CN103585954A - Gasoline desulfurization catalytic adsorbent, and preparation method and desulfurization method thereof - Google Patents
Gasoline desulfurization catalytic adsorbent, and preparation method and desulfurization method thereof Download PDFInfo
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- CN103585954A CN103585954A CN201310536666.4A CN201310536666A CN103585954A CN 103585954 A CN103585954 A CN 103585954A CN 201310536666 A CN201310536666 A CN 201310536666A CN 103585954 A CN103585954 A CN 103585954A
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Abstract
The invention discloses a gasoline desulfurization catalytic adsorbent, and a preparation method and a desulfurization method thereof. The gasoline desulfurization catalytic adsorbent comprises the components by the weight percentage: 40%-60% of Ti3(PW12O40)4, 25%-40% of SiO2, and 15%-20% of Al2O3. Addition of Ti3(PW12O40)4 in the catalytic adsorbent can accelerate decomposition of tert-butyl hydroperoxide, oxygen obtained by decomposing tert-butyl hydroperoxide is increased, and thus an oxidative desulfurization reaction of dibenzothiophene is promoted; and at the same time, the gasoline desulfurization catalytic adsorbent has good catalytic oxidation and adsorption abilities. The gasoline desulfurization catalytic adsorbent can adopt adsorption to remove oxidation products while allowing an oxidation reaction of sulfides in gasoline to be carried out, does not need to adopt water washing extraction or water washing adsorption to remove the oxidation products, thereby omitting water washing extraction or water washing adsorption in the prior art, improving the work efficiency, and reducing the gasoline desulfurization time.
Description
Technical field
The present invention relates to a kind of, especially a kind of gasoline desulfur catalyst-sorbent and preparation method thereof and sulfur method.
Background technology
Along with the enhancing day by day of environmental consciousness in global range, countries in the world have been formulated stricter fuel oil standard constraint sulfur content one after another.Traditional hydrodesulfurization Technology Need operates under high-temperature and high-pressure conditions, severe reaction conditions.Oxidative desulfurization techniques operating condition gentleer (just can carry out under room temperature normal pressure), selective high, and the thiophene-type sulfide that is difficult to remove can oxidized removal under gentle oxidation reaction condition, and do not need hydrogen under hydroconversion condition, therefore more and more receive publicity.
The CN 1382199A(2002 of Philps Petroleum Company) in patent, disclose load bimetallic promoter on zinc oxide, prepared adsorbent, for catalytically cracked gasoline desulfurization.The people such as Ren Jie are at CN 101333454A(2008) disclose in patent oxidation catalyst and phase transfer catalyst have been mixed, and mixes with gasoline, the oxygen of take carries out oxidation processes as oxidant, washing, then adsorb with atlapulgite, obtain sulfur-free gasoline.At CN 102311777A(2011) people such as Ren Jie joins wolframic acid or tungstates oxidation catalyst in acetic acid and hydrogen peroxide mixed solution in patent, preparation Peracetic acid oxidizing solution; With oxidizing solution, under mitigation condition, gasoline is carried out to oxidation processes again, then gasoline is washed, obtain oxidation of gasoline; Then, with extractant, oxidation of gasoline is extracted, again gasoline is washed, realize gasoline desulfur.The people such as Tang Xiaodong are at CN 1923967A(2006) a kind of catalyzing oxygenizing desulfurizing straight-run gasoline method is disclosed in patent.The method is to mix with gasoline with catalyst nitrogen oxide, then passes into dioxygen oxidation, and the direct steaming gasoline after oxidation obtains refining direct steaming gasoline by atlapulgite adsorption treatment.The people such as Yang Yanzhao are at CN 101402877A(2008) oxidation catalyst and phase transfer catalyst are mixed as catalyst in patent, Fenton reagent or Fenton-like reagent carry out gasoline desulfur as oxidant.The people such as Liu Xiaoqin are at CN 102000544A(2011) disclose in patent by stannous chloride and the doped meso-porous silica of aluminium element as adsorbent, for gasoline desulfur.
Sulphur content cloth in gasoline is mainly mercaptan, thioether and thiophene sulphur.Little molecule mercaptan and thioether adopt the method for catalysis alkali cleaning just can remove, and the polarity difference of the polarity of thiophene sulphur and similar structure hydro carbons is little, and the sulfide being oxidized is far longer than not sulfide oxidation polarity as the polarity of sulfone or sulfoxide.So many researchers have carried out large quantity research to the oxidation of thiophene.They first carry out catalytic oxidation to gasoline, and then with extractant extraction or with adsorbent absorption, carry out in two steps; There is operating efficiency lower, the weak point that desulfurization time is long.
Summary of the invention
The gasoline desulfur catalyst-sorbent of adsorption and oxidation product when the technical problem to be solved in the present invention is to provide a kinds of oxidation reaction; The present invention also provides the preparation method of this gasoline desulfur catalyst-sorbent; The present invention also provides the gasoline desulfating method that adopts this gasoline desulfur catalyst-sorbent.
For solving the problems of the technologies described above, the weight percentage of composition of the present invention is: Ti
3(PW
12o
40)
440%～60%, SiO
225%～40% and Al
2o
315%～20%.
The average pore size of catalyst-sorbent of the present invention is 1.52～1.96nm, and pore volume is 0.1～0.5ml/g, and specific area is 305～501m
2/ g.
Preparation method of the present invention is: by Ti
3(PW
12o
40)
4, A1 (NO
3)
39H
2o and ethyl orthosilicate adopt sol-gel process preparation, can obtain described catalyst-sorbent.
A1 (NO described in preparation method of the present invention
3)
39H
2the amount of substance of O is equal to 1/2 Al in described catalyst-sorbent
2o
3amount of substance, the amount of substance of ethyl orthosilicate is equal to SiO in described catalyst-sorbent
2amount of substance.
Described in preparation method of the present invention, sol-gel process is: the A1 (NO that is 20%～30% in mass concentration
3)
39H
2in the O aqueous solution, add successively organic solvent, ethyl orthosilicate and Ti
3(PW
12o
40)
4, then at room temperature stir, gel, finally filter, be dried, roasting.Described baking temperature is 100 ℃, and sintering temperature is 500 ℃～550 ℃, roasting 4h～6h.Described organic solvent is isopropyl alcohol.
Sulfur method of the present invention adopts above-mentioned gasoline desulfur catalyst-sorbent: TBHP is mixed with gasoline, then add described gasoline desulfur catalyst-sorbent to carry out reaction treatment, can obtain sulfur-free gasoline.
Described in sulfur method of the present invention, TBHP consumption is O/S mol ratio=3～7:1; The addition of described gasoline desulfur catalyst-sorbent is 3%～5% of quality of gasoline; Described reaction temperature is 50 ℃～90 ℃, and the reaction time is 1h～2h.
The beneficial effect that adopts technique scheme to produce is: when adopting the present invention can make sulfide in petrol generation oxidation reaction, adopt adsorbing and removing to fall oxidation product, needn't wash again extraction or washing adsorbing and removing oxidation product with water, thereby washing extraction or the washing absorption of prior art have been saved, improve operating efficiency, reduced the gasoline desulfur time.
The specific embodiment
Below in conjunction with specific embodiment, the present invention is further detailed explanation.
In following embodiment, handled gasoline is simulation catalytically cracked gasoline, being about to dibenzothiophenes, to be dissolved in boiling range be in the petroleum ether solution of 90～120 ℃, sulfur content is 326 μ g/g, with Britain ANTEK 9000 fluorescence Sulfur Analysis instrument, measure the sulfur content in solution, desulfurization degree computational methods are: desulfurization degree=(1-treated gasoline sulfur content/feedstock oil sulfur content) * 100%.
Embodiment 1: the composition proportion of this gasoline desulfur catalyst-sorbent, preparation method and sulfur method are as described below.
By 5.5g A1 (NO
3)
39H
2o is made into the 25wt% aqueous solution, then is sequentially added into 7.0mL ethyl orthosilicate and 2.5g Ti
3(PW
12o
40)
4, then at room temperature stir, carry out gel, finally filter, be dried, 500 ℃ of roasting 4h, obtain desulfurization catalyst-sorbent 5.03g.The average pore size of this catalyst-sorbent is 1.73nm, and pore volume is 0.34ml/g, and specific area is 426.53m
2/ g; Each component content: Ti
3(PW
12o
40)
450wt%, SiO
235wt% and Al
2o
315wt%.
Above-mentioned Ti
3(PW
12o
40)
4adopt following method to be prepared from: first tetrabutyl titanate hydrolysis to be made to Ti (OH)
4, Ti (OH) then
4react and make Ti with phosphotungstic acid
3(PW
12o
40)
4, described Ti (OH)
4with the mol ratio of phosphotungstic acid be 3:4.
Get analog gasoline 100g, this desulfurization catalyst-sorbent consumption is quality of gasoline 3%, and TBHP consumption (O/S mol ratio) is 5:1, at 70 ℃, reacts 2h, filters and obtains treated gasoline, and sulfur content is 26 μ g/g, and desulfurization degree reaches 92%.
Embodiment 2: the composition proportion of this gasoline desulfur catalyst-sorbent, preparation method and sulfur method are as described below.
By 7.4g A1 (NO
3)
39H
2o is made into the 20wt% aqueous solution, then is sequentially added into 7.5mL ethyl orthosilicate and 2.0g Ti
3(PW
12o
40)
4, then at room temperature stir, carry out gel, finally filter, be dried, 500 ℃ of roasting 4h, obtain desulfurization catalyst-sorbent 5.05g.The average pore size of this catalyst-sorbent is 1.81nm, and pore volume is 0.37ml/g, and specific area is 435.38m
2/ g; Each component content: Ti
3(PW
12o
40)
440wt%, SiO
240wt% and Al
2o
320wt%.
Get analog gasoline 100g, catalyst amount is quality of gasoline 5%, and TBHP consumption (O/S mol ratio) is 5:1, at 50 ℃, reacts 1h, filters and obtains treated gasoline, and sulfur content is 43 μ g/g, and desulfurization degree reaches 87%.
Embodiment 3: the composition proportion of this gasoline desulfur catalyst-sorbent, preparation method and sulfur method are as described below.
By 7.4g A1 (NO
3)
39H
2o is made into the 25wt% aqueous solution, then is sequentially added into 5.6mL ethyl orthosilicate and 2.5g Ti
3(PW
12o
40)
4, then at room temperature stir, carry out gel, finally filter, be dried, 500 ℃ of roasting 4h, obtain desulfurization catalyst-sorbent 5.00g.The average pore size of this catalyst-sorbent is 1.62nm, and pore volume is 0.26ml/g, and specific area is 395.21m
2/ g; Each component content: Ti
3(PW
12o
40)
450wt%, SiO
230wt% and Al
2o
320wt%.
Get analog gasoline 100g, catalyst amount is quality of gasoline 7%, and TBHP consumption (O/S mol ratio) is 3:1, at 50 ℃, reacts 2h, filters and obtains treated gasoline, and sulfur content is 26 μ g/g, and desulfurization degree reaches 92%.
Embodiment 4: the composition proportion of this gasoline desulfur catalyst-sorbent, preparation method and sulfur method are as described below.
By 5.5g A1 (NO
3)
39H
2o is made into the 30wt% aqueous solution, then is sequentially added into 4.7mL ethyl orthosilicate and 3.0g Ti
3(PW
12o
40)
4, then at room temperature stir, carry out gel, finally filter, be dried, 500 ℃ of roasting 4h, obtain desulfurization catalyst-sorbent 5.01g.The average pore size of this catalyst-sorbent is 1.58nm, and pore volume is 0.23ml/g, and specific area is 352.14m
2/ g; Each component content: Ti
3(PW
12o
40)
460wt%, SiO
225wt% and Al
2o
315wt%.
Get analog gasoline 100g, catalyst amount is quality of gasoline 7%, and TBHP consumption (O/S mol ratio) is 5:1, at 30 ℃, reacts 2h, filters and obtains treated gasoline, and sulfur content is 29 μ g/g, and desulfurization degree reaches 91%.
Recyclability test: adopt the catalyst-sorbent after analog gasoline desulfurization in embodiment 1,550 ℃ of roasting 6h regeneration.Repeat the reaction condition of embodiment 1, after each desulfurization, again regenerate, investigate the recyclability of this catalyst-sorbent, obtain result as shown in table 1.
Table 1: the situation of reusing of catalyst-sorbent
Desulfurized effect contrast test: in order to probe into desulfurization principle, carried out following test.
Test 1: getting analog gasoline 100g, is 70 ℃ in temperature, SiO
2-Al
2o
3make adsorbent, consumption is quality of gasoline 5%, does not add TBHP, and reaction 2h, filters, and analyzes the sulfur content of filtrate and raw material, and desulfurization degree is 30%.
Test 2: getting analog gasoline 100g, is 70 ℃ in temperature, SiO
2-Al
2o
3make adsorbent, consumption is quality of gasoline 5%, under the condition that the mol ratio of TBHP and sulphur is 3, reacts 2h, filters, and analyzes the sulfur content of filtrate and raw material, and desulfurization degree is 60%.
Test 3: getting analog gasoline 100g, is 70 ℃ in temperature, this desulfurization catalyst-sorbent consumption is quality of gasoline 5%, under the condition that the mol ratio of TBHP and sulphur is 3, reacts 2h, filter, the sulfur content of analysis filtrate and raw material, desulfurization degree is 91%.
Above result of the test explanation, is only used SiO
2-Al
2o
3make adsorbent, desulfurization degree only has 30%; After adding TBHP, desulfurization degree increases to 60%, illustrates that the oxidation of TBHP has changed the polarity of dibenzothiophenes, has strengthened the absorption of sulfur-containing compound, promotes the carrying out of desulphurization reaction.Comparative test 3 and test 2 can be found out, Ti
3(PW
12o
40)
4add and make desulfurization degree improve 31 percentage points, Ti is described
3(PW
12o
40)
4add the decomposition of having accelerated TBHP, its oxygen decompositing is increased, thereby has promoted the carrying out of the oxidation desulfur reaction of dibenzothiophenes.According to above analysis, infer that this desulfurization catalyst-sorbent has good catalytic oxidation and the ability of absorption simultaneously.
Claims (9)
1. a gasoline desulfur catalyst-sorbent, is characterized in that, the weight percentage of its composition is: Ti
3(PW
12o
40)
440%～60%, SiO
225%～40% and Al
2o
315%～20%.
2. gasoline desulfur catalyst-sorbent according to claim 1, is characterized in that: the average pore size of described catalyst-sorbent is 1.52～1.96nm, and pore volume is 0.1～0.5ml/g, and specific area is 305～501m
2/ g.
3. a preparation method for gasoline desulfur catalyst-sorbent described in claim 1 or 2, is characterized in that: by Ti
3(PW
12o
40)
4, A1 (NO
3)
39H
2o and ethyl orthosilicate adopt sol-gel process preparation, can obtain described catalyst-sorbent.
4. the preparation method of gasoline desulfur catalyst-sorbent according to claim 3, is characterized in that: described A1 (NO
3)
39H
2the amount of substance of O is equal to 1/2 Al in described catalyst-sorbent
2o
3amount of substance, the amount of substance of ethyl orthosilicate is equal to SiO in described catalyst-sorbent
2amount of substance.
5. according to the preparation method of the gasoline desulfur catalyst-sorbent described in claim 3 or 4, it is characterized in that, described sol-gel process is: the A1 (NO that is 20%～30% in mass concentration
3)
39H
2in the O aqueous solution, add successively organic solvent, ethyl orthosilicate and Ti
3(PW
12o
40)
4, then at room temperature stir, gel, finally filter, be dried, roasting.
6. the preparation method of gasoline desulfur catalyst-sorbent according to claim 5, is characterized in that: described baking temperature is 100 ℃, and sintering temperature is 500 ℃～550 ℃, roasting 4h～6h.
7. the preparation method of gasoline desulfur catalyst-sorbent according to claim 5, is characterized in that: described organic solvent is isopropyl alcohol.
8. the sulfur method of a gasoline, it adopts the gasoline desulfur catalyst-sorbent described in claim 1 or 2, it is characterized in that: TBHP is mixed with gasoline, then add described gasoline desulfur catalyst-sorbent to carry out reaction treatment, can obtain sulfur-free gasoline.
9. the sulfur method of gasoline according to claim 8, is characterized in that: described TBHP consumption is O/S mol ratio=3～7:1; The addition of described gasoline desulfur catalyst-sorbent is 3%～5% of quality of gasoline; Described reaction temperature is 50 ℃～90 ℃, and the reaction time is 1h～2h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107233918A (en) * | 2017-06-16 | 2017-10-10 | 东北师范大学 | Titanium substitution phosphotungstate catalyst and preparation method thereof |
| CN107803192A (en) * | 2017-07-18 | 2018-03-16 | 华南理工大学 | A kind of oxidized desulfurization double-function catalyzing adsorbent clean regeneration process |
| CN115739132A (en) * | 2022-11-30 | 2023-03-07 | 安达市海纳贝尔化工有限公司 | Method for improving yield of 2-bromothiophene by BiOBr microsphere catalyst under assistance of illumination |
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| CN1412280A (en) * | 2001-10-15 | 2003-04-23 | 梅海 | Ultrasonic-catalytic-oxidation desulfurization method for producing ultralow sulfur diesel oil |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107233918A (en) * | 2017-06-16 | 2017-10-10 | 东北师范大学 | Titanium substitution phosphotungstate catalyst and preparation method thereof |
| CN107803192A (en) * | 2017-07-18 | 2018-03-16 | 华南理工大学 | A kind of oxidized desulfurization double-function catalyzing adsorbent clean regeneration process |
| CN115739132A (en) * | 2022-11-30 | 2023-03-07 | 安达市海纳贝尔化工有限公司 | Method for improving yield of 2-bromothiophene by BiOBr microsphere catalyst under assistance of illumination |
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Application publication date: 20140219 |