CN104841357A - Adsorbent for benzene refining desulfurization, and preparation method thereof - Google Patents
Adsorbent for benzene refining desulfurization, and preparation method thereof Download PDFInfo
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- CN104841357A CN104841357A CN201510196835.3A CN201510196835A CN104841357A CN 104841357 A CN104841357 A CN 104841357A CN 201510196835 A CN201510196835 A CN 201510196835A CN 104841357 A CN104841357 A CN 104841357A
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- adsorbent
- ruthenium
- sodium
- refining desulfurization
- benzene refining
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Abstract
The invention discloses an adsorbent for benzene refining desulfurization, and a preparation method thereof. The adsorbent adopts alumina as a supporter to support a precious metal ruthenium, and comprises, by weight, 0.3-2.0% of the precious metal ruthenium, 0-3% of sodium, 0-3% of calcium, 0-5% of silicon, and the balance of the alumina supporter. The preparation method comprises the following steps: dipping several different ruthenium salts on the supporter, sequentially reducing by using a reducing agent, drying, roasting, and reducing to finally obtain the target adsorbent. Especially the desulphurization effect of the adsorbent prepared by using a chlorine-free ruthenium salt is good. The adsorbent has strong adsorption ability on sulfur, reduces the total sulfur content in refined benzene from 1ppm to below 0.01ppm, and has a large sulfur capacity reaching above 1.6g thiophene/kg adsorbent.
Description
Technical field
The present invention relates to a kind of adsorbent, particularly relate to ruthenium adsorbent of a kind of benzene refining desulfurization 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.At present, the subject matter that this industry exists is the organic sulphur components how effectively removed in benzene.Wherein, adsorption desulfurize has that investment is little, technique is simple, condition is easy to control, desulfurization precision advantages of higher, is the main method of organic sulfide removal both at home and abroad at present.But, with the Pd/Al that existing method is obtained
2o
3adsorbent application life in production is short, and adsorbance is limited, is unfavorable for steady production.Therefore exploitation has high sulfur capacity, and the commercial Application life-span benzene refining adsorbent of length is very necessary.
Summary of the invention
The object of the invention is to provide a kind of adsorbent for benzene refining desulfurization and preparation method thereof, this adsorbent has strong adsorption capacity to sulphur, Sulfur capacity reaches 1.60g thiophene/kg adsorbent, and be more than 2 times that conventional method prepares palladium adsorbent, performance is obviously better than existing palladium adsorbent.
In order to realize object of the present invention, being realized by following means: a kind of ruthenium adsorbent for benzene refining desulfurization, it is characterized in that it at least comprises following component by weight:
(1) noble ruthenium content 0.5-3%;
(2) sodium content 0-3%;
(3) calcium content 0-3%;
(4) silicone content 0-5%;
(5) remaining content is alumina support.
In order to realize object of the present invention further, described ruthenium adds for predecessor with ruthenic chloride, acetic acid ruthenium, ten dicarbapentaborane three rutheniums, nitrosyl nitric acid ruthenium; Sodium with sodium salts such as sodium nitrate, sodium carbonate, sodium acid carbonates for predecessor adds, preferred sodium nitrate; Calcium with the calcium salt such as calcium nitrate, calcium carbonate for predecessor adds; Silicon adds for predecessor with sodium metasilicate, Ludox; Alumina support can select spherical, cloverleaf pattern alumina support.
For a preparation method for the ruthenium adsorbent of benzene refining desulfurization, it is characterized in that comprising following preparation process:
(1) by wiring solution-forming soluble in water for ruthenic chloride, or by water-soluble for ten dicarbapentaborane three rutheniums/acetic acid ruthenium/nitrosyl nitric acid ruthenium/organic solvent wiring solution-forming; And optionally in ruthenium liquid, allocate hydrochloric acid or acetic acid into;
(2) alumina support is put into the solution that (1) prepares, be heated to 40-80 DEG C or room temperature immersion 3-12 hour;
(3) with reducing agent hydrazine hydrate or formaldehyde or sodium borohydride solution process 1-6 hour after (2) being flooded, and use a large amount of deionized water rinsing, until neutral without chlorine till;
(4) (3) are washed complete adsorbent and put into baking oven 100-200 DEG C of oven dry, then at 300-600 DEG C, roasting 8-24 hour, eventually passes H in air atmosphere
2at 200-500 DEG C of activation 12-24 hour, i.e. obtained required adsorbent.
In order to realize object of the present invention further, described sodium, calcium or silicon composition and alumina powder jointedly press the weight ratio roller forming of 0.02-10:100 or extruded or forming oil column, 6-24 hour is kept, under 300-800 DEG C of condition roasting 3-12 hour and obtain in 80-200 DEG C of baking oven;
In order to realize object of the present invention further, described ruthenium and the weight ratio of alumina support are 0.5-3:100, preferred 2-2.5:100.
In order to realize object of the present invention further, described reductant concentration controls at 1-10%.Wherein, the preferred 2-6% of hydrazine hydrate solution concentration, the preferred 8-10% of formalin concentration, the preferred 1-5% of sodium borohydride solution concentration.
The present invention can produce following good effect compared with the prior art: the present invention use ruthenium for active constituent loading aluminium oxide or with on the aluminium oxide of sodium calcium Si modification for adsorbent.This adsorbent has the performance of adsorbing sulphur in benzene raw materials preferably, Sulfur capacity is more than 2 times that conventional method prepares palladium adsorbent, reach 1.6g thiophene/kg adsorbent, service life increases greatly, sulphur (organic sulfur) in benzene can be down to several ppb from several ppm, and overall performance is better than existing palladium adsorbent.
Detailed description of the invention:
Below the specific embodiment of the present invention is elaborated:
Embodiment 1
Alumina powder jointedly mix extruded mode with sodium nitrate with 100:0.1 weight ratio and obtain ￠ 1-3mm, the cloverleaf pattern alumina support of bulk density 0.65g/ml.Get 200g to be put in the ruthenic chloride solution (ruthenic chloride is dissolved in the solution be made in watery hydrochloric acid) that 400ml concentration is 0.015mol/L 50 DEG C and to soak after 8 hours, add 5% sodium borohydride solution to reduce 4 hours, leach adsorbent and drain, be washed till neutral without till chlorine by the deionized water of flowing, this adsorbent is first put into the oven dry of 150 DEG C, baking oven, put into high temperature furnace afterwards in 400 DEG C of air atmosphere roastings 8 hours, afterwards at H
2in atmosphere, 500 DEG C activate 12 hours, are required adsorbent.
Embodiment 2
Alumina powder jointedly mix extruded mode with sodium nitrate with 100:0.1 weight ratio and obtain ￠ 1-3mm, the cloverleaf pattern alumina support of bulk density 0.65g/ml.Get 200g and to be put in nitrosyl nitric acid ruthenium solution (nitrosyl nitric acid ruthenium is dissolved in the solution be made in watery hydrochloric acid) that 400ml concentration is 0.02mol/L room temperature immersion after 12 hours, add 2% hydrazine hydrate solution to reduce 4 hours, leach adsorbent and drain, be washed till neutral without till chlorine by the deionized water of flowing, this adsorbent is first put into the oven dry of 150 DEG C, baking oven, put into high temperature furnace afterwards in 400 DEG C of air atmosphere roastings 8 hours, afterwards at H
2in atmosphere, 400 DEG C activate 12 hours, are required adsorbent.
Embodiment 3
Alumina powder jointedly mix rolling molding mode with calcium nitrate with 100:0.2 weight ratio and obtain ￠ 1-3mm, the spherical alumina support of bulk density 0.70g/ml.Get 200g and to be put in the nitrosyl nitric acid ruthenium solution (the nitrosyl nitric acid ruthenium solution be made into soluble in water) that 400ml concentration is 0.02mol/L 40 DEG C of dippings after 10 hours, add 2% hydrazine hydrate solution to reduce 4 hours, leach adsorbent and drain, be washed till neutral without till chlorine by the deionized water of flowing, this adsorbent is first put into the oven dry of 150 DEG C, baking oven, put into high temperature furnace afterwards in 400 DEG C of air atmosphere roastings 8 hours, afterwards at H
2in atmosphere, 400 DEG C activate 12 hours, are required adsorbent.
Embodiment 4
Alumina powder jointedly mix rolling molding mode with calcium carbonate with 100:0.3 weight ratio and obtain ￠ 1-3mm, the spherical alumina support of bulk density 0.70g/ml.Get 200g and to be put in the ruthenic chloride solution (the ruthenic chloride solution be made into soluble in water) that 400ml concentration is 0.04mol/L 50 DEG C of dippings after 8 hours, add 2% hydrazine hydrate solution to reduce 4 hours, leach adsorbent and drain, be washed till neutral without till chlorine by the deionized water of flowing, this adsorbent is first put into the oven dry of 150 DEG C, baking oven, put into high temperature furnace afterwards in 300 DEG C of air atmosphere roastings 8 hours, afterwards at H
2in atmosphere, 500 DEG C activate 12 hours, are required adsorbent.
Embodiment 5
Alumina powder jointedly mix rolling molding mode with sodium metasilicate with 100:0.5 weight ratio and obtain ￠ 1-3mm, the spherical alumina support of bulk density 0.70g/ml.Get 200g and to be put in ten dicarbapentaborane three ruthenium solutions (ten dicarbapentaborane three rutheniums are dissolved in the solution be made in acetone/acetic acid) that 400ml concentration is 0.06mol/L room temperature immersion after 8 hours, add 5% sodium borohydride solution to reduce 3 hours, leach adsorbent and drain, be washed till neutral without till chlorine by the deionized water of flowing, this adsorbent is first put into the oven dry of 150 DEG C, baking oven, put into high temperature furnace afterwards in 400 DEG C of air atmosphere roastings 8 hours, afterwards at H
2in atmosphere, 500 DEG C activate 6 hours, are required adsorbent.
Embodiment 6
Alumina powder jointedly mix rolling molding mode with sodium carbonate with 100:0.2 weight ratio and obtain ￠ 1-3mm, the spherical alumina support of bulk density 0.70g/ml.Get 200g and to be put in ruthenium acetate solution (acetic acid ruthenium is dissolved in the solution be made in acetic acid) that 400ml concentration is 0.06mol/L room temperature immersion after 12 hours, add 5% sodium borohydride solution to reduce 4 hours, leach adsorbent and drain, be washed till neutral without till chlorine by the deionized water of flowing, this adsorbent is first put into the oven dry of 150 DEG C, baking oven, put into high temperature furnace afterwards in 300 DEG C of air atmosphere roastings 8 hours, afterwards at H
2in atmosphere, 400 DEG C activate 8 hours, are required adsorbent.
Comparative example 1
External import palladium alumina adsorbant, particle diameter is about 2mm, and precious metal palladium weight content is 1%.
Comparative example 2
Certain company's palladium alumina adsorbant domestic, particle diameter is about 2mm, and precious metal palladium weight content is 1%.
Adsorbent adopts fixed bed reactors to evaluate, and has two evaluation methods.
Evaluation method one:
Adsorption reaction is carried out in nitrogen atmosphere, reaction temperature 135-150 DEG C, pressure 0.8-1.0Mp, mass space velocity 4h
-1.250g chosen by adsorbent, first uses Hydrogen activation before use.Absorption raw material choose total sulfur content is less than the industrial refining benzene of 1ppm, and thiophene content 0.3ppm in benzene, evaluation time is 120h.Evaluation method flows through adsorbent for getting above-mentioned industrial refining benzene under appointment reaction condition, then adopts the thiophene content of GB/T 14327-2009 detection after sorbent treatment in benzene.
Evaluation result is as follows:
Evaluation method two:
Adsorption reaction is carried out in nitrogen atmosphere, reaction temperature 135-150 DEG C, pressure 0.8-1.0Mp, mass space velocity 4h
-1.250g chosen by adsorbent, first uses Hydrogen activation before use.Thiophene is added inward after absorption raw material choose industry refining benzene, thiophene content is 0.5g/L, evaluation time is 240min, and evaluation method flows through adsorbent for getting above-mentioned industrial refining benzene under appointment reaction condition, then adopts the thiophene content of GB/T 14327-2009 detection after sorbent treatment in benzene.
Evaluation result is as follows:
Above embodiment is only be described the preferred embodiment of the present invention; not scope of the present invention is limited; under not departing from the present invention and designing the prerequisite of spirit; the various distortion that the common engineers and technicians in this area make technical scheme of the present invention and improvement, all should fall in protection domain that claims of the present invention determine.
Claims (10)
1., for an adsorbent for benzene refining desulfurization, it is characterized in that it at least comprises following component by weight:
(1) noble ruthenium content 0.5-3%;
(2) sodium content 0-3%;
(3) calcium content 0-3%;
(4) silicone content 0-5%;
(5) remaining content is alumina support.
2. a kind of adsorbent for benzene refining desulfurization according to claim 1, is characterized in that described ruthenium adds for predecessor with ruthenic chloride, acetic acid ruthenium, ten dicarbapentaborane three rutheniums, nitrosyl nitric acid ruthenium.
3. a kind of adsorbent for benzene refining desulfurization according to claim 1, is characterized in that described sodium with at least one in sodium nitrate, sodium carbonate, sodium acid carbonate for predecessor adds.
4. a kind of adsorbent for benzene refining desulfurization according to claim 1, is characterized in that described calcium with at least one in calcium nitrate, calcium carbonate for predecessor adds.
5. a kind of adsorbent for benzene refining desulfurization according to claim 1, is characterized in that described silicon adds for predecessor with sodium metasilicate, Ludox.
6. a kind of adsorbent for benzene refining desulfurization according to claim 1, it is characterized in that described sodium, calcium or silicon composition and alumina powder jointed by certain weight ratio roller forming or extruded or forming oil column, 6-24 hour is kept, under 300-800 DEG C of condition roasting 3-12 hour and obtain in 80-200 DEG C of baking oven.
7. a kind of adsorbent for benzene refining desulfurization according to claim 1, is characterized in that described alumina support is ball-aluminium oxide or cloverleaf pattern alumina support.
8. a kind of adsorbent for benzene refining desulfurization according to claim 7, is characterized in that described ball-aluminium oxide is the rolling method of forming or oil-drop method manufacture; Cloverleaf pattern aluminium oxide is extrinsion pressing manufacture.
9., for a preparation method for the adsorbent of benzene refining desulfurization, it is characterized in that comprising following preparation process:
(1) by wiring solution-forming soluble in water for ruthenic chloride, or by water-soluble for ten dicarbapentaborane three rutheniums/acetic acid ruthenium/nitrosyl nitric acid ruthenium/organic solvent wiring solution-forming; And optionally in ruthenium liquid, allocate hydrochloric acid or acetic acid into;
(2) alumina support is put into the solution that (1) prepares, be heated to 40-80 DEG C or room temperature immersion 3-12 hour;
(3) with reducing agent hydrazine hydrate or formaldehyde or sodium borohydride solution process 1-6 hour after step (2) being flooded, and use a large amount of deionized water rinsing, until neutral without chlorine till;
(4) (3) are washed complete adsorbent and put into baking oven 100-200 DEG C of oven dry, then at 300-600 DEG C, roasting 8-24 hour, eventually passes H in air atmosphere
2at 200-500 DEG C of activation 12-24 hour, i.e. obtained required adsorbent.
10. the preparation method of a kind of adsorbent for benzene refining desulfurization according to claim 9, it is characterized in that described reductant concentration controls at 1-10%, wherein, the preferred 2-6% of hydrazine hydrate solution concentration, the preferred 8-10% of formalin concentration, the preferred 1-5% of sodium borohydride solution concentration; Described ruthenium and the weight ratio of alumina support are 0.5-3:100, preferred 2-2.5:100.
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| CN201510196835.3A CN104841357A (en) | 2015-04-23 | 2015-04-23 | Adsorbent for benzene refining desulfurization, and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108514891A (en) * | 2018-05-22 | 2018-09-11 | 上海交通大学 | A kind of preparation method of metal load type multistage pore canal HKUST-1 benzene desulphurization catalysts |
| 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 |
-
2015
- 2015-04-23 CN CN201510196835.3A patent/CN104841357A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108514891A (en) * | 2018-05-22 | 2018-09-11 | 上海交通大学 | A kind of preparation method of metal load type multistage pore canal HKUST-1 benzene desulphurization catalysts |
| 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 |
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