CN104629792A - Method for removing nitride from heavy oil - Google Patents
Method for removing nitride from heavy oil Download PDFInfo
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- CN104629792A CN104629792A CN201510057910.8A CN201510057910A CN104629792A CN 104629792 A CN104629792 A CN 104629792A CN 201510057910 A CN201510057910 A CN 201510057910A CN 104629792 A CN104629792 A CN 104629792A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/20—Organic compounds not containing metal atoms
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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Abstract
The invention provides a method for removing nitride from heavy oil. The method comprises the following steps: allowing a supported ionic liquid denitriding agent and the heavy oil to react; after the reaction, cooling a reaction system; centrifugally treating the reaction mixture; separating the denitriding agent to obtain denitrided heavy oil, wherein by selection and combination of each component in the supported ionic liquid denitriding agent and the used amount and by specific technological treatment and parameters of a preparation method, the denitriding agent is good in denitriding effect and excellent in recycle capability, so that the method disclosed by the invention has lots of advantages of simple process, environmental protection and low cost and is a method, which has quite good industrial application prospect, for removing the nitride from the heavy oil.
Description
Technical field
The present invention relates to a kind of method adopting denitrfying agent to remove nitride in heavy oil, particularly the removal methods of nitride in a kind of heavy oil using solid-loaded ionic-liquid to be denitrfying agent, belongs to petrochemical industry.
Background technology
In recent years, along with heaviness and the in poor quality of world wide crude oil, improve the heavy oil conversion degree of depth, increase light-end products output becomes more and more important.At present, the techniques such as coking, heavy oil fluid catalytic cracking and heavy-oil hydrogenation process become main heavy oil upgrading method.
Coking process is as a kind of important hot-work means, the heavy oil of high-sulfur, high nitrogen, high metal content can be processed, technical process is simple, investment and process cost lower, and after coking naphtha hydrogenation, can be used as the raw material of cracking ethylene device, there is unique importance in the inferior heavy oil course of processing.Wax tailings (CGO) is the cut (accounting for 20-40%) that coker yield is maximum, and by the end of the end of the year 2009, annual output will be about 2,180 ten thousand tons.
What wax tailings generally can do catalytic cracking (or hydrocracking) mixes raw material, or as hydrocracking or hydrorefined raw material, but wherein nitride, condensed-nuclei aromatics and gum level are high, can cause that the feedstock conversion degree of depth declines, product slates is deteriorated mixing in refining process, generally can only supplement as the small proportion of hydrocracking or catalytically cracked material.
The a large amount of nitride contained in wax tailings are the major causes affecting its reactivity worth, and have impact to the stability of catalyzer and activity, especially basic nitrogen compound can make poisoning of catalyst.And nitride itself is also unstable, easy condensation green coke causes catalyst deactivation.
At present, the method for heavy oil denitrogenation mainly comprises hydrofining and non-hydrogenation.The method that non-hydrogenation is conventional has the methods such as absorption conversion process, absorption method, acid-base neutralisation method, solvent extraction and Complex denitrogenation, microwave method, microorganism.But by contrast, heavy-oil hydrogenation is refined has comparatively outstanding advantage, and abroad, heavy oil usually all will through hydrofining as fcc raw material.And China is due to hydrogen source anxiety, greatly, hydrofining production cost is high for hydrogen manufacturing and hydrogenation unit investment.Therefore non-hydrogenation also has very large potential at home.
The Zhang Rui of Research Institute of Petro-Chemical Engineering speeds to wait people (Zhang Ruichi, Shi Wenyuan, " catalytic cracking absorption transforms the research and development of processing heavy oil technique ", " refining of petroleum and chemical industry ", 1998,29 (11): 22-26) have developed heavy oil sorption conversion process (DNCC technique) earlier, and achieve industrialization in Shijiazhuang Oil Refinery, but it exists problems such as recycle ratio increases, the high and environmental pollution of process cost.
Because cationic activation resin is larger than common adsorbents (as clay) loading capacity, cationic activation resin adsorption method becomes the method for the basic nitrogen compound in the effective elimination heavy oil of rising in recent years.
The people such as Sun Jingjun (Sun Jingjun, repair Peng Hao, Cong Ming etc., " research of the absorption denitrogenation of heavy oil activated resin and reactivity worth ", " oil and gas chemical industry ", 2014,43 (3): 234-240) D72 cationic activation resin and D001-CC cationic activation resin is adopted to carry out absorption denitrogenation research to heavy oil.Result shows, D001-CC cationic activation resin absorption denitrification percent is 80.1%, D72 activated resin absorption denitrification percent is 79.8%.
The people such as Hu Yang (Hu Yang, Cao Ping, Wang Lei etc., " technical study of shale oil distillate Non-hydrogenation technology ", " chemical industry and engineering ", 2011,28 (1): 55-59) adopt D61 cationic activation resin to remove basic nitrogen in shale oil distillate, result of study shows that the decreasing ratio of basic nitrogen compound is 60%.
Because the nitride in heavy oil is mainly with the quinoline of aromaticity, isoquinoline 99.9 and homologue, the homologue of pyridine, carbazole and homologue thereof, the form of indoles and homologue etc. thereof exists.No matter alkalescence and non-alkaline nitrogenous compound, its nitrogen-atoms is all in ring structure, is nitrogen heterocyclic based compound.Aliphatic nitrogen compound is less discovery in oil.Therefore, adopting polar solvent to carry out selective solvent to heavy oil and refine, is also the method for the impurity such as effective extraction nitride wherein.
But domestic heavy oil solvent treatment technology is also immature, the solvent that solvent also adopts lube oil finishing to utilize substantially: furfural, phenol and N-Methyl pyrrolidone, SO
3and mineral acid, dimethyl amide (DMF) etc., wherein furfural application is wider.
Wan Yinkun (Wan Yinkun, " research of lube oil furfural refining two-section extraction ", " refining of petroleum and chemical industry ", 1996,27 (3): 26-29) research finds, employing furfural is solvent, shunts two sections and refines and can increase substantially oil yield.
But use SO
3with mineral acid extracting, though there is good denitrification effect, selectivity is poor, and a large amount of hydrocarbon ils is drawn out of, and yield of raffinating oil is low, and has the problem of etching apparatus, contaminate environment.US Patent No. 4960508A, after the defect that have studied mineral acid extraction process, proposes the two-step approach novel process removing BNC with organic acid from oil.
Solvent extraction not only can remove the nitride in lubricating oil distillate effectively, and can remove colloid, polycyclic aromatic hydrocarbons, containing oxygen, sulfur-bearing isopolarity compound, be the most basic in current lube oil finishing and application more a kind of technique.But the selectivity of the method has certain limitation, while removing nitride, sulfocompound useful in a large number and hydro carbons are also removed, and along with the raising of working depth, essential oil yield obviously declines, and the content of basic nitrogen compound will tend to balance.The method is suitable for the refining of coarse raw materials, is not suitable for the post-refining of essential oil and the further raising of oil quality.Comprise SO
3in interior acid treating, there is good effect to removing basic nitrogen compound, but still there is optionally problem, and have the problem of environmental pollution and equipment corrosion.The method is comparatively suitable for the denitrogenation of high nitrogenous rock page oil, seldom applies in oil purification.Therefore, for this defect, be developed multiple improving one's methods, such as:
Shen Xizhou (Shen Xizhou, " highly selective removes the oxidation stability that lubricant base neutral and alkali nitride improves lubricant base ", " lubricating oil ", 1997,12 (2): 28-33) denitrfying agent of a kind of WSQ-2 of being called has been invented to remove the basic nitrogen compound in lubricant base, improve the oxidation stability of base oil, denitrification percent can up to more than 80%.
Wang Yanzhen (Yanzhen Wang, Ruili Li, Chenguang Liu; " Removal of nitrogen compounds from lubricating base stocks with complexing of oxalic acid ", " Fuel Processing Technology ", 2005,86:419-427) etc. utilize oxalic acid and atlapulgite to remove the basic nitrogen compound in lubricant base, simultaneously the method oxalic acid and carclazyte is added in lubricant base, then reacts at 100 DEG C ~ 140 DEG C.The method can remove the basic nitrogen compound of more than 95%.
The people such as Sun Yuhua (Sun Yuhua, Chen Yuezhu, Ma Hua, " TTS removes the nitride in paraffin base lubricating oil base oil ", " refining of petroleum and chemical industry ", 1997,28 (5): 25-28) utilize TTS denitrfying agent to remove the nitride in lubricant base, denitrification percent can reach more than 90%, and the concentration of sulfide only has less reduction.
In base oil, the selectivity of Separation by Complexation method is strong, is the effective ways removing impurity compound in base oil.
The people such as Liu Jie (Liu Jie, Li Wenshen, Li Xiaoou, " heavy oil Complex denitrogenation technology ", " petrochemical technology and application ", 2013,31 (3): 185-188) denitrfying agent adopting polarity complexing agent and organic solvent containing Lewis acid to form, carries out Complex denitrogenation to heavy oil.Result shows, with this understanding, oil yield is 94.76%, and denitrification percent is 66.4%.
CN1107875A discloses and uses titanium sulfate crystal denitrfying agent and organic solvent wiring solution-forming, pour in fraction oil vessel, make the nitrogenous compound of oil reservoir and titanium sulfate solution generation chemical reaction through heating, insulation and form title complex, and be dissolved in organic solvent (as alcohols, ether, ketone, furfural etc.), thus making basic nitrogen reduce more than 70%, the method is applicable to lubricating oil distillate denitrogenation.
The people such as Cheng Yanru (Cheng Yanru, Wang Keqiang, Xiao Changyu, " nitride in silica gel load heteropolyacid adsorbing and removing simulated oil ", " oil and gas chemical industry ", 2015,2) take silica gel as carrier, utilize equi-volume impregnating load 3 kinds of different heteropolyacids to prepare a kind of sorbent material, the removal effect that to investigate with the dodecane solution of quinoline be nitride in simulated oil, investigates the impact of sour charge capacity, reaction times, temperature of reaction, agent oil quality comparison oil denitrification rate.Result shows, under optimal conditions, sorbent material can remove nitride in simulated oil by active adsorption, and denitrification percent reaches more than 90%.
But complexing agent uses the muriate of transition metal usually, and processing charges is higher, particularly when processing foreign matter content height in oil plant, owing to consuming more complexing agent, significantly tooling cost can be increased.
As mentioned above, all there is certain defect in current denitrogenation method, up to now, because heavy oil is as large in heavy oil viscosity, complicated component, not yet has the report and prior art that ionic liquid are used for heavy oil denitrogenation simultaneously.
Therefore, ionic liquid how is used from large viscous systems, to carry out denitrogenation processing with simple, efficient method, having very important industrial significance and economic worth, is also the study hotspot at present in this field and emphasis, this also just the basic place that is accomplished of the present invention and power lean on.
Summary of the invention
As mentioned above, for how using ionic liquid to provide novel heavy oil denitrogenation method, the present inventor, to this has been deep research, after paying a large amount of creative work, thus completes the present invention.
Specifically, first aspect, the present invention relates to the removal methods of nitride in a kind of heavy oil, described method comprises the steps: to make solid-loaded ionic-liquid denitrfying agent and heavy oil generation denitrification reaction, after having reacted, reaction system cooled, reaction mixture carries out centrifugal treating, denitrfying agent is separated, obtains the heavy oil after denitrogenation.
In heavy oil of the present invention nitride removal methods in, the weight ratio of described solid-loaded ionic-liquid denitrfying agent and heavy oil is 1:10-100, be preferably 1:50-80, these scopes include wherein any concrete scope and concrete point value, such as can be 1:10,1:20,1:30,1:40,1:50,1:60,1:70,1:80,1:90 or 1:100 in non-limiting manner.
In heavy oil of the present invention nitride removal methods in, temperature of reaction is 80-250 DEG C, be preferably 100-200 DEG C, these scopes include any concrete scope wherein and concrete point value, such as can be 80 DEG C, 100 DEG C, 150 DEG C, 200 DEG C or 250 DEG C in non-limiting manner.
In heavy oil of the present invention nitride removal methods in, reaction times is 10-60 minute, be preferably 20-40 minute, these scopes include any concrete scope wherein and concrete point value, such as can be 10 minutes in non-limiting manner, 15 minutes, 20 minutes, 25 minutes, 30 minutes, 35 minutes, 40 minutes, 45 minutes, 50 minutes, 55 minutes or 60 minutes.
In heavy oil of the present invention nitride removal methods in, described solid-loaded ionic-liquid denitrfying agent is prepared in accordance with the following steps, and its preparation process is as follows in other words:
S1: by [R
1r
2r
3nH] X
1with MX
2 nmix according to mol ratio 1:1-3, be at room temperature uniformly mixed 20-40 minute, then raised temperature is to 80-100 DEG C, and Keep agitation 2-6 hour at such a temperature, after having reacted, naturally cool to room temperature, dry, obtain basic ionic liquid;
S2: joined by solid carrier in acidic solution, reflow treatment, then filters and obtains solids A; By solids A stir process in mixing acid again, filter, by extremely neutral for the solids B deionized water wash obtained, vacuum-drying, obtains drying solid thing;
S3: join in solvent by the basic ionic liquid of step S1, the drying solid thing of step S2, metallic compound, under an inert atmosphere, stirs and is warming up to 60-90 DEG C, reaction 12-25 hour; After reaction terminates, leave standstill cooling, suction filtration, drying, obtain solid;
S4: the gained solid of step S3 is put into apparatus,Soxhlet's, with solvent extraction 3-12 hour, then filters, deionized water wash, dry, obtain described solid-loaded ionic-liquid denitrfying agent.
In heavy oil of the present invention nitride removal methods in, wherein, in step sl, R
1, R
2and R
3be H, C independently of one another
1-6alkyl or benzyl, and wherein at least one is not H;
Described C
1-6alkyl refers to the straight or branched alkyl with 1-6 carbon atom, such as can be methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, n-hexyl or isohexyl etc. in non-limiting manner.
In heavy oil of the present invention nitride removal methods in, wherein, in step sl, X
1, X
2being halogen independently of one another, such as, is F, Cl, Br or I.
In heavy oil of the present invention nitride removal methods in, wherein, in step sl, [R
1r
2r
3nH] X
1such as can be N, N, N-triethylammonium bromide (also referred to as Hydrogen bromide triethylamine or triethylamine hydrobromide), N, N-di-isopropyl ammonium chloride (also referred to as hydrochloric acid Diisopropylamine or Diisopropylamine hydrochloride) or N-benzyl-N-sec.-propyl ammonium chloride (also referred to as hydrochloric acid N-benzyl Isopropylamine or N-benzyl isopropylamine hydrochloride).
In heavy oil of the present invention nitride removal methods in, wherein, in step sl, M is aluminium, iron or zinc.
In heavy oil of the present invention nitride removal methods in, wherein, in step sl, n is the integer of 2-4, such as, can be 2,3 or 4.
Exemplarily, described MX
2 ncan be any one in aluminum chloride, iron trichloride, iron protochloride, zinc chloride, alchlor, ferric bromide, zinc bromide, ferrous bromide etc., most preferably be aluminum chloride, iron trichloride, alchlor or ferric bromide.
In heavy oil of the present invention nitride removal methods in, wherein, in step sl, [R
1r
2r
3nH] X
1with MX
2 nmol ratio be 1:1-3, such as can be 1:1,1:2 or 1:3.
In heavy oil of the present invention nitride removal methods in, wherein, in step sl, after the mixing of two kinds of materials, be at room temperature uniformly mixed 20-40 minute, such as 20 minutes, 30 minutes or 40 minutes.
In heavy oil of the present invention nitride removal methods in, wherein, in step sl, stirred at ambient temperature mixing is after 20-40 minute, raised temperature is to 80-100 DEG C, be such as 80 DEG C, 90 DEG C or 100 DEG C, and Keep agitation 2-6 hour at such a temperature, such as, can be 2 hours, 3 hours, 4 hours, 5 hours or 6 hours.
In heavy oil of the present invention nitride removal methods in, wherein, in step s 2, described solid carrier is selected from gac, SiO
2, any one in aluminum oxide or mesopore molecular sieve or any multiple mixture, wherein mesopore molecular sieve is the very known molecular sieve of one, such as, can be MCM-48 mesopore molecular sieve or SBA-15 mesopore molecular sieve etc.
In heavy oil of the present invention nitride removal methods in, wherein, in step s 2, described acidic solution such as can be aqueous hydrochloric acid, aqueous nitric acid or aqueous sulfuric acid, and its concentration is 1-3mol/L, such as, can be 1mol/L, 2mol/L or 3mol/L.
In heavy oil of the present invention nitride removal methods in, wherein, in step s 2, the mass volume ratio of described solid carrier and described acidic solution is 1:5-25g/ml, namely every 1g solid carrier joins in 5-25ml acidic solution, such as, can be 1:5g/ml, 1:10g/ml, 1:15g/ml, 1:20g/ml or 1:25g/ml.
In heavy oil of the present invention nitride removal methods in, wherein, in step s 2, the return time of described reflow treatment is 2-10 hour, such as, can be 2 hours, 4 hours, 6 hours, 8 hours or 10 hours.
In heavy oil of the present invention nitride removal methods in, wherein, in step s 2, described mixing acid is the mixed solution of the vitriol oil and concentrated nitric acid, and wherein the volume ratio of the vitriol oil and concentrated nitric acid is 2-4:1; The aqueous sulfuric acid of the described vitriol oil and mass percent concentration >=70%, the aqueous nitric acid of concentrated nitric acid and mass percent concentration >=65%.
In heavy oil of the present invention nitride removal methods in, wherein, in step s 2, the mass volume ratio of described solids A and described mixing acid is 1:8-12g/ml, namely every 1g solids A uses 8-12g mixed acid solution, such as, can be 1:8g/ml, 1:10g/ml or 1:12g/ml.
In heavy oil of the present invention nitride removal methods in, wherein, in step s 2, the time of solids A stir process in mixing acid is 20-50 minute, such as, can be 20 minutes, 30 minutes, 40 minutes or 50 minutes.
In heavy oil of the present invention nitride removal methods in, wherein, in step s 2, " solids A " and " solids B " is only used to refer to the solids that twice process obtains, " A " and " B " wherein not special fixing implication.
In heavy oil of the present invention nitride removal methods in, wherein, in step s3, described metallic compound is vitriol or the nitrate of copper, nickel, zinc, silver or cobalt etc., such as, can be any one in copper sulfate, cupric nitrate, cuprous sulfate, single nickel salt, nickelous nitrate, zinc sulfate, zinc nitrate, Sulfuric acid disilver salt, Silver Nitrate or Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES etc. or any multiple mixture; Most preferably be copper sulfate or Silver Nitrate.
In heavy oil of the present invention nitride removal methods in, wherein, in step s3, the mass ratio of the basic ionic liquid of step S1, the drying solid thing of step S2, metallic compound is 1:2-4:0.1-1.5, such as, can be 1:2:0.1,1:2:0.5,1:2:1,1:2:1.5,1:3:0.5,1:3:1,1:3:1.5,1:4:0.5,1:4:1 or 1:4:1.5 etc.
In heavy oil of the present invention nitride removal methods in, wherein, the solvent in step S3 and step S4 is any one in acetonitrile, chloroform, benzene, toluene, ethanol, n-propyl alcohol, propyl carbinol, acetone or ethyl acetate etc.
In heavy oil of the present invention nitride removal methods in, wherein, in step s3, described inert atmosphere such as can be nitrogen atmosphere or argon gas atmosphere.
In heavy oil of the present invention nitride removal methods in, wherein, in step s3, three kinds of materials are joined in solvent, stir intensification 60-90 DEG C in an inert atmosphere, reaction 12-25 hour; Described temperature is 60-90 DEG C, such as, can be 60 DEG C, 70 DEG C, 80 DEG C or 90 DEG C, and the described time is 12-25 hour, such as, can be 12 hours, 15 hours, 18 hours, 21 hours or 25 hours.
In heavy oil of the present invention nitride removal methods in, in step s 4 which, with solvent extraction 3-12 hour, such as, can be 3 hours, 5 hours, 7 hours, 9 hours, 11 hours or 12 hours.
In heavy oil of the present invention nitride removal methods in, in step S3 and S4, the consumption of solvent is not particularly limited, as long as it can make to react in step S3 to carry out smoothly, and the extracting in step S4 is carried out smoothly, those skilled in the art reasonably can determine according to routine techniques means, and this is no longer going to repeat them.
In heavy oil of the present invention nitride removal methods in, described heavy oil is the heavy oil in petrochemical industry on conventional meaning, such as, can be wax tailings, long residuum or vacuum residuum etc.
In heavy oil of the present invention nitride removal methods in, described solid-loaded ionic-liquid denitrfying agent is repeatedly reusable, such as reusable 5-15 time, such as 5 times, 7 times, 9 times, 11 times, 13 times or 15 times further.
Second aspect, the invention still further relates to the solid-loaded ionic-liquid denitrfying agent used in above-mentioned removal methods, described solid-loaded ionic-liquid denitrfying agent of the present invention has good nitrogen removal performance, and cyclical stability is good, be particularly well-suited in the denitrogenation processing of high viscosity systems as various heavy oil, have a good application prospect and industrial value at petrochemical industry.
As mentioned above, the invention provides the removal methods of nitride in a kind of heavy oil and a kind of solid-loaded ionic-liquid denitrfying agent, in this removal methods, by the combination of the use of the solid-loaded ionic-liquid denitrfying agent of uniqueness etc. and processing parameter/collaborative, especially the specific preparation method of solid-loaded ionic-liquid denitrfying agent and the selection of concrete composition, thus make the solid-loaded ionic-liquid denitrfying agent of the present invention of first back loading two kinds of metals can be used for the denitrification reaction of the large heavy oil system of viscosity, and relative to denitrogenation method of the prior art, achieve good technique effect and plurality of advantages, such as:
1, any organic solvent is not used in denitrification reaction of the present invention, thus free from environmental pollution, and not producing the pollutent such as spent solvent, waste water in technological process, is a kind of technological process of environmental protection, has good social effect and environmental value.
2, denitrfying agent of the present invention can very simply with product separation, and can circulate repeatedly use and do not reduce denitrification activity, have good reusability and economic worth, this is even more important in industrial applications, can reduce costs significantly.
3, denitrfying agent of the present invention has excellent denitrification effect, and denitrification percent is up to more than 95%, and the reaction times is shorter, can realize fast denitrogenation, improve production efficiency, accelerate treatment scheme, has processing feature and advantage fast and efficiently.
Embodiment
Below by specific embodiment, the present invention is described in detail; but the purposes of these exemplary embodiments and object are only used for exemplifying the present invention; not any type of any restriction is formed to real protection scope of the present invention, more non-protection scope of the present invention is confined to this.
The preparation of solid-loaded ionic-liquid denitrfying agent
Preparation example 1: the preparation of denitrfying agent T1
S1: by N, N, N-triethylammonium bromide ([(C
2h
5)
3nH] Br, also referred to as Hydrogen bromide triethylamine or triethylamine hydrobromide) and aluminum chloride (AlCl
3) mix according to mol ratio 1:1, be at room temperature uniformly mixed 20 minutes, then raised temperature to 80 DEG C, and Keep agitation 2 hours at such a temperature, after having reacted, naturally cool to room temperature, dry, obtain basic ionic liquid;
S2: gac being joined volumetric molar concentration is (mass volume ratio of gac and aqueous hydrochloric acid is 1:5g/ml) in the aqueous hydrochloric acid of 1mol/L, reflow treatment 2 hours, then filters and obtains solids A; By solids A stir process 20 minutes (mass volume ratio of described solids A and described mixing acid is 1:8g/ml) in mixing acid (volume ratio is the vitriol oil of 2:1 and the mixed solution of concentrated nitric acid) again, filter, by extremely neutral for the solids B deionized water wash obtained, vacuum-drying, obtains drying solid thing;
S3: join in acetonitrile according to mass ratio 1:2:0.1 by the drying solid thing of the basic ionic liquid of step S1, step S2, copper sulfate, in a nitrogen atmosphere, stirs and is warming up to 60 DEG C, react 25 hours; After reaction terminates, leave standstill cooling, suction filtration, drying, obtain solid;
S4: the gained solid of step S3 is put into apparatus,Soxhlet's, with chloroform 4 hours, then filters, deionized water wash, dry, obtains solid-loaded ionic-liquid denitrfying agent CuSO
4/ ([(C
2h
5)
3nH] Br)/AlCl
3/ C, by its called after T1.
Preparation example 2: the preparation of denitrfying agent T2
S1: by N, N-di-isopropyl ammonium chloride ([(i-Pr)
2nH
2] Cl, also referred to as hydrochloric acid Diisopropylamine or Diisopropylamine hydrochloride) and iron trichloride (FeCl
3) mix according to mol ratio 1:2, be at room temperature uniformly mixed 30 minutes, then raised temperature to 90 DEG C, and Keep agitation 4 hours at such a temperature, after having reacted, naturally cool to room temperature, dry, obtain basic ionic liquid;
S2: by SiO
2joining volumetric molar concentration is (SiO in the aqueous nitric acid of 2mol/L
2be 1:15g/ml with the mass volume ratio of aqueous nitric acid), reflow treatment 6 hours, then filters and obtains solids A; By solids A stir process 35 minutes (mass volume ratio of described solids A and described mixing acid is 1:10g/ml) in mixing acid (volume ratio is the vitriol oil of 3:1 and the mixed solution of concentrated nitric acid) again, filter, by extremely neutral for the solids B deionized water wash obtained, vacuum-drying, obtains drying solid thing;
S3: join in toluene according to mass ratio 1:3:0.5 by the drying solid thing of the basic ionic liquid of step S1, step S2, copper sulfate, in a nitrogen atmosphere, stirs and is warming up to 70 DEG C, react 17 hours; After reaction terminates, leave standstill cooling, suction filtration, drying, obtain solid;
S4: the gained solid of step S3 is put into apparatus,Soxhlet's, with benzene extracting 8 hours, then filters, deionized water wash, dry, obtains solid-loaded ionic-liquid denitrfying agent CuSO
4/ ([(i-Pr)
2nH
2] Cl)/FeCl
3/ SiO
2, by its called after T2.
Preparation example 3: the preparation of denitrfying agent T3
S1: by N-benzyl-N-sec.-propyl ammonium chloride ([(i-Pr) (C
6h
5cH
2) NH
2] Cl, also referred to as hydrochloric acid N-benzyl Isopropylamine or N-benzyl isopropylamine hydrochloride) and alchlor (AlBr
3) mix according to mol ratio 1:3, be at room temperature uniformly mixed 40 minutes, then raised temperature to 100 DEG C, and Keep agitation 2 hours at such a temperature, after having reacted, naturally cool to room temperature, dry, obtain basic ionic liquid;
S2: aluminum oxide being joined volumetric molar concentration is (mass volume ratio of aluminum oxide and aqueous sulfuric acid is 1:25g/ml) in the aqueous sulfuric acid of 3mol/L, reflow treatment 10 hours, then filters and obtains solids A; By solids A stir process 50 minutes (mass volume ratio of described solids A and described mixing acid is 1:12g/ml) in mixing acid (volume ratio is the vitriol oil of 4:1 and the mixed solution of concentrated nitric acid) again, filter, by extremely neutral for the solids B deionized water wash obtained, vacuum-drying, obtains drying solid thing;
S3: join in propyl carbinol according to mass ratio 1:4:1 by the drying solid thing of the basic ionic liquid of step S1, step S2, copper sulfate, in a nitrogen atmosphere, stirs and is warming up to 90 DEG C, react 25 hours; After reaction terminates, leave standstill cooling, suction filtration, drying, obtain solid;
S4: the gained solid of step S3 is put into apparatus,Soxhlet's, with acetone extraction 12 hours, then filters, deionized water wash, dry, obtains solid-loaded ionic-liquid denitrfying agent CuSO
4/ ([(i-Pr) (C
6h
5cH
2) NH
2] Cl)/AlBr
3/ Al
2o
3, by its called after T3.
Preparation example 4: the preparation of denitrfying agent T4
Remove the FeCl in the step S1 of preparation example 2
3replace with the FeBr of same amount
3, by the solid carrier in step S2 by SiO
2replace with MCM-48 mesopore molecular sieve, and the drying solid thing of the basic ionic liquid of the step S1 in step S3, step S2, the mass ratio of copper sulfate are replaced with outside 1:3:1.5, to be prepared example 4 with preparation example 2 same way, obtain solid-loaded ionic-liquid denitrfying agent CuSO
4/ ([(i-Pr)
2nH
2] Cl)/FeBr
3/ MCM-48, by its called after T4.
Preparation example 5-8: the preparation of denitrfying agent T5-T8
Except all being replaced with except the Silver Nitrate of same amount by the copper sulfate in the step S3 of preparation example 1-4 respectively, carry out preparation example 5-8 in the mode identical with preparation example 1-4 respectively, specific as follows:
Preparation example 5: the copper sulfate in preparation example 1 step S3 is replaced with Silver Nitrate, gained denitrfying agent is AgNO
3/ ([(C
2h
5)
3nH] Br)/AlCl
3/ C, by its called after T5.
Preparation example 6: the copper sulfate in preparation example 2 step S3 is replaced with Silver Nitrate, gained denitrfying agent is AgNO
3/ ([(i-Pr)
2nH
2] Cl)/FeCl
3/ SiO
2, by its called after T6.
Preparation example 7: the copper sulfate in preparation example 3 step S3 is replaced with Silver Nitrate, gained denitrfying agent is AgNO
3/ ([(i-Pr) (C
6h
5cH
2) NH
2] Cl)/AlBr
3/ Al
2o
3, by its called after T7.
Preparation example 8: the copper sulfate in preparation example 4 step S3 is replaced with Silver Nitrate, gained denitrfying agent is AgNO
3/ ([(i-Pr)
2nH
2] Cl)/FeBr
3/ MCM-48, by its called after T8.
Contrast preparation example 9-16: the preparation of denitrfying agent T9-T16
Except the following MX using same amount in step sl respectively
2 noutward, preparation example 9-16 is contrasted to implement with the same way of preparation example 1-8, by gained denitrfying agent successively called after T9-T16, wherein used MX
2 n, corresponding preparation example and gained denitrfying agent as shown in the table:
The denitrfying agent of preparation example 9-16 is as follows:
T9：CuSO
4/([(C
2H
5)
3NH]Br)/FeCl
2/C；
T10：CuSO
4/([(i-Pr)
2NH
2]Cl)/ZnCl
2/SiO
2；
T11：CuSO
4/([(i-Pr)(C
6H
5CH
2)NH
2]Cl)/ZnBr
2/Al
2O
3；
T12：CuSO
4/([(i-Pr)
2NH
2]Cl)/FeBr
2/MCM-48；
T13：AgNO
3/([(C
2H
5)
3NH]Br)/FeCl
2/C；
T14：AgNO
3/([(i-Pr)
2NH
2]Cl)/ZnCl
2/SiO
2；
T15：AgNO
3/([(i-Pr)(C
6H
5CH
2)NH
2]Cl)/ZnBr
2/Al
2O
3；
T16：AgNO
3/([(i-Pr)
2NH
2]Cl)/FeBr
2/MCM-48。
Contrast preparation example 17-24: the preparation of denitrfying agent T17-T24
Except the following metal compound beyond the region of objective existence using same amount in step s3 respectively, preparation example 17-24 is contrasted to implement with the same way of preparation example 1-8, by gained denitrfying agent successively called after T17-T24, wherein used metallic compound, corresponding preparation example and gained denitrfying agent are as shown in the table:
The denitrfying agent of preparation example 17-24 is as follows:
T17：Cu
2SO
4/([(C
2H
5)
3NH]Br)/AlCl
3/C；
T18：Cu(NO
3)
2/([(i-Pr)
2NH
2]Cl)/FeCl
3/SiO
2；
T19：NiSO
4/([(i-Pr)(C
6H
5CH
2)NH
2]Cl)/AlBr
3/Al
2O
3；
T20：Ni(NO
3)
2/([(i-Pr)
2NH
2]Cl)/FeBr
3/MCM-48；
T21：ZnSO
4/([(C
2H
5)
3NH]Br)/AlCl
3/C；
T22：Zn(NO
3)
2/([(i-Pr)
2NH
2]Cl)/FeCl
3/SiO
2；
T23：Ag
2SO
4/([(i-Pr)(C
6H
5CH
2)NH
2]Cl)/AlBr
3/Al
2O
3；
T24：Co(NO
3)
2/([(i-Pr)
2NH
2]Cl)/FeBr
3/MCM-48。
Contrast preparation example 25-32: the preparation of denitrfying agent T25-T32
Except not carrying out the process of step S2, contrast preparation example 25-32 (namely contrast preparation example 26 to implement with the same way of preparation example 1 to implement with the identical embodiment of preparation example 1-8 respectively, preparation example 27...... forwards is successively contrasted to implement with the same way of preparation example 2, until contrast preparation example 32 to implement with the same way of preparation example 8), by gained denitrfying agent called after T25 in turn, T26, T27, T28, T29, T30, T31 and T32, namely after obtaining basic ionic liquid, by this basic ionic liquid, corresponding solid carrier (not carrying out the process of step S2) and metallic compound carry out the same treatment of step S3-S4 subsequently, thus obtain corresponding denitrfying agent.
Contrast preparation example 33-40: the preparation of denitrfying agent T33-T40
Except not adding respective metal compound in step S3, contrast preparation example 33-40 to implement with the identical embodiment of preparation example 1-8 (namely contrast preparation example 33 to implement with the same way of preparation example 1, contrast preparation example 34...... forwards successively to implement with the same way of preparation example 2 respectively, until contrast preparation example 40 to implement with the same way of preparation example 8), by gained denitrfying agent called after T33, T34, T35, T36, T37, T38, T39 and T40 in turn, i.e. gained denitrfying agent not loaded metal compound.
Contrast preparation example 41-48: the preparation of denitrfying agent T41-T48
Except the soxhlet type etc. not carrying out step S4 processes, contrast preparation example 41-48 to implement with the identical embodiment of preparation example 1-8 (namely contrast preparation example 41 to implement with the same way of preparation example 1, contrast preparation example 42...... forwards successively to implement with the same way of preparation example 2 respectively, until contrast preparation example 40 to implement with the same way of preparation example 8), by gained denitrfying agent called after T41, T42, T43, T44, T45, T46, T47 and T48 in turn, the solid namely finally obtained in step S3 is corresponding final denitrfying agent.
At this, contriver is specially described, for the formation of solid-loaded ionic-liquid denitrfying agent, and such as, " CuSO in preparation example 1
4/ ([(C
2h
5)
3nH] Br)/AlCl
3/ C ", its implication is only that to refer to this solid-loaded ionic-liquid denitrfying agent be " ([(C in the upper load of gac (C)
2h
5)
3nH] Br) and AlCl
3the ionic liquid formed ", then load the second metallic compound " CuSO again
4", instead of say that this denitrfying agent is mixed (in other words, just indicating each material used in its synthetic method) by this several component simply, the component constitutional formula of other denitrfying agent has same similar meaning.
In heavy oil, nitride removes experiment
Use the different denitrfying agents of gained of the present invention, carried out removing process to the nitride in heavy oil, thus investigated its denitrification ability.Wherein, the method for calculation of denitrification percent are the known methods in this area, and this is no longer going to repeat them.
Embodiment 1
Add denitrfying agent T1 in a kettle., airtight stirring, maintain normal pressure, and be warming up to 100 DEG C, then add wax tailings, make the weight ratio of denitrfying agent T1 and wax tailings be 1:10, continue stirring 10 minutes (namely reacting 10 minutes); After reaction terminates, stop stirring, ON cycle is water-cooled to room temperature, and reaction mixture is carried out centrifugal treating, isolates the wax tailings after denitrfying agent and denitrogenation, and the denitrification percent of this wax tailings is 96.4% as calculated.
Embodiment 2
Add denitrfying agent T2 in a kettle., airtight stirring, maintain normal pressure, and be warming up to 150 DEG C, then add long residuum, make the weight ratio of denitrfying agent T2 and long residuum be 1:30, continue stirring 20 minutes (namely reacting 20 minutes); After reaction terminates, stop stirring, ON cycle is water-cooled to room temperature, and reaction mixture is carried out centrifugal treating, isolates the long residuum after denitrfying agent and denitrogenation, and the denitrification percent of this long residuum is 95.1% as calculated.
Embodiment 3
Add denitrfying agent T3 in a kettle., airtight stirring, maintain normal pressure, and be warming up to 200 DEG C, then add vacuum residuum, make the weight ratio of denitrfying agent T3 and vacuum residuum be 1:50, continue stirring 30 minutes (namely reacting 30 minutes); After reaction terminates, stop stirring, ON cycle is water-cooled to room temperature, and reaction mixture is carried out centrifugal treating, isolates the vacuum residuum after denitrfying agent and denitrogenation, and the denitrification percent of this vacuum residuum is 97.4% as calculated.
Embodiment 4
Add denitrfying agent T4 in a kettle., airtight stirring, maintain normal pressure, and be warming up to 250 DEG C, then add wax tailings, make the weight ratio of denitrfying agent T4 and wax tailings be 1:70, continue stirring 40 minutes (namely reacting 40 minutes); After reaction terminates, stop stirring, ON cycle is water-cooled to room temperature, and reaction mixture is carried out centrifugal treating, isolates the wax tailings after denitrfying agent and denitrogenation, and the denitrification percent of this wax tailings is 96.5% as calculated.
Embodiment 5
Add denitrfying agent T5 in a kettle., airtight stirring, maintain normal pressure, and be warming up to 90 DEG C, then add long residuum, make the weight ratio of denitrfying agent T5 and long residuum be 1:90, continue stirring 50 minutes (namely reacting 50 minutes); After reaction terminates, stop stirring, ON cycle is water-cooled to room temperature, and reaction mixture is carried out centrifugal treating, isolates the long residuum after denitrfying agent and denitrogenation, and the denitrification percent of this long residuum is 96.2% as calculated.
Embodiment 6
Add denitrfying agent T6 in a kettle., airtight stirring, maintain normal pressure, and be warming up to 120 DEG C, then add vacuum residuum, make the weight ratio of denitrfying agent T6 and vacuum residuum be 1:100, continue stirring 60 minutes (namely reacting 60 minutes); After reaction terminates, stop stirring, ON cycle is water-cooled to room temperature, and reaction mixture is carried out centrifugal treating, isolates the vacuum residuum after denitrfying agent and denitrogenation, and the denitrification percent of this vacuum residuum is 95.9% as calculated.
Embodiment 7
Add denitrfying agent T7 in a kettle., airtight stirring, maintain normal pressure, and be warming up to 170 DEG C, then add wax tailings, make the weight ratio of denitrfying agent T7 and wax tailings be 1:30, continue stirring 30 minutes (namely reacting 30 minutes); After reaction terminates, stop stirring, ON cycle is water-cooled to room temperature, and reaction mixture is carried out centrifugal treating, isolates the wax tailings after denitrfying agent and denitrogenation, as calculated the denitrification percent 96.8% of this wax tailings.
Embodiment 8
Add denitrfying agent T8 in a kettle., airtight stirring, maintain normal pressure, and be warming up to 190 DEG C, then add long residuum, make the weight ratio of denitrfying agent T8 and long residuum be 1:20, continue stirring 50 minutes (namely reacting 50 minutes); After reaction terminates, stop stirring, ON cycle is water-cooled to room temperature, and reaction mixture is carried out centrifugal treating, isolates the long residuum after denitrfying agent and denitrogenation, and the denitrification percent of this long residuum is 95.8% as calculated.
Embodiment 9-16
(denitrfying agent by embodiment 1 is replaced with T9 by T1, the denitrfying agent in embodiment 2 is replaced with T10...... forwards successively by T2 respectively the denitrfying agent in embodiment 1-8 to be replaced with denitrfying agent T9-T16, until the denitrfying agent in embodiment 8 is replaced with T16 by T8), calculate respective denitrification percent respectively.
Embodiment 17-24
(denitrfying agent by embodiment 1 is replaced with T17 by T1, the denitrfying agent in embodiment 2 is replaced with T18...... forwards successively by T2 respectively the denitrfying agent in embodiment 1-8 to be replaced with denitrfying agent T17-T24, until the denitrfying agent in embodiment 8 is replaced with T24 by T8), calculate respective denitrification percent respectively.
Embodiment 25-32
(denitrfying agent by embodiment 1 is replaced with T25 by T1, the denitrfying agent in embodiment 2 is replaced with T26...... forwards successively by T2 respectively the denitrfying agent in embodiment 1-8 to be replaced with denitrfying agent T25-T32, until the denitrfying agent in embodiment 8 is replaced with T32 by T8), calculate respective denitrification percent respectively.
Embodiment 33-40
(denitrfying agent by embodiment 1 is replaced with T33 by T1, the denitrfying agent in embodiment 2 is replaced with T34...... forwards successively by T2 respectively the denitrfying agent in embodiment 1-8 to be replaced with denitrfying agent T33-T40, until the denitrfying agent in embodiment 8 is replaced with T40 by T8), calculate respective denitrification percent respectively.
Embodiment 41-48
(denitrfying agent by embodiment 1 is replaced with T41 by T1, the denitrfying agent in embodiment 2 is replaced with T42...... forwards successively by T2 respectively the denitrfying agent in embodiment 1-8 to be replaced with denitrfying agent T41-T48, until the denitrfying agent in embodiment 8 is replaced with T48 by T8), calculate respective denitrification percent respectively.
The denitrification percent of above-described embodiment 9-48 is as shown in the table, but in order to contrast more intuitively, will together list the denitrification percent of embodiment 1-8:
As seen from the above table, MX in step sl
2 nin all more options, wherein aluminum chloride, iron trichloride, alchlor or ferric bromide have best effect, and the effect of iron protochloride, zinc chloride, zinc bromide, ferrous bromide decreases (see embodiment 9-16).
And in the metallic compound of step S3, copper sulfate and Silver Nitrate have best denitrification effect, even if the cupric nitrate very similar with copper sulfate, Silver Nitrate and Sulfuric acid disilver salt, its effect also has significantly reduction (see embodiment 17-24).
When solid carrier does not carry out twice strong acid treatment of step S2, its denitrification percent has significant reduction, this may be through acidification and improve denitrification effect, demonstrates to carry out twice acid treatment like this of the present invention to solid carrier and significantly can improve denitrification effect (see embodiment 25-32).
When non-load the second metallic compound, find that denitrification percent has significantly to reduce, be reduced to 26.5-32.6%, this demonstrate that the necessity of load the second metallic compound, only have load the second metallic compound and specific metallic compound, just can obtain best technique effect (see embodiment 17-24 and 33-40).
And from embodiment 41-48, the soxhlet type process of step S4 has certain impact for denitrification effect equally, it may be that extracting process so has washed away unnecessary the second metal ion that contriver infers, thus make the denitrification activity site of this solid-loaded ionic-liquid denitrfying agent more even, the interference of unnecessary non-loaded metal ion can be avoided, thus improve denitrification effect to a certain extent.
The circulation active testing of denitrfying agent
In order to test stabilizing power and the cycling denitrification ability of solid-loaded ionic-liquid denitrfying agent of the present invention, respectively the denitrfying agent separated in embodiment 1-8 is carried out cycling denitrification test under the same terms of respective embodiment, measure respectively its circulation 5 times, 10 times and 15 times after denitrification percent, the denitrification percent measured for wherein 5 times, 10 times and 15 times all refer to the denitrfying agent of embodiment 1-8 circulated respectively after 5 times, test result after circulation 10 times and after circulation 15 times, see the following form:
As seen from the above table, solid-loaded ionic-liquid denitrfying agent of the present invention has and good recycles ability, even if after circulation 15 times, still there is identical high denitrification percent, this demonstrate that it has excellent denitrogenation stabilizing power, thus can repeatedly use, manufacturing cost can be reduced significantly, provide the foundation for heavy industrialization uses.
In sum, can clearly be found out by above-mentioned all embodiments, the invention provides a kind of removal methods with nitride in the heavy oil of desirable denitrification percent, by each component of denitrfying agent in this removal methods, particular procedure in the specific selection of consumption etc. and combination and preparation method and the use of parameter, thus make this denitrfying agent have good denitrification ability and recycle ability, and in denitrogenation operation, without the need to using any organic solvent, thus it is simple to have technique, environmental protection, the plurality of advantages such as with low cost, it is a kind of method removing nitride in heavy oil having very much prospects for commercial application.
Should be appreciated that the purposes of these embodiments is only not intended to for illustration of the present invention limit the scope of the invention.In addition; also should understand; after having read technology contents of the present invention, those skilled in the art can make various change, amendment and/or modification to the present invention, and these all equivalent form of values fall within the protection domain that the application's appended claims limits equally.
Claims (10)
1. the removal methods of nitride in heavy oil, described method comprises the steps: to make solid-loaded ionic-liquid denitrfying agent and heavy oil generation denitrification reaction, after having reacted, reaction system is cooled, reaction mixture carries out centrifugal treating, is separated by denitrfying agent, obtains the heavy oil after denitrogenation.
2. removal methods as claimed in claim 1, is characterized in that: the weight ratio of described solid-loaded ionic-liquid denitrfying agent and heavy oil is 1:10-100; Temperature of reaction is 80-250 DEG C; Reaction times is 10-60 minute.
3. removal methods as claimed in claim 1 or 2, is characterized in that: described solid-loaded ionic-liquid denitrfying agent is prepared in accordance with the following steps:
S1: by [R
1r
2r
3nH] X
1with MX
2 nmix according to mol ratio 1:1-3, be at room temperature uniformly mixed 20-40 minute, then raised temperature is to 80-100 DEG C, and Keep agitation 2-6 hour at such a temperature, after having reacted, naturally cool to room temperature, dry, obtain basic ionic liquid;
S2: joined by solid carrier in acidic solution, reflow treatment, then filters and obtains solids A; By solids A stir process in mixing acid again, filter, by extremely neutral for the solids B deionized water wash obtained, vacuum-drying, obtains drying solid thing;
S3: join in solvent by the basic ionic liquid of step S1, the drying solid thing of step S2, metallic compound, under an inert atmosphere, stirs and is warming up to 60-90 DEG C, reaction 12-25 hour; After reaction terminates, leave standstill cooling, suction filtration, drying, obtain solid;
S4: the gained solid of step S3 is put into apparatus,Soxhlet's, with solvent extraction 3-12 hour, then filters, deionized water wash, dry, obtain described solid-loaded ionic-liquid denitrfying agent.
4. removal methods as claimed in claim 3, is characterized in that: in step sl, R
1, R
2and R
3be H, C independently of one another
1-6alkyl or benzyl, and wherein at least one is not H; X
1, X
2be halogen independently of one another; M is aluminium, iron or zinc; N is the integer of 2-4.
5. the removal methods as described in claim 3 or 4, is characterized in that: in step sl, described MX
2 ncan be any one in aluminum chloride, iron trichloride, iron protochloride, zinc chloride, alchlor, ferric bromide, zinc bromide, ferrous bromide etc., most preferably be aluminum chloride, iron trichloride, alchlor or ferric bromide.
6. the removal methods as described in any one of claim 3-5, is characterized in that: in step s 2, and described solid carrier is selected from gac, SiO
2, any one in aluminum oxide or mesopore molecular sieve or any multiple mixture.
7. the removal methods as described in any one of claim 3-6, is characterized in that: in step s 2, and described mixing acid is the mixed solution of the vitriol oil and concentrated nitric acid, and wherein the volume ratio of the vitriol oil and concentrated nitric acid is 2-4:1.
8. the removal methods as described in any one of claim 3-7, it is characterized in that: in step s3, described metallic compound is any one in copper sulfate, cupric nitrate, cuprous sulfate, single nickel salt, nickelous nitrate, zinc sulfate, zinc nitrate, Sulfuric acid disilver salt, Silver Nitrate or Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES or any multiple mixture; Most preferably be copper sulfate or Silver Nitrate.
9. the removal methods as described in any one of claim 3-8, is characterized in that: in step s3, and the mass ratio of the basic ionic liquid of step S1, the drying solid thing of step S2, metallic compound is 1:2-4:0.1-1.5.
10. the solid-loaded ionic-liquid denitrfying agent in removal methods described in any one of claim 1-9.
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| US8734639B2 (en) * | 2007-04-06 | 2014-05-27 | Exxonmobil Research And Engineering Company | Upgrading of petroleum resid, bitumen or heavy oils by the separation of asphaltenes and/or resins therefrom using ionic liquids |
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| US8734639B2 (en) * | 2007-04-06 | 2014-05-27 | Exxonmobil Research And Engineering Company | Upgrading of petroleum resid, bitumen or heavy oils by the separation of asphaltenes and/or resins therefrom using ionic liquids |
| CN102816584A (en) * | 2012-08-16 | 2012-12-12 | 西安建筑科技大学 | Water-soluble desulfurization agent, preparation and application thereof |
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