CN1624080A - Modifier for improving oil quality - Google Patents
Modifier for improving oil quality Download PDFInfo
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- CN1624080A CN1624080A CN 200310114405 CN200310114405A CN1624080A CN 1624080 A CN1624080 A CN 1624080A CN 200310114405 CN200310114405 CN 200310114405 CN 200310114405 A CN200310114405 A CN 200310114405A CN 1624080 A CN1624080 A CN 1624080A
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- molecular sieve
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Abstract
A modified for improving the quality of gasoline, diesel oil, and lubricating oil by fixed-bed reactor is a carbon-type molecular sieve prepared through carbonizing at 600-12000 deg.C, activating, preparing molecula sieve, surface modifying, washing with distilled water, drying, calcining at 200-5000 deg.C and shaping.
Description
One, technical field: the technology that the invention discloses a kind of car, merchantable fuels oil peculiar to vessel, lubricant upgrading agent.
Two, background technology: (1) diesel modifying state of the art:
1, traditional method for modifying---soda finishing is to adopt the alkaline solution of 25%-30% concentration to remove the sulfide of part oxygenatedchemicals and easy oxidation in the diesel oil, reduce the colloid and the sediment of diesel oil, make diesel quality obtain to a certain degree improvement, this is the method that present domestic refinery generally adopts.Though the diesel quality behind soda finishing is improved, can not fundamentally solve sulphur in the diesel oil, chlorine, problem that aromaticity content is high, especially to diesel oil from the heavy catalytic cracking (heavy oil is urged bavin), it is powerless that soda finishing more seems.
2, hydrofining is more refining at present means, can remove sulphur in the diesel oil, nitrogen, oxygen compound effectively by hydrofining, and make alkene saturated, improves the quality (particularly stability) of urging bavin significantly.But hydrofining is difficult to increase substantially diesel-fuel cetane number, poor effect under the general condition, and pressure will reach more than the 7-8MPa at least, could improve the quality of urging bavin more significantly, but this surpassed hydrorefined scope.
3, MHUG, conventional hydrofining can remove impurity such as the sulphur of urging in the bavin, nitrogen effectively, the color etc. of oil product is improved, but urge the cetane value of bavin to improve seldom for heavy oil.It is wherein aromatic hydrocarbons and naphthene content height that heavy oil is urged the low major cause of the cetane value of bavin, and in total aromatic hydrocarbons half to be arranged be dicyclo and the above aromatic hydrocarbons of dicyclo.Heavy oil urges bavin to carry out hydrofining under middle pressure or lower pressure, the above aromatic hydrocarbons of dicyclo is transformed by a relatively large margin, but owing to be subjected to the restriction of thermodynamic(al)equilibrium, the reaction product that generates mostly is the cycloalkyl mononuclear aromatics, total aromaticity content changes little, therefore cetane value can only improve 5～6 units, can not satisfy the diesel oil requirement of dispatching from the factory, more do not reach new regulation to aromaticity content less than 20 requirement.There is data to show,, then aromaticity content will be reduced by 2%～10%, need the above pressure of 8.0MPa if make heavy oil urge the cetane value of bavin to improve 3-5 unit; If cetane value will be improved 9-12 unit, then to make the aromatic hydrogenation more than 25% saturated, need the reaction pressure of 14.0MPa.
4, solvent treatment adopts the comprehensive method of extraction of Tsing-Hua University that the bavin double solvent extraction is urged in triumph, and yield is 90.8%, and cetane value brings up to 40.2 from 31.6.University of Petroleum utilizes a kind of solvent that poor ignition quality fuel is made with extra care, and has improved the stability of diesel oil, and yield is higher than 95%.What of extraction aromatic hydrocarbons diesel quality after the solvent treatment depend on, China some urge the bavin aromaticity content up to more than 60%, so select suitable solvent, the above aromatic hydrocarbons of dicyclo that removes in the diesel oil is the problem that should inquire into from now on.
(2) the gasoline upgrading state of the art:
The low sulfuration of gasoline upgrading will improve the cost of gasoline undoubtedly.In gasoline pool, catalytic cracking (FCC) is the most important formation component of gasoline, thus vehicle gasoline and sulfur content in vehicle gasoline 90% from FCC gasoline.Concentrate on the heavy naphtha fraction among the FCC, as shown in table 1.
The project boiling range ℃ accounts for FCC gasoline, and % accounts for cut, %
Light naphthar C5～120 60 15
Middle petroleum naphtha 120～175 25 25
Heavy naphtha 175～220 15 60
The desulfurization that focuses on FCC gasoline of gasoline desulfur, at present main employing technology and technology are as follows::
1) reduces FCC gasoline final boiling point.Full range FCC content of sulfur in gasoline is 700～1500ug/g.Because sulphur concentrates on the heavy naphtha fraction of PCC gasoline, if final boiling point is reduced to 1750C, sulphur content just can drop to 400～600ug/g, and the advantage of this method is simple, and shortcoming is the loss yield of gasoline, and octane value also may slightly descend.And sulphur content is also fallen less than below the 50ug/g.
2) FCC gasoline hydrogenation of total effluent is refining.Adopt this method sulphur content can be dropped to 50ug/g, but because the alkene in the light gasoline fraction is able to saturatedly, and gasoline octane rating RON will lose 7～8 units, MON to lose 3-4 unit.
3) FCC gasoline heavy fractioning hydrogenation is refining.Only to FCC gasoline last running to carry out hydrorefined method relatively actual, can avoid the saturated of alkene in the light gasoline fraction, make loss of octane number minimum.
4) FCC gasoline lighting end MEROX extraction process is handled.Sulphur compound in the lighting end of FCC gasoline mainly is a mercaptan, and available MEROX extraction process removes.Compare with the FCC gasoline hydrofinishing, under the identical desulfurization degree, the RON of this method only loses 1.0, and MON only loses 0.8.
5) FCC gasoline last running liquid-liquid extraction process desulfurization.Some many alkyl glycols kind solvents can be extracted sulphur compound effectively out from FCC gasoline, and can reduce the loss of alkene and octane value.
6) FCC gasoline last running cracking again.Catalyst cracker is got back in FCC gasoline last running recirculation, can be made content of sulfur in gasoline reduce by 50%, increase by 4 units of octane value simultaneously, about 6% but gasoline yield descends, and also the liquefied petroleum gas (LPG) productive rate will rise.
7) ISAL selective hydrogenation refining technology.ISAL technology is developed jointly by Venezuela INTEEP SA and Uop Inc., it is refining to be similar to petroleum naphtha hydrogenation, with dual-function catalyst to the full cut of FCC gasoline, petroleum naphtha or heavy constituent (C8, C9) carry out desulfurization, sulphur content can be dropped to very low, alkene obtains saturated, and octane value and yield losses are seldom.
8) the full cut absorption method of FCC gasoline desulfurization.Various zeolites and solid solution all can be used as sorbent material, are used for removing the compound such as sulphur, nitrogen, oxygen of gasoline, as the Hydrotalcite sorbent material, can optionally remove the compound of multiple sulphur, include machine sulfide, thio-alcohol and thiophene-based.This technology is just under development.
(3) the lubricant upgrading state of the art: lubricating oil improves technology and utilizes the adsorptivity of carclazyte to handle more, and the used carclazyte amount of this method is big, and cost is higher, and environmental pollution is serious, and the quality of lubrication oil after the improvement is relatively poor.
More than various technologies can reduce the sulphur content of gasoline to some extent.Also can take some process combination, in the hope of octane value and yield losses minimum.But optimal selection then is the hydrogenation pre-treatment of FCC charging, and raw material is after the hydrogenation pre-treatment, and the ratio of the sulphur content of the gasoline of producing and feed sulphur content has only 1: 20.For example, be the FCC apparatus charging with the decompression gas oil of Arabian light VGO, feed sulphur content is 2.5%, the FCC content of sulfur in gasoline that obtains is 2500ug/g; If this charging is 95% through its desulfurization degree of hydrogenation pre-treatment, then feed sulphur content reduces to 0.125%, and the FCC content of sulfur in gasoline that obtains is reduced to 60ug/g; In addition, can also reduce metal content, nitrogen content and the carbon residue of charging.But the investment of this device is bigger.
Comprehensive the above, merely by desulfurization to improve oil quality, no matter adopt above-mentioned which kind of means, always exist some oil quality to be had the factor of negative impact.Therefore, the upgrading of oil product should be based upon on new technology and the technology basis, with the quality of comprehensive raising tank oil.
Three, summary of the invention: purpose of the present invention is exactly at the present situation of existing oil product modification technology and the problem of existence, proposes a kind of modification agent that is used to improve oil quality, to improve the quality of tank oil.
Technical scheme of the present invention comprises:
This technology adopts a special upgrading material, under mild conditions to poor quality oil particularly catalyzed oil carry out upgrading, with preparation green environment processed oil.This exotic materials, be to utilize process for modifying surface, the carbonaceous molecular sieve is carried out surface modification, make it have the kinds of surface activity, promptly can handle sour sulfur component in the inferior patrol as the surface alkalinty group, the surface acidity group then can be handled alkali nitrogen component wherein.Pore structure that the carbonaceous molecular sieve is special and distribution can effective eliminations to components such as the colloid in the oil product, condensed-nuclei aromaticss.Owing to adopt this collection to react, adsorb, be absorbed in the type material of one, make oil product change technology, quality all is significantly improved.
1, upgrading material and surface modification technology thereof:
The upgrading material of selecting for use is the novel carbonaceous molecular sieve of a class.This molecular sieve analog material is to be raw material with coal tar, heavy oil residue, refinery coke, pitch etc., with basic metal, alkaline earth metal oxide, oxyhydroxide, carbonate, nitrate, transition metal oxide, oxyhydroxide, nitrate are coating materials, under 600～12000C, 0.1～0.5MPa pressure, through making former dose after the treating processess such as charing, activation, molecular sieveization and finishing.Former dose is passed through in distilled water wash, air drying, the vacuum again and (makes carbonaceous molecular sieve finished product after 200～5000C) roastings, the moulding.Its specific surface can effectively be controlled as requested, and generally at 1000～3500m3/g, main aperture is between 0.5～5nm, and density is between 0.2～0.5g/ml.
2, upgrading material and finishing technology thereof:
Synthetic and the modified technique of carbonaceous molecular sieve is through hundreds of inferior continuous experiment and optimizations, and its technology is fixed to:
1) single stage method: i.e. treating processess such as charing, activation, molecular sieveization and finishing were finished in a step, and then made carbonaceous molecular sieve finished product through subsequent disposal.Its processing condition are: raw material, activator, modifier are at first pulverized, and mix, and place in the fixed bed stainless steel cauldron, and at temperature of reaction 600～12000C, sustained reaction 1～5h promptly under the nitrogen protection of 10～50ml/min.
2) two-step approach: i.e. treating processess such as charing, activation, molecular sieveization were finished in a step, carried out finishing then, made carbonaceous molecular sieve finished product through subsequent disposal again.Its processing condition are: raw material, activator are at first pulverized; mix by a certain percentage; place in the fixed bed stainless steel cauldron, at temperature of reaction 600～12000C, sustained reaction 1～5h under the nitrogen protection of 10～50ml/min; finish charing, activation, molecular sieve process; be cooled to room temperature then, add modifier powder or solution, and mix; modify 1～3h at 200～10000C, make through subsequent disposal again.
3) multistep processes: promptly treating processes such as charing, activation was finished in a step, carry out molecular sieveization then, carried out finishing again, made carbonaceous molecular sieve finished product through subsequent disposal at last.Its processing condition are: raw material, activator are at first pulverized; mix; place in the fixed bed stainless steel cauldron; at temperature of reaction 600～12000C; sustained reaction 1～5h under the nitrogen protection of 10～50ml/min; finish charing, reactivation process; again at 600～12000C; finish molecular sieveization in the aqueous vapor of 50～100ml/min or the carbon dioxide gas stream; and then be cooled to room temperature, add modifier powder or solution, and mix; modify 1～3h at 200～10000C, make through subsequent disposal again.
The effect of invention:
1) upgraded condition gentleness, upgrading temperature can utilize the regeneration waste heat to realize that heat optimization uses between room temperature～50 ℃ fully.
2) the upgrading material has surface acidity, can effectively handle alkali nitrogen component in the stock oil, and denitrification percent can reach more than 80%.
3) the upgrading material has certain surface alkalinty through surface modification, can handle the sour sulfur component in the stock oil efficiently, and as mercaptan, the mercaptan removal rate has very high deodorization ability up to more than 90%.Effect obviously is better than oxidation deodorizing, solvent treatment etc.
4) modification agent has the very high ability that removes to complicated sulphur components such as thiophenic sulfurs, and decreasing ratio can reach more than 80%, and this is the incomparable key character of soda finishing, hydrofining.
5) utilize the special microvoid structure of upgrading material, can the effective elimination condensed-nuclei aromatics, heavy constituent such as colloid, improve the performance such as colourity, stability of gasoline.Effect obviously is better than hydrofining.
6) in the upgrading treating processes, owing to do not have processes such as alkene is saturated, so the octane value of gasoline is constant substantially behind the upgrading, the problem that the octane value of effectively having avoided hydrofining to bring descends.
7) this class oil product modification agent can regenerated under the mild conditions relatively, and long service life can reach 2000g gasoline/g modification agent.
8) handle through above non-hydro-upgrading, inferior feedstock oil is reached or be higher than national branded oil standard, net effect obviously is better than soda finishing, solvent treatment and hydrofining etc.
Four, description of drawings: do not have
Five, embodiment:
1. the preparation of carbonaceous molecular sieve: with heavy oil residue 10g is raw material, with alkali metal hydroxide KOH, 30g is an activator, with alkaline earth metal oxide CaO, 10g is a coating materials, in the charing of 800～12000C process, activation, molecular sieveization, finishing makes the agent of carbonaceous molecular screen primary, washing then, dry, the carbonaceous molecular sieve of obtained by molding, its specific surface is 3442m2/g, micropore＜1nm, pore volume 1.98ml/g, micropore (＜1nm) mean pore size 0.58nm, macropore (the pore volume 1.56ml/g of 1nm＜D＜300nm), macropore (the mean pore size 2.51nm of 1nm＜D＜300nm), surface acid amount 0.00057mol/g.cat, surperficial alkali number 0.00043mol/g.cat, ash content 0.5%.
2. the upgrading of inferior patrol: get 10g carbonaceous sieve sample and be loaded on micro fixed-bed reactor, under the 800C condition, introduce inferior patrol (vapour is urged in triumph), make it flow through the modification agent bed, collect reformulated gasoline then, and carry out every index analysis.The result shows that the accessible inferior patrol of this modification agent (vapour is urged in triumph) amount is 5130ml.Then at 1200C with modification agent manipulation of regeneration 2h, continue to handle, until continuing regeneration, the result can handle inferior patrol (vapour is urged in triumph) 5150ml.Be that modification agent/inferior patrol ratio is 1: 923.Repeatedly experiment shows that this ratio is generally at 1: 800～1: 1500.With the quality of stock oil quality, amplitude changes to some extent.After the processing, every index of gasoline all makes moderate progress, and reaches the specification of quality of national premium.As sulphur content 0.014%, mercaptan sulfur 0.0003%, existent gum 0.8mg/100ml, doctor test, copper corrosion are all qualified, and colourity is colourless bright.After placing first quarter moon, colourity is constant.Illustrate that stability increases.
Claims (4)
1, a kind of modification agent that is used to improve oil quality, it is characterized in that the upgrading material of selecting for use is the novel carbonaceous molecular sieve of a class, this molecular sieve analog material is to be raw material with coal tar, heavy oil residue, refinery coke, pitch etc., with basic metal, alkaline earth metal oxide, oxyhydroxide, carbonate, nitrate, transition metal oxide, oxyhydroxide, nitrate are coating materials.
2, the modification agent that is used to improve oil quality according to claim 1, it is characterized in that under 600～12000C, 0.1～0.5MPa pressure, through making former dose after the treating processess such as charing, activation, molecular sieveization and finishing, former dose is passed through in distilled water wash, air drying, the vacuum again and (makes carbonaceous molecular sieve finished product after 200～5000C) roastings, the moulding, its surface effectively is controlled at 1000～2000m3/g, main aperture is between 0.5～5nm, and density is between 0.2～0.5g/m1.
3, the modification agent that is used to improve oil quality according to claim 2; it is characterized in that: raw material, activator, modifier are at first pulverized; mix; place in the fixed bed stainless steel cauldron; at temperature of reaction 600～12000C, sustained reaction 1～5h promptly under the nitrogen protection of 10～50ml/min.
4, the modification agent that is used to improve oil quality according to claim 2; it is characterized in that: raw material, activator are at first pulverized; mix by a certain percentage; place in the fixed bed stainless steel cauldron; at temperature of reaction 600～12000C; sustained reaction 1～5h under the nitrogen protection of 10～50ml/min; finish charing, activation, molecular sieve process; be cooled to room temperature then; add modifier powder or solution; and mix, modify 1～3h at 200～10000C, make through subsequent disposal again.
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| CN 200310114405 CN1624080A (en) | 2003-12-03 | 2003-12-03 | Modifier for improving oil quality |
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| CN 200310114405 CN1624080A (en) | 2003-12-03 | 2003-12-03 | Modifier for improving oil quality |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9228133B2 (en) | 2010-11-05 | 2016-01-05 | Industrial Technology Research Institute | Method for refining oil |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9228133B2 (en) | 2010-11-05 | 2016-01-05 | Industrial Technology Research Institute | Method for refining oil |
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