9
Except the Sm that uses the said method preparation
2O
3-E* is as outside the catalyst, and other operates with embodiment 1.Analysis result is listed in table 1.
Embodiment 10
Except reaction temperature is 450 ℃, other operates with embodiment 9.Analysis result is listed in table 1.
Embodiment 11
Except reaction temperature is 475 ℃, other operates with embodiment 9.Analysis result is listed in table 1.
Table 1
| Embodiment | Catalyst | Reaction temperature (℃) | Reaction pressure (MPa) | Carbon monoxide conversion ratio (%) | Total hydrocarbon-selective (%) | ??C 4Hydrocarbon accounts for total hydrocarbon ratio (%) | C 4I-C in the hydrocarbon 4The ratio of hydrocarbon (%) |
| Example 1 | ??Sm 2O 3-B | ??425 | ??5.0 | ????4.4 | ????56.0 | ????46.2 | ????85.0 |
| Example 2 | ??Sm 2O 3-C | ??425 | ??5.0 | ????3.7 | ????43.8 | ????46.4 | ????88.6 |
| Example 3 | ??Sm 2O 3-D | ??425 | ??5.0 | ????6.7 | ????59.4 | ????54.2 | ????91.1 |
| Example 4 | ??Sm 2O 3-B* | ??425 | ??5.0 | ????2.8 | ????43.2 | ????43.7 | ????43.7 |
| Example 5 | ??Sm 2O 3-D* | ??425 | ??5.0 | ????4.4 | ????68.7 | ????76.8 | ????65.6 |
| Example 6 | ??Sm 2O 3-D* | ??450 | ??5.0 | ????5.7 | ????46.3 | ????76.1 | ????62.8 |
| Example 7 | ??Sm 2O 3-D* | ??475 | ??5.0 | ????6.6 | ????54.3 | ????68.0 | ????58.9 |
| Example 8 | ??Sm 2O 3-D* | ??500 | ??5.0 | ????8.0 | ????55.4 | ????60.1 | ????57.2 |
| Example 9 | ??Sm 2O 3-E* | ??425 | ??5.0 | ????2.8 | ????43.8 | ????43.7 | ????100 |
| Example 10 | ??Sm 2O 3-E* | ??450 | ??5.0 | ????4.2 | ????49.1 | ????46.4 | ????84.8 |
| Example 11 | ??Sm 2O 3-E* | ??475 | ??5.0 | ????6.8 | ????55.6 | ????34.9 | ????80.3 |
Annotate: total hydrocarbon refers to react the isomery C of generation
4The gaseous mixture of hydrocarbon; I-C
4Hydrocarbon refers to isobutene and iso-butane.
Claims (2)
1. the preparation of a samarium oxide catalyst; It is characterized in that: described preparation samarium oxide catalyst is with samaric nitrate (Sm (NO
3)
36H
2O) or samarium trichloride (SmCl
36H
2O) be raw material, be dissolved in deionized water, be mixed with the aqueous solution that concentration is 0.1-0.3mol/L, the ammoniacal liquor that is added drop-wise to concentration and is 20-30wt% accounts in the aqueous solution of 10% (volume ratio), and ageing 2-3h makes Sm (OH)
3Hydrogel; Obtain filter cake with the abundant agitator treating of ionized water, suction filtration then, with filter cake at 110 ℃ of following air or N
2Dry 5-24h in the gas atmosphere, dried sample is air or N in 500-600 ℃ of following Muffle furnace
2Roasting 3-8h makes samarium oxide catalyst in the gas atmosphere.
2. the application of a samarium oxide catalyst, it is characterized in that: being applied to of described samarium oxide catalyst prepare isobutene and iso-butane technology be: the mixed air that uses carbon monoxide and hydrogen carries out in the presence of samarium oxide catalyst, on fixed-bed reactor as the synthetic raw material of isomery; Used fixed bed reactors are stainless steel tubes of liner quartz ampoule, unstripped gas is a carbon monoxide: hydrogen=1: 1 (volume ratio) gaseous mixture, filter through 5A molecular sieve and activated carbon are housed purifies earlier before entering reactor, to remove the trace iron carbonyl compound and the moisture that may contain in the unstripped gas; Samarium oxide catalyst is seated in the crystal reaction tube middle part, and reaction procatalyst elder generation is at the N of 400 ℃ of temperature current downflow
2In preliminary treatment 3 hours, then under 350～500 ℃ of reaction temperatures from N
2Switch to the synthetic reaction unstripped gas, the flow that air velocity is controlled at unstripped gas is 12ml/min, and the pressure of synthesis gas is generally 4～6MPa by counterbalance valve and pressure maintaining valve control, carries out the isomery synthetic reaction, obtains containing isomery C at reactor outlet
4The gaseous mixture of hydrocarbon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100627368A CN1332751C (en) | 2004-07-08 | 2004-07-08 | Preparation and use of samarium oxide catalyst |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100627368A CN1332751C (en) | 2004-07-08 | 2004-07-08 | Preparation and use of samarium oxide catalyst |
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| Publication Number | Publication Date |
|---|---|
| CN1586715A true CN1586715A (en) | 2005-03-02 |
| CN1332751C CN1332751C (en) | 2007-08-22 |
Family
ID=34603762
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|---|---|---|---|
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432056A (en) * | 2011-10-13 | 2012-05-02 | 陕西科技大学 | Method for preparing Sm2O3 nano crystals by solvent thermal method |
| CN103482671A (en) * | 2013-09-16 | 2014-01-01 | 陕西科技大学 | Method for preparing Sm(OH)3 nanometer crystal in homogenous precipitation mode |
| CN103482672A (en) * | 2013-09-16 | 2014-01-01 | 陕西科技大学 | Preparation method of hexagonal-prism-shaped Sm(OH)3 nanocrystalline |
| CN103922384A (en) * | 2014-04-14 | 2014-07-16 | 陕西科技大学 | Method for preparing cubic phase Sm2O3 nano crystal with combination of uniform precipitation-thermal treatment |
| CN108557859A (en) * | 2018-04-11 | 2018-09-21 | 内蒙古科技大学 | The method for preparing samarium oxide with plant precipitating reagent |
| CN110128141A (en) * | 2019-06-10 | 2019-08-16 | 包头市沃野对外贸易有限责任公司 | A kind of novel 2:17 type samarium-cobalt permanent-magnetic material sintering padding preparation method |
| CN111644184A (en) * | 2020-06-16 | 2020-09-11 | 陕西科技大学 | Visible light response Sm10.67S16Photocatalyst and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2051476A1 (en) * | 1990-09-17 | 1992-03-18 | Yasushi Hara | Process for producing an ethylenamine |
| CN1271689A (en) * | 1999-04-27 | 2000-11-01 | 上海跃龙有色金属有限公司 | High-density samarium oxide and its preparing process |
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2004
- 2004-07-08 CN CNB2004100627368A patent/CN1332751C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432056A (en) * | 2011-10-13 | 2012-05-02 | 陕西科技大学 | Method for preparing Sm2O3 nano crystals by solvent thermal method |
| CN102432056B (en) * | 2011-10-13 | 2013-08-14 | 陕西科技大学 | Method for preparing Sm2O3 nano crystals by solvent thermal method |
| CN103482671A (en) * | 2013-09-16 | 2014-01-01 | 陕西科技大学 | Method for preparing Sm(OH)3 nanometer crystal in homogenous precipitation mode |
| CN103482672A (en) * | 2013-09-16 | 2014-01-01 | 陕西科技大学 | Preparation method of hexagonal-prism-shaped Sm(OH)3 nanocrystalline |
| CN103482672B (en) * | 2013-09-16 | 2015-04-22 | 陕西科技大学 | Preparation method of hexagonal-prism-shaped Sm(OH)3 nanocrystalline |
| CN103482671B (en) * | 2013-09-16 | 2015-04-22 | 陕西科技大学 | Method for preparing Sm(OH)3 nanometer crystal in homogenous precipitation mode |
| CN103922384A (en) * | 2014-04-14 | 2014-07-16 | 陕西科技大学 | Method for preparing cubic phase Sm2O3 nano crystal with combination of uniform precipitation-thermal treatment |
| CN108557859A (en) * | 2018-04-11 | 2018-09-21 | 内蒙古科技大学 | The method for preparing samarium oxide with plant precipitating reagent |
| CN110128141A (en) * | 2019-06-10 | 2019-08-16 | 包头市沃野对外贸易有限责任公司 | A kind of novel 2:17 type samarium-cobalt permanent-magnetic material sintering padding preparation method |
| CN111644184A (en) * | 2020-06-16 | 2020-09-11 | 陕西科技大学 | Visible light response Sm10.67S16Photocatalyst and preparation method thereof |
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|---|---|
| CN1332751C (en) | 2007-08-22 |
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