CN101524641A - On-line oxidized regenerating method of oil product desulfurizing and denitrifying absorbent - Google Patents
On-line oxidized regenerating method of oil product desulfurizing and denitrifying absorbent Download PDFInfo
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- CN101524641A CN101524641A CN200910082847A CN200910082847A CN101524641A CN 101524641 A CN101524641 A CN 101524641A CN 200910082847 A CN200910082847 A CN 200910082847A CN 200910082847 A CN200910082847 A CN 200910082847A CN 101524641 A CN101524641 A CN 101524641A
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- 238000000034 method Methods 0.000 title claims abstract description 43
- 230000003009 desulfurizing effect Effects 0.000 title claims abstract description 34
- 239000002250 absorbent Substances 0.000 title claims abstract description 22
- 230000002745 absorbent Effects 0.000 title claims abstract description 22
- 230000001172 regenerating effect Effects 0.000 title claims abstract description 22
- 230000008929 regeneration Effects 0.000 claims abstract description 31
- 238000011069 regeneration method Methods 0.000 claims abstract description 31
- 230000008569 process Effects 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 238000001179 sorption measurement Methods 0.000 claims abstract description 16
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 7
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000004767 nitrides Chemical class 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 3
- 239000003463 adsorbent Substances 0.000 claims description 30
- 230000003647 oxidation Effects 0.000 claims description 25
- 238000007254 oxidation reaction Methods 0.000 claims description 25
- 238000009418 renovation Methods 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000007800 oxidant agent Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000006477 desulfuration reaction Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 8
- 238000010926 purge Methods 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002283 diesel fuel Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 5
- 230000008439 repair process Effects 0.000 claims description 5
- -1 tertbutanol peroxide Chemical class 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N tert-butyl alcohol Substances CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000003570 air Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000010923 batch production Methods 0.000 claims description 2
- 238000010924 continuous production Methods 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000003502 gasoline Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000003350 kerosene Substances 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- IXZDIALLLMRYOU-UHFFFAOYSA-N tert-butyl hypochlorite Chemical compound CC(C)(C)OCl IXZDIALLLMRYOU-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 5
- 239000012492 regenerant Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 235000011149 sulphuric acid Nutrition 0.000 abstract 1
- 239000001117 sulphuric acid Substances 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 35
- 238000005516 engineering process Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 6
- 230000023556 desulfurization Effects 0.000 description 6
- 229910017464 nitrogen compound Inorganic materials 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 230000007420 reactivation Effects 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000002199 base oil Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- HXELDDLUAGVKCK-UHFFFAOYSA-N [N]=O.[S] Chemical class [N]=O.[S] HXELDDLUAGVKCK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
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- 239000000446 fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002897 organic nitrogen compounds Chemical class 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to an on-line oxidized regenerating method of oil product desulfurizing and denitrifying absorbent. The invention is characterized in that the method comprises the steps as follows: (1) firstly, a certain amount of absorbent desulfurizing and denitrifying agent is filled in a fixed bed reactor and oil which contains a certain amount of sulphide and nitride is used as raw material to carry out adsorption; (2) feeding is stopped when the absorbent is saturated and the status is altered into regenerating to carry out on-online regenerating which uses solvent including oxidizing substances, such as sulphuric acid, nitric acid and the like, as regenerant; the regenerating process is carried out under certain temperature, airspeed and pressure; and (3) the whole absorbing bed layer is dried by sweep gas when the regeneration is over, thereby obtaining regenerated desulfurizing and denitrifying absorbent.
Description
Technical field
The invention belongs to the petroleum refining field, relate to a kind of on-line oxidation renovation process of oil product desulfurizing and denitrifying absorbent.
Background technology
Oxysulfide (SOx), nitrogen oxide (NOx) that sulphur in the fuel oil, nitrogen burning back form are pollutant main in the atmosphere, can form acid rain simultaneously, and the serious harm environment destroys the ecological balance; On the other hand, when oil product synthesized other products as initial feed, sulfur-nitrogen compound wherein can pollute the catalyst of using in the production process (particularly noble metal catalyst), reduces its catalytic activity, shortens its service life.Therefore, oil product deep desulfuration, denitride technology have more and more received various countries' oil refining worker's concern, have become one of key technology that improves oil quality.
Difference according to sulfur-bearing, nitrogen-containing compound character in the oil product can adopt diverse ways to remove.The method that reduces at present sulfur-nitrogen compound sulfur-bearing in the oil product mainly contains hydrogenation method and non-hydrogenation method, and hydrogenation method removes the comparison difficulty for condensed ring class sulfide, nitride and derivative thereof, and requires harsh conditions such as high temperature, high pressure and hydrogen existence.
Absorption method desulfurization, denitrogenation are the new methods that removes sulfur-nitrogen compound in the oil product, have characteristics such as simple to operate, the low and environmental nonpollution of investment.The adsorbent desulfurizing and denitrifying technology is because its unique technique advantage has obtained the extensive industrialized application at aspects such as petrol and diesel oil adsorption desulfurize, lubricant base-oil denitrification are refining in recent years, having played more and more important effect aspect saving cost of investment, the minimizing environmental pollution, developed into one of requisite technological means of oil refinery gradually.
At present, the major defect that adsorption technology is applied in oil product (particularly heavy oil product) desulfurization removing nitric is that adsorbent capacity is not high, and the life-span is shorter, needs frequent regeneration; The adsorbent that has even can not adopt the effective method recycling of regenerating, as the atlapulgite that adopts in the lube base oil subtractive process, substantially the recycling of can not regenerating, usually adopt the mode of burying to handle spent sorbents, the a large amount of industrial residues that produce have brought serious harm to environment, so the recycling of the regeneration cycle of adsorbent is the problem that adsorbent desulfurizing and denitrifying presses for solution.Present existing renovation process mainly is high-temperature roasting, but can produce a large amount of sulphur nitrogen oxides on the one hand when adopting this method, and on the other hand, high-temperature roasting may burning-off part oil product, causes the loss of oil product fuel value.Another method is to adopt solvent extraction regeneration, but this method need consume a large amount of solvents, and thorough desorption and regeneration, and need handle solvent again, makes technology loaded down with trivial details, the cost rising.Therefore, it is simple to press for regeneration technology, and desulfurization removing nitric rate height can not influence the renovation process of adsorbent character.
Oxidation sweetening (ODS) is a kind of can carrying out at normal temperatures and pressures, does not expend hydrogen, and equipment investment is less, can have the green desulfurization technology of higher removal efficiency to the DBT compounds that catalytic hydrogenation is difficult to remove.The employed oxidant of oxidation sweetening mainly is divided into two classes, water-soluble oxidizers and oil-soluble oxidant.Although oxidation sweetening has been obtained certain progress in academic research, but brought water in the water-soluble oxidizers oxidizing process in above-mentioned two kinds of oxidants, caused the emulsification of oil easily, the oil-soluble oxidant will be mixed in the oil product and just can work, the subsequent technique complexity is difficult to industrialization.
The present invention uses for reference the oxidation sweetening principle on the basis of consulting a large amount of oxidation sweetening documents, apply it in the regenerative process of saturated adsorbent, has obtained regeneration effect preferably.Carry out on-line oxidation regeneration with the solvent that contains oxidizing substance as the regenerative agent of saturated adsorbent, be converted into material after sulfur-nitrogen compound on the adsorbent is oxidized with certain polarity, be easy to be dissolved in the polar solvent and taken away, thereby reach regeneration effect preferably by solvent.
CN101069839A discloses a kind of renovation process of desulfurizing and denitrogenating adsorbant.The adsorbent adding of having adsorbed organic sulfur compound and organic nitrogen compound is contained the water of desulfurization removing nitric microbial cell and the mixed system of oil phase, at 30 ℃ of reaction regenerations, the adsorbent that filtration, drying, roasting obtain regenerating.This method has certain desulfurization removing nitric effect, adsorbent after the regeneration can take off oil product sulphur nitrogen content below the 50ppm, but there is the water-oil separating step in this technological operation complexity, adsorbent need be drawn off from reactor when regenerating simultaneously, cause operation inconvenience.
The objective of the invention is: at the present situation of prior art adsorbent reactivation difficulty, provide a kind of regeneration technology simple, regeneration back adsorbent activity is recovered a kind of on-line oxidation renovation process of oil product desulfurizing and denitrifying absorbent.
Summary of the invention
For overcoming the deficiencies in the prior art, the present invention provides a kind of technology simple on the basis of using for reference the oxidation sweetening principle, the restorative good on-line oxidation renovation process of regeneration back adsorbent activity.
The present invention relates to a kind of on-line oxidation renovation process of oil product desulfurizing and denitrifying absorbent, it is characterized in that, comprise the steps:
(1) at first loading a certain amount of adsorbent desulfurizing and denitrifying agent in the fixed bed reactors, is that raw material adsorbs with the oil product that contains a certain amount of sulfide and nitride;
(2) adsorbent stops charging after saturated, and switching to reproduced state is that regenerative agent carries out online regeneration with the solvent that contains oxidizing substance, and regenerative process is carried out under uniform temperature, air speed and pressure;
(3) use sweep gas instead after regeneration finishes and whole adsorption bed is carried out drying, the desulfurizing and denitrogenating adsorbant that obtains regenerating;
The renovation process of described oil product desulfurizing and denitrifying absorbent is characterized in that, the oil product that contains a certain amount of sulfide and nitride described in the step (1) is gasoline, kerosene, diesel oil, vacuum distillate, hydrocracking tail oil, the lube base wet goods.
The on-line oxidation renovation process of described oil product desulfurizing and denitrifying absorbent is characterized in that the quality percentage composition of desulfuration adsorbent is: the agent 8～20% of NaOH alkalescence, copper nitrate complexing agent 6～20%, alumina support powder 60～80%, water 6～20%; The quality percentage composition of denitrification adsorbent is: sulfuric acid agent 8～20%, complexing agent ferric sulfate 6～20%, alumina support powder 60～80%, water 6～20%.
The on-line oxidation renovation process of described oil product desulfurizing and denitrifying absorbent, it is characterized in that the oxidizing substance described in the step (2) is selected from nitric acid, sulfuric acid, Peracetic acid, hydrogen peroxide, t-butyl hypochlorite, tertbutanol peroxide, described solvent is selected from methyl alcohol, ethanol, propyl alcohol, formic acid, acetate, water, benzene,toluene,xylene, and oxidizing substance is 5-10% with the ratio of solvent quality mark.
The on-line oxidation renovation process of described oil product desulfurizing and denitrifying absorbent is characterized in that the regenerative process described in the step (2) can be a continuous process, also can be batch process.
The on-line oxidation renovation process of described oil product desulfurizing and denitrifying absorbent is characterized in that the regeneration air speed described in the step (2) is 0.5～10h
-1, regeneration temperature is normal temperature～300 ℃, regeneration pressure is normal pressure～4Mpa.
The on-line oxidation renovation process of described oil product desulfurizing and denitrifying absorbent is characterized in that the sweep gas described in the step (3) is selected from nitrogen, air, helium, argon gas, and purging temperature is 100～300 ℃, air speed 10～10000h
-1, purge time is 0.5～40h.
The invention has the advantages that adopt fixed bed on-line oxidation regeneration technology, method is simple, adsorbent activity is restorative good, can repeatedly reuse, the regeneration of having avoided the high-temperature roasting reproducing adsorbent to bring is not thorough, the oil product calorific value loses defectives such as big, is easy to industrialization.
The specific embodiment
Below in conjunction with specific embodiment purpose of the present invention and effect are described further, but it does not limit the scope of the invention.
Embodiment 1
(the quality percentage composition is: NaOH 8% with the 10ml adsorption desulfurizing agent, copper nitrate 6%, support powder 80%, water 6%) and the 10ml adsorption denitrifier (the quality percentage composition is: sulfuric acid 8%, ferric sulfate 6%, support powder 80%, water 6%) be seated on the miniature adsorption reaction device of 20ml fixed bed, with diesel oil (diesel oil character is as shown in table 1 after hydrocracking tail oil and the hydrotreatment) after domestic certain oil plant hydrocracking tail oil and the hydrotreatment is that raw material carries out the continuous dynamic adsorption experiment, and the absorbing process condition is 100 ℃ of adsorption temps, normal pressure, air speed 1.0h
-1, negate should be carried out the detection of sulphur nitrogen content by preceding 50h product; The saturated back of adsorbent is that regenerative agent carries out online regeneration with tertbutanol peroxide/methyl alcohol (tertbutanol peroxide mass fraction 5% solvent methanol 95%) system, and technological condition of regeneration is: 100 ℃ of regeneration temperatures, normal pressure, air speed 1.0h
-1, recovery time 5h; The regeneration back adopts nitrogen to purge, and the purging condition is: 150 ℃ of temperature, normal pressure, air speed 500h
-1, purge time 10h, back adsorption desulfurizing agent A1, denitrifier B1 obtain regenerating.
Embodiment 2
With embodiment 1, just change regenerative agent into Peracetic acid/acetate (Peracetic acid mass fraction 5%), back adsorption desulfurizing agent A2, denitrifier B2 obtain regenerating.
Embodiment 3
With embodiment 1, the air speed of just will regenerating changes 5.0h into
-1, back adsorption desulfurizing agent A3, denitrifier B3 obtain regenerating.
Embodiment 4
With embodiment 1, the air speed of just will regenerating changes 8.0h into
-1, back adsorption desulfurizing agent A4, denitrifier B4 obtain regenerating.
After the saturated adsorbent reactivation, adopt again that diesel oil is that raw material carries out the continuous dynamic adsorption experiment after hydrocracking tail oil and the hydrotreatment, the absorbing process condition is 100 ℃ of adsorption temps, normal pressure, air speed 1.0h
-1Constant, the adsorbent desulfurizing and denitrifying effect is as shown in table 2 before and after the regeneration:
Table 1 experiment feedstock property
The character of refined oil before and after table 2 adsorbent reactivation
Claims (7)
1, a kind of on-line oxidation renovation process of oil product desulfurizing and denitrifying absorbent is characterized in that, comprises the steps:
(1) at first loading a certain amount of adsorbent desulfurizing and denitrifying agent in the fixed bed reactors, is that raw material adsorbs with the oil product that contains a certain amount of sulfide and nitride;
(2) adsorbent stops charging after saturated, and switching to reproduced state is that regenerative agent carries out online regeneration with the solvent that contains oxidizing substance, and regenerative process is carried out under uniform temperature, air speed and pressure;
(3) use sweep gas instead after regeneration finishes and whole adsorption bed is carried out drying, the desulfurizing and denitrogenating adsorbant that obtains regenerating;
2, according to the on-line oxidation renovation process of the described oil product desulfurizing and denitrifying absorbent of claim 1, it is characterized in that, the oil product that contains a certain amount of sulfide and nitride described in the step (1) is gasoline, kerosene, diesel oil, vacuum distillate, hydrocracking tail oil, the lube base wet goods.
3, according to the on-line oxidation renovation process of the described oil product desulfurizing and denitrifying absorbent of claim 1, it is characterized in that the quality percentage composition of desulfuration adsorbent is: the agent 8～20% of NaOH alkalescence, copper nitrate complexing agent 6～20%, alumina support powder 60～80%, water 6～20%; The quality percentage composition of denitrification adsorbent is: sulfuric acid agent 8～20%, complexing agent ferric sulfate 6～20%, alumina support powder 60～80%, water 6～20%.
4, according to the on-line oxidation renovation process of the described oil product desulfurizing and denitrifying absorbent of claim 1, it is characterized in that, oxidizing substance described in the step (2) is selected from nitric acid, sulfuric acid, Peracetic acid, hydrogen peroxide, t-butyl hypochlorite, tertbutanol peroxide, described solvent is selected from methyl alcohol, ethanol, propyl alcohol, formic acid, acetate, water, benzene,toluene,xylene, and oxidizing substance is 5-10% with the ratio of solvent quality mark.
According to the on-line oxidation renovation process of the described oil product desulfurizing and denitrifying absorbent of claim 1, it is characterized in that 5, the regenerative process described in the step (2) can be a continuous process, also can be batch process.
According to the on-line oxidation renovation process of the described oil product desulfurizing and denitrifying absorbent of claim 1, it is characterized in that 6, the regeneration air speed described in the step (2) is 0.5～10h
-1, regeneration temperature is normal temperature～300 ℃, regeneration pressure is normal pressure～4Mpa.
According to the on-line oxidation renovation process of the described oil product desulfurizing and denitrifying absorbent of claim 1, it is characterized in that 7, the sweep gas described in the step (3) is selected from nitrogen, air, helium, argon gas, purging temperature is 100～300 ℃, air speed 10～10000h
-1, purge time is 0.5～40h.
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| CN108467745A (en) * | 2017-02-23 | 2018-08-31 | 中国石油化工股份有限公司 | The method of nitride in molecular sieve catalytic oxidation removal oil product |
| CN108704630A (en) * | 2018-05-23 | 2018-10-26 | 华南理工大学 | A kind of support type hydroxide desulfurizing agent is for the oxidized regenerating method after gasoline absorbing desulfurization |
| WO2019134428A1 (en) * | 2018-01-04 | 2019-07-11 | 华南理工大学 | Supported hydroxide gasoline deep adsorption desulfurizing agent and preparation method and oxidation regeneration method therefor |
| CN111996030A (en) * | 2020-08-11 | 2020-11-27 | 中海油天津化工研究设计院有限公司 | Method for in-situ regeneration of simulated moving bed adsorbent |
| CN113088326A (en) * | 2021-04-22 | 2021-07-09 | 江苏大学 | Process for diesel adsorption-catalytic oxidation series ultra-deep desulfurization and denitrification |
| CN115672298A (en) * | 2022-10-24 | 2023-02-03 | 中国石油化工股份有限公司 | Green energy-saving regeneration method of adsorbent for removing impurities from ester oil |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1204955C (en) * | 2002-01-29 | 2005-06-08 | 国家电站燃烧工程技术研究中心 | Cyclic fluidized bed active coke desulfurating and sulfur reutilization method |
| CN100486689C (en) * | 2006-05-08 | 2009-05-13 | 中国科学院过程工程研究所 | Method for regenerating desulfurizing and denitrogenating adsorbant |
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Cited By (8)
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| WO2019134428A1 (en) * | 2018-01-04 | 2019-07-11 | 华南理工大学 | Supported hydroxide gasoline deep adsorption desulfurizing agent and preparation method and oxidation regeneration method therefor |
| US11458449B2 (en) | 2018-01-04 | 2022-10-04 | South China University Of Technology | Supported metal hydroxide adsorbent for ultra-deep desulfurization of gasoline and methods for its preparation and its oxidative regeneration |
| CN108704630A (en) * | 2018-05-23 | 2018-10-26 | 华南理工大学 | A kind of support type hydroxide desulfurizing agent is for the oxidized regenerating method after gasoline absorbing desulfurization |
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| CN111996030B (en) * | 2020-08-11 | 2022-03-29 | 中海油天津化工研究设计院有限公司 | Method for in-situ regeneration of simulated moving bed adsorbent |
| CN113088326A (en) * | 2021-04-22 | 2021-07-09 | 江苏大学 | Process for diesel adsorption-catalytic oxidation series ultra-deep desulfurization and denitrification |
| CN115672298A (en) * | 2022-10-24 | 2023-02-03 | 中国石油化工股份有限公司 | Green energy-saving regeneration method of adsorbent for removing impurities from ester oil |
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