CN104941570A - Ruthenium adsorbent for deep benzene desulfurization and preparation method of ruthenium adsorbent - Google Patents
Ruthenium adsorbent for deep benzene desulfurization and preparation method of ruthenium adsorbent Download PDFInfo
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Abstract
The invention provides a ruthenium adsorbent for deep benzene desulfurization and a preparation method of the ruthenium adsorbent. The method includes the steps of preprocessing aluminum oxide small balls, serving as carriers, with an alkali solution, dipping dissolved ruthenium activated components on the carriers, conducting drying, calcinating and reducing on the components to obtain the catalyst. The bulk specific weight of the ruthenium catalyst obtained through the method is 0.5-0.8 kg/L, the ruthenium content is 0.8-2% by weight, and the sulfur content reaches up to 0.8-1.0 g/kg. The sulfur content can be reduced to the ppb level after being adsorbed in the deep benzene desulfurization process, and the quality requirement for benzene raw materials during caprolactam production is met.
Description
Technical field
The invention belongs to chemical production technical field, especially relate to a kind of ruthenium adsorbent for benzene deep desulfuration and preparation method thereof.
Background technology
Benzene is important industrial chemicals, has industrial use very widely, mainly for the production of dyestuff, medicine, disinfectant, explosive and staple fibre etc.Along with organic synthesis industrial expansion, as the benzaldehyde product of one of chemical industry base stock, its status is more and more important.One is that demand constantly increases, and two is day by day harsh to its quality requirement.Such as in preparing process of caprolactam; for protecting follow-up benzene partial catalyst; require that in benzene, sulfur content is ppb level; traditional hydrodesulfurization catalyst generally with W, Ni, Mo for active constituent; take aluminium oxide as carrier, operate under the condition of high hydrogen-oil ratio (150 ~ 800) and higher temperature (180 ~ 350 DEG C).So not only equipment investment is large, and operating condition is high, and the sulfur content after hydrogenation sulfuration in benzene is minimum can only reach ppm level, can not meet demand of industrial production.
The adsorbent of existing alumina load palladium active component can meet industrial production needs, but palladium is expensive.Because ruthenium has the characteristic of absorption sulphur equally, and compare ruthenium low price with palladium, if ruthenium can be utilized to replace palladium as desulfuration adsorbent, will greatly reduce the cost of adsorbent, there is huge economic benefit.
Summary of the invention
In view of this, the present invention is intended to propose a kind of ruthenium adsorbent for benzene deep desulfuration and preparation method thereof, and to solve deficiency of the prior art, the ruthenium adsorbent of preparation has high-specific surface area, and Sulfur capacity is large, high adsorption capacity, and has huge cost advantage.
For achieving the above object, technical scheme of the present invention is achieved in that a kind of ruthenium adsorbent for benzene deep desulfuration, and its bulk density is 0.5 ~ 0.8kg/L, and the mass content of ruthenium is 0.8 ~ 2%, and Sulfur capacity is 0.8 ~ 1.0g/kg, and carrier is alumina support.
Preferably, described alumina support is ball-aluminium oxide, and its diameter is 1.5 ~ 3mm, and preferably, described ball-aluminium oxide is formed by rolling comminution granulation or the manufacture of oil column molding in integral.
Present invention also offers a kind of preparation method of the ruthenium adsorbent for benzene deep desulfuration, comprise the steps,
1) alumina support alkali metal salt soln is carried out pretreatment, alkali metal salt mass concentration is 2% ~ 20%, and the processing time is 0.5h ~ 4h, dries 2 ~ 24h after process at 80 ~ 150 DEG C;
2) by wiring solution-forming soluble in water for the active component of ruthenium, by step 1) in the pretreatment rear oxidation alumina supporter that obtains put into the solution prepared flood 0.5h ~ 24h at 20 DEG C ~ 95 DEG C;
3) by through step 2) carrier that processes spends deionized water and do not measure precipitation to the inspection of 0.1mol/L silver nitrate, put into 80 ~ 150 DEG C, baking oven and dry 2 ~ 24h, then put into Muffle furnace 400 ~ 600 DEG C of roasting 2 ~ 8h;
4) by step 3) in carrier hydrogen after roasting at 100 ~ 200 DEG C, reduce 8 ~ 24h under air speed 10 ~ 50r/h, namely obtain ruthenium adsorbent.
Preferably, step 1) in alkali metal salt be sodium carbonate or potash.
Preferably, step 1) in, the mass concentration of alkali metal salt is 2% ~ 10%, and carrying out the pretreated time is 0.5 ~ 4h, after process, dries 2 ~ 12h at 80-120 DEG C.
Preferably, step 2) in ruthenium active component be one in ruthenic chloride, nitric acid ruthenium, acetic acid ruthenium or ruthenium complex, preferred ruthenium trichloride, the mass ratio of ruthenium active component and carrier is 0.008 ~ 0.02, preferably, 0.008 ~ 0.012.
Preferably, step 2) in, during dipping, temperature used is 50 ~ 80 DEG C, and dip time is 2 ~ 12h, and preferably, temperature is 50 ~ 80 DEG C, and dip time is 2 ~ 4h.
Relative to prior art, ruthenium adsorbent for benzene deep desulfuration of the present invention and preparation method thereof, has following advantage:
1) can be prepared into by the present invention with aluminium oxide is carrier, and ruthenium content is the adsorbent of 0.8 ~ 2%wt, and this adsorbent specific area is large, Sulfur capacity is high, the sulphur of 1 ~ 5ppm in benzene can be taken off to ppb rank, and low price, in commercial Application, have more cost advantage;
2) eliminate the step of aqueous slkali precipitation transition in existing technique in preparation technology, simplify the preparation flow of ruthenium adsorbent, shorten preparation time, reduce production cost to a certain extent.
Detailed description of the invention
The present invention is described in detail below by embodiment.
Embodiment 1.
(1) then the sodium carbonate liquor 100ml preparing 2% concentration puts into 100g alumina support, and reaction 0.5h, then dries 24h by carrier at 80 DEG C.
(2) take the ruthenium trichloride of certain mass according to ruthenium content 0.8% water-soluble, then by step 1) in the carrier that obtains put into 20 DEG C of ruthenium trichloride aqueous solution and flood 24h.
(3) by through step 2) carrier that processes spends deionized water and do not measure precipitation to the inspection of 0.1mol/L silver nitrate, put into 80 DEG C, baking oven and dry 24h, then put into Muffle furnace 400 DEG C of roasting 8h.
(4) by step 3) in carrier after roasting, with hydrogen at 100 DEG C, under air speed 10hr-1, reductase 12 4h, namely obtains ruthenium catalyst.
Embodiment 2.
(1) then the sodium carbonate liquor 100ml preparing 20% concentration puts into 100g alumina support, and reaction 4h, then dries 2h by carrier at 150 DEG C.
(2) take the nitric acid ruthenium of certain mass according to ruthenium content 2% water-soluble, then by step 1) in the carrier that obtains put into 95 DEG C of ruthenium trichloride aqueous solution and flood 0.5h.
(3) by through step 2) carrier that processes spends deionized water and do not measure precipitation to the inspection of 0.1mol/L silver nitrate, put into 150 DEG C, baking oven and dry 2h, then put into Muffle furnace 600 DEG C of roasting 2h.
(4) by step 3) in carrier after roasting, with hydrogen at 200 DEG C, air speed 50hr
-1lower reduction 8h, namely obtains ruthenium catalyst.
Embodiment 3.
(1) then the mixed solution 100ml of the potash and sodium carbonate of preparing 10% concentration puts into 100g alumina support, and reaction 2h, then dries 4h by carrier at 100 DEG C.
(2) take the nitric acid ruthenium of certain mass according to ruthenium content 1% water-soluble, then by step 1) in the carrier that obtains put into 60 DEG C of ruthenium trichloride aqueous solution and flood 2h.
(3) by through step 2) carrier that processes spends deionized water and do not measure precipitation to the inspection of 0.1mol/L silver nitrate, put into 120 DEG C, baking oven and dry 8h, then put into Muffle furnace 550 DEG C of roasting 4h.
(4) by step 3) in carrier after roasting, with hydrogen at 150 DEG C, air speed 20hr
-1lower reduction 10h, namely obtains ruthenium catalyst.
Embodiment 4.
(1) then the sodium carbonate liquor 100ml preparing 5% concentration puts into 100g alumina support, and reaction 3h, then dries 8h by carrier at 100 DEG C.
(2) take the acetic acid ruthenium of certain mass according to ruthenium content 1.5% water-soluble, then by step 1) in the carrier that obtains put into 70 DEG C of ruthenium trichloride aqueous solution and flood 18h.
(3) by through step 2) carrier that processes spends deionized water and do not measure precipitation to the inspection of 0.1mol/L silver nitrate, put into the oven dry of 100 DEG C, baking oven, then put into Muffle furnace 450 DEG C of roasting 6h.
(4) by step 3) in carrier after roasting, with hydrogen at 120 DEG C, under air speed 30hr-1, reduce 10h, namely obtain ruthenium catalyst.
Embodiment 5.
(1) then the sodium carbonate liquor 100ml preparing 15% concentration puts into 100g alumina support, and reaction 1h, then dries 20h by carrier at 100 DEG C.
(2) take the complexing ruthenium of certain mass according to ruthenium content 1.8% water-soluble, then by step 1) in the carrier that obtains put into 40 DEG C of ruthenium trichloride aqueous solution and flood 10h.
(3) by through step 2) carrier that processes spends deionized water and do not measure precipitation to the inspection of 0.1mol/L silver nitrate, put into 100 DEG C, baking oven and dry 16h, then put into Muffle furnace 450 DEG C of roasting 6h.
(4) by step 3) in carrier after roasting, with hydrogen at 120 DEG C, air speed 30hr
-1lower reduction 10h, namely obtains ruthenium catalyst.
Measure the bulk density of the ruthenium catalyst of preparation in embodiment 1 ~ embodiment 2, Sulfur capacity and specific area, the result obtained is as shown in the table:
| Numbering | Bulk density Kg/l | Sulfur capacity g/Kg | Specific area m 2 |
| Embodiment 1 | 0.8 | 0.83 | 273 |
| Embodiment 2 | 0.8 | 1.00 | 262 |
| Embodiment 3 | 0.8 | 0.81 | 263 |
| Embodiment 4 | 0.8 | 0.85 | 267 |
| Embodiment 5 | 0.8 | 0.82 | 265 |
Wherein Sulfur capacity assay method: Sulfur capacity is determined on fixed bed tubular type continuous reaction apparatus and carries out, loaded in stainless steel reactor by a certain amount of catalyst, at nitrogen 1.0MPa, at temperature 150 DEG C, raw material is the benzole soln of the thiophene of 1ppm, and air speed is 4h
-1, stopping desulphurization reaction when exporting when sulfur content is greater than 100ppb, calculating Sulfur capacity.
Sulfur capacity=Σ (import sulfur content-outlet sulfur content) * 32/84/ catalyst weight
The foregoing is only the preferred embodiment of the invention; not in order to limit the invention; within all spirit in the invention and principle, any amendment done, equivalent replacement, improvement etc., within the protection domain that all should be included in the invention.
Claims (7)
1. for a ruthenium adsorbent for benzene deep desulfuration, it is characterized in that: its bulk density is 0.5 ~ 0.8kg/L, the mass content of ruthenium is 0.8 ~ 2%, and Sulfur capacity is 0.8 ~ 1.0g/kg, and carrier is alumina support.
2. the ruthenium adsorbent for benzene deep desulfuration according to claim 1, it is characterized in that: described alumina support is ball-aluminium oxide, and its diameter is 1.5 ~ 3mm, preferably, described ball-aluminium oxide is formed by rolling comminution granulation or the manufacture of oil column molding in integral.
3., for a preparation method for the ruthenium adsorbent of benzene deep desulfuration, it is characterized in that: comprise the steps,
1) alumina support alkali metal salt soln is carried out pretreatment, alkali metal salt mass concentration is 2% ~ 20%, and the processing time is 0.5h ~ 4h, dries 2 ~ 24h after process at 80 ~ 150 DEG C;
2) by wiring solution-forming soluble in water for the active component of ruthenium, by step 1) in the pretreatment rear oxidation alumina supporter that obtains put into the solution prepared flood 0.5h ~ 24h at 20 DEG C ~ 95 DEG C;
3) by through step 2) carrier that processes spends deionized water and do not measure precipitation to the inspection of 0.1mol/L silver nitrate, put into 80 ~ 150 DEG C, baking oven and dry 2 ~ 24h, then put into Muffle furnace 400 ~ 600 DEG C of roasting 2 ~ 8h;
4) by step 3) in carrier hydrogen after roasting at 100 ~ 200 DEG C, reduce 8 ~ 24h under air speed 10 ~ 50r/h, namely obtain ruthenium adsorbent.
4. the preparation method of the ruthenium adsorbent for benzene deep desulfuration according to claim 3, is characterized in that: step 1) in alkali metal salt be sodium carbonate or potash.
5. the preparation method of the ruthenium adsorbent for benzene deep desulfuration according to claim 3 or 4, it is characterized in that: step 1) in, the mass concentration of alkali metal salt is 2% ~ 10%, and carrying out the pretreated time is 0.5 ~ 4h, after process, dry 2 ~ 12h at 80-120 DEG C.
6. the preparation method of the ruthenium adsorbent for benzene deep desulfuration according to claim 3, it is characterized in that: step 2) in ruthenium active component be one in ruthenic chloride, nitric acid ruthenium, acetic acid ruthenium or ruthenium complex, preferred ruthenium trichloride, the mass ratio of ruthenium active component and carrier is 0.008 ~ 0.02, preferably, 0.008 ~ 0.012.
7. the preparation method of the ruthenium adsorbent for benzene deep desulfuration according to claim 3 or 6, is characterized in that: step 2) in, during dipping, temperature used is 50 ~ 80 DEG C, and dip time is 2 ~ 12h, preferably, temperature is 50 ~ 80 DEG C, and dip time is 2 ~ 4h.
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Cited By (5)
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| CN109499534A (en) * | 2018-12-11 | 2019-03-22 | 中国天辰工程有限公司 | A kind of preparation method of the palladium adsorbent for benzene deep desulfuration |
| CN109939662A (en) * | 2019-03-28 | 2019-06-28 | 广东石油化工学院 | Dealkalize nitrogen absorber for light fraction obtained by the rectifying of ethylene production sump oil |
| CN112958083A (en) * | 2021-03-16 | 2021-06-15 | 河南神马催化科技股份有限公司 | Ruthenium catalyst for removing trace sulfide in benzene |
| CN112958082A (en) * | 2021-03-16 | 2021-06-15 | 河南神马催化科技股份有限公司 | Catalyst for desulfurizing aromatic hydrocarbon and preparation method thereof |
| CN114433003A (en) * | 2020-10-16 | 2022-05-06 | 中国石油化工股份有限公司 | Desulfurization adsorbent and preparation method and application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109499534A (en) * | 2018-12-11 | 2019-03-22 | 中国天辰工程有限公司 | A kind of preparation method of the palladium adsorbent for benzene deep desulfuration |
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| CN109939662A (en) * | 2019-03-28 | 2019-06-28 | 广东石油化工学院 | Dealkalize nitrogen absorber for light fraction obtained by the rectifying of ethylene production sump oil |
| CN109939662B (en) * | 2019-03-28 | 2021-11-16 | 广东石油化工学院 | Dealkalized nitrogen adsorbent for light fraction obtained by sump oil rectification in ethylene production process |
| CN114433003A (en) * | 2020-10-16 | 2022-05-06 | 中国石油化工股份有限公司 | Desulfurization adsorbent and preparation method and application thereof |
| CN114433003B (en) * | 2020-10-16 | 2023-08-04 | 中国石油化工股份有限公司 | Desulfurizing adsorbent and preparation method and application thereof |
| CN112958083A (en) * | 2021-03-16 | 2021-06-15 | 河南神马催化科技股份有限公司 | Ruthenium catalyst for removing trace sulfide in benzene |
| CN112958082A (en) * | 2021-03-16 | 2021-06-15 | 河南神马催化科技股份有限公司 | Catalyst for desulfurizing aromatic hydrocarbon and preparation method thereof |
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Application publication date: 20150930 |