Photo-catalytic oxidation desulfurization method and catalyst for diesel or gasoline

The technical field of

[0001] the invention claims a diesel oil or gasoline light catalytic oxidation desulphurization method and the used catalyst the invention claims a * modified polyphenylene oxide resin and its * * he acid compound solid catalyst and its preparation method and used for diesel oil or gasoline photocatalysis oxidizing method for desulphurization of.

Background technology

[3] 0002 ] our nation city air pollution and fog * very serious the main reason is that one sulfur fuel oil in the combustion process and it can avoid the air in s discharge of sulfur compound w and w long time to the energy structure and is not mature the desulphurization technique and so on the one of the environment pollution is serious threat to the living environment of human and social sustainable development of. Data report each year of a vehicle fuel by burning discharges to atmosphere the invention claims s to reach several kilometres to thousands ton the air pollution of the main source one. Along with the environment protection attention of various national continuously reduce the request of oil product sulphur content in produced so it satisfies the environment requirement of the clean fuel and it has important social meaning and wide application foreground.

[0003] transmitting system of removing in fuel oil including sulphur compound the method is as follows adding ammonia desulfurization w but hard to reach the depth de-sulfurization building 50 ppm the requirement of the oil product of diphenyl and * thiophene dbt and its derivatives such as 4 6 dimethyl benzene and * thiophene 4 6 dmdbt wayne difficult to remove ammonia desulfurization and the consumption of the high cost. So the oxidation sweetening absorption desulfurization biological desulphurization and so on a heating ammonia desulphurization method to obtain the more and more the research of the light catalyzing and oxidizing and desulfurizing it has the advantages of mild reaction condition low cost friendly environment and so on.

[0004] but the current oxidation desulphurization for the research of most it adopts the hydrogen peroxide as oxidizing agent for desulphurization process to produce a large amount of waste water at the same time using the polyphenyl adipic * resin and high temperature aging and swelling property can be improved.

- 10 0005 the photocatalytic oxidation catalyst is the light the laser generating light in the lower cavity of the electron redox system the cavity electron pair of the compound quantum efficiency is high using rate is low so that light catalyst in the efficiency is low it needs to reduce the optical cavity of the electron composite probability. At the same time of existing light catalyst most in practical application without recycling method for limiting the industrialization.

The content of invention

[0006] aiming to problem mentioned above the purpose of this invention claims a green economic and high temperature aging and has good desulfurization effect for diesel oil or gasoline the photocatalytic oxidation desulphurization of * modified resin matrix composite catalyst.

[0007] the invention has the other purpose is to provide a by using said * modified resin matrix composite catalyst for diesel oil or gasoline the light catalytic oxidation method for desulphurization of.

[0008] this invention claims a diesel oil or gasoline the photocatalytic oxidation desulphurization catalyst wherein said catalyst is comprised of polyphenyl * its big hole resin the modified * and loading * he acid and its preparation method comprises steps as follows w: *** * they polystyrene resin of the pre-treatment of; *** to the resin to carry through the graft modified *; *** the * he acid loaded on the obtained * modified resin it can get the desulphurization catalyst.

[0009] of said polyphenyl its * resin as dool cc resin.

[0010] the pre-treatment of the invention claims a method for polyphenyl its * resin and cyclohexanol deionized water to wash many times to remove the impurity; Is 0 1 mol/l sulphuric acid solution to marinate for 24 h and then cleaned by de-ionized water until solution is not changed and at last 6 tc and the lower part of the drying to arrive at constant weight.

[0011] said * graft modification method is to walk * * is chloride and 1 1 2 h h * chlorhexidine * f 113 under low temperature form a whole * peroxide and the polyphenyl adipic * resin to carry through the single electron transfer reaction to obtain. The reaction is represented as follows:

<img id="idf0001" file="CN104357080AD00041.tif" img-content="drawing" img-format="tif" />

[0012] said * he acid load method is realized through the * graft modified resin and so on the volume and good * he acid solution to prepare * he acid load *** 15wt 5 wt% of resin desulphurization catalyst and the 60 c the drying to arrive at constant weight.

[0013] activity of catalyst assessment is made by diesel oil or gasoline by photocatalytic oxidation desulfuration by the operation is: Measuring cylinder is firstly weighing a given amount of diesel oil or gasoline for electronic balance weighing the weight percent of the oil product 5***1 0 to 5% of the resin catalyst and add quartz in the conical bottle. The quartz the conical bottle is put into 30***9 tc of the constant temperature oil bath and seizing with the opening is connected with the cooling water through the oxygen and flow rate is controlled at 150 r/min blood. Is connected with 125w ultraviolet light source to be reacting for 1 *** and then taking out the conical bottle after the reaction mixture into the one-off plasma separating it is also in the pipe separating 5 min; Through the separating and processing of the diesel oil or gasoline into the liquid separating funnel and then weighing 90% n-methyl pyrrole by nmp * li water solution as extracting agent and solvent oil ratio of 1: 1 under the condition of mixing oscillation static layer separation at least two phase volume there is no need to change; Extracting the gasoline and diesel oil water cleaning to remove residual extraction agent for; Finally using the micro cullen instrument is measuring oxidizing extracting the back of the diesel oil or gasoline total sulphur content.

[0014] this invention claims a diesel oil or gasoline light catalytic oxidation desulphurization method wherein it comprises the following steps w; W sulphur diesel oil or gasoline as the raw material oxide catalyst catalyst and ultraviolet light source in the presence of the light catalytic oxidation desulphurization reaction after reaction material is separated and extracted by using extraction agent to obtain the products diesel oil or gasoline; Wherein said catalyst is * he acid of the load * modified macro porous acid hexane * polystyrene resin wherein said * he load quantity of acid is 5 wt% *** 15wt; Said oxidizing agent into oxygen; The reaction condition is; Reaction time is 1 *** chemical reaction temperature tc 30***9 125w high voltage packet ultraviolet lamp irradiating oxygen flow of blood 150 r/min for catalyst of gasoline and diesel oil quality of 0 5***1 5 wt percent the extracting agent as the volume ratio is 90% of n-methyl pyrrole by nmp * li water solution and additive of oil volume ratio 1: 1.

[0015] the light catalytic oxidation desulphurization reaction mechanism is as follows: Diesel oil or gasoline of the light catalyzing and oxidizing and desulfurizing it mainly uses the function of catalyst to produce strong oxidizing property of the album *** w and free radical with strong oxidation reduction activity of superoxide anion *** 0 factory of the diesel oil or gas oil in * thiophene compound containing sulfur compound oxide as electrode of the ferrous * and * compound then using polar solvent extracting so that the diesel oil or in gasoline including sulphur compound from falling out.

<img id="idf0002" file="CN104357080AD00042.tif" img-content="drawing" img-format="tif" />

[001] the advantages of this invention is w oxygen as to replace the chemical oxidation desulphurization of oxidizing agents the invention overcomes the problem that the price is high the chemical stability is bad w and desulphurization process to produce large quantity of waste water and so on optical catalytic technology the application of the reaction condition is mild the operating cost is low and it is friendly to environment. Through the polyphenyl its * resin graft * element using carbon bond * it has high energy and w key * atom a strong negative electric and optical property so as to improve the catalyst of high temperature resistance aging resistance w and the photocatalytic oxidation desulphurization capability.

<img id="idf0003" file="CN104357080AD00043.tif" img-content="drawing" img-format="tif" />

<img id="idf0004" file="CN104357080AD00044.tif" img-content="drawing" img-format="tif" />

Specification attached drawing

[0017] picture 1 is dool cc resin b and * the modified dool cc resin a the infrared light spectrum.

[0018] picture 2 is not modified dool cc resin of the scanning electron microscope image.

[0019] picture 3 is after being modified by * a dool cc resin as carrier to load lowt * he acid for forming complex catalyst of scanning electron microscope image.

Specific implementing manner

[0020] a lower surface of the attached drawing and the specific embodiment to detailed explain the invention.

[0021] embodiment 1-5; Diesel oil or gasoline the photocatalytic oxidation desulphurization catalyst preparation method of the big hole of the polystyrene its * dool cc resin finished products resin and cyclohexanol deionized water to wash many times to remove the impurity. Is 0.1 mol/l of vitriol solution to marinate for 24 h and then cleaned by de-ionized water until solution suppressing is not changed the drying box to 60 c the drying to arrive at constant weight.

[0022] the machine for seizing of the blood 100 second orifice glass bottle is dipped in the reaction 25 c freezing salt bath in the slow seizing stirring and adding 100 blood 1 1 2 h h * chlorhexidine * 113 f then adding 8.0 blood 25 wt% of oh water solution of blood w and 1 to 30 wt% 501 st 2 seizing for 5 minutes then quickly adding 6496 4 g the walking * lower * chlorine reaction for 2 min stopping seizing for the reaction mixture separating layer is completely obtaining the lower layer oil layer and they are respectively used for 5 wt % of nahc ^ water solution and the water washing * coating adding anhydrous na2s 501 st 4 shaking few minutes later the cold bath to obtain the pure aside * peroxide.

[002] the lead 5 g dool cc resin and blood 100 di 2 250 in the blood inlet of the upright flask seizing them and the swelling the night the 5 c the inletting the nitrogen for 30 min the total * peroxide solution is gradually dropped into the flask in h. And then the seizing 5c and the lower part of the continuously stirring for 10 to be starch ki h test paper not be detected remaining peroxide can stop the reaction. Product through filtering washing 60 c the vacuum drying box to dry to constant weight obtaining * modified dool cc resin. Picture 1 is dool cc resin and * the modified dool cc resin a an infrared spectrum image contrast can be seen w modified front and back dool cc resin characteristic absorbing peak the same specification * modified resin of the structure and there is no suffers from damage. * modified resin the infrared light wave number spectral diagram of 1100 to 1350 cnfi cnfi and the strong absorption the invention claims a * radical characteristic absorbing peak. Cfs of the characteristic absorbing peak the wave number 1314 cnti cf2 position of characteristic absorbing peak the wave number 1244 cnti w and 1210 cnti processing 821 cnti is the double substituted benzene ring 860-800 cnti of the characteristic absorbing peak proves that double benzene ring the position of the existence of the substituted.

[0024] to respectively weigh 0 263 g 0 405 g 0 556 g 0 714 g 0 882 g * he acid solution to 9ml * steam in water then respectively weighting 5g * modified dool cc resin soaked in said 5 parts of solution adopt equal volume and good method for preparing the * he acid load respectively 7 5wt% to 5 wt percent lowt 12 5 wt percent 15wt w and the percent desulphurizing catalyst of 60 ° c the drying to arrive at constant weight obtaining * modified resin matrix composite catalyst. Picture 2 is not modified dool cc resin of the scanning electron microscope analysis w can see the amplified to 10000 times after dool cc resin on the surface of the hole channel is more obvious it is convenient for the specific surface area as the increasing of the catalyst material of multi-hole structure it is good for the reaction product contacted with hole clearance ratio is high specific surface area is large it is good for the reaction medium contact of the catalytic effect is good so the dool teunis w cc resin can be used as load carrier of catalyst. Picture 3 is after * the modified dool cc resin as carrier to load lowt * he acid for forming composite catalyst 400 times are seen under the surface of which through the load * he acid and the load is more even.

[100] the embodiment of 6-10: Diesel oil or gasoline light catalytic oxidation desulphurization experiment the experiment condition is: Diesel oil of 10 mu dosage of catalyst is diesel oil to 1.0% the quality of the reaction temperature is 80 c * he acid loading amount is 10 wt% oxygen flow is 150 r/min blood 125 w ultraviolet light source nmp more than 90 percent water solution as extracting agent and solvent oil ratio of 1: 1 changes inspecting the reaction time reaction time is respectively the ratio i for 5h of 2 for 5h time of the desulphurization ratio the influence of the experiment result in table 1.

[0026] meter 1 the reaction time the effect of dephosphorization and desulphurization is the influence of

<img id="idf0005" file="CN104357080AD00061.tif" img-content="drawing" img-format="tif" />

Can be seen as the reaction time is prolonged and the desulfurization efficiency is increased gradually 1.5 h after the mutation of the desulfurizing rate increases fast 2 h of the desulfurizing rate reaches 10% 52 2 h and gradually steadily. Thus the optical catalytic oxidation reaction in the process of reaction time is 1-3 h are relatively and it is suitable for.

[0027] embodiment 11-14; Diesel oil or gasoline light catalytic oxidation desulphurization experiment the experiment condition is: Diesel oil of 10 mu dosage of catalyst is diesel oil the quality of 1 wt % the reaction time is 2 h * he acid loading amount is 10 wt% oxygen flow is 150 r/min blood 125 w ultraviolet light source nmp more than 90 percent water solution as extracting agent and solvent oil ratio of 1: 1 changes inspecting the reaction temperature reaction temperature is controlled tc 3 5 7 9 tc tc the desulphurization ratio the influence of the experiment result in the table 2.

[0028] table 2 the reaction temperature the effect of dephosphorization and desulphurization is the influence of

<img id="idf0006" file="CN104357080AD00062.tif" img-content="drawing" img-format="tif" />

Can be seen when the reaction temperature is lower than 90 degrees c when the reaction temperature of the desulfurizing rate gradually increases from 90 ° c the desulphurization ratio is the highest 61 52.

[0029] embodiment 15-19: Diesel oil or gasoline light catalytic oxidation desulphurization experiment the experiment condition is: Diesel oil of 10 mu dosage of catalyst is diesel oil the quality of 1 wt % the reaction temperature is 90 degrees c reaction time is 2 h oxygen flow is 150 r/min blood 125 w ultraviolet light source nmp more than 90 percent water solution as extracting agent and solvent oil ratio of 1: 1 change hpw detected load quantity of active component * he acid loading weight is 5 wt% 5 wt percent lowt 7 to 12 5 wt percent 15wt to the desulphurization ratio the influence of the experiment result in the meter 3.

[0030] meter 3 * he acid load of the desulfurizing effect the influence of

<img id="idf0007" file="CN104357080AD00063.tif" img-content="drawing" img-format="tif" />

Can be seen as the active ingredient * he acid load of the increasing of the light catalyzing and the desulfurization efficiency is firstly increased and reduced in * he acid loading amount is 10 wt% of the desulphurization ratio is the highest 61 52.

[003] u embodiment 20: Diesel oil or gasoline light catalytic oxidation desulphurization test for the specific operation is; 80 c the extraction agent nmp more than 90 percent water solution in reaction initial adding ioml from diesel oil entering the reaction system and agent oil ratio of 1: 1 adding up of diesel quality of 0 to 36 0/0 surface active agent span60 other the reaction condition is not changed dosage of catalyst is diesel oil the quality of iwt percent oxygen flow is 150 ml/min 125w ultraviolet light source 2 h and inspecting effect of dephosphorization and desulphurization is no lifting. The experimental result in the surface 4.

[0032] 4 surface in reaction process adding nmp more than 90 percent the effect of dephosphorization and desulphurization is the influence of _

<img id="idf0008" file="CN104357080AD00064.tif" img-content="drawing" img-format="tif" />

Visible adding extracting agent to react after the photocatalytic oxidation of the desulfurizing efficiency is increased the 68 55% relative to 52 10% it has large this invention claims a local.

<img id="idf0009" file="CN104357080AD00065.tif" img-content="drawing" img-format="tif" />

<img id="idf0010" file="CN104357080AD00066.tif" img-content="drawing" img-format="tif" />

<img id="idf0011" file="CN104357080AD00067.tif" img-content="drawing" img-format="tif" />

<img id="idf0012" file="CN104357080AD00068.tif" img-content="drawing" img-format="tif" />